WO2012100100A2 - Slippery liquid-infused porous surfaces and biological applications thereof - Google Patents

Slippery liquid-infused porous surfaces and biological applications thereof Download PDF

Info

Publication number
WO2012100100A2
WO2012100100A2 PCT/US2012/021929 US2012021929W WO2012100100A2 WO 2012100100 A2 WO2012100100 A2 WO 2012100100A2 US 2012021929 W US2012021929 W US 2012021929W WO 2012100100 A2 WO2012100100 A2 WO 2012100100A2
Authority
WO
WIPO (PCT)
Prior art keywords
fluid
substrate
liquid
article
biological material
Prior art date
Application number
PCT/US2012/021929
Other languages
French (fr)
Other versions
WO2012100100A3 (en
Inventor
Joanna Aizenberg
Benjamin Hatton
Donald Elliott INGBER
Michael Super
Tak Sing Wong
Original Assignee
President And Fellows Of Harvard College
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to AU2012207206A priority Critical patent/AU2012207206B2/en
Priority to US13/980,858 priority patent/US9932484B2/en
Priority to KR1020137021610A priority patent/KR101966272B1/en
Priority to PCT/US2012/021929 priority patent/WO2012100100A2/en
Priority to CN201280012210.1A priority patent/CN103703085B/en
Priority to JP2013550592A priority patent/JP6563173B2/en
Priority to EP12705182.9A priority patent/EP2665783A2/en
Priority to CA2825012A priority patent/CA2825012C/en
Application filed by President And Fellows Of Harvard College filed Critical President And Fellows Of Harvard College
Publication of WO2012100100A2 publication Critical patent/WO2012100100A2/en
Publication of WO2012100100A3 publication Critical patent/WO2012100100A3/en
Priority to AU2016200048A priority patent/AU2016200048B2/en
Priority to AU2017239543A priority patent/AU2017239543B2/en
Priority to US15/944,619 priority patent/US10550272B2/en
Priority to US16/780,792 priority patent/US10982100B2/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1693Antifouling paints; Underwater paints as part of a multilayer system
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/34Oils, fats, waxes or natural resins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/46Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/34Macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L33/00Antithrombogenic treatment of surgical articles, e.g. sutures, catheters, prostheses, or of articles for the manipulation or conditioning of blood; Materials for such treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L33/00Antithrombogenic treatment of surgical articles, e.g. sutures, catheters, prostheses, or of articles for the manipulation or conditioning of blood; Materials for such treatment
    • A61L33/0094Physical treatment, e.g. plasma treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L33/00Antithrombogenic treatment of surgical articles, e.g. sutures, catheters, prostheses, or of articles for the manipulation or conditioning of blood; Materials for such treatment
    • A61L33/06Use of macromolecular materials
    • A61L33/064Use of macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1656Antifouling paints; Underwater paints characterised by the film-forming substance
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1681Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F15FLUID-PRESSURE ACTUATORS; HYDRAULICS OR PNEUMATICS IN GENERAL
    • F15DFLUID DYNAMICS, i.e. METHODS OR MEANS FOR INFLUENCING THE FLOW OF GASES OR LIQUIDS
    • F15D1/00Influencing flow of fluids
    • F15D1/02Influencing flow of fluids in pipes or conduits
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F15FLUID-PRESSURE ACTUATORS; HYDRAULICS OR PNEUMATICS IN GENERAL
    • F15DFLUID DYNAMICS, i.e. METHODS OR MEANS FOR INFLUENCING THE FLOW OF GASES OR LIQUIDS
    • F15D1/00Influencing flow of fluids
    • F15D1/10Influencing flow of fluids around bodies of solid material
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/12Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers

Definitions

  • the present disclosure relates generally to surfaces that prevent adsorption or deposition from fluids, solids, or mixtures of fluids and solids of biological origin, and uses thereof.
  • Biofilms Bacteria exist in their natural state predominantly as members of bio films - structured, multicellular communities adherent to surfaces in natural and anthropogenic environments. These communities are composed of many cells embedded within a polymeric organic matrix. Biofilm formation is of concern to industry and healthcare because it causes contamination of plumbing, oil wells, heat exchangers, building ventilation, food storage, medical implants, and other systems. Biofilms threaten human health by triggering an immune response, releasing harmful endotoxins and exotoxins, and clogging indwelling catheters; in fact, biofilms are responsible for nearly 100,000 nosocomial deaths annually in the United States and 80% or more of all microbial infections in humans.
  • ECM acts as a diffusion barrier and as a charged binding filter for certain antibiotics, and that it complements enzymes and multidrug resistance pumps on cells that remove antimicrobials.
  • the resistance to threats covers a wide range of treatments: biofilms exposed to chlorine bleach for 60 minutes are reported to still have live cells; biofilms in pipes continuously flushed over 7 days with multiple biocides recolonize the pipes, and biofilms have been reported to survive in bottled iodine solution for up to 15 months.
  • Biofilms' resistance to antimicrobials may be related to the extreme nonwettability of their surface as well as resistance to vapor penetration.
  • SLIPS synthetic slippery liquid-infused porous surfaces
  • an article for repelling a biological material comprising a lubricating fluid layer.
  • the lubricating fluid layer is immiscible with the repelled biological material, and forms an ultra-smooth surface.
  • the lubricating fluid layer is stabilized in place by the underlying substrate.
  • the article has a solid substrate on which the lubricating fluid adheres. The substrate is preferentially wetted by the lubricating fluid. The solid substrate and lubricating fluid form a slippery surface configured and arranged to contact a biological material.
  • an article having a repellant surface is disclosed.
  • a lubricating fluid wets and adheres to a solid substrate comprising a roughened surface to form a stabilized liquid overlayer.
  • the roughened surface and the liquid covering it have an affinity for each other such that the lubricating liquid is substantially immobilized on the substrate.
  • a device capable of repelling a biological material comprising a lubricating fluid layer.
  • the lubricating fluid layer is immiscible with the repelled biological material, and forms an ultra-smooth surface.
  • the device has a solid substrate on which the lubricating fluid adheres. The substrate is preferentially wetted by the lubricating fluid.
  • the solid substrate and lubricating fluid form a slippery surface configured and arranged to contact a biological material.
  • a method of preventing adhesion, adsorption, surface- mediated clot formation, or coagulation of a biological material comprises providing a lubricating fluid layer, wherein the lubricating fluid is immiscible with the biological material; providing a solid substrate, wherein the lubricating fluid adheres to the substrate to form a slippery liquid-infused surface; and contacting the biological sample to the surface.
  • a method of making an article having a slippery surface is disclosed.
  • a solid substrate is roughened and contacted with a lubricating liquid that forms a lubricating fluid layer.
  • the roughened solid substrate and the lubricating layer form a slippery surface, and are configured and arranged for contact with a material that is immiscible with the lubricating liquid.
  • an optically transparent device that prevents adhesion of biological material.
  • a roughened surface that is a transparent window is wetted by a lubricating fiuid that adheres to the roughened surface to form an over-coated layer.
  • the roughened surface of the transparent window has a greater affinity towards the lubricating fluid as compared to a biological material.
  • the index of refraction of the lubricating liquid is substantially similar to the index of refraction of the roughened surface.
  • the lubricating liquid and the biological material are substantially chemically inert with each other.
  • the device is a biological sensor window.
  • an article having a low adhesion surface for preventing or reducing biofilm attachment comprises a solid substrate having a roughened surface and a lubricating fiuid that adheres to and
  • the liquid upper surface is configured and arranged to contact a biological material of interest.
  • the lubricating fluid is immiscible with the biological material, and the biological material exhibits little or no adhesion to the article.
  • the following two conditions are satisfied when the article is exposed to Medium X, where X is air/gas/water/immiscible biological material: ?(yBxCOS ⁇ B x - 7AXCOS ⁇ AX) - 7AB > 0 (e2) and ?(yBxCOs6>Bx - 7AXCOS ⁇ AX) + 7AX - 7BX > 0 (e3), wherein ⁇ AX is the interfacial energies of the biological material with a surrounding medium, y B x is the interfacial energies of the lubricating fiuid with the surrounding medium, ⁇ AB is the interfacial energies of the biological material and the lubricating fluid interface, ⁇ is the equilibrium contact angle of the biological material on a flat solid surface immersed under the surrounding medium, 61 ⁇ 2x is the equilibrium contact angle of the lubricating fluid on a flat solid surface immersed under the surrounding medium, and R is a roughness
  • the lubricating fluid prevents adhesion, coagulation, or clot formation of biological materials.
  • the method further mediates inflammation, wound healing, plaque disposition, or foreign body response.
  • the method inhibits inflammation, wound healing, plaque disposition, or foreign body response.
  • the method prevents inflammation, wound healing, plaque disposition, or foreign body response.
  • the method further prevents bacterial contamination.
  • the surface is selected from the group consisting of a cannula, connector, catheter, needle, capillary tube, tubing, syringe and combinations thereof.
  • the surface is selected from the group consisting of a slide, plate, film, work surface, well, well plate, Petri dish, tile, jar, flask, beaker, vial, test tube, column, container, cuvette, bottle, drum, vat, tank, and combinations thereof.
  • the surface is selected from the group consisting of a clamp, skin hook, cuff, retractor, shunt, needle, capillary tube, tubing, and combinations thereof.
  • the surface is selected from the group consisting of an endotracheal tube, ventilator, associated ventilator tubing, drug delivery vehicle, syringe, endoscope, dialysis equipment, central veno-venous hemofiltration device, extracorporeal membrane oxygenation equipment, and combinations thereof.
  • the surface is selected from the group consisting of an organ, artificial organ, implant, and combinations thereof. [0034] In one or more aspects, the surface is selected from the group consisting of a biosensor, biological microelectromechanical devices (bioMEMs), bioelectrode, and combinations thereof.
  • bioMEMs biological microelectromechanical devices
  • the surface is a wound dressing.
  • the substrate is preferentially wetted by the lubricating fluid.
  • the lubricating fluid infiltrates the substrate by capillary action.
  • the solid substrate is electrically conductive, non- conductive, magnetic, non-magnetic, elastic, non-elastic, light sensitive, or not light sensitive.
  • the solid substrate is silanized.
  • the substrate is a roughened surface comprising a porous material.
  • microparticles or nanoparticles are applied to a flat substrate to form a roughened, porous substrate.
  • microparticles or nanoparticles are applied to the substrate using photolithography, projection lithography, e-beam writing or lithography, depositing nanowire arrays, growing nanostructures on the surface of a substrate, soft lithography, replica molding, solution deposition, solution polymerization,
  • the substrate consists of a fluoropolymer.
  • the biological material is a fluid selected from the group consisting of whole blood, plasma, serum, sweat, feces, urine, saliva, tears, vaginal fluid, prostatic fluid, gingival fluid, amniotic fluid, intraocular fluid, cerebrospinal fluid, seminal fluid, sputum, ascites fluid, pus, nasopharengal fluid, wound exudate fluid, aqueous humour, vitreous humour, bile, cerumen, endolymph, perilymph, gastric juice, mucus, peritoneal fluid, pleural fluid, sebum, vomit, and combinations thereof.
  • the biological material is a solution or suspension containing bacteria selected from the group consisting of Actinobacillus ⁇ e.g. , Actinobacillus actinomycetemcomitans), Acinetobacter (e.g., Acinetobacter baumannii), Aeromonas, Bordetella (e.g., Bordetella pertussis, Bordetella bronchiseptica, and
  • Bordetella parapertussis Brevibacillus, Brucella, Bacteroides (e.g., Bacteroides fragilis), Burkholderia (e.g., Burkholderia cepacia and Burkholderia pseudomallei), Borelia (e.g., Borelia burgdorferi), Bacillus (e.g., Bacillus anthracis and Bacillus subtilis),
  • Bacteroides e.g., Bacteroides fragilis
  • Burkholderia e.g., Burkholderia cepacia and Burkholderia pseudomallei
  • Borelia e.g., Borelia burgdorferi
  • Bacillus e.g., Bacillus anthracis and Bacillus subtilis
  • Campylobacter e.g., Campylobacter jejuni
  • Capnocytophaga e.g., Cardiobacterium hominis
  • Citrobacter e.g., Clostridium tetani or
  • Chlamydia e.g., Chlamydia trachomatis, Chlamydia pneumoniae, and Chlamydia psiffaci
  • Eikenella e.g., Eikenella corrodens
  • Enterobacter Escherichia (e.g., Escherichia coli)
  • Francisella e.g., Francisella tularensis
  • Fusobacterium e.g., Francisella tularensis
  • Flavobacterium Haemophilus (e.g., Haemophilus ducreyi or Haemophilus influenzae), Helicobacter (e.g., Helicobacter pylori), Kingella (e.g., Kingella kingae), Klebsiella (e.g., Klebsiella pneumoniae), Legionella (e.g., Legionella pneumophila), Listeria (e.g., Listeria monocytogenes), Leptospirae, Moraxella (e.g., Moraxella catarrhalis), Morganella, Mycoplasma (e.g. , Mycoplasma hominis and Mycoplasma pneumoniae), Mycobacterium (e.g.
  • Neisseria e.g., Neisseria gonorrhoeae or Neisseria meningitidis
  • Pasteur ella e.g.
  • Pasteur ella multocida Proteus (e.g., Proteus vulgaris and Proteus mirablis), Prevotella, Plesiomonas (e.g., Plesiomonas shigelloides), Pseudomonas (e.g., Pseudomonas aeruginosa), Providencia, Rickettsia (e.g., Rickettsia rickettsii and Rickettsia typhi), Stenotrophomonas (e.g., Stenotrophomonas maltophila), Staphylococcus (e.g., Staphylococcus aureus and Staphylococcus epidermidis), Streptococcus (e.g., Streptococcus viridans, Streptococcus pyogenes (group A),
  • Streptococcus agalactiae group B
  • Streptococcus bovis and Streptococcus pneumoniae
  • Streptomyces e.g., Streptomyces hygroscopicus
  • Salmonella e.g., Salmonella enteriditis, Salmonella typhi, and Salmonella typhimurium
  • Serratia e.g., Serratia marcescens
  • Shigella Spirillum (e.g., Spirillum minus
  • Treponema e.g., Treponema pallidum
  • Veillonella Vibrio (e.g., Vibrio cholerae, Vibrio parahaemolyticus, and Vibrio vulnificus)
  • Yersinia e.g., Yersinia enter ocolitica, Yersinia pestis, and Yersinia pseudotuberculosis
  • Xanthomonas
  • the biological material is a solution or suspension containing particles selected from the group consisting of a member of the genus
  • Aspergillus e.g., Aspergillus flavus, Aspergillus fumigatus, Aspergillus glaucus, Aspergillus nidulans, Aspergillus niger, and Aspergillus terreus
  • Blastomyces dermatitidis e.g., Candida albicans, Candida glabrata, Candida tropicalis, Candida parapsilosis, Candida krusei, and Candida guillermondii
  • Coccidioides immitis e.g., Aspergillus flavus, Aspergillus fumigatus, Aspergillus glaucus, Aspergillus nidulans, Aspergillus niger, and Aspergillus terreus
  • Candida e.g., Candida albicans, Candida glabrata, Candida tropicalis, Candida parapsilosis, Candida krusei, and Candida guillermondii
  • Cryptococcus e.g., Cryptococcus neoformans, Cryptococcus albidus, and Cryptococcus laurentii
  • Histoplasma capsulatum var. capsulatum Histoplasma capsulatum var. duboisii
  • Paracoccidioides brasiliensis Sporothrix schenckii
  • Absidia corymbifera Rhizomucor pusillus, Rhizopus arrhizous, and combinations thereof.
  • the biological material is a solution or suspension containing particles selected from the group consisting of normal cells, diseased cells, parasitized cells, cancer cells, foreign cells, stem cells, and infected cells, microorganisms, viruses, virus-like particles, bacteria, bacteriophage, proteins, cellular components, cell organelles, cell fragments, cell membranes, cell membrane fragments, viruses, virus-like particles, cytosolic proteins, secreted proteins, signaling molecules, embedded proteins, nucleic acid/protein complexes, nucleic acid precipitants, chromosomes, nuclei,
  • mitochondria chloroplasts, flagella, biominerals, protein complexes, and minicells.
  • the lubricating fluid is capable of self-healing by wicking back to the damaged region of the substrate after physical damage of the substrate to form an ultra-smooth surface.
  • a recovery time for self-healing occurs in less than 50 ms, 60 ms, 70 ms, 80 ms, 90 ms, 100 ms, 110 ms, 120 ms, 130 ms, 140 ms, 150 ms, 160 ms, 170 ms, 180 ms, 190 ms, 200 ms, 210 ms, 220 ms, 230 ms, 240 ms, 250 ms, 1 second, 5 seconds 10 seconds, 30 seconds, 60 seconds, 90 seconds, or 120 seconds or more.
  • the substrate has a plurality of holes, three- dimensionally interconnected network of holes and one or more materials, or random array of fibrous materials.
  • the substrate consists of a material selected from the group consisting of polymers, metals, sapphire, glass, diamond, graphite, black carbon, or ceramics.
  • the substrate is a hemocompatible material.
  • the hemocompatible material is a silicon rubber or polysulfone.
  • the substrate is a polymer selected from the group consisting of polytetrafluoroethylene, polyvinylfluoride, polyvinylidene fluoride, and fluorinated ethylene propylene.
  • the lubricating fluid has a density greater than the density of the biological material.
  • the lubricating fluid has a density greater than lubricating fluid has a density that is more than 1.0 g/cm 3 , 1.6 g/cm 3 , or 1.9 g/cm 3 .
  • the lubricating fluid comprises a fluid selected from the group consisting of tertiary perfluoroalkylamines,perfiuorotri-n-butylamine,
  • perfluoroalkylsulfides perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocycloethers, perfluoropolyethers, perfluoroalkylphosphines, and perfluoroalkylphosphmeoxides, and combinations thereof.
  • FIG. 1 is an image showing the structure of SLIPS, which is created by infiltrating a porous solid with a low surface energy, a chemically inert liquid that leads to a physically smooth and chemically homogeneous lubricating film on the surface of the substrate; the top and bottom scanning electron microscope (SEM) images FIG. l(i)-(ii) show ultra-smoothness of the lubricating fluid and a porous structure of the rough solid surface, respectively.
  • SEM scanning electron microscope
  • FIG. 2 is a schematic of a self-healing slippery surface in accordance with certain embodiments.
  • FIG. 4 is a schematic comparing the partial wetting of a flat surface (FIG. 4A) and the complete wetting of a nanostructured surface in accordance with certain
  • FIG. 5A is a schematic of a structured surface with raised features over which the slippery surface is formed in accordance with certain embodiments.
  • FIG. 5B is a schematic of a columnar porous material over which the slippery surface is formed in accordance with certain embodiments.
  • FIG. 5C is a schematic of an inverse opal porous material over which the slippery surface is formed in accordance with certain embodiments.
  • FIG. 5D is an image of a random network porous material over which the slippery surface is formed in accordance with certain embodiments.
  • FIG. 6 shows (A) a scanning electron microscope image of the surface morphologies of a 3D porous solid; and (B) a replica of a slippery surface formed by infiltrating the 3D porous solid of 6A with lubricating fluid showing that the lubricating fluid overcoats the surface topographies, forming an ultra-smooth layer without asperity (e.g., average roughness on the order of or less than about 1 nm based on high resolution atomic force microscopy measurements, see inset (6C) as viewed at low (6B) and high (inset 6(D)) resolution in accordance with certain embodiments.
  • 6C average roughness on the order of or less than about 1 nm based on high resolution atomic force microscopy measurements
  • FIG. 7A shows several planar and non-planar surfaces over which the slippery surface can be formed in accordance with certain embodiments.
  • FIG. 7B shows SLIPS formed over a cylindrical solid core in accordance with certain embodiments.
  • FIG. 7C shows SLIPS formed on the sidewall of the interior of a tubing/pipe and the like in accordance with certain embodiments.
  • FIG. 7D shows SLIPS formed on the sidewall of both of the interior and exterior of a tubing/pipe and the like in accordance with certain embodiments.
  • FIG. 7E shows SLIPS formed on the Liquid-B-soaked porous tubing and the like in accordance with certain embodiments.
  • FIG. 8a-b shows a schematic of capillary refilling in accordance with certain embodiments.
  • FIG. 9A shows SLIPS coupled to a Liquid B reservoir that can replenish evaporating or removed Liquid B in accordance with certain embodiments.
  • FIG. 9B shows SLIPS formed inside a cylindrical tube with a Liquid B reservoir that can replenish evaporating or removed Liquid B in accordance with certain embodiments.
  • FIG. 9C shows SLIPS formed along the surface of an arbitrary shaped flow path coupled to a channel for replenishing evaporating or removed Liquid B in accordance with certain embodiments.
  • FIG. 9D shows images of showing the formation of the bottom substrate portion of FIG. 9C in accordance with certain embodiments.
  • FIG. 10 shows images of substrate structures and topologies that can be used to generate SLIPS surfaces; (A) open-cell bricks, (B) post arrays, (C) parallel grooves, (D) open porosity PTFE (ePTFE), (E) plasma-etched PTFE, and (F) sand-blasted
  • FIG. 11 shows sequential images of whole human blood without anticoagulants as it is pipetted onto PDMS (11 A) and the oil-infiltrated PTFE (11B) surfaces.
  • FIG. 12 is a series of images of control and test surfaces after exposure to 0.75 mL of blood flow, which show absorption of blood to the control surfaces (glass (12A),
  • FIG. 13 shows optical (13A(i), 13B(i)) and scanning electron microscope (SEM, 13A(ii), 13B(ii)) surface analysis images of the control and oil-infiltrated PTFE samples from FIG. 11A and 11B in which all the control materials showed evidence of adhered, dried blood species (a mixture of cells, platelets, proteins, see (13 A)), while the oil-PTFE material (13B) showed no evidence of biological material.
  • SEM scanning electron microscope
  • FIG. 14 is a series of diagrams that show exemplary methods by which SLIPS surfaces can be roughened: by spraying or depositing a particulate matter on the substrate (14A); etching (14B); and by growing a nanostructured material on the surface of the substrate (14C).
  • FIG. 15 is a series of images showing the self-healing and optical transparency properties of SLIPS.
  • 15A Time-lapse images showing self-healing capability of SLIPS from a ⁇ 50 ⁇ -wide physical damage on a time scale on the order of 100 ms.
  • 15B Time- lapse images showing the restoration of liquid repellency of SLIPS after physical damage, as compared to a typical hydrophobic flat surface on which oil remains pinned at the damage site.
  • FIG. 16A Optical images showing enhanced optical transparency of an epoxy- resin-based SLIPS (left) as compared to significant scattering in the non-infused super hydrophobic nanostructured surface (right) in the visible light range.
  • 16B Optical transmission measurements for epoxy-resin-based SLIPS in the visible light range (400- 750 nm).
  • 16C Optical transmission measurements for Teflon-based SLIPS in the near- infrared range (800-2300 nm).
  • FIG. 18 is a set of graphs showing the contact angle hysteresis as a function of surface tension of test liquids (indicated) on SLIPS and on an omniphobic surface.
  • advancing and receding contact angles of a liquid droplet are denoted as ( a d v , and ( rec , respectively.
  • a plot (18B) showing the high pressure stability of SLIPS, as evident from the low sliding angle of a decane droplet (y ⁇ 23.6 ⁇ 0.1 mN/m, volume ⁇ 3 ⁇ ) subjected to pressurized nitrogen gas in a pressure chamber. Error bars indicate standard deviations from at least seven independent measurements.
  • FIG. 19 is a series of images demonstrating low-tilt-angle sliding of
  • Pseudomonas aeruginosa PA 14 bio film growth in 2 mL tryptone broth puddles incubated for 24 hours atop liquid slippery surfaces in accordance with certain embodiments.
  • FIG. 20 is a series of fluorescence microscopy images of Pseudomonas aeruginosa (PA 14) bacteria remaining on various slippery liquid surfaces after 2 mL of shaken culture was incubated for 24 hours on the surfaces and subsequently slid off by applying a tilt angle in accordance with certain embodiments.
  • PA 14 Pseudomonas aeruginosa
  • FIG. 21 show a toxicity screening of a number of commercially available products that can satisfy the requirements for the lubricating fluid in accordance with certain embodiments.
  • FIG. 22 is a schematic illustrating the whole wall of a catheter with SLIPS
  • FIG. 23 is a schematic of a wound dressing with SLIPS.
  • FIGS 24A to 24E show the different morphologies that can arise by changing the electrodeposition parameters in accordance with certain embodiments.
  • FIG. 25 is a graph showing the dependence of liquid repellency of SLIPS on the viscosity of Liquid B (here, Krytox 100, 103, and 105 (DuPont)).
  • Liquid B here, Krytox 100, 103, and 105 (DuPont)
  • Liquid A For constant viscosity of Liquid A (here, 25 ⁇ , of glycerol), Liquid A's mobility increases as the viscosity of Liquid B decreases.
  • the mobility of Liquid A increases with reducing viscosity.
  • viscous dissipation plays a major role in the liquid mobility on SLIPS.
  • FIG. 26 shows images of whole human blood in non- wetting contact with SLIPS surfaces made with non perfluorocarbon lubricant liquids.
  • Image (26A) shows a SLIPS surface generated using an infiltration of polydimethylsiloxane (PDMS) liquid (500 MW, X viscosity, OH-terminated, Sigma Aldrich) into an ePTFE membrane (1 ⁇ , Sterlitech).
  • Image (26B) shows a SLIPS surface generated using an infiltration of olive oil into an ePTFE membrane (1 ⁇ , Sterlitech). In both cases the blood was found to not wet the surface, and rolled off without adhering to the surfaces.
  • PDMS polydimethylsiloxane
  • FIG. 27A shows a schematic of a slippery surface having an over-coated Liquid
  • FIG. 27B shows a schematic of a slippery surface with Liquid B infiltrated into the roughened surface in accordance with certain embodiments.
  • FIG. 28A-B shows images of the surface of the present disclosure
  • FIG. 30 shows images of non-anticoagulated whole human blood (diluted 1 : 1 with saline) flowing at 3,000 mL/hr using peristaltic pumping through SLIPS tubing for 20 min without producing clotting including the experimental setup (A) and results which showed no signs of clotting in the tubing (B).
  • FIG. 31A-C shows images of the tubing of FIG. 33 after 20 minutes of 12 mL of fresh human blood free of anticoagulant was pumped through SLIPS tubing. The blood did not clot in the tubing.
  • FIG. 32 is a graph showing the dependence of liquid repellency of SLIPS on the viscosity of Liquid B (here, Krytox 100, 103, and 105 (DuPont)).
  • Liquid B here, Krytox 100, 103, and 105 (DuPont)
  • Liquid A For constant viscosity of Liquid A (here, 25 of glycerol), Liquid A's mobility increases as the viscosity of Liquid A decreases.
  • the mobility of Liquid A increases with reducing viscosity.
  • viscous dissipation plays a major role in the liquid mobility on SLIPS.
  • FIG 33 shows images of ePTFE tubing (Zeus Inc) of increasing inner diameter (ID), from 0.075" to 0.236" (wall thickness is -0.040" for all) fit with an elastic, external, silicone tube casing (VWR) in low (A) and high magnification SEM of the porous ePTFE surface within the tubing (B).
  • ID inner diameter
  • VWR silicone tube casing
  • FIG. 34 shows images of a transparent SLIPS surface, based on the infiltration of a highly-ordered nanoporous Si02 glass layer (A) with perfluorocarbon (FC-70) (B). When fully infiltrated the layer is highly transparent (C) and well suited for applications as a bio-sensor window.
  • A highly-ordered nanoporous Si02 glass layer
  • FC-70 perfluorocarbon
  • FIG. 35 shows images of a process for fabricating a SLIPS tubing from ePTFE membranes.
  • FIG. 36 shows images (A-B) of surface typologies investigated with respect to bio film attachment properties.
  • Biofilm grown on the PTFE and nanostructured superhydrophobic silicon substrates showed complete wetting of the surface and a slimy coffee ring.
  • biofilm on the SLIPS substrate cleanly retracted from the surface as it evaporated.
  • the insets (i) and (ii) show fluorescence micrographs of remaining bacteria on these surfaces following 48 hour incubation of P. aeruginosa biofilm.
  • the relative bacterial biofilm attachment was significantly less on PTFE-based SLIPS compared to the PEGylation surface (C).
  • A-B Photographs of the control PTFE and SLIPS PTFE substrates after the flow cell was opened following 48 hour growth under 10 mL/min flow, both before crystal violet staining (top) and after (bottom). Equal-area samples of the substrates were eluted for crystal violet quantification, a measurement of attached biomass (C). Following 7 days of growth, crystal violet staining-based quantification showed a 99.6% reduction in attached biofilm on SLIPS versus control PTFE.
  • FIG. 38 shows images of a microscale view of P. aeruginosa biofilm attachment on SLIPS and control PTFE surfaces after 24 and 7-day growths in 10 mL/min flow.
  • A-B Growth on the PTFE surface appeared dense, three-dimensional, and uniform (A-B), whereas on the SLIPS, only sparse, isolated single cells or microcolonies were observed (C-D).
  • C-D only sparse, isolated single cells or microcolonies were observed
  • E Referring to the graph, (E), these cells appeared to be unattached or poorly attached, i.e., drifting with convective currents in the fluid, further supporting that a liquid surface provides very low adhesion to the individual bacteria or micro-colonies.
  • FIG. 39 shows images and graphs that demonstrate that biofilm attachment reduction by SLIPS is species independent.
  • FIG. 40 is a set of images from a split- frame movie showing evaporation dynamics of P. aeruginosa culture droplets on a superhydrophobic PTFE porous surface (i- ii) and a PTFE SLIPS surface infused with Krytox 103 (iii-iv).
  • the pinning characteristics as well as the stains remaining on the surfaces upon drying indicated the level of adhesion between the bacterial droplet and the substrate.
  • the droplet follows a nearly constant contact angle mode of evaporation without the formation of a coffee ring stain (iv).
  • the absence of the coffee ring formation also indicated that the adhesion of the bacteria on the SLIPS was small compared to the forces imparted by the meniscus of the droplet.
  • FIG. 41 shows images of a micro view of P. aeruginosa biofilm attachment on SLIPS and control PTFE surfaces after 24 and 48 hr growths in 10 mL/min flow, (a)
  • Fluorescence average intensities (b) average intensity graph showing a 97-98%) average intensity reduction, analogous to the crystal violet global measurement.
  • SLIPS synthetic slippery liquid-infused porous surfaces
  • Liquid A liquid-infused porous surfaces
  • Object A solids
  • Adhesion and absorption of material of biological origin are also reduced or prevented by SLIPS.
  • SLIPS are synthetic surfaces that consist of nano/microstructured substrates infused with a lubricating fluid that is locked in place by a substrate to form a stable, defect-free, inert "slippery" interface capable of repelling complex fluids, gases, and molecules or particulates contained within liquids of varying surface tensions (together referred to as Liquid A), as well as solids.
  • liquids such as hydrocarbons, organic solvents, and the like can be repelled.
  • the biological liquids refer to both pure liquids and complex fluids, such as blood flow (see, e.g., FIG. 11 and FIG. 12).
  • solids like bacteria, proteins, and the like can be repelled by SLIPS.
  • natural and synthetic solutions such as those used in medicines, intravenous solutions, pharmaceutical manufacturing, and medication delivery systems can be repelled by SLIPS.
  • the SLIPS consists of a porous surface layer, or a 'rough' layer of raised surface features in an array, which is infiltrated with a low surface energy liquid.
  • the combination of lubricating fluid over a rough surface creates an ultra-smooth surface that is slippery and resists or reduces adhesion by particles and immiscible liquids.
  • the lubricating fluid is stabilized in place by the underlying substrate.
  • the lubricating fluid is reduced to the level of the features of the substrate.
  • SLIPS are also capable of restoring their exceptional liquid repellency when physically damaged.
  • the fast self-healing times are a result of the lubricating fluid wicking fluid into damaged sites on the underlying substrate to restore SLIPS to a smooth defect-free surface.
  • These surfaces can be used in laboratories, as a coating on medical devices and medical equipment, and for medical applications such as anticoagulation and anti-biofilm formation.
  • SLIPS can be manufactured by providing a liquid (e.g., chemically- inert, high-density fluid) over a roughened surface featuring micro- or nanoscale
  • a liquid e.g., chemically- inert, high-density fluid
  • ultra-smooth surface means a surface having a roughness factor that is equal or close to 1 , where the roughness factor (R) is defined by the ratio of the real surface area to the projected surface area. Because fluid surfaces generally have a roughness factor of 1 , and the top surface in SLIPS is a lubricating fluid that fully coats the substrate above its hills, surfaces such as that shown in FIG.
  • ultra-smooth surface can have an average surface roughness is on the order of or less than about 1 nm.
  • "ultra-smooth” may refer to a substantially molecularly or even atomically flat surface. The absence of any defects or roughness on such a surface may aid in minimizing the pinning points for a sliding fluid, thus reducing the contact angle hysteresis, rendering it nearly friction- free and slippery.
  • a detailed discussion of the ultra- smooth surfaces is found in co-pending U.S. Patent Application No. 61/434,217, filed on January 19, 2011, U.S. Patent Application No. 61/466,352, filed on March 22, 2011, and co-filed PCT Application No. entitled "Slippery Surfaces With High Pressure
  • FIG. 1 A schematic of the overall design of SLIPS is illustrated in FIG. 1.
  • the article includes a surface 100 having raised features 110 that provide a certain roughness with lubricating fluid applied thereon.
  • Lubricating fluid 130 wets the roughened surface, filling the hills and valleys of the roughened surface 110, and forming an ultra- smooth surface 135 over the roughened surface.
  • SEM scanning electron microscope
  • FIG. 6 (A) shows a scanning electron microscope image of the surface morphologies of a 3D porous solid.
  • FIG. 6(B) shows a photograph at the same magnification of a slippery surface formed by infiltrating the 3D porous solid shown in FIG. 6(A) with lubricating fluid.
  • the lubricating fluid overcoats the surface topographies of the porous solid to form an ultra-smooth layer without asperity (e.g., average roughness on the order of or less than about 1 nm based on high resolution atomic force microscopy measurements).
  • the average surface roughness of SLIPS is on the order of or less than about 1 nm based on high resolution atomic force microscopy measurements.
  • any arbitrary liquid e.g., a biological fluid
  • gas, molecule, or particulate contained within liquids may be strongly repelled from the ultra-smooth lubricating fluid surface.
  • ultra-low adhesion characteristics of SLIPS which also prevents adsorption, adhesion, and attachment of objects on SLIPS, prevents contamination of these surfaces by material of biological origin. The adhesion, adsorption, or attachment of biological materials can be completely prevented by SLIPS.
  • SLIPS reduces the adhesion, adsorption, or attachment of biological materials on surfaces. In one aspect, SLIPS significantly reduces adhesion, adsorption, or attachment of biological materials on surfaces. In one or more aspects, SLIPS reduces adhesion, adsorption, or attachment of materials of biological origin on surfaces by 50%, 60%, 70%>, 80%>, 90%>, 95%, 98%, or 99%.
  • a wide range of materials can be repelled by the slippery surfaces of the present disclosure. More specifically, polar and non-polar liquids, as well as polar and non-polar liquids in their solidified forms can be repelled by SLIPS.
  • hydrocarbons and their mixtures e.g., from pentane up to hexadecane and mineral oil, ketones (e.g., acetone, etc.), alcohols (e.g., methanol, ethanol, isopropanol, dipropylene glycol, ethylene glycol, and glycerol, etc.), water (with a broad range of salinity, e.g., sodium chloride from 0 to 6.1 M; potassium chloride from 0 to 4.6 M, etc.), physiological buffers, acids (e.g.,
  • SLIPS concentrated hydrofluoric acid, hydrochloric acid, nitric acid, etc), bases (e.g., potassium hydroxide, sodium hydroxide, etc), ice, and the like can be repelled by SLIPS.
  • biological objects such as small animals, protozoa, bacteria, viruses, and the like can be repelled by surfaces made in accordance with the present disclosure.
  • solid particles suspended in liquid can be repelled by SLIPS.
  • Non- limiting examples of such solid particles in liquid include bodily fluids, fecal matter, and the like.
  • the substrate is a low- surface energy porous solid.
  • the substrate is preferentially wetted by the lubricating fluid rather than by the fluid to be repelled. It can have a roughened or smooth surface.
  • the term "roughened surface” is a substrate that includes both the surface of a three- dimensionally porous material as well as solid surface having certain topographies, whether they have regular, quasi-regular, or random patterns.
  • the substrate is roughened by incorporation of microtextures.
  • the substrate is roughened by incorporation of nanotextures. Physically, the large surface area provided by micro/nanoscale roughness not only facilitates complete wetting by the lubricating fluid but also strengthens the adhesion of lubricating fluid (Liquid B) within the porous solid.
  • SLIPS have properties that are insensitive to the precise geometry of the underlying substrate. Therefore, the geometry of the substrate can be any shape, form, or configuration to suit various-shaped materials and devices.
  • the porous surface can be manufactured over any suitable materials and geometries, such as medical devices, inside of pipes (e.g., metallic or metallized pipes), optical windows, biological sensor windows, medical tubing, hollow metallic structures, patterned electrodes, meshes, wires, porous conductive surfaces, and the like that come into contact with biological materials.
  • Non- limiting examples of shapes, forms, and configurations SLIPS can take include generally spherical (e.g., bead, magnetic particles, and the like), tubular (e.g., for a cannula, connector, catheter, needle, capillary tube, tubing, or syringe) (see FIG. 7A j)), planar (e.g., for application to a microscope slide, plate, film, or laboratory work surface) (see FIG. 7A(c)), or arbitrarily shaped (e.g., well, well plate, Petri dish, tile, jar, flask, beaker, vial, test tube, column, container, cuvette, bottle, drum, vat, or tank) (see FIG.
  • spherical e.g., bead, magnetic particles, and the like
  • tubular e.g., for a cannula, connector, catheter, needle, capillary tube, tubing, or syringe
  • planar e.g
  • FIG. 7A 7A(a)-(b), (d)-(i)).
  • SLIPS can be applied to spherical surfaces, such as magnetic particles that can be actuated inside the body for drug delivery.
  • FIG. 7B-E are perspective illustrations that show how SLIPS can be incorporated into a catheter tube.
  • FIG. 7B shows a SLIPS 700 attached to the outer surface of a cylindrical solid core 710 with a reservoir 720 for Liquid B.
  • SLIPS can also be attached to the inner surfaces of the tubes, pipes, and other irregularly shaped substrates.
  • SLIPS 700 can be can be applied to the inner surface of a cylindrical tube 710 for low drag flow of Liquid A 730.
  • SLIPS can be applied onto both the inner and outer surfaces of a tube/needle for low drag flow of Liquid A and remain slippery/non-sticking to the outside environments where the tube/needle is exposed to.
  • SLIPS can be applied onto a Liquid-B-soaked porous tubing for low drag flow of Liquid A and remain slippery/non- sticking to the outside environments where the porous tube/needle is exposed to.
  • FIG. 5A to FIG. 5D show some exemplary roughened surfaces.
  • the roughened surface is formed over a two-dimensionally flat surface 500 by providing certain raised structures 510 or protrusions (see FIG. 5A).
  • the roughened surface is formed by forming pores 520 over a two- dimensionally flat surface 500 to yield a porous material (see FIG. 5B).
  • Pores can take any geometry and can have pathways, columns (as illustrated in FIG. 5B or more random pathways.
  • a three-dimensionally interconnected network of regular or random pores is used (see FIG. 5C and FIG. 5D).
  • FIG. 10 shows images of substrate structures and topologies that can be used to generate SLIPS surfaces; (A) open- cell bricks, (B) post arrays, (C) parallel grooves, (D) open porosity PTFE (ePTFE), (E) plasma-etched PTFE, and (F) sand-blasted polypropylene (PP).
  • A open- cell bricks
  • B post arrays
  • C parallel grooves
  • D open porosity PTFE
  • E plasma-etched PTFE
  • PP polypropylene
  • a range of surface structures with different feature sizes and porosities can be used.
  • Feature sizes can be in the range of hundreds of nanometers to microns (e.g., 100 to 1000 nm), and have aspect ratios from about 1 : 1 to 10: 1.
  • Porous nano-fibrous structures can be generated in situ on the inner surfaces of metallic microfluidic devices using electrochemical deposition using techniques known in the art (Aizenberg, J., Kim, P.
  • the surface has a large surface area that is readily wetted by the lubricating fluid and which entrains lubricating fluid and retains it on the substrate surface.
  • the substrate surface is a hierarchical surface containing surface features on multiple dimension scales.
  • the surface can have a first topological feature having dimensions on the microscale and a second topological feature on the nanoscale.
  • the first topological feature supports the second smaller topological feature.
  • the second topological features are referred to as "primary structures" as they are meant to denote the smallest feature sizes of the hierarchical structure.
  • the primary structures can include structures, such as nanofibers, nanodots, and the like.
  • Such nanoscale “primary structures” can have at least one kind of feature sizes that are a few to tens or hundreds of nanometers in size, such as less than 5 nm to 200 nm. For example, nanofibers having diameters of approximate 5, 10, 25, 50, or even 100 nm. In such cases, when “primary structures” having feature sizes of about 100 nm diameter is utilized, “secondary structures” having feature sizes that are larger than 100 nm, such as 150 nm, 300 nm, 500 nm, or 1000 nm, and larger. Additional higher order structures, such as “tertiary structures” and the like, which each has larger feature sizes than the lower order structures are contemplated.
  • hierarchical structures having nanofibers as the primary structures may provide a high degree of three-dimensional porosity that may be well-suited for use as porous surfaces described herein.
  • a detailed discussion of hierarchical surfaces suitable for use with a liquid to be repelled is found in International Application No. PCT/US11/44553 entitled “Hierarchically structures surfaces to control wetting by liquids,” filed on July 19, 2011, which is incorporated in their entirety by reference.
  • the roughened surface may have a periodic array of surface protrusions (e.g., posts, peaks, etc.) or any random patterns or roughness (see, e.g., FIG. 5A).
  • the size of the features producing a roughened surface range from 10 nm to 100 ⁇ with geometries ranging from regular posts/open-grid structures to randomly oriented spiky structures.
  • the widths of the raised structures are constant along their heights. In some embodiments, the widths of the raised structures increase as they approach the basal surface from the distal ends.
  • the raised structures can be raised posts of a variety of cross-sections, including, but not limited to, circles, ellipses, or polygons (such as triangles, squares, pentagons, hexagons, octagons, and the like), forming cylindrical, pyramidal, conical or prismatic columns.
  • the exemplary substrates described above illustrate raised posts having uniform shape and size, the shape, orientation and/or size of raised posts on a given substrate can vary.
  • FIG. 35 shows images of a process for fabricating a SLIPS tubing from ePTFE membranes in which (A) A tubular structure (center) is formed from two flat ePTFE membranes (1.0 ⁇ pore size) by being pressed between two U-shaped channel molds (left and right). (B) One ePTFE membrane is pressed between the negative and positive molds, producing an indented channel structure for fluidic flow. This structure was then covered and bound to a flat ePTFE membrane to construct the SLIPS U-shape tube shown in (A).
  • FIG. 33 shows images of ePTFE tubing (Zeus Inc) of increasing inner diameter (ID), from 0.075" to 0.236" (wall thickness is -0.040" for all) (A).
  • ID inner diameter
  • the 0.180" ePTFE tubing (which provides a porous microtexture to the substrate) can be fit with an elastic, external, silicone tube casing (VWR), for example, to provide a fluid flow barrier and/or to facilitate peristaltic pumping.
  • VWR silicone tube casing
  • High magnification SEM of the porous ePTFE surface within the tubing is also shown (B).
  • the roughened surface has a roughness factor, R, greater than 1 , where the roughness factor is defined as the ratio between the real surface area and the projected surface area.
  • R roughness factor
  • the roughness factor of the roughened surface is greater or equal to that defined by the Wenzel relationship (i.e., R ⁇ l/cos( , where ⁇ is the contact angle of lubricating fluid on a flat solid surface). For example, if lubricating fluid has a contact angle of 50° on a flat surface of a specific material, it is desirable for the corresponding roughened surface to have a roughness factor greater than ⁇ 1.5.
  • the roughened surface material can be selected to be chemically inert to the lubricating fluid and to have good wetting properties with respect to lubricating fluid.
  • the roughened surface topographies can be varied over a range of geometries and size scale to provide the desired interaction, e.g., wettability, with lubricating fluid.
  • the micro/nanoscale topographies beneath the lubricating fluid enhance the liquid- wicking property and the adherence of lubricating fluid to the roughened surface.
  • the lubricating fluid can uniformly coat the roughened surface and get entrapped inside at any tilting angles.
  • Non-limiting examples of porous materials include solid substrates having holes (e.g., high aspect ratio holes, cylinders, columns, etc.), three-dimensionally interconnected network of holes and one or more materials (e.g., 3-D ordered colloidal assemblies, block copolymers, etc.), and random array of fibrous materials (e.g., filter paper, fabrics, electrospun films).
  • holes e.g., high aspect ratio holes, cylinders, columns, etc.
  • materials e.g., 3-D ordered colloidal assemblies, block copolymers, etc.
  • random array of fibrous materials e.g., filter paper, fabrics, electrospun films.
  • Non-limiting examples of porous or rough surface structures that can be used include polymers (e.g., polysulfone, PDMS, and polypyrrole) and hydrophobic porous (e.g., Tefion) materials.
  • the roughened surface can be manufactured from polymers (e.g., epoxy, polycarbonate, polyester, nylon, etc.), metals, sapphire, glass, carbon in different forms (such as diamond, graphite, black carbon, etc.), ceramics (e.g., alumina), and the like.
  • polymers e.g., epoxy, polycarbonate, polyester, nylon, etc.
  • metals e.g., aluminum, copper, copper, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium magnesium, magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium
  • the roughened surface is manufactured from a hemocompatible material, non-limiting examples of which include silicon rubber and polysulfones.
  • the roughened surface is manufactured from any suitable materials.
  • the desired material and shape is not electrically conducting, the surfaces of such material and shapes can be rendered electrically conductive by applying a thin layer of conductive material, such as through vapor deposition techniques, sputtering, metallization techniques, and the like.
  • the porous surface can be readily formed on large surface area materials that are commercially important. When necessary, surface functionalization can be carried out to modify the solid surfaces so that the lubricating layer preferentially wets the roughened surface as compared to Liquid A.
  • the raised structures can be produced by any known method for fabricating raised structures onto substrates.
  • Non- limiting examples include molding into the device structure, conventional photolithography, projection lithography, e-beam writing or lithography, depositing nanowire arrays, growing nanostructures on the surface of a substrate, soft lithography, replica molding, solution deposition, solution polymerization, electropolymerization, electrospinning, electroplating, vapor deposition, contact printing, etching, bead blasting, sand blasting, transfer patterning, microimprinting, self-assembly, and the like.
  • the roughened surface can be made, for example, by replica molding procedure described in B. Pokroy, A. K. Epstein, M. C. M. Persson-Gulda, J. Aizenberg, Adv. Mater. 21, 463 (2009), the contents of which is incorporated by reference herein in its entirety.
  • Patterned surfaces can also be obtained as replicas (e.g., epoxy replicas) by a soft lithographic method (see, e.g., J. Aizenberg and B. Pokroy, PCT/US2009/048880, the contents of which is incorporated by reference herein in its entirety).
  • Polymer films with patterned surfaces can be fabricated by means known in the art (e.g., roll-to-roll imprinting or embossing).
  • negative replicas of pre-generated patterns can be made from polydimethylsiloxane, PDMS (e.g., Dow-Sylgard 184) by pouring mixture of prepolymer and curing agent (e.g., 10: 1 ratio) on the patterns followed by thermal curing in an oven. After cooling, the negative PDMS mold can be peeled off and used for fabricating the final replica by pouring the desired material (e.g. UV-curable epoxy resin) into the negative mold. After solidifying the material, the negative mold can be peeled off, leaving the replica of the original pattern. Then, the surface of the replica can be chemically functionalized with low surface energy coating such as (tridecafluoro-l,l,2,2-tetrahydrooctyl)-trichlorosilane.
  • a silicon substrate having a post array such as is illustrated in FIG. 5A can be fabricated by photolithography using the Bosch reactive ion etching method (as described in Plasma Etching: Fundamentals and Applications, M. Sugawara, et al., Oxford University Press, (1998), ISBN-10: 019856287X, the contents of which is incorporated by reference herein in its entirety).
  • Arrays of hydrophobic raised surface structures can be made at the micrometer scale using micromolding techniques.
  • rough surface structures can be arrays of hydrophobic raised surface structures at the micrometer scale, such as posts and intersecting walls patterned in polymers such as epoxy (FIG. lOA-C).
  • the roughened surface may be the surface of a three- dimensionally porous material (see, e.g., FIG. 5B to FIG. 5D).
  • the porous material can be any suitable porous network having a sufficient thickness to stabilize lubricating fluid, such as a thickness from about 5 ⁇ to about 1 mm.
  • the porous material can have any suitable pore sizes to stabilize the lubricating fluid, such as from about 10 nm to about 100 ⁇ .
  • porous alumina is manufactured by the process of anodization as shown in FIG. 5B, where an aluminum substrate is electrochemically oxidized under constant electrical potential.
  • the pore size, inter-pore spacing, and aspect ratio of the pores can be tuned by adjusting the operating parameters of the electrochemical oxidation process.
  • Such a process generates porous through-holes into the substrate, where the size of the porous holes are on the order of 50 nm with aspect ratio larger than 10000 (see, Lee et al, Nature Mater. 5, 741-47, 2006, the contents of which is incorporated by reference herein in its entirety.).
  • mechanical or (electro)chemical methods can be used to roughen metal surfaces.
  • Roughening and non- wetting materials can be spray coated directly onto metal surfaces.
  • Boehmite ( ⁇ - ⁇ ( ⁇ )) formation on aluminum surface by boiling in water can also be used to roughen metallic surfaces such as aluminum.
  • Rotary jet spinning of hydrophobic polymer nano fibers and layered deposition of an appropriate primer can also be used to roughen substrates for use in SLIPS.
  • long range ordered porous structures of silica can be produced by evaporative co-assembly method of sacrificial polymeric colloidal particles together with a hydrolyzed silicate sol-gel precursor solution.
  • a crack-free porous surface on the order of centimeters or larger, with pore sizes of about 100 nm to about 1000 nm and porosity of about 75%.
  • polymer-based porous membrane (such as medical grade PTFE) can be made by mixing PTFE powders with lubricating fluid to form a paste. Then, the paste can be molded into the desired shape by methods such an extrusion molding. The molded PTFE membrane can then be heated up to less than its melting point to drive off the lubricants. Thereafter, a porous PTFE membrane can be formed (see U.S. Patent No.
  • electrodeposition condition can be controlled so that nanofibers of electrically conductive polymer can be formed over an electrically conductive surface.
  • the electrodeposition conditions can further be controlled to provide a desired nanofiber diameter and spacing.
  • the electrodeposition condition can be controlled to provide any other desirable morphology that can provide additional means to stabilize the lubricating layer.
  • the morphology of the conducting organic polymers can be controlled by varying the deposition conditions such as the concentration of monomer, the types of electrolytes and buffers, the deposition temperature and time, and the electrochemical conditions such as applied potential. For example, increasing the concentration of monomer in the electrochemical solution, the applied potential, and/or the temperature generally leads to a faster polymerization rate and many parasitic nucleation sites during growth resulting in a morphology that is similar to a cauliflower (see FIG. 24A). In contrast, lower concentrations of monomer, lower applied potential, and lower temperatures can lead to nanofibrile growth with substantially uniform diameters (see FIG. 24B).
  • the applied voltage can be cycled leading to different oxidation states of the deposited polymer layer which is often manifested as a color change (e.g., from dark blue to a green then to a pale yellow color with increasing applied voltage).
  • the applied voltage can be pulsed at a constant voltage to form polymers only on the tip of the underlying micropost structures, leading to a mushroom-like morphology (see FIG. 24E). Accordingly, the morphology of conducting organic polymers can be finely controlled from nanometers to over micrometer scales, and surface coatings with precisely controlled morphology can be produced by simple modifications, which promise the customization of various surface properties by design and control of the morphology.
  • a roughened surface is further functionalized to improve wetting by lubricating fluid.
  • Surface coating can be achieved by methods well known in the art, including plasma assisted chemical vapor deposition, chemical functionalization, solution deposition, and vapor deposition.
  • surfaces containing hydroxyl groups i.e., -OH
  • fluorosilanes e.g. , tridecafluoro- 1 , 1 ,2,2-tetrahydrooctyl-trichlorosilane, heptadecafluoro- 1 , 1 ,2,2-tetra- hydrodecyl trichlorosilane, etc.
  • many materials having native oxides can be activated to contain -OH functional groups using techniques such as plasma treatment.
  • either vapor or solution deposition techniques can be used to attach silanes so that surfaces with low surface energy can be produced.
  • vapor deposition the deposition can be carried out by exposing the surface to silane vapors.
  • solution deposition the deposition can be carried out by immersing the surface in a silane solution, followed by rinsing and blow-drying after deposition.
  • layered deposition layered deposition of a primer is followed by application of a mixture of sacrificial beads and Liquid B, which is dried and cured. The beads are removed to produce a contiguous porous Teflon- like surface.
  • the surface can be functionalized by first coating it with thin films of metals, such as gold or platinum, and the thin metal films can be functionalized with various commercially available thiols of low surface energy (e.g., heptane thiol, perfluorodecanethiol, etc.).
  • metals such as gold or platinum
  • the thin metal films can be functionalized with various commercially available thiols of low surface energy (e.g., heptane thiol, perfluorodecanethiol, etc.).
  • vapor or solution deposition techniques can be carried out similar to that describe for silane deposition using, for example, alkane thiol solutions.
  • the roughened, porous substrate can be generated by a spraying method, where emulsions consisting of micro/nanoparticles are sprayed onto a flat solid surface (FIG. 14A1). These particles assemble into roughened solid layer upon solvent drying. Such a solid layer can then be infiltrated by lubricating fluid (FIG. 14A2) (which can also be applied by additional spraying).
  • FIG. 14A shows a surface roughened by a spray method.
  • the substrate 140 is roughened by spraying or depositing a particulate matter 142 on the substrate 140 to create a porous coating (Al) and the roughened surface is infiltrated with lubricating liquid 144.
  • Non-limiting examples of micro/ nanoparticles that can be sprayed onto a flat solid surface to form roughened, porous material include titanium dioxide, silicon dioxide, nanodiamonds, metals such as silver, gold, platinum, copper, gold, palladium, zinc, and titanium, hydroxyapatite (HAp) nanoparticles.
  • the roughened, porous substrate is generated by chemical or physical etching, which includes mechanical roughening such as bead blasting and sand blasting.
  • the substrate 140 is roughened by etching (Bl).
  • the etchant 148 is carried by a preformed pipe 146 and deposited onto the substrate 140 to create a roughened surface. Once the surface is roughened, it is functionalized (B2) with a liquid (not shown) or vapor silane 150, and infiltrated with a lubricating liquid 144 (B3).
  • the roughened, porous substrate is made by growing a nanostructured material on the surface.
  • a nanostructured material 152 is grown on the surface of the substrate 140 to create a roughened surface (CI) that is functionalized (C2)) with a liquid (not shown) or vapor silane 150 and infused with a lubricating liquid 144 (C3).
  • CI roughened surface
  • C2 functionalized
  • C3 lubricating liquid
  • these nanostructures include PPy nanofibers, carbon nanotubes, and the like.
  • the surface can be chemically functionalized by silanization (FIG. 14C2) and infiltrated with a lubricating liquid (FIG. 14C3).
  • the roughened surface can be formed over or applied to a variety of planar or non-planar surface (see FIG. 7 and FIG. 8A-B).
  • FIG. 8B shows a porous membrane attached to the outer surface of a cylindrical solid core. It can also be attached to the inner surfaces, outer surfaces, or inner and outer surfaces of tubes and other irregularly shaped substrates.
  • the solid surface may be substantially flat. This situation may be applicable when the critical surface energy of the flat surface is higher than the surface tension of the functional lubricating fluid.
  • the roughened surface can have pores that are comparable or smaller than the material to be repelled.
  • pore sizes that are smaller than the size of protozoa (e.g., 10 ⁇ ), bacteria (e.g., 1 ⁇ ), viruses (e.g., 0.1 ⁇ ), and the like can be utilized.
  • non-limiting examples of surface to which SLIPS is applied include a cannula, connector, catheter (e.g., central line, peripherally inserted central catheter (PICC) line, urinary, vascular, peritoneal dialysis, and central venous catheters), catheter connector (e.g., Leur-Lok and needleless connectors), clamp, skin hook, cuff, retractor, shunt, needle, capillary tube, endotracheal tube, ventilator, associated ventilator tubing, drug delivery vehicle, syringe, microscope slide, plate, film, laboratory work surface, well, well plate, Petri dish, tile, jar, flask, beaker, vial, test tube, tubing connector, column, container, cuvette, bottle, drum, vat, tank, organ, organ implant, or organ component (e.g., intrauterine device, defibrillator, corneal, breast, knee replacement, and hip replacement implants), artificial organ or a component thereof (
  • PICC peripherally inserted central catheter
  • encephaloscope e.g., bandages, sutures, staples, and combinations thereof.
  • Lubricating fluids are selected to create a fluid surface that is intrinsically smooth, stable, and defect free.
  • the lubricating fluid should infiltrate, wet, and stably adhere to the substrate. Moreover, it should be chemically inert with respect to the solid substrate and the fluid to be repelled.
  • a lubricating fluid possesses the ability to form a substantially molecularly flat surface when provided over a roughened surface.
  • a lubricating fluid possesses the ability to form a substantially atomically flat surface when provided over a roughened surface.
  • the lubricant is substantially incompressible.
  • the lubricating fluid is capable of repelling immiscible fluids, and in particular biological fluids of any surface tension.
  • the enthalpy of mixing between the fluid to be repelled and lubricating fluids be may be sufficiently high (e.g., water and oil) that they phase separate from each other when mixed together.
  • the lubricating fluid can be selected such that the fluid to be repelled has a small or substantially no contact angle hysteresis.
  • contact angle hysteresis less than about 5°, 2.5°, 2°, or even less than 1° can be obtained.
  • Low contact angle hysteresis encourages sliding at low tilt angles (e.g., ⁇ 5°), further enhancing fluid repellant properties of the surface.
  • lubricating fluid is inert with respect to the solid surface and biological fluid. Lubricating fluid flows readily into the recesses of the roughened surface and generally possesses the ability to form an ultra-smooth surface when provided over the roughened surface.
  • FIG. 4A shows a droplet 400 of perfluoro- tripentylamine (herein referred to by the trade name "FC-70”) lubricating fluid on an unstructured surface 410 of a flat surface prepared from a slanted epoxy resin.
  • FC-70 perfluoro- tripentylamine
  • FIG. 4B shows the same lubricating fluid on an exemplary roughened surface of the same composition 420 having nanostructures, the features of which are shown in the inset. As shown, the nanostructures greatly enhance the wetting of the lubricating fluid on the surface, creating a uniformly-coated slippery functional layer over the topographies.
  • the resulting ultra-smooth surface is capable of repelling fluids including, but not limited to biological fluids and particles in solution or suspension.
  • Lubricating fluid can be selected from a number of different fluids. These fluids can be selected based on their biocompatibility, low (or high) toxicity, anti-clotting performance, chemical stability under physiological conditions, and levels of leaching from the surfaces of the devices. For example, compounds that are approved for use in biomedical applications (e.g., blood substitutes, MRI contrast agents), such as
  • the lubricating fluid is a chemically- inert, high-density biocompatible fluid, non-limiting examples of which include tertiary perfluoroalkylamines (such as perfluorotri-n-pentylamine, FC-70, perfluorotri-n- butylamine FC-40, etc ), perfluoroalkylsulfides and perfluoroalkylsulfoxides,
  • perfluoroalkylethers perfluorocycloethers (like FC-77) and perfluoropolyethers (such as K YTOX family of lubricants by DuPont), perfluoroalkylphosphines and
  • perfluoroalkylphosphineoxides and combinations thereof are used.
  • long- chain perfluorinated carboxylic acids e.g., perfluorooctadecanoic acid and other homologues
  • fluorinated phosphonic acids e.g., fluorinated silanes, and combinations thereof
  • Liquid B perfluoroalkyls can be linear or branched.
  • the lubricating fluid has a high density.
  • the lubricating fluid has a density that is more than 1.0 g/cm 3 , 1.6 g/cm 3 , or even 1.9 g/cm 3 .
  • the density of the lubricating fluid is greater than that of the biological fluid to enhance fluid repellency. High density fluids reduce the tendency of an impacting fluid to 'sink' below the surface of lubricating fluid and to become entrained therein.
  • the density of Liquid A may be lower than that of the lubricating liquid.
  • density of Liquid A may be at least ⁇ 1.5 times lower than that of the lubricating liquid.
  • the lubricating fluid has a low evaporation rate, such as less than 100 nm/s, less than 10 nm/s, or even less than 1-2 nm/s.
  • the lubricating fluid should be applied in a thickness sufficient to cover the rough surface of the substrate and provide an ultra-smooth surface. Taking a typical thickness of the lubricating fluid to be about 10 ⁇ and an evaporation rate of about 1-2 nm/s, SLIPS can remain highly fluid- repellant for a long period of time without any refilling mechanisms.
  • lubricating fluid has a low freezing temperature, such as less than -5°C, -25°C, or even less than -50°C. Having a low freezing temperature allows lubricating fluid to maintain its slippery behavior to repel a variety of liquids or solidified fluids, such as ice and the like and over a range of temperatures.
  • various different commercially available lubricating liquid can be found at the specified viscosity, such as perfluorinated oils (e.g., 3MTM FluorinertTM and DuPontTM
  • Krytox® oils at temperatures ranging from less than - 80 °C to greater than 260 °C.
  • temperature dependence of liquid viscosity of DuPont Krytox oils is shown in the Table 1 as a specific example (note: data is provided by the manufacturer of DuPont Krytox oils).
  • the viscosities of both Object A and Liquid B affect the performance of SLIPS. Because the liquid repellency of SLIPS is conferred by the presence of the Liquid B, the viscosity of Liquid B can affect the physical characteristics of liquid repellency of SLIPS, such as the velocity of Object A. The more viscous the Liquid B, the less mobile the given Liquid A will be.
  • Liquid A of constant viscosity its velocity on SLIPS reduces with increasing viscosity of Liquid B.
  • a Liquid A of absolute viscosity of 1 cP its velocities on SLIPS with Liquid B of viscosities of 13 cP, 140 cP, and 990 cP are -17 cm/s, -5.8 cm/s, and -0.98 cm/s, respectively. Therefore, to enhance the velocity of Liquid A on SLIPS, it is desirable to use a Liquid B having a lower viscosity. This general trend is consistent for Liquid A of viscosities ranging from 1 cP to 1000 cP.
  • Lubricating fluid can be deposited in any desired thickness, provided the top surface of lubricating fluid forms an ultra-smooth surface and is retained and interacts with the underlying surface. If the liquid layer is too thick, the upper surface is 'unbound' from the underlying surface and will flow with Liquid A from the SLIPS surface.
  • the liquid layer that interacts with and is retained by the underlying surface is referred to as the
  • Film thicknesses substantially on the order of the surface roughness peak-to- valley distance provide good fluid-solid interaction between the substrate and lubricating fluid.
  • lubricating fluids with thicknesses below a characteristic length scale remain substantially adhered to the roughened surface, whereas fluid layers above the characteristic length can flow, creating flow lines (surface defects) and disrupting the flatness of the fluid surface.
  • non-limiting thicknesses for the lubrication fluid are on the order of 5-20 ⁇ when the peak to valley height is -5 um.
  • lubricating fluid can be applied by pupating drops of the fluid onto the roughened surface, or by dipping the roughened surface into a reservoir carrying lubricating fluid.
  • lubricating fluid can be sprayed, cast, or drawn onto the roughened surface. The lubricating liquid can infiltrate the roughened surface by capillary action, which can wet the roughened surface and form a film on top of it.
  • Lubricating fluid and the roughened surface can be both generated by a double-spraying process, where emulsions consisting of nano/microparticles are first sprayed onto a flat solid surface to form a substantially roughened solid layer, and then lubricating fluid can be sprayed onto this freshly formed layer for further infiltration.
  • lubricating fluid may infiltrate into the pores of the roughened surface by capillary action and form an ultra- smooth film on top of the roughened surface.
  • the lubricating fluid may wet the entire roughened surface structure and form an ultra-smooth film over the underlying roughened surface.
  • porous materials may be the presence of the capillary network within the bulk materials, which can further enhance transport of Liquid B through the pores.
  • the porous structure can provide a replenishing fluid at the surface and may be useful to address evaporation or other materials loss of Liquid B from the SLIPS surface. For example, in the case where a portion of Liquid B is reduced at the surface of the materials due to evaporation, sudden pressure purging, physical damage or the like, Liquid B can be replenished by the capillary action in these networks.
  • Replenishing Liquid B is drawn through the porous body of the substrate by capillary wicking to refresh the upper surface of SLIPS.
  • the porous material itself can be utilized as a fluid reservoir to store Liquid B for subsequent capillary refilling purpose.
  • the porous material 905 can be connected to an external fluid reservoir 903 sitting on a solid substrate 901, where the capillary networks within the porous material 905 can help transfer (e.g., via wicking) the Liquid B from the fluid reservoir 903 to the porous material 905.
  • FIG. 9B shows an alternate embodiment where SLIPS having a porous material 905 as the roughened surface is formed in an inner surface of a cylindrical tube.
  • the cylindrical tube 901 has a first annular region 903 serving as a fluid reservoir for Liquid B, followed by an inner annular region of SLIPS having a porous material 905, which surrounds a hollow region 907 for the flow of Liquid A.
  • Liquid B in annular region 903 transfers into the (e.g., via wicking) the porous material 905 to form a SLIPS and Liquid A can flow through the hollow region with little to no drag at the interface between 905 and 907.
  • FIG. 9C shows yet another embodiment where SLIPS is formed in an inner surface of an arbitrarily shaped flow path.
  • the bottom substrate 901 has a channel 903 serving as a fluid replenishment source for Liquid B that is coupled to the porous material 905 of SLIPS.
  • Porous material 905 is formed by combining a bottom substrate 901 having a depressed region mated with a top substrate 909 having a substantially flat porous material 911 formed thereon. The combination of the top and bottom substrate portions forms a hollow region 907 for the flow of Liquid A.
  • FIG. 9D shows some optical micrographs on how the bottom substrate 901 and SLIPS 905 of FIG. 9C can be formed.
  • a TEFLON filter paper 930 having a three-dimensionally random network of pores can be placed between a male mold 940 and female mold 950 defining an arbitrary flow path and the male mold 940 and female mold 950 can be pressed together to replicate the flow path pattern on the TEFLON filter paper 930.
  • the template TEFLON filter paper 930 can be placed inside the female mold 950, which now serves as bottom substrate 901 of FIG.
  • the female mold 950 may further contain channel 903 (not shown) that serves to replenish Liquid B as needed.
  • FIG. 35 shows several other non-limiting embodiments of SLIPS and how Liquid B can be replenished to the SLIPS in each of those embodiments.
  • the left column corresponds to systems where SLIPS is exposed to both Medium X and Liquid A (shown as a droplet).
  • the right column corresponds to systems where SLIPS is exposed to
  • Liquid A substantially only Liquid A (shown as a plug between two SLIPS).
  • Liquid B can be replenished to SLIPS as needed.
  • the top row shows scenarios where there is a finite amount of Liquid B.
  • the middle row shows scenarios where there is a large source (e.g., practically infinite source from the viewpoint of the amount of Liquid B needed to replenish the SLIPS) of Liquid B.
  • the bottom row shows scenarios where Liquid B can be replenished by spraying Liquid B as needed, either manually or automatically. As shown, many different configurations and their derivatives are possible.
  • SLIPS can sustain fluid impact pressures on the order of 10 3 -10 7 Pa (e.g., at least from an order of magnitude to five orders of magnitude higher than the current state- of-the-art surface) and are capable of restoring themselves to exceptional liquid repellency upon critical physical damages with a fast self-healing time on the orders of 100 ms to 1 s (i.e., 4 orders of magnitude faster than the current state-of-the-art surface).
  • the lubricating liquid and the roughened surface can be selected so that they have fast self-healing properties.
  • self-healing refers to re-formation of an ultra-smooth (and even substantially molecularly flat) surface after physical impact (e.g., damage).
  • the lubricating fluid is a self-healing coating that rapidly restores the fluid-repellant function following damage to the porous material by abrasion or impact. Self healing occurs when the lubricating fluid flows toward the damaged area of the substrate by surface energy-driven capillary action to spontaneously fill the physical void. The recovery time is a function of lubricant viscosity.
  • the self-healing time is on the order of 150 ms to 1 s.
  • the self-healing time is on the order of O(10s) or more.
  • the recovery time for a fluid displacement is less than one second. In other embodiments, the recovery time is a fraction of a second.
  • the recovery time is 50 ms, 60 ms, 70 ms, 80 ms, 90 ms, 100 ms, 110 ms, 120 ms, 130 ms, 140 ms, 150 ms, 160 ms, 170 ms, 180 ms, 190 ms, 200 ms, 210 ms, 220 ms, 230 ms, 240 ms, 250 ms, 1 second, 5 seconds 10 seconds, 30 seconds, 60 seconds, 90 seconds, 120 seconds, or more depending on the amount of damage sustained, and the characteristics of the lubricating fluid and substrate used.
  • the self-healing behavior of the liquid repellant surfaces can be a function of the interaction between the lubricating liquid and the roughened surface, as well as the viscosity of the lubricating liquid.
  • Typical kinematic viscosities of the lubricating liquid are in the range of 0.10 cm 2 /s to 10 cm 2 /s.
  • particle impact or scratching can damage the surface by, for example, breaking or removing the topographical features of the surface in a small area.
  • the measured self-recovery time for a ⁇ 50 ⁇ fluid displacement of FC-70 lubrication fluid on epoxy-resin-based SLIPS was only -150 ms (FIG. 28 A).
  • FIG. 28A shows time-lapse images showing self- healing capability of SLIPS from a ⁇ 50 ⁇ -wide physical damage on a time scale on the order of 100 ms.
  • FIG. 28B is a schematic illustration of the type of damage that may occur and the healing process that restores the smooth liquid surface. A reservoir with extra fluid can be available to 'top off the fluid layer thickness to maintain the desired thickness.
  • the roughened surface may be functionalized so that the critical surface energy of the roughened surface is higher than the surface energy of lubricating liquid; under these conditions, complete wetting of the lubricating liquid can spontaneously occur throughout the roughened surface.
  • the roughened surface when the critical surface energy of the roughened surface is lower than the surface energy of the lubricating liquid, the roughened surface may be provided with a high degree of roughness to promote wetting of the lubricating liquid within the pores of the roughened surface.
  • the lubricating liquid has a surface energy that is less than the surface energy of the roughened surface.
  • the surface energy of the liquid B is such that the spreading parameter S is positive.
  • the critical surface tension of the roughened surface i.e., y c _s
  • the surface tension of the lubricating liquid i.e., 7LV-B
  • the critical surface tension of the roughened surface may be at least 1.25 times lower than the surface tension of the lubricating liquid.
  • the lubricating liquid may be non-reactive with the roughened surface.
  • the roughened surface and the lubricating liquid (or liquid to be repelled) can be chosen so that the roughened surface does not dissolve upon contact with the lubricating liquid (or liquid to be repelled).
  • perfluorinated liquids (the lubricating liquid) work exceptionally well to repel a broad range of polar and non-polar Liquids A and their solidified forms.
  • any suitable combination of the roughened surface and the lubricating liquid described above can be employed.
  • a perfluorinated liquid as the lubricating liquid and a nanostructured surface made out of polymer (for example, epoxy resin, silicone, and Teflon) that are chemically functionalized with end-functional group of -CF 3 or other similar fluorocarbon groups can be utilized as the roughened surface.
  • polymer for example, epoxy resin, silicone, and Teflon
  • Other materials including sapphire, diamonds, silicon, glass, and metals (e.g., aluminum) can be also used with suitable chemical functionalization schemes.
  • SLIPS may be incorporated in an environment (1) where the lubricating fluid is exposed substantially only to Object A or (2) where the lubricating fluid is exposed to both Object A and another fluid environment, such as medium X (e.g., atmosphere, underwater, etc.).
  • medium X e.g., atmosphere, underwater, etc.
  • the working combinations of the solid/lubricant/immiscible test liquid may be chosen by satisfying the condition shown in Equation (el).
  • YAX, and y B x represent the surface energies of the Object A-medium X interface, and the lubricating liquid-medium X interface, respectively.
  • ⁇ , and 61 ⁇ 2x are the equilibrium contact angles of Object A and the lubricating fluid on a flat solid surface immersed under medium X environment, respectively.
  • Medium X can also play a role for the fluid repellency.
  • the density of Object A, px may desirably be greater than that of the Medium X, p x (i.e., ⁇ > ⁇ ).
  • the size of Object A may be on the order of, or greater than, its capillary length. Specifically, capillary length is a
  • Table 2 A shows examples of working combinations of the solid, Liquids A and B of the slippery surface based on the predictions from the proposed relationship
  • A, and 7B represents the surface tension of Object B.
  • ⁇ and ( B were estimated from the measured static contact angles on flat substrates from at least three individual
  • medium X is air specifically in this context.
  • Variable > ⁇ represents the interfacial tension for Object A-Liquid B interface.
  • ⁇ AB for water-perfluorocarbon
  • S. Epoxy represents silanized epoxy resin substrate.
  • non-polar Liquid B with fluorocarbon functional groups may adhere well with roughened solid surface that is functionalized with fluorocarbon groups (e.g., -CF 3 , -CF 2 ).
  • polar Liquid B may adhere well with roughened solid surface that is functionalized with hydroxyl groups (i.e., -OH).
  • the roughened surface may be functionalized with low surface energy coatings (e.g., less than 30 mJ/m 2 ), such as -CF 3 , -CF 2 H, -CF 3 and -CF 2 -,
  • Liquid B may be selected to also exhibit low surface energy (e.g., less than 20 mJ/m 2 ), such as perfluorotributylamine, perfluorotri-n-pentylamine, perfluorohexane, perfluoro(2-butyl- tetrahydrofuran), perfluorocycloether, perfluoro n-alkyl morpholines, perfluoroalkylethers, perfluorotripropylamine, and the like.
  • low surface energy e.g., less than 20 mJ/m 2
  • perfluorotributylamine perfluorotri-n-pentylamine, perfluorohexane, perfluoro(2-butyl- tetrahydrofuran), perfluorocycloether, perfluoro n-alkyl morpholines, perfluoroalkylethers, perfluorotripropylamine, and the like.
  • Liquid A when Liquid A is a high surface tension liquid (e.g., water, condensation) or a solidified fluid, Liquid B can be selected from other higher surface energy fluids (i.e., -20 mJ/m 2 or higher), such as polydimethylsiloxane, other liquid silicone elastomers or commercial food grade lubricants (e.g., K YTOX(TM) FG lubricants), oils (e.g, vegetable or mineral oil (see FIG. 26B)), and the like.
  • FIG. 26 shows a SLIPS surface generated using an infiltration of polydimethylsiloxane (PDMS) liquid (500 MW, X viscosity, OH-terminated, Sigma Aldrich) into an ePTFE membrane (1 ⁇ , Sterlitech).
  • Image (B) in FIG. 26 shows a SLIPS surface generated using an infiltration of olive oil into an ePTFE membrane (1 ⁇ , Sterlitech). In both cases the blood was found to not wet the surface, and rolled off without adhering to the surfaces.
  • PDMS polydimethylsiloxane
  • the roughened surface may be functionalized with low surface energy coatings (e.g., less than 30 mJ/m 2 ), such as -CF 3 , - CF 2 H, -CF 3 and -CF 2 - -CF 2 -CF 3 , -CF 2 -CFH- -CF 2 -CH 2 - -CFH-CH 2 - and the like.
  • low surface energy coatings e.g., less than 30 mJ/m 2
  • Table 3 shows some non-limiting examples of combinations of substrates, lubricating liquid (Liquid B), and liquid to be repelled (Liquid A).
  • the solid substrate can be selected from the group consisting of
  • lubricating liquids such as liquid silicone elastomers (e.g.,
  • polydimethylsiloxane vegetable or mineral oil, liquid hydrocarbons, and combinations thereof can be applied to the solid substrate to create a SLIPS surface to repel materials such as simple aqueous fluids (e.g., water), complex aqueous fluids (e.g., blood), solidified fluids, and combinations thereof (Table 3, row 1).
  • the solid substrate can be selected from the group consisting of fluoro-silanized metals (e.g., fluoro-silanized aluminum, silver, gold, platinum, copper, gold, palladium, zinc, titanium, and the like), fluoro-silanized natural polymers (e.g., fluoro-silanized synthetic polymers (e.g., fluoro-silanized epoxy resin, silicone, silicone rubber, latex, polytetrafluoroethylene, polyvinylfluoride, polyvinylidene fluoride, fluorinated ethylene propylene, thermoplastic elastomers, Teflon, and the like), and combinations thereof.
  • Lubricating liquids such as perfluorinated fluids can be applied these solid substrates to repel any non-perfluorinated liquid (Table 3, row 2).
  • FIG. 16A-C shows optical images showing enhanced optical transparency of an epoxy-resin-based SLIPS (left) as compared to significant scattering in the non-infused super hydrophobic nanostructured surface (right) in the visible light range.
  • FIG. 16B shows optical transmission measurements for epoxy-resin-based SLIPS in the visible light range (400-750 nm).
  • FIG. 64 shows images of a transparent SLIPS surface made by the infiltration of a highly-ordered nanoporous Si02 glass layer (A) with perfluorocarbon (FC-70) (B). When fully infiltrated, the layer is highly transparent (C).
  • An equilibrium contact angle, ⁇ is the angle at which a liquid/vapor interface meets a solid surface, which is determined by the interactions across the three interfaces, e.g.,
  • contact angle measurement can be performed by a number of different well-established techniques, such as the sessile drop method and the Wilhelmy method.
  • the sessile drop method is among the most popular technique for contact angle measurement.
  • a liquid droplet is deposited on a targeted solid surface, where the liquid profile is captured by an optical system of a goniometer and geometrically fitted to obtain the contact angle.
  • the contact angle measured from a static liquid droplet deposited on the surface is known as the static contact angle, ( sta tic.
  • advancing contact angle, (9A can be measured while the volume of the drop is increasing until the wetting line starts to advance.
  • Receding contact angle, (9R) can be measured by decreasing the volume of the drop and determining the contact angle just before the wetting line recedes.
  • the advancing and the receding angles of the liquid drop can also be determined by gradually tilting the solid surface until the liquid drop starts to move.
  • Fluid-fluid interfacial tension can be measured by many well-established techniques, such as the Wilhelmy plate method, the Du Noiiy ring method, and the pendant drop method (e.g., see Drelich et al., in Encyclopedia of Surface and Colloid Science, pp. 3152 - 3166, Marcel Dekker Inc, 2002, the contents of which is incorporated by reference herein in its entirety).
  • the pendant drop method is among the most popular and versatile technique, which can be easily extended to a two-liquid system.
  • the pendant drop method measures the shape of a fluid-fluid interface and quantifies the shape distortion due to the competition between the fluid- fluid interfacial tension and gravity.
  • a drop of denser fluid e.g., Object A
  • medium X i.e., air/water/the lubricating fluid
  • the denser liquid droplet will be deformed as the liquid volume increases.
  • the shape profile of the liquid droplet is captured by an optical system and subsequently analyzed by a computer software when the liquid volume is increased to the maximum possible size (i.e., before the liquid drop is detached from the syringe needle).
  • Roughness of a surface can be quantitatively estimated by a number of indirect and direct approaches.
  • one of the simplest indirect methods to quantify surface roughness is the use of Wenzel's relationship to estimate the roughness by measuring the apparent contact angle of a surface.
  • the surface roughness can be quantitatively measured by using an atomic force microscope or by a scanning electron microscope.
  • AFM atomic force microscope
  • a suitable AFM probe is selected for the measurements depending on the aspect ratio of the surface features (note: aspect ratio is defined as the ratio between the height and the width of the surface features).
  • aspect ratio is defined as the ratio between the height and the width of the surface features.
  • sharp AFM probes i.e., radius of tip curvature ⁇ 10 nm
  • very high aspect ratio i.e. > 10
  • the use of scanning electron microscope can also be used for the measurement of the top view and cross sectional view of the surface morphologies for the estimation of the surface roughness.
  • the roughness of a 3-D porous material can be estimated by measuring the surface morphology of the top-most layer of the porous material. Particularly, the estimation may be particularly well-suited when complete wetting of a surface is predominately induced by the roughness at the surface layer of the material that is in intimate contact with the fluid.
  • the lubricating fluid is an organofluorine oil, (i.e., perfluorinated oils including, without limitation, tertiary perfluoroalkylamines (such as perfluorotri-n-pentylamine, FC-70; perfluorotri-n- butylamine FC-40, etc), perfluoroalkylsulfides, perfluoroalkylsulfoxides,
  • organofluorine oil i.e., perfluorinated oils including, without limitation, tertiary perfluoroalkylamines (such as perfluorotri-n-pentylamine, FC-70; perfluorotri-n- butylamine FC-40, etc), perfluoroalkylsulfides, perfluoroalkylsulfoxides,
  • perfluoroalkylethers perfluorocycloethers (like FC-77), perfluoropolyethers (such as K YTOX family of lubricants by DuPont), perfluoroalkylphosphines, and
  • the slippery surface of the present disclosure has a coefficient of friction that is lower than polytetrafluoroethylene (PTFE or TEFLON). In certain embodiments, the coefficient of friction is less than 0.1, less than 0.05, or even less than 0.04. In certain embodiments, the coefficient of friction can be measured against polished steel, Teflon, or the slippery surface of the present disclosure itself (e.g., slippery surface/slippery surface).
  • PTFE polytetrafluoroethylene
  • TEFLON polytetrafluoroethylene
  • the coefficient of friction is less than 0.1, less than 0.05, or even less than 0.04. In certain embodiments, the coefficient of friction can be measured against polished steel, Teflon, or the slippery surface of the present disclosure itself (e.g., slippery surface/slippery surface).
  • the lubricating liquid (Liquid B) overcoats the roughened solid surface, and forms an ultra- smooth surface.
  • Liquid B can wet the roughened surface, filling the hills and valleys of the roughened surface, and forming an ultra-smooth surface over the roughened surface.
  • Liquid B can form a liquid layer over the roughened surface so that the liquid layer covers the roughened surface to form an ultra- smooth surface of Liquid B (FIGS. 6 A and 6B).
  • the average surface roughness of the surface is on the order of or less than about 1 nm based on high resolution atomic force microscopy measurements.
  • the presence of the micro/nanostructures can significantly enhance the wetting of Liquid B, thereby creating a uniformly-coated slippery functional layer over the topographies.
  • the first configuration may be useful for repelling a liquid, gas, or molecules or particulates contained within liquids.
  • the lubricating fluid (Liquid B) infiltrates within the solid textures, forming a composite solid-liquid interface.
  • the lubricating fluid (Liquid B) can infiltrate the roughened solid surface and form a thin coating thereon that follows the topography of the underlying roughened solid surface.
  • the thin coating may be conformally coating the top surface of the roughened surface.
  • “conformal coating” can encompass forming a molecular monolayer or multiple molecular layers that surround the materials of the roughened surface. However, the "conformal coating" is not thick enough to form an over-coat layer to form an ultra-smooth surface, such as described in FIG. 27A.
  • the second configuration may be particularly useful for repelling materials in their solid forms.
  • the lubricating fluid (Liquid B) In order for the lubricating fluid (Liquid B) to remain attached with the roughened surface, at least the following three properties are desirable: (1) the lubricating fluid (Liquid B) readily imbibes into, wets, and stably adheres within the substrate, (2) the roughened surface is preferentially wetted by the lubricating fluid (Liquid B) rather than by the material to be repelled, and (3) the lubricating fluid (Liquid B) and the material to be repelled are immiscible.
  • the solidification temperature of the lubricating liquid may be lower than that of Liquid A.
  • the lubricating liquid can maintain its liquid state below the solidification temperature of Liquid A, thereby retaining its slippery property. Without wishing to be bound by theory, there may be at least two reasons to maintain the lubricating liquid in a liquid state even while Liquid A solidifies.
  • Second, having the lubricating liquid maintained in the liquid state may result in reduced adhesion at the interface between Object A and the lubricating liquid in the directions normal and tangential to the substrate surface, as compared to that of the interface between the solidified form of the material to be repelled and other solid surfaces (i.e., roughened surfaces).
  • Adhesion between surfaces may be proportional to the contact surface area, where the smoothness of the lubricating liquid surface can minimize contact area between Object A and the lubricating liquid, due to the smaller surface area at the interface compared to a roughened surface.
  • the reduced adhesion may facilitate removal of Object A from the lubricating liquid surface at much reduced force per unit area.
  • the ultra-smooth surface of the lubricating liquid may also reduce the condensation of Liquid A from the air (i.e., assuming the vaporized form of Liquid A is present in air) when the surface of the lubricating liquid is cooled to the temperature below the solidification temperature of Liquid A. This may be due to the fact that there are few or even no nucleation sites on the lubricating liquid surface, which greatly reduce the nucleation probability of the repelled liquid.
  • the formation of fog and frost i.e., solidified form of the repelled liquid at the micro- and nanoscale
  • the solidification temperature of the lubricating liquid may be 25
  • the boiling temperature of the lubricating liquid may be higher than the solidification temperature of Liquid A.
  • the lubricating liquid may be able to maintain its liquid state above the solidification temperature of Liquid A. Additionally, maintaining the liquid state may facilitate the removal of Liquid A from the lubricating liquid surface due to the aforementioned liquid- slippery function, while the surface is held at a temperature above the solidification temperature of Liquid A. This may be particularly important for applications in surface defrosting, where the lubricating liquid may be defrosted using minimal energy input (e.g., at a lower temperature) as compared to other solid surfaces.
  • the boiling temperature of the lubricating liquid may be 215 °C higher than the solidification temperature of Liquid A at atmospheric pressure.
  • the solid to be repelled may slide off from the surface of the lubricating liquid by gravity when the surface is tilted at an angle with respect to the horizontal, given that Object A is larger than a characteristic size.
  • capillary length is a characteristic length scale that quantifies the dominance of body force over surface force on an object
  • Object A which can be quantitatively expressed as ( ⁇ /pg) , where y, p, and g are surface tension and density of the liquid, and gravity, respectively.
  • Object A may be at least 3 times larger than the capillary length of Liquid A.
  • the lubricating liquid may be selected to satisfy additional criteria needed for Solid A or Object A.
  • the lubricating liquid can be selected so that the lubricating liquid is not toxic to Object A so that facile transport of Object A to desired locations without reducing the biological activity of Object A.
  • the lubricating liquid can be selected so that the lubricating liquid is toxic to Object A so that removal of Object A can be further coupled with reducing the biological activity of Object A.
  • Porous Material having a high degree of physical roughness for the roughened surface may be particularly advantageous.
  • the presence of such physical roughness may induce not only the complete wetting of the lubricating fluid, but also provide additional capillary adhesion for the lubricating fluid within the porous solid to further enhance the mechanical stability, wicking characteristics and the ability to "hold” Liquid B "in place” even at high tilt angles.
  • porous material can be a self-supporting, free-standing membrane which can be attached/glued/adhered to the external or internal surfaces of materials with any kind of geometry (see FIGS. 7 and 8).
  • one of the unique features of using porous materials may be the presence of the capillaries network within the bulk materials, which can further enhance transport of Liquid B through the pores.
  • the porous material itself can be utilized as a fluid reservoir to store the fluorinated liquid for subsequent capillary refilling (see FIG. 8).
  • the porous material can also be connected to an external fluid reservoir or larger storage capacity, where the capillary networks can help autonomously transfer the liquids from the fluid reservoir to the bulk material itself (see FIG. 8).
  • the pore size of the porous material can roughly be on the order of the capillary length of Liquid B or smaller. Such size may allow stabilizing
  • the surface tension of fluorinated liquids is in the range of about 10 - 20 mN/m at a typical density of about 1800 kg/m 3 .
  • Typical pore sizes can range from about 50 nm to about 100 ⁇ or up to about 1 mm, such as about 750 um - 1 mm.
  • use of a porous material for the roughened surface may provide even higher resistance to pressure change than the high pressure changes that can be obtained using solid surfaces having certain topographies. For example, while a 2.5D (vertically extruded) nanostructured structure shown in FIG.
  • 5A may be able to sustain a maximum rate of pressure change on the order of 10 5 Pa per second
  • a porous material e.g., Teflon membrane
  • use of a porous material may be able to tolerate pressure change up to about 6 x 10 6 Pa per second without displacing Liquid B.
  • the improved pressure tolerance of the 3D porous material can be attributed to the enhanced capillary interactions between the intricate 3D porous network and Liquid B.
  • use of a porous material for the roughened surface may provide even higher pressure stabilities than the high pressure stability that can be obtained using solid surfaces having certain topographies (e.g., "2.5D" nanostructured surface).
  • a porous material e.g., Teflon membrane
  • use of a porous material may be able to tolerate absolute pressure up to about 6.9 x lO 7 Pa while maintaining its liquid slippery function.
  • the improved pressure tolerance of the 3D porous material can be attributed to the incompressibility of the lubricating layer, as well as the resistance of liquid penetration into the porous structure.
  • SLIPS Materials (Object As) that can be repelled by SLIPS include microbes such as bacteria. Bacteria primarily exist in robust, surface-associated communities known as bio films, which are ubiquitous in both natural and anthropogenic environments.
  • Bacteria can physically attach to a vast variety of surfaces - from hydrophilic to hydrophobic, by a variety of mechanisms (O'Toole et al, 2000; De Beer et al, 2006;
  • conditioning layer proteins, known as conditioning layer, by physical or chemical adsorption, which precedes the attachment of the bacteria itself.
  • Conditioning films which may contain fibronectin, fibrinogen, collagen, and other proteins, coat a biomaterial surface almost immediately and provide receptor sites for bacterial or tissue adhesion (Gristina, 1987).
  • Bio film formation is of concern to industry and healthcare because it causes contamination of plumbing, oil wells, heat exchangers, building ventilation, food storage, medical implants, and other systems.
  • Biofilms threaten human health by triggering an immune response, releasing harmful endotoxins and exotoxins, and clogging indwelling catheters; in fact, biofilms are responsible for nearly 100,000 nosocomial deaths annually in the United States and 80% or more of all microbial infections in humans.
  • any defects or voids in the surface chemistry could serve as nucleation sites for bacterial attachment.
  • Structured superhydrophobic surfaces in the Cassie (trapped air) state are prone to irreversible wetting (Wenzel transition), especially with the production of bacterial surfactant, which seriously limits their lifetime in submerged environments (Poetes, Pv., et al., Metastable Underwater Superhydrophobicity. Physical Review Letters, 2010. 105(16)).
  • ECM acts as a diffusion barrier and as a charged binding filter for certain antibiotics, and that it complements enzymes and multidrug resistance pumps on cells that remove antimicrobials.
  • the resistance to threats covers a wide range of treatments: bio films exposed to chlorine bleach for 60 minutes are reported to still have live cells; biofilms in pipes continuously flushed over 7 days with multiple biocides recolonize the pipes, and biofilms have been reported to survive in bottled iodine solution for up to 15 months.
  • Biofilms' resistance to antimicrobials may be related to the extreme nonwettability of their surface as well as resistance to vapor penetration.
  • SLIPS can repel various types of bacteria and prevent bio film formation. SLIPS can repel, or prevent or reduce attachment of bacteria suspended in solution, airborne bacteria, and the like. In one embodiment, the type of bacteria repelled by SLIPS is gram positive bacteria. In another embodiment, the type of bacteria repelled by SLIPS is a gram negative bacteria.
  • Non- limiting examples of bacteria repelled by SLIPS include members of the genus selected from the group consisting of Actinobacillus ⁇ e.g., Actinobacillus actinomycetemcomitans), Acinetobacter (e.g., Acinetobacter baumannii), Aeromonas, Bordetella (e.g., Bordetella pertussis, Bordetella bronchiseptica, and Bordetella
  • Burkholderia e.g., Burkholderia cepacia and Burkholderia pseudomallei
  • Borelia e.g., Borelia burgdorferi
  • Bacillus e.g., Bacillus anthracis and Bacillus subtilis
  • Campylobacter e.g., Campylobacter jejuni
  • Capnocytophaga e.g., Cardiobacterium hominis
  • Citrobacter e.g., Clostridium tetani or
  • Chlamydia e.g., Chlamydia trachomatis, Chlamydia pneumoniae, and Chlamydia psiffaci
  • Eikenella e.g., Eikenella corrodens
  • Enterobacter Escherichia (e.g., Escherichia coli)
  • Francisella e.g., Francisella tularensis
  • Fusobacterium Flavobacterium, Haemophilus ⁇ e.g., Haemophilus ducreyi or Haemophilus influenzae
  • Helicobacter e.g., Helicobacter pylori
  • Kingella e.g., Kingella kingae
  • Klebsiella e.g., Klebsiella pneumoniae
  • Legionella e.g., Legionella pneumophila
  • Listeria e.g., Listeria monocytogenes
  • Leptospirae e.g., Moraxella catar
  • Mycoplasma hominis and Mycoplasma pneumoniae Mycobacterium (e.g. , Mycobacterium tuberculosis or Mycobacterium leprae), Neisseria (e.g., Neisseria gonorrhoeae or Neisseria meningitidis), Pasteur ella (e.g.
  • Pasteur ella multocida Proteus (e.g., Proteus vulgaris and Proteus mirablis), Prevotella, Plesiomonas (e.g., Plesiomonas shigelloides), Pseudomonas (e.g., Pseudomonas aeruginosa), Providencia, Rickettsia (e.g., Rickettsia rickettsii and Rickettsia typhi), Stenotrophomonas (e.g., Stenotrophomonas maltophila), Staphylococcus (e.g., Staphylococcus aureus and Staphylococcus epidermidis), Streptococcus (e.g., Streptococcus viridans, Streptococcus pyogenes (group A),
  • Streptococcus agalactiae group B
  • Streptococcus bovis and Streptococcus pneumoniae
  • Streptomyces e.g., Streptomyces hygroscopicus
  • Salmonella e.g., Salmonella enteriditis, Salmonella typhi, and Salmonella typhimurium
  • Serratia e.g., Serratia marcescens
  • Shigella Spirillum (e.g., Spirillum minus
  • Treponema e.g., Treponema pallidum
  • Veillonella Vibrio (e.g., Vibrio cholerae, Vibrio parahaemolyticus, and Vibrio vulnificus)
  • Yersinia e.g., Yersinia enter ocolitica, Yersinia pestis, and Yersinia pseudotuberculosis
  • Xanthomonas
  • SLIPS has been shown to prevent 99.6% of common bacterial biofilm attachment under both flow and static conditions, which represents at least a 30x reduction in biofilm attachment over best-case-scenario, state-of-the-art surface treatments based on PEGylation.
  • SLIPS can repel various types of fungi.
  • Non-limiting examples of fungi repelled by SLIPS include members of the genus Aspergillus ⁇ e.g., Aspergillus flavus, Aspergillus fumigatus, Aspergillus glaucus, Aspergillus nidulans, Aspergillus niger, and Aspergillus terreus), Blastomyces dermatitidis, Candida ⁇ e.g., Candida albicans, Candida glabrata, Candida tropicalis, Candida parapsilosis, Candida krusei, and Candida guillermondii), Coccidioides immitis, Cryptococcus ⁇ e.g., Cryptococcus neoformans, Cryptococcus albidus, and Cryptococcus laurentii), Histoplasma capsulatum var.
  • capsulatum Histoplasma capsulatum var. duboisii, Paracoccidioides brasiliensis, Sporothrix schenckii, Absidia corymbifera; Rhizomucor pusillus, Rhizopus arrhizous, and combinations thereof.
  • SLIPS can also repel various types of viruses and virus-like particles.
  • the virus repelled by SLIPS is selected from the group consisting of dsDNA viruses, ssDNA viruses, dsRNA viruses, (+)ssRNA viruses, (-)ssRNA viruses, ssRNA-PvT viruses, dsDNA-RT viruses, and combinations thereof.
  • Non-limiting examples of viruses repelled by SLIPS include cytomegalovirus (CMV), dengue, Epstein-Barr, Hantavirus, human T-cell lymphotropic virus (HTLV I/II), Parvovirus, hepatitides (e.g., hepatitis A, hepatitis B, and hepatitis C), human papillomavirus (HPV), human
  • CMV cytomegalovirus
  • HTLV I/II human T-cell lymphotropic virus
  • HPV human papillomavirus
  • HIV immunodeficiency virus
  • AIDS acquired immunodeficiency syndrome
  • RSV respiratory syncytial virus
  • Varicella zoster West Nile, herpes, polio, smallpox, yellow fever, rhinovirus, coronavirus, Orthomyxoviridae (influenza viruses) ⁇ e.g., Influenzavirus A, Influenzavirus B, Influenzavirus C, Isavirus and Thogotovirus), and combinations thereof.
  • SLIPS is capable of repelling particles in suspension or solution without causing surface adhesion, surface-mediated clot formation, fouling, or aggregation.
  • the omniphobic nature of SLIPS allows it to protect surfaces from a wide range of contaminants.
  • Non- limiting examples of a particles in suspension or solution include cells (e.g., normal cells, diseased cells, parasitized cells, cancer cells, foreign cells, stem cells, and infected cells), microorganisms (e.g., viruses, virus-like particles, bacteria, bacteriophages), proteins and cellular components (e.g., cell organelles, cell fragments, cell membranes, cell membrane fragments, viruses, virus-like particles, bacteriophage, cytosolic proteins, secreted proteins, signaling molecules, embedded proteins, nucleic acid/protein complexes, nucleic acid precipitants, chromosomes, nuclei, mitochondria, chloroplasts, flagella, biominerals, protein complexes, and minicells).
  • cells e.g., normal cells, diseased cells, parasitized cells, cancer cells, foreign cells, stem cells, and infected cells
  • microorganisms e.g., viruses, virus-like particles, bacteria, bacteriophages
  • proteins and cellular components e
  • SLIPS repels natural and synthetic solutions used in medicines, intravenous solutions, pharmaceutical manufacturing, and medication delivery systems.
  • SLIPS is used to prevent or reduce protein adsorption.
  • Biocompatibility and contamination issues associated with the contact of foreign surfaces involve nonspecific protein adsorption. Biocompatibility is the ability of a material to allow an appropriate host response in a specific environment or application. In general, foreign surfaces of medical instruments and medical devices attract a variety of biological adsorption events and biological responses, and it is very difficult to prevent, reduce, or control these processes (Ratner (Ed.), Biomaterials Science, Academic Press (2004)).
  • Proteins have an inherent tendency to deposit on surfaces as a tightly bound adsorbate, which strongly influences subsequent cellular (or microbial) interactions with the surface (Ratner (Ed.), Biomaterials Science, Academic Press (2004)). Bacteria attach to surfaces by means of a conditioning layer of proteins. Implanted biomaterials or medical devices are rapidly coated by constituents of the blood serum and surrounding matrix, which include fibronectin, osteonectin, vitronectin, albumin, fibrinogen, laminin, collagen and covalently-bound short-chain oligosaccharides (Ratner (Ed.), Biomaterials Science, Academic Press (2004); Gristina, A.G., et al., Biomaterial-centered sepsis and the total artificial heart. Microbial adhesion vs tissue integration. JAMA 259:870-874 (1988)). Both bacteria and tissue cells can then attach to these various proteins.
  • Protein adsorption also occurs when devices trigger an immune response in the body.
  • complement proteins opsonize the foreign surface for phagocytosis.
  • Complement activation leads to deposition of complement components, which foul the foreign surface (Skattum L, et al, Mol. Immunol, 48(14): 1643- 55 (2011)).
  • SLIPS can be used to prevent or reduce adsorption of proteins that come into contact with SLIPS.
  • Fluids such as biological fluids that are applied to, or come into contact with, SLIPS are strongly repelled by the lubricating fluid.
  • fluids includes fluids and particles in suspensions or solution, including those from living organisms and synthetic solutions used in medicines.
  • This surface design represents a completely new approach to controlling the adhesion of biological fluids.
  • biological fluids that can be repelled by SLIPS without causing surface adhesion or aggregation include whole blood, serum, plasma, water, sweat, feces, urine, saliva, tears, vaginal fluid, prostatic fluid, gingival fluid, amniotic fluid, intraocular fluid, cerebrospinal fluid, seminal fluid, sputum, ascites fluid, pus, nasopharengal fluid, wound exudate fluid, aqueous humour, vitreous humour, bile, cerumen, endolymph, perilymph, gastric juice, mucus, peritoneal fluid, pleural fluid, sebum, vomit, synthetic fluid (e.g., synthetic blood, hormones, nutrients), and combinations thereof.
  • synthetic fluid e.g., synthetic blood, hormones, nutrients
  • SLIPS is applied to a medial device that comes into contact with complex fluids such as blood to create an anti-coagulation surface.
  • Blood clotting on synthetic surfaces is a long-standing and widespread problem in medicine (Thompson, A.R. & Harker, L.A. Manual ofHemostasis and Thrombosis, (F. A. Davis, Philadelphia, 1983); Colman, R.W., Hirsch, J., Marder, V.J. & Salzman, E.W. (eds.).
  • Thrombosis is initiated on surfaces first by protein absorption, which promotes platelet adhesion, activation and release of thrombin that cleaves fibrinogen and activates fibrin clot formation ((Thompson, A.R. & Harker, L.A. Manual of Hemostasis and Thrombosis, (F. A. Davis, Philadelphia, 1983); Colman, R.W., Hirsch, J., Marder, V.J. & Salzman, E.W. (eds.). Hemostasis and Thrombosis, (Lippincott Williams and Wilkins, 2005))).
  • Results demonstrate that SLIPS does not allow blood to wet, and adhere to, SLIPS.
  • Anti-coagulant surfaces that prevent or reduce blood coagulation can be developed by creating an ultra-low drag clot-free surface, much like living endothelium does (see Example 2).
  • Anti-coagulation surfaces disclosed herein represent a novel and surprisingly effective method for controlling the adhesion of blood components, such as platelets and fibrin, involved in the clotting cascade mechanism. Anti-coagulation surfaces do not allow blood to wet, or adhere to, SLIPS by creating an ultra-low drag clot free surface, much like living endothelium does.
  • FIG. 1 shows the porous or rough layer with the low surface energy, chemically inert, perfluorinated liquid, infiltrated around it. The perfluorinated oil may be held in place by the features of SLIPS structures.
  • This combination leads to a physically smooth, ultra-repellant, and chemically homogeneous lubricating film on the surface of the substrate because the porous structure holds the low energy fluid in place.
  • the presence of the physical roughness of the porous material not only induces the complete wetting of the lubricating fluid, but can also provide additional adhesion for the lubricating fluid within the porous solid.
  • Thin lubricating film minimizes surface inhomogeneities, reduces retention forces, and enhances fluid mobility along SLIPS, not unlike the lipid bilayer in the endothelial cell membrane. As a result, the drag forces on fluid in contact with SLIPS are minimal, and the fluid remains highly mobile on SLIPS.
  • the lubricating film is generated through a fluid infiltration process induced by the porous materials.
  • SLIPS supports blood flow at 100 mL/hr for 1, 2, 3, 4, 5, or 10 hours or more without platelet activation or clotting. In other aspects, SLIPS supports blood flow at 500 mL/hr for 8, 10, 15, or 20 hours or more without platelet activation or clotting. In still other aspects, SLIPS supports blood flow at 1000 mL/hr for 12, 15, 20, or 24 hours or more without platelet activation or clotting. In other aspects, SLIPS supports blood flow at 1250 mL/hr for 24, 36, or 48 or more hours without platelet activation or clotting. In still other aspects, SLIPS supports blood flow at 1250 mL/hr for a period of days, months, or years.
  • SLIPS is incorporated into medical devices to prevent or reduce adhesion of proteins, microbes, blood, tissue, and the like.
  • Medical devices and biomedical implants in the body can cause injury to the tissue surrounding the device or implant. Inflammation, wound healing, plaque disposition, and foreign body response are common reactions to these injuries. Medical devices and implants can cause chronic inflammation, formation of granulation tissue, and an end-stage healing response of fibrosis or fibrous encapsulation (Ratner (Ed.), Biomaterials Science, Academic Press (2004)). However, no device or coating exists that prevents these injuries from occurring.
  • catheters, cannulas, and shunts are commonly used inside and outside the body to allow drainage, administration of fluids or gases, or access by surgical instruments. They can be temporary or permanent ⁇ e.g., indwelling catheter). These medical devices can be made of a range of polymers, including silicone rubber, latex, and thermoplastic elastomers. Bacterial infection and colonization of catheters and cannulas and shunts often cause serious related medical conditions such as sepsis (Crnich, C.J. & G. Maki, D.G. The Promise of Novel Technology for the Prevention of Intravascular Device- Related Bloodstream Infection. II. Long-Term Devices. Clinical Infectious Diseases 34: 1362-1368 (2002)).
  • stents are also prone to bacterial contamination that can cause serious infections in the body.
  • a stent is inserted into a natural passage or conduit in the body to prevent or counteract a disease-induced, localized flow constriction. It can also be used to temporarily hold a natural conduit open during surgery. Stents are often heparinized to reduce thrombosis and the effects of bacterial infection.
  • problems associated with clot formation, infection, wound response, and bacterial colonization persist (Garg, N., Garg, R., Gordon, C, Singh, R. & Singh, A.
  • Adhesion, attachment, and wound responses often occur when biosensors and bioelectrodes are implanted in the body.
  • the useful life of in vivo biosensors is typically limited due to infection, fouling, and inflammatory response (Wilson, G.S. & Gifford, R. Biosensors for real-time in vivo measurements. Biosens. Bioelectron. 20:2388-2403 (2005); Reichert, W.M., Koschwanez, H.E., Yap, F.Y. & Klitzman, B. In vitro and in vivo characterization of porous poly-L-lactic acid coatings for subcutaneously implanted glucose sensors.
  • pacemakers, and bioelectrodes, such as neural electrodes also face frequent problems of infection, fouling and inflammatory response (S. Karnam, et al.
  • Endoscopes are difficult to clean and sterilize, and therefore present issues related to the transfer of bacterial, fungal, or viral infection from one patient to another (Beilenhoff, U., et al. ESGE-ESGENA guideline: Cleaning and disinfection in
  • SLIPS are used to prevent, reduce, or delay various fluids and other biological materials from wetting surfaces and particles from adhering to surfaces.
  • SLIPS can be incorporated into a microfluidic device, which controls the flow of minute amounts of fluids or gases (e.g., a lab-on-a-chip), for manipulating biological fluids.
  • SLIPS surfaces are useful for preventing, reducing, or delaying inflammatory responses, blood coagulation, antifouling, and adhesion of other products of biological origin in and on devices including wound dressings catheters, stents, and other biomedical devices (e.g., stents, dialysis machines, central veno-venous hemofiltration device, extracorporeal membrane oxygenation equipment, and linking catheters), so that devices can support flow of fluids without permitting wetting of fluids, attachment, or adhesion of particles (see, e.g., FIG. 22A-B).
  • Surfaces of medical instruments and medical devices attract a variety of biological adsorption events and biological responses that are difficult to prevent, reduce, and control.
  • SLIPS can be applied to medical instruments and medical devices to reduce, prevent, or mediate processes associated with protein adsorption, cell attachment, bacterial infection, and inflammatory response.
  • SLIPS can be used in wound care, including wounds caused by, e.g., cuts, bruises, punctures, scrapes, tears, and burns.
  • SLIPS is used to prevent or reduce further damage to damaged skin and to oxygenate the tissue that the SLIPS surface covers.
  • One aspect of this embodiment is burn wound care. Burn wounds become hypoxic because of the layer of damaged tissue. Current burn treatments involve exposing the damaged tissue to high levels of oxygen. This can be accomplished in, e.g., a hyperbaric chamber. However, such wounds must either be covered by a wound dressing, which prevents or reduces the damaged tissue from being exposed to much needed oxygen, or be left exposed and vulnerable to infection.
  • a SLIPS-treated wound dressing that has been infused with oxygenated lubricating fluid can be used to both protect the wound from infection caused by exposure to the environment without adhering to the wound, and provide the wound with oxygen to promote healing.
  • Surgical instruments and intravascular devices such as catheters have many potential sources for infection.
  • the adherence of microorganisms to catheter surfaces is among the most important characteristics associated with the pathogenesis of infection caused by catheter use. Even a single bacterium cell that successfully adheres to surface can develop into a robust and infectious bacterial film and cause disease. Therefore an effective strategy for prevention or reduction of bacterial adhesion is needed.
  • SLIPS Wound Dressings
  • SLIPS surfaces do not permit adhesion of proteins or cells when contacted with biological fluids.
  • perfluorocarbons have a high solubility for oxygen (Clark, Leland C; Gollan, F. Science 152(3720): 1755-56 (1966); Shaffer, T.H. et al, Pulmonol. 14: 102-109 (1992)).
  • a wound dressing that incorporates SLIPS with, e.g., a perfluorocarbon substrate, provides a breathable surface that prevents adhesion of proteins or cells to promote faster wound healing (see, e.g., FIG. 23).
  • a set of SLIPS was fabricated to repel fluids spanning a broad range of surface tensions.
  • two types of porous solids were tested.
  • the porous solids were periodically ordered and random: (i) arrays of nanoposts functionalized with a low- surface-energy polyfluoroalkyl silane, and (ii) a random network of Teflon nano fibres distributed throughout the bulk substrate (FIG. 17).
  • Low-surface-tension perfluorinated liquids e.g.
  • FC-70, 7B 17.1 mN/m; or Dupont TM Krytox ® oils) that are non- volatile and immiscible with both aqueous and hydrocarbon phases and therefore able to form a stable, slippery interface with substrates (i.e., > 0 and E 2 > 0) for a variety of polar and non- polar liquids including water, acids and bases, alkanes, alcohols, and ketones (FIG. 15 and FIG. 17) were chosen for the lubricating fluid.
  • the SLIPS were generated through liquid infiltration into the porous materials, which resulted in a homogeneous and nearly molecularly smooth surface with a roughness of ⁇ 1 nm.
  • Each of these SLIPS exhibited extreme fluid repellency as signified by very low contact angle hysteresis (CAH, ⁇ ⁇ 2.5°, FIG. 17 and FIG. 18A) and by very low sliding angles (a ⁇ 5° for droplet volume > 2 ⁇ ) against fluids of surface tension ranging from -17.2 ⁇ 0.5 mN/m (i.e., n-pentane) to 72.3 ⁇ 0.3 mN/m (i.e., water).
  • CAH the difference between the advancing and receding contact angles of a moving droplet, and sliding angle, the surface tilt required for droplet motion, directly characterize resistance to mobility; the low values therefore confirm a lack of pinning, consistent with a nearly defect-free surface.
  • the disclosed surfaces provide an ultra-smooth surface capable of preventing, reducing, or delaying surface wetting of fluids that come into contact with SLIPS.
  • FIG. 11 shows sequential images of the blood sample being added to PDMS (FIG.
  • FIG. 11 A and microstructured PTFE impregnated with perfluorinated oil (FIG. 11B).
  • the SLIPS that consisted of microstructured PTFE impregnated with perfluorinated oil (FIG. 11B) caused the blood sample to immediately bead into droplets and slide along SLIPS.
  • FIG. 13 subsequent analysis of these surfaces using optical (FIGS. 12(A)(i), 12(B)(i)) and scanning (FIGS. 12(A)(ii), 12(B)(ii)) electron microscopy, to show that while blood species such as cells, platelets, and proteins are visibly deposited on the untreated glass, PDMS, and PTFE control surfaces, there is nothing visible on the oil- infiltrated PTFE material. Thus, this 'fluid-like' surface appears to be extremely effective at preventing or reducing adhesion of platelets and fibrin clot formation when in contact with fresh unheparinized human blood.
  • Example 3 [0266] Experiments using 2 ⁇ polystyrene particles showed that force of adhesion to slippery surfaces was extremely low, such that the particles were easily dragged by a fluid/air boundary interface across SLIPS, and concentrated into the center of a drying droplet instead of leaving a 'coffee ring' deposition.
  • Leaching can also be monitored by extracting fluid that has passed over SLIPS into a fluorinated solvent followed by followed by chromatography and mass spectrometry and 19F-NMR.
  • the slippery surfaces produced in accordance with the present methods showed excellent prevention of attachment and/or facilitation of low-force detachment of mature bacterial biofilm incubated on the surface. Specifically, this capability is demonstrated for Pseudomonas aeruginosa, a human opportunistic pathogen, and one of the most common nosocomial infections in the lining of catheters and the lungs of cystic fibrosis patients.
  • the surface was fabricated by wicking 100 of various commercial fluids satisfying criteria for a lubricating fluid into 30 mm round Teflon filter membranes with 0.2 ⁇ pore size, which were then mounted onto standard polystyrene Petri dishes. Atop the slippery surfaces, 2 mL tryptone broth puddles for 24 hours that were inoculated at 1% with Pseudomonas aeruginosa preculture were deposited and statically incubated. The bacteria formed a mature biofilm during this timeframe, and the slime-like matrix binding the constituent cells tends to gel the puddle.
  • the slippery surfaces produced in accordance with the present disclosure caused the slimy mass to readily slide off when tilted, as shown in FIG. 19, even at tilt angles below 10°.
  • the effective slide-off removal of biofilm slime on the slippery surfaces produced in accordance with the present disclosure contrasts to the adhesion and pinning of the basal layer of slime on unfilled 0.2 ⁇ Teflon filters (left of FIG. 19) as well as on fluorosilanized super hydrophobic silicon micro/nanostructure arrays (right of FIG. 19), whose fluid repellency properties failed during the conditioning film and slime production of biofilm.
  • the slippery surfaces produced in accordance with the present disclosure can be designed to be nontoxic by appropriate selection of the lubricating fluid, enabling applications with medical and environmental requirements.
  • the commercial fluids already available eight products that can satisfy the requirements for a lubricating fluid were screened and five candidates were identified for low toxicity (see FIG. 21).
  • the toxicity screening assay was based on adding 1% and 0.01% of each commercial product to 10 mL aliquots of tryptone broth, which were inoculated with 1% initial seeding concentration of Pseudomonas aeruginosa (PA- 14) preculture and incubated at 37° C overnight in an orbital shaker.
  • PA- 14 Pseudomonas aeruginosa
  • CFU colony forming unit
  • Teflon and silicon wafer SLIPS surfaces prepared in accordance with the present disclosure were shown to prevent bacterial attachment.
  • lubricating liquid (Dupont TM Krytox ® 100 and 103) was added onto the porous solids, Teflon membranes with average pore sizes of > 200 nm and about 60 - 80 ⁇ thick (Sterlitech Corporation, WA, USA), to form an over-coated layer.
  • the fluid spread spontaneously onto the whole substrate through capillary wicking.
  • the wafer was rinsed with EtOH, oxygen plasma treated for 30 seconds, and was rendered hydrophobic by putting the sample in a vacuum desiccator overnight with a glass vial containing 0.2 mL heptadecafiuoro-1,1,2,2- tetrahydrodecyltrichlorosilane (Gelest Inc).
  • Bacterial strains Pseudomonas aeruginosa PA14, Staphylococcus aureus SCOl, and Escherichia coli ZK2686 were each grown in LB medium (EMD LB Broth Miller) overnight at 37°C in loosely capped tubes on an orbital shaker to the stationary phase. This LB preculture was then seeded at 1% concentration in one of the following: TB growth medium (BD Bacto Tryptone) for P. aeruginosa; TSB medium supplemented with 0.5% glucose and 3% NaCl for S. aureus; or M9 medium for E. coli. These cultures were incubated on the bench at room temperature during experiments.
  • TB growth medium BD Bacto Tryptone
  • TSB medium supplemented with 0.5% glucose and 3% NaCl for S. aureus
  • M9 medium for E. coli.
  • the tubing was configured to allow flow in series through the two chambers.
  • the bottom surface and sidewalls of each chamber were lined with press-fit porous Teflon membrane; one was infused with Krytox 103 to create a SLIPS and the other was left untreated as a control.
  • Bacterial culture was pumped into each tube until the loop was full and trapped air had been eliminated though a bubble escape, after which the pump was operated at 10 mL/min.
  • the average intensity image of each sample's micrograph set was generated in ImageJ and the average [(R+G+B)/3] pixel value and standard deviation were computed for each average intensity image.
  • Biofilm quantification by crystal violet staining [0283] PTFE substrates were carefully sectioned with a scalpel into 3 x 3 cm segments, removed from the flow cell, gently rinsed in PBS, and stained by 0.1% crystal violet for 20 minutes. The stained samples were rinsed in a DIW bath and the bound crystal violet on each was eluted into 4 mL of 100% EtOH. Absorbance values at 590 nm were measured on a Perkin Elmer Lambda 40 UV-Vis spectrometer.
  • FIG. 36A In a simple test scheme, Pseudomonas aeruginosa TB culture was deposited in puddles that were statically grown upon three surface typologies, two of which are shown in FIG. 36A.
  • a porous PTFE membrane (0.2 ⁇ pore size) served as a flat, conventional low-adhesive control surface; a fluorosilanized patterned silicon wafer (not shown) featuring four different high-aspect-ratio micropost arrays presented superhydrophobicity, the capacity to repel and roll off water; and a PTFE membrane infused with Krytox-103 provided a SLIPS liquid slippery surface.
  • test surfaces were manually tilted to compare the adhesion of the macroscopic biofilm slime.
  • Biofilm grown on the control and superhydrophobic substrates showed complete wetting of the surface and left a film of slime on the PTFE as it was tilted.
  • biofilm on the SLIPS substrate slid readily without leaving any slime film or other visible residue behind.
  • Biofilm growing in contact with the bare polystyrene Petri dish at the edge of the SLIPS remained pinned. However, it was not attached to the SLIPS substrate underneath: when part of the pinned puddle was disconnected from the edge and manipulated toward the center, it became fully mobile.
  • the contact line pinning characteristics of the surfaces were characterized by monitoring the evaporation dynamics of the bacterial culture droplets as well as the stains that remained on the surfaces upon drying. In the absence of pinning, the droplet should follow a nearly constant contact angle mode of evaporation without the formation of a coffee ring stain.
  • These hypotheses were consistent with observations of the bacteria droplet' s evaporation on SLIPS. The absence of the coffee ring formation also indicated that the adhesion of the bacteria on the SLIPS was small compared to the forces imparted by the meniscus of the droplet, and it was demonstrated that the dried biofilm was easily removed from SLIPS by adhesive tape.
  • aeruginosa on Ti-coated glass slides was found to differ by ⁇ 19%> from PTFE, indicating similar long- term biofilm attachment on these two controls and thus a similar starting point for attachment reduction. Even if PEG desorption is assumed to not occur due to recent advances in multi-tether attachment, and even if no chemical masking occurred after 7 days submerged in bacterial culture, the 14% of remaining biofilm would be ⁇ 35 times more than on the SLIPS substrate. [0290] It is worth noting that the flow velocity in this experiment of ⁇ 1 cm/s is a conservatively gentle condition.
  • typical flow velocities can be on the order of 1 m/s and 10 m/s respectively, with proportionately higher shear forces that would support biofilm removal from a SLIPS substrate.
  • flow velocities are also frequently more aggressive, on the order of 10-100 cm/s.
  • the average fluorescence intensities of 20 representative fields of view per substrate were computed as numeric pixel averages [(R+G+B)/3]. While not fully capturing intensity from out-of-focus biofilm structure on the control surface, the control values may be considered a lower bound; thus there is at least a 98% average intensity reduction in the fluorescence signal from PTFE to SLIPS, similar to the global
  • FIG. 31 A shows the experimental setup in included a 24" loop of SLIPS tubing (ePTFE+FC70) and a 24" loop of standard silicone tubing (0.250"ID) as a control.
  • the preformed ePTFE tube was saturated with PFC FC70 oil, and encased in a silicone tube to help prevent oil loss and evaporation.
  • Both the ePTFE SLIPS tube and the silicone tube control were filled with 12 mL of the diluted blood.
  • a 24" preformed ePTFE tube was saturated with PFC FC-70, and encased in a silicone tube where it interfaced with a peristaltic pump and Tygon tubing in other regions to create an FC-70 reservoir.
  • Fresh whole human blood (12 mL, diluted 1 : 1 with saline) free of anticoagulant was pumped through both sets of tubing at 3,000 mL/hr. After 20 minutes, there was no sign of clotting within the entire length of tubing (FIG. 30 and FIG. 31B). There was some staining (surface adsorption) in the region of the peristaltic pump roller contact (FIG. 30B), suggesting potential mechanical damage and infiltration of blood into the ePTFE at this site. After 30 min of flow there was no sign of clotting and minimal surface adhesion within the entire length of SLIPS tubing (FIG. 31C). In the silicone tubing there were signs of clotting and significant surface adhesion within the tube.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Hematology (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Transplantation (AREA)
  • Wood Science & Technology (AREA)
  • Dermatology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Physics & Mathematics (AREA)
  • Surgery (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Fluid Mechanics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Clinical Laboratory Science (AREA)
  • Materials For Medical Uses (AREA)
  • Polymers & Plastics (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)

Abstract

A self-healing, scratch resistant slippery surface that is manufactured by wicking a chemically-inert, high-density liquid coating over a roughened solid surface featuring micro and nanoscale topographies is described. Such a slippery surface shows anti-wetting properties, as well as exhibits significant reduction of adhesion of a broad range of biological materials, including particles in suspension or solution. Specifically, the slippery surfaces can be applied to medical devices and equipment to effectively repel biological materials such as blood, and prevent, reduce, or delay coagulation and surface-mediated clot formation. Moreover, the slippery surfaces can be used to prevent fouling by microorganisms such as bacteria.

Description

SLIPPERY LIQUID-INFUSED POROUS SURFACES AND BIOLOGICAL
APPLICATIONS THEREOF
RELATED APPLICATIONS
[0001] This application claims priority to U.S. Patent Application No. 61/434,217, filed on January 19, 2011; U.S. Patent Application No. 61/466,352, filed on March 22, 2011; U.S. Patent Application No. 61/470,973, filed on April 1, 2011; U.S. Patent Application No. 61/496,883, filed on June 14, 2011; U.S. Patent Application No. 61/509,488, filed on July 19, 2011, U.S. Patent Application No. 61/529,734 filed on Aug 31 2011; U.S. Patent Application No. 61/538,100, filed on September 22, 2011, the contents of which are incorporated by reference herein in their entireties.
INCORPORATION BY REFERENCE
[0002] All patents, patent applications, and publications cited herein are hereby incorporated by reference in their entirety in order to more fully describe the state of the art as known to those skilled therein as of the date of the invention described herein.
FIELD OF THE INVENTION
[0003] The present disclosure relates generally to surfaces that prevent adsorption or deposition from fluids, solids, or mixtures of fluids and solids of biological origin, and uses thereof.
BACKGROUND
[0004] Current development of liquid-repellent surfaces is inspired by the self-cleaning abilities of many natural surfaces on animals, insects, and plants. Water droplets on these natural surfaces maintain a near-spherical shape and roll off easily, carrying dirt away with them. The water-repellency function has been attributed to the presence of
micro/nanostructures on many of these natural surfaces. These observations have led to enormous interest in the past decade in manufacturing biomimetic water-repellent surfaces, owing to their broad spectrum of potential applications, which range from water-repellent fabrics to friction reduction surfaces.
[0005] More specifically, synthetic liquid-repellent surfaces in the art are inspired by the lotus effect (Barthlott, W. & Neinhuis, C. Purity of the sacred lotus, or escape from contamination in biological surfaces. Planta 202, 1-8 (1997)) in which water droplets are supported by surface textures on a composite solid/air interface that enables water droplets to easily roll off the surface (Cassie, A. B. D. & Baxter, S. Wettability of porous surfaces. Trans. Faraday Soc. 40, 0546 - 0550 (1944); Cassie, A. B. D. & Baxter, S. Large contact angles of plant and animal surfaces. Nature 155, 21-22 (1945)). However, this approach has inherent limitations that severely restrict its applicability. First, trapped air is a largely ineffective cushion against organic fluids or complex mixtures that, unlike water, have low surface tension that strongly destabilizes suspended droplets (Shafrin, E. G. & Zisman, W. A. Constitutive relations in the wetting of low energy surfaces and the theory of the retraction method of preparing monolayers. J. Phys. Chem. 64, 519-524 (I960)).
[0006] Moreover, air trapped within surface textures cannot withstand pressure, so that liquids - particularly those with low surface tension - can easily penetrate the surface texture under even slightly elevated pressures or upon impact, conditions commonly encountered with driving rain or in underground transport pipes (Nguyen, T. P. N., Brunei, P., Coffmier, Y. & Boukherroub, R. Quantitative testing of robustness on superomniphobic surfaces by drop impact. Langmuir 26, 18369-18373 (2010)). Furthermore, synthetic textured solids are prone to irreversible defects arising from mechanical damage and fabrication imperfections (Quere, D. Wetting and roughness. Annu. Rev. Mater. Res. 38, 71-99 (2008); Bocquet, L. & Lauga, E. A smooth future? Nature Mater. 10, 334-337 (2011)). Because each defect enhances the likelihood of the droplet pinning and sticking in place, textured surfaces are not only difficult to optimize for liquid mobility but inevitably stop working over time as damage accumulates. Recent progress in pushing these limits with increasingly complex structures and chemistries remains outweighed by substantial tradeoffs in physical stability, optical properties, large-scale feasibility, and/or difficulty and expense of fabrication (Tuteja, A. et al, Science 318, 1618-1622 (2007); Tuteja, A., et al, Proc. Natl. Acad. Sci. USA 105, 18200-18205 (2008); Ahuja, A., et al, Langmuir 24, 9- 14 (2008); Li, Y., et al, Angew. Chem. Int. Ed. 49, 6129-6133 (2010)).
[0007] Despite over a decade of intense research, surfaces in the art are still plagued with problems that restrict their practical applications: they exhibit limited oleophobicity with high contact angle hysteresis; fail under pressure; cannot self-heal when damaged; and are expensive to produce.
[0008] For example, no surfaces that delay or prevent blood clotting, a process that relies on adhesion of platelets and proteins to a surface as a first step, have been developed. Soluble anti-coagulants, such as heparin, must be added to flowing blood in any
extracorporeal shunt to prevent clot formation. Certain polymeric species, such as polyethylene glycol (PEG) chains, can influence the surface hydration layer to prevent protein adsorption and control blood clotting to a limited extent (Barstad, R.M, et al, Thrombosis and haemostasis 79, 302-305 (1998); Niimi, Y., et al, Anesth. Analg. 89, 573- 579 (1999); Chen, S. et al, Polymer 51, 5283-5293 (2010)). However, they are not fully effective and soluble anticoagulants still must be added to the blood.
[0009] Bacteria exist in their natural state predominantly as members of bio films - structured, multicellular communities adherent to surfaces in natural and anthropogenic environments. These communities are composed of many cells embedded within a polymeric organic matrix. Biofilm formation is of concern to industry and healthcare because it causes contamination of plumbing, oil wells, heat exchangers, building ventilation, food storage, medical implants, and other systems. Biofilms threaten human health by triggering an immune response, releasing harmful endotoxins and exotoxins, and clogging indwelling catheters; in fact, biofilms are responsible for nearly 100,000 nosocomial deaths annually in the United States and 80% or more of all microbial infections in humans.
[0010] Systemic and topical antimicrobial products have become extensively used to combat biofilm contamination in health care, agriculture, and industrial settings, and increasingly by the general public as well. Commercial products employ a wide variety of active chemical agents, or biocides, often delivered in liquid form and sometimes as vapor. One review of antiseptics and disinfectants identifies 12 classes of liquid agents and 5 common types of vapor-phase sterilants. Regardless of the particular chemistry or mechanism, biocides must be able to reach the target cell to cause damage. At the multicellular level, therefore, the effective biocide must penetrate into the extracellular matrix (ECM)— the slime-like "cement" of biofilm. Biofilms, however, offer their member cells protection from environmental threats. It has been reported that ECM acts as a diffusion barrier and as a charged binding filter for certain antibiotics, and that it complements enzymes and multidrug resistance pumps on cells that remove antimicrobials. The resistance to threats covers a wide range of treatments: biofilms exposed to chlorine bleach for 60 minutes are reported to still have live cells; biofilms in pipes continuously flushed over 7 days with multiple biocides recolonize the pipes, and biofilms have been reported to survive in bottled iodine solution for up to 15 months. Biofilms' resistance to antimicrobials may be related to the extreme nonwettability of their surface as well as resistance to vapor penetration.
[0011] Developing biomedical materials that are resistant to bio film formation before it causes damage or that prevent its robust attachment would significantly reduce the rate of nosocomial infections and the costs associated with treating them. Many negative effects of bacterial colonization stem from the formation of bio films as protective structures and the associated cooperative behavior of bacterial cells. Persistently bacteria-resistant materials are difficult to achieve by surface chemistry alone. Even if bacteria are unable to attach directly to a material, nonspecific adsorption of proteins or secreted surfactants to the surface eventually masks the underlying chemical functionality with a "conditioning film." These organic molecules will change the wettability and surface charge of the original surface, and after about 4 hours, a certain degree of uniformity is reached and the composition of the adsorbed material becomes material independent. Materials that rely on leaching impregnated antimicrobials such as silver ion (Ag+) for their function are furthermore limited by the finite reservoir of the active agent. Furthermore, the use of leaching paints containing copper or triorganotin to resist biofouling on ship hulls is increasingly prohibited because of their high environmental toxicity. Some recent research on the effects of nano- or microscale topographical features on bacterial adhesion and subsequent biofilm formation has suggested a possibly more persistent and environmentally sustainable form of controlling bacterial attachment to surfaces, but no evidence yet suggests that this approach can effectively prevent mature biofilm formation or attachment.
[0012] There exists a need for an inexpensive, chemically inactive, synthetic slippery surface capable of repelling fluids, withstanding high-impact pressure, and self-healing.
SUMMARY OF THE INVENTION
[0013] Disclosed herein are synthetic slippery liquid-infused porous surfaces ("SLIPS") for repelling fluids of biological origin.
[0014] In one embodiment, an article for repelling a biological material comprising a lubricating fluid layer is disclosed. The lubricating fluid layer is immiscible with the repelled biological material, and forms an ultra-smooth surface. In some embodiments, the lubricating fluid layer is stabilized in place by the underlying substrate. The article has a solid substrate on which the lubricating fluid adheres. The substrate is preferentially wetted by the lubricating fluid. The solid substrate and lubricating fluid form a slippery surface configured and arranged to contact a biological material.
[0015] In another embodiment, an article having a repellant surface is disclosed.
A lubricating fluid wets and adheres to a solid substrate comprising a roughened surface to form a stabilized liquid overlayer. The roughened surface and the liquid covering it have an affinity for each other such that the lubricating liquid is substantially immobilized on the substrate.
[0016] In another embodiment, a device capable of repelling a biological material comprising a lubricating fluid layer is disclosed. The lubricating fluid layer is immiscible with the repelled biological material, and forms an ultra-smooth surface. The device has a solid substrate on which the lubricating fluid adheres. The substrate is preferentially wetted by the lubricating fluid. The solid substrate and lubricating fluid form a slippery surface configured and arranged to contact a biological material.
[0017] In another embodiment, a method of preventing adhesion, adsorption, surface- mediated clot formation, or coagulation of a biological material is disclosed. The method comprises providing a lubricating fluid layer, wherein the lubricating fluid is immiscible with the biological material; providing a solid substrate, wherein the lubricating fluid adheres to the substrate to form a slippery liquid-infused surface; and contacting the biological sample to the surface.
[0018] In one or more embodiments, a method of making an article having a slippery surface is disclosed. A solid substrate is roughened and contacted with a lubricating liquid that forms a lubricating fluid layer. The roughened solid substrate and the lubricating layer form a slippery surface, and are configured and arranged for contact with a material that is immiscible with the lubricating liquid.
[0019] In another embodiment, an optically transparent device that prevents adhesion of biological material is disclosed. A roughened surface that is a transparent window is wetted by a lubricating fiuid that adheres to the roughened surface to form an over-coated layer. The roughened surface of the transparent window has a greater affinity towards the lubricating fluid as compared to a biological material. Moreover, the index of refraction of the lubricating liquid is substantially similar to the index of refraction of the roughened surface. The lubricating liquid and the biological material are substantially chemically inert with each other. In one or more aspects, the device is a biological sensor window.
[0020] In one or more embodiments, an article having a low adhesion surface for preventing or reducing biofilm attachment is disclosed. The article comprises a solid substrate having a roughened surface and a lubricating fiuid that adheres to and
preferentially wets the substrate to form a liquid upper surface. The liquid upper surface is configured and arranged to contact a biological material of interest. The lubricating fluid is immiscible with the biological material, and the biological material exhibits little or no adhesion to the article.
[0021] In any of the preceding embodiments, the following condition is satisfied:
7BXCOS( BX - 7AXCOS( AX > 0 (el), wherein ^AX is the interfacial energies of the biological material with a surrounding medium, and wherein }¾x is the interfacial energies of the lubricating fluid with the surrounding medium, and wherein ΘΑΧ is the equilibrium contact angle of the biological material on a flat solid surface immersed under the surrounding medium, and wherein 6¾x is the equilibrium contact angle of the liquid of the lubricating fluid on a flat solid surface immersed under the surrounding medium.
[0022] In one or more embodiments, the following two conditions are satisfied when the article is exposed to Medium X, where X is air/gas/water/immiscible biological material: ?(yBxCOS< Bx - 7AXCOS< AX) - 7AB > 0 (e2) and ?(yBxCOs6>Bx - 7AXCOS< AX) + 7AX - 7BX > 0 (e3), wherein ^AX is the interfacial energies of the biological material with a surrounding medium, yBx is the interfacial energies of the lubricating fiuid with the surrounding medium, ^AB is the interfacial energies of the biological material and the lubricating fluid interface, ΘΑ is the equilibrium contact angle of the biological material on a flat solid surface immersed under the surrounding medium, 6½x is the equilibrium contact angle of the lubricating fluid on a flat solid surface immersed under the surrounding medium, and R is a roughness factor of the roughened surface.
[0023] In one or more aspects, the lubricating fluid prevents adhesion, coagulation, or clot formation of biological materials.
[0024] In the above embodiments, wherein the method further mediates inflammation, wound healing, plaque disposition, or foreign body response.
[0025] In the above embodiments, the method inhibits inflammation, wound healing, plaque disposition, or foreign body response.
[0026] In the above embodiments, the method prevents inflammation, wound healing, plaque disposition, or foreign body response.
[0027] In the above embodiments, the method further prevents bacterial contamination.
[0028] In one or more aspects, wherein the biological material is contacted with the surface at a fluid impact pressures is on the order of 103-107 Pa.
[0029] In one or more aspects, the surface is selected from the group consisting of a cannula, connector, catheter, needle, capillary tube, tubing, syringe and combinations thereof.
[0030] In one or more aspects, the surface is selected from the group consisting of a slide, plate, film, work surface, well, well plate, Petri dish, tile, jar, flask, beaker, vial, test tube, column, container, cuvette, bottle, drum, vat, tank, and combinations thereof.
[0031] In one or more aspects, the surface is selected from the group consisting of a clamp, skin hook, cuff, retractor, shunt, needle, capillary tube, tubing, and combinations thereof.
[0032] In one or more aspects, the surface is selected from the group consisting of an endotracheal tube, ventilator, associated ventilator tubing, drug delivery vehicle, syringe, endoscope, dialysis equipment, central veno-venous hemofiltration device, extracorporeal membrane oxygenation equipment, and combinations thereof.
[0033] In one or more aspects, the surface is selected from the group consisting of an organ, artificial organ, implant, and combinations thereof. [0034] In one or more aspects, the surface is selected from the group consisting of a biosensor, biological microelectromechanical devices (bioMEMs), bioelectrode, and combinations thereof.
[0035] In one or more aspects, the surface is a wound dressing.
[0036] In one or more aspects, the substrate is preferentially wetted by the lubricating fluid. In one or more aspects, the lubricating fluid infiltrates the substrate by capillary action.
[0037] In one or more aspects, the solid substrate is electrically conductive, non- conductive, magnetic, non-magnetic, elastic, non-elastic, light sensitive, or not light sensitive.
[0038] In one or more aspects, the solid substrate is silanized.
[0039] In one or more aspects, the substrate is a roughened surface comprising a porous material.
[0040] In the above embodiments, microparticles or nanoparticles are applied to a flat substrate to form a roughened, porous substrate.
[0041] In the above embodiments, microparticles or nanoparticles are applied to the substrate using photolithography, projection lithography, e-beam writing or lithography, depositing nanowire arrays, growing nanostructures on the surface of a substrate, soft lithography, replica molding, solution deposition, solution polymerization,
electropolymerization, electrospinning, electroplating, vapor deposition, layered deposition, rotary jet spinning of polymer nanofibers, contact printing, etching, transfer patterning, microimprinting, self-assembly, boehmite (γ-ΑΙΟ(ΟΗ)) formation, spray coated, and combinations thereof.
[0042] In one or more aspects, the substrate consists of a fluoropolymer.
[0043] In one or more aspects, the biological material is a fluid selected from the group consisting of whole blood, plasma, serum, sweat, feces, urine, saliva, tears, vaginal fluid, prostatic fluid, gingival fluid, amniotic fluid, intraocular fluid, cerebrospinal fluid, seminal fluid, sputum, ascites fluid, pus, nasopharengal fluid, wound exudate fluid, aqueous humour, vitreous humour, bile, cerumen, endolymph, perilymph, gastric juice, mucus, peritoneal fluid, pleural fluid, sebum, vomit, and combinations thereof.
[0044] In one or more aspects, the biological material is a solution or suspension containing bacteria selected from the group consisting of Actinobacillus {e.g. , Actinobacillus actinomycetemcomitans), Acinetobacter (e.g., Acinetobacter baumannii), Aeromonas, Bordetella (e.g., Bordetella pertussis, Bordetella bronchiseptica, and
Bordetella parapertussis), Brevibacillus, Brucella, Bacteroides (e.g., Bacteroides fragilis), Burkholderia (e.g., Burkholderia cepacia and Burkholderia pseudomallei), Borelia (e.g., Borelia burgdorferi), Bacillus (e.g., Bacillus anthracis and Bacillus subtilis),
Campylobacter (e.g., Campylobacter jejuni), Capnocytophaga, Cardiobacterium (e.g., Cardiobacterium hominis), Citrobacter, Clostridium (e.g., Clostridium tetani or
Clostridium difficile), Chlamydia (e.g., Chlamydia trachomatis, Chlamydia pneumoniae, and Chlamydia psiffaci), Eikenella (e.g., Eikenella corrodens), Enterobacter, Escherichia (e.g., Escherichia coli), Francisella (e.g., Francisella tularensis), Fusobacterium,
Flavobacterium, Haemophilus (e.g., Haemophilus ducreyi or Haemophilus influenzae), Helicobacter (e.g., Helicobacter pylori), Kingella (e.g., Kingella kingae), Klebsiella (e.g., Klebsiella pneumoniae), Legionella (e.g., Legionella pneumophila), Listeria (e.g., Listeria monocytogenes), Leptospirae, Moraxella (e.g., Moraxella catarrhalis), Morganella, Mycoplasma (e.g. , Mycoplasma hominis and Mycoplasma pneumoniae), Mycobacterium (e.g. , Mycobacterium tuberculosis or Mycobacterium leprae), Neisseria (e.g., Neisseria gonorrhoeae or Neisseria meningitidis), Pasteur ella (e.g. , Pasteur ella multocida), Proteus (e.g., Proteus vulgaris and Proteus mirablis), Prevotella, Plesiomonas (e.g., Plesiomonas shigelloides), Pseudomonas (e.g., Pseudomonas aeruginosa), Providencia, Rickettsia (e.g., Rickettsia rickettsii and Rickettsia typhi), Stenotrophomonas (e.g., Stenotrophomonas maltophila), Staphylococcus (e.g., Staphylococcus aureus and Staphylococcus epidermidis), Streptococcus (e.g., Streptococcus viridans, Streptococcus pyogenes (group A),
Streptococcus agalactiae (group B), Streptococcus bovis, and Streptococcus pneumoniae), Streptomyces (e.g., Streptomyces hygroscopicus), Salmonella (e.g., Salmonella enteriditis, Salmonella typhi, and Salmonella typhimurium), Serratia (e.g., Serratia marcescens), Shigella, Spirillum (e.g., Spirillum minus), Treponema (e.g., Treponema pallidum), Veillonella, Vibrio (e.g., Vibrio cholerae, Vibrio parahaemolyticus, and Vibrio vulnificus), Yersinia (e.g., Yersinia enter ocolitica, Yersinia pestis, and Yersinia pseudotuberculosis), Xanthomonas (e.g., Xanthomonas maltophilia) and combinations thereof.
[0045] In one or more aspects, the biological material is a solution or suspension containing particles selected from the group consisting of a member of the genus
Aspergillus (e.g., Aspergillus flavus, Aspergillus fumigatus, Aspergillus glaucus, Aspergillus nidulans, Aspergillus niger, and Aspergillus terreus), Blastomyces dermatitidis, Candida (e.g., Candida albicans, Candida glabrata, Candida tropicalis, Candida parapsilosis, Candida krusei, and Candida guillermondii), Coccidioides immitis,
Cryptococcus (e.g., Cryptococcus neoformans, Cryptococcus albidus, and Cryptococcus laurentii), Histoplasma capsulatum var. capsulatum, Histoplasma capsulatum var. duboisii, Paracoccidioides brasiliensis, Sporothrix schenckii, Absidia corymbifera; Rhizomucor pusillus, Rhizopus arrhizous, and combinations thereof.
[0046] In one or more aspects, the biological material is a solution or suspension containing particles selected from the group consisting of normal cells, diseased cells, parasitized cells, cancer cells, foreign cells, stem cells, and infected cells, microorganisms, viruses, virus-like particles, bacteria, bacteriophage, proteins, cellular components, cell organelles, cell fragments, cell membranes, cell membrane fragments, viruses, virus-like particles, cytosolic proteins, secreted proteins, signaling molecules, embedded proteins, nucleic acid/protein complexes, nucleic acid precipitants, chromosomes, nuclei,
mitochondria, chloroplasts, flagella, biominerals, protein complexes, and minicells.
[0047] In one or more aspects, the lubricating fluid is capable of self-healing by wicking back to the damaged region of the substrate after physical damage of the substrate to form an ultra-smooth surface.
[0048] In the above embodiments, a recovery time for self-healing occurs in less than 50 ms, 60 ms, 70 ms, 80 ms, 90 ms, 100 ms, 110 ms, 120 ms, 130 ms, 140 ms, 150 ms, 160 ms, 170 ms, 180 ms, 190 ms, 200 ms, 210 ms, 220 ms, 230 ms, 240 ms, 250 ms, 1 second, 5 seconds 10 seconds, 30 seconds, 60 seconds, 90 seconds, or 120 seconds or more.
[0049] In one or more aspects, the substrate has a plurality of holes, three- dimensionally interconnected network of holes and one or more materials, or random array of fibrous materials.
[0050] In one or more aspects, the substrate consists of a material selected from the group consisting of polymers, metals, sapphire, glass, diamond, graphite, black carbon, or ceramics. In one or more embodiments, the substrate is a hemocompatible material. In one aspect, the hemocompatible material is a silicon rubber or polysulfone.
[0051] In one or more aspects, the substrate is a polymer selected from the group consisting of polytetrafluoroethylene, polyvinylfluoride, polyvinylidene fluoride, and fluorinated ethylene propylene. [0052] In one or more aspects, the lubricating fluid has a density greater than the density of the biological material.
[0053] In one or more aspects, the lubricating fluid has a density greater than lubricating fluid has a density that is more than 1.0 g/cm3, 1.6 g/cm3, or 1.9 g/cm3.
[0054] In one or more aspects, the lubricating fluid comprises a fluid selected from the group consisting of tertiary perfluoroalkylamines,perfiuorotri-n-butylamine,
perfluoroalkylsulfides, perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocycloethers, perfluoropolyethers, perfluoroalkylphosphines, and perfluoroalkylphosphmeoxides, and combinations thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0055] FIG. 1 is an image showing the structure of SLIPS, which is created by infiltrating a porous solid with a low surface energy, a chemically inert liquid that leads to a physically smooth and chemically homogeneous lubricating film on the surface of the substrate; the top and bottom scanning electron microscope (SEM) images FIG. l(i)-(ii) show ultra-smoothness of the lubricating fluid and a porous structure of the rough solid surface, respectively.
[0056] FIG. 2 is a schematic of a self-healing slippery surface in accordance with certain embodiments.
[0057] FIG. 3A-C shows time sequence images on the sliding motion of a droplet of hexane (yiiquid = 18.6 ± 0.5 mN/m, volume ~ 3.6 μί) along a SLIPS at low sliding angle (a = 3.0°) in accordance with certain embodiments.
[0058] FIG. 4 is a schematic comparing the partial wetting of a flat surface (FIG. 4A) and the complete wetting of a nanostructured surface in accordance with certain
embodiments (FIG. 4B).
[0059] FIG. 5A is a schematic of a structured surface with raised features over which the slippery surface is formed in accordance with certain embodiments.
[0060] FIG. 5B is a schematic of a columnar porous material over which the slippery surface is formed in accordance with certain embodiments.
[0061] FIG. 5C is a schematic of an inverse opal porous material over which the slippery surface is formed in accordance with certain embodiments.
[0062] FIG. 5D is an image of a random network porous material over which the slippery surface is formed in accordance with certain embodiments. [0063] FIG. 6 shows (A) a scanning electron microscope image of the surface morphologies of a 3D porous solid; and (B) a replica of a slippery surface formed by infiltrating the 3D porous solid of 6A with lubricating fluid showing that the lubricating fluid overcoats the surface topographies, forming an ultra-smooth layer without asperity (e.g., average roughness on the order of or less than about 1 nm based on high resolution atomic force microscopy measurements, see inset (6C) as viewed at low (6B) and high (inset 6(D)) resolution in accordance with certain embodiments.
[0064] FIG. 7A shows several planar and non-planar surfaces over which the slippery surface can be formed in accordance with certain embodiments.
[0065] FIG. 7B shows SLIPS formed over a cylindrical solid core in accordance with certain embodiments.
[0066] FIG. 7C shows SLIPS formed on the sidewall of the interior of a tubing/pipe and the like in accordance with certain embodiments.
[0067] FIG. 7D shows SLIPS formed on the sidewall of both of the interior and exterior of a tubing/pipe and the like in accordance with certain embodiments.
[0068] FIG. 7E shows SLIPS formed on the Liquid-B-soaked porous tubing and the like in accordance with certain embodiments.
[0069] FIG. 8a-b shows a schematic of capillary refilling in accordance with certain embodiments.
[0070] FIG. 9A shows SLIPS coupled to a Liquid B reservoir that can replenish evaporating or removed Liquid B in accordance with certain embodiments.
[0071] FIG. 9B shows SLIPS formed inside a cylindrical tube with a Liquid B reservoir that can replenish evaporating or removed Liquid B in accordance with certain embodiments.
[0072] FIG. 9C shows SLIPS formed along the surface of an arbitrary shaped flow path coupled to a channel for replenishing evaporating or removed Liquid B in accordance with certain embodiments.
[0073] FIG. 9D shows images of showing the formation of the bottom substrate portion of FIG. 9C in accordance with certain embodiments.
[0074] FIG. 10 shows images of substrate structures and topologies that can be used to generate SLIPS surfaces; (A) open-cell bricks, (B) post arrays, (C) parallel grooves, (D) open porosity PTFE (ePTFE), (E) plasma-etched PTFE, and (F) sand-blasted
polypropylene (PP).
[0075] FIG. 11 shows sequential images of whole human blood without anticoagulants as it is pipetted onto PDMS (11 A) and the oil-infiltrated PTFE (11B) surfaces.
[0076] FIG. 12 is a series of images of control and test surfaces after exposure to 0.75 mL of blood flow, which show absorption of blood to the control surfaces (glass (12A),
PDMS (12B), dry PTFE (12C)) but no apparent absorption to the oil-infiltrated PTFE
(12D).
[0077] FIG. 13 shows optical (13A(i), 13B(i)) and scanning electron microscope (SEM, 13A(ii), 13B(ii)) surface analysis images of the control and oil-infiltrated PTFE samples from FIG. 11A and 11B in which all the control materials showed evidence of adhered, dried blood species (a mixture of cells, platelets, proteins, see (13 A)), while the oil-PTFE material (13B) showed no evidence of biological material.
[0078] FIG. 14 is a series of diagrams that show exemplary methods by which SLIPS surfaces can be roughened: by spraying or depositing a particulate matter on the substrate (14A); etching (14B); and by growing a nanostructured material on the surface of the substrate (14C).
[0079] FIG. 15 is a series of images showing the self-healing and optical transparency properties of SLIPS. 15A. Time-lapse images showing self-healing capability of SLIPS from a ~50 μιη-wide physical damage on a time scale on the order of 100 ms. 15B. Time- lapse images showing the restoration of liquid repellency of SLIPS after physical damage, as compared to a typical hydrophobic flat surface on which oil remains pinned at the damage site.
[0080] FIG. 16A Optical images showing enhanced optical transparency of an epoxy- resin-based SLIPS (left) as compared to significant scattering in the non-infused super hydrophobic nanostructured surface (right) in the visible light range. 16B. Optical transmission measurements for epoxy-resin-based SLIPS in the visible light range (400- 750 nm). 16C. Optical transmission measurements for Teflon-based SLIPS in the near- infrared range (800-2300 nm).
[0081] FIG. 17 is a series of images showing the omniphobicity and high pressure stability of SLIPS. Time sequence images comparing mobility of pentane droplets (^A = 17.2 ± 0.5 mN/m, volume ~ 30 μί) on a SLIPS and a super hydrophobic, air-containing Teflon porous surface. While pentane is repelled on the SLIPS, it wets and stains the traditional super hydrophobic surface.
[0082] FIG. 18 is a set of graphs showing the contact angle hysteresis as a function of surface tension of test liquids (indicated) on SLIPS and on an omniphobic surface. In the inset (18A), advancing and receding contact angles of a liquid droplet are denoted as ( adv, and ( rec, respectively. SLIPS 1, 2, and 3 refer to the surfaces made of 1) Teflon porous membrane, 2) array of epoxy posts of geometry 1 (pitch = 2 μιη; height = 5 μιη; and post diameter = 300 nm), and 3) array of epoxy posts of geometry 2 (pitch = 900 nm; height = 500 nm to 2 μιη; and post diameter = 300 nm), respectively. A plot (18B) showing the high pressure stability of SLIPS, as evident from the low sliding angle of a decane droplet (y^ = 23.6 ± 0.1 mN/m, volume ~ 3 μί) subjected to pressurized nitrogen gas in a pressure chamber. Error bars indicate standard deviations from at least seven independent measurements.
[0083] FIG. 19 is a series of images demonstrating low-tilt-angle sliding of
Pseudomonas aeruginosa (PA 14) bio film growth in 2 mL tryptone broth puddles incubated for 24 hours atop liquid slippery surfaces in accordance with certain embodiments.
[0084] FIG. 20 is a series of fluorescence microscopy images of Pseudomonas aeruginosa (PA 14) bacteria remaining on various slippery liquid surfaces after 2 mL of shaken culture was incubated for 24 hours on the surfaces and subsequently slid off by applying a tilt angle in accordance with certain embodiments.
[0085] FIG. 21 show a toxicity screening of a number of commercially available products that can satisfy the requirements for the lubricating fluid in accordance with certain embodiments.
[0086] FIG. 22 is a schematic illustrating the whole wall of a catheter with SLIPS
(22A) and a catheter lined with a dense, nonporous material and SLIPS (22B).
[0087] FIG. 23 is a schematic of a wound dressing with SLIPS.
[0088] FIGS 24A to 24E show the different morphologies that can arise by changing the electrodeposition parameters in accordance with certain embodiments.
[0089] FIG. 25 is a graph showing the dependence of liquid repellency of SLIPS on the viscosity of Liquid B (here, Krytox 100, 103, and 105 (DuPont)). For constant viscosity of Liquid A (here, 25 μΐ, of glycerol), Liquid A's mobility increases as the viscosity of Liquid B decreases. Likewise, for constant viscosity of Liquid A, the mobility of Liquid A increases with reducing viscosity. Thus viscous dissipation plays a major role in the liquid mobility on SLIPS.
[0090] FIG. 26 shows images of whole human blood in non- wetting contact with SLIPS surfaces made with non perfluorocarbon lubricant liquids. Image (26A) shows a SLIPS surface generated using an infiltration of polydimethylsiloxane (PDMS) liquid (500 MW, X viscosity, OH-terminated, Sigma Aldrich) into an ePTFE membrane (1 μιη, Sterlitech). Image (26B) shows a SLIPS surface generated using an infiltration of olive oil into an ePTFE membrane (1 μιη, Sterlitech). In both cases the blood was found to not wet the surface, and rolled off without adhering to the surfaces.
[0091] FIG. 27A shows a schematic of a slippery surface having an over-coated Liquid
B formed over a roughened surface in accordance with certain embodiments.
[0092] FIG. 27B shows a schematic of a slippery surface with Liquid B infiltrated into the roughened surface in accordance with certain embodiments.
[0093] FIG. 28A-B shows images of the surface of the present disclosure
demonstrating self-healing properties, where the self-healing time scale is on the order of
100 ms in accordance with certain embodiments.
[0094] FIG. 29 is a chart showing restoration of liquid repellency function after critical physical damage (test liquid = decane, YLV = 23.6 ± 0.1 mN/m) in accordance with certain embodiments.
[0095] FIG. 30 shows images of non-anticoagulated whole human blood (diluted 1 : 1 with saline) flowing at 3,000 mL/hr using peristaltic pumping through SLIPS tubing for 20 min without producing clotting including the experimental setup (A) and results which showed no signs of clotting in the tubing (B).
[0096] FIG. 31A-C shows images of the tubing of FIG. 33 after 20 minutes of 12 mL of fresh human blood free of anticoagulant was pumped through SLIPS tubing. The blood did not clot in the tubing.
[0097] FIG. 32 is a graph showing the dependence of liquid repellency of SLIPS on the viscosity of Liquid B (here, Krytox 100, 103, and 105 (DuPont)). For constant viscosity of Liquid A (here, 25 of glycerol), Liquid A's mobility increases as the viscosity of Liquid A decreases. Likewise, for constant viscosity of Liquid B, the mobility of Liquid A increases with reducing viscosity. Thus viscous dissipation plays a major role in the liquid mobility on SLIPS. [0098] FIG. 33 shows images of ePTFE tubing (Zeus Inc) of increasing inner diameter (ID), from 0.075" to 0.236" (wall thickness is -0.040" for all) fit with an elastic, external, silicone tube casing (VWR) in low (A) and high magnification SEM of the porous ePTFE surface within the tubing (B).
[0099] FIG. 34 shows images of a transparent SLIPS surface, based on the infiltration of a highly-ordered nanoporous Si02 glass layer (A) with perfluorocarbon (FC-70) (B). When fully infiltrated the layer is highly transparent (C) and well suited for applications as a bio-sensor window.
[0100] FIG. 35 shows images of a process for fabricating a SLIPS tubing from ePTFE membranes.
[0101] FIG. 36 shows images (A-B) of surface typologies investigated with respect to bio film attachment properties. The remains of an evaporated drop of Pseudomonas aeruginosa biofilm-forming culture is shown on each surface, a superhydrophobic nanoporous PTFE surface (A) and a slippery liquid infused porous surface (SLIPS) (B). Biofilm grown on the PTFE and nanostructured superhydrophobic silicon substrates showed complete wetting of the surface and a slimy coffee ring. In contrast, biofilm on the SLIPS substrate cleanly retracted from the surface as it evaporated. The insets (i) and (ii) show fluorescence micrographs of remaining bacteria on these surfaces following 48 hour incubation of P. aeruginosa biofilm. The relative bacterial biofilm attachment was significantly less on PTFE-based SLIPS compared to the PEGylation surface (C).
[0102] FIG. 37 shows images of a macroscale view of biofilm attachment inhibition on SLIPS. Growth was conducted in a peristaltic pump at 10 mL/min (velocity ~1 cm/s) and dual-chamber 3D-printed flow cells with h = 1 mm, 1 = 10 cm, w = 1 cm channels. (A-B) Photographs of the control PTFE and SLIPS PTFE substrates after the flow cell was opened following 48 hour growth under 10 mL/min flow, both before crystal violet staining (top) and after (bottom). Equal-area samples of the substrates were eluted for crystal violet quantification, a measurement of attached biomass (C). Following 7 days of growth, crystal violet staining-based quantification showed a 99.6% reduction in attached biofilm on SLIPS versus control PTFE.
[0103] FIG. 38 shows images of a microscale view of P. aeruginosa biofilm attachment on SLIPS and control PTFE surfaces after 24 and 7-day growths in 10 mL/min flow. (A-B). Growth on the PTFE surface appeared dense, three-dimensional, and uniform (A-B), whereas on the SLIPS, only sparse, isolated single cells or microcolonies were observed (C-D). Referring to the graph, (E), these cells appeared to be unattached or poorly attached, i.e., drifting with convective currents in the fluid, further supporting that a liquid surface provides very low adhesion to the individual bacteria or micro-colonies.
[0104] FIG. 39 shows images and graphs that demonstrate that biofilm attachment reduction by SLIPS is species independent. The attachment of Staphylococcus aureus (A) and Escherichia coli (B), was reduced by 97.2% and 96%, respectively, versus PTFE following 48 hour growth under identical flow conditions to P. aeruginosa. While neither of these species formed as robust biofilms as does, their final attachment to SLIPS was comparably minimal(C-F). Visualized by fluorescence, dense uniform biofilm coverage and sparse, isolated cells respectively attached to the control and SLIPS substrates.
[0105] FIG. 40 is a set of images from a split- frame movie showing evaporation dynamics of P. aeruginosa culture droplets on a superhydrophobic PTFE porous surface (i- ii) and a PTFE SLIPS surface infused with Krytox 103 (iii-iv). The pinning characteristics as well as the stains remaining on the surfaces upon drying indicated the level of adhesion between the bacterial droplet and the substrate. In the absence of contact line pinning, the droplet follows a nearly constant contact angle mode of evaporation without the formation of a coffee ring stain (iv). The absence of the coffee ring formation also indicated that the adhesion of the bacteria on the SLIPS was small compared to the forces imparted by the meniscus of the droplet.
[0106] FIG. 41 shows images of a micro view of P. aeruginosa biofilm attachment on SLIPS and control PTFE surfaces after 24 and 48 hr growths in 10 mL/min flow, (a)
Fluorescence average intensities (b) average intensity graph showing a 97-98%) average intensity reduction, analogous to the crystal violet global measurement.
DETAILED DESCRIPTION OF THE INVENTION
[0107] Disclosed herein are synthetic slippery liquid-infused porous surfaces ("SLIPS") for repelling, preventing attachment, or reducing attachment of fluids ("Liquid A") or solids ("Object A") of biological origin. As referred to herein, Liquid A, Object A, and biological material are used interchangeably. Adhesion and absorption of material of biological origin are also reduced or prevented by SLIPS. [0108] SLIPS are synthetic surfaces that consist of nano/microstructured substrates infused with a lubricating fluid that is locked in place by a substrate to form a stable, defect-free, inert "slippery" interface capable of repelling complex fluids, gases, and molecules or particulates contained within liquids of varying surface tensions (together referred to as Liquid A), as well as solids. For example, liquids such as hydrocarbons, organic solvents, and the like can be repelled. The biological liquids refer to both pure liquids and complex fluids, such as blood flow (see, e.g., FIG. 11 and FIG. 12). As another example, solids like bacteria, proteins, and the like can be repelled by SLIPS. In addition, natural and synthetic solutions such as those used in medicines, intravenous solutions, pharmaceutical manufacturing, and medication delivery systems can be repelled by SLIPS.
[0109] The SLIPS consists of a porous surface layer, or a 'rough' layer of raised surface features in an array, which is infiltrated with a low surface energy liquid. The combination of lubricating fluid over a rough surface creates an ultra-smooth surface that is slippery and resists or reduces adhesion by particles and immiscible liquids. In some embodiments, the lubricating fluid is stabilized in place by the underlying substrate. In one or more aspects, the lubricating fluid is reduced to the level of the features of the substrate. These unique features of SLIPS allow the passage of biological material at high flow rates without permitting the material to form clots on, adhere to, attach, or otherwise foul SLIPS. SLIPS are also capable of restoring their exceptional liquid repellency when physically damaged. The fast self-healing times are a result of the lubricating fluid wicking fluid into damaged sites on the underlying substrate to restore SLIPS to a smooth defect-free surface. These surfaces can be used in laboratories, as a coating on medical devices and medical equipment, and for medical applications such as anticoagulation and anti-biofilm formation.
[0110] Generally, SLIPS can be manufactured by providing a liquid (e.g., chemically- inert, high-density fluid) over a roughened surface featuring micro- or nanoscale
topographies, where the fluid fills the voids and spaces defined by the roughened surface and covers the topographical features. The fluid repellency and the self-healing property of SLIPS can be attributed to the ultra-smoothness of the surface of the fluid, which is capable of recovering its original shape upon external deformation. As used herein, "ultra-smooth" surface means a surface having a roughness factor that is equal or close to 1 , where the roughness factor (R) is defined by the ratio of the real surface area to the projected surface area. Because fluid surfaces generally have a roughness factor of 1 , and the top surface in SLIPS is a lubricating fluid that fully coats the substrate above its hills, surfaces such as that shown in FIG. 1 can be called ultra-smooth. In certain embodiments, ultra-smooth surface can have an average surface roughness is on the order of or less than about 1 nm. In certain embodiments, "ultra-smooth" may refer to a substantially molecularly or even atomically flat surface. The absence of any defects or roughness on such a surface may aid in minimizing the pinning points for a sliding fluid, thus reducing the contact angle hysteresis, rendering it nearly friction- free and slippery. A detailed discussion of the ultra- smooth surfaces is found in co-pending U.S. Patent Application No. 61/434,217, filed on January 19, 2011, U.S. Patent Application No. 61/466,352, filed on March 22, 2011, and co-filed PCT Application No. entitled "Slippery Surfaces With High Pressure
Stability, Optical Transparency, and Self-Healing Characteristics" filed January 19, 2012, which are incorporated by reference in their entirety.
[0111] A schematic of the overall design of SLIPS is illustrated in FIG. 1. As shown, the article includes a surface 100 having raised features 110 that provide a certain roughness with lubricating fluid applied thereon. Lubricating fluid 130 wets the roughened surface, filling the hills and valleys of the roughened surface 110, and forming an ultra- smooth surface 135 over the roughened surface. The top (i) and bottom (ii) scanning electron microscope (SEM) images in the inset of FIG. 1 ultra-smoothness of the SLIPS surface and the porous structure of the underlying rough solid surface, respectively. The surface smoothing effect of the SLIPS device is further illustrated in FIG. 6A and FIG. 6B). FIG. 6 (A) shows a scanning electron microscope image of the surface morphologies of a 3D porous solid. FIG. 6(B) shows a photograph at the same magnification of a slippery surface formed by infiltrating the 3D porous solid shown in FIG. 6(A) with lubricating fluid. The lubricating fluid overcoats the surface topographies of the porous solid to form an ultra-smooth layer without asperity (e.g., average roughness on the order of or less than about 1 nm based on high resolution atomic force microscopy measurements). In certain embodiments, the average surface roughness of SLIPS is on the order of or less than about 1 nm based on high resolution atomic force microscopy measurements. The presence of the micro/nanostructures can significantly enhance the wetting of lubricating fluid, thereby creating a uniformly-coated slippery functional layer over the topographies. [0112] Any arbitrary liquid (e.g., a biological fluid), gas, molecule, or particulate contained within liquids may be strongly repelled from the ultra-smooth lubricating fluid surface. Moreover, the ultra-low adhesion characteristics of SLIPS, which also prevents adsorption, adhesion, and attachment of objects on SLIPS, prevents contamination of these surfaces by material of biological origin. The adhesion, adsorption, or attachment of biological materials can be completely prevented by SLIPS. In some embodiments, SLIPS reduces the adhesion, adsorption, or attachment of biological materials on surfaces. In one aspect, SLIPS significantly reduces adhesion, adsorption, or attachment of biological materials on surfaces. In one or more aspects, SLIPS reduces adhesion, adsorption, or attachment of materials of biological origin on surfaces by 50%, 60%, 70%>, 80%>, 90%>, 95%, 98%, or 99%.
[0113] A wide range of materials can be repelled by the slippery surfaces of the present disclosure. More specifically, polar and non-polar liquids, as well as polar and non-polar liquids in their solidified forms can be repelled by SLIPS. For example, hydrocarbons and their mixtures (e.g., from pentane up to hexadecane and mineral oil, ketones (e.g., acetone, etc.), alcohols (e.g., methanol, ethanol, isopropanol, dipropylene glycol, ethylene glycol, and glycerol, etc.), water (with a broad range of salinity, e.g., sodium chloride from 0 to 6.1 M; potassium chloride from 0 to 4.6 M, etc.), physiological buffers, acids (e.g.,
concentrated hydrofluoric acid, hydrochloric acid, nitric acid, etc), bases (e.g., potassium hydroxide, sodium hydroxide, etc), ice, and the like can be repelled by SLIPS. Moreover, biological objects, such as small animals, protozoa, bacteria, viruses, and the like can be repelled by surfaces made in accordance with the present disclosure. Similarly, solid particles suspended in liquid can be repelled by SLIPS. Non- limiting examples of such solid particles in liquid include bodily fluids, fecal matter, and the like.
[0114] The list is intended to be exemplary and the slippery surfaces of the present disclosure are envisioned to successfully repel numerous other types of biological materials.
Substrates
[0115] In one embodiment, the substrate is a low- surface energy porous solid. In the disclosed embodiments, the substrate is preferentially wetted by the lubricating fluid rather than by the fluid to be repelled. It can have a roughened or smooth surface. As used herein, the term "roughened surface" is a substrate that includes both the surface of a three- dimensionally porous material as well as solid surface having certain topographies, whether they have regular, quasi-regular, or random patterns. In some embodiments, the substrate is roughened by incorporation of microtextures. In other embodiments, the substrate is roughened by incorporation of nanotextures. Physically, the large surface area provided by micro/nanoscale roughness not only facilitates complete wetting by the lubricating fluid but also strengthens the adhesion of lubricating fluid (Liquid B) within the porous solid.
[0116] SLIPS have properties that are insensitive to the precise geometry of the underlying substrate. Therefore, the geometry of the substrate can be any shape, form, or configuration to suit various-shaped materials and devices. In certain embodiments, the porous surface can be manufactured over any suitable materials and geometries, such as medical devices, inside of pipes (e.g., metallic or metallized pipes), optical windows, biological sensor windows, medical tubing, hollow metallic structures, patterned electrodes, meshes, wires, porous conductive surfaces, and the like that come into contact with biological materials. Some exemplary shapes over which the porous surface can be formed are shown in FIGS. 7A-E. Non- limiting examples of shapes, forms, and configurations SLIPS can take include generally spherical (e.g., bead, magnetic particles, and the like), tubular (e.g., for a cannula, connector, catheter, needle, capillary tube, tubing, or syringe) (see FIG. 7A j)), planar (e.g., for application to a microscope slide, plate, film, or laboratory work surface) (see FIG. 7A(c)), or arbitrarily shaped (e.g., well, well plate, Petri dish, tile, jar, flask, beaker, vial, test tube, column, container, cuvette, bottle, drum, vat, or tank) (see FIG. 7A(a)-(b), (d)-(i)). For example, SLIPS can be applied to spherical surfaces, such as magnetic particles that can be actuated inside the body for drug delivery. FIG. 7B-E are perspective illustrations that show how SLIPS can be incorporated into a catheter tube. For example, FIG. 7B shows a SLIPS 700 attached to the outer surface of a cylindrical solid core 710 with a reservoir 720 for Liquid B. Alternatively, SLIPS can also be attached to the inner surfaces of the tubes, pipes, and other irregularly shaped substrates. For example, as shown in FIG. 7C, SLIPS 700 can be can be applied to the inner surface of a cylindrical tube 710 for low drag flow of Liquid A 730. In addition, as shown in FIG. 7D, SLIPS can be applied onto both the inner and outer surfaces of a tube/needle for low drag flow of Liquid A and remain slippery/non-sticking to the outside environments where the tube/needle is exposed to. Also, as shown in FIG. 7E, SLIPS can be applied onto a Liquid-B-soaked porous tubing for low drag flow of Liquid A and remain slippery/non- sticking to the outside environments where the porous tube/needle is exposed to.
[0117] FIG. 5A to FIG. 5D show some exemplary roughened surfaces. In one embodiment, the roughened surface is formed over a two-dimensionally flat surface 500 by providing certain raised structures 510 or protrusions (see FIG. 5A). In another embodiment, the roughened surface is formed by forming pores 520 over a two- dimensionally flat surface 500 to yield a porous material (see FIG. 5B). Pores can take any geometry and can have pathways, columns (as illustrated in FIG. 5B or more random pathways. In yet another embodiment, a three-dimensionally interconnected network of regular or random pores is used (see FIG. 5C and FIG. 5D). FIG. 10 shows images of substrate structures and topologies that can be used to generate SLIPS surfaces; (A) open- cell bricks, (B) post arrays, (C) parallel grooves, (D) open porosity PTFE (ePTFE), (E) plasma-etched PTFE, and (F) sand-blasted polypropylene (PP).
[0118] A range of surface structures with different feature sizes and porosities can be used. Feature sizes can be in the range of hundreds of nanometers to microns (e.g., 100 to 1000 nm), and have aspect ratios from about 1 : 1 to 10: 1. Porous nano-fibrous structures can be generated in situ on the inner surfaces of metallic microfluidic devices using electrochemical deposition using techniques known in the art (Aizenberg, J., Kim, P.
Hierarchical Structured Surfaces Resistant to Wetting by Liquids. United States
Provisional Patent, Application No.: 61/353,505, filed on 7/19/2010; Kim, P., Epstein, A.K., Khan, M., Zarzar, L.D., Lipomi, D.J., Whitesides, G.M., Aizenberg, J. Structural Transformation by Electrodeposition on Patterned Substrates (STEPS): A New Versatile Nanofabrication Method", Nano Letters, in press (2011)).
[0119] In certain embodiments, the surface has a large surface area that is readily wetted by the lubricating fluid and which entrains lubricating fluid and retains it on the substrate surface. In certain embodiments, the substrate surface is a hierarchical surface containing surface features on multiple dimension scales. By way of example, the surface can have a first topological feature having dimensions on the microscale and a second topological feature on the nanoscale. The first topological feature supports the second smaller topological feature. The second topological features are referred to as "primary structures" as they are meant to denote the smallest feature sizes of the hierarchical structure. The primary structures can include structures, such as nanofibers, nanodots, and the like. Such nanoscale "primary structures" can have at least one kind of feature sizes that are a few to tens or hundreds of nanometers in size, such as less than 5 nm to 200 nm. For example, nanofibers having diameters of approximate 5, 10, 25, 50, or even 100 nm. In such cases, when "primary structures" having feature sizes of about 100 nm diameter is utilized, "secondary structures" having feature sizes that are larger than 100 nm, such as 150 nm, 300 nm, 500 nm, or 1000 nm, and larger. Additional higher order structures, such as "tertiary structures" and the like, which each has larger feature sizes than the lower order structures are contemplated.
[0120] Particularly, hierarchical structures having nanofibers as the primary structures may provide a high degree of three-dimensional porosity that may be well-suited for use as porous surfaces described herein. A detailed discussion of hierarchical surfaces suitable for use with a liquid to be repelled is found in International Application No. PCT/US11/44553 entitled "Hierarchically structures surfaces to control wetting by liquids," filed on July 19, 2011, which is incorporated in their entirety by reference.
[0121] In certain embodiments, the roughened surface may have a periodic array of surface protrusions (e.g., posts, peaks, etc.) or any random patterns or roughness (see, e.g., FIG. 5A). In some embodiments, the size of the features producing a roughened surface range from 10 nm to 100 μιη with geometries ranging from regular posts/open-grid structures to randomly oriented spiky structures. In some embodiments, the widths of the raised structures are constant along their heights. In some embodiments, the widths of the raised structures increase as they approach the basal surface from the distal ends. The raised structures can be raised posts of a variety of cross-sections, including, but not limited to, circles, ellipses, or polygons (such as triangles, squares, pentagons, hexagons, octagons, and the like), forming cylindrical, pyramidal, conical or prismatic columns. Although the exemplary substrates described above illustrate raised posts having uniform shape and size, the shape, orientation and/or size of raised posts on a given substrate can vary.
[0122] Open porosity PTFE (ePTFE) membranes can be pressed or molded to take on a variety of shapes, as is illustrated in FIGS. 35A-C and FIG. 33). FIG. 35 shows images of a process for fabricating a SLIPS tubing from ePTFE membranes in which (A) A tubular structure (center) is formed from two flat ePTFE membranes (1.0 μιη pore size) by being pressed between two U-shaped channel molds (left and right). (B) One ePTFE membrane is pressed between the negative and positive molds, producing an indented channel structure for fluidic flow. This structure was then covered and bound to a flat ePTFE membrane to construct the SLIPS U-shape tube shown in (A). Low (left) and high (right) magnification views of scanning electron microscope (SEM) images (C) of a cross-section of the pressed ePTFE membrane; porous fibrous structure is visible at the right. FIG. 33 shows images of ePTFE tubing (Zeus Inc) of increasing inner diameter (ID), from 0.075" to 0.236" (wall thickness is -0.040" for all) (A). The commercially available tubing is made by expanding PTFE tubing during the manufacturing process to create microscopic pores in the structure of the material. The 0.180" ePTFE tubing (which provides a porous microtexture to the substrate) can be fit with an elastic, external, silicone tube casing (VWR), for example, to provide a fluid flow barrier and/or to facilitate peristaltic pumping. High magnification SEM of the porous ePTFE surface within the tubing is also shown (B).
[0123] In certain embodiments, the roughened surface has a roughness factor, R, greater than 1 , where the roughness factor is defined as the ratio between the real surface area and the projected surface area. For complete wetting of lubricating fluid to occur, it is desirable to have the roughness factor of the roughened surface to be greater or equal to that defined by the Wenzel relationship (i.e., R≥ l/cos( , where Θ is the contact angle of lubricating fluid on a flat solid surface). For example, if lubricating fluid has a contact angle of 50° on a flat surface of a specific material, it is desirable for the corresponding roughened surface to have a roughness factor greater than ~1.5.
[0124] The roughened surface material can be selected to be chemically inert to the lubricating fluid and to have good wetting properties with respect to lubricating fluid. In addition, the roughened surface topographies can be varied over a range of geometries and size scale to provide the desired interaction, e.g., wettability, with lubricating fluid.
[0125] In certain embodiments, the micro/nanoscale topographies beneath the lubricating fluid enhance the liquid- wicking property and the adherence of lubricating fluid to the roughened surface. As a result, the lubricating fluid can uniformly coat the roughened surface and get entrapped inside at any tilting angles.
[0126] Non-limiting examples of porous materials include solid substrates having holes (e.g., high aspect ratio holes, cylinders, columns, etc.), three-dimensionally interconnected network of holes and one or more materials (e.g., 3-D ordered colloidal assemblies, block copolymers, etc.), and random array of fibrous materials (e.g., filter paper, fabrics, electrospun films). [0127] Non-limiting examples of porous or rough surface structures that can be used include polymers (e.g., polysulfone, PDMS, and polypyrrole) and hydrophobic porous (e.g., Tefion) materials. For example, the roughened surface can be manufactured from polymers (e.g., epoxy, polycarbonate, polyester, nylon, etc.), metals, sapphire, glass, carbon in different forms (such as diamond, graphite, black carbon, etc.), ceramics (e.g., alumina), and the like. For example, fluoropolymers such as polytetrafluoroethylene (PTFE), polyvinylfluoride, polyvinylidene fluoride, fluorinated ethylene propylene, and the like can be used as substrates. Many porous materials are commercially available, or can be made by a number of well-established manufacturing techniques. For example,
polytetrafluoroethylene (also known by the trade name "Teflon" and abbreviation "PTFE") filter materials are commercially available. In some embodiments, the roughened surface is manufactured from a hemocompatible material, non-limiting examples of which include silicon rubber and polysulfones. In certain embodiments, the roughened surface is manufactured from any suitable materials. In certain embodiments, if the desired material and shape is not electrically conducting, the surfaces of such material and shapes can be rendered electrically conductive by applying a thin layer of conductive material, such as through vapor deposition techniques, sputtering, metallization techniques, and the like. Moreover, the porous surface can be readily formed on large surface area materials that are commercially important. When necessary, surface functionalization can be carried out to modify the solid surfaces so that the lubricating layer preferentially wets the roughened surface as compared to Liquid A.
[0128] The raised structures can be produced by any known method for fabricating raised structures onto substrates. Non- limiting examples include molding into the device structure, conventional photolithography, projection lithography, e-beam writing or lithography, depositing nanowire arrays, growing nanostructures on the surface of a substrate, soft lithography, replica molding, solution deposition, solution polymerization, electropolymerization, electrospinning, electroplating, vapor deposition, contact printing, etching, bead blasting, sand blasting, transfer patterning, microimprinting, self-assembly, and the like.
[0129] In certain embodiments, the roughened surface can be made, for example, by replica molding procedure described in B. Pokroy, A. K. Epstein, M. C. M. Persson-Gulda, J. Aizenberg, Adv. Mater. 21, 463 (2009), the contents of which is incorporated by reference herein in its entirety. Patterned surfaces can also be obtained as replicas (e.g., epoxy replicas) by a soft lithographic method (see, e.g., J. Aizenberg and B. Pokroy, PCT/US2009/048880, the contents of which is incorporated by reference herein in its entirety). Polymer films with patterned surfaces can be fabricated by means known in the art (e.g., roll-to-roll imprinting or embossing). By way of non-limiting example, negative replicas of pre-generated patterns can be made from polydimethylsiloxane, PDMS (e.g., Dow-Sylgard 184) by pouring mixture of prepolymer and curing agent (e.g., 10: 1 ratio) on the patterns followed by thermal curing in an oven. After cooling, the negative PDMS mold can be peeled off and used for fabricating the final replica by pouring the desired material (e.g. UV-curable epoxy resin) into the negative mold. After solidifying the material, the negative mold can be peeled off, leaving the replica of the original pattern. Then, the surface of the replica can be chemically functionalized with low surface energy coating such as (tridecafluoro-l,l,2,2-tetrahydrooctyl)-trichlorosilane.
[0130] For example, a silicon substrate having a post array such as is illustrated in FIG. 5A can be fabricated by photolithography using the Bosch reactive ion etching method (as described in Plasma Etching: Fundamentals and Applications, M. Sugawara, et al., Oxford University Press, (1998), ISBN-10: 019856287X, the contents of which is incorporated by reference herein in its entirety).
[0131] Arrays of hydrophobic raised surface structures can be made at the micrometer scale using micromolding techniques. For example, rough surface structures can be arrays of hydrophobic raised surface structures at the micrometer scale, such as posts and intersecting walls patterned in polymers such as epoxy (FIG. lOA-C).
[0132] In certain embodiments, the roughened surface may be the surface of a three- dimensionally porous material (see, e.g., FIG. 5B to FIG. 5D). The porous material can be any suitable porous network having a sufficient thickness to stabilize lubricating fluid, such as a thickness from about 5 μιη to about 1 mm. Moreover, the porous material can have any suitable pore sizes to stabilize the lubricating fluid, such as from about 10 nm to about 100 μιη.
[0133] In another embodiment, porous alumina is manufactured by the process of anodization as shown in FIG. 5B, where an aluminum substrate is electrochemically oxidized under constant electrical potential. The pore size, inter-pore spacing, and aspect ratio of the pores can be tuned by adjusting the operating parameters of the electrochemical oxidation process. Such a process generates porous through-holes into the substrate, where the size of the porous holes are on the order of 50 nm with aspect ratio larger than 10000 (see, Lee et al, Nature Mater. 5, 741-47, 2006, the contents of which is incorporated by reference herein in its entirety.).
[0134] In some embodiments, mechanical or (electro)chemical methods can be used to roughen metal surfaces. Roughening and non- wetting materials can be spray coated directly onto metal surfaces. Boehmite (γ-ΑΙΟ(ΟΗ)) formation on aluminum surface by boiling in water can also be used to roughen metallic surfaces such as aluminum. Rotary jet spinning of hydrophobic polymer nano fibers and layered deposition of an appropriate primer can also be used to roughen substrates for use in SLIPS.
[0135] In yet another embodiment, long range ordered porous structures of silica, as shown in FIG. 5C, can be produced by evaporative co-assembly method of sacrificial polymeric colloidal particles together with a hydrolyzed silicate sol-gel precursor solution. Such a method generates a crack-free porous surface on the order of centimeters or larger, with pore sizes of about 100 nm to about 1000 nm and porosity of about 75%. (See, Hatton, et al, Proc. Natl. Acad. Sci. 107, 10354-10359, 2010 and U.S. Patent Application No. 13/058,611, filed on February 11, 2011, the contents of which is incorporated by reference herein in its entirety.).
[0136] Referring to FIG. 5D, polymer-based porous membrane (such as medical grade PTFE) can be made by mixing PTFE powders with lubricating fluid to form a paste. Then, the paste can be molded into the desired shape by methods such an extrusion molding. The molded PTFE membrane can then be heated up to less than its melting point to drive off the lubricants. Thereafter, a porous PTFE membrane can be formed (see U.S. Patent No.
5,476,589, the content of which is incorporated by reference herein in its entirety).
[0137] In yet another embodiment, the porous material can be generated in-situ on a metal surface by an electrodeposition method, such as the STEP method (STEP = structural transformation by electrodeposition on patterned substrates, see, PCT Application No. PCT/US11/44553, filed on July 19, 2011, and Kim, et al, Nano Lett., in press, (2011), the contents of which are incorporated by reference herein in their entirety. The
electrodeposition condition can be controlled so that nanofibers of electrically conductive polymer can be formed over an electrically conductive surface. The electrodeposition conditions can further be controlled to provide a desired nanofiber diameter and spacing. In certain embodiments, the electrodeposition condition can be controlled to provide any other desirable morphology that can provide additional means to stabilize the lubricating layer.
[0138] The morphology of the conducting organic polymers can be controlled by varying the deposition conditions such as the concentration of monomer, the types of electrolytes and buffers, the deposition temperature and time, and the electrochemical conditions such as applied potential. For example, increasing the concentration of monomer in the electrochemical solution, the applied potential, and/or the temperature generally leads to a faster polymerization rate and many parasitic nucleation sites during growth resulting in a morphology that is similar to a cauliflower (see FIG. 24A). In contrast, lower concentrations of monomer, lower applied potential, and lower temperatures can lead to nanofibrile growth with substantially uniform diameters (see FIG. 24B).
Further decrease in concentration of monomer or applied potential can lead to short rods of polymer nano fibers with low surface coverage (see FIG. 24C). In another example, increasing the type of electrolytes and buffers to obtain a more acidic solution can lead to the formation of a cauliflower shape (see FIG. 24A) or overgrowth of polymers (see
FIG. 24D). In another example, the applied voltage can be cycled leading to different oxidation states of the deposited polymer layer which is often manifested as a color change (e.g., from dark blue to a green then to a pale yellow color with increasing applied voltage). In yet another example, the applied voltage can be pulsed at a constant voltage to form polymers only on the tip of the underlying micropost structures, leading to a mushroom-like morphology (see FIG. 24E). Accordingly, the morphology of conducting organic polymers can be finely controlled from nanometers to over micrometer scales, and surface coatings with precisely controlled morphology can be produced by simple modifications, which promise the customization of various surface properties by design and control of the morphology.
[0139] In other embodiments, a roughened surface is further functionalized to improve wetting by lubricating fluid. Surface coating can be achieved by methods well known in the art, including plasma assisted chemical vapor deposition, chemical functionalization, solution deposition, and vapor deposition. For example, surfaces containing hydroxyl groups (i.e., -OH) can be functionalized with various commercially available fluorosilanes (e.g. , tridecafluoro- 1 , 1 ,2,2-tetrahydrooctyl-trichlorosilane, heptadecafluoro- 1 , 1 ,2,2-tetra- hydrodecyl trichlorosilane, etc.) to improve wetting by low surface tension fluids. In certain embodiments, many materials having native oxides, such as silicon, glass, and alumina, can be activated to contain -OH functional groups using techniques such as plasma treatment. After activation, either vapor or solution deposition techniques can be used to attach silanes so that surfaces with low surface energy can be produced. For vapor deposition, the deposition can be carried out by exposing the surface to silane vapors. For solution deposition, the deposition can be carried out by immersing the surface in a silane solution, followed by rinsing and blow-drying after deposition. For layered deposition, layered deposition of a primer is followed by application of a mixture of sacrificial beads and Liquid B, which is dried and cured. The beads are removed to produce a contiguous porous Teflon- like surface.
[0140] In some other embodiments, where hydroxyl groups is absent on the surface, the surface can be functionalized by first coating it with thin films of metals, such as gold or platinum, and the thin metal films can be functionalized with various commercially available thiols of low surface energy (e.g., heptane thiol, perfluorodecanethiol, etc.).
Similarly, vapor or solution deposition techniques can be carried out similar to that describe for silane deposition using, for example, alkane thiol solutions.
[0141] In another embodiment, the roughened, porous substrate can be generated by a spraying method, where emulsions consisting of micro/nanoparticles are sprayed onto a flat solid surface (FIG. 14A1). These particles assemble into roughened solid layer upon solvent drying. Such a solid layer can then be infiltrated by lubricating fluid (FIG. 14A2) (which can also be applied by additional spraying). FIG. 14A shows a surface roughened by a spray method. Here, the substrate 140 is roughened by spraying or depositing a particulate matter 142 on the substrate 140 to create a porous coating (Al) and the roughened surface is infiltrated with lubricating liquid 144. Non-limiting examples of micro/ nanoparticles that can be sprayed onto a flat solid surface to form roughened, porous material include titanium dioxide, silicon dioxide, nanodiamonds, metals such as silver, gold, platinum, copper, gold, palladium, zinc, and titanium, hydroxyapatite (HAp) nanoparticles.
[0142] In one or more embodiments, the roughened, porous substrate is generated by chemical or physical etching, which includes mechanical roughening such as bead blasting and sand blasting. Referring to FIG. 14B, the substrate 140 is roughened by etching (Bl). The etchant 148 is carried by a preformed pipe 146 and deposited onto the substrate 140 to create a roughened surface. Once the surface is roughened, it is functionalized (B2) with a liquid (not shown) or vapor silane 150, and infiltrated with a lubricating liquid 144 (B3).
[0143] In other embodiments, the roughened, porous substrate is made by growing a nanostructured material on the surface. In FIG. 14C, a nanostructured material 152 is grown on the surface of the substrate 140 to create a roughened surface (CI) that is functionalized (C2)) with a liquid (not shown) or vapor silane 150 and infused with a lubricating liquid 144 (C3). Non-limiting examples of these nanostructures include PPy nanofibers, carbon nanotubes, and the like. One the nanostructures are in place, the surface can be chemically functionalized by silanization (FIG. 14C2) and infiltrated with a lubricating liquid (FIG. 14C3).
[0144] In certain embodiments, the roughened surface can be formed over or applied to a variety of planar or non-planar surface (see FIG. 7 and FIG. 8A-B). For example, FIG. 8B shows a porous membrane attached to the outer surface of a cylindrical solid core. It can also be attached to the inner surfaces, outer surfaces, or inner and outer surfaces of tubes and other irregularly shaped substrates.
[0145] In certain embodiments, the solid surface may be substantially flat. This situation may be applicable when the critical surface energy of the flat surface is higher than the surface tension of the functional lubricating fluid.
[0146] In certain embodiments, the roughened surface can have pores that are comparable or smaller than the material to be repelled. For example, pore sizes that are smaller than the size of protozoa (e.g., 10 μιη), bacteria (e.g., 1 μιη), viruses (e.g., 0.1 μιη), and the like can be utilized.
[0147] In one or more of the above embodiments, non-limiting examples of surface to which SLIPS is applied include a cannula, connector, catheter (e.g., central line, peripherally inserted central catheter (PICC) line, urinary, vascular, peritoneal dialysis, and central venous catheters), catheter connector (e.g., Leur-Lok and needleless connectors), clamp, skin hook, cuff, retractor, shunt, needle, capillary tube, endotracheal tube, ventilator, associated ventilator tubing, drug delivery vehicle, syringe, microscope slide, plate, film, laboratory work surface, well, well plate, Petri dish, tile, jar, flask, beaker, vial, test tube, tubing connector, column, container, cuvette, bottle, drum, vat, tank, organ, organ implant, or organ component (e.g., intrauterine device, defibrillator, corneal, breast, knee replacement, and hip replacement implants), artificial organ or a component thereof (e.g., heart valve, ventricular assist devices, total artificial hearts, cochlear implant, visual prosthetic, and components thereof), dental tool, dental implant (e.g., root form, plate form, and subperiosteal implants), biosensor (e.g., glucose and insulin monitor, blood oxygen sensor, hemoglobin sensor, biological microelectromechanical devices (bioMEMs), sepsis diagnostic sensor, and other protein and enzyme sensors), bioelectrode, endoscope
(hysteroscope, cystoscope, amnioscope, laparoscope, gastroscope, mediastinoscope, bronchoscope, esophagoseope, rhinoscope, arthroscope, proctoscope, eoloiioscope, nephroscope, atigioscope, thoracoscope, esophagoseope, laryngoscope, and
encephaloscope) wound dressing (e.g., bandages, sutures, staples), and combinations thereof.
Lubricating Fluids (Liquid B)
[0148] Lubricating fluids are selected to create a fluid surface that is intrinsically smooth, stable, and defect free. The lubricating fluid should infiltrate, wet, and stably adhere to the substrate. Moreover, it should be chemically inert with respect to the solid substrate and the fluid to be repelled. In certain embodiments, a lubricating fluid possesses the ability to form a substantially molecularly flat surface when provided over a roughened surface. In certain other embodiments, a lubricating fluid possesses the ability to form a substantially atomically flat surface when provided over a roughened surface. In one or more embodiments, the lubricant is substantially incompressible.
[0149] Further, the lubricating fluid is capable of repelling immiscible fluids, and in particular biological fluids of any surface tension. For example, the enthalpy of mixing between the fluid to be repelled and lubricating fluids be may be sufficiently high (e.g., water and oil) that they phase separate from each other when mixed together. In certain embodiments, the lubricating fluid can be selected such that the fluid to be repelled has a small or substantially no contact angle hysteresis. For example, contact angle hysteresis less than about 5°, 2.5°, 2°, or even less than 1° can be obtained. Low contact angle hysteresis encourages sliding at low tilt angles (e.g., < 5°), further enhancing fluid repellant properties of the surface.
[0150] The effectiveness of a given lubricating fluid's ability to repel fluids can be confirmed by visualization techniques known in the art including fluorescence microscopy and scanning electron microscopy (SEM). [0151] In one or more embodiments, lubricating fluid is inert with respect to the solid surface and biological fluid. Lubricating fluid flows readily into the recesses of the roughened surface and generally possesses the ability to form an ultra-smooth surface when provided over the roughened surface. FIG. 4A shows a droplet 400 of perfluoro- tripentylamine (herein referred to by the trade name "FC-70") lubricating fluid on an unstructured surface 410 of a flat surface prepared from a slanted epoxy resin. The dashed line represents the location of the upper surface of the substrate. The droplet spreads out on the flat surface, but retains a droplet form. FIG. 4B shows the same lubricating fluid on an exemplary roughened surface of the same composition 420 having nanostructures, the features of which are shown in the inset. As shown, the nanostructures greatly enhance the wetting of the lubricating fluid on the surface, creating a uniformly-coated slippery functional layer over the topographies. The resulting ultra-smooth surface is capable of repelling fluids including, but not limited to biological fluids and particles in solution or suspension.
[0152] Lubricating fluid can be selected from a number of different fluids. These fluids can be selected based on their biocompatibility, low (or high) toxicity, anti-clotting performance, chemical stability under physiological conditions, and levels of leaching from the surfaces of the devices. For example, compounds that are approved for use in biomedical applications (e.g., blood substitutes, MRI contrast agents), such as
perfluorinated hydrocarbons and organosilicone compounds (e.g. silicone elastomer) can be used as lubricating fluids. In one or more aspects, the lubricating fluid is a chemically- inert, high-density biocompatible fluid, non-limiting examples of which include tertiary perfluoroalkylamines (such as perfluorotri-n-pentylamine, FC-70, perfluorotri-n- butylamine FC-40, etc ), perfluoroalkylsulfides and perfluoroalkylsulfoxides,
perfluoroalkylethers, perfluorocycloethers (like FC-77) and perfluoropolyethers (such as K YTOX family of lubricants by DuPont), perfluoroalkylphosphines and
perfluoroalkylphosphineoxides, and combinations thereof are used. . In addition, long- chain perfluorinated carboxylic acids (e.g., perfluorooctadecanoic acid and other homologues), fluorinated phosphonic acids, fluorinated silanes, and combinations thereof can be used as Liquid B. Perfluoroalkyls can be linear or branched.
[0153] In certain embodiments, the lubricating fluid has a high density. For example, the lubricating fluid has a density that is more than 1.0 g/cm3, 1.6 g/cm3, or even 1.9 g/cm3. In certain embodiments, the density of the lubricating fluid is greater than that of the biological fluid to enhance fluid repellency. High density fluids reduce the tendency of an impacting fluid to 'sink' below the surface of lubricating fluid and to become entrained therein. In certain embodiments, the density of Liquid A may be lower than that of the lubricating liquid. For example, density of Liquid A may be at least ~1.5 times lower than that of the lubricating liquid.
[0154] In certain embodiments, the lubricating fluid has a low evaporation rate, such as less than 100 nm/s, less than 10 nm/s, or even less than 1-2 nm/s. The lubricating fluid should be applied in a thickness sufficient to cover the rough surface of the substrate and provide an ultra-smooth surface. Taking a typical thickness of the lubricating fluid to be about 10 μιη and an evaporation rate of about 1-2 nm/s, SLIPS can remain highly fluid- repellant for a long period of time without any refilling mechanisms.
[0155] In certain embodiments, lubricating fluid has a low freezing temperature, such as less than -5°C, -25°C, or even less than -50°C. Having a low freezing temperature allows lubricating fluid to maintain its slippery behavior to repel a variety of liquids or solidified fluids, such as ice and the like and over a range of temperatures.
[0156] Experimentally, it is observed that Object A can become highly mobile on the surface of the lubricating liquid when the kinematic viscosity of the lubricating liquid is less than 1 cm2/s. Since liquid viscosity is a function of temperature (i.e., liquid viscosity reduces with increasing temperature), choosing the appropriate lubricant that operates at the aforementioned viscosity (i.e., < 1 cm2/s) at specific temperature range is desirable.
Particularly, various different commercially available lubricating liquid can be found at the specified viscosity, such as perfluorinated oils (e.g., 3M™ Fluorinert™ and DuPont™
Krytox® oils), at temperatures ranging from less than - 80 °C to greater than 260 °C. For example, the temperature dependence of liquid viscosity of DuPont Krytox oils is shown in the Table 1 as a specific example (note: data is provided by the manufacturer of DuPont Krytox oils).
Table 1. Temperature dependence of liquid viscosity of DuPont Krytox Oils.
Viscosity (cm2/s)
Temperature Krytox Krytox Krytox Krytox Krytox Krytox Krytox Krytox
100 101 102 103 104 105 106 107
20 0.124 0.174 0.38 0.82 1.77 5.22 8.22 15.35 40 0.055 0.078 0.15 0.30 0.60 1.60 2.43 4.50 100 0.02 0.03 0.05 0.084 0.18 0.25 0.42
204 0.031 0.041 0.06
260 0.024 0.033
[0157] The viscosities of both Object A and Liquid B affect the performance of SLIPS. Because the liquid repellency of SLIPS is conferred by the presence of the Liquid B, the viscosity of Liquid B can affect the physical characteristics of liquid repellency of SLIPS, such as the velocity of Object A. The more viscous the Liquid B, the less mobile the given Liquid A will be.
[0158] For a Liquid A of constant viscosity, its velocity on SLIPS reduces with increasing viscosity of Liquid B. For example, referring to FIG. 36, for a 50 of Liquid A of absolute viscosity of 1 cP, its velocities on SLIPS with Liquid B of viscosities of 13 cP, 140 cP, and 990 cP are -17 cm/s, -5.8 cm/s, and -0.98 cm/s, respectively. Therefore, to enhance the velocity of Liquid A on SLIPS, it is desirable to use a Liquid B having a lower viscosity. This general trend is consistent for Liquid A of viscosities ranging from 1 cP to 1000 cP.
[0159] Lubricating fluid can be deposited in any desired thickness, provided the top surface of lubricating fluid forms an ultra-smooth surface and is retained and interacts with the underlying surface. If the liquid layer is too thick, the upper surface is 'unbound' from the underlying surface and will flow with Liquid A from the SLIPS surface. The liquid layer that interacts with and is retained by the underlying surface is referred to as the
'characteristic thickness' of the liquid layer. The characteristic thickness will vary
depending on the underlying surface and the ambient conditions, e.g., temperature, pressure, etc. Film thicknesses substantially on the order of the surface roughness peak-to- valley distance provide good fluid-solid interaction between the substrate and lubricating fluid. When the solid substrate is tilted at a position normal to the horizontal plane, lubricating fluids with thicknesses below a characteristic length scale remain substantially adhered to the roughened surface, whereas fluid layers above the characteristic length can flow, creating flow lines (surface defects) and disrupting the flatness of the fluid surface. For example, non-limiting thicknesses for the lubrication fluid (as measured from the valleys of the roughened surface are on the order of 5-20 μιη when the peak to valley height is -5 um. [0160] In certain embodiments, lubricating fluid can be applied by pupating drops of the fluid onto the roughened surface, or by dipping the roughened surface into a reservoir carrying lubricating fluid. In some embodiments, lubricating fluid can be sprayed, cast, or drawn onto the roughened surface. The lubricating liquid can infiltrate the roughened surface by capillary action, which can wet the roughened surface and form a film on top of it. Lubricating fluid and the roughened surface can be both generated by a double-spraying process, where emulsions consisting of nano/microparticles are first sprayed onto a flat solid surface to form a substantially roughened solid layer, and then lubricating fluid can be sprayed onto this freshly formed layer for further infiltration. In addition, lubricating fluid may infiltrate into the pores of the roughened surface by capillary action and form an ultra- smooth film on top of the roughened surface. In certain embodiments, when sufficient quantity of the lubricating fluid is provided, the lubricating fluid may wet the entire roughened surface structure and form an ultra-smooth film over the underlying roughened surface.
Facile Replenishment of Liquid B
[0161] Another advantageous feature of using porous materials may be the presence of the capillary network within the bulk materials, which can further enhance transport of Liquid B through the pores. The porous structure can provide a replenishing fluid at the surface and may be useful to address evaporation or other materials loss of Liquid B from the SLIPS surface. For example, in the case where a portion of Liquid B is reduced at the surface of the materials due to evaporation, sudden pressure purging, physical damage or the like, Liquid B can be replenished by the capillary action in these networks.
Replenishing Liquid B is drawn through the porous body of the substrate by capillary wicking to refresh the upper surface of SLIPS. In certain embodiments, the porous material itself can be utilized as a fluid reservoir to store Liquid B for subsequent capillary refilling purpose.
[0162] In certain embodiments, as shown in FIG. 9A, to further prolong the life time of the slippery surface of the present disclosure, the porous material 905 can be connected to an external fluid reservoir 903 sitting on a solid substrate 901, where the capillary networks within the porous material 905 can help transfer (e.g., via wicking) the Liquid B from the fluid reservoir 903 to the porous material 905. [0163] FIG. 9B shows an alternate embodiment where SLIPS having a porous material 905 as the roughened surface is formed in an inner surface of a cylindrical tube. As shown, the cylindrical tube 901 has a first annular region 903 serving as a fluid reservoir for Liquid B, followed by an inner annular region of SLIPS having a porous material 905, which surrounds a hollow region 907 for the flow of Liquid A. In operation, Liquid B in annular region 903 transfers into the (e.g., via wicking) the porous material 905 to form a SLIPS and Liquid A can flow through the hollow region with little to no drag at the interface between 905 and 907.
[0164] FIG. 9C shows yet another embodiment where SLIPS is formed in an inner surface of an arbitrarily shaped flow path. As shown, the bottom substrate 901 has a channel 903 serving as a fluid replenishment source for Liquid B that is coupled to the porous material 905 of SLIPS. Porous material 905 is formed by combining a bottom substrate 901 having a depressed region mated with a top substrate 909 having a substantially flat porous material 911 formed thereon. The combination of the top and bottom substrate portions forms a hollow region 907 for the flow of Liquid A.
[0165] FIG. 9D shows some optical micrographs on how the bottom substrate 901 and SLIPS 905 of FIG. 9C can be formed. As shown, a TEFLON filter paper 930 having a three-dimensionally random network of pores can be placed between a male mold 940 and female mold 950 defining an arbitrary flow path and the male mold 940 and female mold 950 can be pressed together to replicate the flow path pattern on the TEFLON filter paper 930. The template TEFLON filter paper 930 can be placed inside the female mold 950, which now serves as bottom substrate 901 of FIG. 9C, and a substantially flat substrate 909 having another substantially flat TEFLON filter paper, serving as SLIPS 911, can be applied thereon (not shown) to form the flow path 907 shown in FIG. 9C. The female mold 950 may further contain channel 903 (not shown) that serves to replenish Liquid B as needed.
[0166] FIG. 35 shows several other non-limiting embodiments of SLIPS and how Liquid B can be replenished to the SLIPS in each of those embodiments. The left column corresponds to systems where SLIPS is exposed to both Medium X and Liquid A (shown as a droplet). The right column corresponds to systems where SLIPS is exposed to
substantially only Liquid A (shown as a plug between two SLIPS). In either system, Liquid B can be replenished to SLIPS as needed. The top row shows scenarios where there is a finite amount of Liquid B. The middle row shows scenarios where there is a large source (e.g., practically infinite source from the viewpoint of the amount of Liquid B needed to replenish the SLIPS) of Liquid B. The bottom row shows scenarios where Liquid B can be replenished by spraying Liquid B as needed, either manually or automatically. As shown, many different configurations and their derivatives are possible.
[0167] It should be noted that while the embodiments described herein refers to a porous material, any other suitable roughened surface described herein can be utilized.
Substrate-Lubricating Fluid Combinations
[0168] SLIPS can sustain fluid impact pressures on the order of 103-107 Pa (e.g., at least from an order of magnitude to five orders of magnitude higher than the current state- of-the-art surface) and are capable of restoring themselves to exceptional liquid repellency upon critical physical damages with a fast self-healing time on the orders of 100 ms to 1 s (i.e., 4 orders of magnitude faster than the current state-of-the-art surface).
[0169] In certain embodiments, the lubricating liquid and the roughened surface can be selected so that they have fast self-healing properties. As used herein, "self-healing" refers to re-formation of an ultra-smooth (and even substantially molecularly flat) surface after physical impact (e.g., damage). The lubricating fluid is a self-healing coating that rapidly restores the fluid-repellant function following damage to the porous material by abrasion or impact. Self healing occurs when the lubricating fluid flows toward the damaged area of the substrate by surface energy-driven capillary action to spontaneously fill the physical void. The recovery time is a function of lubricant viscosity. For example, for Krytox 100, the self-healing time is on the order of 150 ms to 1 s. For Krytox 103, which is more viscous than Krytox 100 the self-healing time is on the order of O(10s) or more. In one or more embodiments, the recovery time for a fluid displacement is less than one second. In other embodiments, the recovery time is a fraction of a second. In still other embodiments, the recovery time is 50 ms, 60 ms, 70 ms, 80 ms, 90 ms, 100 ms, 110 ms, 120 ms, 130 ms, 140 ms, 150 ms, 160 ms, 170 ms, 180 ms, 190 ms, 200 ms, 210 ms, 220 ms, 230 ms, 240 ms, 250 ms, 1 second, 5 seconds 10 seconds, 30 seconds, 60 seconds, 90 seconds, 120 seconds, or more depending on the amount of damage sustained, and the characteristics of the lubricating fluid and substrate used. The self-healing behavior of the liquid repellant surfaces can be a function of the interaction between the lubricating liquid and the roughened surface, as well as the viscosity of the lubricating liquid. Typical kinematic viscosities of the lubricating liquid are in the range of 0.10 cm2/s to 10 cm2/s. Referring to FIGS. 28 and 29, particle impact or scratching can damage the surface by, for example, breaking or removing the topographical features of the surface in a small area. In one embodiment, the measured self-recovery time for a ~50 μιη fluid displacement of FC-70 lubrication fluid on epoxy-resin-based SLIPS was only -150 ms (FIG. 28 A). Typically the impact can also displace the lubricating liquid, resulting in a scratch or pit and exposing the substrate surface. Due to the wicking capability and good wetting properties of the lubricating liquid, however, the liquid layer can flow back to refill the pit or scratch and to regenerate the smooth fluid surface. FIG. 28A shows time-lapse images showing self- healing capability of SLIPS from a ~50 μιη-wide physical damage on a time scale on the order of 100 ms. FIG. 28B is a schematic illustration of the type of damage that may occur and the healing process that restores the smooth liquid surface. A reservoir with extra fluid can be available to 'top off the fluid layer thickness to maintain the desired thickness. Even more surprising, SLIPS can repeatedly restore their fluid-repellent function to surfaces sustaining large areas of physical damage. FIG. 29 is a chart showing restoration of liquid repellency function after critical physical damage (test liquid = decane, YLV = 23.6 ± 0.1 mN/m) in accordance with certain embodiments.
[0170] In certain embodiments, the roughened surface may be functionalized so that the critical surface energy of the roughened surface is higher than the surface energy of lubricating liquid; under these conditions, complete wetting of the lubricating liquid can spontaneously occur throughout the roughened surface.
[0171] In certain embodiments, when the critical surface energy of the roughened surface is lower than the surface energy of the lubricating liquid, the roughened surface may be provided with a high degree of roughness to promote wetting of the lubricating liquid within the pores of the roughened surface.
[0172] In certain embodiments, the lubricating liquid has a surface energy that is less than the surface energy of the roughened surface. In general, when the surface energy of the liquid B is lower than the surface energy of the underlying roughened surface, it tends to wet the solid well. More precisely, the spreading of a liquid depends on the spreading parameter (S), where S=[Esubstate]dry-[Esubstrate]wet = YSO-(YSL+Y), with yso , YSL, and γ as the surface energy of at the solid/air, solid/liquid, and liquid/air interfaces, respectively. The liquid wets a surface completely if S>0 while the drop partially wet a surface if S<0. {See, e.g., P.-G. de Gennes, F. Brochard-Wyart, D. Quere, Capillarity and Wetting Phenomena: drops, bubbles, pearls, waves, Springer (New York, NY), 2004, the contents of which is incorporated by reference herein in its entirety). Thus, in certain embodiments, the surface energy of the liquid B is such that the spreading parameter S is positive.
[0173] In certain embodiments, the critical surface tension of the roughened surface (i.e., yc_s) may be comparable or lower than the surface tension of the lubricating liquid (i.e., 7LV-B)- For example, the critical surface tension of the roughened surface may be at least 1.25 times lower than the surface tension of the lubricating liquid.
[0174] In certain embodiments, the lubricating liquid (and similarly Liquid A) may be non-reactive with the roughened surface. For example, the roughened surface and the lubricating liquid (or liquid to be repelled) can be chosen so that the roughened surface does not dissolve upon contact with the lubricating liquid (or liquid to be repelled). In particular, perfluorinated liquids (the lubricating liquid) work exceptionally well to repel a broad range of polar and non-polar Liquids A and their solidified forms.
[0175] Any suitable combination of the roughened surface and the lubricating liquid described above can be employed. For example, a perfluorinated liquid as the lubricating liquid and a nanostructured surface made out of polymer (for example, epoxy resin, silicone, and Teflon) that are chemically functionalized with end-functional group of -CF3 or other similar fluorocarbon groups can be utilized as the roughened surface. Other materials including sapphire, diamonds, silicon, glass, and metals (e.g., aluminum) can be also used with suitable chemical functionalization schemes.
[0176] It is contemplated that SLIPS may be incorporated in an environment (1) where the lubricating fluid is exposed substantially only to Object A or (2) where the lubricating fluid is exposed to both Object A and another fluid environment, such as medium X (e.g., atmosphere, underwater, etc.).
[0177] When SLIPS is incorporated in the first environment (e.g., inside the interior of medical tubing, outside the exterior of the medical tubing, and the like) (see FIG. 9B), the working combinations of the solid/lubricant/immiscible test liquid may be chosen by satisfying the condition shown in Equation (el).
AEo = 7BXCOS< BX - 7A COS< AX > 0 (el)
where YAX, and yBx represent the surface energies of the Object A-medium X interface, and the lubricating liquid-medium X interface, respectively. Also, ΘΑΧ, and 6½x are the equilibrium contact angles of Object A and the lubricating fluid on a flat solid surface immersed under medium X environment, respectively.
[0178] On the other hand, when SLIPS is incorporated in the second environment (e.g., exposed to atmosphere/underwater/other immiscible fluid environments), satisfying the following two conditions can provide a suitable SLIPS.
AEi = ?0BxCOs6>Bx - 7AXCOS6>AX) - 7AB > 0 (e2)
AE2 =
Figure imgf000041_0001
- 7AXCOS6>AX) + 7AX - 7BX > 0 (e3)
where >ΆΒ represent the surface energies of the Object A-the lubricating fluid interface.
[0179] In addition, when SLIPS is operated in a fully immersed environment (i.e., air/water/other immiscible fluids), the density difference between the Object A and
Medium X can also play a role for the fluid repellency. For example, in order for Object A to slide off from SLIPS by gravity, the density of Object A, px, may desirably be greater than that of the Medium X, px (i.e., ρκ > ρχ). Moreover, the size of Object A may be on the order of, or greater than, its capillary length. Specifically, capillary length is a
characteristic length scale that quantifies the dominance of body force over surface force on
1/2
an object, which can be quantitatively expressed as (γ/pg) , where y, p, and g are surface tension and density of the liquid, and gravity, respectively.
[0180] The different parameters noted in (el), (e2) and (e3) (i.e. ΘΑΧ, #BX, 7AX, 7BX, 7AB, R) can be obtained or estimated utilizing the following standard techniques. While the following standard techniques are described, other techniques can be utilized.
[0181] Table 2 A shows examples of working combinations of the solid, Liquids A and B of the slippery surface based on the predictions from the proposed relationship,
R(yBxCOS0Bx - 7AXCOS( AX) + 7AX - 7BX > 0. When the relationship holds, the lubricating liquid will stay in intimate contact with the porous solid without being displaced by Liquid A. Note that the equilibrium contact angles were estimated from the average values of the advancing and receding contact angles of Liquid A and the lubricating liquid on the flat solid surface. Satisfying the relationship can help promote the operation stability of the slippery surface where the liquid layer is substantially completely covered by the test liquid (i.e., two-phase environments that involve a single fluid interface between the test liquid and the liquid layer) and where the liquid layer contacts a droplet of the test fluid as well as air (i.e., three-phase environments that involve three fluid interfaces of (i) test liquid-liquid layer, (ii) test liquid-air, and (iii) liquid layer-air). [0182] In Table 2A, "Y" indicates that Liquid B forms a stable lubricating film, and is not displaced by Object A, and "N" indicates that Liquid B is displaced by Object A. R represents the roughness factor of the substrate, 7A represents the surface tension of Object
A, and 7B represents the surface tension of Object B. ΘΑ and ( B were estimated from the measured static contact angles on flat substrates from at least three individual
measurements (see Table 2B).
Table 2A. Comparison of the Governing Relationships with Experimental Observations for Various Solid-Liquid-A-Liquid-B Combinations.
Solid Liquid Liquid R 7A 7B 7AB ΘΑ ΘΒ Δ£„ ΑΕ2 Stable Film?
A B Theory Εχρ.
S. Epoxy H20 FC-70 2 72.4 17.1 56.0 1 13.1 14.1 45.0 34.0 145.3 Y Υ
S. Epoxy Cl6¾4 FC-70 2 27.2 17.1 8.2 70.5 14.1 7.5 6.8 25.1 Y Υ
S. Epoxy C13H28 FC-70 2 25.9 17.1 7.7 63.5 14.1 5.0 2.4 18.9 Υ Υ
S. Epoxy C10H22 FC-70 2 23.6 17.1 6.7 60.0 14.1 4.8 2.9 16.1 Υ Υ
S. Epoxy CsHig FC-70 2 21.4 17.1 4.4 50.7 14.1 3.0 1.7 10.4 Υ Υ
S. Epoxy C6¾4 FC-70 2 18.6 17.1 2.6 40.1 14.1 2.4 2.1 6.2 Υ Υ
S. Epoxy C5H12 FC-70 2 17.2 17.1 2.5 30.8 14.1 1.8 1.1 3.7 Υ Υ
Epoxy H20 FC-70 2 72.4 17.1 56.0 92.6 33.5 17.5 -20.9 90.4 Υ/Ν Υ
Epoxy Cl6¾4 FC-70 2 27.2 17.1 8.2 30.6 33.5 -9.2 -26.5 -8.2 Ν Ν
Epoxy C13H28 FC-70 2 25.9 17.1 7.7 26.9 33.5 -8.8 -25.4 -8.9 Ν Ν
Epoxy C10H22 FC-70 2 23.6 17.1 6.7 14.2 33.5 -8.6 -23.9 -10.7 Ν Ν
Epoxy CsHig FC-70 2 21.4 17.1 4.4 7.9 33.5 -6.9 -18.3 -9.6 Ν Ν
Epoxy C6¾4 FC-70 2 18.6 17.1 2.6 0 33.5 -4.3 -1 1.3 -7.2 Ν Ν
Epoxy C5H12 FC-70 2 17.2 17.1 2.5 0 33.5 -2.9 -8.4 -5.8 Ν Ν
Epoxy H20 FC-70 1 72.4 17.1 56.0 92.6 33.5 17.5 -38.5 72.8 Υ/Ν Ν
Epoxy Cl6¾4 FC-70 1 27.2 17.1 8.2 30.6 33.5 -9.2 -17.4 0.9 Υ/Ν Ν
Epoxy C13H28 FC-70 1 25.9 17.1 7.7 26.9 33.5 -8.8 -16.5 0.0 Υ/Ν Ν
Epoxy C10H22 FC-70 23.6 17.1 6.7 14.2 33.5 -8.6 -15.3 -2.1 Ν Ν
1
Silicon Cl6¾4 H20 1 27.2 72.4 51.1 5.6 13.1 43.4 -7.7 -1.8 Ν Ν
Silicon C10H22 H20 1 23.6 72.4 50.8 5.0 13.1 47.0 -3.8 -1.8 Ν Ν
Silicon CsHig H20 1 21.4 72.4 50.8 5.0 13.1 49.2 -1.6 -1.8 Ν Ν
Silicon C6¾4 H20 1 18.6 72.4 50.9 5.0 13.1 52.0 1.1 -1.8 Υ/Ν Ν
Silicon C5H12 H20 17.2 72.4
1 51.0 5.0 13.1 53.4 2.4 -1.8 Υ/Ν Ν
PDMS Water PDMS 1 72.4 21.3 43 1 10 5.0 46.0 3.0 97.1 Υ Υ
PP Water PDMS 1 72.4 21.3 43 108 5.0 46.0 0.6 94.7 Υ Υ
ΡΡ Water PDMS 2 72.4 21.3 43 108 5.0 43.6 44.2 138.3 Υ Υ
PTFE Water PDMS 2 72.4 21.3 43 1 15 5.0 51.8 60.6 154.7 Υ Υ Table 2B. Measured Contact Angles of Various Liquids on Different Flat Solids.
Liquids
Solids H?0 Ci 1fi6HΠ34 Cn 13HΠ22 Cm 10HΠ22 CgHig Cfi 6HΠ14 C,H 12 FC-
S. 0. adv 118.9±1.7 76.3±1.4 72.8±0.2 66.0±4.1 57.7±2.5 52.5±0.3 36.4±2.5 23.7±< static ii3.i±2.8 70.5±2.0 63.5±2.8 60.0±2.8 50.7±3.0 40.1±4.2 30.8±3.1 14.1±( Ep0Xy Θ. 90.8±0.9 50.0±3.9 48.1 ±3.1 38.5±0.7 23.8±4.0 22.8±1.7 17.0±1.8 0.0±0
Epoxy ( adv mo.3±3.1 32.8±1.4 28.3±1.1 1 .0±1.6 9.7±1.2 -0.0 -0.0 35.1±(
Static 92.6±1.8 30.6±0.4 26.9±1.7 14.2±0.7 7.9±0.7 -0.0 -0.0 33.5±: ^rec 67.0±4.5 25.7±0.9 25.4±0.7 13.7±0.9 6.1 ±0.2 -0.0 -0.0 26.7±
Silicon 17.3±1.6 7.9±1.0 <5.0 <5.0 <5.0
5.6±1.1 <5.0 <5.0 <5.0 <5.0
Figure imgf000043_0001
~0-0 ~0-0 ^OJl ^OJl
Table 2C. Measured Surface Tension for Various Polar and Non-Polar Liquids.
Liquid Surface Tension (niN/m) n
Watpr 79 4 + n 1 116
Glvre nl f n ± 1 1
F.thvlerie Glvrnl 48 1 ± Ω 9
ninrnnvlerie Glvrnl ± Ω
F.xtra-lipht Cm He Oil* 27 Ω ± Ω 8 1
Tiptit CniHe Oil** 9 f ± Ω 9 1
HexaHerane 27 9 ± Ω 9
Tri Hera rie 9 9 ± Ω 1
DnHerane 7 ± Ω 1 9
TTriHerarie 24 f ± Ω 9 9
Derarie 9 f ± Ω 1 9
Nnnane 22 f ± Ω 9
Ortarie 91 4 ± Ω 9
Hentane 1Q 9 ± Ω 9
Hexarie 18 f ± Ω
Pentarie 17 9 ± Ω 7 FlimrinertTM ρΓ-70 17 1 + 0 1 4^
[0183] Notice that yA and yB are equivalent to 7A and yBx defined in the text, and
medium X is air specifically in this context. Variable >ΆΒ represents the interfacial tension for Object A-Liquid B interface. Specifically, ^AB for water-perfluorocarbon and
hydrocarbon-perfluorocarbon interfaces were measured by the pendant droplet method (see Table 2D) except the water-hydrocarbon interfaces, which are estimated from the formulation: 7AB = 7A + 7B - ^{rir )m, where γκ Α and are the dispersion force contributions of the liquid surface tensions (Fowkes, F. M., Ind. Eng. Chem. 56, 40 - 42, 1964; Israelachvili, J. N. Intermolecular and Surface Forces, Academic Press, 2011). The dispersion force contribution of water surface tension is 21.8 mN/m (Fowkes, F. M., Ind. Eng. Chem. 56, 40 - 42, 1964). S. Epoxy represents silanized epoxy resin substrate.
Alkanes are represented in CnH2N+2 where n = 5, 6, 8, 10, 13, and 16.
Table 2D. Measured Interfacial Tension between a Perfluorocarbon and Various
Liquids.
Liquid/Liquid Interfacial Tension (mN/m) n
FC-70/Water 56.0 ± 0.9 12
FC-70/Hexadecane 8.2 ± 0.2 25
FC-70/Tridecane 7.7 ± 0.3 26
FC-70/Decane 6.7 ± 0.2 26
FC-70/Octane 4.4 ± 0.2 25
FC-70/Hexane 2.6 ± 0.1 40
FC-70/Pentane <2.5 10
[0184] Generally, it may be important to have the chemical nature between the roughened solid and the Liquid B be similar. For example, non-polar Liquid B with fluorocarbon functional groups may adhere well with roughened solid surface that is functionalized with fluorocarbon groups (e.g., -CF3, -CF2). In another example, polar Liquid B may adhere well with roughened solid surface that is functionalized with hydroxyl groups (i.e., -OH).
[0185] In most of the cases, it may be desirable to have the surface energies of the roughened solid and Liquid B to be lower than the surface energy of Liquid A so that Liquid A will not displace Liquid B from the roughened solid.
[0186] In certain embodiments, when Liquid A is a low surface tension non-polar liquid (e.g., less than 30 mN/m), the roughened surface may be functionalized with low surface energy coatings (e.g., less than 30 mJ/m2), such as -CF3, -CF2H, -CF3 and -CF2-,
-CF2-CF3, -CF2-CFH-, -CF2-CH2- -CFH-CH2- and the like. Moreover, Liquid B may be selected to also exhibit low surface energy (e.g., less than 20 mJ/m2), such as perfluorotributylamine, perfluorotri-n-pentylamine, perfluorohexane, perfluoro(2-butyl- tetrahydrofuran), perfluorocycloether, perfluoro n-alkyl morpholines, perfluoroalkylethers, perfluorotripropylamine, and the like.
[0187] In certain embodiments, when Liquid A is a high surface tension liquid (e.g., water, condensation) or a solidified fluid, Liquid B can be selected from other higher surface energy fluids (i.e., -20 mJ/m2 or higher), such as polydimethylsiloxane, other liquid silicone elastomers or commercial food grade lubricants (e.g., K YTOX(TM) FG lubricants), oils (e.g, vegetable or mineral oil (see FIG. 26B)), and the like. Image (A) in FIG. 26 shows a SLIPS surface generated using an infiltration of polydimethylsiloxane (PDMS) liquid (500 MW, X viscosity, OH-terminated, Sigma Aldrich) into an ePTFE membrane (1 μιη, Sterlitech). Image (B) in FIG. 26 shows a SLIPS surface generated using an infiltration of olive oil into an ePTFE membrane (1 μιη, Sterlitech). In both cases the blood was found to not wet the surface, and rolled off without adhering to the surfaces. In certain embodiments, as with low surface tension liquids, the roughened surface may be functionalized with low surface energy coatings (e.g., less than 30 mJ/m2), such as -CF3, - CF2H, -CF3 and -CF2- -CF2-CF3, -CF2-CFH- -CF2-CH2- -CFH-CH2- and the like.
[0188] Table 3 shows some non-limiting examples of combinations of substrates, lubricating liquid (Liquid B), and liquid to be repelled (Liquid A). For example, in one embodiment, the solid substrate can be selected from the group consisting of
polydimethylsiloxane, polypropylene, polytetrafluoroethylene, and the like. In this embodiment, lubricating liquids such as liquid silicone elastomers (e.g.,
polydimethylsiloxane), vegetable or mineral oil, liquid hydrocarbons, and combinations thereof can be applied to the solid substrate to create a SLIPS surface to repel materials such as simple aqueous fluids (e.g., water), complex aqueous fluids (e.g., blood), solidified fluids, and combinations thereof (Table 3, row 1).
[0189] In another embodiment, the solid substrate can be selected from the group consisting of fluoro-silanized metals (e.g., fluoro-silanized aluminum, silver, gold, platinum, copper, gold, palladium, zinc, titanium, and the like), fluoro-silanized natural polymers (e.g., fluoro-silanized synthetic polymers (e.g., fluoro-silanized epoxy resin, silicone, silicone rubber, latex, polytetrafluoroethylene, polyvinylfluoride, polyvinylidene fluoride, fluorinated ethylene propylene, thermoplastic elastomers, Teflon, and the like), and combinations thereof. Lubricating liquids such as perfluorinated fluids can be applied these solid substrates to repel any non-perfluorinated liquid (Table 3, row 2).
Table 3. Examples of Combinations of Materials for Making SLIPS Surfaces
Figure imgf000046_0001
[0190] In some embodiments, it may be desirable to have SLIPS that are optically transparent. By choosing a substrate and lubricating fluid with matching refractive indices, SLIPS can be made optically transparent in visible and/or near-infrared wavelengths (FIG. 16A-C). FIG. 16A shows optical images showing enhanced optical transparency of an epoxy-resin-based SLIPS (left) as compared to significant scattering in the non-infused super hydrophobic nanostructured surface (right) in the visible light range. FIG. 16B. shows optical transmission measurements for epoxy-resin-based SLIPS in the visible light range (400-750 nm). FIG. 16C shows optical transmission measurements for Teflon-based SLIPS in the near-infrared range (800-2300 nm).For example, FIG. 64 shows images of a transparent SLIPS surface made by the infiltration of a highly-ordered nanoporous Si02 glass layer (A) with perfluorocarbon (FC-70) (B). When fully infiltrated, the layer is highly transparent (C).
Measurement of Θαχ, Advancing and Receding Angles, Static Angles
[0191] The behavior of liquids on surfaces is described by an equilibrium contact angle.
An equilibrium contact angle, θ, is the angle at which a liquid/vapor interface meets a solid surface, which is determined by the interactions across the three interfaces, e.g.,
solid/liquid/vapor. Experimentally, the most stable equilibrium contact angle of a liquid droplet on a real surface can be difficult to attain. Liquid droplets sitting on the surface exhibit a variety of contact angles bound by two extreme values. The upper limit is known as the apparent advancing contact angle ((9A), whereas the lower limit is referred as the apparent receding contact angle (9R). The difference between these values is known as contact angle hysteresis (i.e., Αθ = ΘΑ - <9R, where ΘΑ≥ θ> 9R), which characterizes the liquid repellency of a surface. Conventionally, equilibrium contact angle can be roughly estimated by the average of the advancing and receding angles (i.e., θ = (ΘΑ + 9R)/2), or by a static contact angle, ( static (i.e., Θ = (9static).
[0192] In practice, contact angle measurement can be performed by a number of different well-established techniques, such as the sessile drop method and the Wilhelmy method. In particular, the sessile drop method is among the most popular technique for contact angle measurement. In this technique, a liquid droplet is deposited on a targeted solid surface, where the liquid profile is captured by an optical system of a goniometer and geometrically fitted to obtain the contact angle. The contact angle measured from a static liquid droplet deposited on the surface is known as the static contact angle, ( static. Using the same system, advancing contact angle, (9A, can be measured while the volume of the drop is increasing until the wetting line starts to advance. Receding contact angle, (9R, can be measured by decreasing the volume of the drop and determining the contact angle just before the wetting line recedes. Alternatively, the advancing and the receding angles of the liquid drop can also be determined by gradually tilting the solid surface until the liquid drop starts to move.
Measurement of Fluid-Fluid Interfacial Tension: AX, yBx, AB
[0193] Fluid-fluid interfacial tension can be measured by many well-established techniques, such as the Wilhelmy plate method, the Du Noiiy ring method, and the pendant drop method (e.g., see Drelich et al., in Encyclopedia of Surface and Colloid Science, pp. 3152 - 3166, Marcel Dekker Inc, 2002, the contents of which is incorporated by reference herein in its entirety). Among all of the techniques, the pendant drop method is among the most popular and versatile technique, which can be easily extended to a two-liquid system. The pendant drop method measures the shape of a fluid-fluid interface and quantifies the shape distortion due to the competition between the fluid- fluid interfacial tension and gravity. In practice, a drop of denser fluid (e.g., Object A) is suspended by a syringe needle in medium X (i.e., air/water/the lubricating fluid). Owing to the influence of gravity, the denser liquid droplet will be deformed as the liquid volume increases. The shape profile of the liquid droplet is captured by an optical system and subsequently analyzed by a computer software when the liquid volume is increased to the maximum possible size (i.e., before the liquid drop is detached from the syringe needle). The interfacial tension of the fluid-fluid interface, y, can then be deduced from the formula, y = ApgD2/H, where Ap is the density difference between the two immiscible fluids, g is gravity, D is equatorial diameter of the liquid droplet, and H is drop shape dependent parameters which is a function of the shape profile of the droplet.
Measurement of Surface Roughness: R
[0194] Roughness of a surface can be quantitatively estimated by a number of indirect and direct approaches. For example, one of the simplest indirect methods to quantify surface roughness is the use of Wenzel's relationship to estimate the roughness by measuring the apparent contact angle of a surface. Specifically, the Wenzel's relationship can be described by the formula, cos( * = Rcos9, where Θ* and Θ are the measured apparent contact angle of the roughened surface, and the equilibrium contact angle of a substantially flat surface (of same material), respectively.
[0195] For direct measurements, the surface roughness can be quantitatively measured by using an atomic force microscope or by a scanning electron microscope. Specifically, the use of atomic force microscope (AFM) allows for simple, and direct 3 -dimensional mapping of the surface morphology. In practice, a suitable AFM probe is selected for the measurements depending on the aspect ratio of the surface features (note: aspect ratio is defined as the ratio between the height and the width of the surface features). As a rule of thumb, sharp AFM probes (i.e., radius of tip curvature < 10 nm) of very high aspect ratio (i.e. > 10) would allow for relatively precise measurements of surfaces with general morphologies. Alternatively or in addition, the use of scanning electron microscope can also be used for the measurement of the top view and cross sectional view of the surface morphologies for the estimation of the surface roughness.
[0196] In certain embodiments, the roughness of a 3-D porous material can be estimated by measuring the surface morphology of the top-most layer of the porous material. Particularly, the estimation may be particularly well-suited when complete wetting of a surface is predominately induced by the roughness at the surface layer of the material that is in intimate contact with the fluid.
[0197] In some embodiments in which SLIPS is used to repel complex biological fluids without permitting adhesion, clot formation, or fouling, the lubricating fluid is an organofluorine oil, (i.e., perfluorinated oils including, without limitation, tertiary perfluoroalkylamines (such as perfluorotri-n-pentylamine, FC-70; perfluorotri-n- butylamine FC-40, etc), perfluoroalkylsulfides, perfluoroalkylsulfoxides,
perfluoroalkylethers, perfluorocycloethers (like FC-77), perfluoropolyethers (such as K YTOX family of lubricants by DuPont), perfluoroalkylphosphines, and
perfluoroalkylphosphineoxides) .
[0198] In certain embodiments, the slippery surface of the present disclosure has a coefficient of friction that is lower than polytetrafluoroethylene (PTFE or TEFLON). In certain embodiments, the coefficient of friction is less than 0.1, less than 0.05, or even less than 0.04. In certain embodiments, the coefficient of friction can be measured against polished steel, Teflon, or the slippery surface of the present disclosure itself (e.g., slippery surface/slippery surface).
[0199] As shown in FIGS. 27A and 27B, there are two working configurations for the invention. In the first configuration, as shown in FIG. 27A, the lubricating liquid (Liquid B) overcoats the roughened solid surface, and forms an ultra- smooth surface. Liquid B can wet the roughened surface, filling the hills and valleys of the roughened surface, and forming an ultra-smooth surface over the roughened surface. Particularly, Liquid B can form a liquid layer over the roughened surface so that the liquid layer covers the roughened surface to form an ultra- smooth surface of Liquid B (FIGS. 6 A and 6B). In certain embodiments, the average surface roughness of the surface is on the order of or less than about 1 nm based on high resolution atomic force microscopy measurements. The presence of the micro/nanostructures can significantly enhance the wetting of Liquid B, thereby creating a uniformly-coated slippery functional layer over the topographies. The first configuration may be useful for repelling a liquid, gas, or molecules or particulates contained within liquids.
[0200] In the second configuration shown in FIG. 27B, the lubricating fluid (Liquid B) infiltrates within the solid textures, forming a composite solid-liquid interface. Rather than forming the ultra-smooth surface of FIG. 27A the lubricating fluid (Liquid B) can infiltrate the roughened solid surface and form a thin coating thereon that follows the topography of the underlying roughened solid surface. In certain embodiments, the thin coating may be conformally coating the top surface of the roughened surface. As used herein, "conformal coating" can encompass forming a molecular monolayer or multiple molecular layers that surround the materials of the roughened surface. However, the "conformal coating" is not thick enough to form an over-coat layer to form an ultra-smooth surface, such as described in FIG. 27A. In certain embodiments, the second configuration may be particularly useful for repelling materials in their solid forms.
[0201] In order for the lubricating fluid (Liquid B) to remain attached with the roughened surface, at least the following three properties are desirable: (1) the lubricating fluid (Liquid B) readily imbibes into, wets, and stably adheres within the substrate, (2) the roughened surface is preferentially wetted by the lubricating fluid (Liquid B) rather than by the material to be repelled, and (3) the lubricating fluid (Liquid B) and the material to be repelled are immiscible.
Object A and Lubricating Liquid Combinations
[0202] In certain embodiments, the solidification temperature of the lubricating liquid may be lower than that of Liquid A. In certain embodiments, the lubricating liquid can maintain its liquid state below the solidification temperature of Liquid A, thereby retaining its slippery property. Without wishing to be bound by theory, there may be at least two reasons to maintain the lubricating liquid in a liquid state even while Liquid A solidifies.
[0203] First, having the lubricating liquid maintained in the liquid state may result in reduced adhesion at the interface between Object A and the lubricating liquid in the directions normal and tangential to the substrate surface, as compared to that of the interface between the solidified form of the material to be repelled and other solid surfaces (i.e., roughened surfaces). Adhesion between surfaces may be proportional to the contact surface area, where the smoothness of the lubricating liquid surface can minimize contact area between Object A and the lubricating liquid, due to the smaller surface area at the interface compared to a roughened surface. The reduced adhesion may facilitate removal of Object A from the lubricating liquid surface at much reduced force per unit area.
[0204] Second, the ultra-smooth surface of the lubricating liquid may also reduce the condensation of Liquid A from the air (i.e., assuming the vaporized form of Liquid A is present in air) when the surface of the lubricating liquid is cooled to the temperature below the solidification temperature of Liquid A. This may be due to the fact that there are few or even no nucleation sites on the lubricating liquid surface, which greatly reduce the nucleation probability of the repelled liquid. As a result, the formation of fog and frost (i.e., solidified form of the repelled liquid at the micro- and nanoscale) on the surface can require more stringent conditions (e.g., lower temperature or a higher vapor pressure of Liquid A in the air) as compared to the other solid surfaces. To maintain the lubricating liquid in the liquid state, the solidification temperature of the lubricating liquid may be 25
C lower than that of Liquid A at atmospheric pressure.
[0205] In certain embodiments, the boiling temperature of the lubricating liquid may be higher than the solidification temperature of Liquid A. In certain embodiments, the lubricating liquid may be able to maintain its liquid state above the solidification temperature of Liquid A. Additionally, maintaining the liquid state may facilitate the removal of Liquid A from the lubricating liquid surface due to the aforementioned liquid- slippery function, while the surface is held at a temperature above the solidification temperature of Liquid A. This may be particularly important for applications in surface defrosting, where the lubricating liquid may be defrosted using minimal energy input (e.g., at a lower temperature) as compared to other solid surfaces. To maintain the lubricating liquid in the liquid state, the boiling temperature of the lubricating liquid may be 215 °C higher than the solidification temperature of Liquid A at atmospheric pressure.
[0206] In certain embodiments, the solid to be repelled (or Object A) may slide off from the surface of the lubricating liquid by gravity when the surface is tilted at an angle with respect to the horizontal, given that Object A is larger than a characteristic size.
Specifically, the effect of gravity on Object A may be more dominant when its size is much larger than the capillary length of Liquid A. Specifically, capillary length is a characteristic length scale that quantifies the dominance of body force over surface force on an object,
1/2
which can be quantitatively expressed as (γ/pg) , where y, p, and g are surface tension and density of the liquid, and gravity, respectively. For example, Object A may be at least 3 times larger than the capillary length of Liquid A.
[0207] In certain embodiments, the lubricating liquid may be selected to satisfy additional criteria needed for Solid A or Object A. For example, when Object A is a biological object, the lubricating liquid can be selected so that the lubricating liquid is not toxic to Object A so that facile transport of Object A to desired locations without reducing the biological activity of Object A. In another example, the lubricating liquid can be selected so that the lubricating liquid is toxic to Object A so that removal of Object A can be further coupled with reducing the biological activity of Object A.
Certain Advantages for Porous Material [0208] In certain embodiments, use of a porous material having a high degree of physical roughness for the roughened surface may be particularly advantageous. The presence of such physical roughness may induce not only the complete wetting of the lubricating fluid, but also provide additional capillary adhesion for the lubricating fluid within the porous solid to further enhance the mechanical stability, wicking characteristics and the ability to "hold" Liquid B "in place" even at high tilt angles.
[0209] Moreover, another important feature for the use of porous material may be that further structuring of the surface may not be needed, since the physical structures are already embedded within the bulk material. In such cases, the porous material can be a self-supporting, free-standing membrane which can be attached/glued/adhered to the external or internal surfaces of materials with any kind of geometry (see FIGS. 7 and 8).
[0210] In addition, one of the unique features of using porous materials may be the presence of the capillaries network within the bulk materials, which can further enhance transport of Liquid B through the pores. For example, in the case where a portion of Liquid B is consumed locally at the surface of the material due to evaporation, sudden pressure purging, physical damage or the like, Liquid B can be replenished effectively by the capillary action in these networks. In certain embodiments, the porous material itself can be utilized as a fluid reservoir to store the fluorinated liquid for subsequent capillary refilling (see FIG. 8).
[0211] In certain embodiments, to further prolong the life time of the slippery surface of the present disclosure, the porous material can also be connected to an external fluid reservoir or larger storage capacity, where the capillary networks can help autonomously transfer the liquids from the fluid reservoir to the bulk material itself (see FIG. 8).
[0212] In certain embodiments, the pore size of the porous material can roughly be on the order of the capillary length of Liquid B or smaller. Such size may allow stabilizing
Liquid B in the porous material. Capillary length, c, can be defined as Ac =
Figure imgf000052_0001
, where γ is the surface tension of Liquid B, p is the density of Liquid B, and g is gravity.
[0213] Taking the exemplary case of utilizing fluorinated liquids as Liquid B, the surface tension of fluorinated liquids is in the range of about 10 - 20 mN/m at a typical density of about 1800 kg/m3. Typical pore sizes can range from about 50 nm to about 100 μιη or up to about 1 mm, such as about 750 um - 1 mm. [0214] In certain embodiments, use of a porous material for the roughened surface may provide even higher resistance to pressure change than the high pressure changes that can be obtained using solid surfaces having certain topographies. For example, while a 2.5D (vertically extruded) nanostructured structure shown in FIG. 5A may be able to sustain a maximum rate of pressure change on the order of 105 Pa per second, use of a porous material (e.g., Teflon membrane) may be able to tolerate pressure change up to about 6 x 106 Pa per second without displacing Liquid B. Without wishing to be bound by theory, the improved pressure tolerance of the 3D porous material can be attributed to the enhanced capillary interactions between the intricate 3D porous network and Liquid B.
[0215] In certain embodiments, use of a porous material for the roughened surface may provide even higher pressure stabilities than the high pressure stability that can be obtained using solid surfaces having certain topographies (e.g., "2.5D" nanostructured surface). For example, use of a porous material (e.g., Teflon membrane) may be able to tolerate absolute pressure up to about 6.9 x lO7 Pa while maintaining its liquid slippery function. Without wishing to be bound by theory, the improved pressure tolerance of the 3D porous material can be attributed to the incompressibility of the lubricating layer, as well as the resistance of liquid penetration into the porous structure.
Prevention or Reduction of Microbial Attachment and Biofilm Formation
[0216] Materials (Object As) that can be repelled by SLIPS include microbes such as bacteria. Bacteria primarily exist in robust, surface-associated communities known as bio films, which are ubiquitous in both natural and anthropogenic environments.
Contamination of surfaces by microbial attachment occurs easily, and is the first step towards the development of bacterial bio films as multicellular communal super-organisms (De Beer, D. & Stoodley, P. Microbial Biofilms. Prokaryotes 1 :904-937 (2006); O'Toole, G., Kaplan, H.B. & Kolter, R. Biofilm Formation as Microbial Development. Annu. Rev. Microbiol. 54:49-79 (2000)). Mature biofilms resist a wide range of antimicrobial treatments and pose persistent pathogenic threats.
[0217] Bacteria can physically attach to a vast variety of surfaces - from hydrophilic to hydrophobic, by a variety of mechanisms (O'Toole et al, 2000; De Beer et al, 2006;
O'Toole 2003; Christensen et al, 1985; Costerton et al, 1987; Gristina, 1987; Jacques et al., 1987). The typical mechanisms include an initial deposition of proteins, known as conditioning layer, by physical or chemical adsorption, which precedes the attachment of the bacteria itself. Conditioning films, which may contain fibronectin, fibrinogen, collagen, and other proteins, coat a biomaterial surface almost immediately and provide receptor sites for bacterial or tissue adhesion (Gristina, 1987).
[0218] Bio film formation is of concern to industry and healthcare because it causes contamination of plumbing, oil wells, heat exchangers, building ventilation, food storage, medical implants, and other systems. Biofilms threaten human health by triggering an immune response, releasing harmful endotoxins and exotoxins, and clogging indwelling catheters; in fact, biofilms are responsible for nearly 100,000 nosocomial deaths annually in the United States and 80% or more of all microbial infections in humans.
[0219] Treatment or removal of adherent bio film is difficult, costly, and in medical systems is frequently impossible. It is imperative to prevent rather than treat biofilm formation, and accordingly a wide range of bacteria-resistant surfaces have been proposed. At the same time, strategies for biofilm prevention based on surface chemistry treatments have been found to only transiently affect initial attachment. Most current strategies for preventing biofilm formation rely either on a release of biocidal compounds or on inhibiting adhesion (Banerjee, I., R.C. Pangule, and R.S. Kane, Antifouling coatings: recent developments in the design of surfaces that prevent fouling by proteins, bacteria, and marine organisms. Advanced Materials, 2011; Zhao, L., et al., Antibacterial coatings on titanium implants. Journal of Biomedical Materials Research Part B: Applied Biomaterials, 2009. 91(1): p. 470-480).
[0220] In the first case, traditional techniques involve the design of coatings that release agents such as antibiotics, quaternary ammonium salts, and silver ions into the surrounding aqueous environment. Such agents have been incorporated into a variety of engineering polymers and other materials (Banerjee (2011)).
[0221] The latter approach has focused on the use of surface chemical functional groups that inhibit protein adsorption as a means to inhibit bacterial adhesion. One of the most commonly studied such surface modifications is poly(ethylene glycol), or PEG (Park, K.D., et al., Bacterial adhesion on PEG modified polyurethane surfaces. Biomaterials, 1998. 19(7-9): p. 851-859; Prime, K.L. and G.M. Whitesides, Self-assembled organic monolayers: model systems for studying adsorption of proteins at surfaces. Science (New York, NY), 1991. 252(5010): p. 1164.)). [0222] More recently, structured superhydrophobic surfaces have been suggested for preventing biofilm attachment owing to the trapped air between their micro/nanoscale surface features and therefore, in principle, the reduced available solid attachment area for biofilm (see, e.g., U.S. Patent Application No. 61/434,217, filed on January 19, 2011, which is incorporated herein in its entirety).
[0223] These strategies, however, are generally transient. Materials that persistently resist bacteria are difficult to achieve by surface chemistry alone. The surface chemistry is subject to desorption over time, a limitation that has driven much research in the area of strengthening the physisorption of, e.g., PEG coatings (Banerjee (2011). However, even if no desorption occurs and bacteria are unable to attach directly to a substrate, nonspecific adsorption of proteins and surfactants secreted by bacteria can still mask the underlying chemical functionality (Bos, R., et al., Retention of bacteria on a substratum surface with micro patterned hydrophobicity. Ferns Microbiology Letters, 2000. 189(2): p. 311-315). Additionally, any defects or voids in the surface chemistry could serve as nucleation sites for bacterial attachment. Structured superhydrophobic surfaces in the Cassie (trapped air) state are prone to irreversible wetting (Wenzel transition), especially with the production of bacterial surfactant, which seriously limits their lifetime in submerged environments (Poetes, Pv., et al., Metastable Underwater Superhydrophobicity. Physical Review Letters, 2010. 105(16)).
[0224] Strategies involving leaching of biocides are limited over a longer timescale since their reservoir is finite and subject to depletion (Zhao, L., et al, Antibacterial coatings on titanium implants. Journal of Biomedical Materials Research Part B: Applied Biomaterials, 2009. 91(1): p. 470-480). Also, the emergence of antibiotic- and silver- resistant pathogenic strains, along with new restrictions on the use of biocide-releasing coatings in the marine environment, has necessitated the development of new strategies (Hall-Stoodley, L., J.W. Costerton, and P. Stoodley, Bacterial biofilms: from the natural environment to infectious diseases. Nature Reviews Microbiology, 2004. 2(2): p. 95-108; Trevors, J., Silver resistance and accumulation in bacteria. Enzyme and Microbial Technology, 1987. 9(6): p. 331-333; Costerton, J., P. Stewart, and E. Greenberg, Bacterial biofilms: a common cause of persistent infections. Science, 1999. 284(5418): p. 1318.).
[0225] Systemic and topical antimicrobial products have become extensively used to combat biofilm contamination in health care, agriculture, and industrial settings, and increasingly by the general public as well. Commercial products employ a wide variety of active chemical agents, or biocides, often delivered in liquid form and sometimes as vapor. One review of antiseptics and disinfectants identifies 12 classes of liquid agents and 5 common types of vapor-phase sterilants. Regardless of the particular chemistry or mechanism, biocides must be able to reach the target cell to cause damage. At the multicellular level, therefore, the effective biocide must penetrate into the extracellular matrix (ECM)— the slime-like "cement" of bio film. Bio films, however, offer their member cells protection from environmental threats. It has been reported that ECM acts as a diffusion barrier and as a charged binding filter for certain antibiotics, and that it complements enzymes and multidrug resistance pumps on cells that remove antimicrobials. The resistance to threats covers a wide range of treatments: bio films exposed to chlorine bleach for 60 minutes are reported to still have live cells; biofilms in pipes continuously flushed over 7 days with multiple biocides recolonize the pipes, and biofilms have been reported to survive in bottled iodine solution for up to 15 months. Biofilms' resistance to antimicrobials may be related to the extreme nonwettability of their surface as well as resistance to vapor penetration.
[0226] SLIPS can repel various types of bacteria and prevent bio film formation. SLIPS can repel, or prevent or reduce attachment of bacteria suspended in solution, airborne bacteria, and the like. In one embodiment, the type of bacteria repelled by SLIPS is gram positive bacteria. In another embodiment, the type of bacteria repelled by SLIPS is a gram negative bacteria. Non- limiting examples of bacteria repelled by SLIPS include members of the genus selected from the group consisting of Actinobacillus {e.g., Actinobacillus actinomycetemcomitans), Acinetobacter (e.g., Acinetobacter baumannii), Aeromonas, Bordetella (e.g., Bordetella pertussis, Bordetella bronchiseptica, and Bordetella
parapertussis), Brevibacillus, Brucella, Bacteroides (e.g., Bacteroides fragilis),
Burkholderia (e.g., Burkholderia cepacia and Burkholderia pseudomallei), Borelia (e.g., Borelia burgdorferi), Bacillus (e.g., Bacillus anthracis and Bacillus subtilis),
Campylobacter (e.g., Campylobacter jejuni), Capnocytophaga, Cardiobacterium (e.g., Cardiobacterium hominis), Citrobacter, Clostridium (e.g., Clostridium tetani or
Clostridium difficile), Chlamydia (e.g., Chlamydia trachomatis, Chlamydia pneumoniae, and Chlamydia psiffaci), Eikenella (e.g., Eikenella corrodens), Enterobacter, Escherichia (e.g., Escherichia coli), Francisella (e.g., Francisella tularensis), Fusobacterium, Flavobacterium, Haemophilus {e.g., Haemophilus ducreyi or Haemophilus influenzae), Helicobacter (e.g., Helicobacter pylori), Kingella (e.g., Kingella kingae), Klebsiella (e.g., Klebsiella pneumoniae), Legionella (e.g., Legionella pneumophila), Listeria (e.g., Listeria monocytogenes), Leptospirae, Moraxella (e.g., Moraxella catarrhalis), Morganella, Mycoplasma (e.g. , Mycoplasma hominis and Mycoplasma pneumoniae), Mycobacterium (e.g. , Mycobacterium tuberculosis or Mycobacterium leprae), Neisseria (e.g., Neisseria gonorrhoeae or Neisseria meningitidis), Pasteur ella (e.g. , Pasteur ella multocida), Proteus (e.g., Proteus vulgaris and Proteus mirablis), Prevotella, Plesiomonas (e.g., Plesiomonas shigelloides), Pseudomonas (e.g., Pseudomonas aeruginosa), Providencia, Rickettsia (e.g., Rickettsia rickettsii and Rickettsia typhi), Stenotrophomonas (e.g., Stenotrophomonas maltophila), Staphylococcus (e.g., Staphylococcus aureus and Staphylococcus epidermidis), Streptococcus (e.g., Streptococcus viridans, Streptococcus pyogenes (group A),
Streptococcus agalactiae (group B), Streptococcus bovis, and Streptococcus pneumoniae), Streptomyces (e.g., Streptomyces hygroscopicus), Salmonella (e.g., Salmonella enteriditis, Salmonella typhi, and Salmonella typhimurium), Serratia (e.g., Serratia marcescens), Shigella, Spirillum (e.g., Spirillum minus), Treponema (e.g., Treponema pallidum), Veillonella, Vibrio (e.g., Vibrio cholerae, Vibrio parahaemolyticus, and Vibrio vulnificus), Yersinia (e.g., Yersinia enter ocolitica, Yersinia pestis, and Yersinia pseudotuberculosis), Xanthomonas (e.g., Xanthomonas maltophilia) and combinations thereof.
[0227] In particular, SLIPS has been shown to prevent 99.6% of common bacterial biofilm attachment under both flow and static conditions, which represents at least a 30x reduction in biofilm attachment over best-case-scenario, state-of-the-art surface treatments based on PEGylation.
[0228] Moreover, SLIPS can repel various types of fungi. Non-limiting examples of fungi repelled by SLIPS include members of the genus Aspergillus {e.g., Aspergillus flavus, Aspergillus fumigatus, Aspergillus glaucus, Aspergillus nidulans, Aspergillus niger, and Aspergillus terreus), Blastomyces dermatitidis, Candida {e.g., Candida albicans, Candida glabrata, Candida tropicalis, Candida parapsilosis, Candida krusei, and Candida guillermondii), Coccidioides immitis, Cryptococcus {e.g., Cryptococcus neoformans, Cryptococcus albidus, and Cryptococcus laurentii), Histoplasma capsulatum var.
capsulatum, Histoplasma capsulatum var. duboisii, Paracoccidioides brasiliensis, Sporothrix schenckii, Absidia corymbifera; Rhizomucor pusillus, Rhizopus arrhizous, and combinations thereof.
[0229] SLIPS can also repel various types of viruses and virus-like particles. In one or more embodiments, the virus repelled by SLIPS is selected from the group consisting of dsDNA viruses, ssDNA viruses, dsRNA viruses, (+)ssRNA viruses, (-)ssRNA viruses, ssRNA-PvT viruses, dsDNA-RT viruses, and combinations thereof. Non-limiting examples of viruses repelled by SLIPS include cytomegalovirus (CMV), dengue, Epstein-Barr, Hantavirus, human T-cell lymphotropic virus (HTLV I/II), Parvovirus, hepatitides (e.g., hepatitis A, hepatitis B, and hepatitis C), human papillomavirus (HPV), human
immunodeficiency virus (HIV), acquired immunodeficiency syndrome (AIDS), respiratory syncytial virus (RSV), Varicella zoster, West Nile, herpes, polio, smallpox, yellow fever, rhinovirus, coronavirus, Orthomyxoviridae (influenza viruses) {e.g., Influenzavirus A, Influenzavirus B, Influenzavirus C, Isavirus and Thogotovirus), and combinations thereof.
[0230] In still another embodiment, SLIPS is capable of repelling particles in suspension or solution without causing surface adhesion, surface-mediated clot formation, fouling, or aggregation. The omniphobic nature of SLIPS allows it to protect surfaces from a wide range of contaminants. Non- limiting examples of a particles in suspension or solution include cells (e.g., normal cells, diseased cells, parasitized cells, cancer cells, foreign cells, stem cells, and infected cells), microorganisms (e.g., viruses, virus-like particles, bacteria, bacteriophages), proteins and cellular components (e.g., cell organelles, cell fragments, cell membranes, cell membrane fragments, viruses, virus-like particles, bacteriophage, cytosolic proteins, secreted proteins, signaling molecules, embedded proteins, nucleic acid/protein complexes, nucleic acid precipitants, chromosomes, nuclei, mitochondria, chloroplasts, flagella, biominerals, protein complexes, and minicells).
[0231] In other embodiments, SLIPS repels natural and synthetic solutions used in medicines, intravenous solutions, pharmaceutical manufacturing, and medication delivery systems.
Prevention of or Reduction Protein Adsorption
[0232] In one embodiment, SLIPS is used to prevent or reduce protein adsorption.
[0233] Biocompatibility and contamination issues associated with the contact of foreign surfaces involve nonspecific protein adsorption. Biocompatibility is the ability of a material to allow an appropriate host response in a specific environment or application. In general, foreign surfaces of medical instruments and medical devices attract a variety of biological adsorption events and biological responses, and it is very difficult to prevent, reduce, or control these processes (Ratner (Ed.), Biomaterials Science, Academic Press (2004)).
There is a complex variety of biological responses to foreign surfaces, in vivo and ex vivo, associated with biofouling events, immune response, protein adsorption, thrombus formation, and the like (Ratner (Ed.), Biomaterials Science, Academic Press (2004)).
Proteins have an inherent tendency to deposit on surfaces as a tightly bound adsorbate, which strongly influences subsequent cellular (or microbial) interactions with the surface (Ratner (Ed.), Biomaterials Science, Academic Press (2004)). Bacteria attach to surfaces by means of a conditioning layer of proteins. Implanted biomaterials or medical devices are rapidly coated by constituents of the blood serum and surrounding matrix, which include fibronectin, osteonectin, vitronectin, albumin, fibrinogen, laminin, collagen and covalently-bound short-chain oligosaccharides (Ratner (Ed.), Biomaterials Science, Academic Press (2004); Gristina, A.G., et al., Biomaterial-centered sepsis and the total artificial heart. Microbial adhesion vs tissue integration. JAMA 259:870-874 (1988)). Both bacteria and tissue cells can then attach to these various proteins.
[0234] Protein adsorption also occurs when devices trigger an immune response in the body. When the immune response is triggered, complement proteins opsonize the foreign surface for phagocytosis. Complement activation leads to deposition of complement components, which foul the foreign surface (Skattum L, et al, Mol. Immunol, 48(14): 1643- 55 (2011)).
[0235] To date, surface modifications such as the attachment of antithrombotic agents (heparin) or the immobilization of polyethylene oxide (PEO) or polyethylene glycol (PEG) have been thoroughly tested, but their success at avoiding protein adsorption remains limited (George, P. A., et al, J.J. Self-assembling polystyrene-block-poly(ethylene oxide) copolymer surface coatings: resistance to protein and cell adhesion. Biomaterials 30: 2449- 2456 (2009)). Although PEG-based surfaces resist non-specific protein adsorption and cell adhesion, they eventually oxidize in most biochemical environments (Ratner (Ed.), Biomaterials Science, Academic Press (2004); Chen, S., et al. Surface hydration: Principles and applications toward low-fouling/non-fouling biomaterials. Polymer 51 :5283-5293 (2010)). The non- fouling properties of antifouling materials is generally caused by a tightly-bound water layer acts as a physical and energetic barrier to protein adsorption. Chen, S., et al. Polymer 51 :5283-5293 (2010). However, these surfaces eventually deteriorate and allow adsorption to occur.
[0236] Thus, in one or more embodiments, SLIPS can be used to prevent or reduce adsorption of proteins that come into contact with SLIPS.
Preventing or Reducing Adhesion of Biological Fluids
[0237] Fluids such as biological fluids that are applied to, or come into contact with, SLIPS are strongly repelled by the lubricating fluid. As used herein, "fluids" includes fluids and particles in suspensions or solution, including those from living organisms and synthetic solutions used in medicines.
[0238] This surface design represents a completely new approach to controlling the adhesion of biological fluids. Non-limiting examples of biological fluids that can be repelled by SLIPS without causing surface adhesion or aggregation include whole blood, serum, plasma, water, sweat, feces, urine, saliva, tears, vaginal fluid, prostatic fluid, gingival fluid, amniotic fluid, intraocular fluid, cerebrospinal fluid, seminal fluid, sputum, ascites fluid, pus, nasopharengal fluid, wound exudate fluid, aqueous humour, vitreous humour, bile, cerumen, endolymph, perilymph, gastric juice, mucus, peritoneal fluid, pleural fluid, sebum, vomit, synthetic fluid (e.g., synthetic blood, hormones, nutrients), and combinations thereof.
Applications for SLIPS
Anticoagulation Surface
[0239] Surfaces that prevent or reduce blood coagulation by repelling blood components, such as platelets and fibrin, involved in the clotting cascade mechanism, can be made in accordance with the present disclosure. In one embodiment, SLIPS is applied to a medial device that comes into contact with complex fluids such as blood to create an anti-coagulation surface. Blood clotting on synthetic surfaces is a long-standing and widespread problem in medicine (Thompson, A.R. & Harker, L.A. Manual ofHemostasis and Thrombosis, (F. A. Davis, Philadelphia, 1983); Colman, R.W., Hirsch, J., Marder, V.J. & Salzman, E.W. (eds.). Hemostasis and Thrombosis, (Lippincott Williams and Wilkins, 2005)). Thrombosis is initiated on surfaces first by protein absorption, which promotes platelet adhesion, activation and release of thrombin that cleaves fibrinogen and activates fibrin clot formation ((Thompson, A.R. & Harker, L.A. Manual of Hemostasis and Thrombosis, (F. A. Davis, Philadelphia, 1983); Colman, R.W., Hirsch, J., Marder, V.J. & Salzman, E.W. (eds.). Hemostasis and Thrombosis, (Lippincott Williams and Wilkins, 2005))).
[0240] Results demonstrate that SLIPS does not allow blood to wet, and adhere to, SLIPS. Anti-coagulant surfaces that prevent or reduce blood coagulation can be developed by creating an ultra-low drag clot-free surface, much like living endothelium does (see Example 2).
[0241] Anti-coagulation surfaces disclosed herein represent a novel and surprisingly effective method for controlling the adhesion of blood components, such as platelets and fibrin, involved in the clotting cascade mechanism. Anti-coagulation surfaces do not allow blood to wet, or adhere to, SLIPS by creating an ultra-low drag clot free surface, much like living endothelium does. FIG. 1 shows the porous or rough layer with the low surface energy, chemically inert, perfluorinated liquid, infiltrated around it. The perfluorinated oil may be held in place by the features of SLIPS structures. This combination leads to a physically smooth, ultra-repellant, and chemically homogeneous lubricating film on the surface of the substrate because the porous structure holds the low energy fluid in place. The presence of the physical roughness of the porous material not only induces the complete wetting of the lubricating fluid, but can also provide additional adhesion for the lubricating fluid within the porous solid. Thin lubricating film minimizes surface inhomogeneities, reduces retention forces, and enhances fluid mobility along SLIPS, not unlike the lipid bilayer in the endothelial cell membrane. As a result, the drag forces on fluid in contact with SLIPS are minimal, and the fluid remains highly mobile on SLIPS. The lubricating film is generated through a fluid infiltration process induced by the porous materials.
[0242] In one or more aspect of the disclosed embodiments, SLIPS supports blood flow at 100 mL/hr for 1, 2, 3, 4, 5, or 10 hours or more without platelet activation or clotting. In other aspects, SLIPS supports blood flow at 500 mL/hr for 8, 10, 15, or 20 hours or more without platelet activation or clotting. In still other aspects, SLIPS supports blood flow at 1000 mL/hr for 12, 15, 20, or 24 hours or more without platelet activation or clotting. In other aspects, SLIPS supports blood flow at 1250 mL/hr for 24, 36, or 48 or more hours without platelet activation or clotting. In still other aspects, SLIPS supports blood flow at 1250 mL/hr for a period of days, months, or years.
Medical Devices
[0243] In other embodiments, SLIPS is incorporated into medical devices to prevent or reduce adhesion of proteins, microbes, blood, tissue, and the like.
[0244] Foreign surfaces associated with medical devices used in biomedical
environments are commonly contaminated with bacterial, viral, and fungal microorganisms. Contaminated medical-device surfaces can develop into persistent biofilm infection, and cause infection in other places of the body (Ratner (Ed.), Biomaterials Science, Academic Press (2004)). Currently, there are no materials that can prevent, delay, or reduce biological processes associated with protein adsorption, bacterial attachment, and inflammation response. Many materials or coatings, such as heparinized surfaces and Teflon (PTFE), prevent biochemical attachment and response by chemical or biochemical means. Because such materials and coatings rely on chemical or biochemical means to prevent biochemical attachment and response, the use of these materials is limited to certain environments. Moreover, the ability of these materials to repel fluids is limited to certain biological species.
[0245] Medical devices and biomedical implants in the body can cause injury to the tissue surrounding the device or implant. Inflammation, wound healing, plaque disposition, and foreign body response are common reactions to these injuries. Medical devices and implants can cause chronic inflammation, formation of granulation tissue, and an end-stage healing response of fibrosis or fibrous encapsulation (Ratner (Ed.), Biomaterials Science, Academic Press (2004)). However, no device or coating exists that prevents these injuries from occurring.
[0246] Various attempts have been made to coat catheter surfaces with nontoxic antiseptic or antimicrobial drug, or to incorporate such a substance into the catheter material itself (Crnich et al., 2002). These anti-bacterial surfaces have been based on the principle of incorporating compounds such as Ag-particle composite structures, antiseptics, and antibiotics. However, these approaches are ultimately limited in their effectiveness due to the limitations antibiotic species to diffuse from the material, as demonstrated in the large number of infections associated with medical instruments (Crnich 2002, Gristina 1987).
[0247] For example, catheters, cannulas, and shunts are commonly used inside and outside the body to allow drainage, administration of fluids or gases, or access by surgical instruments. They can be temporary or permanent {e.g., indwelling catheter). These medical devices can be made of a range of polymers, including silicone rubber, latex, and thermoplastic elastomers. Bacterial infection and colonization of catheters and cannulas and shunts often cause serious related medical conditions such as sepsis (Crnich, C.J. & G. Maki, D.G. The Promise of Novel Technology for the Prevention of Intravascular Device- Related Bloodstream Infection. II. Long-Term Devices. Clinical Infectious Diseases 34: 1362-1368 (2002)).
[0248] Other problems include inflammation and wound response. Stents commonly fail or malfunction because of infection or clogging (Tuli, S., Drake, J., Lawless, J., Wigg, M. & Lamberti-Pasculli, M. Risk factors for repeated cerebrospinal shunt failures in pediatric patients with hydrocephalus. J. Neurosurg. 92:31-38 (2000); Noetzel, M.J. & Baker, R.P. Shunt fluid examination: risks and benefits in the evaluation of shunt malfunction and infection. J. Neurosurg. 61 :328-332 (1984)).
[0249] Further, stents are also prone to bacterial contamination that can cause serious infections in the body. A stent is inserted into a natural passage or conduit in the body to prevent or counteract a disease-induced, localized flow constriction. It can also be used to temporarily hold a natural conduit open during surgery. Stents are often heparinized to reduce thrombosis and the effects of bacterial infection. However, despite this precaution, problems associated with clot formation, infection, wound response, and bacterial colonization persist (Garg, N., Garg, R., Gordon, C, Singh, R. & Singh, A. Acute Coronary Syndrome Caused by Coronary Artery Mycotic Aneurysm Due to Late Stent Infection Localized With Radiolabeled Autologous Leukocyte Imaging. Clin. Nucl. Med. 34:753-755 (2009); Dieter, R.S. Coronary artery stent infection. Catheter. Cardio. Inte. 62:281-281 (2004); Dieter, R.S. Coronary artery stent infection. Clin. Cardiol. 23:808-810 (2000); Hearn, A.T., et al. Endovascular stent infection with delayed bacterial challenge. American Journal of Surgery 174:157-159 (1997)).
[0250] Still other medical devices and implants cause problems associated with adhesion and attachment. Artificial heart valves, ventricular assist devices (VAD), and total artificial hearts (TAHs) often cause bacterial infection, endocarditis, and general inflammation (Cribier, A., et al. Percutaneous transcatheter implantation of an aortic valve prosthesis for calcific aortic stenosis - First human case description. Circulation 106:3006- 3008 (2002), Dismukes, et al. Prosthetic valve endocarditis. Analysis of 38 cases.
Circulation 48:365-377 (1973); Karchmer, A.W., et al. Staphylococcus epidermidis causing prosthetic valve endocarditis: microbiologic and clinical observations as guides to therapy. Ann Intern Med 98:447-455 (1983); Gristina, A.G., et al. Biomaterial-centered sepsis and the total artificial heart. Microbial adhesion vs tissue integration. JAMA 259:870-874 (1988)).
[0251] Adhesion, attachment, and wound responses often occur when biosensors and bioelectrodes are implanted in the body. The useful life of in vivo biosensors is typically limited due to infection, fouling, and inflammatory response (Wilson, G.S. & Gifford, R. Biosensors for real-time in vivo measurements. Biosens. Bioelectron. 20:2388-2403 (2005); Reichert, W.M., Koschwanez, H.E., Yap, F.Y. & Klitzman, B. In vitro and in vivo characterization of porous poly-L-lactic acid coatings for subcutaneously implanted glucose sensors. Journal of Biomedical Materials Research Part A 87A:792-807 (2008); Munro, W.A., Thomas, C.L.P., Simpson, I., Shaw, J. & Dodgson, J. Deterioration of pH electrode response due to biofilm formation on the glass membrane. Sensor Actuat B-Chem 37:187- 194 (1996)).
[0252] Also, pacemakers, and bioelectrodes, such as neural electrodes, also face frequent problems of infection, fouling and inflammatory response (S. Karnam, et al.
Mycobacterium phlei, a previously unreported cause of pacemaker infection: Thinking outside the box in cardiac device infections. Cardiology Journal 17 (2010); Sohail, M.R., et al. Risk factor analysis of permanent pacemaker infection. Clin Infect Dis 45: 166-173
(2007) ).
[0253] Endoscopes are difficult to clean and sterilize, and therefore present issues related to the transfer of bacterial, fungal, or viral infection from one patient to another (Beilenhoff, U., et al. ESGE-ESGENA guideline: Cleaning and disinfection in
gastrointestinal endoscopy Update 2008. Endoscopy 40:939-957 (2008); Banerjee, S., et al. Infection control during GI endoscopy. Gastrointest Endosc 67:781-790 (2008)). Further, endotracheal tubes, ventilators, and associated ventilator tubing are typically contaminated with persistent bacterial biofilms, and thus require frequent cleaning and replacement (Afessa, B., et al. Association Between a Silver-Coated Endotracheal Tube and Reduced Mortality in Patients With Ventilator- Associated Pneumonia. Chest 137: 1015-1021 (2010)).
[0254] Additionally, the success of implanted in vivo drug delivery devices is often limited by biofouling processes within the body, which reduces effectiveness of drug delivery (Bhardwaj, U, et al. A review of the development of a vehicle for localized and controlled drug delivery for implantable biosensors. J Diabetes Sci Technol 2: 1016-1029
(2008) ; Voskerician, G., et al. Biocompatibility and biofouling of MEMS drug delivery devices. Biomaterials 24: 1959-1967 (2003)).
[0255] SLIPS are used to prevent, reduce, or delay various fluids and other biological materials from wetting surfaces and particles from adhering to surfaces. For example, SLIPS can be incorporated into a microfluidic device, which controls the flow of minute amounts of fluids or gases (e.g., a lab-on-a-chip), for manipulating biological fluids. SLIPS surfaces are useful for preventing, reducing, or delaying inflammatory responses, blood coagulation, antifouling, and adhesion of other products of biological origin in and on devices including wound dressings catheters, stents, and other biomedical devices (e.g., stents, dialysis machines, central veno-venous hemofiltration device, extracorporeal membrane oxygenation equipment, and linking catheters), so that devices can support flow of fluids without permitting wetting of fluids, attachment, or adhesion of particles (see, e.g., FIG. 22A-B). Surfaces of medical instruments and medical devices attract a variety of biological adsorption events and biological responses that are difficult to prevent, reduce, and control. SLIPS can be applied to medical instruments and medical devices to reduce, prevent, or mediate processes associated with protein adsorption, cell attachment, bacterial infection, and inflammatory response.
[0256] For example, SLIPS can be used in wound care, including wounds caused by, e.g., cuts, bruises, punctures, scrapes, tears, and burns. In one embodiment, SLIPS is used to prevent or reduce further damage to damaged skin and to oxygenate the tissue that the SLIPS surface covers. One aspect of this embodiment is burn wound care. Burn wounds become hypoxic because of the layer of damaged tissue. Current burn treatments involve exposing the damaged tissue to high levels of oxygen. This can be accomplished in, e.g., a hyperbaric chamber. However, such wounds must either be covered by a wound dressing, which prevents or reduces the damaged tissue from being exposed to much needed oxygen, or be left exposed and vulnerable to infection. A SLIPS-treated wound dressing that has been infused with oxygenated lubricating fluid can be used to both protect the wound from infection caused by exposure to the environment without adhering to the wound, and provide the wound with oxygen to promote healing.
Medical/ Surgical Instruments
[0257] An important consequence of bacterial contamination and population of surfaces is the infection of surgical instruments, biomedical materials and prosthetics such as catheters (Costerton, J.W., et al. Bacterial biofilms in nature and disease. Ann. Rev.
Microbiol. 41 :435-464 (1987); Gristina, A.G., Dobbins, J.J., Giammara, B., Lewis, J.C. & DeVries, W.C. Biomaterial-centered sepsis and the total artificial heart. Microbial adhesion vs tissue integration. JAMA 259:870-874 (1988)). Bloodstream infection caused by surgical instrument-related bacterial contamination is a frequent and serious complication associated with procedures involving catheters and implants (Costerton et al, 1987;
Gristina, 1988). Such infections trigger an immune response in the body, which can lead to inflammation of the infection site.
[0258] Surgical instruments and intravascular devices (IVD) such as catheters have many potential sources for infection. The adherence of microorganisms to catheter surfaces is among the most important characteristics associated with the pathogenesis of infection caused by catheter use. Even a single bacterium cell that successfully adheres to surface can develop into a robust and infectious bacterial film and cause disease. Therefore an effective strategy for prevention or reduction of bacterial adhesion is needed.
Wound Dressings [0259] In another embodiment, SLIPS is incorporated into a wound dressing. SLIPS surfaces do not permit adhesion of proteins or cells when contacted with biological fluids. Moreover, perfluorocarbons have a high solubility for oxygen (Clark, Leland C; Gollan, F. Science 152(3720): 1755-56 (1966); Shaffer, T.H. et al, Pulmonol. 14: 102-109 (1992)). Thus, a wound dressing that incorporates SLIPS with, e.g., a perfluorocarbon substrate, provides a breathable surface that prevents adhesion of proteins or cells to promote faster wound healing (see, e.g., FIG. 23).
EXAMPLES
[0260] The following examples are presented for the purpose of illustration only and are not intended to be limiting.
Example 1
[0261] A set of SLIPS was fabricated to repel fluids spanning a broad range of surface tensions. To generate roughness, two types of porous solids were tested. The porous solids were periodically ordered and random: (i) arrays of nanoposts functionalized with a low- surface-energy polyfluoroalkyl silane, and (ii) a random network of Teflon nano fibres distributed throughout the bulk substrate (FIG. 17). Low-surface-tension perfluorinated liquids (e.g. FC-70, 7B = 17.1 mN/m; or Dupont Krytox® oils) that are non- volatile and immiscible with both aqueous and hydrocarbon phases and therefore able to form a stable, slippery interface with substrates (i.e.,
Figure imgf000067_0001
> 0 and E2 > 0) for a variety of polar and non- polar liquids including water, acids and bases, alkanes, alcohols, and ketones (FIG. 15 and FIG. 17) were chosen for the lubricating fluid. The SLIPS were generated through liquid infiltration into the porous materials, which resulted in a homogeneous and nearly molecularly smooth surface with a roughness of ~1 nm.
[0262] Each of these SLIPS exhibited extreme fluid repellency as signified by very low contact angle hysteresis (CAH, ΑΘ < 2.5°, FIG. 17 and FIG. 18A) and by very low sliding angles (a < 5° for droplet volume > 2 μί) against fluids of surface tension ranging from -17.2 ±0.5 mN/m (i.e., n-pentane) to 72.3 ±0.3 mN/m (i.e., water). CAH, the difference between the advancing and receding contact angles of a moving droplet, and sliding angle, the surface tilt required for droplet motion, directly characterize resistance to mobility; the low values therefore confirm a lack of pinning, consistent with a nearly defect-free surface. Based on the measured CAH and droplet volume (~4.5 μί), the estimated fluid retention force on SLIPS was 0.83±0.22 μΝ, n = 6. This performance was nearly an order of magnitude better than the state-of-the-art lotus-leaf-inspired omniphobic surfaces, whose fluid retention forces are of the order of 5 μΝ for low-surface-tension fluids (i.e., 7A < 25 mN/m) at similar fluid volumes. Moreover, the f uid-repellency of SLIPS was insensitive to texture geometry (FIG. 18A), provided that the lubricating layer covered the textures. Additionally, unlike lotus-based omniphobic surfaces where CAH depends on fluid surface tension and increases dramatically upon decrease of surface tension (FIG. 18A), such a dependence was absent for SLIPS due to the chemical homogeneity and physical smoothness of the fluid-fluid interface.
Example 2
[0263] The disclosed surfaces provide an ultra-smooth surface capable of preventing, reducing, or delaying surface wetting of fluids that come into contact with SLIPS.
[0264] An experiment was conducted in which the difference in surface adhesion of blood on PDMS was compared to that of an oil-infiltrated PTFE surface. 0.75 mL of fresh whole blood from a human subject was used, without the addition of heparin. The whole blood was pipetted onto four surfaces, one consisted of microstructured PTFE (Teflon; 1 μιη pore size) impregnated with perfluorinated oil (FC-70), the second consisted of untreated microstructured PTFE which served as the control, the third surface was untreated glass, and the fourth surface was untreated PDMS. FIG. 11 shows sequential images of the blood sample being added to PDMS (FIG. 11 A) and microstructured PTFE impregnated with perfluorinated oil (FIG. 11B). The surfaces made of PDMS (FIG. 11 A), microstructured PTFE (FIG. 12D), and glass (FIG. 12A), all allowed the blood sample to wet the surfaces and rapidly coagulate and adhere to these materials. The SLIPS that consisted of microstructured PTFE impregnated with perfluorinated oil (FIG. 11B) caused the blood sample to immediately bead into droplets and slide along SLIPS.
[0265] Referring to FIG. 13, subsequent analysis of these surfaces using optical (FIGS. 12(A)(i), 12(B)(i)) and scanning (FIGS. 12(A)(ii), 12(B)(ii)) electron microscopy, to show that while blood species such as cells, platelets, and proteins are visibly deposited on the untreated glass, PDMS, and PTFE control surfaces, there is nothing visible on the oil- infiltrated PTFE material. Thus, this 'fluid-like' surface appears to be extremely effective at preventing or reducing adhesion of platelets and fibrin clot formation when in contact with fresh unheparinized human blood.
Example 3 [0266] Experiments using 2 μιη polystyrene particles showed that force of adhesion to slippery surfaces was extremely low, such that the particles were easily dragged by a fluid/air boundary interface across SLIPS, and concentrated into the center of a drying droplet instead of leaving a 'coffee ring' deposition.
Example 4
[0267] Experiments were conducted to determine whether fluid from SLIPS leach into the surrounding biological fluid. A nanostructured post array surface (2 μιη tall posts, 300 nm diameter, 0.9 μιη spacing) with infiltrated perfluorinated oil (Fluorinert FC-70) was integrated into a microfluidic system. Deionized water flowed into the channel at a rate of 12 mL/min (i.e., 720 mL/hr) for 5 minutes. It was found that the perfluorinated oil remained intact on the nanostructured surface. The slipperiness of the surface was examined by putting a droplet of decane on the surface. If decane applied to the surface maintains its mobility on the surface, then the lubricants remain attached on the structured surface. However, if decane remains pinned on the surface, the lubricant layer has not been maintained. Leaching can also be monitored by extracting fluid that has passed over SLIPS into a fluorinated solvent followed by followed by chromatography and mass spectrometry and 19F-NMR.
[0268] Defining maximum leaching of the infiltrated fluid as the ratio between the total amounts of the perfluorinated oil infiltrated the surface and the volume of water processed in the microfluidic system, the maximum leaching was < 0.2%. Because perfluorocarbons are already approved by the Food and Drug Administration as blood substitutes, leaching of this amount of oil is expected to be harmless. The effective viscosity can be increased to reduce the amount of leaching while maintaining the 'fluid- like' surface that resists blood clot attachment.
Example 5
[0269] The slippery surfaces produced in accordance with the present methods showed excellent prevention of attachment and/or facilitation of low-force detachment of mature bacterial biofilm incubated on the surface. Specifically, this capability is demonstrated for Pseudomonas aeruginosa, a human opportunistic pathogen, and one of the most common nosocomial infections in the lining of catheters and the lungs of cystic fibrosis patients.
[0270] The surface was fabricated by wicking 100 of various commercial fluids satisfying criteria for a lubricating fluid into 30 mm round Teflon filter membranes with 0.2 μιη pore size, which were then mounted onto standard polystyrene Petri dishes. Atop the slippery surfaces, 2 mL tryptone broth puddles for 24 hours that were inoculated at 1% with Pseudomonas aeruginosa preculture were deposited and statically incubated. The bacteria formed a mature biofilm during this timeframe, and the slime-like matrix binding the constituent cells tends to gel the puddle.
[0271] The slippery surfaces produced in accordance with the present disclosure caused the slimy mass to readily slide off when tilted, as shown in FIG. 19, even at tilt angles below 10°. The effective slide-off removal of biofilm slime on the slippery surfaces produced in accordance with the present disclosure contrasts to the adhesion and pinning of the basal layer of slime on unfilled 0.2 μιη Teflon filters (left of FIG. 19) as well as on fluorosilanized super hydrophobic silicon micro/nanostructure arrays (right of FIG. 19), whose fluid repellency properties failed during the conditioning film and slime production of biofilm.
[0272] In addition to the visually apparent slide -off of biofilm slime, the slippery surfaces produced in accordance with the present disclosure showed nearly no adherent bacteria on the surfaces. Any remaining adherent bacteria was fixed with 5%
glutaraldehyde in phosphate buffered saline, permeabilized, and marked with a nucleic acid stain for fluorescent cell imaging. Fluorescent microscopy revealed a lack of biofilm structures or any microcolonies remaining on the slippery surfaces produced in accordance with the present methods following 24 hour incubation, as shown in FIG. 20. In contrast, significant remaining biomass was left on the unfilled 0.2 μιη Teflon filters as well as on three different fluorosilanized super hydrophobic silicon micro/nanostructure arrays (submicron posts and 10 μιη and 5 μιη "brick wall" patterns).
Example 6
[0273] The slippery surfaces produced in accordance with the present disclosure can be designed to be nontoxic by appropriate selection of the lubricating fluid, enabling applications with medical and environmental requirements. Among the commercial fluids already available, eight products that can satisfy the requirements for a lubricating fluid were screened and five candidates were identified for low toxicity (see FIG. 21). The toxicity screening assay was based on adding 1% and 0.01% of each commercial product to 10 mL aliquots of tryptone broth, which were inoculated with 1% initial seeding concentration of Pseudomonas aeruginosa (PA- 14) preculture and incubated at 37° C overnight in an orbital shaker. The shaken culture was serially diluted, plated, and incubated for colony forming unit (CFU) quantification. Significantly reduced CFU at the 1% concentration versus 0.01% concentration of FC70, Krytox 100, and Perfluorodecalin indicated an inhibitive effect and screened out these products for toxicity-sensitive applications. The remaining five products— Krytox 103/104/105 and FG40/45— are viable candidates for slippery fluid surfaces designed to minimize bacterial adhesion as well as toxicity.
Example 7
[0274] Teflon and silicon wafer SLIPS surfaces prepared in accordance with the present disclosure were shown to prevent bacterial attachment.
SLIPS fabrication
[0275] To prepare SLIPS, lubricating liquid (Dupont Krytox® 100 and 103) was added onto the porous solids, Teflon membranes with average pore sizes of > 200 nm and about 60 - 80 μιη thick (Sterlitech Corporation, WA, USA), to form an over-coated layer. The fluid spread spontaneously onto the whole substrate through capillary wicking.
Silicon Microstructure Array Fabrication
[0276] Superhydrophobic microstructure arrays were fabricated on a 4" silicon wafer by the Bosch process (M. Sugawara, e.a., Plasma Etching: Fundamentals and Applications . Series on semiconductor science and technology. Vol. 7. 1998, New York: Oxford
University Press). The microstructures consisted of four types of geometries: d = 500 nm HAR nanoposts, 2 μιη pitch; d = 1 μιη HAR microposts, p = 3 μιη; 5 μιη T-shaped microposts; and 10 μιη T-shaped microposts. The wafer was rinsed with EtOH, oxygen plasma treated for 30 seconds, and was rendered hydrophobic by putting the sample in a vacuum desiccator overnight with a glass vial containing 0.2 mL heptadecafiuoro-1,1,2,2- tetrahydrodecyltrichlorosilane (Gelest Inc).
Bacterial Preparation and Growth
[0277] Bacterial strains Pseudomonas aeruginosa PA14, Staphylococcus aureus SCOl, and Escherichia coli ZK2686 were each grown in LB medium (EMD LB Broth Miller) overnight at 37°C in loosely capped tubes on an orbital shaker to the stationary phase. This LB preculture was then seeded at 1% concentration in one of the following: TB growth medium (BD Bacto Tryptone) for P. aeruginosa; TSB medium supplemented with 0.5% glucose and 3% NaCl for S. aureus; or M9 medium for E. coli. These cultures were incubated on the bench at room temperature during experiments.
Flow Cell Setup [0278] A Tygon tube of inner diameter 1/8" was mounted in a peristaltic pump (Cole Parmer) and connected via hose barb fittings (World Precision Instruments) to a dual- chamber 3D-printed flow cell (chamber dimensions 1 = 10 cm, w = 1 cm, h = 1 mm).
[0279] The tubing was configured to allow flow in series through the two chambers. The bottom surface and sidewalls of each chamber were lined with press-fit porous Teflon membrane; one was infused with Krytox 103 to create a SLIPS and the other was left untreated as a control. Bacterial culture was pumped into each tube until the loop was full and trapped air had been eliminated though a bubble escape, after which the pump was operated at 10 mL/min.
Toxicity Screening
[0280] Shaken cultures of 1% P. aeruginosa in TB were grown in triplicate with 1% by volume of the following reagents: Krytox 100, Krytox 103, Perfluorodecalin, FC70, bleach, and 0.1% of AgN03 and glutaraldehyde. Background samples containing only media and reagents were also prepared, as well as control cultures without added reagents. Samples were incubated in an orbital shaker at 37 °C at 200 rpm. Optical density measurements at 550 nm were taken at 3, 6, 9, and 30 hours on a Perkin Elmer Lambda 40 UV-Vis spectrometer. Optical densities were normalized by subtracting backgrounds, i.e., the reagents in TB only.
Imaging and Analysis
[0281] For fluorescence imaging of attached bacterial cells, the PTFE substrates mounted in the flow cell were removed, gently rinsed in phosphate buffered saline (PBS) (lx) (Lonza Biowhittaker), and the adherent bacteria were fixed by 5% glutaraldehyde solution for at least 1 hour. 0.01% Triton XI 00 in PBS (PBST) was used to permeabilized the bacteria membranes over 15 minutes, after which the cells were stained with 0.5 μΜ SYTOX green nucleic acid stain (Invitrogen) in PBST for 30 minutes. Imaging was performed on a Leica DMX microscope.
[0282] To analyze the fluorescence intensity of the micrographs from the control and SLIPS flow cell substrates, the average intensity image of each sample's micrograph set was generated in ImageJ and the average [(R+G+B)/3] pixel value and standard deviation were computed for each average intensity image.
Biofilm quantification by crystal violet staining [0283] PTFE substrates were carefully sectioned with a scalpel into 3 x 3 cm segments, removed from the flow cell, gently rinsed in PBS, and stained by 0.1% crystal violet for 20 minutes. The stained samples were rinsed in a DIW bath and the bound crystal violet on each was eluted into 4 mL of 100% EtOH. Absorbance values at 590 nm were measured on a Perkin Elmer Lambda 40 UV-Vis spectrometer.
Prevention of Biofilm Attachment/ Formation
[0284] In a simple test scheme, Pseudomonas aeruginosa TB culture was deposited in puddles that were statically grown upon three surface typologies, two of which are shown in FIG. 36A. A porous PTFE membrane (0.2 μιη pore size) served as a flat, conventional low-adhesive control surface; a fluorosilanized patterned silicon wafer (not shown) featuring four different high-aspect-ratio micropost arrays presented superhydrophobicity, the capacity to repel and roll off water; and a PTFE membrane infused with Krytox-103 provided a SLIPS liquid slippery surface. After 48 hours of room temperature growth, the viable cell concentration of the imposed bacterial cultures on both surfaces was on the order of 108 mL"1. The bacteria were fixed and stained, and the fluorescence micrographs of resulting growth are shown in FIG. 36A, insets. While robust and uniform biofilm coverage was observed on both flat PTFE and superhydrophobic silicon (not shown), only sparse and isolated cells were seen on the SLIPS (see, e.g., FIG. 36C).
[0285] The test surfaces were manually tilted to compare the adhesion of the macroscopic biofilm slime. Biofilm grown on the control and superhydrophobic substrates showed complete wetting of the surface and left a film of slime on the PTFE as it was tilted. In contrast, biofilm on the SLIPS substrate slid readily without leaving any slime film or other visible residue behind. Biofilm growing in contact with the bare polystyrene Petri dish at the edge of the SLIPS remained pinned. However, it was not attached to the SLIPS substrate underneath: when part of the pinned puddle was disconnected from the edge and manipulated toward the center, it became fully mobile.
[0286] The contact line pinning characteristics of the surfaces (i.e., SLIPS and porous Teflon) were characterized by monitoring the evaporation dynamics of the bacterial culture droplets as well as the stains that remained on the surfaces upon drying. In the absence of pinning, the droplet should follow a nearly constant contact angle mode of evaporation without the formation of a coffee ring stain. [0287] These hypotheses were consistent with observations of the bacteria droplet' s evaporation on SLIPS. The absence of the coffee ring formation also indicated that the adhesion of the bacteria on the SLIPS was small compared to the forces imparted by the meniscus of the droplet, and it was demonstrated that the dried biofilm was easily removed from SLIPS by adhesive tape. In contrast, an evaporating droplet on the porous Teflon was strongly pinned, leading to a constant contact area mode of evaporation which also resulted in the formation of an irremovable coffee ring. These demonstrations of biofilm non- attachment to SLIPS and resisting 3.5 x 108 mL"1 bacterial liquid were consistent with both macroscopic and microscopic quantification data obtained herein.
[0288] Most submerged biofilm formation occurs under various flow conditions, e.g., in plumbing, ship hulls, catheters, and the like. Accordingly, biofilm attachment was studied on test surfaces lining a dual 3D-printed flow cell, through which the bacterial culture was continuously circulated by a peristaltic pump. Under flow conditions of 10 mL/min and ~1 cm/s, both a control PTFE and SLIPS surface were exposed in parallel to PA14 bacterial culture for 24 hour, 48 hour, and 7-day (168 hour) periods. Photographs of the two substrates following 48 hour growth show a yellowish, slimy control substrate and a visually uncontaminated SLIPS (FIG. 37A-B).
[0289] When tilted, biofilm slime spread on the control substrate but slid off the SLIPS. The attached biofilm was also stained by crystal violet for both visual inspection and quantitative biomass comparison by optical density. This macroscopic assay showed a dramatic difference between the substrates, as shown in (FIG. 37A-B). Indeed, crystal violet absorbance, proportional to the attached biomass, showed a 99.6% average reduction in biofilm on SLIPS as compared to control PTFE following the 7-day bacterial growth (FIG. 37C). By comparison, PEGylated titanium surfaces have been reported to reduce biofilm attachment by 86% after 5 hours of growth. The 48 hour growth of P. aeruginosa on Ti-coated glass slides was found to differ by < 19%> from PTFE, indicating similar long- term biofilm attachment on these two controls and thus a similar starting point for attachment reduction. Even if PEG desorption is assumed to not occur due to recent advances in multi-tether attachment, and even if no chemical masking occurred after 7 days submerged in bacterial culture, the 14% of remaining biofilm would be ~35 times more than on the SLIPS substrate. [0290] It is worth noting that the flow velocity in this experiment of ~1 cm/s is a conservatively gentle condition. In other environments where biofilms form, e.g., a ½-inch building water pipe or a ship hull at 20 knot cruise speed, typical flow velocities can be on the order of 1 m/s and 10 m/s respectively, with proportionately higher shear forces that would support biofilm removal from a SLIPS substrate. In biological and biomedical systems such as indwelling catheters, urinary tracts, and the human vascular system, flow velocities are also frequently more aggressive, on the order of 10-100 cm/s.
[0291] To characterize biofilm attachment to PTFE and SLIPS substrates on the microscale, multiple sample areas following 24 hour, 48 hour, and 7-day flow condition growths were fluorescently imaged. The results were analogous to those achieved in the initial static growth experiment. Biofilm on the control surface appeared characteristically dense, three-dimensional, and uniform (FIG. 38A-B). On the SLIPS, only sparse, isolated single cells or microcolonies were observed (FIG. 38C-D), and these appeared to be unattached, i.e., drifting with convective currents in the ambient fluid. This observation further supports that a liquid surface provides very low adhesion to the individual bacteria or micro-colonies. The average fluorescence intensities of 20 representative fields of view per substrate were computed as numeric pixel averages [(R+G+B)/3]. While not fully capturing intensity from out-of-focus biofilm structure on the control surface, the control values may be considered a lower bound; thus there is at least a 98% average intensity reduction in the fluorescence signal from PTFE to SLIPS, similar to the global
quantification by crystal violet.
[0292] To confirm that the dramatic biofilm attachment inhibition on SLIPS substrates was not a result of cytotoxicity of the SLIPS liquids, four of the liquids were screened for effects on bacterial growth. These included the Krytox 103 used for SLIPS fabrication in this study, as well as FC70, Krytox 100, and perfluorodecalin (traditionally used as a blood- substitute). The growth curves of P. aeruginosa were measured following growth in shaken TB cultures— thereby assuring uniform exposure— with 1% and 0.1% concentrations of each SLIPS liquid. As seen in FUG, 38E, optical densities showed statistically
indistinguishable bacterial growth at 3, 6, 9, and 30 hours for all tested SLIPS liquids and concentrations as compared to the control culture. Equivalent concentrations of three negative controls—silver nitrate (a common antiseptic compound and representative of silver impregnated surfaces), bleach, and glutaraldehyde (commonly used for clinical tool sterilization)— were also tested. As expected, all three exhibited massive toxicity within these timeframes, in contrast to the null effect of the SLIPS liquids.
[0293] The attachment of two other clinically important, pathogenic, biofilm-forming species, Staphylococcus aureus (SCOl) and Escherichia coli (ZK2686) was studied for 48 hours under identical flow conditions. SLIPS performance comparable to that of
Pseudomonas aeruginosa was observed. As shown in FIG. 39A-B, S. aureus attachment was reduced by 97.2% and E. coli by 96% versus PTFE. While neither of these species formed as robust biofilms as did P. aeruginosa, their final attachment to SLIPS was similarly low based on crystal violet absorbance. Visualized by fluorescence in FIG. 39D- F, dense uniform coverage and sparse, isolated cells respectively attached to the control surface and SLIPS. This indicated that SLIPS 's anti-bio film function was nonspecific and spanned phylogenetically diverse pathogenic bacteria.
[0294] Thus, it is apparent that the bacteria were presented with a smooth liquid "surface," and as such, were unable to anchor to the surface via pili and other cellular mechanisms as would be possible on a solid surface. The SLIPS lubricating liquid was also immiscible with the aqueous bacterial medium (Liquid A), and the surface tension at the interface (on the order of 50 mN/m) was likely difficult for bacteria to penetrate, even with bacterial surfactant production. Indeed, bacteria embedding within the SLIPS was not observe, which indicates that bacteria could not swim through the interface. Without access to the solid material beneath the lubricating liquid, bacteria were unable to attach, and remained subject to ambient flow and thus subject to passive removal.
Example 8
[0295] SLIPS can be used to coat medical devices, including tubing, to prevent, reduce, or delay blood clot formation and cell adhesion. FIG. 31 A shows the experimental setup in included a 24" loop of SLIPS tubing (ePTFE+FC70) and a 24" loop of standard silicone tubing (0.250"ID) as a control. The preformed ePTFE tube was saturated with PFC FC70 oil, and encased in a silicone tube to help prevent oil loss and evaporation. Both the ePTFE SLIPS tube and the silicone tube control were filled with 12 mL of the diluted blood. A 24" preformed ePTFE tube was saturated with PFC FC-70, and encased in a silicone tube where it interfaced with a peristaltic pump and Tygon tubing in other regions to create an FC-70 reservoir. Fresh whole human blood (12 mL, diluted 1 : 1 with saline) free of anticoagulant was pumped through both sets of tubing at 3,000 mL/hr. After 20 minutes, there was no sign of clotting within the entire length of tubing (FIG. 30 and FIG. 31B). There was some staining (surface adsorption) in the region of the peristaltic pump roller contact (FIG. 30B), suggesting potential mechanical damage and infiltration of blood into the ePTFE at this site. After 30 min of flow there was no sign of clotting and minimal surface adhesion within the entire length of SLIPS tubing (FIG. 31C). In the silicone tubing there were signs of clotting and significant surface adhesion within the tube.
[0296] As will be apparent to one of ordinary skill in the art from a reading of this disclosure, aspects of the present disclosure can be embodied in forms other than those specifically disclosed above. The particular embodiments described above are, therefore, to be considered as illustrative and not restrictive. Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, numerous equivalents to the specific embodiments described herein. The scope of the invention is as set forth in the appended claims and equivalents thereof, rather than being limited to the examples contained in the foregoing description.
[0297] What is claimed is:

Claims

1. An article for repelling a biological material, comprising: a lubricating fluid layer, wherein the lubricating fluid is immiscible with a biological material, the lubricating layer forming an ultra-smooth surface over a roughened solid substrate; wherein the lubricating fluid adheres to the substrate and the substrate is
preferentially wetted by the lubricating fluid, the solid substrate and lubricating fluid forming a slippery surface configured and arranged to contact a biological material.
2. The article of claim 1 , wherein the article satisfies the following condition yBxcos6>Bx - 7AXCOS( AX > 0 (el) wherein ^AX is the interfacial energies of the biological material with a surrounding medium; wherein yBx is the interfacial energies of the lubricating fluid with the surrounding medium; wherein ΘΑΧ is the equilibrium contact angle of the biological material on a flat solid surface immersed under the surrounding medium; and wherein 6½χ is the equilibrium contact angle of the liquid of the lubricating fluid on a flat solid surface immersed under the surrounding medium.
3. The article of claim 1 , wherein the article satisfies the following two conditions when the article is exposed to Medium X, where X is air/gas/water/immiscible biological material: ?(yBxCOs6>Bx - 7AXCOS6>AX) - 7AB > 0 (e2) ?(yBxCOs6>Bx - 7AXCOS6>AX) + 7AX - 7BX > 0 (e3) wherein ^AX is the interfacial energies of the biological material with a surrounding medium; wherein }¾x is the interfacial energies of the lubricating fluid with the surrounding medium; wherein }ΆΒ is the interfacial energies of the biological material and the lubricating fluid interface; wherein ΘΑΧ is the equilibrium contact angle of the biological material on a flat solid surface immersed under the surrounding medium; wherein 6½χ is the equilibrium contact angle of the lubricating fluid on a flat solid surface immersed under the surrounding medium wherein R is a roughness factor of the roughened surface.
4. The article of claim 1 , wherein the substrate is a roughened surface comprising a porous material.
5. The article of claim 1 , wherein the solid substrate is electrically conductive, non- conductive, magnetic, non-magnetic, elastic, non-elastic, light sensitive, or not light sensitive.
6. The article of claim 4, wherein porous material includes a solid substrate having a plurality of holes, three-dimensionally interconnected network of holes and one or more materials, or random array of fibrous materials.
7. The article of claim 1 , wherein microparticles or nanoparticles are applied to a flat substrate to form a roughened, porous substrate.
8. The article of claim 1 , wherein the substrate is silanized.
9. The article of claim 1 , wherein the lubricating fluid infiltrates the substrate by capillary action.
10. The article of claim 7, wherein the substrate is roughened using photolithography, projection lithography, e-beam writing or lithography, depositing nanowire arrays, growing nanostructures on the surface of a substrate, soft lithography, replica molding, solution deposition, solution polymerization, electropolymerization, electrospinning, electroplating, vapor deposition, layered deposition, rotary jet spinning of polymer nanofibers, contact printing, etching, transfer patterning, microimprinting, self-assembly, boehmite (γ-ΑΙΟ(ΟΗ)) formation, spray coated, and combinations thereof.
11. The article of claim 1 , wherein the substrate consists of a fluoropolymer.
12. The article of claim 1, wherein substrate is selected from the group consisting of a polydimethylsiloxane, polypropylene, polytetrafluoroethylene, and combinations thereof.
13. The article of claim 12, wherein the lubricating fluid is selected from the group consisting of liquid silicone elastomers, vegetable or mineral oil, liquid hydrocarbons, and combinations thereof.
14. The article of claims 12 or 13, wherein the biological material is selected from the group consisting of a simple aqueous fluid, a complex aqueous fluid, a solidified fluid, and combinations thereof.
15. The article of claims 1, wherein the biological material does not adhere to the surface.
16. The article of claim 1, wherein the substrate is selected from the group consisting of fluoro-silanized metals, fluoro-silanized natural polymers, fluoro-silanized synthetic polymers, and combinations thereof.
17. The article of claim 16, wherein the lubricating fluid is a perfluorinated fluid.
18. The article of claims 16 or 17, wherein biological material a non-perfluorinated fluid.
19. The article of claim 1, wherein the biological material is selected from the group consisting of whole blood, plasma, serum, sweat, feces, urine, saliva, tears, vaginal fluid, prostatic fluid, gingival fluid, amniotic fluid, intraocular fluid, cerebrospinal fluid, seminal fluid, sputum, ascites fluid, pus, nasopharengal fluid, wound exudate fluid, aqueous humour, vitreous humour, bile, cerumen, endolymph, perilymph, gastric juice, mucus, peritoneal fluid, pleural fluid, sebum, vomit, and combinations thereof.
20. The article of claim 1, wherein the biological material is a solution or suspension containing bacteria selected from the group consisting of Actinobacillus {e.g. , Actinobacillus actinomycetemcomitans), Acinetobacter {e.g., Acinetobacter baumannii), Aeromonas, Bordetella (e.g., Bordetella pertussis, Bordetella bronchiseptica, and Bordetella
parapertussis), Brevibacillus, Brucella, Bacteroides (e.g., Bacteroides fragilis),
Burkholderia (e.g., Burkholderia cepacia and Burkholderia pseudomallei), Borelia (e.g., Borelia burgdorfen), Bacillus (e.g., Bacillus anthracis and Bacillus subtilis), Campylobacter (e.g., Campylobacter jejuni), Capnocytophaga, Cardiobacterium (e.g., Cardiobacterium hominis), Citrobacter, Clostridium (e.g. , Clostridium tetani or Clostridium difficile), Chlamydia (e.g., Chlamydia trachomatis, Chlamydia pneumoniae, and Chlamydia psiffaci), Eikenella (e.g., Eikenella corrodens), Enterobacter, Escherichia (e.g., Escherichia coli), Francisella (e.g., Francisella tularensis), Fusobacterium, Flavobacterium, Haemophilus (e.g., Haemophilus ducreyi or Haemophilus influenzae), Helicobacter (e.g., Helicobacter pylori), Kingella (e.g., Kingella kingae), Klebsiella (e.g., Klebsiella pneumoniae), Legionella (e.g., Legionella pneumophila), Listeria (e.g., Listeria monocytogenes), Leptospirae, Moraxella (e.g., Moraxella catarrhalis), Morganella, Mycoplasma (e.g. , Mycoplasma hominis and Mycoplasma pneumoniae), Mycobacterium (e.g. , Mycobacterium tuberculosis or Mycobacterium leprae), Neisseria (e.g., Neisseria gonorrhoeae or Neisseria
meningitidis), Pasteurella (e.g., Pasteurella multocida), Proteus (e.g., Proteus vulgaris and Proteus mirablis), Prevotella, Plesiomonas (e.g., Plesiomonas shigelloides), Pseudomonas (e.g., Pseudomonas aeruginosa), Providencia, Rickettsia (e.g., Rickettsia rickettsii and Rickettsia typhi), Stenotrophomonas (e.g. , Stenotrophomonas maltophila), Staphylococcus (e.g., Staphylococcus aureus and Staphylococcus epidermidis), Streptococcus (e.g.,
Streptococcus viridans, Streptococcus pyogenes (group A), Streptococcus agalactiae (group B), Streptococcus bovis, and Streptococcus pneumoniae), Streptomyces (e.g., Streptomyces hygroscopicus), Salmonella (e.g., Salmonella enteriditis, Salmonella typhi, and Salmonella typhimurium), Serratia (e.g., Serratia marcescens), Shigella, Spirillum (e.g., Spirillum minus), Treponema (e.g., Treponema pallidum), Veillonella, Vibrio (e.g., Vibrio cholerae, Vibrio parahaemolyticus, and Vibrio vulnificus), Yersinia (e.g., Yersinia enter ocolitica, Yersinia pestis, and Yersinia pseudotuberculosis), Xanthomonas (e.g., Xanthomonas maltophilia) and combinations thereof.
21. The article of claim 1, wherein the biological material is a solution or suspension containing fungi selected from the group consisting of a member of the genus Aspergillus (e.g., Aspergillus flavus, Aspergillus fumigatus, Aspergillus glaucus, Aspergillus nidulans, Aspergillus niger, and Aspergillus terreus), Blastomyces dermatitidis, Candida (e.g. , Candida albicans, Candida glabrata, Candida tropicalis, Candida parapsilosis, Candida krusei, and Candida guillermondii), Coccidioides immitis, Cryptococcus (e.g., Cryptococcus neoformans, Cryptococcus albidus, and Cryptococcus laurentii), Histoplasma capsulatum var. capsulatum, Histoplasma capsulatum var. duboisii, Paracoccidioides brasiliensis, Sporothrix schenckii, Absidia corymbifera; Rhizomucor pusillus, Rhizopus arrhizous, and combinations thereof.
22. The article of claim 1, wherein the biological material is a solution or suspension containing viruses selected from the group consisting of cytomegalovirus (CMV), dengue, Epstein-Barr, Hantavirus, human T-cell lymphotropic virus (HTLV I/II), Parvovirus, hepatitides (e.g., hepatitis A, hepatitis B, and hepatitis C), human papillomavirus (HPV), human immunodeficiency virus (HIV), acquired immunodeficiency syndrome (AIDS), respiratory syncytial virus (RSV), Varicella zoster, West Nile, herpes, polio, smallpox, yellow fever, rhinovirus, coronavirus, Orthomyxoviridae (influenza viruses) (e.g.,
Influenzavirus A, Influenzavirus B, Influenzavirus C, Isavirus and Thogotovirus), and combinations thereof.
23. The article of claim 1, wherein the biological material is a solution or suspension containing particles selected from the group consisting of normal cells, diseased cells, parasitized cells, cancer cells, foreign cells, stem cells, and infected cells, microorganisms, viruses, virus-like particles, bacteria, bacteriophages, proteins, cellular components, cell organelles, cell fragments, cell membranes, cell membrane fragments, viruses, virus-like particles, bacteriophage, cytosolic proteins, secreted proteins, signaling molecules, embedded proteins, nucleic acid/protein complexes, nucleic acid precipitants, chromosomes, nuclei, mitochondria, chloroplasts, flagella, biominerals, protein complexes, and minicells.
24. The article of claim 1, wherein the biological material is a natural or synthetic solution used in medicines, intravenous solutions, pharmaceutical manufacturing, or medication delivery systems.
25. The article of claim 1, wherein the lubricating fluid is capable of self-healing by wicking back to the damaged region of the substrate after physical damage of the substrate to form the ultra-smooth surface.
26. The article of claim 25, wherein a recovery time for self-healing occurs in less than 50 ms, 60 ms, 70 ms, 80 ms, 90 ms, 100 ms, 110 ms, 120 ms, 130 ms, 140 ms, 150 ms, 160 ms, 170 ms, 180 ms, 190 ms, 200 ms, 210 ms, 220 ms, 230 ms, 240 ms, 250 ms, 1 second, 5 seconds 10 seconds, 30 seconds, 60 seconds, 90 seconds, or 120 seconds or more.
27. The article of claim 1, wherein the substrate has a plurality of holes, three- dimensionally interconnected network of holes and one or more materials, or random array of fibrous materials.
28. The article of claim 1, wherein the substrate consists of a material selected from the group consisting of polymers, metals, sapphire, glass, diamond, graphite, black carbon, or ceramics.
29. The article of claim 1, wherein the substrate is a hemocompatible material.
30. The article of claim 1, wherein the substrate is a polymer selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylfluoride, polyvinylidene fluoride, and fluorinated ethylene propylene.
31. The article of claim 1 , wherein the lubricating fluid has a density greater than the density of the biological material.
32. The article of claim 1, wherein the lubricating fluid has a density greater than lubricating fluid has a density that is more than 1.0 g/cm3, 1.6 g/cm3, or 1.9 g/cm3.
33. The article of claim 1, wherein the lubricating fluid comprises a fluid selected from the group consisting of tertiary perfluoroalkylamines,perfluorotri-n-butylamine,
perfluoroalkylsulfides, perf uoroalkylsulfoxides, perf uoroalkylethers, perfluorocycloethers, perfluoropolyethers, perfluoroalkylphosphines, perfluoroalkylphosphineoxides, and combinations thereof.
34. The article of claim 1, wherein the lubricating fluid prevents, reduces, or delays adhesion, coagulation, or clot formation of biological materials.
35. An article having a repellant surface, the article comprising:
a solid substrate comprising a roughened surface; and a lubricating fluid wetting and adhering to the roughened surface to form a stabilized liquid overlayer, wherein the liquid covers the roughened surface, wherein the roughened surface and the lubricating liquid have an affinity for each other such that the lubricating liquid is substantially immobilized on the substrate.
36. A device capable of repelling a biological material, comprising: a lubricating fluid layer, wherein the lubricating fluid is immiscible with the biological material, the lubricating layer forming an ultra-smooth surface; and a solid substrate, wherein the lubricating fluid adheres to the substrate and the substrate is preferentially wetted by the lubricating fluid, the solid substrate and lubricating fluid forming a slippery surface configured and arranged to contact a biological material, wherein the device satisfies the following condition yBxcos6>Bx - 7AXCOS( AX > 0 (el) wherein ^AX is the interfacial energies of the biological material with a surrounding medium; wherein yBx is the interfacial energies of the lubricating fluid with the surrounding medium; wherein ΘΑΧ is the equilibrium contact angle of the biological material on a flat solid surface immersed under the surrounding medium; and wherein 6½χ is the equilibrium contact angle of the liquid of the lubricating fluid on a flat solid surface immersed under the surrounding medium.
37. The device of claim 36, wherein the device further satisfies the following two conditions when the article is exposed to Medium X, where X is air/gas/water/immiscible biological material: ?(yBxCOs6>Bx - 7AXCOS6>AX) - 7AB > 0 (e2) ?(yBxCOs6>Bx - 7AXCOS6>AX) + 7AX - 7BX > 0 (e3) wherein ^AX is the interfacial energies of the biological material with a surrounding medium; wherein }¾x is the interfacial energies of the lubricating fluid with the surrounding medium; wherein }ΆΒ is the interfacial energies of the biological material and the lubricating fluid interface; wherein ΘΑΧ is the equilibrium contact angle of the biological material on a flat solid surface immersed under the surrounding medium; wherein 6½χ is the equilibrium contact angle of the lubricating fluid on a flat solid surface immersed under the surrounding medium wherein the solid substrate is a roughened surface, and R is a roughness factor of the roughened surface.
38. The device of claim 36, wherein the solid substrate is silanized.
39. The device of claim 36, wherein the solid substrate is electrically conductive, non- conductive, magnetic, non-magnetic, elastic, non-elastic, light sensitive, or not light sensitive.
40. A device selected from the group of cannula, connector, catheter, needle, capillary tube, tubing, syringe and combinations thereof, wherein at least a portion of the device comprises the article of any one of claims 1-34.
41. A device selected from the group consisting of a slide, plate, film, work surface, well, well plate, Petri dish, tile, jar, flask, beaker, vial, test tube, column, container, cuvette, bottle, drum, vat, tank, and combinations thereof, wherein at least a portion of the device comprises the article of claim 1-34.
42. A device selected from the group consisting of a clamp, skin hook, cuff, retractor, shunt, needle, capillary tube, tubing, and combinations thereof, wherein at least a portion of the device comprises the article of claim 1-34.
43. A device selected from the group consisting of an endotracheal tube, ventilator, associated ventilator tubing, drug delivery vehicle, intrauterine device, syringe, endoscope, and combinations thereof, wherein at least a portion of the device comprises the article of claim 1-34.
44. A device selected from the group consisting of an organ, artificial organ, implant, and combinations thereof, wherein at least a portion of the device comprises the article of claim 1-34.
45. A device selected from the group consisting of a biosensor, diagnostic devices used in and on biological and non-biological material, biological microelectromechanical devices (bioMEMs), bioelectrode, and combinations thereof, wherein at least a portion of the device comprises the article of claim 1-34.
46. A device comprising a wound dressing, wherein at least a portion of the device comprises the article of claim 1-34.
47. A method of preventing, reducing, or delaying adhesion, adsorption, surface- mediated clot formation, or coagulation of a biological material onto a device in contact therewith, comprising: providing the device comprising a low-adhesion surface having a substrate comprising a roughened surface; and a lubricating fluid wetting and adhering to the roughened surface to form a stabilized liquid overlayer, wherein the liquid covers the roughened surface, and wherein the roughened surface and the lubricating liquid have an affinity for each other such that the lubricating liquid is substantially immobilized on the substrate; and
contacting the biological sample to the low-adhesion surface.
48. The method of claim 47, wherein said providing and contacting are carried out to satisfy the following condition yBxcos6>Bx - 7AXCOS( AX > 0 (el) wherein ^AX is the interfacial energies of the biological material with a surrounding medium; wherein yBx is the interfacial energies of the lubricating fluid with the surrounding medium; wherein ΘΑΧ is the equilibrium contact angle of the biological material on a flat solid surface immersed under the surrounding medium; and wherein ΘΒΧ is the equilibrium contact angle of the liquid of the lubricating fluid on a flat solid surface immersed under the surrounding medium.
49. The method of claim 47, wherein said providing and contacting are carried out to satisfy the following two conditions when the slippery surface is exposed to Medium X, where X is air/gas/water/immiscible biological material: ?(yBxCOs6>Bx - 7AXCOS6>AX) - 7AB > 0 (e2) ?(yBxCOs6>Bx - 7AXCOS6>AX) + 7AX - 7BX > 0 (e3) wherein ^AX is the interfacial energies of the biological material with a surrounding medium; wherein }¾x is the interfacial energies of the lubricating fluid with the surrounding medium; wherein }ΆΒ is the interfacial energies of the biological material and the lubricating fluid interface; wherein ΘΑΧ is the equilibrium contact angle of the biological material on a flat solid surface immersed under the surrounding medium; wherein 6½x is the equilibrium contact angle of the lubricating fluid on a flat solid surface immersed under the surrounding medium; wherein the solid substrate is a roughened surface, and
R is a roughness factor of the roughened surface.
50. The method of claim 47, wherein the method inhibits, mediates, or prevents inflammation, wound healing, plaque disposition, or foreign body response.
51. The method of claim 47, wherein the method further prevents, reduces, or delays bacterial contamination.
52. The method of claim 47, wherein the biological material is contacted with the surface at a fluid impact pressures is on the order of 103-107 Pa.
53. The method of claim 47, wherein the solid substrate is silanized.
54. The method of claim 47, wherein the surface is selected from the group consisting of a cannula, connector, catheter, needle, capillary tube, tubing, syringe and combinations thereof.
55. The method of claim 47, wherein the device is selected from the group consisting of a slide, plate, film, work surface, well, well plate, Petri dish, tile, jar, flask, beaker, vial, test tube, column, container, cuvette, bottle, drum, vat, tank, and combinations thereof.
56. The method of claim 47, wherein the device is selected from the group consisting of a clamp, skin hook, cuff, retractor, shunt, needle, capillary tube, tubing, and combinations thereof.
57. The method of claim 47, wherein the device is selected from the group consisting of an endotracheal tube, ventilator, associated ventilator tubing, drug delivery vehicle, intrauterine device, syringe, endoscope, and combinations thereof.
58. The method of claim 47, wherein the device is selected from the group consisting of an organ, artificial organ, implant, and combinations thereof.
59. The method of claim 47, wherein the device is selected from the group consisting of a biosensor, diagnostic devices used in and on biological and non-biological material, biological microelectromechanical devices (bioMEMs), bioelectrode, and combinations thereof.
60. The method of claim 47, wherein the device is a wound dressing.
61. The method of claim 47, wherein the substrate is preferentially wetted by the lubricating fluid.
62. The method of claim 47, wherein the solid substrate is electrically conductive, non- conductive, magnetic, non-magnetic, elastic, non-elastic, light sensitive, or not light sensitive.
63. The method of claim 47, wherein the lubricating fluid infiltrates the substrate by capillary action.
64. The method of claim 47, wherein the substrate is a roughened surface comprising a porous material.
65. The method of claim 47, wherein microparticles or nanoparticles are applied to a flat substrate to form a roughened, porous substrate.
66. The method of claim 65, wherein microparticles or nanoparticles are applied to the substrate using photolithography, projection lithography, e-beam writing or lithography, depositing nanowire arrays, growing nanostructures on the surface of a substrate, soft lithography, replica molding, solution deposition, solution polymerization,
electropolymerization, electrospinning, electroplating, vapor deposition, layered deposition, rotary jet spinning of polymer nanofibers, contact printing, etching, transfer patterning, microimprinting, self-assembly, boehmite (γ-ΑΙΟ(ΟΗ)) formation, spray coated, and combinations thereof.
67. The method of claim 47, wherein the substrate consists of a fluoropolymer.
68. The method of claim 47, wherein the biological material is selected from the group consisting of a simple aqueous fluid, a complex aqueous fluid, a solidified fluid, and combinations thereof.
69. The method of claim 47, wherein the biological material is a fluid selected from the group consisting of whole blood, plasma, serum, sweat, feces, urine, saliva, tears, vaginal fluid, prostatic fluid, gingival fluid, amniotic fluid, intraocular fluid, cerebrospinal fluid, seminal fluid, sputum, ascites fluid, pus, nasopharengal fluid, wound exudate fluid, aqueous humour, vitreous humour, bile, cerumen, endolymph, perilymph, gastric juice, mucus, peritoneal fluid, pleural fluid, sebum, vomit, and combinations thereof.
70. The method of claim 47, wherein the biological material is a solution or suspension containing bacteria selected from the group consisting of Actinobacillus {e.g. , Actinobacillus actinomycetemcomitans), Acinetobacter (e.g., Acinetobacter baumannii), Aeromonas, Bordetella (e.g., Bordetella pertussis, Bordetella bronchiseptica, and Bordetella
parapertussis), Brevibacillus, Brucella, Bacteroides (e.g., Bacteroides fragilis),
Burkholderia (e.g., Burkholderia cepacia and Burkholderia pseudomallei), Borelia (e.g., Borelia burgdorfen), Bacillus (e.g., Bacillus anthracis and Bacillus subtilis), Campylobacter (e.g., Campylobacter jejuni), Capnocytophaga, Cardiobacterium (e.g., Cardiobacterium hominis), Citrobacter, Clostridium (e.g. , Clostridium tetani or Clostridium difficile), Chlamydia (e.g., Chlamydia trachomatis, Chlamydia pneumoniae, and Chlamydia psiffaci), Eikenella (e.g., Eikenella corrodens), Enterobacter, Escherichia (e.g., Escherichia coli), Francisella (e.g., Francisella tularensis), Fusobacterium, Flavobacterium, Haemophilus (e.g., Haemophilus ducreyi or Haemophilus influenzae), Helicobacter (e.g., Helicobacter pylori), Kingella (e.g., Kingella kingae), Klebsiella (e.g., Klebsiella pneumoniae), Legionella (e.g., Legionella pneumophila), Listeria (e.g., Listeria monocytogenes), Leptospirae, Moraxella (e.g., Moraxella catarrhalis), Morganella, Mycoplasma (e.g. , Mycoplasma hominis and Mycoplasma pneumoniae), Mycobacterium (e.g. , Mycobacterium tuberculosis or Mycobacterium leprae), Neisseria (e.g., Neisseria gonorrhoeae or Neisseria
meningitidis), Pasteurella (e.g., Pasteurella multocida), Proteus (e.g., Proteus vulgaris and Proteus mirablis), Prevotella, Plesiomonas (e.g., Plesiomonas shigelloides), Pseudomonas (e.g., Pseudomonas aeruginosa), Providencia, Rickettsia (e.g., Rickettsia rickettsii and Rickettsia typhi), Stenotrophomonas (e.g. , Stenotrophomonas maltophila), Staphylococcus (e.g., Staphylococcus aureus and Staphylococcus epidermidis), Streptococcus (e.g.,
Streptococcus viridans, Streptococcus pyogenes (group A), Streptococcus agalactiae (group B), Streptococcus bovis, and Streptococcus pneumoniae), Streptomyces (e.g., Streptomyces hygroscopicus), Salmonella (e.g., Salmonella enteriditis, Salmonella typhi, and Salmonella typhimurium), Serratia (e.g., Serratia marcescens), Shigella, Spirillum (e.g., Spirillum minus), Treponema (e.g., Treponema pallidum), Veillonella, Vibrio (e.g., Vibrio cholerae, Vibrio parahaemolyticus, and Vibrio vulnificus), Yersinia (e.g., Yersinia enter ocolitica, Yersinia pestis, and Yersinia pseudotuberculosis), Xanthomonas (e.g., Xanthomonas maltophilia) and combinations thereof.
71. The method of claim 47, wherein the biological material is a solution or suspension containing fungi selected from the group consisting of a member of the genus Aspergillus (e.g., Aspergillus flavus, Aspergillus fumigatus, Aspergillus glaucus, Aspergillus nidulans, Aspergillus niger, and Aspergillus terreus), Blastomyces dermatitidis, Candida (e.g. , Candida albicans, Candida glabrata, Candida tropicalis, Candida parapsilosis, Candida krusei, and Candida guillermondii), Coccidioides immitis, Cryptococcus (e.g., Cryptococcus neoformans, Cryptococcus albidus, and Cryptococcus laurentii), Histoplasma capsulatum var. capsulatum, Histoplasma capsulatum var. duboisii, Paracoccidioides brasiliensis, Sporothrix schenckii, Absidia corymbifera; Rhizomucor pusillus, Rhizopus arrhizous, and combinations thereof.
72. The method of claim 47, wherein the biological material is a solution or suspension containing viruses selected from the group consisting of cytomegalovirus (CMV), dengue, Epstein-Barr, Hantavirus, human T-cell lymphotropic virus (HTLV I/II), Parvovirus, hepatitides (e.g., hepatitis A, hepatitis B, and hepatitis C), human papillomavirus (HPV), human immunodeficiency virus (HIV), acquired immunodeficiency syndrome (AIDS), respiratory syncytial virus (RSV), Varicella zoster, West Nile, herpes, polio, smallpox, yellow fever, rhinovirus, coronavirus, Orthomyxoviridae (influenza viruses) {e.g.,
Influenzavirus A, Influenzavirus B, Influenzavirus C, Isavirus and Thogotovirus), and combinations thereof.
73. The method of claim 47, wherein the biological material is a solution or suspension containing particles selected from the group consisting of normal cells, diseased cells, parasitized cells, cancer cells, foreign cells, stem cells, and infected cells, microorganisms, viruses, virus-like particles, bacteria, bacteriophage, proteins, cellular components, cell organelles, cell fragments, cell membranes, cell membrane fragments, viruses, virus-like particles, cytosolic proteins, secreted proteins, signaling molecules, embedded proteins, nucleic acid/protein complexes, nucleic acid precipitants, chromosomes, nuclei,
mitochondria, chloroplasts, flagella, biominerals, protein complexes, and minicells.
74. The method of claim 47 , wherein the biological material is a natural or synthetic solution used in medicines, intravenous solutions, pharmaceutical manufacturing, or medication delivery systems.
75. The method of claim 47, wherein the lubricating fluid is capable of self-healing by wicking back to the damaged region of the substrate after physical damage of the substrate to form an ultra- smooth surface.
76. The method of claim 75, wherein a recovery time for self-healing occurs in less than 50 ms, 60 ms, 70 ms, 80 ms, 90 ms, 100 ms, 110 ms, 120 ms, 130 ms, 140 ms, 150 ms, 160 ms, 170 ms, 180 ms, 190 ms, 200 ms, 210 ms, 220 ms, 230 ms, 240 ms, 250 ms, 1 second, 5 seconds 10 seconds, 30 seconds, 60 seconds, 90 seconds, or 120 seconds or more.
77. The method of claim 47, wherein the substrate has a plurality of holes, three- dimensionally interconnected network of holes and one or more materials, or random array of fibrous materials.
78. The method of claim 47, wherein the substrate consists of a material selected from the group consisting of polymers, metals, sapphire, glass, diamond, graphite, black carbon, or ceramics.
79. The method of claim 47, wherein the substrate is a hemocompatible material.
80. The method of claim 47, wherein the substrate is a polymer selected from the group consisting of polytetrafluoroethylene, polyvinylfluoride, polyvinylidene fluoride, and fluorinated ethylene propylene.
81. The method of claim 47, wherein the lubricating fluid has a density greater than the density of the biological material.
82. The method of claim 47, wherein the lubricating fluid has a density greater than lubricating fluid has a density that is more than 1.0 g/cm3, 1.6 g/cm3, or 1.9 g/cm3.
83. The method of claim 47, wherein the lubricating fluid comprises a fluid selected from the group consisting of tertiary perfluoroalkylamines,perfluorotri-n-butylamine, perfluoroalkylsulfides, perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocycloethers, perfluoropolyethers, perfluoroalkylphosphines, and perfluoroalkylphosphineoxides, and combinations thereof.
84. An optically transparent device that prevents, reduces, or delays adhesion of biological material, the device comprising:
a roughened surface, wherein the surface is a transparent window;
a lubricating fluid that wets and adheres to the roughened surface to form an over- coated layer; and
wherein the roughened surface has a greater affinity towards the lubricating fluid as compared to a biological material; and wherein the index of refraction of the lubricating liquid is substantially similar to the index of refraction of the roughened surface; and
wherein the lubricating liquid and the biological material are substantially chemically inert with each other.
85. The device of claim 84, wherein the device is a biological sensor window.
86. An article having a low adhesion surface for preventing or reducing biofilm attachment, comprising: a solid substrate having a roughened surface;
a lubricating fluid that adheres to and preferentially wets the substrate to form a liquid upper surface, the liquid upper surface configured and arranged to contact a biological material of interest,
wherein the lubricating fluid is immiscible with the biological material, and wherein the biological material exhibits little or no adhesion to the article.
PCT/US2012/021929 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof WO2012100100A2 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
EP12705182.9A EP2665783A2 (en) 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof
KR1020137021610A KR101966272B1 (en) 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof
PCT/US2012/021929 WO2012100100A2 (en) 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof
CN201280012210.1A CN103703085B (en) 2011-01-19 2012-01-19 Smooth fluid injection porous surface and its biological applications
JP2013550592A JP6563173B2 (en) 2011-01-19 2012-01-19 Porous surface infused with slippery liquid and its biological use
AU2012207206A AU2012207206B2 (en) 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof
CA2825012A CA2825012C (en) 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof
US13/980,858 US9932484B2 (en) 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof
AU2016200048A AU2016200048B2 (en) 2011-01-19 2016-01-06 Slippery liquid-infused porous surfaces and biological applications thereof
AU2017239543A AU2017239543B2 (en) 2011-01-19 2017-10-05 Slippery liquid-infused porous surfaces and biological applications thereof
US15/944,619 US10550272B2 (en) 2011-01-19 2018-04-03 Slippery liquid-infused porous surfaces and biological applications thereof
US16/780,792 US10982100B2 (en) 2011-01-19 2020-02-03 Slippery liquid-infused porous surfaces and biological applications thereof

Applications Claiming Priority (15)

Application Number Priority Date Filing Date Title
US201161434217P 2011-01-19 2011-01-19
US61/434,217 2011-01-19
US201161466352P 2011-03-22 2011-03-22
US61/466,352 2011-03-22
US201161470973P 2011-04-01 2011-04-01
US61/470,973 2011-04-01
US201161496883P 2011-06-14 2011-06-14
US61/496,883 2011-06-14
US201161509488P 2011-07-19 2011-07-19
US61/509,488 2011-07-19
US201161529734P 2011-08-31 2011-08-31
US61/529,734 2011-08-31
US201161538100P 2011-09-22 2011-09-22
US61/538,100 2011-09-22
PCT/US2012/021929 WO2012100100A2 (en) 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US13/980,858 A-371-Of-International US9932484B2 (en) 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof
US15/944,619 Continuation US10550272B2 (en) 2011-01-19 2018-04-03 Slippery liquid-infused porous surfaces and biological applications thereof

Publications (2)

Publication Number Publication Date
WO2012100100A2 true WO2012100100A2 (en) 2012-07-26
WO2012100100A3 WO2012100100A3 (en) 2012-10-18

Family

ID=49919888

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/021929 WO2012100100A2 (en) 2011-01-19 2012-01-19 Slippery liquid-infused porous surfaces and biological applications thereof

Country Status (8)

Country Link
US (3) US9932484B2 (en)
EP (1) EP2665783A2 (en)
JP (1) JP6563173B2 (en)
KR (1) KR101966272B1 (en)
CN (1) CN103703085B (en)
AU (3) AU2012207206B2 (en)
CA (1) CA2825012C (en)
WO (1) WO2012100100A2 (en)

Cited By (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013022467A3 (en) * 2011-08-05 2013-06-13 Massachusetts Institute Of Technology Devices incorporating a liquid - impregnated surface
WO2013130118A1 (en) * 2012-02-29 2013-09-06 Massachusetts Institute Of Technology Articles and methods for modifying condensation on surfaces
US8535779B1 (en) 2012-03-23 2013-09-17 Massachusetts Institute Of Technology Self-lubricating surfaces for food packaging and food processing equipment
WO2014078867A1 (en) * 2012-11-19 2014-05-22 Massachusetts Institute Of Technology Apparatus and methods employing liquid-impregnated surfaces
WO2014110511A1 (en) 2013-01-11 2014-07-17 President And Fellows Of Harvard College Protective barriers for preventing or reducing transfer of microorganisms
WO2014012078A3 (en) * 2012-07-13 2014-07-24 President And Fellows Of Harvard College Selective wetting and transport surfaces
WO2014145528A1 (en) * 2013-03-15 2014-09-18 President And Fellows Of Harvard College Antifouling microfluidic devices and methods thereof
WO2014149465A1 (en) * 2013-03-15 2014-09-25 President And Fellows Of Harvard College Omniphobic paper devices
WO2014197667A1 (en) * 2013-06-05 2014-12-11 The Gillette Company Razor components with novel coating
WO2014209441A3 (en) * 2013-03-13 2015-04-02 President And Fellows Of Harvard College Solidifiable composition for preparation of liquid-infused slippery surfaces and methods of applying
WO2014179283A3 (en) * 2013-04-29 2015-04-09 Gvd Corporation Liquid-impregnated coatings and devices containing the same
WO2015069820A1 (en) 2013-11-06 2015-05-14 The Procter & Gamble Company Easy to empty flexible containers
WO2015166191A1 (en) 2014-04-30 2015-11-05 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for purifying, cooling and separating a gaseous mixture and associated apparatus
WO2015179410A1 (en) * 2014-05-19 2015-11-26 President And Fellows Of Harvard College Robust cementitious materials with mobile liquid-infused barrier layer
US9254496B2 (en) 2011-08-03 2016-02-09 Massachusetts Institute Of Technology Articles for manipulating impinging liquids and methods of manufacturing same
JP2016507307A (en) * 2013-02-13 2016-03-10 カルティヒール(2009)リミティド Solid substrate for the reduction or prevention of cell and tissue attachment and angiogenesis
US9309162B2 (en) 2012-03-23 2016-04-12 Massachusetts Institute Of Technology Liquid-encapsulated rare-earth based ceramic surfaces
US9427679B2 (en) 2013-04-16 2016-08-30 Massachusetts Institute Of Technology Systems and methods for unipolar separation of emulsions and other mixtures
US9498934B2 (en) 2013-02-15 2016-11-22 Massachusetts Institute Of Technology Grafted polymer surfaces for dropwise condensation, and associated methods of use and manufacture
US9585757B2 (en) 2013-09-03 2017-03-07 Massachusetts Institute Of Technology Orthopaedic joints providing enhanced lubricity
US9625075B2 (en) 2012-05-24 2017-04-18 Massachusetts Institute Of Technology Apparatus with a liquid-impregnated surface to facilitate material conveyance
US9630224B2 (en) 2012-07-13 2017-04-25 President And Fellows Of Harvard College Slippery liquid-infused porous surfaces having improved stability
US9932484B2 (en) 2011-01-19 2018-04-03 President And Fellows Of Harvard College Slippery liquid-infused porous surfaces and biological applications thereof
US9932482B2 (en) 2011-01-19 2018-04-03 President And Fellows Of Harvard College Slippery surfaces with high pressure stability, optical transparency, and self-healing characteristics
US9947481B2 (en) 2014-06-19 2018-04-17 Massachusetts Institute Of Technology Lubricant-impregnated surfaces for electrochemical applications, and devices and systems using same
US9963597B2 (en) 2012-07-12 2018-05-08 President And Fellows Of Harvard College Slippery self-lubricating polymer surfaces
US9968965B2 (en) 2014-04-25 2018-05-15 Toyo Seikan Group Holdings, Ltd. Structure having liquid film on the surface thereof
US10011800B2 (en) 2012-07-13 2018-07-03 President And Fellows Of Harvard College Slips surface based on metal-containing compound
EP3326806A4 (en) * 2015-07-17 2018-08-08 Nissan Motor Co., Ltd. Antifouling structure and method for producing same
US10099027B2 (en) 2014-01-24 2018-10-16 Cole Research & Design Oral suction device
EP3292586A4 (en) * 2015-05-07 2018-12-05 Landsdowne Laboratories, Inc. Biocompatible hydrophobic batteries, systems and methods related thereto
US10221321B2 (en) 2015-08-28 2019-03-05 Battelle Memorial Institute Paintable hydrophobic and lubricant-infused surface coatings and processes for making and using same
US10391530B2 (en) 2013-09-27 2019-08-27 The Regents Of The University Of California Liquid-repellent surfaces made of any materials
CN110253873A (en) * 2019-04-24 2019-09-20 常州三提新材料有限公司 Equipment, method and the film obtained of micro-nano porous structure are generated on film
US10434542B2 (en) 2015-04-24 2019-10-08 The Penn State Research Foundation Slippery rough surfaces
EP3603577A1 (en) 2018-07-30 2020-02-05 Technische Universität Berlin Inertisation of surfaces of materials by functionalized perfluorinated molecules
US10577511B2 (en) 2016-01-20 2020-03-03 Battelle Memorial Institute Stretchable hydrophobic materials and methods for making the same
US10899933B2 (en) 2016-09-13 2021-01-26 Nissan Motor Co., Ltd. Antifouling structure
US10927005B2 (en) 2015-01-26 2021-02-23 The Regents Of The University Of California Method for manufacturing doubly re-entrant microstructures
FR3103492A1 (en) 2019-11-26 2021-05-28 Centre National De La Recherche Scientifique PROCESS FOR MANUFACTURING A SUBTRATE OF WHICH AT LEAST ONE SURFACE IS NON-ADHESIVE
FR3103397A1 (en) 2019-11-26 2021-05-28 Centre National De La Recherche Scientifique NON-STICK SURFACE AND USE IN ANTI-BIOFILM APPLICATIONS
WO2021105633A1 (en) 2019-11-26 2021-06-03 Structurys Biotech Method for producing a substrate having at least one non-stick surface
US11041058B2 (en) 2013-07-26 2021-06-22 Toyo Seikan Group Holdings, Ltd. Resin structure having a liquid layer on the surface thereof
US11058803B2 (en) 2012-05-24 2021-07-13 Massachusetts Institute Of Technology Medical devices and implements with liquid-impregnated surfaces
US11079141B2 (en) 2013-12-20 2021-08-03 Massachusetts Institute Of Technology Controlled liquid/solid mobility using external fields on lubricant-impregnated surfaces
US11105352B2 (en) 2012-06-13 2021-08-31 Massachusetts Institute Of Technology Articles and methods for levitating liquids on surfaces, and devices incorporating the same
US11168276B2 (en) 2015-08-28 2021-11-09 Battelle Memorial Institute Reinforced composites with repellent and slippery properties
EP3915377A1 (en) * 2020-05-26 2021-12-01 AgXX Intellectual Property Holding GmbH Antiseptic hybrid layer for local wound treatment
US11259918B2 (en) 2016-10-03 2022-03-01 Carena Healthcare Ltd Frame for an implantable medical device and a method of manufacturing a frame for an implantable medical device
US11266344B2 (en) 2016-09-21 2022-03-08 Samsung Electronics Co., Ltd. Method for measuring skin condition and electronic device therefor
US11291779B2 (en) 2016-07-15 2022-04-05 Koninklijke Philips N.V. Aerosolization device and an aerosol drug delivery device
CN114292593A (en) * 2022-01-17 2022-04-08 山东中凯华瑞工程材料有限公司 Nano micron and submicron micron spacing structure bionic all-hydrophobic material and preparation method thereof
WO2022127631A1 (en) * 2020-12-18 2022-06-23 南京鼓楼医院 Preparation method for ultra-smooth porous surface for lubricating oil infusion of medical catheter
EP4067448A1 (en) 2021-04-01 2022-10-05 Friedrich-Alexander-Universität Erlangen-Nürnberg Silicone- or fluorosilicone-coated solid substrates and process for their preparation
US11492500B2 (en) 2012-11-19 2022-11-08 Massachusetts Institute Of Technology Apparatus and methods employing liquid-impregnated surfaces
US11883558B2 (en) 2019-09-13 2024-01-30 Spotless Materials Inc. Formulations and processes to generate repellent surfaces on medical devices
US11998369B2 (en) 2021-04-12 2024-06-04 Freeflow Medical Devices Llc Packaging for medical devices coated with perfluorinated liquids or dispersions thereof

Families Citing this family (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2463181B (en) 2007-05-14 2013-03-27 Univ New York State Res Found Induction of a physiological dispersion response in bacterial cells in a biofilm
ES2513866T3 (en) 2009-05-13 2014-10-27 Sio2 Medical Products, Inc. Container coating and inspection
WO2013170052A1 (en) 2012-05-09 2013-11-14 Sio2 Medical Products, Inc. Saccharide protective coating for pharmaceutical package
US9458536B2 (en) 2009-07-02 2016-10-04 Sio2 Medical Products, Inc. PECVD coating methods for capped syringes, cartridges and other articles
US11624115B2 (en) 2010-05-12 2023-04-11 Sio2 Medical Products, Inc. Syringe with PECVD lubrication
EP2595764A1 (en) * 2010-07-19 2013-05-29 President and Fellows of Harvard College Hierarchically structured surfaces to control wetting characteristics
US9878101B2 (en) 2010-11-12 2018-01-30 Sio2 Medical Products, Inc. Cyclic olefin polymer vessels and vessel coating methods
US9272095B2 (en) 2011-04-01 2016-03-01 Sio2 Medical Products, Inc. Vessels, contact surfaces, and coating and inspection apparatus and methods
CN103930595A (en) 2011-11-11 2014-07-16 Sio2医药产品公司 Passivation, ph protective or lubricity coating for pharmaceutical package, coating process and apparatus
US11116695B2 (en) 2011-11-11 2021-09-14 Sio2 Medical Products, Inc. Blood sample collection tube
US10689178B2 (en) 2012-07-13 2020-06-23 Toyo Seikan Group Holdings, Ltd. Packing container having excellent slipping property for the content
JP6062199B2 (en) 2012-09-28 2017-01-18 ユニ・チャーム株式会社 Absorbent articles
WO2014071061A1 (en) 2012-11-01 2014-05-08 Sio2 Medical Products, Inc. Coating inspection method
US9670304B2 (en) * 2012-11-05 2017-06-06 Liang Wang Composite for preventing ice adhesion
US9903782B2 (en) 2012-11-16 2018-02-27 Sio2 Medical Products, Inc. Method and apparatus for detecting rapid barrier coating integrity characteristics
AU2013352436B2 (en) 2012-11-30 2018-10-25 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition on medical syringes, cartridges, and the like
US9764093B2 (en) 2012-11-30 2017-09-19 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition
CN110077686B (en) 2013-02-08 2020-10-09 东洋制罐集团控股株式会社 Container having excellent sliding property for fluid contents
KR101753676B1 (en) 2013-02-14 2017-07-04 도요세이칸 그룹 홀딩스 가부시키가이샤 Pouring tool exhibiting excellent slip properties for fluid substance
EP2961858B1 (en) 2013-03-01 2022-09-07 Si02 Medical Products, Inc. Coated syringe.
US9937099B2 (en) 2013-03-11 2018-04-10 Sio2 Medical Products, Inc. Trilayer coated pharmaceutical packaging with low oxygen transmission rate
CN110074968B (en) 2013-03-11 2021-12-21 Sio2医药产品公司 Coated packaging material
WO2014144926A1 (en) 2013-03-15 2014-09-18 Sio2 Medical Products, Inc. Coating method
EP2969257B1 (en) * 2013-03-15 2018-05-02 Liquiglide Inc. Apparatus having a durable liquid-impregnated surface.
US9850046B2 (en) * 2013-11-06 2017-12-26 The Procter & Gamble Company Flexible containers with vent systems
CA2927199C (en) 2013-11-06 2019-06-18 The Procter & Gamble Company Flexible containers having flexible valves
EP3693493A1 (en) 2014-03-28 2020-08-12 SiO2 Medical Products, Inc. Antistatic coatings for plastic vessels
US10226566B2 (en) * 2014-04-23 2019-03-12 Genadyne Biotechnologies, Inc. System and process for removing bodily fluids from a body opening
CN104310302A (en) * 2014-09-30 2015-01-28 中国科学院深圳先进技术研究院 Method for manufacturing super-smooth surface
US20160122677A1 (en) * 2014-10-30 2016-05-05 The Trustees Of Princeton University Liquid-Infused Surfaces Featuring Reduced Drag Characteristics, and Methods for Fabricating the Same
KR101971817B1 (en) 2015-04-10 2019-04-23 더 프록터 앤드 갬블 캄파니 Flexible container with product dispensing visualization
EP3280658A1 (en) 2015-04-10 2018-02-14 The Procter and Gamble Company Flexible containers with integral dispensing spout
JP5968491B1 (en) 2015-04-20 2016-08-10 東洋製罐株式会社 Structure having liquid film and method for producing the same
JP6587823B2 (en) 2015-04-24 2019-10-09 東洋製罐株式会社 Container with solid particles distributed on the surface
CN104759019A (en) * 2015-04-28 2015-07-08 贺鹏举 Lacrimal passage bypass rebuilding pipe
WO2016179588A1 (en) * 2015-05-07 2016-11-10 President And Fellows Of Harvard College Dynamic immiscible liquid interfaces for cell sheet detachment
JP6001726B1 (en) 2015-05-21 2016-10-05 東洋製罐株式会社 Structure having a gel-like coating on the surface
US10648298B2 (en) * 2015-07-01 2020-05-12 Shell Oil Company Method of expanding a tubular and expandable tubular
JP6069426B2 (en) 2015-07-09 2017-02-01 東洋製罐グループホールディングス株式会社 Container whose inner surface is formed of an olefin resin layer
US11801332B2 (en) * 2015-08-03 2023-10-31 The Administrators Of The Tulane Educational Fund Load-induced hydrodynamic lubrication of porous substrates
EP3337915B1 (en) 2015-08-18 2021-11-03 SiO2 Medical Products, Inc. Pharmaceutical and other packaging with low oxygen transmission rate
MX2018004199A (en) * 2015-10-05 2019-01-21 Bvw Holding Ag Low normal force retracting device comprising a microstructured surface.
WO2017094123A1 (en) 2015-12-01 2017-06-08 東洋製罐グループホールディングス株式会社 Package to be stored in low temperature environment and method of use therefor
JP6706419B2 (en) * 2016-03-14 2020-06-10 住友ゴム工業株式会社 Rubber tube and method for producing the same
WO2017165411A1 (en) * 2016-03-21 2017-09-28 Massachusetts Institute Of Technology Omniphobic materials for bio-applications
JP6598138B2 (en) * 2016-03-23 2019-10-30 日産自動車株式会社 Antifouling structure and automobile parts provided with the antifouling structure
US10557042B2 (en) * 2016-03-28 2020-02-11 Wisconsin Alumni Research Foundation Slippery liquid-infused porous surfaces that prevent microbial surface fouling
US20190136070A1 (en) * 2016-04-27 2019-05-09 President And Fellows Of Harvard College Anti-fouling endoscopes and uses thereof
WO2017199423A1 (en) 2016-05-20 2017-11-23 日産自動車株式会社 Soil-resistant structure and automobile component provided with said soil-resistant structure
EP3249004A1 (en) 2016-05-24 2017-11-29 Clariant International Ltd Release components to increase anti-adhesion properties of thermoplastic packaging material
CN109310805A (en) * 2016-06-16 2019-02-05 心脏起搏器股份公司 The hydrophiling and antifoulingization of the metal surface of enhancing
DE102016113956A1 (en) * 2016-07-28 2018-02-01 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Device with a structured coating
EP3496771B1 (en) 2016-08-09 2023-01-04 Cardiac Pacemakers, Inc. Functionalized peg for implantable medical devices
CN106245011B (en) * 2016-08-19 2019-01-04 南京理工大学 A kind of lyophoby superslide interface and preparation method thereof
CN106442701B (en) * 2016-11-28 2023-07-21 山东省分析测试中心 Mass spectrum imaging analysis method based on single-pixel solid-phase extraction technology and application thereof
CN106806038B (en) * 2017-03-21 2018-08-14 上海市第一人民医院 A kind of blood vessel merging object with super-hydrophobic oleophobic composite Nano coating
CA3060261A1 (en) * 2017-04-13 2018-10-18 LiquiGlide Inc. Durable lubricious surfaces
KR101985094B1 (en) * 2017-09-14 2019-05-31 고려대학교 산학협력단 Artificial metallic object and manufacturing method thereof
US11709155B2 (en) 2017-09-18 2023-07-25 Waters Technologies Corporation Use of vapor deposition coated flow paths for improved chromatography of metal interacting analytes
US11709156B2 (en) 2017-09-18 2023-07-25 Waters Technologies Corporation Use of vapor deposition coated flow paths for improved analytical analysis
CN107759818A (en) * 2017-09-30 2018-03-06 昆明理工大学 A kind of preparation method on superslide polytetrafluoroethylstephanoporate stephanoporate surface
WO2019078621A2 (en) 2017-10-17 2019-04-25 한양대학교 산학협력단 Coating composition for producing article having slippery surface
WO2019136401A1 (en) * 2018-01-05 2019-07-11 Freeflow Medical Devices Llc Extracorporeal membrane oxygenation apparatuses and methods of their preparation and use
CN108543116B (en) * 2018-05-02 2021-04-27 深圳市华异生物科技有限责任公司 Sodium alginate and gelatin composite hydrogel 3D islet scaffold and preparation method thereof
WO2019222644A1 (en) 2018-05-17 2019-11-21 Hollister Incorporated Methods of making sleeved hydrophilic catheter assemblies
DE102018208469B4 (en) * 2018-05-29 2024-02-08 Kautex Textron Gmbh & Co. Kg ARRANGEMENT AND METHOD FOR EMPTYING AT LEAST ONE LINE CONNECTED TO A LIQUID TANK
US11541105B2 (en) 2018-06-01 2023-01-03 The Research Foundation For The State University Of New York Compositions and methods for disrupting biofilm formation and maintenance
CN109504616B (en) * 2018-09-30 2020-06-30 中国石油大学(华东) Crude oil degrading bacterium and application thereof in petroleum pollution remediation
MX2021003780A (en) * 2018-10-02 2021-09-08 Harvard College Hydrophobic barrier layer for ceramic indirect evaporative cooling systems.
WO2020077160A1 (en) * 2018-10-11 2020-04-16 Freeflow Medical Devices Llc Fluoropolymer based anti-thrombotic coatings
CN109453966A (en) * 2018-10-24 2019-03-12 北京科技大学 A kind of the liquid autocrine superslide coating and preparation method of long-lasting protection
KR102255551B1 (en) * 2018-12-05 2021-05-24 한국세라믹기술원 SLIPS pollution prevention structure comprising self-assembled monolayer and manufacturing method thereof
WO2020197609A2 (en) * 2019-01-04 2020-10-01 Northwestern University Self-healing coating compositions
CN110052385A (en) * 2019-03-20 2019-07-26 湖北大学 The method on the stabilization superslide surface of fixed lubricant layer is prepared by grafting dimethyl silicone polymer brush
KR102277536B1 (en) * 2019-04-25 2021-07-15 동국대학교 산학협력단 Anti-biofouling implantable medical device and method of forming anti-biofouling film on surface of implantable medical device
CN109932354B (en) * 2019-05-06 2021-10-08 中山大学 In-situ separation and enrichment device for surface enhanced Raman spectroscopy trace analysis and application
WO2020236619A1 (en) * 2019-05-17 2020-11-26 Art, Ltd Improved intraocular lens
KR102222511B1 (en) * 2019-06-04 2021-03-03 (주)옵토레인 Well array for pcr
CN110201244B (en) * 2019-07-17 2022-09-20 山东百多安医疗器械股份有限公司 Lyophobic low functional catheter that glues
US11324581B2 (en) * 2019-08-24 2022-05-10 Conical Cover LLC Silicone prosthesis delivery apparatus and methods of use
CN110596429B (en) * 2019-10-11 2020-11-03 中国石油大学(北京) Characterization method for regulating and controlling oil drop mechanical behavior by block type polymer
CN110591980A (en) * 2019-10-22 2019-12-20 中国石油化工股份有限公司 Microbial compound inoculant for degrading high pour point oil and application thereof
CN110811944A (en) * 2019-12-13 2020-02-21 东华大学 Support system with super smooth surface of imitative pitcher plant
EP4090157A4 (en) 2020-01-13 2023-07-05 The Regents of The University of California Devices and methods for high-stability supercooling of aqueous media and biological matter
US11918936B2 (en) 2020-01-17 2024-03-05 Waters Technologies Corporation Performance and dynamic range for oligonucleotide bioanalysis through reduction of non specific binding
US11825845B2 (en) 2020-07-30 2023-11-28 Wisconsin Alumni Research Foundation Slippery liquid-infused porous surfaces that release hydrophilic and hydrophobic agents
CN112144287B (en) * 2020-09-28 2021-09-28 江南大学 Method for preparing super-smooth antifouling surface by grafting modified hollow microsphere with lubricating oil
CN112546434A (en) * 2020-12-11 2021-03-26 深圳先进技术研究院 Implantable flexible microelectrode array and preparation method thereof
CN112697661B (en) * 2020-12-25 2024-01-26 环必静(苏州)环境科技有限公司 Roller type water surface layer enriched organic matter concentration detection device and detection method thereof
WO2022173816A1 (en) * 2021-02-12 2022-08-18 University Of Georgia Research Foundation, Inc. Superhydrophobic antifouling coating compositions and applications thereof
CN113185578B (en) * 2021-04-25 2022-05-27 中国地质大学(武汉) Modular polypeptide-AIE probe MP, synthetic method thereof and kit containing modular polypeptide-AIE probe MP
EP4334024A1 (en) * 2021-05-05 2024-03-13 Salus Discovery, LLC Stable interface systems and compositions
CN113528010A (en) * 2021-08-27 2021-10-22 电子科技大学 Preparation and application of super-smooth coating with long-acting ice-thinning characteristic
CN114470340A (en) * 2022-01-25 2022-05-13 徐州工程学院 Functional liquid compounded porous medical catheter and preparation method thereof
CN115028888B (en) * 2022-05-12 2022-12-13 中国石油大学(华东) Underwater flexible anti-fouling skin device based on laser-induced bionic texturing
WO2023240276A1 (en) * 2022-06-09 2023-12-14 Volta Labs, Inc. Surface structure for fluid manipulation
US20240023543A1 (en) * 2022-07-20 2024-01-25 BioChoric, Inc. Method and apparatus for reducing excess pressure in isochoric systems
KR20240029653A (en) 2022-08-26 2024-03-06 포항공과대학교 산학협력단 Preparaion method of low-drag and antifouling surfaces inspired from the epidermis of marine life

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5476589A (en) 1995-03-10 1995-12-19 W. L. Gore & Associates, Inc. Porpous PTFE film and a manufacturing method therefor
WO2009048880A1 (en) 2007-10-09 2009-04-16 Dharan C K Hari Fiber-reinforced foamed resin structural composite materials and methods for producing composite materials

Family Cites Families (139)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL254721A (en) 1959-08-10
US3274007A (en) 1963-08-01 1966-09-20 Lockheed Aircraft Corp High-temperature resistant self-healing coating and method of application
JPS5126119A (en) 1974-08-27 1976-03-03 Mitsubishi Heavy Ind Ltd RINTENINSATSUKINIOKERU ORIKI
US4386170A (en) 1980-10-31 1983-05-31 Dow Corning Corporation Curable fluorinated silicone elastomer
JPS57134318A (en) 1981-02-12 1982-08-19 Nissan Motor Co Ltd Air mixing construction of air conditioner
JPS60259269A (en) 1984-06-04 1985-12-21 テルモ株式会社 Medical device and its production
EP0166998B1 (en) 1984-06-04 1991-05-08 TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION Medical instrument and method for making
FR2573079B1 (en) 1984-11-13 1987-08-14 Atochem FLUOROSILANES AND THEIR PREPARATION PROCESS
JPS6263219A (en) 1985-09-13 1987-03-19 Ibiden Co Ltd Sliding member consisting of seramic compound material
JPS6291560A (en) 1985-10-18 1987-04-27 Asahi Glass Co Ltd Lubricating resin composition
JPS62252477A (en) 1986-04-24 1987-11-04 Chugoku Toryo Kk Anti-icing paint composition
US4861511A (en) 1987-06-26 1989-08-29 Nalco Chemical Company Toilet bowl cleaner and stain-inhibiting composition
JPH01170932A (en) * 1987-12-25 1989-07-06 Nippon Sheet Glass Co Ltd Production with low-friction thin film
US5013717A (en) 1988-04-18 1991-05-07 Becton, Dickinson And Company Blood compatible, lubricious article and composition and method therefor
EP0361034A3 (en) 1988-09-28 1990-07-11 Siemens Aktiengesellschaft Ink writing head
US5091205A (en) 1989-01-17 1992-02-25 Union Carbide Chemicals & Plastics Technology Corporation Hydrophilic lubricious coatings
GB9026687D0 (en) 1990-12-07 1991-01-23 Vascutek Ltd Process for providing a low-energy surface on a polymer
DE69231787T2 (en) 1991-01-28 2001-08-02 Matsushita Electric Ind Co Ltd Medical article and process for its manufacture
CA2060294C (en) 1991-02-06 2000-01-18 Kazufumi Ogawa Chemically absorbed film and method of manufacturing the same
JPH04270649A (en) 1991-02-26 1992-09-28 Toray Ind Inc Release film
EP0501298B1 (en) 1991-02-27 1996-06-05 Matsushita Electric Industrial Co., Ltd. Self-lubricating device
FR2675377B1 (en) 1991-04-22 1995-02-03 Oreal POROUS MICROSPHERES COATED WITH PERFLUORINATED OIL, FLUORINATED SILICONE OIL OR SILICONE GUM AND THEIR USE IN COSMETICS.
WO1993015254A1 (en) 1992-01-27 1993-08-05 Daikin Industries, Ltd. Treatment agent for fiber product, method of treating fiber product, and fiber product treated thereby
JPH05229402A (en) 1992-02-19 1993-09-07 Railway Technical Res Inst Snow/ice icing preventing body
AU3663693A (en) 1992-02-21 1993-09-13 Ronald K. Dunton Poly(fluorinated ethylene) coatings
JPH05240251A (en) * 1992-02-28 1993-09-17 Ntn Corp Sintered oil retaining bearing
JP3387139B2 (en) 1992-03-31 2003-03-17 ソニー株式会社 Magneto-optical disk
JP2593080Y2 (en) 1992-12-21 1999-03-31 住友ベークライト株式会社 Medical tube introduction tool
CA2119286A1 (en) 1993-04-15 1994-10-16 Hubert S. Smith, Iii Internally lubricated elastomers for use in biomedical applications
DE4414982A1 (en) 1993-05-13 1994-11-17 Gen Electric Silicone pressure-sensitive adhesive compositions
CA2132783C (en) 1993-10-18 2001-12-25 Leonard Pinchuk Lubricious silicone surface modification
JPH07242769A (en) 1994-01-12 1995-09-19 Daikin Ind Ltd Oil-containing porous body
BE1009209A3 (en) 1995-03-14 1996-12-03 Pharo Ltd LIQUID RESISTANT covering.
DK0851908T3 (en) 1995-06-07 2003-08-25 Lee County Mosquito Control Di Lubricant composition and method
US5798409A (en) 1995-10-03 1998-08-25 Minnesota Mining & Manufacturing Company Reactive two-part polyurethane compositions and optionally self-healable and scratch-resistant coatings prepared therefrom
US5804318A (en) 1995-10-26 1998-09-08 Corvita Corporation Lubricious hydrogel surface modification
US5624713A (en) * 1996-01-25 1997-04-29 Zardoz Llc Method of increasing lubricity of snow ski bases
US6060546A (en) 1996-09-05 2000-05-09 General Electric Company Non-aqueous silicone emulsions
JPH10183049A (en) 1996-11-08 1998-07-07 Daikin Ind Ltd Film-forming composition
US6156389A (en) 1997-02-03 2000-12-05 Cytonix Corporation Hydrophobic coating compositions, articles coated with said compositions, and processes for manufacturing same
DE19818956A1 (en) * 1997-05-23 1998-11-26 Huels Chemische Werke Ag Materials e.g. polymer, metal or glass with micro-roughened, bacteria-repellent surface
EP0893164A2 (en) * 1997-06-28 1999-01-27 Hüls Aktiengesellschaft Bioactive coating of surfaces using crosslinking agents
JPH1164772A (en) 1997-08-25 1999-03-05 Koyo Seiko Co Ltd Bearing for scanner motor of polygon mirror
US6071981A (en) 1997-09-30 2000-06-06 Aveka, Inc. Anti-immunoresponsive polymeric material and its use in biological applications
US6127320A (en) 1998-01-19 2000-10-03 University Of Cincinnati Methods and compositions for increasing lubricity of rubber surfaces
JPH11345441A (en) 1998-06-01 1999-12-14 Sony Chem Corp Composition for protective film and optical recording medium
WO1999063022A1 (en) 1998-06-04 1999-12-09 Nippon Sheet Glass Co., Ltd. Process for producing article coated with water-repellent film, article coated with water-repellent film, and liquid composition for water-repellent film coating
JP3500973B2 (en) 1998-07-15 2004-02-23 信越化学工業株式会社 Oil bleed silicone rubber composition
US6485794B1 (en) 1999-07-09 2002-11-26 Ecolab Inc. Beverage container and beverage conveyor lubricated with a coating that is thermally or radiation cured
US6247603B1 (en) 1999-08-20 2001-06-19 Continental Plastic Containers, Inc. Container coating for increasing product outage
JP3527866B2 (en) 1999-11-04 2004-05-17 株式会社久留米リサーチ・パーク Vulcanized rubber composition preventing adhesion of marine organisms and method of preventing adhesion of marine organisms
AU2001253456A1 (en) 2000-04-13 2001-10-30 Emory University Antithrombogenic membrane mimetic compositions and methods
AU2001283055A1 (en) 2000-07-28 2002-02-13 Emory University Biological component comprising artificial membrane
JP2002194378A (en) * 2000-12-27 2002-07-10 Nippon Zeon Co Ltd Composition for forming lubricant layer, method for forming lubricant layer and article bearing lubricant layer
US7232932B2 (en) * 2001-07-10 2007-06-19 E. I. Du Pont De Nemours And Company Thermally stable perfluoropolyethers and processes therefor and therewith
DE10138036A1 (en) 2001-08-03 2003-02-20 Creavis Tech & Innovation Gmbh Structured self-cleaning surface is hydrophobic, and has a pattern of raised surfaces with lower burrs linking neighboring projections
JP2004136630A (en) 2001-11-08 2004-05-13 Nippon Sheet Glass Co Ltd Functional film coated article, and its manufacturing method
JP3944633B2 (en) 2001-12-06 2007-07-11 株式会社ブリヂストン Hard coat film and hard coat film adherend
GB0206930D0 (en) 2002-03-23 2002-05-08 Univ Durham Method and apparatus for the formation of hydrophobic surfaces
US6887836B2 (en) 2002-05-09 2005-05-03 The Procter & Gamble Company Home care compositions comprising a dicarboxy functionalized polyorganosiloxane
JP2004037764A (en) * 2002-07-02 2004-02-05 Fuji Xerox Co Ltd Image fixing device and electrophotographic system using the same
US8541060B2 (en) 2006-10-19 2013-09-24 Northwestern University Surface-independent, surface-modifying, multifunctional coatings and application thereof
JP2004076231A (en) 2002-08-21 2004-03-11 Du Pont Kk Heat resistant organic fiber having high strength, excellent in water repellent, oil repellent and soil-preventing properties, fibrous product of the same and method for roducing them
US20100210745A1 (en) 2002-09-09 2010-08-19 Reactive Surfaces, Ltd. Molecular Healing of Polymeric Materials, Coatings, Plastics, Elastomers, Composites, Laminates, Adhesives, and Sealants by Active Enzymes
US7192993B1 (en) 2003-03-04 2007-03-20 The United States Of America As Represented By The Secretary Of The Army Self-healing coating and microcapsules to make same
US7431989B2 (en) 2003-05-06 2008-10-07 Tribofilm Research, Inc. Article with lubricated surface and method
WO2005014742A1 (en) 2003-07-22 2005-02-17 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Liquid-repellent coating composition and coating having high alkali resistance
JP2005082848A (en) 2003-09-08 2005-03-31 Mitsubishi Alum Co Ltd Surface treated aluminum material having excellent corrosion resistance, hydrophilicity retainability and formability
US7666514B2 (en) 2003-09-16 2010-02-23 Shin-Etsu Chemical Co., Ltd. Antifouling condensation curing organopolysiloxane composition and underwater structure
US7189934B2 (en) 2003-11-13 2007-03-13 Honeywell International Inc. Self-healing liquid contact switch
US7560492B1 (en) 2003-11-25 2009-07-14 Advanced Cardiovascular Systems, Inc. Polysulfone block copolymers as drug-eluting coating material
JP4467300B2 (en) 2003-12-26 2010-05-26 株式会社日立製作所 Wiring board
US7732555B2 (en) 2004-01-27 2010-06-08 Ppg Industries Ohio, Inc. Urethane polyol precursors for coating compositions
JP4620363B2 (en) 2004-02-17 2011-01-26 三菱鉛筆株式会社 Contents visible writing instrument member and writing instrument
EP1728256B1 (en) 2004-03-24 2015-05-13 Showa Denko K.K. Crosslinked self-doping type electrically conducting polymer, production process thereof, product coated with the polymer and electronic device
WO2005121288A1 (en) 2004-06-10 2005-12-22 Ntn Corporation Sliding material and sliding bearing
US7258731B2 (en) * 2004-07-27 2007-08-21 Ut Battelle, Llc Composite, nanostructured, super-hydrophobic material
US7655275B2 (en) 2004-08-02 2010-02-02 Hewlett-Packard Delopment Company, L.P. Methods of controlling flow
DE102004046385A1 (en) 2004-09-24 2006-04-06 Construction Research & Technology Gmbh Liquid fluorine-containing compositions for surface treatment of mineral and non-mineral substrates
US20060159645A1 (en) 2004-10-04 2006-07-20 Jonathan Miller Method of providing lubricious surfaces
BRPI0608506A2 (en) 2005-03-18 2010-01-05 Cinv Ag process for preparing sintered porous metal materials
JP4649567B2 (en) 2005-04-05 2011-03-09 アルケア株式会社 Lubricating composition for pouch for excrement containing orthosis and pouch for excreta containing appliance
US20060240060A1 (en) * 2005-04-22 2006-10-26 Cardiac Pacemakers, Inc. Lubricious compound and medical device made of the same
CN101198542A (en) * 2005-04-22 2008-06-11 塞尔顿技术公司 Product including carbon nano-tube and method for purifying fluid with the carbon nano-tube
EP1907482B1 (en) 2005-05-04 2011-06-08 SupraPolix B.V. Hydrogen bonded hydrogels
CN100457834C (en) 2005-06-21 2009-02-04 中国科学院合肥物质科学研究院 Alumina insulating coating and its preparation method
EP1907202B1 (en) 2005-07-01 2016-01-20 Carolyn M. Dry Multiple function, self-repairing composites with special adhesives
US8308927B2 (en) 2005-08-17 2012-11-13 University Of Cincinnati Electrofluidic textiles and cleaning implements using such electrofluidic textiles
EP1949920B1 (en) * 2005-10-17 2018-12-26 Kaneka Corporation Medical catheter tubes and process for production thereof
US8017687B2 (en) 2005-11-15 2011-09-13 Momentive Performance Materials Inc. Swollen silicone composition and process of producing same
US20070141306A1 (en) 2005-12-21 2007-06-21 Toshihiro Kasai Process for preparing a superhydrophobic coating
US7723405B2 (en) 2006-01-05 2010-05-25 The Board Of Trustees Of The University Of Illinois Self-healing coating system
US20070166344A1 (en) 2006-01-18 2007-07-19 Xin Qu Non-leaching surface-active film compositions for microbial adhesion prevention
US7581568B2 (en) 2006-02-07 2009-09-01 International Textile Group, Inc. Water jet woven air bag fabric made from sized yarns
WO2007130734A2 (en) 2006-03-03 2007-11-15 C. R. Bard, Inc. Antimicrobial coating
EP1832629B1 (en) 2006-03-10 2016-03-02 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor
US7998559B2 (en) 2006-03-23 2011-08-16 Alcatel Lucent Super-phobic surface structures
US20070254000A1 (en) 2006-04-28 2007-11-01 Xiaoping Guo Biocompatible self-lubricating polymer compositions and their use in medical and surgical devices
US20080004394A1 (en) * 2006-06-30 2008-01-03 Stefan Reinartz Method of providing repellency
JP2009544807A (en) 2006-07-25 2009-12-17 フジフィルム ハント スマート サーフェイシーズ,エルエルシー Polysiloxane-based in situ polymer blends-compositions, articles and methods for their preparation
DE102006037067B4 (en) * 2006-08-08 2011-06-16 Metoxit Ag Method for producing an implant with a porous, ceramic surface layer
JP2008223003A (en) 2006-12-28 2008-09-25 Toto Ltd Self-cleaning member and coating composition
EP2111482A2 (en) 2007-02-13 2009-10-28 Cinvention Ag Medical devices with extended or multiple reservoirs
CN101675156A (en) 2007-03-29 2010-03-17 犹他州立大学研究基金会 Materials for removing contaminants from fluids using supports with biologically-derived functionalized groups and methods of forming and using the same
JPWO2008120505A1 (en) 2007-03-29 2010-07-15 コニカミノルタホールディングス株式会社 Water repellent articles, architectural window glass and vehicle window glass
US7877968B2 (en) 2007-05-15 2011-02-01 Kraft Foods Global Brands Llc Method for forming a container with improved release properties
US20100009583A1 (en) 2007-09-21 2010-01-14 Bigsky Technologies Llc Flame retardant, stain and soil resistant textile article
CN101918621B (en) 2007-10-03 2012-08-15 阿山特斯有限公司 Method of manufacturing metal with biocidal properties
US7998529B2 (en) 2007-10-10 2011-08-16 Ppg Industries Ohio, Inc. Methods for making polymeric substrates comprising a haze-free, self-healing coating and coated substrates made thereby
US8512731B2 (en) 2007-11-13 2013-08-20 Medtronic Minimed, Inc. Antimicrobial coatings for medical devices and methods for making and using them
EP2254653A1 (en) 2008-02-15 2010-12-01 Nypro Inc. Self-lubricating elastomeric components for use in medical devices
WO2009128883A1 (en) 2008-04-16 2009-10-22 Dow Corning Corporation Preparation of silicone microemulsions
US7841022B2 (en) 2008-07-15 2010-11-30 Luthai Textile Co., Ltd. Garment having various functional finishes
WO2011009096A1 (en) 2009-07-16 2011-01-20 Micell Technologies, Inc. Drug delivery medical device
US7976692B2 (en) 2008-07-25 2011-07-12 Xerox Corporation Metallization process for making fuser members
EP2163295A1 (en) 2008-09-15 2010-03-17 Services Pétroliers Schlumberger A micro-structured surface having tailored wetting properties
US8629210B2 (en) 2008-10-10 2014-01-14 Ndsu Research Foundation Zwitterionic/amphiphilic pentablock copolymers and coatings therefrom
ES2432388T3 (en) 2008-12-05 2013-12-03 Semprus Biosciences Corporation Anti-fouling, antimicrobial and antithrombogenic graft compositions from the surface
CN101444777B (en) 2008-12-29 2011-07-20 大连海事大学 Method for improving antifouling property of surface material of boat hull
JP5258595B2 (en) 2009-01-23 2013-08-07 株式会社豊田中央研究所 Flow resistance reduction structure
US20120052241A1 (en) 2009-02-17 2012-03-01 The Board Of Trustees Of The University Of Illinoi S Flexible Microstructured Superhydrophobic Materials
FR2943066B1 (en) 2009-03-13 2011-04-22 Veronique Roulleaux AQUEOUS FORMULATION OF AN ANTI-SLIP COATING SYSTEM FOR SUBMERSIBLE SUBSTRATES, PROCESSING METHOD AND USE THEREOF
FI20095392A0 (en) 2009-04-09 2009-04-09 Upm Kymmene Corp Method of treating the surface of a substrate
CN101538395B (en) 2009-04-23 2010-12-08 宁波登天氟材有限公司 Oil stain-resistant polyfluortetraethylene microporous membrane and processing method thereof
CN101580753B (en) 2009-06-19 2012-09-26 大庆石油学院 Novel polyetheretherketone self-lubricating hard wearing compound material and method for preparing same
WO2011005200A1 (en) 2009-07-10 2011-01-13 Milux Holding S.A. Joint device and method
EP2490663B1 (en) 2009-10-23 2017-09-20 Dow Corning Corporation Silicone compositions comprising a swollen silicone gel
EP2363438A1 (en) 2010-02-26 2011-09-07 Severn Marine Technologies, LLC Optically clear biofouling resistant coating compositions for marine instruments and application methods
US8563485B2 (en) * 2010-05-20 2013-10-22 GM Global Technology Operations LLC Tribo-system and method for reducing particle conglomeration therein
WO2011156603A2 (en) 2010-06-09 2011-12-15 Semprus Biosciences Corp. Articles having non-fouling surfaces and processes for preparing the same without altering bulk physical properties
JP5240251B2 (en) 2010-08-06 2013-07-17 ダイキン工業株式会社 Packing material
CN103180421B (en) 2010-10-25 2015-07-22 Skf公司 Dry lubricant containing fibers and method of using the same
US20120141052A1 (en) 2010-12-05 2012-06-07 New Hampshire Ball Bearings, Inc. Self lubricated bearing compositions and methods of making the same
CA2825012C (en) 2011-01-19 2021-03-23 President And Fellows Of Harvard College Slippery liquid-infused porous surfaces and biological applications thereof
CA2825008C (en) 2011-01-19 2020-10-13 President And Fellows Of Harvard College Slippery surfaces with high pressure stability, optical transparency, and self-healing characteristics
AU2011374899A1 (en) 2011-08-05 2014-02-20 Massachusetts Institute Of Technology Devices incorporating a liquid - impregnated surface
US20130110222A1 (en) 2011-08-19 2013-05-02 Joram Slager Medical devices including superhydrophobic or superoleophobic surfaces
WO2013115868A2 (en) 2011-11-04 2013-08-08 President And Fellows Of Harvard College Dynamic and switchable slippery surfaces
EP2802630B1 (en) 2012-01-10 2018-05-30 President and Fellows of Harvard College Modification of surfaces for fluid and solid repellency

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5476589A (en) 1995-03-10 1995-12-19 W. L. Gore & Associates, Inc. Porpous PTFE film and a manufacturing method therefor
WO2009048880A1 (en) 2007-10-09 2009-04-16 Dharan C K Hari Fiber-reinforced foamed resin structural composite materials and methods for producing composite materials

Non-Patent Citations (71)

* Cited by examiner, † Cited by third party
Title
"Biomaterials Science", 2004, ACADEMIC PRESS
"Hemostasis and Thrombosis", 2005, LIPPINCOTT WILLIAMS AND WILKINS
AFESSA, B. ET AL.: "Association Between a Silver-Coated Endotracheal Tube and Reduced Mortality in Patients With Ventilator-Associated Pneumonia", CHEST, vol. 137, 2010, pages 1015 - 1021
AHUJA, A. ET AL., LANGMUIR, vol. 24, 2008, pages 9 - 14
B. POKROY; A. K. EPSTEIN; M. C. M. PERSSON-GULDA; J. AIZENBERG, ADV. MATER., vol. 21, 2009, pages 463
BANERJEE, I.; R.C. PANGULE; R.S. KANE: "Antifouling coatings: recent developments in the design ofsurfaces that prevent fouling by proteins, bacteria, and marine organisms", ADVANCED MATERIALS, 2011
BANERJEE, S. ET AL.: "Infection control during GI endoscopy", GASTROINTEST ENDOSC, vol. 67, 2008, pages 781 - 790
BARSTAD, R.M ET AL., THROMBOSIS AND HAEMOSTASIS, vol. 79, 1998, pages 302 - 305
BARTHLOTT, W.; NEINHUIS, C.: "Purity of the sacred lotus, or escape from contamination in biological surfaces", PLANTA, vol. 202, 1997, pages 1 - 8
BEILENHOFF, U. ET AL.: "ESGE-ESGENA guideline: Cleaning and disinfection in gastrointestinal endoscopy Update 2008", ENDOSCOPY, vol. 40, 2008, pages 939 - 957
BHARDWAJ, U ET AL.: "A review of the development of a vehicle for localized and controlled drug delivery for implantable bioscnsors", J DIABETES SCI TECHNOL, vol. 2, 2008, pages 1016 - 1029
BOCQUET, L.; LAUGA, E. A SMOOTH FUTURE?, NATURE MATER., vol. 10, 2011, pages 334 - 337
BOS, R. ET AL.: "Retention of bacteria on a substratum surface with micro patterned hydrophohicity", FEMS MICROBIOLOGY LETTERS, vol. 189, no. 2, 2000, pages 311 - 315
CASSIC, A. B. D.; BAXTER, S.: "Wcttability of porous surfaces", TRANS. FARADAY SOC., vol. 40, 1944, pages 0546 - 0550
CASSIE, A. B. D.; BAXTER, S.: "Large contact angles of plant and animal surfaces", NATURE, vol. 155, 1945, pages 21 - 22
CHEN, S. ET AL., POLYMER, vol. 51, 2010, pages 5283 - 5293
CHEN, S. ET AL.: "Surface hydration: Principles and applications toward low-fouling/non-fouling biomaterials", POLYMER, vol. 51, 2010, pages 5283 - 5293
CLARK, LELAND C.; GOLLAN, F., SCIENCE, vol. 152, no. 3720, 1966, pages 1755 - 56
COSTERTON, J.; P. STEWART; E. GREENBERG: "Bacterial biofilms: a common cause of persistent infections", SCIENCE, vol. 284, no. 5418, 1999, pages 1318
COSTERTON, J.W. ET AL.: "Bacterial biofilms in nature and disease", ANN. REV. MICROBIOL., vol. 41, 1987, pages 435 - 464
CRIBIER, A. ET AL.: "Percutaneous transcatheter implantation of an aortic valve prosthesis for calcific aortic stenosis - First human case description", CIRCULATION, vol. 106, 2002, pages 3006 - 3008
CRNICH, C.J.; G. MAKI, D.G: "The Promise of Novel Technology for the Prevention of Intravascular Device-Related Bloodstream Infection. II. Long-Term Devices", CLINICAL INFECTIOUS DISEASES, vol. 34, 2002, pages 1362 - 1368
DE BEER, D.; STOODLEY, P.: "Microbial Biofilms", PROKARYOTES, vol. 1, 2006, pages 904 - 937
DIETER, R.S.: "Coronary artery stent infection", CATHETER. CARDIO. INTE., vol. 62, 2004, pages 281 - 281
DIETER, R.S.: "Coronary artery stent infection", CLIN. CARDIOL., vol. 23, 2000, pages 808 - 810
DISMUKES ET AL.: "Prosthetic valve endocarditis. Analysis of 38 cases", CIRCULATION, vol. 48, 1973, pages 365 - 377
DRELICH ET AL.: "Encyclopedia of Surface and Colloid Science", 2002, MARCEL DEKKER INC, pages: 3152 - 3166
FOWKES, F. M., IND. ENG. CHEM., vol. 56, 1964, pages 40 - 42
GARG, N.; GARG, R.; GORDON, C.; SINGH, R.; SINGH, A.: "Acute Coronary Syndrome Caused by Coronary Artery Mycotic Aneurysm Due to Late Stent Infection Localized With Radiolabeled Autologous Leukocyte Imaging", CLIN. NUCL. MED., vol. 34, 2009, pages 753 - 755
GEORGE, P.A. ET AL.: "J.J. Self-assembling polystyrene-block-poly(ethylene oxide) copolymer surface coatings: resistance to protein and cell adhesion", BIOMATERIALS, vol. 30, 2009, pages 2449 - 2456
GRISTINA, A.G. ET AL.: "Biomaterial-centered sepsis and the total artificial heart. Microbial adhesion vs tissue integration", JAMA, vol. 259, 1988, pages 870 - 874
GRISTINA, A.G.: "Biomatcrial-ccntcrcd sepsis and the total artificial heart. Microbial adhesion vs tissue integration", JAMA, vol. 259, 1988, pages 870 - 874
GRISTINA, A.G; DOBBINS, J.J.; GIAMMARA, B.; LEWIS, J.C.; DCVRIES, W.C.: "Biomatcrial-ccntcrcd sepsis and the total artificial heart. Microbial adhesion vs tissue integration", JAMA, vol. 259, 1988, pages 870 - 874
HALL-STOODLEY, L.; J.W. COSTERTON; P. STOODLEY: "Bacterial biofilms: from the natural environment to infectious diseases", NATURE REVIEWS MICROBIOLOGY, vol. 2, no. 2, 2004, pages 95 - 108
HATTON ET AL., PROC. NATL. ACAD. SCI., vol. 107, 2010, pages 10354 - 10359
HEARN, A.T. ET AL.: "Endovascular stent infection with delayed bacterial challenge", AMERICAN JOURNAL OF SURGERY, vol. 174, 1997, pages 157 - 159
ISRAELACHVILI, J. N.: "Intermolecular and Surface Forces", 2011, ACADEMIC PRESS
KARCHMER, A.W. ET AL.: "Staphylococcus epidermidis causing prosthetic valve endocarditis: microbiologic and clinical observations as guides to therapy", ANN INTERN MED, vol. 98, 1983, pages 447 - 455
KIM ET AL., NANO LETT., 2011
KIM, P.; EPSTEIN, A.K.; KHAN, M.; ZARZAR, L.D.; LIPOMI, D.J.; WHITESIDES, G.M.; AIZENBERG, J.: "Structural Transformation by Electrodeposition on Patterned Substrates (STEPS): A New Versatile Nanofabrication Method", NANO LETTERS, 2011
LEE ET AL., NATURE MATER., vol. 5, 2006, pages 741 - 47
LI, Y. ET AL., ANGEW. CHEM. INT. ED., vol. 49, 2010, pages 6129 - 6133
M. SUGAWARA ET AL.: "Plasma Etching: Fundamentals and Applications", 1998, OXFORD UNIVERSITY PRCSS
M. SUGAWARA: "Series on semiconductor science and technology", vol. 7, 1998, OXFORD UNIVERSITY PRESS, article "Plasma Etching: Fundamentals and Applications"
MUNRO, W.A.; THOMAS, C.L.P.; SIMPSON, 1.; SHAW, J.; DODGSON, J.: "Deterioration of pH electrode response due to biofilm formation on the glass membrane", SENSOR ACTUAT B-CHEM, vol. 37, 1996, pages 187 - 194
NGUYEN, T. P. N.; BRUNET, P.; COFFINIER, Y.; BOUKHERROUB, R.: "Quantitative testing of robustness on superomniphobic surfaces by drop impact", LANGMUIR, vol. 26, 2010, pages 18369 - 18373
NIIMI, Y. ET AL., ANESTH. ANALG, vol. 89, 1999, pages 573 - 579
NOETZEL, M.J.; BAKER, R.P.: "Shunt fluid examination: risks and benefits in the evaluation of shunt malfunction and infection", J. NEUROSURG., vol. 61, 1984, pages 328 - 332
O'TOOLE, G.; KAPLAN, H.B.; KOLTER, R.: "Biofilm Formation as Microbial Development", ANNU. REV. MICROBIOL., vol. 54, 2000, pages 49 - 79
P.-G. DE GENNES; F. BROCHARD-WYART; D. QUERE: "Capillarity and Wetting Phenomena: drops, bubbles, pearls, waves", 2004, SPRINGER
PARK, K.D. ET AL.: "Bacterial adhesion on PEG modified polyurethane surfaces", BIOMATERIALS, vol. 19, no. 7-9, 1998, pages 851 - 859
POETES, R. ET AL.: "Metastable Underwater Superhydrophobicity", PHYSICAL REVIEW LETTERS, vol. 105, no. 16, 2010
PRIME, K.L.; G.M. WHITESIDES: "Self-assembled organic monolayers: model systems for studying adsorption of proteins at surfaces", SCIENCE, vol. 252, no. 5010, 1991, pages 1164
QUERE, D.: "Wetting and roughness", ANNU. REV. MATER. RES., vol. 38, 2008, pages 71 - 99
REICHERT, W.M.; KOSCHWANEZ, H.E.; YAP, F.Y.; KLITZMAN, B.: "In vitro and in vivo characterization of porous poly-L-lactic acid coatings for subcutaneously implanted glucose sensors", JOURNAL OF BIOMEDICAL MATERIALS RESEARCH PART A, vol. 87A, 2008, pages 792 - 807
S. KARNAM ET AL.: "Mycobacterium phlei, a previously unreported cause of pacemaker infection: Thinking outside the box in cardiac device infections", CARDIOLOGY JOURNAL, vol. 17, 2010
See also references of EP2665783A2
SHAFFER, T.H. ET AL., PULMONOL, vol. 14, 1992, pages 102 - 109
SHAFRIN, E. G.; ZISMAN, W. A.: "Constitutive relations in the wetting of low energy surfaces and the theory of the retraction method of preparing monolayers", J PHYS. CHEM., vol. 64, 1960, pages 519 - 524
SKATTUM L ET AL., MOL. IMMUNOL., vol. 48, no. 14, 2011, pages 1643 - 55
SOHAIL, M.R. ET AL.: "Risk factor analysis of permanent pacemaker infection", CLIN INFECT DIS, vol. 45, 2007, pages 166 - 173
THOMPSON, A.R.; HARKER, L.A.: "Manual of Hemostasis and Thrombosis", 1983, F. A. DAVIS
THOMPSON, A.R.; HARKER, L.A.: "Manual ofHemostasis and Thrombosis", 1983, F. A. DAVIS
TREVORS, J.: "Silver resistance and accumulation in bacteria", ENZYME AND MICROBIAL TECHNOLOGY, vol. 9, no. 6, 1987, pages 331 - 333
TULI, S.; DRAKE, J.; LAWLESS, J.; WIGG, M.; LAMBERTI-PASCULLI, M.: "Risk factors for repeated cerebrospinal shunt failures in pediatric patients with hydrocephalus", J. NEUROSURG., vol. 92, 2000, pages 31 - 38
TUTEJA, A. ET AL., PROC. NATL. ACAD. SCI. USA, vol. 105, 2008, pages 18200 - 18205
TUTEJA, A. ET AL., SCIENCE, vol. 318, 2007, pages 1618 - 1622
VOSKERICIAN, G.: "Biocompatibility and biofouling ofMEMS drug delivery devices", BIOMATERIALS, vol. 24, 2003, pages 1959 - 1967
WILSON, G.S.; GIFFORD, R.: "Biosensors for real-time in vivo measurements", BIOSENS. BIOELECTRON, vol. 20, 2005, pages 2388 - 2403
ZHAO, L. ET AL.: "Antibacterial coatings on titanium implants", JOURNAL OF BIOMEDICAL MATERIALS RESEARCH PART B: APPLIED BIOMATERIALS, vol. 91, no. 1, 2009, pages 470 - 480
ZHAO, L.: "Antibacterial coatings on titanium implants", JOURNAL OF BIOMEDICAL MATERIALS RESEARCH PART B: APPLIED BIOMATERIALS, vol. 91, no. 1, 2009, pages 470 - 480

Cited By (93)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10982100B2 (en) 2011-01-19 2021-04-20 President And Fellows Of Harvard College Slippery liquid-infused porous surfaces and biological applications thereof
US9932484B2 (en) 2011-01-19 2018-04-03 President And Fellows Of Harvard College Slippery liquid-infused porous surfaces and biological applications thereof
US10233334B2 (en) 2011-01-19 2019-03-19 President And Fellows Of Harvard College Containers, bottles, drums, vats, and tanks having a slippery surface
US10550272B2 (en) 2011-01-19 2020-02-04 President And Fellows Of Harvard College Slippery liquid-infused porous surfaces and biological applications thereof
US9932482B2 (en) 2011-01-19 2018-04-03 President And Fellows Of Harvard College Slippery surfaces with high pressure stability, optical transparency, and self-healing characteristics
US11118067B2 (en) 2011-01-19 2021-09-14 President And Fellows Of Harvard College Sanitation systems and components thereof having a slippery surface
US9381528B2 (en) 2011-08-03 2016-07-05 Massachusetts Institute Of Technology Articles for manipulating impinging liquids and methods of manufacturing same
US9254496B2 (en) 2011-08-03 2016-02-09 Massachusetts Institute Of Technology Articles for manipulating impinging liquids and methods of manufacturing same
US11933551B2 (en) 2011-08-05 2024-03-19 Massachusetts Institute Of Technology Liquid-impregnated surfaces, methods of making, and devices incorporating the same
US20180180364A1 (en) * 2011-08-05 2018-06-28 Massachusetts Institute Of Technology Liquid-impregnated surfaces, methods of making, and devices incorporating the same
JP2017094738A (en) * 2011-08-05 2017-06-01 マサチューセッツ インスティテュート オブ テクノロジー Liquid-impregnated surfaces, methods of making, and devices incorporating the same
WO2013022467A3 (en) * 2011-08-05 2013-06-13 Massachusetts Institute Of Technology Devices incorporating a liquid - impregnated surface
US8574704B2 (en) 2011-08-05 2013-11-05 Massachusetts Institute Of Technology Liquid-impregnated surfaces, methods of making, and devices incorporating the same
WO2013130118A1 (en) * 2012-02-29 2013-09-06 Massachusetts Institute Of Technology Articles and methods for modifying condensation on surfaces
US8940361B2 (en) 2012-03-23 2015-01-27 Massachusetts Institute Of Technology Self-lubricating surfaces for food packaging and food processing equipment
US10968035B2 (en) 2012-03-23 2021-04-06 Massachusetts Institute Of Technology Self-lubricating surfaces for food packaging and food processing equipment
US9309162B2 (en) 2012-03-23 2016-04-12 Massachusetts Institute Of Technology Liquid-encapsulated rare-earth based ceramic surfaces
US8535779B1 (en) 2012-03-23 2013-09-17 Massachusetts Institute Of Technology Self-lubricating surfaces for food packaging and food processing equipment
US9371173B2 (en) 2012-03-23 2016-06-21 Massachusetts Institute Of Technology Self-lubricating surfaces for food packaging and food processing equipment
US11058803B2 (en) 2012-05-24 2021-07-13 Massachusetts Institute Of Technology Medical devices and implements with liquid-impregnated surfaces
US11684705B2 (en) 2012-05-24 2023-06-27 Massachusetts Institute Of Technology Medical devices and implements with liquid-impregnated surfaces
US9625075B2 (en) 2012-05-24 2017-04-18 Massachusetts Institute Of Technology Apparatus with a liquid-impregnated surface to facilitate material conveyance
US11105352B2 (en) 2012-06-13 2021-08-31 Massachusetts Institute Of Technology Articles and methods for levitating liquids on surfaces, and devices incorporating the same
US11186731B2 (en) 2012-07-12 2021-11-30 President And Fellows Of Harvard College Slippery self-lubricating polymer surfaces
US9963597B2 (en) 2012-07-12 2018-05-08 President And Fellows Of Harvard College Slippery self-lubricating polymer surfaces
US9630224B2 (en) 2012-07-13 2017-04-25 President And Fellows Of Harvard College Slippery liquid-infused porous surfaces having improved stability
WO2014012078A3 (en) * 2012-07-13 2014-07-24 President And Fellows Of Harvard College Selective wetting and transport surfaces
US10011800B2 (en) 2012-07-13 2018-07-03 President And Fellows Of Harvard College Slips surface based on metal-containing compound
US11492500B2 (en) 2012-11-19 2022-11-08 Massachusetts Institute Of Technology Apparatus and methods employing liquid-impregnated surfaces
US10882085B2 (en) 2012-11-19 2021-01-05 Massachusetts Institute Of Technology Apparatus and methods employing liquid-impregnated surfaces
JP2019115906A (en) * 2012-11-19 2019-07-18 マサチューセッツ インスティテュート オブ テクノロジー Device and method utilizing liquid impregnation surface
JP2019135047A (en) * 2012-11-19 2019-08-15 マサチューセッツ インスティテュート オブ テクノロジー Device and method utilizing liquid impregnation surface
CN105188967A (en) * 2012-11-19 2015-12-23 麻省理工学院 Apparatus and methods employing liquid-impregnated surfaces
JP7097312B2 (en) 2012-11-19 2022-07-07 マサチューセッツ インスティテュート オブ テクノロジー Equipment and methods using liquid impregnated surface
JP2016510252A (en) * 2012-11-19 2016-04-07 マサチューセッツ インスティテュート オブ テクノロジー Apparatus and method utilizing liquid impregnated surface
WO2014078867A1 (en) * 2012-11-19 2014-05-22 Massachusetts Institute Of Technology Apparatus and methods employing liquid-impregnated surfaces
WO2014110511A1 (en) 2013-01-11 2014-07-17 President And Fellows Of Harvard College Protective barriers for preventing or reducing transfer of microorganisms
US10806823B2 (en) 2013-02-13 2020-10-20 Cartiheal (2009) Ltd. Solid substrates for promoting cell and tissue growth
JP2016509873A (en) * 2013-02-13 2016-04-04 カルティヒール(2009)リミティド Solid substrate for promoting cell and tissue growth
US11878090B2 (en) 2013-02-13 2024-01-23 Cartiheal (2009) Ltd. Solid substrates for promoting cell and tissue growth
US11116873B2 (en) 2013-02-13 2021-09-14 Cartiheal (2009) Ltd. Solid substrates for promoting cell and tissue growth
JP2016507307A (en) * 2013-02-13 2016-03-10 カルティヒール(2009)リミティド Solid substrate for the reduction or prevention of cell and tissue attachment and angiogenesis
US9498934B2 (en) 2013-02-15 2016-11-22 Massachusetts Institute Of Technology Grafted polymer surfaces for dropwise condensation, and associated methods of use and manufacture
US10385181B2 (en) 2013-03-13 2019-08-20 President And Fellows Of Harvard College Solidifiable composition for preparaton of liquid-infused slippery surfaces and methods of applying
EP2969258A4 (en) * 2013-03-13 2016-11-30 Harvard College Solidifiable composition for preparation of liquid-infused slippery surfaces and methods of applying
WO2014209441A3 (en) * 2013-03-13 2015-04-02 President And Fellows Of Harvard College Solidifiable composition for preparation of liquid-infused slippery surfaces and methods of applying
WO2014145528A1 (en) * 2013-03-15 2014-09-18 President And Fellows Of Harvard College Antifouling microfluidic devices and methods thereof
WO2014149465A1 (en) * 2013-03-15 2014-09-25 President And Fellows Of Harvard College Omniphobic paper devices
US10155179B2 (en) 2013-04-16 2018-12-18 Massachusetts Institute Of Technology Systems and methods for unipolar separation of emulsions and other mixtures
US9427679B2 (en) 2013-04-16 2016-08-30 Massachusetts Institute Of Technology Systems and methods for unipolar separation of emulsions and other mixtures
US9975064B2 (en) 2013-04-16 2018-05-22 Massachusetts Institute Of Technology Systems and methods for unipolar separation of emulsions and other mixtures
WO2014179283A3 (en) * 2013-04-29 2015-04-09 Gvd Corporation Liquid-impregnated coatings and devices containing the same
US10543516B2 (en) 2013-04-29 2020-01-28 Gvd Corporation Liquid-impregnated coatings and devices containing the same
WO2014197667A1 (en) * 2013-06-05 2014-12-11 The Gillette Company Razor components with novel coating
US11041058B2 (en) 2013-07-26 2021-06-22 Toyo Seikan Group Holdings, Ltd. Resin structure having a liquid layer on the surface thereof
US9585757B2 (en) 2013-09-03 2017-03-07 Massachusetts Institute Of Technology Orthopaedic joints providing enhanced lubricity
US10391530B2 (en) 2013-09-27 2019-08-27 The Regents Of The University Of California Liquid-repellent surfaces made of any materials
WO2015069820A1 (en) 2013-11-06 2015-05-14 The Procter & Gamble Company Easy to empty flexible containers
US11079141B2 (en) 2013-12-20 2021-08-03 Massachusetts Institute Of Technology Controlled liquid/solid mobility using external fields on lubricant-impregnated surfaces
US10099027B2 (en) 2014-01-24 2018-10-16 Cole Research & Design Oral suction device
US9968965B2 (en) 2014-04-25 2018-05-15 Toyo Seikan Group Holdings, Ltd. Structure having liquid film on the surface thereof
WO2015166191A1 (en) 2014-04-30 2015-11-05 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Method for purifying, cooling and separating a gaseous mixture and associated apparatus
FR3020669A1 (en) * 2014-04-30 2015-11-06 Air Liquide METHOD AND APPARATUS FOR PURIFYING AND COOLING A GAS MIXTURE
US20170088472A1 (en) * 2014-05-19 2017-03-30 President And Fellows Of Harvard College Robust cementitious materials with mobile liquid-infused barrier layer
WO2015179410A1 (en) * 2014-05-19 2015-11-26 President And Fellows Of Harvard College Robust cementitious materials with mobile liquid-infused barrier layer
US9947481B2 (en) 2014-06-19 2018-04-17 Massachusetts Institute Of Technology Lubricant-impregnated surfaces for electrochemical applications, and devices and systems using same
US10927005B2 (en) 2015-01-26 2021-02-23 The Regents Of The University Of California Method for manufacturing doubly re-entrant microstructures
US10434542B2 (en) 2015-04-24 2019-10-08 The Penn State Research Foundation Slippery rough surfaces
EP3292586A4 (en) * 2015-05-07 2018-12-05 Landsdowne Laboratories, Inc. Biocompatible hydrophobic batteries, systems and methods related thereto
EP3326806A4 (en) * 2015-07-17 2018-08-08 Nissan Motor Co., Ltd. Antifouling structure and method for producing same
US11168276B2 (en) 2015-08-28 2021-11-09 Battelle Memorial Institute Reinforced composites with repellent and slippery properties
US10221321B2 (en) 2015-08-28 2019-03-05 Battelle Memorial Institute Paintable hydrophobic and lubricant-infused surface coatings and processes for making and using same
US10577511B2 (en) 2016-01-20 2020-03-03 Battelle Memorial Institute Stretchable hydrophobic materials and methods for making the same
US11291779B2 (en) 2016-07-15 2022-04-05 Koninklijke Philips N.V. Aerosolization device and an aerosol drug delivery device
US10899933B2 (en) 2016-09-13 2021-01-26 Nissan Motor Co., Ltd. Antifouling structure
US11266344B2 (en) 2016-09-21 2022-03-08 Samsung Electronics Co., Ltd. Method for measuring skin condition and electronic device therefor
US11259918B2 (en) 2016-10-03 2022-03-01 Carena Healthcare Ltd Frame for an implantable medical device and a method of manufacturing a frame for an implantable medical device
WO2020025591A1 (en) 2018-07-30 2020-02-06 Technische Universität Berlin Inerting material surfaces by functionalized perfluorinated molecules
EP3603577A1 (en) 2018-07-30 2020-02-05 Technische Universität Berlin Inertisation of surfaces of materials by functionalized perfluorinated molecules
CN110253873B (en) * 2019-04-24 2024-06-04 常州三提新材料有限公司 Apparatus, method for forming micro-nano porous structure on film and film produced thereby
CN110253873A (en) * 2019-04-24 2019-09-20 常州三提新材料有限公司 Equipment, method and the film obtained of micro-nano porous structure are generated on film
US11883558B2 (en) 2019-09-13 2024-01-30 Spotless Materials Inc. Formulations and processes to generate repellent surfaces on medical devices
WO2021105633A1 (en) 2019-11-26 2021-06-03 Structurys Biotech Method for producing a substrate having at least one non-stick surface
FR3103492A1 (en) 2019-11-26 2021-05-28 Centre National De La Recherche Scientifique PROCESS FOR MANUFACTURING A SUBTRATE OF WHICH AT LEAST ONE SURFACE IS NON-ADHESIVE
FR3103397A1 (en) 2019-11-26 2021-05-28 Centre National De La Recherche Scientifique NON-STICK SURFACE AND USE IN ANTI-BIOFILM APPLICATIONS
WO2021239851A1 (en) * 2020-05-26 2021-12-02 Agxx Intellectual Property Holding Gmbh Antiseptic hybrid dressing for local wound treatment
EP3915377A1 (en) * 2020-05-26 2021-12-01 AgXX Intellectual Property Holding GmbH Antiseptic hybrid layer for local wound treatment
WO2022127631A1 (en) * 2020-12-18 2022-06-23 南京鼓楼医院 Preparation method for ultra-smooth porous surface for lubricating oil infusion of medical catheter
WO2022207703A1 (en) 2021-04-01 2022-10-06 Friedrich-Alexander-Universität Erlangen-Nürnberg Silicone- or fluorosilicone-coated solid substrates and process for their preparation
EP4067448A1 (en) 2021-04-01 2022-10-05 Friedrich-Alexander-Universität Erlangen-Nürnberg Silicone- or fluorosilicone-coated solid substrates and process for their preparation
US11998369B2 (en) 2021-04-12 2024-06-04 Freeflow Medical Devices Llc Packaging for medical devices coated with perfluorinated liquids or dispersions thereof
CN114292593A (en) * 2022-01-17 2022-04-08 山东中凯华瑞工程材料有限公司 Nano micron and submicron micron spacing structure bionic all-hydrophobic material and preparation method thereof
US12005161B2 (en) 2023-05-15 2024-06-11 Massachusetts Institute Of Technology Medical devices and implements with liquid-impregnated surfaces

Also Published As

Publication number Publication date
KR20140004723A (en) 2014-01-13
AU2012207206B2 (en) 2015-10-08
KR101966272B1 (en) 2019-04-08
AU2017239543B2 (en) 2019-02-28
JP2014504519A (en) 2014-02-24
AU2017239543A1 (en) 2017-10-26
US20180298203A1 (en) 2018-10-18
AU2016200048B2 (en) 2017-07-06
CA2825012A1 (en) 2012-07-26
CN103703085A (en) 2014-04-02
AU2016200048A1 (en) 2016-01-28
CA2825012C (en) 2021-03-23
JP6563173B2 (en) 2019-08-21
CN103703085B (en) 2016-09-28
US20200291246A1 (en) 2020-09-17
US10982100B2 (en) 2021-04-20
US10550272B2 (en) 2020-02-04
WO2012100100A3 (en) 2012-10-18
EP2665783A2 (en) 2013-11-27
US20140187666A1 (en) 2014-07-03
US9932484B2 (en) 2018-04-03

Similar Documents

Publication Publication Date Title
US10982100B2 (en) Slippery liquid-infused porous surfaces and biological applications thereof
AU2012207206A1 (en) Slippery liquid-infused porous surfaces and biological applications thereof
JP2017140405A (en) Slippery liquid-infused porous surfaces and biological applications thereof
Han et al. Combinational biomimicking of lotus leaf, mussel, and sandcastle worm for robust superhydrophobic surfaces with biomedical multifunctionality: antithrombotic, antibiofouling, and tissue closure capabilities
AU2012207205A1 (en) Slippery surfaces with high pressure stability, optical transparency, and self-healing characteristics
Xia et al. Multifunction of biomimetic liquid infused systems derived from SLIPS theory: a review
US20240132732A1 (en) Superhydrophobic antifouling coating compositions and applications thereof
Jia et al. Recent Developments in Slippery Liquid-Infused Porous Surface Coatings for Biomedical Applications

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12705182

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 2825012

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2013550592

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2012207206

Country of ref document: AU

Date of ref document: 20120119

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20137021610

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2012705182

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 13980858

Country of ref document: US