WO2008049251A1 - Microbicidal nano- and meso-polymer fibers produced from polymers and honey, for textile applications - Google Patents

Microbicidal nano- and meso-polymer fibers produced from polymers and honey, for textile applications Download PDF

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Publication number
WO2008049251A1
WO2008049251A1 PCT/CH2007/000510 CH2007000510W WO2008049251A1 WO 2008049251 A1 WO2008049251 A1 WO 2008049251A1 CH 2007000510 W CH2007000510 W CH 2007000510W WO 2008049251 A1 WO2008049251 A1 WO 2008049251A1
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WO
WIPO (PCT)
Prior art keywords
honey
polymer
microbicidal
fibers
polymer fibers
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PCT/CH2007/000510
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German (de)
French (fr)
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WO2008049251B1 (en
Inventor
Andreas Greiner
Judith Hehl
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Schoeller Textil Ag
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Publication of WO2008049251A1 publication Critical patent/WO2008049251A1/en
Publication of WO2008049251B1 publication Critical patent/WO2008049251B1/en

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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/103Agents inhibiting growth of microorganisms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0208Tissues; Wipes; Patches
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • A61K8/027Fibers; Fibrils
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8129Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/98Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution of animal origin
    • A61K8/987Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution of animal origin of species other than mammals or birds
    • A61K8/988Honey; Royal jelly, Propolis
    • 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
    • A61L15/225Mixtures of macromolecular compounds
    • 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
    • A61L15/40Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing ingredients of undetermined constitution or reaction products thereof, e.g. plant or animal extracts
    • 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
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005Antimicrobial preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • D01D5/003Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm
    • 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/30Compounds of undetermined constitution extracted from natural sources, e.g. Aloe Vera
    • 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents

Definitions

  • the present invention describes a process for producing electrospun fibers comprising at least one polymer and honey.
  • honey allows the microbicidal and especially the antibacterial finish of electrospinnable polymers.
  • the honey can be mixed as such in the solution of the at least one polymer which is to be electro-spun, and / or the honey can be incorporated in encapsulated form into the polymer fibers via electrospinning, e.g. in the form of microcapsules.
  • the polymer fibers obtainable by the process according to the invention can be used for textile fibers, for example for the production of fibers for functional clothing or for nonwovens or fiber mats for cell culture substrates.
  • the present invention relates to the fields of macromolecular chemistry, process engineering, textile and material sciences.
  • a polymer melt or a polymer solution is usually exposed to a high electric field at an edge serving as an electrode, for example, by passing the polymer melt or polymer solution under low pressure through an electric field in an electric field A cannula connected to one pole of a voltage source is extruded.
  • DE 10 2004 009 887 A1 relates to a process for producing fibers with a diameter of ⁇ 50 ⁇ m by electrostatic spinning or spraying a melt of at least one thermoplastic polymer.
  • DE 101 33 393 A1 discloses a process for producing hollow fibers having an inner diameter of 1 to 100 nm, in which a solution of a water-insoluble polymer-for example a poly-L-lactide solution in dichloromethane or a polyamide-46 Solution in pyridine - is electrospun.
  • a solution of a water-insoluble polymer-for example a poly-L-lactide solution in dichloromethane or a polyamide-46 Solution in pyridine - is electrospun.
  • a similar method is also known from WO 01/09414 A1 and DE 103 55 665 A1.
  • DE 196 00 162 A1 discloses a process for the production of lawnmower wire or textile fabrics in which polyamide, polyester or polypropylene are combined, melted and mixed together as a fiber-forming polymer, a maleic anhydride-modified polyethylene / polypropylene rubber and one or more aging stabilizers before this melt is melt-spun.
  • Microorganisms are understood as meaning bacteria, fungi, algae, protozoa and viruses. Fibers with antimicrobial properties are particularly important for the medical in the field of interest, for example as wound dressings or for textiles for patients and / or medical personnel. Further fields of application for such textile products arise in biotechnology, for example as carrier materials for cell cultures.
  • honey is considered to be a concentrated aqueous solution of invert sugars.
  • Invertose is a mixture of equal parts of grape (glucose) and fructose. It is known to the person skilled in the art that honey has antibiotic, in particular anti-microbial properties. Special attention is paid to the antibacterial nature of honey. This is described, for example, in KM Russell, PC Molan, AL Wilkins, PT Holland, Journal of Agricultural and Food Chemistry 1990, 38, 10-13. Unless otherwise stated, the terms microbicide and microbicide are to be used below as collective headings for agents for controlling microorganisms or for an antimicrobial effect.
  • honey is known to be microbicidal, not only because of its low water hardness (about 15 to 18%) and its low pH (about pH 3 to 4, for honeydew honey pH 5 to 6) - for example antibacterial - acts, but in particular that it contains microbicidal agents - for example, inhibins.
  • Hydrogen peroxide is the best known inhibin, but there are also several non-peroxides inhibins, such as lysozyme, flavonoids and aromatic acids known and described in the literature. S Bogdanov and P Blumer, Swiss Center for Bee Research 2001, described that these non-peroxyd inhibins are partly of plant origin, but that bees also contribute to the microbicidal action of honey.
  • the object of the present invention is to provide polymer fibers with microbicidal properties and processes for their preparation.
  • polymer fibers having microbicidal properties is achieved according to the invention by polymer fibers comprising at least one electrospinnable polymer and honey.
  • the at least one electrospinnable polymer is selected from the group poly (p-xylylene); Polyvinylidene halides, polyesters such as polyethylene terephthalates, polybutylene terephthalate; polyether; Polyolefins such as polyethylene, polypropylene, poly (ethylene / propylene) (EPDM); polycarbonates; polyurethanes; natural polymers, eg rubber; polycarboxylic acids; Polysulfonic acids; sulfated polysaccharides; polylactides; polyglycosides; polyamides; Homopolymers and copolymers of aromatic vinyl compounds such as poly (alkyl) styrenes), for example polystyrenes, poly-alpha-methylstyrenes; Polyacrylonitriles, polymethacrylonitriles; polyacrylamides; polyimides; Polyphenylene; polysilanes; polysiloxanes; Polybenzimidazoles;
  • honey is a natural sweetener produced by honey bees from nectar or secretions of living parts of plants or excretions of plant-sucking insects on living parts of plants that collect honeybees, by mixing with specific substances of their own, deposit, thicken, store and mature in honeycombs.
  • Honeydew honey is honey derived mainly from excretions of plant-sucking insects (Hemiptera) from living parts of plants or from the secretions of living plants.
  • Honey bees are states forming insects of the genus Apis from the superfamily of bees ⁇ aceadea).
  • the genus Apis includes nine species of honeybees, eight of them are found in Asia, one from Europe.
  • the native species of the genus Apis in Asia include: - Apis laboriosa (Cliff Honeybee), Apis dorsata (Giant Honeybee),
  • the Western honey bee Apis mellifera originating from Europe, comprises the following subspecies: Apis mellifera ligustica, Apis mellifera carnica, Apis mellifera macedonia, Apis mellifera sicula, Apis mellifera cecropia,
  • Apis mellifera mellifera Apis mellifera iberica, Apis mellifera sahariensis, Apis mellifera intermissa, Apis meHfera meda, Apis mellifera adami, Apis mellifera cypria, Apis mellifera caucasica, Apis mellifera armeniaca, Apis mellifera anatolica, Apis mellifera major, Apis mellifera adansonii, Apis mellifera unicolor, Apis mellifera capensis, Apis mellifera monticola, Apis mellifera scutellata, Apis mellifera lamarkii, Apis mellifera yemenitica, Apis mellifera litorea.
  • Honey is produced by bees picking up nectar juices or other sweet juices on living plants, enriching them by the body's own substances, modifying them in their bodies, storing them in honeycombs and allowing them to ripen there.
  • the main source is the nectar of flowering plants, an evolutionary mutual dependence between plants and mainly insects over millions of years for more effective pollination.
  • Another honey source is honeydew of leaf, bark and / or scale insects in some of the world's most temperate climatic regions. More rarely, extrafloral plant nectaries, e.g. of corn, a roll.
  • the bee sucks the nectar or honeydew over her trunk, and in the honey bladder it is transported home to the hive. There the sugary juice is passed on to the stock bees. These add native substances and reduce the water content.
  • the enzymes added by the bee cause a change in the sugar spectrum and the formation of inhibitors - these inhibit the growth of microorganisms, in particular of yeasts and / or bacteria.
  • the reduction of the water content is done in two steps: First, a drop of nectar is spread over the nest of brood on the honeycomb cells. By vigorous Fanning with the wings and the prevailing temperature, water is evaporated until the honey reaches a water content of about 16-18%. Now the storage cells of the honey are coated with an impermeable wax layer. For the beekeeper this is the sure sign that the honey is ripe and can be harvested.
  • Honey is a viscous to solid (partially crystallized) substance, which tastes very sweet due to its high content of fruit and glucose.
  • honey contains 15-21% water (heather). honey to 23%) as well as enzymes, vitamins, amino acids, pollen, and flavorings
  • honey is divided into:
  • Honeydew Honey It is obtained using exchangeable frames by ejecting the previously uncovered honeycombs in a honey extractor utilizing centrifugal force.
  • Disc honey It consists of non-hatched honeycomb pieces as pure natural constructions (honeycomb completely built by the bees themselves), especially at
  • Honeycomb honey It resembles the disc honey, but the honeycomb construction may contain so-called middle walls (pressed by the beekeeper to the people given pressed wax plate as a "building template") - Seim-, dripping, pressing or ramming honey: The honey is obtained from the honeycomb by leaking or squeezing ,
  • Nectar is a liquid that is rich in cane sugar, glucose and fructose and also contains minerals and fragrances.
  • the nectar is excreted from the flowers of plants as glandular secretions from the nectaries (honey glands) to attract animals to transport the pollen of these plants to flowers of the same species for the purpose of reproduction (sexual reproduction).
  • Nectar serves as a source of food for many animals and is, in addition to honeydew, the raw material from which bees produce honey.
  • Honeydew is a sugar-containing excrement product of various beaked hens (Hemiptera), especially the aphids (Aphidina), bark lice (Cinara), scale insects (Coccina), Balttflöhe (Psyllina), moth sign lice (Aleyrodina) and various cicadas (Auchenorrhyncha). These insects feed on juice from sieve tubes (phloem) of various plants. Since the phloem sap is rich in sugars but relatively low in nitrogenous compounds (amino acids), the plant teat must absorb large amounts of phloem sap. to meet their nitrogen needs. The superfluous sugar is excreted in the form of honeydew.
  • Hemiptera especially the aphids (Aphidina), bark lice (Cinara), scale insects (Coccina), Balttflöhe (Psyllina), moth sign lice (Aleyrodina) and various cicadas (Auch
  • Honeydew is a popular food source for a variety of insects that feed on the sweet juice or use it as an adjunct. It is known that begging honeydew by ants (Formicidae), which hold aphids like dairy cows and protect them from predators. Most other insects lick the honeydew from leaves or needles, such as many
  • Honeydew is clear when fresh. It is rich in sugars, especially in fruit, grape and cane sugar. In addition, maltose, fructomaltose and melezitose as well as other oligosaccharides are also present in smaller quantities. In addition, honeydew contains ferments, organic acids, vitamins and adenosine phosphates.
  • honey bees also collect honeydew instead of nectar if they have sufficient supply. This then forms the basis for various honey varieties, which are referred to as leaf, fir or forest honey.
  • honey varieties which are referred to as leaf, fir or forest honey.
  • the color and aroma of these honeys vary greatly depending on their origin, especially in the forest honey from firs and spruces.
  • honeys which can be used in the present invention include, for example, but not exhaustively:
  • honey comprises all the honeys mentioned in each case individually or in any desired combination with one another, in any desired mixing ratio and regardless of botanical origin, method of production and / or honeys and irrespective of whether they are honeydew flowers or honeydew honey
  • honey also comprises sugar solutions and mixtures of sugar solutions, in particular concentrated sugar solutions, which have microbicidal or other cosmetic, medicinal or pharmaceutical effects on humans or animals.
  • the honey can be used in encapsulated form.
  • Processes for the preparation of active ingredient-containing microcapsules are known to the person skilled in the art and can be used without departing from the scope of the patent claims.
  • active substance-containing means "containing honey as active ingredient”
  • Honey in encapsulated form means "microcapsules containing honey as active ingredient”.
  • Active ingredient-containing microcapsules can be prepared, for example, by polymerizing honey and at least one polymer by microreaction technology in the micromixer crosslinking.
  • the polymer fibers having microbicidal properties according to the invention comprising at least one electrospinnable polymer and honey may comprise honey as "honey” as defined above and / or as "honey in encapsulated form”.
  • the polymer fibers according to the invention with microbicidal properties are prepared by a process characterized by the following steps: a) preparing a solution of the at least one electrospinnable polymer, b) adding honey and / or honey in encapsulated form and mixing with the polymer solution, c) electrospinning the Mix to fibers.
  • the electrospinnable polymer is dissolved in a mixture of at least one suitable organic solvent and water.
  • there the ratio of at least one organic solvent to water is 95: 5 (v / v) to 70:30 (v / v).
  • the polymer content in this solution is according to the invention between 3 wt .-% and 20 wt .-%.
  • honey and / or honey in encapsulated form are added to the solution of the at least one polymer.
  • the proportion of honey and / or honey in encapsulated form in this mixture is according to the invention between 1 wt .-% and 20 wt .-% based on the polymer solution, regardless of the proportion of the polymer or polymers in the solution.
  • This mixture is exposed to a high electric field at an edge serving as an electrode.
  • this can be done by extruding the honey nanoparticle-containing solution of the electro-spinnable polymer in an electric field under low pressure through a cannula connected to a pole of a voltage source.
  • the result is a flow of material directed at the counterelectrode, which solidifies on the way to the counterelectrode.
  • polymer fibers according to the invention with microbicidal properties which were prepared by the above process according to the invention, can subsequently be coated with at least one further layer of at least one further polymer.
  • This coating can be, for example, by vapor deposition, knife coating, spin coating, dip coating, spraying or plasma deposition of polymers such as poly (p-xylylene), polyacrylamide, polyimides, polyesters, polyolefins, polycarbonates, polyamides, polyethers, polyphenylenes, polysilanes , Polysiloxanes, Polybenzimidazoles, polybenzothiazoles, polyoxazoles, polysulfides, polyesteramides, polyarylenevinylenes, polylactides, polyetherketones, polyurethanes, poly-sulfones, ormocers, polyacrylates, silicones, wholly aromatic copolyesters, poly-N-vinylpyrrolidone, polyhydroxyethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polymethacrylonitrile, polyacrylonitrile, polyvinyl acetate , Neoprene, Buna N, polybut
  • polymer fibers according to the invention having microbicidal properties inhibit the growth and / or proliferation of microorganisms.
  • polymer fibers having microbicidal properties are prepared by preparing a solution of at least one electro-spinnable polymer, mixing it with honey, and electro-spanning it. If there is no addition of honey in encapsulated form and / or if the additional optional coating with at least one further polymer is dispensed with, the resulting polymer fibers are water-stable; however, the honey dissolves on contact with aqueous media.
  • fibers according to the invention having microbicidal properties are prepared with honey as defined above, without these fibers subsequently being coated with at least one further polymer, the polymer fibers themselves are water-stable.
  • the honey is essentially completely dissolved out on contact with aqueous media within a few days.
  • Fibers of this embodiment are therefore preferably suitable for the production of products in which a short-term, but extensive microbicidal action is desirable.
  • Such products are, for example, wound dressings or cosmetic products such as cleansing and care wipes or pads.
  • polymer fibers having microbicidal properties are produced by preparing a solution of at least one electro-spinnable polymer, mixing it with honey and electrospinning, wherein honey is added in encapsulated form and / or the polymer fibers are subsequently treated with at least one further polymer. be layered. Fibers of this embodiment are also water stable, and the honey contained in them is released slowly and in a controlled manner. Fibers of this embodiment are therefore suitable for the manufacture of products which are used permanently. These are, for example, textile fibers for functional clothing, protective clothing for medical personnel and protective clothing for patients.
  • PVB fibers The antibacterial effectiveness of the PVB fibers, the different proportions of Manuka honey or Dr. med. Krieger's bee honey, contained, was investigated.
  • agar plates were either inoculated with Micrococcus luteus, mixed with a suitable nutrient medium and incubated to confluency.
  • FIGS. 2 to 5 show the results of the investigations.
  • TQ PVB fiber mat with 6% by weight honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
  • M1 PVB fiber mat with 1% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
  • M3 PVB fiber mat with 3% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
  • M6 PVB fiber mat with 6% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
  • honey-containing fiber mats had more or less pronounced bacteria-free zones around the mats (most clearly in sample M6), but the fiber mats themselves were not bacteria-free.
  • the device comprises a syringe 3, at the tip of which is a capillary nozzle 2.
  • This capillary nozzle 2 is connected to a pole of a voltage source 1.
  • the syringe 3 receives the polyelectrolyte solutions 4 to be spun.
  • a counterelectrode 5 connected to the other pole of the voltage source 1 is arranged at a distance of about 20 cm, which acts as a collector for the fibers formed.
  • a voltage between 18 kV and 35 kV is set at the electrodes 2 and 5, and the polyelectrolyte solution 4 is discharged through the capillary nozzle 2 of the syringe 3 at a low pressure. Due to the electrostatic charge of the polyelectrolytes in the solution due to the strong electric field of 0.9 to 2 kV / cm, a material flow directed towards the counterelectrode 5, which solidifies on the way to the counterelectrode 5 with fiber formation 6, arises as a result on the counterelectrode 5 fibers 7 with diameters in the micro and nanometer range. Fig. 2
  • Fig. 2 is a comparative sample of a 2 x 1 cm is large electro-spun fiber mat of Mowital B 60 T ® (polyvinyl butyral, PVB), which was placed for 24 hours at room temperature to a confluent layer of Micrococcus luteus.
  • Mowital B 60 T ® polyvinyl butyral, PVB
  • no honey was added to the polyvinyl butyrate solution prior to electrospinning. No antibacterial effect of the fiber mat could be detected.
  • Fig. 3 shows electrospun fiber mats (2 x 1 cm) of Mowital B 60 T ® (polyvinyl butyrate).
  • 0 means: comparative sample of a PVB fiber mat without honey, laid on a confluent layer of Micrococcus luteus T1: PVB fiber mat with 1% by weight honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
  • M1 PVB fiber mat with 1% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
  • Fig. 4 shows electrospun fiber mats (2 x 1 cm) of Mowital B 60 T ® (polyvinyl butyrate). It means
  • T6 PVB fiber mat with 6% by weight honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
  • M3 PVB fiber mat with 3% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
  • M6 PVB fiber mat with 6% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
  • sample M6 Manuka honey

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Abstract

The invention relates to polymer fibers with microbicidal properties, comprising at least one polymer that can be electrospun and honey and to a method for producing said fibers. The use of honey allows polymers that can be electrospun to be provided with a microbicidal, especially antibacterial finish. The honey as such can be admixed to the solution of the at least one polymer that is to be electrospun, and/or the honey can be incorporated into the polymer fibers in encapsulated form via electrospinning, e.g. in the form of microcapsules. The fibers so obtained can optionally be coated with at least one additional layer of at least one polymer. The polymer fibers that can be obtained by the method according to the invention can be used for textile fibers, for example for producing fibers for activity clothing, protective clothing for medical staff and protective clothing for patients, for medical drapes and dressings or for cosmetic cleaning and care wipes and pads.

Description

Mikrobizide Nano- und Mesopolymerfasern aus Polymeren und Honig für textile Anwendungen Microbicidal nano- and mesopolymer fibers of polymers and honey for textile applications
Die vorliegende Erfindung beschreibt ein Verfahren zur Herstellung elektroge- sponnener Fasern umfassend mindestens ein Polymer und Honig. Die Verwendung von Honig erlaubt die mikrobizide und besonders die antibakterielle Ausrüstung elektrospinnbarer Polymere. Dabei kann der Honig als solcher in die Lösung des mindestens einen Polymers eingemischt werden, welches elektroversponnen werden soll, und/oder der Honig kann in verkapselter Form in die Polymerfasern via Elektrospinnen eingebaut werden, z.B. in Form von Mikrokapseln. Die mit dem erfindungsgemäßen Verfahren erhältlichen Polymerfasern können für textile Fasern verwendet werden, beispielsweise für die Herstellung von Fasern für Funktionskleidung oder für Vliese oder Fasermatten für Zellkultursubstrate.The present invention describes a process for producing electrospun fibers comprising at least one polymer and honey. The use of honey allows the microbicidal and especially the antibacterial finish of electrospinnable polymers. In this case, the honey can be mixed as such in the solution of the at least one polymer which is to be electro-spun, and / or the honey can be incorporated in encapsulated form into the polymer fibers via electrospinning, e.g. in the form of microcapsules. The polymer fibers obtainable by the process according to the invention can be used for textile fibers, for example for the production of fibers for functional clothing or for nonwovens or fiber mats for cell culture substrates.
Beschreibung und Einleitung des allgemeinen Gebietes der ErfindungDescription and introduction of the general field of the invention
Die vorliegende Erfindung betrifft die Gebiete makromolekulare Chemie, Verfahrenstechnik, Textil- und Materialwissenschaften.The present invention relates to the fields of macromolecular chemistry, process engineering, textile and material sciences.
Stand der TechnikState of the art
Zur Herstellung von Nano- und Mesofasern sind dem Fachmann eine Vielzahl an Verfahren bekannt, von denen dem Elektrospinnverfahren („Electrospinning") derzeit die größte Bedeutung zukommt. Bei diesem Verfahren, welches beispielsweise von D.H. Reneker, H. D. Chun in Nanotechn. 7 (1996), Seite 216 f beschrie- ben ist, wird üblicherweise eine Polymerschmelze oder eine Polymerlösung an einer als Elektrode dienenden Kante einem hohen elektrischen Feld ausgesetzt. Dies kann beispielsweise dadurch erreicht werden, dass die Polymerschmelze oder Polymerlösung in einem elektrischen Feld unter geringem Druck durch eine mit einem Pol einer Spannungsquelle verbundene Kanüle extrudiert wird. Auf Grund der dadurch erfolgenden elektrostatischen Aufladung der Polymerschmelze oder Polymerlösung entsteht ein auf die Gegenelektrode gerichteter Materialstrom, der sich auf dem Weg zur Gegenelektrode verfestigt. In Abhängigkeit von den Elektrodengeometrien werden mit diesem Verfahren Vliese bzw. so genannte Nonwovens oder Ensembles geordneter Fasern erhalten. Während mit Polymerschmelzen bisher nur Fasern mit Durchmessern größer 1000 nm erhalten werden, kann man aus Polymerlösungen Fasern mit Durchmessern größer oder gleich 5 nm herstellen.For the production of nano- and mesofibers, the skilled person is familiar with a large number of methods, of which the electrospinning method (electrospinning) is of greatest importance at present, In this method, which is described, for example, by DH Reneker, HD Chun in Nanotechn. , Page 216 f, a polymer melt or a polymer solution is usually exposed to a high electric field at an edge serving as an electrode, for example, by passing the polymer melt or polymer solution under low pressure through an electric field in an electric field A cannula connected to one pole of a voltage source is extruded. Due to the resulting electrostatic charge of the polymer melt or polymer solution, a material flow directed onto the counterelectrode, which solidifies on the way to the counterelectrode, is produced. Depending on the electrode geometries, nonwovens or ensembles of ordered fibers are obtained with this method. While with polymer melts so far only fibers with diameters greater than 1000 nm are obtained, one can produce from polymer solutions fibers with diameters greater than or equal to 5 nm.
Der Stand der Technik kennt einige Verfahren zur Herstellung von Polymerfasem mittels Elektrospinning:The prior art knows some processes for the production of polymer fibers by means of electrospinning:
Die DE 10 2004 009 887 A1 betrifft ein Verfahren zur Herstellung von Fasern mit einem Durchmesser von < 50 μm durch elektrostatisches Verspinnen oder Ver- sprühen einer Schmelze von mindestens einem thermoplastischen Polymeren.DE 10 2004 009 887 A1 relates to a process for producing fibers with a diameter of <50 μm by electrostatic spinning or spraying a melt of at least one thermoplastic polymer.
In der DE 101 33 393 A1 wird ein Verfahren zur Herstellung von Hohlfasern mit einem Innendurchmesser von 1 bis 100 nm offenbart, bei dem eine Lösung eines wasserunlöslichen Polymers - beispielsweise eine Poly-L-Iactid-Lösung in Di- chlormethan oder eine Polyamid-46-Lösung in Pyridin - elektroversponnen wird. Ein ähnliches Verfahren ist auch aus der WO 01/09414 A1 und der DE 103 55 665 A1 bekannt.DE 101 33 393 A1 discloses a process for producing hollow fibers having an inner diameter of 1 to 100 nm, in which a solution of a water-insoluble polymer-for example a poly-L-lactide solution in dichloromethane or a polyamide-46 Solution in pyridine - is electrospun. A similar method is also known from WO 01/09414 A1 and DE 103 55 665 A1.
Aus DE 196 00 162 A1 ist ein Verfahren zur Herstellung von Rasenmäherdraht oder textilen Flächengebilden bekannt, bei dem Polyamid, Polyester oder Polypropylen als fadenbildendes Polymer, ein maleinsäureanhydrid-modifizierter Polyethylen/Polypropylen-Kautschuk sowie ein oder mehrere Alterungsstabilisatoren zusammengegeben, aufgeschmolzen und miteinander vermischt werden, bevor diese Schmelze schmelzversponnen wird.DE 196 00 162 A1 discloses a process for the production of lawnmower wire or textile fabrics in which polyamide, polyester or polypropylene are combined, melted and mixed together as a fiber-forming polymer, a maleic anhydride-modified polyethylene / polypropylene rubber and one or more aging stabilizers before this melt is melt-spun.
Für einige Anwendungsbereiche von Fasern ist es wünschenswert, das Wachstum und/oder die Proliferation von Mikroorganismen inhibieren zu können. Unter Mikroorganismen werden dabei Bakterien, Pilze, Algen, Protozoen und Viren verstanden. Fasern mit antimikrobiellen Eigenschaften sind besonders für den medi- zinischen Bereich interessant, beispielsweise als Wundauflagen oder für Textilien für Patienten und/oder medizinisches Personal. Weitere Anwendungsbereiche für solche Textilprodukte ergeben sich in der Biotechnologie, zum Beispiel als Trägermaterialien für Zellkulturen.For some applications of fibers, it is desirable to be able to inhibit the growth and / or proliferation of microorganisms. Microorganisms are understood as meaning bacteria, fungi, algae, protozoa and viruses. Fibers with antimicrobial properties are particularly important for the medical in the field of interest, for example as wound dressings or for textiles for patients and / or medical personnel. Further fields of application for such textile products arise in biotechnology, for example as carrier materials for cell cultures.
In der Lebensmittelindustrie wird Honig als eine konzentrierte wässrige Lösung von Invertzuckern betrachtet. Als Invertzucker (Invertose) wird ein Gemisch aus gleichen Teilen Trauben- (Glucose) und Fruchtzucker (Fructose) bezeichnet. Dem Fachmann ist bekannt, dass Honig antibiotische insbesondere anti-mikrobielle Eigenschaften aufweist. Besondere Beachtung findet die antibakterielle Natur des Honigs. Dies ist beispielsweise in KM Russell, PC Molan, AL Wilkins, PT Holland, Journal of Agricultural and Food Chemistry 1990, 38, 10-13, beschrieben. Im Folgenden soll, sofern nicht ausdrücklich anders erwähnt, die Begriffe Mikrobizid und mikrobizid als Sammelbezeichnungen für Mittel zur Bekämpfung von Mikroorga- nismen respektive für eine antimikrobielle Wirkung verwendet werden. Die Wirkung kann dabei reversibel oder irreversibel wachstumshemmend (zum Beispiel Bakteriostatika oder Fungistatika) oder abtötend (zum Beispiel Bakterizide oder Fungizide) sein. Vom Honig ist bekannt, dass er nicht nur auf Grund seines niedrigen Wasserge- hartes (ca. 15 bis 18%) und seines niedrigen pH-Wertes (ca. pH 3 bis 4, bei Honigtauhonigen pH 5 bis 6) mikrobizid - zum Beispiel antibakteriell - wirkt, sondern dass er insbesondere mikrobizide Wirkstoffe - zum Beispiel Inhibine - enthält. Wasserstoffperoxid ist das bekannteste Inhibin, aber es sind auch etliche nicht- peroxide Inhibine, wie zum Beispiel Lysozym, Flavonoide und aromatische Säuren bekannt und in der Literatur beschrieben. Von S Bogdanov und P Blumer, Schweizerisches Zentrum für Bienenforschung 2001 , ist beschrieben, dass diese nicht-peroxiden Inhibine zum Teil Pflanzlichen Ursprungs sind, die Bienen aber ebenfalls einen Beitrag zur mikrobiziden Wirkung des Honigs leisten.In the food industry, honey is considered to be a concentrated aqueous solution of invert sugars. Invertose is a mixture of equal parts of grape (glucose) and fructose. It is known to the person skilled in the art that honey has antibiotic, in particular anti-microbial properties. Special attention is paid to the antibacterial nature of honey. This is described, for example, in KM Russell, PC Molan, AL Wilkins, PT Holland, Journal of Agricultural and Food Chemistry 1990, 38, 10-13. Unless otherwise stated, the terms microbicide and microbicide are to be used below as collective headings for agents for controlling microorganisms or for an antimicrobial effect. The effect may be reversible or irreversible growth inhibiting (for example, bacteriostats or fungistatics) or killing (for example, bactericides or fungicides). Honey is known to be microbicidal, not only because of its low water hardness (about 15 to 18%) and its low pH (about pH 3 to 4, for honeydew honey pH 5 to 6) - for example antibacterial - acts, but in particular that it contains microbicidal agents - for example, inhibins. Hydrogen peroxide is the best known inhibin, but there are also several non-peroxides inhibins, such as lysozyme, flavonoids and aromatic acids known and described in the literature. S Bogdanov and P Blumer, Swiss Center for Bee Research 2001, described that these non-peroxyd inhibins are partly of plant origin, but that bees also contribute to the microbicidal action of honey.
Bislang kennt der Stand der Technik kein praktikables Verfahren, um Textilfasem dauerhaft oder kurzfristig mit Honig auszurüsten und somit den Fasern eine mikrobizide und insbesondere bakterizide Wirkung zu verleihen. AufgabeSo far, the prior art knows no practicable method to provide textile fibers permanently or in the short term with honey and thus to give the fibers a microbicidal and especially bactericidal effect. task
Aufgabe der vorliegenden Erfindung ist es, Polymerfasern mit mikrobiziden Eigenschaften sowie Verfahren zu ihrer Herstellung bereitzustellen.The object of the present invention is to provide polymer fibers with microbicidal properties and processes for their preparation.
Lösung der AufgabeSolution of the task
Die Aufgabe der Bereitstellung von Polymerfasern mit mikrobiziden Eigenschaften wird erfindungsgemäß gelöst durch Polymerfasern umfassend mindestens ein elektrospinnbares Polymer und Honig.The object of providing polymer fibers having microbicidal properties is achieved according to the invention by polymer fibers comprising at least one electrospinnable polymer and honey.
Erfindungsgemäß wird das mindestens ein elektrospinnbares Polymer ausgewählt aus der Gruppe Poly-(p-xylylen); Polyvinylidenhalogenide, Polyester wie PoIy- ethylenterephthalate, Polybutylenterephthalat; Polyether; Polyolefine wie PoIy- ethylen, Polypropylen, Poly(Ethylen/Propylen) (EPDM); Polycarbonate; Polyurethane; natürliche Polymere, z.B. Kautschuk; Polycarbonsäuren; Polysulfon- säuren; sulfatierte Polysaccharide; Polylactide; Polyglycoside; Polyamide; Homo- und Copolymerisate von aromatischen Vinylverbindungen wie Poly(alkyl)styrole), z.B. Polystyrole, Poly-alpha-methylstyrole; Polyacrylnitrile, Polymethacrylnitrile; Polyacrylamide; Polyimide; Polyphenylene; Polysilane; Polysiloxane; Polybenzimi- dazole; Polybenzothiazole; Polyoxazole; Polysulfide; Polyesteramide; Polyarylen- vinylene; Polyetherketone; Polyurethane, Polysulfone, anorganisch-organische Hybrid polymere wie ORMOCER® der Fraunhofer Gesellschaft zur Förderung der angewandten Forschung e.V. München; Silicone; vollaromatische Copolyester; Poly(alkyl)acrylate; Poly(alkyl)methacry!ate; Polyhydroxyethylmethacrylate; PoIy- vinylacetate, Polyvinylbutyrate; Polyisopren; synthetische Kautschuke wie Chlorbutadien-Kautschuke, z.B. Neopren® von DuPont; Nitril-Butadien-Kautschuke, z.B. Buna N®; Polybutadien; Polytetrafluorethylen; modifizierte und nicht modifi- zierte Cellulosen, Homo- und Copolymerisate von alpha-Olefinen und Copoly- meren aufgebaut aus zwei oder mehr die vorstehend genannten Polymere bildenden Monomereinheiten; Polyvinylalkohole, Polyalkylenoxide, z.B. Polyethylen- oxide; Poly-N-vinylpyrrolidon; Hydroxymethylcellulosen; Maleinsäuren; Alginate; Collagene. Alle vorgenannten Polymere können in den erfindungsgemäßen Polymerfasern mit mikrobiziden Eigenschaften jeweils einzeln oder in beliebigen Kombinationen miteinander eingesetzt werden, und zwar in jedem beliebigen Mischungsverhältnis.According to the invention, the at least one electrospinnable polymer is selected from the group poly (p-xylylene); Polyvinylidene halides, polyesters such as polyethylene terephthalates, polybutylene terephthalate; polyether; Polyolefins such as polyethylene, polypropylene, poly (ethylene / propylene) (EPDM); polycarbonates; polyurethanes; natural polymers, eg rubber; polycarboxylic acids; Polysulfonic acids; sulfated polysaccharides; polylactides; polyglycosides; polyamides; Homopolymers and copolymers of aromatic vinyl compounds such as poly (alkyl) styrenes), for example polystyrenes, poly-alpha-methylstyrenes; Polyacrylonitriles, polymethacrylonitriles; polyacrylamides; polyimides; Polyphenylene; polysilanes; polysiloxanes; Polybenzimidazoles; polybenzothiazoles; polyoxazoles; polysulfides; polyester; Polyarylene-vinylenes; polyether ketones; Polyurethanes, polysulfones, inorganic-organic hybrid polymers such as ORMOCER® of the Fraunhofer Society for the Advancement of Applied Research Munich; silicones; wholly aromatic copolyesters; Poly (alkyl) acrylates; Poly (alkyl) methacry ate!; polyhydroxyethylmethacrylates; Polyvinyl acetates, polyvinyl butyrates; polyisoprene; synthetic rubbers such as chlorobutadiene rubbers, eg Neoprene® from DuPont; Nitrile butadiene rubbers, eg Buna N®; polybutadiene; polytetrafluoroethylene; modified and unmodified celluloses, homopolymers and copolymers of alpha-olefins and copolymers made up of two or more monomer units forming the abovementioned polymers; Polyvinyl alcohols, polyalkylene oxides, for example polyethylene oxides; Poly-N-vinylpyrrolidone; hydroxymethylcelluloses; maleic; alginates; Collagens. All of the abovementioned polymers can be used in the polymer fibers according to the invention having microbicidal properties in each case individually or in any desired combinations with one another, in any desired mixing ratio.
Gemäß EU-Norm ist Honig ein natürlicher Süßstoff, der von Honigbienen hergestellt wird aus Blütennektar oder Absonderungen lebender Pflanzenteile oder Ausscheidungen pflanzensaugender Insekten auf lebenden Pflanzenteilen, welche die Honigbienen sammeln, durch Vermischung mit spezifischen eigenen Sub- stanzen verändern, ablagern, eindicken, lagern und in Honigwaben reifen lassen. Dabei ist „Blütenhonig" Honig, der aus dem Nektar von Blüten stammt. „Honigtauhonig" ist Honig, der hauptsächlich von Ausscheidungen pflanzensaugender Insekten (Hemiptera) aus lebenden Teilen von Pflanzen oder von Absonderungen lebender Pflanzen stammt.According to the EU standard, honey is a natural sweetener produced by honey bees from nectar or secretions of living parts of plants or excretions of plant-sucking insects on living parts of plants that collect honeybees, by mixing with specific substances of their own, deposit, thicken, store and mature in honeycombs. Honeydew honey is honey derived mainly from excretions of plant-sucking insects (Hemiptera) from living parts of plants or from the secretions of living plants.
Honigbienen sind Staaten bildende Fluginsekten der Gattung Apis aus der Überfamilie der Bienen {Apoidea). Die Gattung Apis umfasst neun Arten von Honigbienen, acht davon kommen in Asien vor, eine stammt aus Europa. Die in Asien beheimateten Species der Gattung Apis umfassen: - Apis laboriosa (Kliffhonigbiene), Apis dorsata (Riesenhonigbiene),Honey bees are states forming insects of the genus Apis from the superfamily of bees {Apoidea). The genus Apis includes nine species of honeybees, eight of them are found in Asia, one from Europe. The native species of the genus Apis in Asia include: - Apis laboriosa (Cliff Honeybee), Apis dorsata (Giant Honeybee),
- Apis koschevnikovi v. (Asiatische Rote Honigbiene), Apis nigrocincta,- Apis koschevnikovi v. (Asian Red Honeybee), Apis nigrocincta,
- Apis cerana (östliche Honigbiene) mit den Subspecies Apis cerana cerana, Apis cerana himalaya, Apis cerana indica, Apis cerana japonica,- Apis cerana (eastern honeybee) with the subspecies Apis cerana cerana, Apis cerana himalaya, Apis cerana indica, Apis cerana japonica,
Apis florea (Zwerghonigbiene),Apis florea (dwarf honeybee),
Apis andreniformis (Zwergbuschbiene).Apis andreniformis (dwarf bush bee).
Die aus Europa stammende westliche Honigbiene Apis mellifera umfasst folgende Subspecies: - Apis mellifera ligustica, Apis mellifera carnica, Apis mellifera macedonia, Apis mellifera sicula, Apis mellifera cecropia,The Western honey bee Apis mellifera, originating from Europe, comprises the following subspecies: Apis mellifera ligustica, Apis mellifera carnica, Apis mellifera macedonia, Apis mellifera sicula, Apis mellifera cecropia,
- Apis mellifera mellifera, Apis mellifera iberica, Apis mellifera sahariensis, Apis mellifera intermissa, - Apis meIHfera meda, Apis mellifera adami, Apis mellifera cypria, Apis mellifera caucasica, Apis mellifera armeniaca, Apis mellifera anatolica, Apis mellifera major, Apis mellifera adansonii, Apis mellifera unicolor, Apis mellifera capensis, Apis mellifera monticola, Apis mellifera scutellata, Apis mellifera lamarkii, Apis mellifera yemenitica, Apis mellifera litorea.- Apis mellifera mellifera, Apis mellifera iberica, Apis mellifera sahariensis, Apis mellifera intermissa, Apis meHfera meda, Apis mellifera adami, Apis mellifera cypria, Apis mellifera caucasica, Apis mellifera armeniaca, Apis mellifera anatolica, Apis mellifera major, Apis mellifera adansonii, Apis mellifera unicolor, Apis mellifera capensis, Apis mellifera monticola, Apis mellifera scutellata, Apis mellifera lamarkii, Apis mellifera yemenitica, Apis mellifera litorea.
Honig entsteht, indem Bienen Nektariensäfte oder auch andere süße Säfte an lebenden Pflanzen aufnehmen, durch körpereigene Stoffe bereichern, in ihrem Körper verändern, in Waben speichern und dort reifen lassen. Die Hauptquelle ist der Nektar von Blütenpflanzen, eine in Jahrmillionen durch die Evolution entstandene gegenseitige Abhängigkeit zwischen Pflanzen und hauptsächlich Insekten zur effektiveren Bestäubung. Als weitere Quelle für Honig kommt in einigen - hauptsächlich gemässigteren - Klimaregionen der Erde der Honigtau von Blatt, Rinden- und/oder Schildläusen hinzu. Seltener spielen auch extraflorale Nektarien von Pflanzen, z.B. von Mais, eine Rolle.Honey is produced by bees picking up nectar juices or other sweet juices on living plants, enriching them by the body's own substances, modifying them in their bodies, storing them in honeycombs and allowing them to ripen there. The main source is the nectar of flowering plants, an evolutionary mutual dependence between plants and mainly insects over millions of years for more effective pollination. Another honey source is honeydew of leaf, bark and / or scale insects in some of the world's most temperate climatic regions. More rarely, extrafloral plant nectaries, e.g. of corn, a roll.
Die Biene saugt den Nektar oder Honigtau über ihren Rüssel auf, und in der Honigblase wird dieser in den Stock heimtransportiert. Dort wird der zuckerhaltige Saft an die Stockbienen weitergegeben. Diese geben bieneneigene Stoffe hinzu und reduzieren den Wassergehalt. Die durch die Biene hinzugefügten Enzyme bewirken eine Veränderung des Zuckerspektrums und die Entstehung von Inhibi- nen - diese hemmen das Wachstum von Mikroorganismen, insbesondere von Hefen und/oder Bakterien. Die Reduzierung des Wassergehalts erfolgt in zwei Schritten: Zuerst wird ein Tropfen Nektar über dem Brutnest auf den Wabenzellen ausgebreitet. Durch kräftiges Fächeln mit dem Flügeln und die dort herrschende Temperatur wird Wasser verdunstet, bis der Honig einen Wassergehalt von ca. 16-18 % erreicht. Nun werden die Lagerzellen des Honigs mit einer luftundurchlässigen Wachsschicht überzogen. Für den Imker ist dies das sichere Zeichen dafür, dass der Honig reif ist und geerntet werden kann.The bee sucks the nectar or honeydew over her trunk, and in the honey bladder it is transported home to the hive. There the sugary juice is passed on to the stock bees. These add native substances and reduce the water content. The enzymes added by the bee cause a change in the sugar spectrum and the formation of inhibitors - these inhibit the growth of microorganisms, in particular of yeasts and / or bacteria. The reduction of the water content is done in two steps: First, a drop of nectar is spread over the nest of brood on the honeycomb cells. By vigorous Fanning with the wings and the prevailing temperature, water is evaporated until the honey reaches a water content of about 16-18%. Now the storage cells of the honey are coated with an impermeable wax layer. For the beekeeper this is the sure sign that the honey is ripe and can be harvested.
Honig ist eine dickflüssige bis feste (teilweise kristallisierte) Substanz, die auf Grund ihres hohen Anteils an Frucht- und Traubenzucker sehr süß schmeckt. Neben diesen und weiteren Zuckerarten enthält Honig 15-21 % Wasser (Heide- honig bis 23 %) sowie Enzyme, Vitamine, Aminosäuren, Pollen, Aromastoffe undHoney is a viscous to solid (partially crystallized) substance, which tastes very sweet due to its high content of fruit and glucose. In addition to these and other sugars, honey contains 15-21% water (heather). honey to 23%) as well as enzymes, vitamins, amino acids, pollen, and flavorings
Mineralstoffe.Minerals.
Die Ernte des Honigs für den menschlichen Gebrauch erfolgt traditionell durchThe harvest of honey for human use is traditionally done by
Imker, die die Bienenvölker hegen. Entsprechend der Gewinnungsart wird der Honig eingeteilt in:Beekeepers harboring the bee colonies. According to the type of extraction, the honey is divided into:
Schleuderhonig: Er wird gewonnen bei Verwendung von austauschbaren Rähmchen durch Ausschleudern der vorher entdeckelten Bienenwaben in einer Honigschleuder unter Ausnutzung der Zentrifugalkraft. Scheibenhonig: Er besteht aus unbebrüteten Wabenstücken ais reinem Natur- bau (vollständig von den Bienen selbst errichtetes Wabenwerk), vor allem beiHoneydew Honey: It is obtained using exchangeable frames by ejecting the previously uncovered honeycombs in a honey extractor utilizing centrifugal force. Disc honey: It consists of non-hatched honeycomb pieces as pure natural constructions (honeycomb completely built by the bees themselves), especially at
Heidehonig.Heather honey.
- Wabenhonig. Er ähnelt dem Scheibenhonig, aber der Wabenbau darf sogenannte Mittelwände enthalten (vom Imker ins Volk gegebene gepresste Wachsplatte als „Bauvorlage"). - Seim-, Tropf-, Press- oder Stampfhonig: Dabei wird der Honig aus den Waben durch Auslaufenlassen oder Auspressen gewonnen.Honeycomb honey. It resembles the disc honey, but the honeycomb construction may contain so-called middle walls (pressed by the beekeeper to the people given pressed wax plate as a "building template") - Seim-, dripping, pressing or ramming honey: The honey is obtained from the honeycomb by leaking or squeezing ,
Nektar bezeichnet eine Flüssigkeit, die reich an Rohrzucker, Traubenzucker und Fruchtzucker ist und auch Mineralstoffe und Duftstoffe enthält. Der Nektar wird von den Blüten von Pflanzen als Drüsensekret aus den Nektarien (Honigdrüsen) ausgeschieden, um Tiere anzulocken, die den Pollen dieser Pflanzen zu Blüten der gleichen Art zum Zweck der Fortpflanzung (geschlechtliche Vermehrung) transportieren sollen. Nektar dient vielen Tieren als Nahrungsquelle und ist neben Honigtau der Rohstoff, aus dem Bienen Honig erzeugen.Nectar is a liquid that is rich in cane sugar, glucose and fructose and also contains minerals and fragrances. The nectar is excreted from the flowers of plants as glandular secretions from the nectaries (honey glands) to attract animals to transport the pollen of these plants to flowers of the same species for the purpose of reproduction (sexual reproduction). Nectar serves as a source of food for many animals and is, in addition to honeydew, the raw material from which bees produce honey.
Honigtau ist ein zuckerhaltiges Ausscheidungsprodukt verschiedener Schnabelkerfe (Hemiptera), vor allem der Blattläuse (Aphidina), Rindenläuse (Cinara), Schildläuse (Coccina), Balttflöhe (Psyllina), Mottenschildläuse (Aleyrodina) sowie verschiedener Zikaden (Auchenorrhyncha). Diese Insekten ernähren sich vom Saft aus den Siebröhren (Phloem) verschiedener Pflanzen. Da der Phloemsaft reich an Zuckern, aber relativ arm an stickstoffhaltigen Verbindungen (Aminosäuren) ist, müssen die Pflanzensauger große Mengen von Phloemsaft aufneh- men um ihren Stickstoffbedarf zu decken. Den überflüssigen Zucker scheiden sie in Form von Honigtau aus.Honeydew is a sugar-containing excrement product of various beaked hens (Hemiptera), especially the aphids (Aphidina), bark lice (Cinara), scale insects (Coccina), Balttflöhe (Psyllina), moth sign lice (Aleyrodina) and various cicadas (Auchenorrhyncha). These insects feed on juice from sieve tubes (phloem) of various plants. Since the phloem sap is rich in sugars but relatively low in nitrogenous compounds (amino acids), the plant teat must absorb large amounts of phloem sap. to meet their nitrogen needs. The superfluous sugar is excreted in the form of honeydew.
Honigtau stellt eine beliebte Nahrungsquelle für verschiedene Insekten dar, die sich von dem süßen Saft ernähren oder ihn als Beikost verwenden. Bekannt ist das Erbetteln von Honigtau durch Ameisen (Formicidae), welche sich Blattläuse wie Milchkühe halten und diese auch vor Fraßräubern schützen. Die meisten anderen Insekten lecken den Honigtau von Blättern oder Nadeln ab, so etwa vieleHoneydew is a popular food source for a variety of insects that feed on the sweet juice or use it as an adjunct. It is known that begging honeydew by ants (Formicidae), which hold aphids like dairy cows and protect them from predators. Most other insects lick the honeydew from leaves or needles, such as many
Zweiflügler (Diptera), wo der Honigtau einen dicken und klebrigen Film bilden kann (auch auf Fahrzeugen unter stark besiedelten Bäumen erkennbar).Diptera, where the honeydew can form a thick and sticky film (also recognizable on vehicles under heavily populated trees).
Im frischen Zustand ist Honigtau klar. Er ist reich an Zuckern, vor allem an Frucht-, Trauben- und Rohrzucker, daneben kommen auch Maltose, Fructo- maltose und Melezitose sowie weitere Oligosaccharide in kleineren Mengen vor. Daneben enthält der Honigtau Fermente, organische Säuren, Vitamine und Ade- nosinphosphate.Honeydew is clear when fresh. It is rich in sugars, especially in fruit, grape and cane sugar. In addition, maltose, fructomaltose and melezitose as well as other oligosaccharides are also present in smaller quantities. In addition, honeydew contains ferments, organic acids, vitamins and adenosine phosphates.
Wie bereits erwähnt, sammeln auch Honigbienen bei ausreichendem Angebot Honigtau statt Nektar. Dieser stellt dann die Grundlage für verschiedene Honig- sorten dar, die als Blatt-, Tannen- oder Waldhonige bezeichnet werden. Die Farbe und das Aroma dieser Honige variieren je nach Herkunft sehr stark, vor allem bei den von Tannen und Fichten stammenden Waldhonigen.As already mentioned, honey bees also collect honeydew instead of nectar if they have sufficient supply. This then forms the basis for various honey varieties, which are referred to as leaf, fir or forest honey. The color and aroma of these honeys vary greatly depending on their origin, especially in the forest honey from firs and spruces.
Zu den Honigsorten, die im Rahmen der vorliegenden Erfindung verwendet wer- den können, gehören beispielsweise, aber nicht erschöpfend:The honeys which can be used in the present invention include, for example, but not exhaustively:
Akazienhonig, Bergblütenhonig, Blütenhonig mit Mimose, Buchweizenhonig, Edelkastanienhonig, Eichenwaldhonig, Erdbeerbaumhonig, Eukalyptushonig, Gebirgs- blütenhonig, Heidehonig, Kleehonig, Landhonig, Lavendelblütenhonig, Lindenblütenhonig, Löwenzahnhonig, Manukahonig, Obstblütenhonig, Orangenblüten- honig, Phaceliahonig, Pinienhonig, Quillayahonig, Rapshonig, Sommerhonig, Sommerblütenhonig, Sonnenblumenhonig, Tamariskenhonig, Tasmanischer Lederholzhonig, Thymianhonig, Waldhonig, Weißtannenhonig und Wildblütenhonig. „Honig" im Sinne der vorliegenden Erfindung umfasst alle genannten Honige jeweils einzeln oder in beliebigen Kombinationen miteinander, und zwar in jedem beliebigen Mischungsverhältnis und unabhängig von botanischer Herkunft, Gewinnungsart und/oder Honigsorte sowie unabhängig davon, ob es sich um Blüten- oder Honigtauhonige handelt. „Honig" im Sinne der vorliegenden Erfindung umfasst zudem Zuckerlösungen und Gemische von Zuckerlösungen, insbesondere konzentrierte Zuckerlösungen, die mikrobizide oder weitere kosmetische, medizinische oder pharmazeutische Wirkungen an Menschen oder Tieren entfalten.Acacia honey, mountain flower honey, flower honey with mimosa, buckwheat honey, Chestnut honey, oak forest honey, strawberry tree honey, eucalyptus honey, mountain flower honey, heather honey, clover honey, country honey, lavender honey, linden honey, dandelion honey, Manuka honey, fruit blossom honey, orange blossom honey, Phaceliahonig, pine honey, Quillayahonig, oilseed rape honey, Summer honey, summer honey, sunflower honey, tamarisk honey, Tasmanian leather honey, thyme honey, wild honey, white fir honey and wild flower honey. For the purposes of the present invention, "honey" comprises all the honeys mentioned in each case individually or in any desired combination with one another, in any desired mixing ratio and regardless of botanical origin, method of production and / or honeys and irrespective of whether they are honeydew flowers or honeydew honey For the purposes of the present invention, "honey" also comprises sugar solutions and mixtures of sugar solutions, in particular concentrated sugar solutions, which have microbicidal or other cosmetic, medicinal or pharmaceutical effects on humans or animals.
Optional kann der Honig in verkapselter Form eingesetzt werden. Verfahren zur Herstellung von wirkstoffhaltigen Mikrokapseln sind dem Fachmann bekannt und können, ohne den Schutzbereich der Patentansprüche zu verlassen, verwendet werden. Dabei bedeutet „wirkstoffhaltig" im Sinne der vorliegenden Erfindung „enthaltend Honig als Wirkstoff"; „Honig in verkapselter Form" bedeutet „Mikro- kapseln enthaltend Honig als Wirkstoff". Wirkstoffhaltige Mikrokapseln können beispielsweise hergestellt werden, indem Honig und mindestens ein Polymer mittels Mikroreaktionstechnik im Mikromischer vernetzend polymerisiert werden.Optionally, the honey can be used in encapsulated form. Processes for the preparation of active ingredient-containing microcapsules are known to the person skilled in the art and can be used without departing from the scope of the patent claims. In the context of the present invention, "active substance-containing" means "containing honey as active ingredient"; "Honey in encapsulated form" means "microcapsules containing honey as active ingredient". Active ingredient-containing microcapsules can be prepared, for example, by polymerizing honey and at least one polymer by microreaction technology in the micromixer crosslinking.
Die erfindungsgemäßen Polymerfasern mit mikrobiziden Eigenschaften umfas- send mindestens ein elektrospinnbares Polymer und Honig können Honig als „Honig" gemäß obiger Definition und/oder als „Honig in verkapselter Form" umfassen.The polymer fibers having microbicidal properties according to the invention comprising at least one electrospinnable polymer and honey may comprise honey as "honey" as defined above and / or as "honey in encapsulated form".
Die erfindungsgemäßen Polymerfasern mit mikrobiziden Eigenschaften werden hergestellt durch ein Verfahren gekennzeichnet durch folgende Schritte: a) Herstellen einer Lösung des mindestens einen elektrospinnbaren Polymers, b) Zugabe von Honig und/oder von Honig in verkapselter Form und Mischen mit der Polymerlösung, c) Elektroverspinnen der Mischung zu Fasern.The polymer fibers according to the invention with microbicidal properties are prepared by a process characterized by the following steps: a) preparing a solution of the at least one electrospinnable polymer, b) adding honey and / or honey in encapsulated form and mixing with the polymer solution, c) electrospinning the Mix to fibers.
Um die Lösung des mindestens einen elektrospinnbaren Polymers gemäß Schritt a) herzustellen, wird das elektrospinnbare Polymer in einem Gemisch aus mindesten einem geeigneten organischen Lösungsmittel und Wasser gelöst. Dabei beträgt das Verhältnis von mindestens einem organischem Lösungsmittel zu Wasser 95:5 (V/V) bis 70:30 (V/V). Dem Fachmann ist bekannt, welche Polymere sich in welchen organischen Lösungsmitteln lösen, welche organischen Lösungsmittel in welchem Verhältnis mit Wasser mischbar sind und welche Gemische aus organischen Lösungsmitteln und Wasser zur Lösung welcher Polymere geeignet sind. Er kann dieses Fachwissen anwenden, ohne den Schutzbereich der Patentansprüche zu verlassen.In order to prepare the solution of the at least one electrospinnable polymer according to step a), the electrospinnable polymer is dissolved in a mixture of at least one suitable organic solvent and water. there the ratio of at least one organic solvent to water is 95: 5 (v / v) to 70:30 (v / v). It is known to those skilled in the art which polymers dissolve in which organic solvents, which organic solvents are miscible with water in what proportion, and which mixtures of organic solvents and water are suitable for dissolving which polymers. He can apply this expertise without departing from the scope of the claims.
Der Polymeranteil in dieser Lösung beträgt erfindungsgemäß zwischen 3 Gew.-% und 20 Gew.-%.The polymer content in this solution is according to the invention between 3 wt .-% and 20 wt .-%.
Anschließend wird gemäß Schritt b) des erfindungsgemäßen Verfahrens Honig und/oder von Honig in verkapselter Form zur Lösung des mindestens einen Polymers gegeben. Der Anteil von Honig und/oder von Honig in verkapselter Form in dieser Mischung beträgt erfindungsgemäß zwischen 1 Gew.-% und 20 Gew.-% bezogen auf die Polymerlösung, und zwar unabhängig vom Anteil des Polymers oder der Polymere in der Lösung.Subsequently, according to step b) of the process according to the invention, honey and / or honey in encapsulated form are added to the solution of the at least one polymer. The proportion of honey and / or honey in encapsulated form in this mixture is according to the invention between 1 wt .-% and 20 wt .-% based on the polymer solution, regardless of the proportion of the polymer or polymers in the solution.
Diese Mischung wird an einer als Elektrode dienenden Kante einem hohem elektrischen Feld ausgesetzt. Beispielsweise kann dies geschehen, indem die Honig- Nanopartikel enthaltende Lösung des elektroverspinnbaren Polymers in einem elektrischen Feld unter geringem Druck durch eine mit einem Pol einer Spannungsquelle verbundenen Kanüle extrudiert wird. Es entsteht ein auf die Gegenelektrode gerichteter Materialstrom, der sich auf dem Weg zur Gegenelektrode verfestigt.This mixture is exposed to a high electric field at an edge serving as an electrode. For example, this can be done by extruding the honey nanoparticle-containing solution of the electro-spinnable polymer in an electric field under low pressure through a cannula connected to a pole of a voltage source. The result is a flow of material directed at the counterelectrode, which solidifies on the way to the counterelectrode.
Optional können erfindungsgemäße Polymerfasern mit mikrobiziden Eigenschaften, welche nach obigem erfindungsgemäßen Verfahren hergestellt wurden, anschließend mit mindestens einer weiteren Schicht mindestens einen weiteren Polymers belegt werden.Optionally, polymer fibers according to the invention with microbicidal properties, which were prepared by the above process according to the invention, can subsequently be coated with at least one further layer of at least one further polymer.
Diese Beschichtung kann z.B. durch Gasphasenabscheidung, Rakeln, Spin- Coating, Dip-Coating, Besprühen oder Plasmaabscheidung von Polymeren wie Poly-(p-xylylen), Polyacrylamid, Polyimiden, Polyestem, Polyolefinen, Polycarbo- naten, Polyamiden, Polyethem, Polyphenylenen, Polysilanen, Polysiloxanen, Polybenzimidazolen, Polybenzthiazolen, Polyoxazolen, Polysulfiden, Polyestera- miden, Polyarylenvinylenen, Polylactiden, Polyetherketonen, Polyurethanen, PoIy- sulfonen, Ormoceren, Polyacrylaten, Siliconen, vollaromatischen Copolyestem, Poly-N-vinylpyrrolidon, Polyhydroxyethylmethacrylat, Polyethylenterephthalat, Polybutylenterephthalat, Polymethacrylnitril, Polyacrylnitril, Polyvinylacetat, Neopren, Buna N, Polybutadien, Polytetrafluorethylen, Cellulose (modifiziert oder nicht modifiziert), Alginate oder Collagen, deren Homo- und Copolymerisate und/oder Blends erfolgen.This coating can be, for example, by vapor deposition, knife coating, spin coating, dip coating, spraying or plasma deposition of polymers such as poly (p-xylylene), polyacrylamide, polyimides, polyesters, polyolefins, polycarbonates, polyamides, polyethers, polyphenylenes, polysilanes , Polysiloxanes, Polybenzimidazoles, polybenzothiazoles, polyoxazoles, polysulfides, polyesteramides, polyarylenevinylenes, polylactides, polyetherketones, polyurethanes, poly-sulfones, ormocers, polyacrylates, silicones, wholly aromatic copolyesters, poly-N-vinylpyrrolidone, polyhydroxyethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polymethacrylonitrile, polyacrylonitrile, polyvinyl acetate , Neoprene, Buna N, polybutadiene, polytetrafluoroethylene, cellulose (modified or unmodified), alginates or collagen whose homo- and copolymers and / or blends are made.
Die erfindungsgemäßen Polymerfasern mit mikrobiziden Eigenschaften inhibieren das Wachstum und/oder die Proliferation von Mikroorganismen. In einer Ausführungsform der vorliegenden Erfindung werden Polymerfasern mit mikrobiziden Eigenschaften hergestellt, indem eine Lösung mindestens eines elektroverspinnbaren Polymers hergestellt, mit Honig gemischt und elektrover- spönnen wird. Erfolgt keine Zugabe von Honig in verkapselter Form und/oder wird auf die zusätzliche optionale Beschichtung mit mindestens einem weiteren Polymer verzichtet, so sind die erhaltenen Polymerfasern wasserstabil; der Honig löst sich jedoch beim Kontakt mit wässrigen Medien. Werden erfindungsgemäße Fasern mit mikrobiziden Eigenschaften mit Honig ge- maß obiger Definition hergestellt, ohne dass diese Fasern anschließend mit mindestens einem weiteren Polymer beschichtet werden, so sind die Polymerfasern selbst wasserstabil. Der Honig wird jedoch beim Kontakt mit wässrigen Medien innerhalb weniger Tage im Wesentlichen vollständig herausgelöst. Fasern dieser Ausführungsform sind daher bevorzugt für die Herstellung von Pro- dukte geeignet, bei denen eine kurzzeitige einmalige, dafür aber weitflächige mikrobizide Wirkung wünschenswert ist. Bei derartigen Produkten handelt es sich beispielsweise um Wundauflagen oder Kosmetikprodukte wie Reinigungs- und Pflegetücher bzw. -pads.The polymer fibers according to the invention having microbicidal properties inhibit the growth and / or proliferation of microorganisms. In one embodiment of the present invention, polymer fibers having microbicidal properties are prepared by preparing a solution of at least one electro-spinnable polymer, mixing it with honey, and electro-spanning it. If there is no addition of honey in encapsulated form and / or if the additional optional coating with at least one further polymer is dispensed with, the resulting polymer fibers are water-stable; however, the honey dissolves on contact with aqueous media. If fibers according to the invention having microbicidal properties are prepared with honey as defined above, without these fibers subsequently being coated with at least one further polymer, the polymer fibers themselves are water-stable. However, the honey is essentially completely dissolved out on contact with aqueous media within a few days. Fibers of this embodiment are therefore preferably suitable for the production of products in which a short-term, but extensive microbicidal action is desirable. Such products are, for example, wound dressings or cosmetic products such as cleansing and care wipes or pads.
In weiteren Ausführungsformen werden Polymerfasern mit mikrobiziden Eigenschaften hergestellt, indem eine Lösung mindestens einen elektroverspinnbaren Polymers hergestellt, mit Honig gemischt und elektrover- sponnen wird, wobei eine Zugabe von Honig in verkapselter Form erfolgt und/oder die Polymerfasern anschließend mit mindestens einem weiteren Polymer be- schichtet werden. Fasern dieser Ausführungsform sind ebenfalls wasserstabil, und der in ihnen enthaltene Honig wird langsam und kontrolliert freigesetzt. Fasern dieser Ausführungsform sind daher für die Herstellung von Produkten geeignet, die dauerhaft eingesetzt werden. Dabei handelt es sich beispielsweise um Textilfasern für Funktionskleidung, Schutzkleidung für medizinisches Personal und Schutzkleidung für Patienten. In further embodiments, polymer fibers having microbicidal properties are produced by preparing a solution of at least one electro-spinnable polymer, mixing it with honey and electrospinning, wherein honey is added in encapsulated form and / or the polymer fibers are subsequently treated with at least one further polymer. be layered. Fibers of this embodiment are also water stable, and the honey contained in them is released slowly and in a controlled manner. Fibers of this embodiment are therefore suitable for the manufacture of products which are used permanently. These are, for example, textile fibers for functional clothing, protective clothing for medical personnel and protective clothing for patients.
Ausführungsbeispieleembodiments
1. Herstellung von Polyvinylbutyratfasern (PVB-Fasern) umfassend Honig1. Preparation of polyvinyl butyrate (PVB) fibers comprising honey
Zur Herstellung der Fasern wurde eine Elektrospinnapparatur verwendet wie beschrieben in M. Bognitzki et al. Adv. Mater. 12, 637 (2000). Zu einer 5 % (w/w) Lösung von kommerziellem Mowital B 60 T (Mw = 50000- 60000, Polyvinylbutyrat) in einem Gemisch aus Ethanol und entionisiertem Wasser (80:20) wurden je 1 , 3 und 6 Gewichtsprozent Active UMF20+ Manuka Honey der Firma Honey New Zealand bzw. Bienenhonig der Firma Dr. Krieger's zugegeben.To prepare the fibers, an electrospinning apparatus was used as described in M. Bognitzki et al. Adv. Mater. 12, 637 (2000). To a 5% (w / w) solution of commercial Mowital B 60 T (M w = 50,000-60,000, polyvinyl butyrate) in a mixture of ethanol and deionized water (80:20) was added 1, 3 and 6 weight percent Active UMF20 + Manuka Honey from the company Honey New Zealand or bee honey from Dr. Ing. Krieger's admitted.
Diese Lösungen sowie eine Vergleichslösung, die nur aus Mowital B 60 T und dem Ethanol/entionisiertem Wasser bestand, wurden bei 20 0C und 65 % rel. Luftfeuchtigkeit aus einer Spritze (1 mL) auf Backpapier gesponnen. Die verwen- dete Spannung betrug 25 kV, der Abstand zwischen Kanüle und Backpapier 20 cm und der Vortrieb 4 cm/h.These solutions and a comparison solution, which consisted only of Mowital B 60 T and the ethanol / deionized water, were at 20 0 C and 65% rel. Humidity from a syringe (1 mL) spun onto baking paper. The applied voltage was 25 kV, the distance between cannula and baking paper was 20 cm and the drive 4 cm / h.
2. Untersuchung der antibakteriellen Wirksamkeit der hergestellten Nano- faserviiese2. Investigation of the antibacterial activity of the nanoparticles produced
Die antibakterielle Wirksamkeit der PVB-Fasern, die unterschiedliche Anteile an Manukahonig bzw. Dr. Krieger's Bienenhonig, enthielten, wurde untersucht. Hierzu wurden Agarplatten entweder mit Micrococcus luteus geimpft, mit einem passenden Nährmedium versetzt und bis zur Konfluenz inkubiert.The antibacterial effectiveness of the PVB fibers, the different proportions of Manuka honey or Dr. med. Krieger's bee honey, contained, was investigated. For this purpose, agar plates were either inoculated with Micrococcus luteus, mixed with a suitable nutrient medium and incubated to confluency.
Anschließend wurden Proben der Manukahonig bzw. Dr. Krieger's Bienenhonig enthaltenden Polyvinylbutyrat-Fasermatten (ca. 2 x 1 cm) auf die konfluenten Micrococcus /uteus-Zellen aufgebracht und weitere 48 h bei Raumtemperatur in- kubiert. Anschließend wurde die Auswirkung der Fasern auf das Wachstum der Bakterien mit einer Kamera festgehalten. Die Figuren 2 bis 5 zeigen die Ergebnisse der Untersuchungen.Subsequently, samples of the Manuka honey or Dr. 2 × 1 cm) were applied to the confluent micrococcus / uterus cells and incubated for a further 48 h at room temperature. Subsequently, the effect of the fibers on the growth of the bacteria was recorded with a camera. FIGS. 2 to 5 show the results of the investigations.
Dabei bedeutenMean
O: Vergleichsprobe einer PVB-Fasermatte ohne Honig, aufgelegt auf eine konfluente Schicht von Micrococcus luteus T1 : PVB-Fasermatte mit 1 Gew.-% Bienenhonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteus T3: PVB-Fasermatte mit 3 Gew.-% Bienenhonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteusO: Comparative sample of a non-honey PVB fiber mat placed on a confluent layer of Micrococcus luteus T1: PVB fiber mat containing 1% by weight of bee honey in the spinning solution, laid on a confluent layer of Micrococcus luteus T3: PVB fiber mat with 3 wt .-% bee honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
TQ: PVB-Fasermatte mit 6 Gew.-% Bienenhonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteusTQ: PVB fiber mat with 6% by weight honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
M1 : PVB-Fasermatte mit 1 Gew.-% Manukahonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteus M3: PVB-Fasermatte mit 3 Gew.-% Manukahonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteus M6: PVB-Fasermatte mit 6 Gew.-% Manukahonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteusM1: PVB fiber mat with 1% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus M3: PVB fiber mat with 3% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus M6: PVB fiber mat with 6% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
Bei der Vergleichsprobe konnte keine mikrobizide, insbesondere keine antibakterielle, Wirkung festgestellt werden. Bei den Honig enthaltenden Fasermatten waren mehr oder weniger stark ausgeprägte bakterienfreie Zonen um die Matten (am deutlichsten bei Probe M6) zu erkennen, jedoch waren die Fasermatten selbst nicht bakterienfrei. In the comparative sample no microbicidal, especially no antibacterial, effect could be detected. The honey-containing fiber mats had more or less pronounced bacteria-free zones around the mats (most clearly in sample M6), but the fiber mats themselves were not bacteria-free.
BezugszeichenlisteLIST OF REFERENCE NUMBERS
1 Spannungsquelle1 voltage source
2 Kapillardüse 3 Spritze2 capillary nozzle 3 syringe
4 Polyelektrolytlösung4 polyelectrolyte solution
5 Gegenelektrode5 counter electrode
6 Faserbildung6 fiber formation
7 Fasermatte7 fiber mat
AbbildungslegendenFigure legends
Fig. 1 Fig. 1 zeigt eine schematische Darstellung einer zur Durchführung des erfindungsgemäßen Elektrospinnverfahrens geeigneten Vorrichtung. Die Vorrichtung umfasst eine Spritze 3, an deren Spitze sich eine Kapillardüse 2 befindet. Diese Kapillardüse 2 ist mit einem Pol einer Spannungsquelle 1 verbunden. Die Spritze 3 nimmt die zu verspinnenden Polyelektrolytlösungen 4 auf. Ge- genüber dem Ausgang der Kapillardüse 2 ist in einem Abstand von etwa 20 cm eine mit dem anderen Pol der Spannungsquelle 1 verbundene Gegenelektrode 5 angeordnet, die als Kollektor für die gebildeten Fasern fungiert. Während der Betriebs der Vorrichtung wird an den Elektroden 2 und 5 eine Spannung zwischen 18 kV und 35 kV eingestellt und die Polyelektrolytlösung 4 unter einem geringen Druck durch die Kapillardüse 2 der Spritze 3 ausgetragen. Auf Grund der durch das starke elektrische Feld von 0,9 bis 2 kV/cm erfolgenden elektrostatischen Aufladung der Polyelektrolyte in der Lösung entsteht ein auf die Gegenelektrode 5 gerichteter Materialstrom, der sich auf dem Wege zur Gegenelektrode 5 unter Faserbildung 6 verfestigt, infolge dessen sich auf der Gegen- elektrode 5 Fasern 7 mit Durchmessern im Mikro- und Nanometerbereich abscheiden. Fig. 21 shows a schematic representation of a device suitable for carrying out the electrospinning process according to the invention. The device comprises a syringe 3, at the tip of which is a capillary nozzle 2. This capillary nozzle 2 is connected to a pole of a voltage source 1. The syringe 3 receives the polyelectrolyte solutions 4 to be spun. Opposite the outlet of the capillary nozzle 2, a counterelectrode 5 connected to the other pole of the voltage source 1 is arranged at a distance of about 20 cm, which acts as a collector for the fibers formed. During operation of the device, a voltage between 18 kV and 35 kV is set at the electrodes 2 and 5, and the polyelectrolyte solution 4 is discharged through the capillary nozzle 2 of the syringe 3 at a low pressure. Due to the electrostatic charge of the polyelectrolytes in the solution due to the strong electric field of 0.9 to 2 kV / cm, a material flow directed towards the counterelectrode 5, which solidifies on the way to the counterelectrode 5 with fiber formation 6, arises as a result on the counterelectrode 5 fibers 7 with diameters in the micro and nanometer range. Fig. 2
Fig. 2 zeigt eine Vergleichsprobe einer 2 x 1 cm großen elektrogesponnenen Fasermatte aus Mowital B 60 T® (Polyvinylbutyrat, PVB), die für 24 h bei Raumtemperatur auf eine konfluente Schicht von Micrococcus luteus aufgelegt wurde. Bei der Herstellung der Fasermatte wurde der Polyvinylbutyratlösung vor dem Elektrospinnen kein Honig zugesetzt. Es konnte keine antibakterielle Wirkung der Fasermatte festgestellt werden.Fig. 2 is a comparative sample of a 2 x 1 cm is large electro-spun fiber mat of Mowital B 60 T ® (polyvinyl butyral, PVB), which was placed for 24 hours at room temperature to a confluent layer of Micrococcus luteus. In preparing the fiber mat, no honey was added to the polyvinyl butyrate solution prior to electrospinning. No antibacterial effect of the fiber mat could be detected.
Fig. 3 Fig. 3 zeigt elektrogesponnene Fasermatten (2 x 1 cm) aus Mowital B 60 T® (Polyvinylbutyrat). Es bedeuten 0: Vergleichsprobe einer PVB-Fasermatte ohne Honig, aufgelegt auf eine konfluente Schicht von Micrococcus luteus T1 : PVB-Fasermatte mit 1 Gew.-% Bienenhonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteusFig. 3 Fig. 3 shows electrospun fiber mats (2 x 1 cm) of Mowital B 60 T ® (polyvinyl butyrate). 0 means: comparative sample of a PVB fiber mat without honey, laid on a confluent layer of Micrococcus luteus T1: PVB fiber mat with 1% by weight honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
13: PVB-Fasermatte mit 3 Gew.-% Bienenhonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteus13: PVB fiber mat with 3 wt .-% honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
M1: PVB-Fasermatte mit 1 Gew.-% Manukahonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteusM1: PVB fiber mat with 1% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
Bei den Proben T1 , T3 und M1 zeigten sich bakterienfreie Zonen um die Fasermatten; die Fasermatten selbst waren jedoch nicht bakterienfrei. Bei der Vergleichsprobe konnte keine antibakterielle Wirkung festgestellt werden. In samples T1, T3 and M1, bacteria-free zones appeared around the fiber mats; however, the fiber mats themselves were not bacteria-free. In the comparative sample no antibacterial effect could be detected.
Fig. 4Fig. 4
Fig. 4 zeigt elektrogesponnene Fasermatten (2 x 1 cm) aus Mowital B 60 T® (Polyvinylbutyrat). Es bedeutenFig. 4 shows electrospun fiber mats (2 x 1 cm) of Mowital B 60 T ® (polyvinyl butyrate). It means
T6: PVB-Fasermatte mit 6 Gew.-% Bienenhonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteusT6: PVB fiber mat with 6% by weight honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
M3: PVB-Fasermatte mit 3 Gew.-% Manukahonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteus M6: PVB-Fasermatte mit 6 Gew.-% Manukahonig in der Spinnlösung, aufgelegt auf eine konfluente Schicht von Micrococcus luteusM3: PVB fiber mat with 3% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus M6: PVB fiber mat with 6% by weight of manuka honey in the spinning solution, placed on a confluent layer of Micrococcus luteus
Bei den Proben T6, M3 und M6 zeigten sich bakterienfreie Zonen um die Fasermatten; die Fasermatten selbst waren jedoch nicht bakterienfrei.For samples T6, M3 and M6, bacteria-free zones appeared around the fiber mats; however, the fiber mats themselves were not bacteria-free.
Fiα 5Fiα 5
Fig. 5 zeigt elektrogesponnene Fasermatten (2 x 1 cm) aus Mowital B 60 T® (Polyvinylbutyrat), wobei der Spinnlösung 6 Gew.-% Manukahonig zugegeben wurden (= Probe M6). Bei dieser Probe zeigte sich die am stärksten ausgeprägte bakterienfreie Zone um eine Fasermatte von allen untersuchten Proben. Fig. 5 shows electrospun fiber mats (2 x 1 cm) of Mowital B 60 T ® (polyvinyl butyrate), wherein the spinning solution were added 6 wt .-% Manuka honey (= sample M6). In this sample, the most prominent bacteria-free zone was one fiber mat of all the samples tested.

Claims

Ansprüche claims
1. Polymerfasern mit mikrobiziden Eigenschaften, umfassend mindestens ein elektrospinnbares Polymer und Honig.1. polymer fibers having microbicidal properties, comprising at least one electrospinnable polymer and honey.
2. Polymerfasern mit mikrobiziden Eigenschaften gemäß Anspruch 1 , dadurch gekennzeichnet, dass das elektrospinnbare Polymer ausgewählt ist aus der Gruppe Poly-(p-xylylen); Polyvinylidenhalogenide, Polyester; Polyether; Polyolefine; Polycarbonate; Polyurethane; natürliche Polymere; Polycarbon- säuren; Polysulfonsäuren; sulfatierte Polysaccharide; Polylactide; Polyglyco- side; Polyamide; Homo- und Copolymerisate von aromatischen Vinylverbin- dungen; Polyacrylnitrile, Polymethacrylnitrile; Polyacrylamide; Polyimide; Polyphenylene; Polysilane; Polysiloxane; Polybenzimidazole; Polybenzothia- zole; Polyoxazole; Polysulfide; Polyesteramide; Polyarylenvinylene; PoIy- etherketone; Polyurethane, Polysulfone, anorganisch-organische Hybridpolymere; Silicone; vollaromatische Copolyester; Poly(alkyl)acrylate; Poly(alkyl)methacrylate; Polyhydroxyethylmethacrylate; Polyvinylacetate, Polyvinylbutyrate; Polyisopren; synthetische Kautschuke; Polytetrafluor- ethylen; modifizierte und nicht modifizierte Cellulosen, Homo- und Copo- lymerisate von alpha-Olefinen und Copolymeren aufgebaut aus zwei oder mehr die vorstehend genannten Polymere bildenden Monomereinheiten; Polyvinylalkohole, Polyalkylenoxide, z.B. Polyethylenoxide; Poly-N-vinyl- pyrrolidon; Hydroxymethylcellulosen; Maleinsäuren; Alginate; Collagene.2. polymer fibers having microbicidal properties according to claim 1, characterized in that the electrospinnable polymer is selected from the group poly (p-xylylene); Polyvinylidene halides, polyesters; polyether; polyolefins; polycarbonates; polyurethanes; natural polymers; Polycarboxylic acids; polysulfonic; sulfated polysaccharides; polylactides; Polyglycoside; polyamides; Homopolymers and copolymers of aromatic vinyl compounds; Polyacrylonitriles, polymethacrylonitriles; polyacrylamides; polyimides; Polyphenylene; polysilanes; polysiloxanes; polybenzimidazoles; Polybenzothiazoles; polyoxazoles; polysulfides; polyester; Polyarylenvinylene; Polyether ketones; Polyurethanes, polysulfones, inorganic-organic hybrid polymers; silicones; wholly aromatic copolyesters; Poly (alkyl) acrylates; Poly (alkyl) methacrylates; polyhydroxyethylmethacrylates; Polyvinyl acetates, polyvinyl butyrates; polyisoprene; synthetic rubbers; Polytetrafluoroethylene; modified and unmodified celluloses, homopolymers and copolymers of alpha-olefins and copolymers composed of two or more monomer units forming the abovementioned polymers; Polyvinyl alcohols, polyalkylene oxides, e.g. Polyethylene oxides; Poly-N-vinyl-pyrrolidone; hydroxymethylcelluloses; maleic; alginates; Collagens.
3. Polymerfasern mit mikrobiziden Eigenschaften gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Honig ausgewählt ist aus der Gruppe Akazienhonig, Bergblütenhonig, Blütenhonig mit Mimose, Buchweizenhonig, Edelkastanienhonig, Eichenwaldhonig, Erdbeerbaumhonig, Eukalyptushonig, Gebirgsblütenhonig, Heidehonig, Kleehonig, Landhonig, Lavendelblüten- honig, Lindenblütenhonig, Löwenzahnhonig, Manukahonig, Obstblütenhonig,3. polymer fibers having microbicidal properties according to claim 1 or 2, characterized in that the honey is selected from the group acacia honey, mountain blossom honey, honey with mimosa, buckwheat honey, sweet chestnut honey, oak forest honey, strawberry honey, eucalyptus honey, mountain blossom honey, heather honey, clover honey, Landhonig, lavender flowers - honey, linden honey, dandelion honey, manuka honey, fruit blossom honey,
Orangenblütenhonig, Phaceliahonig, Pinienhonig, Quillayahonig, Rapshonig, Sommerhonig, Sommerblütenhonig, Sonnenblumenhonig, Tamariskenhonig, Tasmanischer Lederholzhonig, Thymianhonig, Waldhonig, Weißtannenhonig, Wildblütenhonig und Zuckern, Zuckerlösungen und Gemische von Zuckerlösungen, insbesondere konzentrierte Zuckerlösungen, die mikrobizide oder kosmetische, medizinische oder pharmazeutische Wirkungen an Menschen oder Tieren entfalten .Orange blossom honey, phacelia honey, pine honey, quillaya honey, rapeseed honey, summer honey, summer honey, sunflower honey, tamarisk honey, Tasmanian leather honey, thyme honey, wild honey, silver fir honey, wildflower honey and sugars, sugar solutions and mixtures of Sugar solutions, in particular concentrated sugar solutions, which develop microbicidal or cosmetic, medicinal or pharmaceutical effects on humans or animals.
4. Polymerfasern mit mikrobiziden Eigenschaften gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Polymerfasern elektroversponnen sind.4. polymer fibers having microbicidal properties according to any one of claims 1 to 3, characterized in that the polymer fibers are electrospun.
5. Verfahren zur Herstellung von mikrobiziden Polymerfasem gemäß einem der Ansprüche 1 bis 4, gekennzeichnet durch die Schritte a) Herstellen einer Lösung des mindestens einen elektrospinnbaren Polymers, b) Zugabe von Honig und/oder von Honig in verkapselter Form und Mischen mit der Polymerlösung, c) Elektroverspinnen der Mischung zu Fasern.5. A process for the preparation of microbicidal polymer fibers according to any one of claims 1 to 4, characterized by the steps a) preparing a solution of the at least one electrospinnbaren polymer, b) adding honey and / or honey in encapsulated form and mixing with the polymer solution, c) electrospinning the mixture into fibers.
6. Verfahren zur Herstellung von mikrobiziden Polymerfasern gemäß Anspruch 5, dadurch gekennzeichnet, dass die mikrobiziden Polymerfasern anschließend mit mindestens einer Schicht mindestens eines weiteren Polymers be- legt werden.6. A process for the preparation of microbicidal polymer fibers according to claim 5, characterized in that the microbicidal polymer fibers are subsequently coated with at least one layer of at least one further polymer.
7. Verfahren zur Herstellung von mikrobiziden Polymerfasern gemäß Anspruch 5 oder 6, dadurch gekennzeichnet, dass Anteil von Honig und/oder von Honig in verkapselter Form in der Polymerlösung zwischen 1 Gew.-% und 20 Gew.-% beträgt.7. A process for the preparation of microbicidal polymer fibers according to claim 5 or 6, characterized in that proportion of honey and / or honey in encapsulated form in the polymer solution is between 1 wt .-% and 20 wt .-%.
8. Mikrobizide Polymerfaser, erhältlich durch Verfahren gemäß Anspruch 5.8. A microbicidal polymer fiber obtainable by the process according to claim 5.
9. Mikrobizide Polymerfaser, erhältlich durch Verfahren gemäß Anspruch 6.9. A microbicidal polymer fiber obtainable by the method according to claim 6.
10. Verwendung von mikrobiziden Polymerfasern gemäß Anspruch 8 zur Herstellung von Wundauflagen oder zur Herstellung von Fasern für Kosmetikprodukte. 10. Use of microbicidal polymer fibers according to claim 8 for the production of wound dressings or for the production of fibers for cosmetic products.
11. Verwendung von mikrobiziden Polymerfasem gemäß Anspruch 9 zur Herstellung von Textilfasern für Funktionskleidung, Schutzkleidung für medizinisches Personal und Schutzkleidung für Patienten. 11. Use of microbicidal polymer fibers according to claim 9 for the production of textile fibers for functional clothing, protective clothing for medical personnel and protective clothing for patients.
PCT/CH2007/000510 2006-10-23 2007-10-17 Microbicidal nano- and meso-polymer fibers produced from polymers and honey, for textile applications WO2008049251A1 (en)

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GB2484319A (en) * 2010-10-06 2012-04-11 Univ Bolton Electrospinning fibres comprising honey and biocompatible polymer
US20150030688A1 (en) * 2013-07-25 2015-01-29 Saint Louis University Honey and growth factor eluting scaffold for wound healing and tissue engineering
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