WO2019033199A1 - Compositions et procédés de revêtement pour empêcher la formation de biofilms sur des surfaces - Google Patents

Compositions et procédés de revêtement pour empêcher la formation de biofilms sur des surfaces Download PDF

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WO2019033199A1
WO2019033199A1 PCT/CA2018/050947 CA2018050947W WO2019033199A1 WO 2019033199 A1 WO2019033199 A1 WO 2019033199A1 CA 2018050947 W CA2018050947 W CA 2018050947W WO 2019033199 A1 WO2019033199 A1 WO 2019033199A1
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short
teos
chain
tetraalkoxysilane
alkyltrialkoxysilane
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PCT/CA2018/050947
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English (en)
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Olivier Marion
Gary Whipp
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Mirapakon Inc.
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

  • the present disclosure generally relates to anti- biofilm sol-gel films. More particularly, the invention relates to ORMOSIL (organically modified silica) anti-biofilms coatings.
  • ORMOSIL organic modified silica
  • Biofouling of man-made underwater structures has been a significant problem. For instance, material deterioration, losses in heat transfer efficiency, mechanical blockages of fluids transport and increase fuel consumption for vessels are all problems resulting from biofouling .
  • microorganisms biofilms are the root cause of biofouling.
  • Microorganisms also known as microbes
  • microbes are microscopic organism that are single-celled or multicellular. Microorganisms are very diverse and include bacteria, archaea, protozoa and also some fungi, some algae and some micro-animals.
  • Microbial growth on surface is a serious problem. Underwater surfaces, like boat hull, are rapidly colonized by microorganisms (e.g. diatoms, bacteria) forming a biofilm layer in the first stage of marine biofouling.
  • a biofilm also called the slime
  • a biofilm is an agglomeration of microorganisms on a surface that is surrounded or held together by an organic matrix of extracellular polymeric substances. After about one week under water, the biofilm found on an untreated immersed surface is rich in nutrients. At this point, secondary and tertiary macrofoulers (e.g. algae, tube worms, mussels, barnacles) can easily attach to the biofilm.
  • secondary and tertiary macrofoulers e.g. algae, tube worms, mussels, barnacles
  • the present disclosure provides a combination of silanes, a sol-gel matrix obtained from said silanes, a mixture of said sol-gel matrix and antifouling compounds, as well as surface coating compositions (also referred to as ORMOSIL films) comprising said combination of silanes or sol- gel matrix and optionally said antifouling compounds that can be used to generate a xerogel film.
  • surface coating compositions also referred to as ORMOSIL films
  • the present disclosure also provides methods to reduce or prevent biofilm formation on a surface, comprising applying on said surface, prior to said biofilm formation, a combination of silanes, a sol-gel matrix obtained from said silanes, a mixture of said sol-gel matrix and antifouling compound, as well as surface coating compositions comprising said combination of silanes or sol-gel matrix as defined herein .
  • the present disclosure provides surface coatings prepared from a combination of silanes, a sol-gel matrix obtained from said silanes, a mixture of said sol-gel matrix and antifouling compounds, as well as surface coating compositions .
  • FIG. 1 shows the bacterial evolution in aquarium water using the flux cytometry methodology.
  • the present disclosure relates to a combination of silanes, a sol-gel matrix obtained from said silanes, optionally an antifouling compound, as well as anti-biofilm coating compositions comprising said combination of silanes or sol-gel matrix and said optional antifouling additives, that can be used to generate a xerogel film.
  • the present disclosure provides methods for reducing or preventing biofilm formation on surfaces comprising applying, prior to formation of said biofilm, the combination of silanes, the sol-gel matrix, and optionally antifouling compound, composition or coating described herein, on said surfaces .
  • the organically-modified, hybrid xerogel coatings of the present disclosure are used in methods for reducing or preventing biofilm formation by microorganisms on surfaces with which they come in contact.
  • the xerogel surfaces are inexpensive and the alkyl silane are essential in the mixture to form a crackles, smooth, defect free surface with desirable hydrophobicity and roughness/topography.
  • the hydrophobicity of the xerogel surface i.e. hydrophobic surface provides fouling release properties.
  • a xerogel is a solid formed from a sol-gel matrix by drying with unhindered shrinkage. Compared to usual silica gel solids obtained by the sol-gel method, a xerogel film has a lower surface area. (150m 2 /g instead of 800-900m 2 /g) with very small pore size (lower than 2 nm) . Also, silica xerogel films (and ORMOSIL films) are not free flowing solids (small solid particles) like silica gels comprising distinct particles . Silica xerogel films form a continuous three-dimensional cross-linked network consisting of Si-O-Si units on the treated surface.
  • alkyl groups include methyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butyl groups, i-butyl groups, s-butyl groups, pentyl groups, hexyl groups, octyl groups, nonyl groups, and decyl groups and octadecyl groups.
  • the alkyl group can be unsubstituted or substituted with groups such as halides (-F, -CI, -Br, and - I), alkenes, alkynes, aliphatic groups, aryl groups, alkoxides, carboxylates , carboxylic acids, and ether groups.
  • the alkyl group can be perfluorinated .
  • a sol-gel matrix is comprising two or more silanes, some of which having been partially hydrolyzed
  • the sol-gel matrix is obtained from mixing a combination of silanes, and a catalyst for partially hydrolyzing alkoxy groups on the silanes.
  • the catalyst is an acid, such as an aqueous acid.
  • a composition is comprising a combination of silanes or a sol-gel matrix as defined herein and an organic solvent.
  • a composition may be comprising an organic solvent.
  • the solvent is a water miscible solvent
  • the solvent is an alcohol or a mixture o alcohols.
  • Non-limiting examples include methanol, ethanol isopropanol or mixtures thereof .
  • the composition as defined herein is prepared by mixing a combination of silanes, and a catalyst for partially hydrolyzing alkoxy groups on the silanes, wherein said catalyst is an aqueous acid in admixture with a water miscible solvent.
  • the molar amount of catalyst for partially hydrolyzing alkoxy groups is from about 0,001 mol% to about 10 mol% .
  • one or more antifouling compounds are added to the composition or in the sol-gel matrix precursors, either by solubilisation or by suspension in the composition or in the sol-gel matrix precursors.
  • the molar amount of the antifouling compound is from about 0,0001 mol% to about 60 mol% .
  • Antifouling compound as used herein refer to any agent that prevent biofouling.
  • antifouling compounds include metal-based compounds such as copper, copper thiocyanate, dicopper oxide, ZinebTM (zinc ethane-1, 2-diylbis (dithiocarbamate) , copper pyrithione, zinc oxide, zinc pyrithione (bis (2- pyridylthio ) zinc 1 , 1 ' -dioxide ) , Ti02, and silver as well as organic-based compounds such as Tolylfluanid (N-
  • the amount of antifouling compound can be adapted by the skilled person based on the composition used.
  • a copper-based antifouling compound may be used in a range of 0.01% to 60% (mass basis), or 0.1% to 30%, or 20% to 30%.
  • copper pyrithion may be present in an amount of 0.01% to 10%, or 0.1% to 5%, or about 1%.
  • Methods for reducing or preventing biofilm formation refer to one or more of the following : reducing or eliminating biofilms growth, reducing the biofilm thickness, reducing cellular activity in the biofilm, reducing the amount of surface cover by the biofilm, reducing the viability of microorganisms in the biofilm, reducing the biodiversity in the biofilm, reducing the ability of the biofilm to adhere or bond on surfaces or killing (partially or completely) microorganism that come in contact with the surface.
  • Biofilm refers to any agglomeration of microorganism adherent on a surface. Frequently, these adherent microorganisms are surrounded or held together by an organic matrix of extracellular polymeric substances . Biofilms may form on living or non-living surfaces . Biofilms can contain many different types of microorganism but some organisms can form single-species films under the right conditions.
  • the biofilm is a marine biofilm (i.e. grown in an aqueous environment) .
  • the marine biofilm may be one growing as the natural diversity of the usual marine microbial organisms .
  • the biofilm may be microbiofouling composed of multispecies bacteria in natural growth condition.
  • microorganisms include Vibrio spectacularus, Pseudoalteromonas haloplanktis, Shewanella colwelliana, Roseobacter denitrificans and Planococcus kocurii.
  • the xerogel materials have tunable surface hydrophobicity, surface energies and fouling release proprieties (by selection of appropriate sol-gel alkyl silane precursors) and are thinner (10-30 ⁇ ) with higher elastic modulus than silicone films.
  • the appropriate alkyl silane precursor will generate a smooth surface devoid of cracks and imperfection, with a good adherence on substrate. When two or more layers of coating are applied, the thickness will proportionally increase (e.g. 20-60 ⁇ for 2 layers, etc.) .
  • Hydrophobic surface refers to surface that present a static water contact angle greater than 85 degrees as measured by the sessile drop technique where the angle between a 15 ⁇ , drop of water and the surface is measured with a contact angle goniometer.
  • an example of a xerogel surface is incorporating 1 mole % of an n- octadecyltrimethoxysilane (C18) precursor in combination with 0.1 mole % of an organo-functional ammonium- chloridetrimethoxysilane (SiOAC) and with an n- octyltriethoxysilane (C8) and tetraethoxysilane (TEOS) .
  • SiOAC organo-functional ammonium- chloridetrimethoxysilane
  • TEOS tetraethoxysilane
  • an example of a xerogel surface is incorporating 1 mole % of an n- octadecyltrimethoxysilane (C18) precursor in combination with 49 mole % of an n-octyltriethoxysilane (C8) and tetraethoxysilane (TEOS).
  • xerogel surfaces include xerogels prepared from 1 mole % of an organo-functional ammonium-chloridetrimethoxysilane (SiOAC) with an n-octyltriethoxysilane (C8) and tetraethoxysilane
  • TEOS TEOS
  • xerogel surfaces include xerogels prepared from 0.1 mole % of an organo-functional ammonium-chloridetrimethoxysilane (SiOAC) with an n-octyltriethoxysilane (C8) and tetraethoxysilane
  • TEOS TEOS
  • xerogel surfaces include xerogels prepared from 0.1 mole % of an organo-functional ammonium-chloridetrimethoxysilane (SiOAC) with an n-propyltriethoxysilane (C3) and tetraethoxysilane
  • TEOS TEOS
  • xerogel surfaces include xerogels prepared from 0.1 mole % of an organo-functional ammonium-chloridetrimethoxysilane (SiOAC) with an n-octyltriethoxysilane (C8) and tetraethoxysilane
  • xerogel surfaces include xerogels prepared from an n- octyltriethoxysilane (C8) and tetraethoxysilane (TEOS) with an addition of 0.1 % mass of copper (I) oxide (Cu 2 0) .
  • xerogel surfaces include xerogels prepared from an n- octyltriethoxysilane (C8) and tetraethoxysilane (TEOS) with an addition of 30 % mass of copper (I) oxide (CU 2 O) .
  • xerogel surfaces include xerogels prepared from an n- octyltriethoxysilane (C8) and tetraethoxysilane (TEOS) with an addition of 30 % mass of copper (I) oxide (Cu 2 0) and an addition of 20 % mass of zinc oxide (ZnO) .
  • xerogel surfaces include xerogels prepared from:
  • Cu 2 0, said short-chain alkyltrialkoxysilane, and said tetraalkoxysilane; Cu 2 0 and ZnO, said short-chain alkyltrialkoxysilane, and said tetraalkoxysilane;
  • said alkyltrialkoxysilane is C3 alkyltri (C1-C3 ) alkoxysilane or C 8 alkyltri (C1-C3 ) alkoxysilane (such as n-propyltriethoxysilane and n-octyltriethoxysilane ) ; said long-chain alkyltrialkoxysilane is C18alkyltri (Cl- C3 ) alkoxysilane (such as n-octadecyltriethoxysilane ) ; said quaternary ammonium silane has the formula ( RO ) 3 Si-Z-N + R 2 R 3 R 4 X ⁇ , wherein R is C1-C3 alkyl, Z is C3 alkylene, R2-R3 are C1-C2 alkyl and R4 is Cl-C18alkyl or CH 2 C 6 H 5 and X is CI or Br 'such as
  • zineb about 1% mass of zineb; about 50 mole % of said short- chain alkyltrialkoxysilane and about 50 mole % of said tetraalkoxysilane;
  • said alkyltrialkoxysilane is C3 alkyltri (C1-C3 ) alkoxysilane or C 8 alkyltri (C1-C3 ) alkoxysilane (such as n-propyltriethoxysilane and n-octyltriethoxysilane ) ; said long-chain alkyltrialkoxysilane is C18alkyltri (Cl- C3 ) alkoxysilane (such as n-octadecyltriethoxysilane ) ; said quaternary ammonium silane has the formula ( RO ) 3 Si-Z-N + R 2 R 3 R 4 X ⁇ , wherein R is C1-C3 alkyl, Z is C3 alkylene, R2-R3 are C1-C2 alkyl and R4 is Cl-C18alkyl or CH 2 C 6 H 5 and X is CI or Br 'such as
  • the xerogel surfaces are preferably optically transparent but pigments additives can be added to the sol-gel matrix to generate a colored xerogel without loss of antifouling activity.
  • the xerogel require no "tie” coat, such as an adhesive or an adhesive made of double-sided sticky sheets, for bonding to a variety of surface.
  • methods for reducing biofilms growth by killing (partially or completely) microorganism that come in contact with the surface comprising providing a xerogel film as defined herein, on at least a portion of said surface.
  • the xerogel is obtained by applying the sol-gel matrix or the composition as defined herein in a non-solid form (e.g. liquid or gel form), and as such the method does not require any crushing or other manipulation of a solid to coat the surface of an object for which reducing biofilms growth is desired.
  • a non-solid form e.g. liquid or gel form
  • the method is comprising providing a xerogel on at least a portion of a surface that can be subjected to biofilm growth, wherein said xerogel is obtained by applying the composition as defined herein on said surface, and wherein said composition is comprising two or more silanes, some of which having been partially hydrolyzed and/or condensed, and said composition further comprising a water miscible organic solvent.
  • the present disclosure uses a sol-gel matrix or a composition comprising same for coating a surface.
  • the xerogel film is formed from the sol-gel obtained from hydrophobic silanes (alkyl silane).
  • Antifouling compounds can be incorporated as additives in the xerogel by dissolution or suspension in the sol-gel.
  • Pigments, markers, emulsifiers and thickeners can be incorporated as additives in the xerogel by dissolution or suspension in the sol-gel.
  • the surface coatings are used in methods for reducing or preventing biofilms formation on surfaces .
  • the coatings are preferably obtained from a multi- component ORMOSIL (organically modified silica) xerogel films (also referred to herein as hybrid films) .
  • ORMOSIL organically modified silica
  • the xerogel films can be formed by sol-gel methods, such as disclosed herein.
  • a biofilm growth reducing surface coating composition comprises a sol-gel matrix.
  • the composition comprises two, three or more partially hydrolyzed and/or condensed silanes.
  • the biofilms growth reducing coating consists essentially of a sol-gel matrix and the composition consists essentially of partially hydrolyzed and/or condensed silanes.
  • the biofilms growth reducing coating consists essentially of a sol-gel matrix and the composition consists essentially of three partially hydrolyzed and/or condensed silanes.
  • the biofilms growth reducing coating consists essentially of a sol-gel matrix and the composition consists essentially of four partially hydrolyzed and/or condensed silanes.
  • the biofilms growth reducing coating consists of a sol-gel matrix and the composition consists of two partially hydrolyzed and/or condensed silanes. In yet another embodiment, the biofilms growth reducing coating consists of a sol-gel matrix and the composition consists of three partially hydrolyzed and/or condensed silanes. In yet another embodiment, the biofilms growth reducing coating consists of a sol-gel matrix and the composition consists of four partially hydrolyzed and/or condensed silanes.
  • the biofilms growth reducing surface coating composition comprises a sol-gel matrix obtained from two, three or four partially hydrolyzed and/or condensed silanes, and the composition is optionally further comprising one or more antifouling compounds additives, preferably incorporated by solubilisation or by suspension in the sol-gel matrix precursors.
  • the antifouling compounds are sequestered in the structure of the hydrophobic xerogel surface in order to generate the biofilms growth reducing activity.
  • a sequestered antifouling compound refer to a compound that is presenting a leaching profile of less than 10 ⁇ g/cm 2 /d in a standard leaching test in water described herein.
  • the leaching profile should be less than 1 ⁇ g/cm 2 /d or even more preferably, less than 0,1 ⁇ g/cm 2 /d.
  • the biofilms growth reducing surface coating composition comprises xerogel film is prepared from a sol-gel matrix obtained from partial hydrolysis of silanes
  • composition e.g., long-chain alkyltrialkoxysilanes , short-chain alkyltrialkoxysilanes , perfluororalkyltrialkoxysilanes , trialkoxysilane-tetraalkylammonium halide composition.
  • long-chain alkyltrialkoxysilanes e.g., long-chain alkyltrialkoxysilanes , short-chain alkyltrialkoxysilanes , perfluororalkyltrialkoxysilanes , trialkoxysilane-tetraalkylammonium halide
  • Antifouling compound additives are optionally incorporated in the sol-gel matrix either by solubilisation or by suspension.
  • the surface coatings are used in a method for reducing biofilms growth on surfaces .
  • the method can reduce biofilms growth by killing (partially or completely) microorganism that come in contact with the surface .
  • the biofilms growth reducing surface coating composition comprises a sol-gel matrix obtained from two, three or four partially hydrolyzed and/or condensed silanes, and the composition is further comprising a solvent, preferably an alcohol or a mixture of alcohols and even more preferably methanol, ethanol, isopropanol or octanol or mixtures thereof.
  • a first silane is a long-chain alkyltrialkoxysilane or a perfluoalkyltrialkoxysilane .
  • a second silane is a shorter-chain alkyltrialkoxysilane .
  • a third silane is a tetraalkoxysilane .
  • the third silane makes up the remainder of the precursor composition.
  • the mole % of the described silanes account for the relative amounts of the silanes.
  • the total mole % of any combination in any given embodiment accounts to 100%.
  • the three-component xerogel surface incorporates 0.01 mole % to 5.0 mole % of a quaternary ammonium silanes silane precursor in combination with 20 mole % to 55 mole % of a shorter-chain alkyltrialkoxysilane (such as, but not limited to, methyltrimethoxysilane (CI), n- propyltrimethoxysilane (C3) or n-octyltriethoxysilane (C8)) and a tetraalkoxysilane (such as, but not limited to, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), or tetraisopropoxysilane (TIPOS).
  • a shorter-chain alkyltrialkoxysilane such as, but not limited to, methyltrimethoxysilane (CI), n- propyltrimethoxysilane (C3) or n-oc
  • the three-component xerogel surface incorporates 0.01 mole % to 5.0 mole % of a long-chain alkyltrialkoxy silane (where long-chain refers to ten (10) or more carbons, such as, but not limited to, n- dodecyltriethoxysilane (C12) or n-octadecyltriethoxysilane
  • C18 in combination with 20 mole % to 55 mole % of a shorter-chain alkyltrialkoxysilane (such as, but not limited to, methyltrimethoxysilane (CI), n-propyltrimethoxysilane (C3) or n-octyltriethoxysilane (C8)) and a tetraalkoxysilane (such as, but not limited to, tetramethoxysilane (TMOS) , tetraethoxysilane (TEOS), or tetraisopropoxysilane (TIPOS) .
  • a shorter-chain alkyltrialkoxysilane such as, but not limited to, methyltrimethoxysilane (CI), n-propyltrimethoxysilane (C3) or n-octyltriethoxysilane (C8)
  • a tetraalkoxysilane such as, but not limited to,
  • the four-component xerogel surface incorporates 0.01 mole % to 5.0 mole % of a quaternary ammonium silane precursor and 0.25 mole % to 5.0 mole % of a long-chain alkyltrialkoxy silane (where long-chain refers to ten (10) or more carbons, such as, but not limited to, n- dodecyltriethoxysilane (C12) or n-octadecyltriethoxysilane
  • a shorter-chain alkyltrialkoxysilane such as, but not limited to, n-propyltrimethoxysilane (C3) or n-octyltriethoxysilane
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • TIPOS tetraisopropoxysilane
  • the four-component xerogel surface incorporates 0.01 mole % to 5.0 mole % of a quaternary ammonium silane precursor, 1 mole % to 45 mole % of a long- chain perfluoroalkyltrialkoxysilane (where long-chain refers to eight (8) or more carbons such as, but not limited to, tridecafluorooctyltriethoxysilane (TDF) or tridecafluorooctyltrimethoxysilane ) in combination with 20 mole % to 55 mole % of a shorter-chain alkyltrialkoxysilane
  • TDF tridecafluorooctyltriethoxysilane
  • TDF tridecafluorooctyltrimethoxysilane
  • n-propyltrimethoxysilane (C3) or n-octyltriethoxysilane (C8) n-propyltrimethoxysilane (C3) or n-octyltriethoxysilane (C8)
  • a tetraalkoxysilane such as, but not limited to, tetramethoxysilane (TMOS) , tetraethoxysilane (TEOS), or tetraisopropoxysilane (TIPOS) are incorporated in the surface.
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • TIPOS tetraisopropoxysilane
  • the three-component xerogel surface incorporates 0.01 mole % to 5.0 mole % of a quaternary ammonium silane precursor in combination with 20 mole % to 55 mole % of a shorter-chain alkyltrialkoxysilane (such as, but not limited to, methyltrimethoxysilane (CI), n- propyltrimethoxysilane (C3) or n-octyltriethoxysilane (C8)) and a tetraalkoxysilane (such as, but not limited to, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), or tetraisopropoxysilane (TIPOS)) and an antifouling compound from 0.001 mass % to 60 mass %, or preferably of 0.1 % to 30% mass .
  • a shorter-chain alkyltrialkoxysilane such as, but not limited to, methyltri
  • the two-component xerogel surface incorporates 20 mole % to 55 mole of a shorter-chain alkyltrialkoxysilane (such as, but not limited to, methyltrimethoxysilane (CI), n-propyltrimethoxysilane (C3) or n-octyltriethoxysilane (C8)) and 20 mole % to 55 mole % of a tetraalkoxysilane (such as, but not limited to, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), or tetraisopropoxysilane (TIPOS)) and an antifouling compound from 0.001 mass % to 60 mass %, or preferably of 0.1 % to 50% mass .
  • a shorter-chain alkyltrialkoxysilane such as, but not limited to, methyltrimethoxysilane (CI), n-propyltrimethoxy
  • a first silane is a quaternary ammonium silane
  • a second silane is short-chain alkyltrialkoxysilane
  • a third silane is a tetraalkoxysilane.
  • 1:49:50 mole % of said quaternary ammonium silane, alkyltrialkoxysilane, and said tetraalkoxysilane are present.
  • a first silane is a quaternary ammonium silane
  • a second silane is short-chain alkyltrialkoxysilane
  • a third silane is a tetraalkoxysilane .
  • 0.1:49.9:50 mole % of said quaternary ammonium silane, alkyltrialkoxysilane, and said tetraalkoxysilane are present.
  • an antifouling compound is added, preferably 0.001 mass % to 60 mass %, to the sol-gel matrix.
  • the antifouling compound is a metal-based compound (such as copper (I) oxide
  • CU 2 O or zinc oxide (ZnO)
  • ZnO zinc oxide
  • a first silane is a long-chain alkyltrialkoxysilane
  • a second silane is short-chain alkyltrialkoxysilane
  • a third silane is a tetraalkoxysilane.
  • 1:49:50 mole % of said long-chain alkyltrialkoxysilane, short-chain alkyltrialkoxysilane, and said tetraalkoxysilane are present.
  • an antifouling compound is added, preferably 0.001 mass % to 60 mass % of, to the sol-gel matrix.
  • the antifouling compound is a metal-based compound (such as copper(I) oxide (Cu 2 0) or zinc oxide (ZnO)) and is in an amount of 0.1 % to 50% mass.
  • a first silane is a short-chain alkyltrialkoxysilane
  • a second silane is a tetraalkoxysilane.
  • 50:50 mole % of said short-chain alkyltrialkoxysilane, and said tetraalkoxysilane are present.
  • an antifouling compound is added, preferably 0.001 mass % to 60 mass % of, to the sol-gel matrix.
  • the antifouling compound is a metal-based compound (such as copper(I) oxide (Cu 2 0) or zinc oxide (ZnO) ) and is in an amount of 0.1 % to 50% mass.
  • a first silane is a short-chain alkyltrialkoxysilane
  • a second silane is a tetraalkoxysilane
  • 50:50 mole % of said short-chain alkyltrialkoxysilane, and said tetraalkoxysilane are present.
  • a combination of antifouling compounds are added, preferably 0.001 mass % to 60 mass % of, to the sol-gel matrix.
  • the antifouling compound is a metal-based compound (such as copper (I) oxide (Cu 2 0) or zinc oxide (ZnO) ) and is in an amount of 0.1 % to 50% mass.
  • the sol-gel precursors are long-chain alkyltrialkoxysilanes , short-chain alkyltrialkoxysilanes , perfluororalkyltrialkoxysilanes and quaternary ammonium silane.
  • the sol-gel precursors can be obtained from commercial sources or synthesized by known methods.
  • the long-chain alkyltrialkoxysilane has a long-chain alkyl group and three alkoxy groups.
  • the long-chain alkyltrialkoxysilane has the following structure: where, in this structure, R' is a long-chain alkyl group and R is an alkyl group of an alkoxy group.
  • the long chain alkyl group is a Cio to C30, including all integer numbers of carbons and ranges there between, alkyl group.
  • the alkoxy groups are, independently, Ci, C 2 , or C 3 alkoxy groups.
  • the alkoxy groups can have the same number of carbons .
  • the long-chain alkyltrialkoxysilane is present as a first component at from 0.25 mole % to 5.0 mole %, including all values to the 0.1 mole % and ranges there between, or as a second component at 1 mole % to 45 mole %, including all integer mole % values and ranges there between.
  • suitable long-chain alkyltrialkoxysilanes include n-dodecyltriethoxysilane, n- octadecyltriethoxysilane, and n-decyltriethoxysilane .
  • An alkane functionality can be incorporated within the xerogel coatings using the sol-gel process .
  • Mixed alkane and perfluoroalkane modifications can be incorporated from appropriate perfluoroalkyl- and alkyltrialkoxysilanes precursors .
  • the short-chain alkyltrialkoxysilane has the following structure:
  • R' is a short-chain alkyl group and R is an alkyl group of an alkoxy group.
  • the short-chain alkyltrialkoxysilane has a short-chain alkyl group and three alkoxy groups.
  • the short-chain alkyl group is a C3 to Ce, including all integer numbers of carbons and ranges there between, alkyl group
  • the alkoxy groups are, independently, Ci, C 2 , or C 3 alkoxy groups.
  • the alkoxy groups can have the same number of carbons.
  • the short-chain alkyltrialkoxysilane is present at 20 mole % to 55 mole %, including all integer mole % values and ranges there between.
  • Suitable short-chain alkyltrialkoxysilanes include n-propyltrimethoxy silane, n-butyltriethoxysilane , n-pentyltriethoxysilane, n- hexyltriethoxysilane, n-heptyltriethoxysilane, n- octyltriethoxysilane, and branched analogues thereof.
  • the silane is a short-chain amino- alkyltrialkoxysilane has the following structure:
  • R' is a short-chain alkyl group and R is an alkyl group of an alkoxy group.
  • the short-chain alkyltrialkoxysilane has a short-chain alkyl group and three alkoxy groups.
  • the short-chain alkyl group is a C 3 to C 8 , including all integer numbers of carbons and ranges there between, alkyl group
  • the alkoxy groups are, independently, Ci, C2, or C3 alkoxy groups.
  • the alkoxy groups can have the same number of carbons.
  • the short-chain alkyltrialkoxysilane is present at 20 mole % to 55 mole %, including all integer mole % values and ranges there between. Examples of suitable short- chain alkyltrialkoxysilanes include 3- Aminopropyltrimethoxysilane (SiNH 2 ).
  • a fluoroalkane functionality can be incorporated within the xerogel coatings using the sol-gel process .
  • Mixed alkane and perfluoroalkane modifications can be incorporated from appropriate perfluoroalkyl- and alkyltrialkoxysilanes precursors .
  • the perfluoroalkyltrialkoxysilane has the following structure:
  • R' is a perfluoroalkyl group and R is an alkyl group of an alkoxy group.
  • the perfluoroalkyltrialkoxysilane has a perfluoroalkyl group and three alkoxy groups.
  • the pefluoroalkyl group is a C 8 to C 30 , including all integer numbers of carbons and ranges there between, alkyl group.
  • the alkoxy groups are, independently, Ci , C 2 , or C 3 alkoxy groups.
  • the alkoxy groups can have the same number of carbons.
  • the perfluoroalkyltrialkoxysilane is present at 1 mole % to 45 mole %, including all integer mole values and ranges therebetween. Examples of suitable perfluoroalkyltrialkoxysilanes include tridecafluorooctadecyltriethoxysilane and tridecafluorooctyltrimethoxysilane .
  • Quaternary ammonium salts functionality can also be incorporated within the xerogel coatings using the sol-gel process .
  • Mixed quaternary ammonium salts modifications can be incorporate from appropriate quaternary ammonium silanes .
  • the quaternary ammonium silanes have one, two or three quaternary ammonium group and one, two or three alkoxy groups.
  • the quaternary ammonium silanes has the following structure:
  • each R independently represents an alkyl group having 1 to 4 carbon atoms
  • Z represents an alkylene group having 1 to 30 carbon atoms
  • each of the groups R 2 R 3 and R 4 independently represents an alkyl or hydroxyalkyl group having 1 to 30 carbon atoms or an aralkyl radical having 7 to 10 carbon atoms
  • X represents an anion.
  • Two of the groups R 2 R 3 and R 4 may be joined to form a heterocyclic ring, or the N+R 2 R 3 R 4 moiety can be a pyridinium group.
  • each R independently represents an alkyl group having 1 to 3 carbon atoms;
  • Z represents an alkylene group having 1 to 5 carbon atoms;
  • each of the groups R 2 R 3 and R 4 independently represents an alkyl or hydroxyalkyl group having 1 to 20 carbon atoms or an aralkyl- radical comprising 1-3 alkyl carbon atoms and 6 aryl carbon atoms; or
  • N + R 2 R 3 R 4 can be a pyridinium group and X represents an anion selected from chloride, bromide, fluoride, iodide, sulphonate group, or acetate .
  • each R independently represents CH3- or CH3CH2-; Z represents a propylene; each of the groups R 2 R 3 and R 4 independently represents CH 3 , CH 3 CH 2 , Ci 0 H 2 i, Ci 8 H 3 7 or CH 2 C 6 H 5 ; and X represents a chloride or bromide .
  • the quaternary ammonium silanes is present as a first component at from 0.001 mole % to 10.0 mole %, including all values to the 0.001 mole % and ranges there between, or as a second component at 1 mole % to 45 mole %, including all integer mole % values and ranges there between.
  • quaternary ammonium silanes include (CH 3 0) 3Si (CH2)3 + (CH 3 ) 2 C18H37 CI,
  • the quaternary ammonium silanes can be partially hydrolysed, that is some of the groups RO- can be HO- groups .
  • the quaternary ammonium organosilane can be in pure monomeric form or can be partially condensed.
  • the quaternary ammonium organosilane preferably retains an average of at least one silicon-bonded alkoxy group per silicon atom.
  • Short-chain amino-alkyltrialkoxysilanes and quaternary ammonium silanes as defined herein are not mixed together to form a combination of silanes as part of this disclosure.
  • the tetraalkoxysilane has the following structure:
  • R is an alkyl group of an alkoxy group.
  • the alkoxy groups are, independently, Ci, C 2 , or C 3 alkoxy groups.
  • the alkoxy groups can have the same number of carbons .
  • the antifouling compound is any agent that kill biofouling organisms or stop their growth.
  • the antifouling compound is present in solution or as disperse solid particles at from 0.001 mass % to 60.0 mass %, including all values to the 0.001 mole % and ranges there between.
  • the sol-gel matrix or coating compositions comprise functional groups derived from the precursor silanes .
  • coatings formed using perfluoroalkyltrialkoxysilanes have perfluoroalkyl groups.
  • the surface coatings also have residual silanol functional groups.
  • the groups can be on the surface of the film or in the bulk matrix of the film.
  • the thickness of the xerogel can be varied based on the deposition method and/or parameters of the deposition process (e.g., concentrations of the precursor components) .
  • the film can have a thickness of 1 micron to 150 microns, including all integer thickness values and ranges there between.
  • the sol-gel matrix surface coatings have desirable properties.
  • the coatings have desirable wetting properties (which can be measured by, for example, contact angle) and fouling release properties.
  • the biofilms growth reducing surface coating composition comprises a sol-gel matrix made by a method comprising the following steps: forming a precursor composition comprising two, three or more sol-gel precursor components, coating the precursor composition on a surface such that a sol-gel matrix film is formed on the surface.
  • the biofilms growth reducing surface coating composition comprises a sol-gel matrix made by a method comprising the following steps: forming a precursor composition comprising two, three or more sol-gel precursor components, adding one or more antifouling compounds, coating the precursor composition on a surface such that a sol-gel matrix film is formed on the surface.
  • the precursor composition (referred to herein as a sol or sol-gel) is formed by combining two, three or more sol-gel precursor components and allowing the components to stand for a period of time such that a desired amount of hydrolysis and polymerization of the precursors occurs .
  • This precursor composition is coated on a surface and allowed to stand for a period of time such that a xerogel film is formed.
  • specific reaction conditions e.g., mixing times, standing times, acid/base concentration, solvent (s)
  • the present disclosure provides methods for reducing biofilms growth by killing (partially or completely) marine microorganism that come in contact with a surface comprising applying to the surface, prior to biofilms formation, the combination of silanes, the sol-gel matrix, and optionally antifouling compound, composition or coating described herein.
  • the present invention provides methods for preventing biofilm growth on surfaces subjected to an aqueous environment comprising applying, prior to exposing said surface to said aqueous environment, the combination of silanes, the sol-gel matrix, and optionally antifouling compound, composition or coating described herein.
  • the methods can prevent biofilm growth by lowering (partially or completely) the biofilm thickness.
  • the present invention provides methods for preventing biofilm growth on surfaces subjected to an aqueous environment comprising applying to the surface, prior to exposing said surface to said aqueous environment, the combination of silanes, the sol-gel matrix, and optionally antifouling compound, composition or coating described herein.
  • the methods can prevent biofilm growth by lowering (partially or completely) the biofilm coverage area.
  • the present invention provides methods for preventing biofilm growth on surfaces subjected to an aqueous environment comprising applying to the surface, prior to exposing said surface to said aqueous environment, the combination of silanes, the sol-gel matrix, and optionally antifouling compound, composition or coating described herein.
  • the methods can prevent biofilm growth by lowering (partially or completely) the cellular viability in the biofilm.
  • Aqueous environments are any aqueous media in which biofilms can form. Examples of such aqueous environments include freshwater and saltwater environments. The aqueous environments can be naturally occurring or man-made. Examples of aqueous environments include tanks of freshwater or saltwater, rivers, lakes and oceans. The aqueous environments can also occur following the condensation of vapor on a cold surface .
  • the present invention provides methods for preventing natural biofilm growth on surfaces subjected to sea water from the gulf of the Saint Lawrence River comprising applying to the surface, prior to exposing said surface to said water, the combination of silanes, the sol-gel matrix, and optionally antifouling compound, composition or coating described herein.
  • the methods can prevent biofilm growth by lowering (partially or completely) the biofilm coverage area and by lowering (partially or completely) the cellular viability in the biofilm when compared to an unprotected surface.
  • the present invention provides methods for preventing natural biofilm growth on surfaces subjected to marine bacterial strains like Vibrio spectacularus , Pseudoaltermonas haloplanktis , Shewanella colwelliana , Planococcus kocurii and Roseobacter denitrificans comprising applying to the surface, prior to exposing said surface to said marine bacterial strains, the combination of silanes, the sol-gel matrix, and optionally antifouling compound, composition or coating described herein.
  • the methods can prevent biofilm growth by lowering (partially or completely) the biofilm coverage area.
  • the surface is any surface that can be colonised by biofilms .
  • the surfaces can be materials such as metals (such as marine grade aluminum), plastics, composites (such as fiberglass), glass, wood, or other natural fibers.
  • suitable surfaces include surfaces of a water-borne vessel such as a boat, ship and personal watercraft . Others examples of suitable surfaces includes concreate, sandwich walls and stainless steel.
  • the method comprises the step of applying the combination of silanes, the sol-gel matrix, and optionally antifouling compound, composition or coating described herein as described herein to at least a portion of a surface to form an ORMOSIL xerogel film prior to biofilm colonisation on the surface.
  • the coating of biofilms growth reduction coating composition can be applied by a variety of coating methods .
  • suitable coating methods including spray coating, dip coating, brush coating, or spread coating.
  • the sol-gel matrix coating can be formed by acid- catalyzed hydrolysis and polymerization of the precursor components.
  • the biofilms growth reduction precursor composition further comprises an acidic component that makes the pH of the composition sufficiently acidic so that the components undergo acid-catalyzed hydrolysis to form the sol-gel matrix.
  • suitable acidic components include aqueous acids such as hydrochloric acid, hydrobromic acid and trifluoroacetic acid.
  • suitable acidic components include organic acids such as acetic acid, cinnamic acid and salicylic acid. Conditions and components required for acid-based hydrolysis of sol-gel components are known in the art .
  • the coating After applying the coating of the biofilms growth reduction coating composition, the coating is allowed to stand for a time sufficient to form the xerogel .
  • the standing time is, for example, from 1 hour to 72 hours including all integer numbers of hours and ranges there between and up to 1 or more days .
  • the steps of the methods described in the various embodiments and examples disclosed herein are sufficient to practice the methods of the present disclosure.
  • the method consists essentially of a combination of the steps of a method disclosed herein.
  • the method consists of such steps.
  • Isopropanol was purchased from Quantum Chemical Corp.
  • Hydrochloric acid was obtained from Fisher Scientific Co.
  • Copper thiocyanate and titanium dioxide were purchased from Alfa Aesar and used as received.
  • Zinc pyrithione and IrganolTM were purchased from CombiBlock and used as received.
  • Zineb and Econea were purchased from BOC Science and used as received. Borosilicate glass microscope slides were obtained from Fisher Scientific, Inc.
  • the sol/xerogel composition is designated in terms of the molar ratio of Si-containing precursors.
  • a 50:50 C8/TEOS composition contains 50 mole % C8 and 50 mole % TEOS.
  • General procedure Unless noted, all sol are prepared in isopropanol using aqueous HC1 as the catalyst. Alkyl silanes are placed in a round bottomed flask equipped with mechanical stirrer along with the alcohol and the TEOS . This mixture is stirred for 5 minutes and a 0.1 N solution of the acid in water is slowly added. The reaction mixture is then capped and stirred at ambient temperature for 24 hours.
  • SiNH2 /C8 /TEOS 0.1:49.9:50 SiNH2 /C8 /TEOS .
  • the anti-biofilm / sol-gel composition is designated as mass ratio.
  • a 1% Cu 2 O-50:50 C8/TEOS contain 0.1 g of Cu 2 0 in 10 g of the 50:50 C8/TEOS sol.
  • Zinc pyrithione-50 50 C8/TEOS. 1 g of zinc pyrithione was placed in 100 g of the 50:50 C8/TEOS and the mixture was shaken at room temperature for 4h. [0131] 5% Zinc pyrithione-50 : 50 C8/TEOS. 5 g of zinc pyrithione was placed in 100 g of the 50:50 C8/TEOS and the mixture was shaken at room temperature for 4h.
  • 1% Zineb-50:50 C8/TEOS 1 g was placed in 100 g of the 50:50 C8/TEOS and the mixture was shaken at room temperature for 4h.
  • Zinc pyrithione-50 50 C3/TEOS. 5 g of zinc pyrithione was placed in 100 g of the 50:50 C3/TEOS and the mixture was shaken at room temperature for 4h. [0146] 1% Irgarol-50 : 50 C8/TEOS. 1 g of irgarol was placed in 100 g of the 50:50 C8/TEOS and the mixture was shaken at room temperature for 4h.
  • Biofilms were analysed by confocal laser scanning microscopy (CLSM) with a LSM700 (Carl Zeiss, Germany) using a 40X magnification. Biofilms were directly stained with LIVE/DEAD® Bac LightTM Bacterial Viability Kit. The CLSM was used to measured 4 parameters; biofilm thickness, cellular disposition in the biofilm, amount of surface cover by the biofilm, amount of biofilm removed with a water jet (from a cleaning flask) . Statistical analysis of the result was performed using an ANOVA factor with SYSTAT 12.0 (Systat Software Inc., Chicago, USA) with a probability of 0.05. Normality of data was tested using the Kolmogorov-Smirnov methodology .
  • Pseudoaltermonas haloplanktis (ATCC ® 14393TM) ; Shewanella colwelliana (ATCC ® 39565TM); Planococcus kocurii (ATCC ® 43650TM) and Roseobacter denitrificans (ATCC ® 33942TM) ) were chosen to studies the bacterial adhesion in presence of the antifouling paint.
  • Each marine bacterial strain was grown overnight in Marine Broth medium (Difco 2216) at room temperature. Cultures were centrifuged at 5 000 rpm for 5 min.
  • Bacterial cell pellets were washed thrice in physiological water ( 9 ⁇ of NaCl, pH 7.2, 0.2 ⁇ im filtered and autoclaved) to remove any residual growth medium. Then, bacterial cell suspensions were diluted in sterile physiological water to obtain working bacterial suspensions containing 10 8 cell.mL -1 . Preparation of adhesion surfaces and formation of marine biofilm. Coatings were applied to wells of a 96-well microplate using a foam brush. Two coats of paint were applied in the wells at one-hour intervals. All biofilms were formed in 96-well microplates for 48 hours at room temperature without agitation in 8 replicates.
  • the biofilms were composed of one strain, two, three, four or five bacterial strains in the presence of all antifouling paints. All biofilms were formed with 10 7 cell.mL- 1 . After 48 hours, the biofilms formed were analyzed by spectrometry according to modify protocol of Jackson et al . (2002, Journal of Bacteriology 184:290-301) . Briefly, the microplates were inverted to remove the supernatant and all wells were cleaned with phosphate buffer water (pH 7.2, 0.2 ⁇ im filtered and autoclaved) three times to remove any unadhered bacterial cells. Subsequently, 0.1% crystal violet was added to each of the wells to mark the adhered cells for 15 minutes.
  • phosphate buffer water pH 7.2, 0.2 ⁇ im filtered and autoclaved
  • FIG. 1 shows the bacterial evolution in each aquarium water using the flux cytometry methodology. After 3 weeks of immersion for the 50:50 C8/TEOS, the 1:49:50 C18/C8/TEOS, the 1:49:50 QAC/C8/TEOS, the 0.1:49.9:50 QAC/C8/TEOS, the 0.1% Cu 2 O-50:50 C8/TEOS and the 0.1% Cu 2 O-0.1 : 49.9: 50 QAC/C8/TEOS, bacterial evolution was showed to be normal. Only the presence of the 30% Cu 2 O-20% ZnO-50:50 C8/TEOS xerogel was showed to lower the bacterial count in the water after 21 days.
  • Results from experiment #2 show that the 30% Cu20- 20% ZnO 50:50 C8/TEOS coating forms a very potent anti-biofilm surface. Confocal laser scanning microscopy shows a total absence of bacterial activity on glass slides treated with this material. Results also show that there is a significant difference between the blank control and both 0.1% Cu 2 0- 50:50 C8/TEOS and 0.1% Cu 2 0- 0.1:49.9:50 QAC/C8/TEOS coatings at the level of biofilm coverage area and cellular viability on the surface, an indication of anti-biofilm activity. After three weeks, the microorganisms on the control glass slides were viable and the biofilm was getting mature.
  • Biofilm thickness ( ⁇ ) 29,00 ⁇ 8,66 21,53 ⁇ 4,31 16,53 ⁇ 2,80* Biofilm area coverage
  • QAC/C8/TEOS coatings is showing an important synergy between the action of the anti-fouling additive (copper (I) oxide) and the quaternary ammonium group. Indeed, the 0.1% CU 2 O- 0.1:49.9:50 QAC/C8/TEOS coatings is notably more efficient than both the 0.1:49.9:50 QAC/C8/TEOS and the 0.1% Cu 2 0- 50:50 C8/TEOS coating regarding the biofilm area coverage and cellular viability on the surfaces.
  • Pk Planococcus kocurii ATCC 43650
  • Adhesions are expressed as percent adhesion according to the following equation:
  • Results presented in table 1 show a range of antibiofilm activity from xerogel and biocide containing xerogel. Copper and titane salt offer moderate to good antibiofilm properties but zinc pyrithione was found to be extremely efficient in reducing the adhesion of the microorganisms on the xerogels, even when used in low concentrations. Organic antifouling compounds like irgarol and econea also impart a range of antibiofilm activity to the xerogel.

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Abstract

La présente invention concerne de manière générale des compositions de revêtement antibiofilm comprenant une combinaison de silanes ou de matrice sol-gel et éventuellement d'un additif antisalissure qui peut être utilisé pour générer un film de xérogel. L'invention concerne également des procédés de réduction ou de prévention de formation de biofilm sur des surfaces, comprenant l'application, avant la formation dudit biofilm, de la combinaison de silanes, de la matrice sol-gel et éventuellement du composé antisalissure sur la surface.
PCT/CA2018/050947 2017-08-16 2018-08-02 Compositions et procédés de revêtement pour empêcher la formation de biofilms sur des surfaces WO2019033199A1 (fr)

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JP2021529866A (ja) * 2018-06-29 2021-11-04 エアロゲル アンパーツゼルスカブ カプセル化殺生物剤及び生物忌避剤
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JP7485644B2 (ja) 2018-06-29 2024-05-16 エアロゲル アンパーツゼルスカブ カプセル化殺生物剤及び生物忌避剤
JP7485620B2 (ja) 2018-06-29 2024-05-16 エアロゲル アンパーツゼルスカブ カプセル化殺生物剤及び生物忌避剤
KR20220125975A (ko) * 2021-03-08 2022-09-15 (주)동양유지 초발수성·방오성·항균성·발유성을 갖는 코어 코로나(Core-corona)형 유무기 하이브리드화 나노입자 및 이의 제조방법
KR102495579B1 (ko) * 2021-03-08 2023-02-06 (주)동양유지 초발수성·방오성·항균성·발유성을 갖는 코어 코로나(Core-corona)형 유무기 하이브리드화 나노입자 및 이의 제조방법
WO2024028618A1 (fr) * 2022-08-01 2024-02-08 Papadopoulos Nikolaos-Xafakis Sotirios G.P. Systèmes de nano-revêtement antisalissure à activité antimicrobienne améliorée

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