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WO2024077382A1 - Microparticules antimicrobiennes omniphobes et compositions associées - Google Patents

Microparticules antimicrobiennes omniphobes et compositions associées Download PDF

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Publication number
WO2024077382A1
WO2024077382A1 PCT/CA2023/051342 CA2023051342W WO2024077382A1 WO 2024077382 A1 WO2024077382 A1 WO 2024077382A1 CA 2023051342 W CA2023051342 W CA 2023051342W WO 2024077382 A1 WO2024077382 A1 WO 2024077382A1
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WIPO (PCT)
Prior art keywords
omniphobic
microparticle
antimicrobial
nanoparticles
polymer
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PCT/CA2023/051342
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English (en)
Inventor
Noor Abu JARAD
Tohid F. DIDAR
Leyla Soleymani
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McMaster University
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McMaster University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/206—Hardening; drying

Definitions

  • the present application relates to an omniphobic and antimicrobial wrinkled microparticle comprising a polymeric core that comprises a wrinkled shell covering at least a portion of the core, and one or more hydrophobic molecular layers and one or more nanoparticle layers attached to the shell.
  • the present application also relates to an optionally sprayable composition comprising the microparticles of the present application, and methods and uses thereof.
  • the present application further relates to methods of preparing the microparticles of the present application.
  • Health care providers that come in contact with contaminated surfaces have a 42% to 52% risk of contaminating their hand or glove - a level of risk similar to what is seen following direct contact with infected patients.
  • 181 Surface transmission is further highlighted within closed environments, such as aircraft cabins. In fact, studies have found that in less than 2 to 3 hours, most high touch surfaces within an aircraft cabin are contaminated. The rapid transmission of pathogenic agents within such an environment is further highlighted by the fact that virtually all touchable surfaces are contaminated within 5 to 6 hours. 161 Ultimately, there is a need for methods that prevent the transmission of pathogens via high touch surfaces, in order to reduce the prevalence of resultant infections.
  • biocides such as antibiotics, disinfectants, antiseptics, inorganic metal ions, or preservatives have shown great promise in reducing contamination by instantaneously killing bacteria. 13 ’ 9-121
  • biocides can pose harmful health effects, such as eye irritation (hydrogen peroxide), long term damage to DNA and fertility (quaternary ammonium compounds), and the in vivo enrichment of metal ions, paired with respiratory complications (bleach). 113-151 In addition, they aggravate biofilm formation and increase microbial resistance.
  • Hierarchal-structured surfaces represent a class of omniphobic surfaces that show bacterial repellency through a reduction in the contact area available for bacterial attachment.
  • 120 ’ 211 Although promising, the fabrication of such hierarchically-structured surfaces involves methods such as electrospinning, 1221 photolithography, 123241 laser ablation, 1251 or photoablation, 1261 which are limited to specific materials and form factors and are too difficult to scale up for large volume manufacturing.
  • a universal and simple surface coating method applicable to a wide range of materials and form factors is highly desirable to combat the adhesion, accumulation, proliferation, and subsequent biofilm formation of bacteria on surfaces.
  • coating methods such as drop casting, 1291 dip coating, 1301 and spin-coating, 1311 spray coating demonstrates significant advantages as it can be applied to surfaces during manufacturing via roll-to-roll processing, or introduced post substrate fabrication, regardless of its material properties and shape.
  • spray coating provides a unique flow field that can localize particle deposition, thus facilitating the fabrication of hierarchically textured surfaces.
  • a bi-functional coating that can be deposited universally onto a variety of surfaces via different coating methods, for example via spray coating.
  • the coating employs hierarchically structured, wrinkled polymeric, for example PDMS or PLA, microparticles decorated with metal-based nanoparticles such as gold nanoparticles (AuNPs).
  • the particle-based coating possesses a three-tiered structural hierarchy including polymeric particles at a microscale, structural wrinkles at a tens of microns scale, and metal-based nanoparticles (e.g. gold nanoparticles) at a nanoscale. These tiers worked synergistically to “repel and kill” bacteria and viruses.
  • This coating was applied to glass, polystyrene, stainless steel, textile, and paper substrates.
  • the repellency and biocidal activity of the coating were shown comprehensively via wettability studies, as well as bacterial and viral adhesion and growth tests. These biological tests demonstrated the efficacy of the coating against societal relevant pathogens including Staphylococcus aureus (MRSA), Pseudomonas aeruginosa, and Phi6 - a bacterial virus often used as a surrogate for SARS-CoV-2.
  • MRSA Staphylococcus aureus
  • Pseudomonas aeruginosa Pseudomonas aeruginosa
  • Phi6 - a bacterial virus often used as a surrogate for SARS-CoV-2.
  • the present application includes an omniphobic and antimicrobial microparticle comprising a polymeric core comprising a wrinkled shell covering at least a portion of the core; and one or more hydrophobic molecular layers and one or more nanoparticle layers attached to the shell.
  • the present application includes a method of preparing an omniphobic and antimicrobial microparticle comprising combining a polymer and a surfactant to obtain a polymer microparticle comprising a polymeric core and a shell covering at least a portion of the core, the shell comprising the surfactant; treating the polymer microparticle under conditions to wrinkle at least a portion of the shell; and coating the polymer microparticle with one or more hydrophobic molecular layers and one or more nanoparticle layers through attachment to the shell to obtain the omniphobic and antimicrobial microparticle.
  • the present application includes an omniphobic and antimicrobial surface treatment composition comprising the omniphobic and antimicrobial microparticle of the present application or an omniphobic and antimicrobial microparticle prepared by a method of the present application; and a solvent.
  • the present application includes a method of surface treatment of a substrate to provide omniphobic and/or antimicrobial properties comprising applying a binder on a surface of the substrate; applying a layer of an omniphobic and antimicrobial surface treatment composition of the present application on the surface of the substrate; and drying the surface of the substrate applied with the binder and the surface treatment composition.
  • the present application includes a substrate surface treated by a surface treatment method of the present application.
  • the present application includes a material comprising a substrate and the omniphobic and antimicrobial microparticle of the present application or an omniphobic and antimicrobial microparticle prepared by a method of the present application, wherein the microparticle is present on a surface of the substrate.
  • the present application includes a device or an article comprising a material of the present application.
  • the present application includes a device or article comprising a surface, wherein at least a portion of the surface comprises a material of the present application.
  • the present application includes a device or article comprising a surface, wherein at least a portion of the surface has been treated by a surface treatment method of the present application.
  • the present application includes a method of preventing, reducing, or delaying adhesion, or adsorption of a biological material onto a device in contact therewith, comprising: treating at least one surface of the device with an omniphobic and antimicrobial surface treatment composition of the present application, optionally by a surface treatment method of the present application.
  • the present application includes a use of an omniphobic and antimicrobial microparticle of the present application or a surface treatment composition of the present application in preventing, reducing, or delaying adhesion, or adsorption of a biological material onto a device in contact therewith.
  • Figure 1 shows the development of wrinkled omniphobic microparticles and their subsequent characterizations,
  • FIG. 2 shows SEM images of exemplary microparticles.
  • SEM Scanning electron microscopy
  • FIG. 3 shows energy-dispersive X-ray spectroscopy (EDS) analysis of an exemplary coated glass side. The analysis was conducted on top left SEM image at 5 different spectra confirming presence of gold nanoparticles within the wrinkles.
  • EDS energy-dispersive X-ray spectroscopy
  • Figure 4 shows the characterization results of microparticle coatings, (a) Surface characterizations illustrating the wetting properties of PDMS microparticles (MPs), FOTS-treated microparticles, and exemplary hMPs. (b) Hexadecane CA and water SA of various exemplary hMP spray-coated substrates, (c) Optical images depicting the change in the spherical shape of water (blue-dyed) and hexadecane droplets on exemplary coated (left) and uncoated (right) substrates, (d) Water CA of various substrates before and after exemplary hMP spray coating. All reported values are the mean of at least three measurements and associated error bars represent one standard deviation from the mean.
  • Figure 5 shows the results from physical characterizations of the exemplary coating of Example 2.
  • Figure 6 shows investigation of various surface texturing on the omniphobicity of the exemplary coating of Example 2.
  • Figure 7 shows the results from stability, durability, and robustness testing of the coating of Example 3.
  • Figure 8 shows results from self-cleaning test of hMP-coated glass surfaces. Colony forming unit assay was conducted at 2 time points using methicillin- resistant Staphylococcus aureus (MRSA). Graphs are depicted on a logarithmic scale representing the mean value of four different surfaces.
  • MRSA methicillin- resistant Staphylococcus aureus
  • Figure 9 shows the results of pathogen repellency and killing tests, (a) Schematic illustrating the repellency and killing behavior of different exemplary tiered microparticles, (b-d) Colony forming unit assay performed at different time points on glass surfaces using (b) MRSA, (c) P. aeruginosa, and (d) Phi6 depicting the pathogen adherence, (e) SEM images of glass surfaces stamped with (i, ii) P. aeruginosa and (iii, iv) MRSA on uncoated glass surfaces (left) and coated glass surfaces (right). Red arrow points towards the MRSA colonies found on the surface of PDMS microparticles.
  • Graphs are depicted on a logarithmic scale and error bars represent one standard deviation from the mean. Each measurement consists of at least four data points. The red dotted line represents the initial inoculum of bacteria. Significance is shown through asterisks corresponding to *P ⁇ 0.05, **P ⁇ 0.01 , ***P ⁇ 0.001 and ****P ⁇ 0.0001.
  • Figure 10 shows the antimicrobial activity of functionalized gold nanoparticles.
  • Growth assay using MRSA depicts the substantial reduction in bacterial growth for functionalized gold nanoparticles relative to pure gold nanoparticles.
  • Graphs are depicted on a logarithmic scale and error bars represent standard errorfrom the mean. Each measurement consists of at least four data points.
  • FIG 11 shows an evaluation of the stability of gold nanoparticles in solution on the omniphobic microparticles (OMPs).
  • Trial 1 depicts the colony forming unit of a spray-coated 96 well plate using MRSA relative to the control (uncoated 96 wellplate). Between the trials, the plate was excessively washed, and the growth assay was performed another time (trial 2), 4 weeks later. Graphs are depicted on a logarithmic scale and error bars represent standard error from the mean. The red dotted line represents the initial inoculum of bacteria.
  • Figure 12 shows the effect of AuNP size and density on antimicrobial activity
  • Figure 13 shows the results from pathogen transfer assays under real-world conditions
  • microparticle(s) of the application or “microparticle(s) of the present application” and the like as used herein refers to an omniphobic, antimicrobial wrinkled microparticle comprising PDMS core and metal-based nanoparticles.
  • microparticles of the application include the hierarchal microparticles as described herein.
  • composition(s) of the application or “composition(s) of the present application” and the like as used herein refers to a composition, such a sprayable composition, comprising one or more microparticles of the application.
  • the second component as used herein is chemically different from the other components or first component.
  • a “third” component is different from the other, first, and second components, and further enumerated or “additional” components are similarly different.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), "including” (and any form of including, such as “include” and “includes”) or “containing” (and any form of containing, such as “contain” and “contains”), are inclusive or open-ended and do not exclude additional, unrecited elements or process steps.
  • suitable means that the selection of the particular compound or conditions would depend on the specific synthetic manipulation to be performed, and the identity of the molecule(s) to be transformed, but the selection would be well within the skill of a person trained in the art. All process/method steps described herein are to be conducted under conditions sufficient to provide the product shown. A person skilled in the art would understand that all reaction conditions, including, for example, reaction solvent, reaction time, reaction temperature, reaction pressure, reactant ratio and whether or not the reaction should be performed under an anhydrous or inert atmosphere, can be varied to optimize the yield of the desired product and it is within their skill to do so.
  • alkyl as used herein, whether it is used alone or as part of another group, means straight or branched chain, saturated alkyl groups.
  • the number of carbon atoms that are possible in the referenced alkyl group are indicated by the prefix “Cni-n2”.
  • C1-1 oal ky I means an alkyl group having 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.
  • alkylene whether it is used alone or as part of another group, means straight or branched chain, saturated alkylene group, that is, a saturated carbon chain that contains substituents on two of its ends.
  • the number of carbon atoms that are possible in the referenced alkylene group are indicated by the prefix “Cni-n2”.
  • C2-6alkylene means an alkylene group having 2, 3, 4, 5 or 6 carbon atoms.
  • alkane as used herein means straight or branched chain, saturated alkane, that is a saturated carbon chain.
  • hydrolysable group as used herein means a functional group that can be cleaved or displaced by a nucleophilic group such as water, hydroxyl groups, amine groups, etc.
  • halo refers to a halogen atom and includes F, Cl, Br and I.
  • atmosphere refers to atmosphere
  • MS mass spectrometry
  • hMPs refers to hierarchal microparticles.
  • HCI as used herein refers to hydrochloric acid.
  • room temperature means a temperature in the range of about 20°C and 25°C.
  • wrinkleling refers to any process for forming wrinkles in a material.
  • wrinkleled shell refers to a surface or a portion of a surface that contains microscale to nanoscale folds.
  • Hierarchical refers to a material having a range of microscale to nanoscale structural features on the surface of the material.
  • naked nanoparticle or the like as used herein refers to a nanoparticle that is not attached to a linker such as an organosilane linker.
  • omniphobic refers to a material that exhibits both hydrophobic (low wettability for water and other polar liquids) and oleophobic (low wettability for low surface tension and nonpolar liquids) properties. Such omniphobic materials with very high contact angles are often regarded as “selfcleaning” materials, as contaminants will typically bead up and roll off the surface.
  • the present application includes an omniphobic and antimicrobial microparticle comprising a polymeric core comprising a wrinkled shell covering at least a portion of the core; and one or more hydrophobic molecular layers and one or more nanoparticle layers attached to the shell.
  • the shell covering at least a portion of the core is a rigid layer covering substantially all of the core.
  • wrinkles are introduced in the shell by using mechanical tension, mechanical stretching, mechanical compression, heat or swelling induced stress, or a combination thereof.
  • wrinkles are formed by exerting stress o greater than a critical wrinkled stress Oc of the shell.
  • the polymeric core comprises an elastomeric polymer.
  • the polymeric core comprises a viscoelastic polymer with low Young’s modulus, low intermolecular forces and/or withstands elastic deformation.
  • the polymeric core comprises a polymer selected from natural rubber, silicone elastomers, polyurethane, polybutadiene, PDMS, polylactic acid (PLA), and mixtures thereof.
  • the polymer comprises PDMS, or polylactic acid (PLA).
  • the polymer is PDMS, polylactic acid (PLA), or a mixture thereof.
  • the polymer is PDMS.
  • polymers include polymers that are formed by monomers that are soluble in organic solvents and hydrolysable, but less soluble or insoluble in aqueous medium. In some embodiments, the polymers are biocompatible.
  • the shell comprises a surfactant that comprises a plurality of hydroxyl groups.
  • the surfactant is partially hydrolyzed to provide the plurality of hydroxyl groups.
  • the surfactant is a siloxane surfactant.
  • the surfactant is selected from 3-(2- methoxyethoxy)propyl-methyl-bis(trimethylsilyloxy)silane, ethane-1 ,2-diol;propane-1 ,2- diol, polyoxyethylene (20) sorbitan monolaurate, 3-(3-hydroxypropyl)- heptamethyltrisiloxane, ethoxylated, acetate, and combinations thereof.
  • the one or more hydrophobic molecular layers comprise a fluorosilane layer.
  • the fluorosilane layer comprises fluorosilane moieties, each of the fluorosilane moieties having a structure of Formula I
  • X is a single bond or is Ci-6alkylene; n is an integer of from 0 to 12; and
  • R 1 , R 2 and R 3 are each independently a point of attachment to a hydroxyl group of the plurality of hydroxyl groups of the shell, a hydroxyl group, or a hydrolysable group, wherein at least one of R 1 , R 2 and R 3 is the point of attachment to the shell.
  • n is 4 to 9. In some embodiments, n is 5 to 7.
  • X is Ci-3alkylene, In some embodiments X is CH2CH2.
  • the hydrolysable group is an alkoxy such as an C1- ealkoxy, halo such as Cl, or Br, or trihaloalkylsulfonate such as trifluoromethylsulfonate.
  • the fluorosilane layer comprises (1 H,1 H, 2H,2H- perfluorooctyl)silane, (1 H,1 H, 2H,2H-perfluorodecyl)silane, or combinations thereof.
  • the one or more nanoparticle layers comprises nanoparticles selected from polymer nanoparticles, insulator nanoparticles, metal-based nanoparticles, and combinations thereof.
  • the metal-based nanoparticles are metal nanoparticles, metal oxide nanoparticles, semiconductor nanoparticles, or combinations thereof.
  • the metal-based nanoparticles comprise a metal selected from Au, Ag, Cu, Zn, Ti, Mg, and combinations thereof.
  • the semiconductor nanoparticles comprise a semiconductor selected from ZnO, CdS, ZnS and combinations thereof.
  • the metal oxide nanoparticles comprise a metal oxide selected from TiO2, ZnO, Ag2O, MgO, Fe2O3, CuO, CaO, CdO and combinations thereof.
  • the polymer nanoparticles are selected from poly(lactide-co-glycolide) (PLGA), polylactide (PLA), polyglycolide, polycaprolactone (PCL), poly(d.l-lactide), and PLGA-polyethylene glycol (PEG).
  • the insulator nanoparticles are selected from silica, titanium dioxide, aluminum oxide, and combinations thereof.
  • the nanoparticles are Au nanoparticles.
  • the nanoparticles are bound to the shell through the one or more functionalised organosilane linkers.
  • the linker is selected based on the nature of the nanoparticles to be bound.
  • the one or more functionalised organosilane linkers are selected from APTES, EDC- functionalised organosilane, glutaraldehyde-functionalised organosilane, and thiol organosilane linkers.
  • the functionalised organosilane linker is a thiol organosilane linker for attachment of Au nanoparticles due to the affinity between sulfur and Au.
  • each of the one or more functionalised organosilane linkers is attached to one of the nanoparticles at a reactive functional group of the functionalised organosilane linker.
  • each of the nanoparticles is attached to a plurality of the functionalised organosilane linkers; wherein the plurality of the functionalised organosilane linkers form a silanol layer around each of the nanoparticles; and wherein the silanol layer is attached to the shell.
  • the one or more functionalised organosilane linkers are one or more thiol organosilane linkers.
  • the thiol organosilane linker is formed using a reagent selected from (3-mercaptopropyl)trimethoxysiloxane, 3-mercaptopropionic acid (3-MPA), 11-mercaptoundecanoic acid (MUA), polyethylene glycol 2-mercaptoethyl methyl ether, polyethylene glycol) methyl ether thiol, 3-(trimethoxysilyl)-1 -propanethiol, and combinations thereof.
  • a reagent selected from (3-mercaptopropyl)trimethoxysiloxane, 3-mercaptopropionic acid (3-MPA), 11-mercaptoundecanoic acid (MUA), polyethylene glycol 2-mercaptoethyl methyl ether, polyethylene glycol) methyl ether thiol, 3-(trimethoxysilyl)-1 -propanethiol, and combinations thereof.
  • the silanol layer is further functionalised with one or more hydrophobic fluoroorganosilane functionalities of a structure of Formula I as herein; or wherein the nanoparticles are functionalised with a thiofluorohydrocarbon of Formula II
  • * is the point of attachment to the nanoparticles, r is an integer of from 0 to 5; and q is an integer of from 0 to 12.
  • r is 1 to 4, 1 to 3, 2 to 3, or 2. In some embodiments, q is 5 to 10, 5 to 9, or 7.
  • the microparticle has a diameter of about 2 pm to about 30 pm, about 10 pm to about 30 pm, about 15 pm to about 25 pm, or about 20 pm.
  • the microparticle has a modulus of elasticity of 250 kPa to 280 kPa.
  • the present application includes an omniphobic and antimicrobial surface treatment composition comprising the omniphobic and antimicrobial microparticle of the present application or an omniphobic and antimicrobial microparticle prepared by a method of the present application; and a solvent.
  • the solvent of the omniphobic and antimicrobial surface treatment composition is selected from an alcohol, tetrahydrofuran, water, and combinations thereof.
  • the alcohol is ethanol.
  • the surface treatment composition comprises about 50 mg/mL to about 200 mg/mL, about 75 mg/mL to about 175 mg/mL, about 80 mg/mL to about 150 mg/mL, about 80 mg/mL to about 125 mg/mL, about 90 mg/mL to about 110 mg/mL, or about 100 mg/mL of the omniphobic and antimicrobial microparticle.
  • the composition is sprayable.
  • the present application includes a method of preparing an omniphobic and antimicrobial microparticle comprising combining a polymer and a surfactant to obtain a polymer microparticle comprising a polymeric core and a shell covering at least a portion of the core, the shell comprising the surfactant; treating the polymer microparticle under conditions to wrinkle at least a portion of the shell; and coating the polymer microparticle with one or more hydrophobic molecular layers and one or more nanoparticle layers through attachment to the shell to obtain the omniphobic and antimicrobial microparticle.
  • the treating of the polymer microparticle exerts a compressive stress o greater than a critical wrinkled stress o c of the microparticle, thereby wrinkling at least a portion of the shell.
  • the polymer comprises natural rubber, silicone elastomers, polyurethane, polybutadiene, PDMS, polylactic acid (PLA), or mixtures thereof.
  • the polymer comprises PDMS, PLA, or mixtures thereof.
  • the polymer is PDMS or PLA.
  • the surfactant comprises a plurality of hydroxyl groups.
  • the surfactant is partially hydrolyzed to provide the plurality of hydroxyl groups.
  • the method further comprises partially hydrolyzing the surfactant.
  • partial hydrolysis of the surfactant can be carried out by methods known in the art.
  • the partially hydrolyzing can be carried out by exposing the surfactant to water.
  • the combining of the polymer and the surfactant can be carried in the presence of water to partially hydrolyze the surfactant while obtaining the polymer microparticle.
  • the partially hydrolyzing of the surfactant can be carried out prior to the combining of the polymer and the surfactant.
  • the surfactant is as described herein.
  • the surfactant is an anionic trisiloxane alkoxylate surfactant.
  • the surfactant is an anionic trisiloxane ethoxylate surfactant.
  • the surfactant is selected from 3-(2-methoxyethoxy)propyl-methyl- bis(trimethylsilyloxy)silane (e.g. Silwet L-77 TM ), ethane-1 ,2-diol; propane-1 , 2-diol (e.g. Pluronic F-68 TM ), polyoxyethylene (20) sorbitan monolaurate (e.g. Tween 20TM), 3-(3- hydroxypropyl) -heptamethyltrisiloxane, ethoxylated, acetate (e.g. Sylgard ® 309 Silicone), and combinations thereof.
  • 3-(2-methoxyethoxy)propyl-methyl- bis(trimethylsilyloxy)silane
  • the one or more hydrophobic molecular layers and the one or more nanoparticle layers are attached to the shell through the plurality of hydroxyl groups.
  • the combining of the polymer and the surfactant is carried out under conditions to obtain a homogenous emulsion comprising the polymer microparticle.
  • the combining of the polymer and the surfactant is carried out in an organic solvent.
  • the organic solvent is selected from acetone, ethanol, dichloromethane, toluene, chloroform, and combinations thereof.
  • the organic solvent is acetone.
  • the combining of the polymer and the surfactant is carried out in the presence of water.
  • the conditions for combining the polymer and the surfactant comprise sonication.
  • the sonication is ultrasonication.
  • the ultrasonication is performed at about 30 to about 50 kHz, about 30 to about 40 kHz, or about 35 kHz.
  • the shell covering at least a portion of the core is a rigid layer covering substantially all of the core.
  • the one or more hydrophobic molecular layers comprise a fluorosilane.
  • the fluorosilane is as described herein.
  • the coating of the polymer microparticle comprises fluorosilanating the polymer microparticles using one or more fluorosilanation agents as described herein.
  • the fluorosilanation agents have the structure of Formula III as defined herein.
  • the one or more fluorosilanation agents are selected from trichloro(1 H,1 H,2H,2H-perfluorooctyl)silane, 1 H,1 H,2H,2H- perfluorooctyltriethoxysilane, and combinations thereof.
  • the one or more nanoparticle layers comprise one or more nanoparticles as described herein.
  • the nanoparticles comprise one or more hydrophobic fluoroorganosilane functionalities attached thereto.
  • the hydrophobic fluoroorganosilane functionalities are as described herein.
  • the nanoparticles are as described herein.
  • the treating of the polymer microparticle to obtain the wrinkled microparticle comprises stirring, particle drying, surface chemical modification such as wet surface chemical oxidation, or combinations thereof.
  • the treating of the polymer microparticles comprises mechanical tension, mechanical stretching, mechanical compression, heat or swelling induced stress, or a combination thereof.
  • the stirring is as described herein, for example the stirring is performed at about 8000 RPM to about 12000 RPM, about 9000 RPM to about 11000 RPM, about 9500 RPM to about 10500 RPM, or about 10000 RPM.
  • the stirring is carried out at about 60°C to about 100°C, about 70°C to about 90°C, or about 80°C.
  • the stirring is carried out for about 2 hours to about 5 hours, about 2.5 hour to about 4.5 hours, about 2 hours to about 4 hours, or about 2 hours.
  • the surface chemical modification is as described herein.
  • the surface chemical modification comprises wet chemical surface oxidation using for example acids (e.g. H2SO4 and/or HNO3).
  • the coating of the wrinkled microparticle with the one or more nanoparticle layers comprises attaching the one or more nanoparticle layers to the shell through one or more functionalised organosilane linkers.
  • the functionalised organosilane linkers are as described herein.
  • the functionalised organosilane linkers are a compound of Formula IV as described herein.
  • the antimicrobial and omniphobic microparticles have a diameter of about 2 pm to about 30 pm, about 15 pm to about 25 pm, or about 20 pm.
  • each of the nanoparticles is attached to a plurality of the functionalised organosilane linkers; wherein the plurality of the functionalised organosilane linkers form a silanol shell around each of the nanoparticles; wherein the silanol shell comprises hydroxyl groups; and wherein at least a portion of the hydroxyl groups of the silanol shell is for attachment to the shell of the polymer microparticle.
  • another portion of the hydroxyl groups of the silanol shell around each of the nanoparticles is functionalised with fluorosilane functionalities.
  • the fluorosilane functionalities have a structure of Formula I as defined herein.
  • the method further comprises combining naked nanoparticles and a coupling agent to obtain the nanoparticles attached to the plurality of the functionalised organosilane linkers.
  • the functionalised organosilane linker is thiol organosilane linker and the coupling agent is of Formula IV:
  • R 7 , R 8 and R 9 are each independently a hydrolysable group.
  • p is 1 to 6, 1 to 4, 1 to 3, 2 to 3, or 3.
  • R 7 , R 8 and R 9 are each independently C1-3 alkoxy or halo. In some embodiments, R 7 , R 8 and R 9 are each independently methoxy, ethoxy, or Cl.
  • the coupling agent is selected from (3- mercaptopropyl)trimethoxysilane, 3-mercaptopropionic acid (3-MPA), 11- mercaptoundecanoic acid (MUA), polyethylene glycol 2-mercaptoethyl methyl ether, polyethylene glycol) methyl ether thiol, and 3-(trimethoxysilyl)-1 -propanethiol.
  • the functionalising of the wrinkled PDMS microparticles with the plurality of metal-based nanoparticles occurs prior to the fluorosilanating of the wrinkled PDMS microparticles.
  • the naked nanoparticles are combined with the coupling agent in the presence of a thiol fluorohydrocarbon of Formula V
  • t is 1 to 4, 1 to 3, 2 to 3, or 2. In some embodiments, s is 5 to 10, 5 to 9, or 7.
  • the thiol fluorohydrocarbon is 1 H,1 H,2H,2H- perfluorodecanethiol.
  • the method of preparing the omniphobic and antimicrobial microparticle further comprises washing and drying the omniphobic and antimicrobial microparticle.
  • the omniphobic and antimicrobial microparticle is the omniphobic and antimicrobial microparticle of the present application as described herein.
  • the present application includes a method of surface treatment of a substrate to provide omniphobic and/or antimicrobial properties comprising applying a binder on a surface of the substrate; applying a layer of an omniphobic and antimicrobial surface treatment composition of the present application on the surface of the substrate; and drying the surface of the substrate applied with the binder and the surface treatment composition.
  • the present application includes a method of preventing, reducing, or delaying adhesion, or adsorption of a biological material onto a device in contact therewith, comprising: treating at least one surface of the device with an omniphobic and antimicrobial surface treatment composition of the present application, optionally by a surface treatment method of the present application.
  • the present application includes a use of an omniphobic and antimicrobial microparticle of the present application or a surface treatment composition of the present application in preventing, reducing, or delaying adhesion, or adsorption of a biological material onto a device in contact therewith.
  • the method of surface treatment further comprises applying one or more additional layers of the surface treatment composition prior to the drying of the surface.
  • the applying of the layer(s) of the surface treatment composition comprises spraying and/or painting the surface treatment composition. In some embodiments, the applying of the layer(s) of the surface treatment composition comprises dipping or immersing the surface of the substate in the surface treatment composition.
  • the binder is an epoxy resin binder or aluminum phosphate. In some embodiments, the binder is the epoxy resin binder. In some embodiments, the epoxy resin binder is selected from polyacrylic acid (PAA), polyvinyl alcohol (PVA), PDMS, methylphenyl silicone resin, polyurethane, and mixtures thereof.
  • PAA polyacrylic acid
  • PVA polyvinyl alcohol
  • PDMS methylphenyl silicone resin
  • polyurethane polyurethane
  • the drying of the surface comprises heating at about 60°C to about 100°C, about 70°C to about 90°C, or about 80°C.
  • the substrate is selected from glass, polystyrene, stainless steel, textile, paper, and combinations thereof.
  • the present application includes a substrate surface treated by a surface treatment method of the present application.
  • the present application includes a material comprising a substrate and the omniphobic and antimicrobial microparticles of the present application or omniphobic and antimicrobial microparticles prepared by a method of the present application, wherein the microparticle is present on a surface of the substrate.
  • the material has a water static contact angle of 130° to about 190°, about 145° to about 175°, about 150° to about 170°, about 155° to about 165°, or about 160° as measured at room temperature using a goniometer.
  • the material has a hexadecane static contact angle of about 90° to about 130°, about 100° to about 120°, about 110° to about 115°, about 112° to about 115°, or about 113° as measured at room temperature using a goniometer.
  • the material has a water sliding angles of about 8° to about 15°, about 10° to about 13°, or about 12°, as determined at room temperature using a digital angle level.
  • the material has a surface roughness of about 5 pm to about 12 pm, or about 8 pm to about 10 pm, or about 9.6 pm as measured using vertical scanning interferometry.
  • the material is stable to thermal treatment of about 100°C, about 150°C, about 200°C, about 250°C, about 300°C, about 350°C, or at least about 300°C, for about 30 minutes to about 2.5 hours, about 1 hour to about 2.5 hours, about 2 hours, or at least about 2hours.
  • the material is stable to UV irradiation at 10 mW/cm 2 at a wavelength of 340 nm for at least about 1 hour, at least about 2 hours, at least about 4 hours, or about 6 hours.
  • the material is stable to sonication at 35 kHz for at least about 5 minutes, at least about 10 minutes, or at least about 15 minutes.
  • the material exhibits repellency to liquids.
  • the material exhibits repellency to biospecies.
  • the biospecies are selected from MRSA, P. aeruginosa, Phi6, SARS- CoV2, and combinations thereof.
  • the material exhibits repellency to bacteria, virus, fungus, and biofilm formation.
  • the bacteria are selected from MRSA, P. aeruginosa, vancomycin-resistant Enterococcus, Escherichia coli, Klebsiella pneumoniae, Acinetobacter baumanii, Salmonella Typhimurium, Enterobacter aerogenes, Burkholderia cenocepacia, and Proteus mirabilis, and combinations thereof.
  • the virus is selected from Phi6, SARS-CoV2, Middle East respiratory syndrome (MERS-CoV), Herpes simplex virus, and influenza A viruses, and combinations thereof.
  • the present application includes a device or an article comprising a material of the present application.
  • the present application includes a device or article comprising a surface, wherein at least a portion of the surface comprises a material of the present application.
  • the present application includes a device or article comprising a surface, wherein at least a portion of the surface has been treated by a surface treatment method of the present application.
  • the device or article is selected from:
  • plastic material that is disposed of for fouling or contamination, including, but not limited to plastic shopping bags, shower curtains and children’s toys (such as blow up pools and slip and slides water toys);
  • - wearable articles including, but not limited to, protective clothing such as gloves, scrubs, and face masks; consumable research equipment including, but not limited to, centrifuge tubes, micropipette tips and multiwell plates, a cannula, a connector, a catheter, a catheter, a clamp, a skin hook, a cuff, a retractor, a shunt, a needle, a capillary tube, an endotracheal tube, a ventilator, a ventilator tubing, a drug delivery vehicle, a syringe, a microscope slide, a plate, a film, a laboratory work surface, a well, a well plate, a Petri dish, a tile, a jar, a flask, a beaker, a vial, a test tube, a tubing connector, a column, a container, a cuvette, a bottle, a drum, a vat, a tank, a dental tool, a dental implant,
  • the biological material is selected from the group consisting of whole blood, plasma, serum, sweat, feces, urine, saliva, tears, vaginal fluid, prostatic fluid, gingival fluid, amniotic fluid, intraocular fluid, cerebrospinal fluid, seminal fluid, sputum, ascites fluid, pus, nasopharengal fluid, wound exudate fluid, aqueous humour, vitreous humour, bile, cerumen, endolymph, perilymph, gastric juice, mucus, peritoneal fluid, pleural fluid, sebum, vomit, and combinations thereof.
  • a 10:1 weight ratio of polydimethylsiloxane (SYLGARD 184TM) (Dow Corning, United States) to curing agent was prepared and degassed for 30 mins to remove any air bubbles.
  • Silwet L-77TM (10 wt%) (PhytoTech Labs, Canada) was mixed thoroughly with (3 g) PDMS to produce a homogenous emulsion at room temperature. The emulsion was then sonicated in glass vials at 35 KHz in an ultrasonication bath (VWR, Canada) for 2 hours to produce 20 pm sized uniform microparticles.
  • microparticles were then collected and vigorously stirred at 10000 RPM for 2 hours using a pneumaticbased overhead stirrer (AP10, ThermoFisher Scientific, Canada) at 80°C to cure and dry the interfacial layer.
  • AP10 pneumaticbased overhead stirrer
  • AP10 ThermoFisher Scientific, Canada
  • the functionalized AuNP solution was then added to the FOTS-treated PDMS microparticles and stirred for 2 hours.
  • the resultant hMPs were then centrifugally washed with water (x4) and ethanol (x2).
  • the microparticles were then incorporated in a spray consisting of absolute ethanol with a final concentration of 100 mg ml’ 1 .
  • PLA based microparticles were prepared. Briefly, 15 mg/mL of PLA was dissolved in acetone. Then, 15 mg/mL of Silwet L-77 was dissolved in water. The 2 solutions were mixed using an overhead stirrer at 10000 RPM and heated at 80°C for 2 hours. The particles were washed and collected through centrifugation in ethanol and water.
  • VSI vertical scanning interferometric
  • coated glass slides were subjected to 350°C on a hot plate for 2 hours.
  • the coated glass slides were irradiated under a UV lamp (approximately 10 mW cm -2 ) with a wavenumber of 340 nm for 6 hours at a perpendicular distance of 10 cm .
  • a sonication test was also conducted, whereas a coated glass slide was fully immersed in a falcon tube containing ethanol and sonicated in an ultrasonic bath (VWR, Mississauga, Canada) at 35 kHz for 5, 10, 15 minutes. After the stability tests, contact angle measurements were examined.
  • Pseudomonas aeruginosa PA01 [441 and Staphylococcus aureus USA300 JE2 (MRSA) [451 were streaked onto LB agar from frozen and allowed to grow overnight at 37 °C. Overnight cultures were then diluted 1/100 into MOPS-minimal media supplemented with (0.4%) glucose and (0.5%) casamino acids (TekNova, United States) for P. aeruginosa, or tryptic soy broth supplemented with (0.4%) glucose and (3%) NaCI for MRSA [461 . Concentrated MRSA and P. aeruginosa bacterial suspensions were then prepared in small petri dishes.
  • Agar plugs were fabricated from (3%) agar by dissolving (3 g) agarose in Milli-Q water (100 ml) under magnetic stirring at room temperature. The agarose was then heated in the microwave until no bubbles were seen, and then poured onto a petri dish to cool down at room temperature. Once the agarose cured, agar plugs were harvested by poking 15 mm tubes into the solidified agarose. The stamp assay was conducted by initially dipping the harvested agar plugs into the concentrated bacterial suspensions and immediately stamping the surfaces to transfer the bacteria. Surfaces were then incubated in petri dishes covered with a lid at room temperature for 1 , 2, 4, and 8 hours.
  • the stamped surfaces were incubated with shaking for 20 minutes in tubes containing equal volumes (2.5 mL) of bacteria growth media and recombinant trypsin solution (TrypLE Express, Gibco) to disperse biofilms, as well as adhered bacterial cells from the surfaces. From this solution, 100 pL of each sample was taken in order to run a CFU assay by plating serial dilutions on LB agar Petri dishes.
  • Elemental fraction percentages were measured from the XPS spectra of hMP-coated glass surfaces under different incubation parameters, i.e., submerged in water for 1 , 3, and 7 days.
  • the XPS spectra were obtained using a Physical Electronics (PHI) Quantera-ll XPS Microprobe spectrometer.
  • the survey spectra were produced with a monochromatic X-ray source at 25 W using a voltage of 15 kV and a pass energy of 26 eV. All spectra were obtained with a take-off angle of 45° and a step size of 0.8 eV for the survey and 0.1 eV for elemental data. Data is collected at 3 different locations.
  • Pseudomonas Phi6 (DSM-21518) and its host bacterium Pseudomonas syringae van Hall 1902 (DSM-21482) were purchased from Leibniz Institute DSMZ, (Braunschweig Germany). The bacterial strains were stored at -80°C in 50% glycerol. All bacteria were grown in Tryptic soy broth (TSB) supplemented by (5 mM) Magnesium sulfate and (6 g L -1 ) yeast extract (VWR, Canada).
  • TTB Tryptic soy broth
  • 5 mM Magnesium sulfate
  • (6 g L -1 yeast extract
  • Bacterial overnight culture was aseptically inoculated from a frozen stock in (3 mL) supplemented TSB media and was grown at 25°C for24 h with orbital shaking at 180 rpm.
  • (50 pL) virus stock and (1 mL) P. syringae in the exponential growth phase were added to (30 mL) supplemented TSB media.
  • the suspension was incubated in a shaking incubator at 25°C and 180 rpm for 12 hours.
  • the viral lysate was centrifuged at 7000 ref at 4°C for 20 min and the supernatant was filtered with sterile 0.2 pm pore size syringe filters (Fisher Scientific, Canada).
  • the titer of viral suspension was determined using the double-layer agar [47] method and was stored at 4°C until use.
  • PDMS stamps were fabricated by initially degassing a 10:1 weight ratio of PDMS: curing agent for 30 minutes followed by curing at 150°C for 1 hour. Square-like stamps with sizes identical to the samples were harvested by cutting the PDMS using a scalpel. The PDMS stamps were then plasma treated for 30 seconds and then inoculated with (5 pL) Phi6 solution with an initial concentration of 10 6 PFU mL’ 1 . The inoculated stamps were left to dry for around 5 minutes and then immediately stamped onto glass coated and uncoated samples. Surfaces were incubated for 2 hours in a humidity chamber with relative humidity of 80%.
  • MRSA and P. aeruginosa were grown on spray coated 96-well plates, using uncoated 96-well plates and FOTS spray coated 96- well plates as controls. Each well was flooded with (500 pL) the bacterial suspensions containing around 10 5 CFU ml’ 1 of MRSA and 10 6 CFU ml’ 1 of P. aeruginosa. The plates were then incubated without shaking at 37°C. Post incubation based on the designated time, CFUs were quantified by taking 10 pL from each well and plating serial dilutions on LB agar Petri dishes.
  • the stamped glass coated surfaces were stained with the Live/Dead BacLightTM kit (SYTO9 and propidium iodide (PI)) (Thermo Fisher Scientific, Canada). A mixture of (10 pmol I -1 ) SYTO9 and (60 pmol I -1 ) PI was added to each coated surface. Then, the samples were incubated for 30 min at room temperature in the dark.
  • SYTO9 and PI propidium iodide
  • the contaminated gloves were then collected, suspended in bacteria media, and incubated in a shaking incubator for 40 minutes. 100 pL of each sample was taken to run a CFU assay by plating serial dilutions on LB agar Petri dishes. The same assay was performed using a suspension of Phi6 with initial concentration of 10 6 PFU mL. Coated and uncoated gloves were similarly dipped into a suspension of virus and then contaminated secondary clean glass surfaces a series of 10 and 50 times, respectively. Contaminated glove surfaces were then collected and suspended in TSB media for 20 minutes. From each vortexed solution, 20 pL of solution was then taken for PFU plating on TSB agar Petri dishes containing a lawn of bacteria with (0.3%) soft agar and (200 pL) P. syringae.
  • a pair of tweezers with a coated and uncoated side were used for the glove transfer assay using MRSA. Post the assay, each side of the tweezers were fully immersed into bacteria media for 30 minutes, followed by incubation in a shaking incubator for 40 minutes. 100 pL of each sample was taken for CFU plating. Lastly, two equal sizes of textile were collected and initially sterilized, followed by spray-coating one of them. The two pieces of textile were taped using two-sided tape onto a lab coat, whereas the subject wearing the lab coat performed experiments wearing the lab coat for a series of 10 days. The surfaces were then suspended in bacteria media and incubated in a shaking incubator for 40 minutes. Post incubation, CFUs were quantified by taking 10 pL from each well and plating serial dilutions on LB agar Petri dishes.
  • rRNA 16S ribosomal RNA (rRNA) gene sequencing
  • the 16s rRNA gene was amplified from each contaminant colony by PCR using the 8F (5’AGAGTTTGATCCTGGCTCAG 3’, SEQ ID NO:1) and 1492R (5’GGTTACCTTGTTACGACTT 3’, SEQ ID NO:2) primers. Amplicons from this reaction were PCR purified and sequenced by Sanger sequencing. Resulting sequences were run through NCBI Nucleotide BLAST to identify the bacterial colonies.
  • Silwet L-77 is an anionic trisiloxane ethoxylate surfactant with the chemical structure CH3Si(OsiMe3)2(CH2)3O(CH2)sCH3, whereby its hydrophobic tail is adsorbed by PDMS, resulting in the formation of a stiff siloxane oxidised shell around the microparticles.
  • the high frequency from the ultrasonic waves paired with the resultant shear forces, were large enough to overcome the entropy-driven coalescence interactions between the oligomer chains, leading to mechanical shear and subdivision which in turn produces smooth uniform microparticles.
  • the resultant FOTS-treated microparticles were then coated with functionalized AuNPs using a mixed silane solution of 1 H,1 H,2H,2H-Perfluorodecanethiol (PFDT) - a thiol-based fluorosilane, and (3- mercaptopropyl)trimethoxysilane (MPTMS) to induce omniphobicity.
  • MPTMS acted as a coupling agent, using its thiol head (-SH) to bind to AuNPs and its three methoxy (-OCH3) functional groups to bind to PDMS.
  • the self-assembled AuNPs were closely packed within the wrinkles of the PDMS microparticles (Figure 1f).
  • microparticles comprise Si (52.15%), Au (48.07%), C (27.61 %), O (20.25%), S (1.52%), and F (1.02%). These wrinkled, functionalized, and AuNP-decorated hierarchical microparticles were termed hMPs.
  • hMPs were washed and incorporated into a spray. Coatings were achieved by spraying an epoxy resin binder solution, followed by the hMP spray solution onto target substrates. Optical imaging confirmed full coverage of a spray- coated glass slide, through the presence of a uniform coating of hMPs across the surface. Without wishing to be bound by theory, it is hypothesized that the hierarchical texture and high fluorine surface content of spray-coated surfaces would be capable of trapping pockets of air, resulting in a stable solid-liquid-air interface against both high and low surface tension liquids. 122 ’ 31 321
  • CAH Contact angle hysteresis
  • the thickness of the coating was quantified using an optical profilometry test to evaluate the thickness of h MPs coated glass surface.
  • the thickness was measured using the vertical scanning interferometry mode of an optical profilometer. Based on the Rz value, the thickness of the coating is 27 / m as seen in Figure 5a.
  • the surface roughness of a coated and uncoated glass slide was quantitatively assessed using vertical scanning interferometry. A significant difference of 99.8% was seen between coated glass slides relative to uncoated glass slides, whereby the average roughness of the coated and uncoated glass slides were 9.63 pm and 0.02 pm, respectively (Figure 5b).
  • This multi-leveled coating exhibited firm adhesion to the underlying substrate and provided dense substrate coverage. Its improved repellency is attributed to the entrapment of a larger volume of air, due to the hollow voids present between the greater number of tightly packed hMPs.
  • the degree of wrinkling on the surface of the PDMS microparticles, as well as the size of the PDMS microparticles could contribute to the overall level of omniphobicity of the coating. Wrinkling occurs on the surface of the microparticles to minimize the system’s overall potential energy when the compressive stress is higher than a critical value.
  • the compressive stress is induced during the in-plane compression as a consequence of a strain mismatch which is dependent on the swelling degree of the PDMS microspheres.
  • the swelling is in turn dependent on the size and radius of the microparticles, the curing temperature and time, shell thickness, and the Young’s modulus of PDMS.
  • the resultant wrinkling topography is determined by the competition between the bending stiffness of the thin siloxane shell around the microparticle (short wavelengths) and the bulk elastic energy of the core deformation (long wavelengths), which in turn determines the curvature, critical wrinkling stress, overstress, and the resulting wrinkling morphologies. 154-561 Studies investigating the effect of temperature, curing time, weight ratio of PDMS: curing agent, and particle size on the omniphobicity of the coating are seen in Figure 6a-c. High curing temperature resulted in a higher degree of sinusoidal undulations.
  • the decrease in the wrinkle size from micro to nanoscale length decreases the wettability of the coating due to the reduced solid-liquid interfacial layer and entrapment of air pockets in the underlying interface.
  • Increasing the curing temperature to 6 hours led to a higher degree of wrinkling with the formation of more secondary wrinkles with nanoscale lengths for the particles fabricated at 80°C and 50°C as seen in Figures 7a, i (water and hexadecane CAH of 2.7° and 5.7°) and Figure 6a, iii (water and hexadecane CAH of 5.3° and 12.3°), corresponding to the increased water and hexadecane contact angles relative to shorter incubation times seen in coatings in figures 7a, ii and 7a, iv.
  • the shell thickness is determined by the type and concentration of surfactant, thus a 10% anionic surfactant results in a thick shell leading to an increase in the critical wrinkling stress and a final decrease in the overstress (applied stress/critical wrinkling stress) on a spherical core/shell resulting in a larger swelling extent. 148571
  • the Young’s modulus of PDMS can be tailored by the cross-linking density of PDMS. Using a high weight ratio of PDMS/ curing agent results in a stiffer microparticle with a higher degree of wrinkling, whereas the bridged dimples are favorable.
  • the coating consisting of -20 / m sized PDMS microparticles demonstrated the highest degree of omniphobicity with water and hexadecane CAH of 4 ⁇ 1 ° and 6 ⁇ 1 °, respectively, relative to the coating consisting of -60 / msized particles with water and hexadecane CAH of 6 ⁇ 1.5° and 10 ⁇ 2°, as well as the coating with -100 fim sized particles with water and hexadecane CAH of 13 ⁇ 3° and 18 ⁇ 2°, respectively.
  • the surfaces were then scratched perpendicularly using the provided scratching tool. They were then cleaned using a brush and tape to remove any debris. The surfaces were then optically imaged on a Nikon EclipseTM Ti2 Series at low magnification as seen in Figure 7f.
  • the scratch patterns were compared with the ASTM classifications. Based on the ASTM classifications provided in the Elcometer’s user’s manual, the surfaces clearly belong to ASTM class 5B exhibiting a high level of stability. Cross hatch pattern shows no deterioration, especially at the intersections between scratches.
  • the viscoelastic behaviour of the coating essentially determines the flexibility of the coating. This is mainly defined by the coating thickness, coating material, and the adhesion between the binder and the coating. Given the extremely low elasticity of the individual chain of the PDMS, its large cross-sectional area, and the weak intra/interchain noncovalent interactions, the PDMS-based coating is highly flexible as seen on a coated textile in Figure 7g. Flattening or bending a coated substrate in any direction does not affect omniphobicity of the coating neither does it compromise its physical or mechanical properties. 1311 Moreover, the use of epoxy resin glue as a binder between the substrate and the coating further ensures the strong adhesive strength of the coating and permits the flexibility of any coated substrate, given the substrate is flexible.
  • MRSA and P. aeruginosa are two multidrug-resistant pathogens, which have been identified by the World Health Organization as priority pathogens. 1691 Based on the topographical features, roughness, and wettability of the PDMS microparticles, the repellency or killing of bacteria can vary (Figure 9a). Wrinkled superhydrophobic microparticles possess a hierarchal structure with microscale roughness capable of repelling bacteria using steric or electrostatic repulsion techniques, compared to smooth hydrophilic microparticles.
  • the entrapped air layer on the wrinkled hydrophobic microparticles causes the bacterial suspension to partially rest on air cushion and low energy protrusions.
  • 170 ’ 711 Incorporating bactericidal gold nanoparticles on the wrinkled microparticles further promotes the repellency of the microparticles by increasing the nanoscale roughness and hierarchy, thus further restricting the surface area available for bacterial attachment; as well as activates the bacterial killing effect.
  • 172 731 A stamp assay was conducted to evaluate the bacteria repellency of hMP spray-coated glass surfaces relative to uncoated glass surfaces. Surfaces were stamped with agar plugs inoculated with MRSA and P. aeruginosa.
  • hMP-coated surfaces revealed superior bacterial repellency (Figure 9c).
  • the hMP spray-coated surfaces showed a 97% (P ⁇ 0.001) reduction in bacterial adhesion relative to uncoated surfaces.
  • the hMP coating-mediated reduction in bacterial adhesion had surpassed 99.9% (P ⁇ 0.0001 ), relative to uncoated surfaces.
  • the immediate reduction in bacterial adhesion exhibited by hMP-coated surfaces at 0 hours demonstrates the bacterial repellency of the coating.
  • the subsequent decrease in bacterial counts observed by these coated surfaces over an 8- hour timeframe points to their bactericidal capabilities. This clearly demonstrates the dual “repel and kill” properties of the developed spray.
  • SEM images were captured to visualize the interaction of MRSA and P. aeruginosa with hMP-coated and uncoated glass surfaces under conditions where mature biofilm formation was possible. After stamping the surfaces with agar plugs inoculated with bacteria, the coated and uncoated surfaces were imaged and compared. The uncoated glass surface revealed an abundance of MRSA bacteria, whereas the hMP spray-coated surfaces showed a significantly reduced number of adhered bacteria. Similarly, with P. aeruginosa, uncoated surfaces suffered from an abundance of adhered bacteria along with the formation of a biofilm matrix. However, no bacteria were visually identified on the hMP-coated surfaces. The improved performance against P.
  • aeruginosa was attributed to its rod-like shape, compared to the coccoid-like shape of MRSA, the latter of which allows for some degree of entrapment on the microscale structures ( Figure 9e) - a finding in line with previous studies. 121 281 Based on these observations, it was concluded that the spray-coated hMPs are capable of sterically hindering the attachment and subsequent biofilm formation of both Gram-negative and Gram-positive bacteria.
  • hMP-coated wells showed a significant decrease in bacteria to the order of 4 x10 4 CFU ml -1 , corresponding to a 98.7% (P ⁇ 0.001) reduction in bacteria relative to uncoated wells, a 97.2% (P ⁇ 0.001 ) reduction relative to FOTS microparticle-coated wells, and a 96.9% (P ⁇ 0.001) reduction relative to the initial inoculum of bacteria.
  • a substantial amount of bacterial growth was seen within the uncoated wells, reaching 7.8x10 8 CFU ml -1 , while FOTS microparticle-coated wells showed 2.2x10 7 CFU ml -1 bacteria.
  • hMP-coated wells showed an increase in bacteria after 2 hours, they still exhibited a significant decrease in bacterial presence relative to the uncoated wells, corresponding to a reduction factor of 99.7% (P ⁇ 0.0001).
  • a similar trend was seen at 24 hours, whereby hMPs treated surfaces exhibited the same reduction factor of 99.7% (P ⁇ 0.0001) relative to uncoated wells.
  • hMP- coated wells exhibited a relative bacteria reduction factor of 91 % (P ⁇ 0.01 ) at 8 hours and 97.2% (P ⁇ 0.001) after 24 hours.
  • the antimicrobial activity of AuNPs is attributed to their direct contact with bacterial cell walls, which induces cellular deformation, initiation of intracellular effects via interactions with DNA and proteins, an increase in the concentration of intracellular reactive oxygen species, and inhibition of biofilm formation through the application of mechanical stretch on their cell membrane of bacteria.
  • 112 ’ 74-761 As such, surfaces coated with hMPs were capable of remarkable bactericidal activity against both Gram- negative and Gram-positive bacteria.
  • AuNPs concentrations of 5 ⁇ g/mL and 50 ⁇ g/mL revealed a 95% (P ⁇ 0.01 ) and 97.9% (P ⁇ 0.0001 ) reduction in bacterial growth, respectively.
  • Higher concentrations of AuNPs leads to an increase in the stretching and subsequent rupturing of the bacterial cell membrane, as the diameter of the aggregated nanoparticles or cluster diameter is increased.
  • the attractive forces between the AuNPs and the bacterial membrane are mediated by inherent characteristics such as nanoparticle surface charge, hydrophobicity, and roughness which are increased.

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Abstract

La présente invention concerne des microparticules omniphobes et antimicrobiennes comprenant un noyau polymère, le noyau comprenant une enveloppe plissée, et une ou plusieurs couches moléculaires ou de nanoparticules fixées à l'enveloppe. La présente invention concerne en outre des procédés de préparation des microparticules de la présente invention et des compositions comprenant les microparticules. La présente invention concerne également des procédés et des utilisations des microparticules et des compositions de la présente invention dans le traitement d'un substrat pour fournir des propriétés omniphobes et antimicrobiennes.
PCT/CA2023/051342 2022-10-11 2023-10-11 Microparticules antimicrobiennes omniphobes et compositions associées Ceased WO2024077382A1 (fr)

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CN119081480A (zh) * 2024-08-28 2024-12-06 南京林业大学 一种具有广谱吸收的光能吸附材料、制备方法及应用

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WO2020243833A1 (fr) * 2019-06-03 2020-12-10 Mcmaster University Surfaces omniphobes à structures hiérarchiques, et leurs procédés de fabrication et d'utilisation

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CN119081480A (zh) * 2024-08-28 2024-12-06 南京林业大学 一种具有广谱吸收的光能吸附材料、制备方法及应用

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