Omniphobic coating compositions and methods for making and using the same

Abstract

Described herein are methods for producing omniphobic coating compositions. The methods provide an extremely facile and economic synthetic process that can be extended to a wide range of substrates for widespread real-world applicability. The omniphobic coating compositions produced herein possess numerous advantageous properties including, but not limited to, high physical durability, aqueous chemical stability, thermal and UV resistance, prolonged room temperature storage, cytocompatibility and impeccable anti-biofouling properties including anti-platelet adhesion. In one aspect, the omniphobic coating composition is produced by the method comprising (a) functionalizing a surface of the article with a plurality of nucleophilic groups to produce a pre-functionalized surface, and (b) contacting the pre-functionalized surface with a perfluorolkylsiloxane comprising an electrophilic group, wherein the plurality of nucleophilic groups on the surface of the article react with the electrophilic group on the perfluoroalkylsiloxane to covalently bond the perfluoroalkylsiloxane to the surface of the article.

Description

T|H Docket: 222105-2260 ID: 2024-048-02 OMNIPHOBIC COATING COMPOSITIONS AND METHODS FOR MAKING AND USING THE SAME STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0001] This invention was made with government support under grant number R01 HL134899 and R01 HL151473 awarded by the NIH. The government has certain rights in the invention. CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to co-pending U.S. Provisional Patent Application No. 63 / 619,890, filed on January 11, 2024, the contents of which are incorporated by reference herein in their entireties. BACKGROUND

[0003] Over the years, the appropriate combination of heirarchal morphology and low surface energy chemistry have been studied to obtain bio-inspired, transparent omniphobic materials for tackling major environmental, biomedical and energy related concerns.1In 2011, Aizenberg et al., introduced the Nepenthes Pitcher plant inspired defect-free, pressure-stable omniphobic slippery liquid infused surfaces (SLIPS) that has garnered much attention owing to its ability to overcome the limitations of metastable-superhydrophobicity and superamphiphobicity.2However, the infused lubricant in SLIPS is prone to depletion over prolonged usage, volatilization, and migration, thus, inevitably compromising the embedded liquid slippery aspect of the surface.3,4

[0004] To overcome these limitations (i.e. volatile liquid lubricant and delicate surface textures), ‘liquid-like’ ultra-smooth slippery surfaces without any infused lubricant known as solid slippery surfaces were introduced.5McCarthy et al. laid down the relationship between the covalently tethered flexible chains on a surface and dynamic surface dewetting.6-8The free rotational ability of the low surface energy chains impart the desired ‘liquid-like’ lubricant characteristics to the surface, thus, aiding the mobility of the beaded liquid droplet.9Over the years, omniphobic solid slippery surfaces have been developed mostly using polymer brushes,9-10alkyl / fluoro-monolayers,11-12polyhedral oligomeric silsesquioxane,13-14metal- organic frameworks,15for applications in anti-icing,16anti-inking,17and combating biofouling of medical devices18-23. Interestingly, there are a dearth of chemical approaches that strategically utilizes a mixture of organosilanes to provide a ‘reactive’ avenue that can aid in integrating the slippery chemical formulation with pre-functionalized surfaces for developing anti-biofoulingT|H Docket: 222105-2260 ID: 2024-048-02 solid slippery coatings as well as open up possibilities for liquid manipulation and transport, water harvesting, diagnostics etc.5

[0005] While solid slippery surfaces with ultra-low liquid sliding angles have been reported for different practical applications, in general, a) the lack of mechanical and chemical robustness,9-12,24-27b) complex and harsh fabrication process,13-14,26c) fragile and non-covalent adhesion with the underlying substrate,28-30and d) failure to resist elevated temperatures31are the various major practical concerns that needs to be addressed. Moreover, there exists a glaring gap in translating the reported solid slippery coatings for practical biomedical use owing to the lack of blood interaction studies, which is a major pre-requisite while translating a biomaterial for applicability in blood contacting medical devices. SUMMARY

[0006] Described herein are methods for producing omniphobic coating compositions. The methods provide an extremely facile and economic synthetic process that can be extended to a wide range of substrates for widespread real-world applicability. The omniphobic coating compositions produced herein possess numerous advantageous properties including, but not limited to, high physical durability, aqueous chemical stability, thermal and UV resistance, prolonged room temperature storage, cytocompatibility and impeccable anti-biofouling properties including anti-platelet adhesion.

[0007] In one aspect, the omniphobic coating composition is produced by the method comprising (a) functionalizing a surface of the article with a plurality of nucleophilic groups to produce a pre-functionalized surface, and (b) contacting the pre-functionalized surface with a perfluorolkylsiloxane comprising an electrophilic group, wherein the plurality of nucleophilic groups on the surface of the article react with the electrophilic group on the perfluoroalkylsiloxane to covalently bond the perfluoroalkylsiloxane to the surface of the article.

[0008] Other compositions, apparatus, methods, features, and advantages will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional compositions, apparatus, methods, features and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. BRIEF DESCRIPTION OF THE DRAWINGST|H Docket: 222105-2260 ID: 2024-048-02

[0009] Further aspects of the present disclosure will be more readily appreciated upon review of the detailed description of its various embodiments, described below, when taken in conjunction with the accompanying drawings.

[0010] FIGS.1A-1E. (A-B) Schematic depicting the hydrolysis and condensation between the hydroxyl groups of the low-surface energy molecule perfluorooctyl triethoxysilane (PFOTS) and 3-Glycidyloxypropyl)trimethoxysilane (GPTMS) to obtain a ‘reactive’ solution with ‘reactive’ epoxy functionalities that can be exploited for further covalent modifications. Apart from imparting the ‘reactive’ characteristics, the presence of GPTMS ensured optimum spacing (acts as a molecular spacer) between the rigid PFOTS chains to impart chain- flexibility. Thereafter, the ‘reactive’ solution was applied on a (3-Aminopropyl)trimethoxy (APTMS) pre-treated surface such that the epoxy groups underwent ring opening with the surface amines to anchor onto the surface (C-D) covalently and robustly. Thus, the covalently bound and optimally spaced ‘reactive’ solution resulted in a ‘liquid-like’ omniphobic solid coating (LL-OSC) that exhibited liquid repellence characteristics (D) along with anti-biofouling behaviour (E).

[0011] FIGS.2A-2L. (A-C) Schematic depicting the effect of perfluorooctyl triethoxysilane (PFOTS) grafting density on the droplet mobility across the LL-OSC. D) Bar diagram depicting the change in sliding angles of water (blue), diiodomethane (yellow), hexadecane (grey) and ethanol (maroon) on varying the PFOTS concentration in the ‘reactive’ solution. E-H) Digital images illustrating the sliding of water (E-F) and ethanol across the LL-OSC on glass at 18° and 12° tilting angles, respectively. I) Scanning electron microscopy image depicting the surface morphology of the as-developed ‘liquid-like’ omniphobic solid surface. J) AFM analysis depicting the defect-free morphology of LL-OSC. K) Graph accounting for the sliding angles of solvents with varying surface tensions on the LL-OSC. L) Attenuated Fourier transform infrared spectroscopy of APTMS pre-functionalized surface (green) that was coated with the ‘reactive’ solution (red) to result in the LL-OSC (black).

[0012] FIGS. 3A-3Q. (A-L) Digital images depicting sandpaper abrasion (A), pencil hardness test (E), adhesive tape test (I) on a ‘liquid-like’ omniphobic solid coating on a glass substrate and the subsequent sliding of water (B,F,J), diiodomethane (C,G,K) and hexadecane (D,H,L) droplet from the surface. M) Graph accounting for the sliding angles of water (black), hexadecane (red) and diiodomethane (yellow) after performing sandpaper abrasion. N) Graph depicting the sliding angles of water (black), hexadecane (red) and diiodomethane (yellow) after performing adhesive tape peeling for 100 consecutive cycles. O) Graph illustrating the stability of the ‘liquid-like’ omniphobic coating after thermal treatment (100ºC) for 30 days. P) Graph accounting for the room temperature storage stability of the ‘liquid-like’ omniphobic coating upto 180 days. Q) Graph accounting for the sliding angles of different liquids after 48 hours of continuous exposure to different chemically contaminatedT|H Docket: 222105-2260 ID: 2024-048-02 aqueous phases. All sliding angle data corresponding to durability analysis were acquired using liquid droplet volume =15 μL

[0013] FIGS.4A-4H. (A-B) Schematic depicting the mechanism of biofilm formation on an uncoated surface and the prevention of biofilm formation on LL-OSC. C-D) Graph depicting the E. coli (C) and S. aureus (D) biomass accumulation following a 48 h drip flow bioreactor experiment on an uncoated surface, APTMS coated surface and LL-OSC. E-H) Scanning electron microscopy images depicting the E. coli (E-F) and S. aureus (G-H) biomass accumulation on an uncoated surface and LL-OSC. *p^≤^.05, and ****p^≤^.0001. All data are represented as mean^±^SD.

[0014] FIGS. 5A-5L. (A) Schematic depicting the anti-biofouling characteristics of LL- OSC. B) Bar diagram depicting the cell viability (>90%) of LL-OSC in comparison to the cell control. C-H) Fluorescence microscopy images illustrating the adhered cells (C-E) and the cycto-skeleton area of the adhered cells (F-H) on an uncoated surface (C, F), APTMS treated surface (D,G) and LL-OSC (E, H). I-J) Bar diagrams accounting for the nucleus per frame (I) and the cycto-skeleton area (J) for different substrates. K) Bar diagram accounting for the fibrinogen adsorbed on the control surfaces and LL-OSC. L) Bar diagram depicting the anti- platelet adhesive characteristics of LL-OSC in comparison to the control groups. *p^≤^.05, **p^≤^.01, ***p^≤^.001 and ****p^≤^.0001. All data are represented as mean^±^SD.

[0015] Figures 6A-6P. (A-B) Schematic depicting the static and spreading behaviour of water (A) and ethanol (B) on any uncoated surface. C-H) Digital images depicting the water and ethanol sliding behaviour from the surface of the ‘liquid-like’ omniphobic PDMS (C-D), aluminium (E-F) and stainless steel (G-H). I) Bar diagram depicting the sliding angles of liquids of various surface tensions from the surface of LL-OSC-PDMS (black), aluminium (blue) and stainless steel (green). J) Bar diagram accounting for the sliding angles of water and diiodomethane after performing sand paper abrasion covering a total distance of ^300 cm on the ‘liquid-like’ omniphobic PDMS, aluminium and stainless steel. K-P) Digital images depicting the anti-inking performance on an uncoated polyethylene terephthalate (PET) film (K-M) and LL-OSC-PET surface (N-P). All sliding angle data were acquired using liquid droplet volume = 15 μL.

[0016] The drawings illustrate only example embodiments and are therefore not to be considered limiting of the scope described herein, as other equally effective embodiments are within the scope and spirit of this disclosure. The elements and features shown in the drawings are not necessarily drawn to scale, emphasis instead being placed upon clearly illustrating the principles of the embodiments. Additionally, certain dimensions may be exaggerated to help visually convey certain principles. In the drawings, similar reference numerals between figures designate like or corresponding, but not necessarily the same, elements.T|H Docket: 222105-2260 ID: 2024-048-02 DETAILED DESCRIPTION

[0017] Many modifications and other embodiments disclosed herein will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein.

[0018] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0019] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure.

[0020] Any recited method can be carried out in the order of events recited or in any other order that is logically possible. That is, unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0021] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation.T|H Docket: 222105-2260 ID: 2024-048-02

[0022] While aspects of the present disclosure can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present disclosure can be described and claimed in any statutory class.

[0023] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0024] Prior to describing the various aspects of the present disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in the present disclosure. Definitions

[0025] As used herein, “comprising” is to be interpreted as specifying the presence of the stated features, integers, steps, or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Moreover, each of the terms “by”, “comprising,” “comprises”, “comprised of,” “including,” “includes,” “included,” “involving,” “involves,” “involved,” “having,” and “such as” are used in their open, non-limiting sense and may be used interchangeably. Further, the term “comprising” is intended to include examples and aspects encompassed by the terms “consisting essentially of” and “consisting of.” Similarly, the term “consisting essentially of” is intended to include examples encompassed by the term “consisting of.

[0026] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a polysiloxane” includes, but is not limited to, mixtures or combinations of two or more such polysiloxanes, and the like.

[0027] It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. RangesT|H Docket: 222105-2260 ID: 2024-048-02 can be expressed herein as from “about” one particular value, and / or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0028] When a range is expressed, a further aspect includes from the one particular value and / or to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’. The range can also be expressed as an upper limit, e.g. ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘less than x’, less than y’, and ‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y’, and ‘greater than z’. In addition, the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”.

[0029] It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1% to 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range.

[0030] As used herein, the terms “about,” “approximate,” “at or about,” and “substantially” mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In such cases, it is generally understood, as used herein, that “about” and “at or about” mean the nominal value indicated ±10% variation unless otherwise indicated or inferred. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about,” “approximate,” or “at or about” whether or not expressly stated to be such. It isT|H Docket: 222105-2260 ID: 2024-048-02 understood that where “about,” “approximate,” or “at or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0031] The term “omniphobic coating” and “omniphobic surface” is a coating or surface that repels water, oils, and a variety of organic solvents so that the liquid for the most part will not spread on the surface of the article.

[0032] The term "alkyl group" refers to the radical of saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl- substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups.

[0033] In some embodiments, a straight chain or branched chain alkyl group has 30 or fewer carbon atoms in its backbone (e.g., C1-C30 for straight chains, C3-C30 for branched chains), 20 or fewer, 12 or fewer, or 7 or fewer. Likewise, in some embodiments cycloalkyls have from 3-10 carbon atoms in their ring structure, e.g. have 5, 6 or 7 carbons in the ring structure. The term "alkyl" (or "lower alkyl") as used throughout the specification, examples, and claims is intended to include both "unsubstituted alkyls" and "substituted alkyls", the latter of which refers to alkyl moieties having one or more substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone. Such substituents include, but are not limited to, halogen, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, a phosphinate, amino, amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, aralkyl, or an aromatic or heteroaromatic moiety.

[0034] Unless the number of carbons is otherwise specified, "lower alkyl" as used herein means an alkyl group, as defined above, having from one to ten carbons, or from one to six carbon atoms in its backbone structure. Likewise, "lower alkenyl" and "lower alkynyl" have similar chain lengths. In embodiments described in the present application, preferred alkyl groups are lower alkyls. In some embodiments, a substituent designated herein as alkyl is a lower alkyl.

[0035] In some embodiments, a straight chain or branched chain alkyl group has 30 or fewer carbon atoms in its backbone (e.g., C1-C30for straight chains, C3-C30for branched chains), 20 or fewer, 12 or fewer, or 7 or fewer.

[0036] The term "perfluoroalkyl group" refers to an alkyl group as defined herein where two or more hydrogen atoms on the alkyl group are substituted with a fluorine atom. In one aspect, all of the hydrogen atoms on the alkyl group are substituted with a fluorine atom. FIG.T|H Docket: 222105-2260 ID: 2024-048-02 1A provides an exemplary structure of a perfluoroalkyl group bonded to a siloxane group (-Si(OEt)3).

[0037] The term “cycloalkyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and the like. The term “heterocycloalkyl” is a type of cycloalkyl group as defined above, and is included within the meaning of the term “cycloalkyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl group and heterocycloalkyl group can be substituted or unsubstituted. The cycloalkyl group and heterocycloalkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol as described herein.

[0038] The term “aromatic group” as used herein refers to a ring structure having cyclic clouds of delocalized π electrons above and below the plane of the molecule, where the π clouds contain (4n+2) π electrons. A further discussion of aromaticity is found in Morrison and Boyd, Organic Chemistry, (5th Ed., 1987), Chapter 13, entitled “ Aromaticity,” pages 477-497, incorporated herein by reference. The term “aromatic group” is inclusive of both aryl and heteroaryl groups.

[0039] The term “aryl” as used herein is a group that contains any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, anthracene, and the like. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, ─NH2, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein. The term “biaryl” is a specific type of aryl group and is included in the definition of “aryl.” In addition, the aryl group can be a single ring structure or comprise multiple ring structures that are either fused ring structures or attached via one or more bridging groups such as a carbon-carbon bond. For example, biaryl to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl. Fused aryl groups including, but not limited to, indene and naphthalene groups are also contemplated.

[0040] The terms “alkoxy” and “alkoxyl” as used herein refer to an alkyl group bonded through an ether linkage; that is, an “alkoxy” group can be defined as —OA1where A1is alkyl as defined above. “Alkoxy” also includes polymers of alkoxy groups as just described; that is,T|H Docket: 222105-2260 ID: 2024-048-02 an alkoxy can be a polyether such as —OA1—OA2or —OA1—(OA2)a—OA3, where “a” is an integer of from 1 to 200 and A1, A2, and A3are alkyl groups.

[0041] The terms “cycloalkoxy” and “cycloalkoxyl” as used herein refer to a cycloalkyl group bonded through an ether linkage; that is, a “cycloalkoxy” group can be defined as — OA1where A1is cycloalkyl as defined above. “Cycloalkoxy” also includes polymers of cycloalkoxy groups as just described; that is, a cycloalkoxy can be a polyether such as — OA1—OA2or —OA1—(OA2)a—OA3, where “a” is an integer of from 1 to 200 and A1, A2, and A3are cycloalkyl groups.

[0042] The terms “aryloxy” and “aryloxyl” as used herein refer to an aryl group bonded through an ether linkage; that is, an “aryloxy” group can be defined as —OA1where A1is aryl as defined above. “Aryloxy” also includes polymers of aryloxy groups as just described; that is, an aryloxy can be a polyether such as —OA1—OA2or —OA1—(OA2)a—OA3, where “a” is an integer of from 1 to 200 and A1, A2, and A3are aryl groups.

[0043] The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (A1A2)C=C(A3A4) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C=C. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.

[0044] The term “cycloalkenyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms and containing at least one carbon-carbon double bound, i.e., C=C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term “heterocycloalkenyl” is a type of cycloalkenyl group as defined above, and is included within the meaning of the term “cycloalkenyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl group and heterocycloalkenyl group can be substituted or unsubstituted. The cycloalkenyl group and heterocycloalkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.

[0045] The term “alkynyl” as used herein is a hydrocarbon group of 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon triple bond. The alkynyl groupT|H Docket: 222105-2260 ID: 2024-048-02 can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.

[0046] The term “cycloalkynyl” as used herein is a non-aromatic carbon-based ring composed of at least seven carbon atoms and containing at least one carbon-carbon triple bound. Examples of cycloalkynyl groups include, but are not limited to, cyclooctynyl, cyclononynyl, and the like. The term “heterocycloalkynyl” is a type of cycloalkenyl group as defined above and is included within the meaning of the term “cycloalkynyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkynyl group and heterocycloalkynyl group can be substituted or unsubstituted. The cycloalkynyl group and heterocycloalkynyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.

[0047] The term “hydroxyl” or “hydroxy” as used herein is represented by the formula - OH.

[0048] The term “thiol” as used herein is represented by the formula -SH.

[0049] The terms “amine” or “amino” as used herein are represented by the formula — NA1A2, where A1and A2can be, independently, hydrogen or alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. A specific example of amino is ─NH2.

[0050] The term “carboxylic acid” as used herein is represented by the formula —C(O)OH.

[0051] The term “ester” as used herein is represented by the formula —OC(O)A1or -C(O)OA1, where A1can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

[0052] The term “unsubstituted epoxide group” as used herein is represented by the structure below, where each R is hydrogen. The term “substituted epoxide group” as used herein is represented by the structure below, where one or more R is not hydrogen (e.g., alkyl, aryl, cycloalkyl, etc.).T|H Docket: 222105-2260 ID: 2024-048-02

[0053] The term “unsubstituted acrylate group” as used herein is represented by the structure below, where R is hydrogen. The term “substituted acrylate group” as used herein is represented by the structure below, where R is not hydrogen (e.g., alkyl, aryl, cycloalkyl, etc.). X can H (i.e., carboxylic acid) or an alkyl, aryl, cycloalkyl (i.e., ester).

[0054] The term “nucleophilic is defined as a group that is capableof donating a pair of electrons and a bond with an electrophilic group.

[0055] The term “electrophilic group” as used herein is defined as a group that is capable of receiving a pair of electrons and forming a covalent bond with a nucleophilic group.

[0056] The term “prevent” or “preventing” as used herein is defined as eliminating or reducing the likelihood of the occurrence of one or more symptoms of a disease or disorder (e.g., biofilm formation) when using the compositions as described herein when compared to a control where the composition is not used. Omniphobic Coating Compositions and Methods for Making and Using the Same

[0057] Described herein are methods for producing omniphobic coating compositions. The methods provide an extremely facile and economic synthetic process that can be extended to a wide range of substrates for widespread real-world applicability. The omniphobic coating compositions produced herein possess numerous advantageous properties including, but not limited to, high physical durability, aqueous chemical stability, thermal and UV resistance, prolonged room temperature storage, cytocompatibility and impeccable anti-biofouling properties including anti-platelet adhesion.

[0058] In one aspect, the omniphobic coating composition is produced by the method comprising (a) functionalizing a surface of the article with a plurality of nucleophilic groups to produce a pre-functionalized surface, and (b) contacting the pre-functionalized surface with a perfluorolkylsiloxane comprising an electrophilic group, wherein the plurality of nucleophilic groups on the surface of the article react with the electrophilic group on the perfluoroalkylsiloxane to covalently bond the perfluoroalkylsiloxane to the surface of the article.

[0059] The first step of the process involves functionalizing a surface of the article with a plurality of nucleophilic groups to produce a pre-functionalized surface. The surface of theT|H Docket: 222105-2260 ID: 2024-048-02 article can be contacted with one or more compounds possessing a nucleophilic group. Depending upon the material of the article, the compound with the nucleophilic group can be covalently bonded to the surface of the article via a number of different techniques. For example, the compound with the nucleophilic group can include a functional group that reacts with the material of the article to form a covalent bond.

[0060] In one aspect, the surface of the article is functionalized with a silane compound comprising a nucleophilic group. In another aspect, the surface of the article is functionalized with a silane compound comprising at least one hydroxyl group, thiol group, or amino group. In another aspect, the surface of the article is functionalized with an aminosilane. In another aspect, the surface of the article is functionalized with a compound having the structure Iwherein each R1is independently an alkoxy group, cycloalkoxy group, or aryloxy group, and o is an integer from 1 to 10. In one aspect, each R1is the same alkoxy group (e.g., methoxy, ethoxy), and o is 1, 2, or 3.

[0061] In one aspect, the aminosilane is 3-aminopropyltrimethoxysilane, 3- aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, N-methyl-3-amino-2- methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3- amino-2-methylpropyldiethoxymethylsilane, N-ethyl-3-amino-2-methylpropyltriethoxysilane, N-ethyl-3-amino-2-methylpropylmethyldimethoxysilane, N-butyl-3-amino-2- methylpropyltrimethoxysilane, 3-(N-methyl-2-amino-1-methyl-1-ethoxy)- propyltrimethoxysilane, N-ethyl-4-amino-3,3-dimethyl-butyldimethoxymethylsilane, N-ethyl-4- amino-3,3-dimethylbutyltrimethoxy-silane, N-(cyclohexyl)-3-aminopropyltrimethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxy- silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, aminopropyltriethoxysilane, bis-(3-trimethoxysilyl-2-methylpropyl)amine and N-(3'-trimethoxysilylpropyl)-3-amino-2- methylpropyltrimethoxysilane.

[0062] The surface of the article can be contacted with the compound possessing nucleophilic group by techniques known in the art including dipping, coating, or spraying the compound on the surface of the article. Exemplary non-limiting methods for functionalizing the surface of the article are provided in the Examples.

[0063] After the surface of the article has been pre-functionalized, the pre-functionalized surface is contacted with a perfluorolkylsiloxane comprising an electrophilic group. In thisT|H Docket: 222105-2260 ID: 2024-048-02 step, the plurality of nucleophilic groups on the surface of the article react with the electrophilic group on the perfluoroalkylsiloxane to covalently bond the perfluoroalkylsiloxane to the surface of the article

[0064] In one aspect, the perfluoroalkylsiloxane comprising an electrophilic group comprises the reaction product between a perfluorolkylsiloxane and a silane compound comprising at least one electrophilic group. The perfluorolkylsiloxane is a compound having a perfluoroalkyl group covalently bonded to a siloxane group. In one aspect, the perfluorolkylsiloxane can have the formula R2-Si(OR1)3, wherein R1is a substituted or unsubstituted C1-C20alkyl group, and R2is a C1-C20perfluoroalkyl group. In other aspects, R1can be a C1to C4alkyl group. R2can be a C1to C10perfluoroalkyl group. In one aspect, each R1can be methyl or ethyl, and R2can be a C8perfluoroalkyl group.

[0065] In one aspect, the silane compound used to produce the perfluoroalkylsiloxane comprising an electrophilic group comprises a glycidyl silane compound. In one aspect, the silane compound comprising at least one epoxide group is a compound having the structure IIwherein each R4is independently an alkoxy group, cycloalkoxy group, or aryloxy group, Y is O or S; n is an integer from 1 to 10; and m is an integer from 1 to 10.

[0066] In one aspect, n in structure II is 3 and m is 1. In another aspect, n in structure II is 3, m is 1, and Y is O. In another aspect, n in structure II is 3, m is 1, Y is O, and each R4is a C1 to C5 alkoxy group.

[0067] In one aspect, the silane compound comprising at least one epoxide group is 3- glycidoxyalkyltrialkoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidyloxypropyltrialkoxysilane, beta-(3,4-epoxycyclohexyl)ethyltriethoxysilane, beta-(3,4- epoxycyclohexyl)ethyltrimethoxysilane, beta-(3,4-epoxycyclohexl)methyltriethoxysilane, beta- (3,4-epoxycyclohexl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)propyltriethoxysilane, (3,4-epoxycyclohexyl)propyltrimethoxysilane, (3,4-epoxybuty)triethoxysilane, or (3,4- epoxybuty)trimethoxysilane.T|H Docket: 222105-2260 ID: 2024-048-02

[0068] In one aspect, the silane compound comprising at least one acrylate group is 3- methacryloxypropyltriethoxysilane, 3-methacryloxypropyitrimethoxysilane, gamma- methacryloxypropyitriethoxysilane, or gamma-methacryloxypropyitrimethoxysilane.

[0069] In one aspect, the reaction product between the perfluorolkylsiloxane and the silane compound comprising at least one electrophilic group can be performed by mixing the perfluorolkylsiloxane and the silane compound together using techniques known in the art. In one aspect, the perfluorolkylsiloxane and the silane compound are mixed with one another at room temperature (e.g., 20oC to 25oC) or at elevated temperature.

[0070] In one aspect, the molar ratio of the perfluoroalkylsiloxane to the silane compound comprising at least one electrophilic group is from about 1:1 to about 1:3. In another aspect, the molar ratio of the perfluoroalkylsiloxane to the silane compound comprising at least one electrophilic group is from about 1:1 to about 1:3, is 1:1, 1.5:1, 2:1, 2.5:1, or 3:1, where any value can be a lower and upper endpoint of a range (e.g., 1.5:1 to 2.5:1). Exemplary non- limiting methods for producing the perfluorolkylsiloxane comprising an electrophilic group are provided in the Examples and FIG.1A.

[0071] The perfluorolkylsiloxane comprising an electrophilic group can be applied to the pre-functionalized surface composed of a plurality of nucleophilic groups using techniques known in the art including, but not limited to, dipping, coating, or spraying the perfluorolkylsiloxane comprising an electrophilic group on the pre-functionalized surface of the article. Exemplary non-limiting methods for applying the perfluorolkylsiloxane comprising an electrophilic group on the pre-functionalized surface of the article are provided in the Examples.

[0072] The article used herein can be composed of a variety of different materials. In one aspect, the article is composed of glass. In another aspect, the article is composed of a polymer (e.g., polysiloxane such as polydimethylsiloxane, a polydiethylsiloxane, a polydipropylsiloxane, or a polydiphenylsiloxane) or a metal (e.g., aluminum or stainless steel).

[0073] In certain aspect, the surface of the article can be pre-treated prior to pre- functionalizing the surface with a plurality of nucleophilic groups. In one aspect, the surface of the article is contacted with a solvent to remove any impurities. Examples of solvent include organic solvents such as, for example, acetone or ethanol. In another aspect, the surface of the article can be treated with an acid or base. For example, when the article is made of glass, treating the surface with an acid can promote the formation of surface hydroxyl group that can subsequently react with a compound possessing a nucleophilic group to produce the pre- functionalized surface. In another aspect, the surface of the article can be treated with plasma to alter or modify the surface properties of the article. Exemplary non-limiting methods for pre- treating the surface of the article are provided in the Examples.T|H Docket: 222105-2260 ID: 2024-048-02

[0074] The methods described herein provide an efficient means for covalently bonding a perfluorolkylsiloxane to the surface of an article. In one aspect, the article produced herein comprises the structure III wherein Surface is the at leastA is a residue of an aminosilaneB is a residue of a silane compound comprising at least one epoxide group; and C is a residue of a perfluorolkylsiloxane.

[0075] In one aspect, A in structure III is wherein each R1is group, or aryloxy group, ando is an integer from 1 to 10.

[0076] In one aspect, B in structure III is wherein each R4isor aryloxy group, wherein at least one of R4 is a residue of the perfluorolkylsiloxane; Y is O or S; n is an integer from 1 to 10; and m is an integer from 1 to 10.

[0077] The article to be coated can be any article or surface where it is desirable to reduce or prevent biofouling (e.g. growth of bacteria, adhesion of platelets, adhesion of fibrinogen). Biofilm and thrombus formation on surfaces results in significant morbidity and mortality worldwide, which highlights the importance of the development of efficacious fouling- prevention approaches. Provided herein are highly robust and omniphobic coatings withT|H Docket: 222105-2260 ID: 2024-048-02 outstanding multi-liquid repellency, bactericidal performance, and extremely low bacterial and blood adhesion.

[0078] In one aspect, the omniphobic coatings and articles composed of the omniphobic coating are useful in applications where it is desirable to reduce or prevent biofouling. Implantable medical devices are a leading cause of infection such as nosocomial infections. Implantable devices coated with or constructed by the methods described herein can reduce or prevent biofouling in a subject when the device is introduced into the subject. In one aspect, the omniphobic coatings and articles composed of the omniphobic coating can reduce or prevent bacterial growth on a surface of an implantable device. In another aspect, the omniphobic coatings and articles composed of the omniphobic coating can reduce or prevent biofilm formation on a surface of an implantable device. In another aspect, the omniphobic coatings and articles composed of the omniphobic coating can reduce or prevent fibrinogen formation on a surface of an implantable device.

[0079] In one aspect, the implantable device is a urinary catheter, artificial heart valve, a vascular catheter, a graft, or a stent. In other aspects, the device is intended to contact human blood or tissue. In one aspect, the device is a hemodialysis device or a component thereof. The coatings applied to the articles are biocompatible (e.g., with fibroblast cells), which makes them useful in implantable medical devices.

[0080] In another aspect, the omniphobic coatings and articles composed of the omniphobic coating are useful in applications where it is desirable to reduce or prevent biofouling on polymeric medical grade materials (e.g. silicone, polyvinyl chloride (PVC), polyurethane (PU)). In other aspects, the omniphobic coatings and articles composed of the omniphobic coating are useful in applications where it is desirable to reduce or prevent biofouling on metals (e.g. steel, titanium). In other aspects, the omniphobic coatings and articles composed of the omniphobic coating are useful in applications where it is desirable to reduce or prevent biofouling on hospital touch surfaces (e.g. bed rails, bed frames, and handles).

[0081] In other aspects, the omniphobic coatings and articles composed of the omniphobic coating are useful in applications where it is desirable to reduce or prevent biofouling caused by the exposure to the environment. For example, the methods described herein can be used to apply omniphobic coatings to any substrate that is exposed to environmental elements such as rain, snow, salt water, or other conditions that can cause or promote biofouling. In one aspect, the compositions described herein can be applied to automobile surfaces, boat hulls, or aircraft.

[0082] In one aspect, the omniphobic coatings and articles composed of the omniphobic coating can prevent the growth of bacteria on an article, in which the method includes applying the omniphobic coating composition as above to at least one surface of the article. The coatedT|H Docket: 222105-2260 ID: 2024-048-02 article can prevent about at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, or 100% of the growth of bacteria when compared to an uncoated article.

[0083] In one aspect, the omniphobic coatings and articles composed of the omniphobic coating can prevent the adhesion of fibrinogen on an article, in which the method includes applying the omniphobic coating composition as above to at least one surface of the article. The coated article can prevent about at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, or 100% of the adhesion of fibrinogen when compared to an uncoated article.

[0084] In one aspect, the omniphobic coatings and articles composed of the omniphobic coating can prevent the adhesion of platelets on an article, in which the method includes applying the omniphobic coating composition as above to at least one surface of the article. The coated article can prevent about at least 80%, at least 85%, at least 90%, at least 95%, at least 99%, or 100% of the adhesion of platelets when compared to an uncoated article.

[0085] The omniphobic coating compositions described herein are “slippery” liquids, where a variety of different liquids, which makes them useful in a number of different applications. In one aspect, the coated articles described herein have a sliding angle of less than 20.0 degrees for water or an organic solvent. In another aspect, the coated articles described herein have a sliding angle of about 2.0 degrees, 4.0 degrees, 6.0 degrees, 8.0 degrees, 10.0 degrees, 12.0 degrees, 14.0 degrees, 16.0 degrees, 18.0 degrees, or 20.0 degree for water or an organic solvent, where any value can be a lower and upper endpoint of a range (e.g., 4.0 degrees to 16.0 degrees). In one aspect, the wherein the organic solvent is diiodomethane, ethylene glycol, DMSO, DMF, hexadecane, or ethanol.

[0086] Additionally, the omniphobic coating compositions and articles coated with the compositions possess numerous advantageous properties including, but not limited to, high physical durability, aqueous chemical stability, thermal and UV resistance, prolonged room temperature storage, cytocompatibility and impeccable anti-biofouling properties including anti-platelet adhesion.

[0087] Aspects Aspect 1. An article comprising of a perfluoroalkylsiloxane covalently bonded to a surface of the article, wherein the article is produced by the method comprising: (a) functionalizing a surface of the article with a plurality of nucleophilic groups to produce a pre-functionalized surface, and (b) contacting the pre-functionalized surface with a perfluorolkylsiloxane comprising an electrophilic group, wherein the plurality of nucleophilic groups on the surface of the article react with the electrophilic group on the perfluoroalkylsiloxane to covalently bond the perfluoroalkylsiloxane to the surface of the article.T|H Docket: 222105-2260 ID: 2024-048-02 Aspect 2. The article of Aspect 1, wherein the nucleophilic group is a hydroxyl group, a thiol group, an amino group, or any combination thereof. Aspect 3. The article of Aspect 1, wherein at least the surface of the article is functionalized with a silane compound comprising a nucleophilic group. Aspect 4. The article of Aspect 1, wherein at least the surface of the article is functionalized with a silane compound comprising at least one hydroxyl group, thiol group, or amino group. Aspect 5. The article of Aspect 1, wherein at least the surface of the article is functionalized with an aminosilane. Aspect 6. The article of Aspect 1, wherein at least the surface of the article is functionalized with a compound having the structure I I wherein each R1is independently an alkoxy group, cycloalkoxy group, or aryloxy group, and o is an integer from 1 to 10. Aspect 7. The article of any one of Aspects 1-6, wherein the electrophilic group comprises a substituted or unsubstituted epoxide group, a substituted or unsubstituted acrylate group, an ester, or a carboxylic acid group. Aspect 8. The article of any one of Aspects 1-6, wherein the electrophilic group comprises an unsubstituted epoxide group. Aspect 9. The article of any one of Aspects 1-8, wherein the perfluoroalkylsiloxane comprising an electrophilic group comprises the reaction product between a perfluorolkylsiloxane and a silane compound comprising at least one electrophilic group. Aspect 10. The article of Aspect 9, wherein the perfluoroalkylsiloxane has the formula R3-Si(OR2)3, wherein R2is a substituted or unsubstituted C1-C20alkyl group, and R3is a C1-C20perfluoroalkyl group. Aspect 11. The article of Aspect 10, wherein R2is a C1to C4alkyl group. Aspect 12. The article of Aspect 10, wherein R3is a C1to C10perfluoroalkyl group.T|H Docket: 222105-2260 ID: 2024-048-02 Aspect 13. The article of Aspect 10, wherein each R2is methyl or ethyl, and R3is a C8perfluoroalkyl group. Aspect 14. The article of any one of Aspects 9-13, wherein the silane compound comprising at least one epoxide group comprises a glycidyl silane compound. Aspect 15. The article of any one of Aspects 9-13, wherein the silane compound comprising at least one epoxide group is a compound having the structure IIwherein group, or aryloxy group, Y is O or S; n is an integer from 1 to 10; and m is an integer from 1 to 10. Aspect 16. The article of Aspect 15, wherein n is 3 and m is 1. Aspect 17. The article of Aspect 15, wherein n is 3, m is 1, and Y is O. Aspect 18. The article of Aspect 15, wherein n is 3, m is 1, Y is O, and each R4is a C1 to C5 alkoxy group. Aspect 19. The article of any one of Aspects 9-18, wherein the reaction product between the perfluoroalkylsiloxane and the silane compound comprising at least one electrophilic group is performed in the absence of a solvent. Aspect 20. The article of any one of Aspects 9-19, wherein the molar ratio of the perfluoroalkylsiloxane to the silane compound comprising at least one electrophilic group is from about 1:1 to about 1:3. Aspect 21. The article of any one of Aspects 1-20, wherein prior to step (a), the at least one surface of the article is cleaned to remove substantially all impurities. Aspect 22. The article of any one of Aspects 1-20, wherein prior to step (a), the at least one surface of the article is contacted with an acid or base. Aspect 23. An article comprising a perfluorolkylsiloxane covalently bonded to at least one surface of the article, wherein the article has at least one structural unit comprising the structure IIIT|H Docket: 222105-2260 ID: 2024-048-02 wherein Surface is the A is a residue of anB is a residue of a silane compound comprising at least one epoxide group; and C is a residue of a perfluorolkylsiloxane. Aspect 24. The article of Aspect 23, wherein A is wherein each R1is cycloalkoxy group, oraryloxy group, and o is an integer from 1 to 10. Aspect 25. The article of Aspect 23 or 24, wherein B is whereingroup, or aryloxy group, wherein at least one of R4 is a residue of the perfluorolkylsiloxane; Y is O or S; n is an integer from 1 to 10; and m is an integer from 1 to 10. Aspect 26. The article of any one of Aspects 1-25, wherein the article comprises glass, a polymer, or a metal. Aspect 27. The article of Aspect 26, wherein the metal is aluminum or stainless steel.T|H Docket: 222105-2260 ID: 2024-048-02 Aspect 28. The article of any one of Aspects 1-27, wherein the surface comprising the perfluorolkylsiloxane has a sliding angle of less than 20.0 degrees for water or an organic solvent. Aspect 29. The article of Aspect 28, wherein the organic solvent comprises diiodomethane, ethylene glycol, DMSO, DMF, hexadecane, or ethanol. Aspect 30. The article of any one of Aspects 1-29, wherein the surface comprising the perfluorolkylsiloxane is transparent. Aspect 31. The article of any one of Aspects 1-30, wherein the article comprises a polymeric grade material, a medical device, a surface or article in a hospital or medical facility, a surface in an automobile, boat, or aircraft, or an electronic display screen. Aspect 32. The article of any one of Aspects 1-31, wherein the article prevents the growth of microbes on the article. Aspect 33. The article of any one of Aspects 1-31, wherein the article prevents the adhesion of fibrinogen on the article. Aspect 34. The article of any one of Aspects 1-31, wherein the article prevents the adhesion of platelets on the article. EXAMPLES

[0088] Now having described the embodiments of the disclosure, in general, the examples describe some additional embodiments. While embodiments of the present disclosure are described in connection with the example and the corresponding text and figures, there is no intent to limit embodiments of the disclosure to these descriptions. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of embodiments of the present disclosure. MATERIALS AND METHODS

[0089] Materials: (3-aminopropyl) trimethoxysilane (APTMS), 3- Glycidyloxypropyl)trimethoxysilane (GPTMS), sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB), hydrochloric acid (HCl), hydrogen peroxide(H2O2), sulphuric acid (H2SO4), magnesium chloride (MgCl2), magnesium sulphate(MgSO4), sodium chloride (NaCl), calcium chloride (CaCl2), triton-X, phosphate buffer saline(PBS),bovine serum albumin, nitric acid, sodium citrate dihydrate, methylene blue, oil red,Glutaraldehyde (50% aqueous solution), 4′,6-diamidino-2-phenylindole (DAPI), Yellow 3- (4,5- dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) and Cell counting Kit-8 (CCK-8) were purchased from Sigma-Aldrich (St. Louis, MO). Hexamethyldisilazane (HMDS)T|H Docket: 222105-2260 ID: 2024-048-02 was obtained from Electron Microscopy Sciences (Hatfield, PA). Perfluorooctyl triethoxysilane (PFOTS) was purchased from Oakwood Chemical, Inc. (South Carolina, USA). Paraformaldehyde was purchased from ChemCruz. Diiodomethane, dimethyl sulfoxide (DMSO), ethylene glycol, ethanol, and fluorescein isothiocyanate was purchased from Fisher Scientific (Hampton, NH). Standard glass slides (11 cm X 6 cm), double sided adhesive tape and pencil hardness testing kit were purchased from Amazon. Sand, Aluminium sheet, stainless steel sheet, Krylon colormaster paint and sandpaper was collected from a local home depot. Polydimethylsiloxane (Sylgard 184) was purchased from Ellsworth Adhesives, USA. Alexafluor® 488 conjugated to Phalloidin was procured from Invitrogen, USA. The bacterial strains Escherichia Coli (ATCC 25922), Staphylococcus Aureus (ATCC 6538), 3T3 mouse fibroblast cells (CRL 1658, ATCC) and human umbilical vein endothelial cells (HUVECs) (PCS-100-010, ATCC) were procured from American Type Culture Collection (ATCC). Luria- Bertani Broth (LB) was procured from Fischer Bioreagents (Fair Lawn, NJ). Tryptic soy broth (TSB) was obtained from Millipore Sigma (Burlington, MA). Dulbecco’s Modified Eagle Medium (DMEM) was procured from Gibco, USA. Penicillin-Streptomycin antibiotic and fetal bovine serum was purchased from Avantor, VWR. Human fibrinogen was purchased from Innovative Research (Novi, MI). Trypsin-EDTA was purchased from Corning (Manassas, VA). Calcium and magnesium-free PBS (1x) was purchased from Corning Incorporated. Drabkin’s reagent was purchased from Ricca Chemical Company. High-density polyethylene (HDPE) was purchased from eBay (.030" x 12" x 21.5").

[0090] General Considerations: Liquid contact angles and sliding angles were recorded at three different positions for each sample type under ambient conditions using a DSA-100 contact angle instrument. Scanning electron microscopy (SEM Model: FEI Teneo) was used to image the surface morphology of samples at an operating voltage of 5.00 kV. Sample preparation of the biomass accumulated surfaces (drip flow bioreactor studies) prior to SEM imaging was performed as follows; all sample types were gently rinsed with 1x sterile PBS after completion of 48 h biomass accumulation and stored overnight in 3% glutaraldehyde at 4°C to fix the biomass on the surface of the samples. Afterwards, the samples were dehydrated by sequential soaking in different concentrations (50,60,70,80,90,100% respectively) of ethanol for 20 min. For the final dehydration step, the samples were soaked in a 2:1 ethanolic mixture of hexamethyldisilane (HMDS) for 15 minutes and thereafter, soaked overnight in 100% HMDS followed by SEM imaging. Chemical analysis and mapping were performed using energy dispersive X-ray spectroscopy (EDX, Oxford Instruments) at an operating voltage of 20.00 kV. The samples were sputtered with gold-palladium coating (~10 nm) prior to imaging using a Leica sputter coater. Atomic Force microscopy (Model: Bruker Nanoscope) was utilized to scan the surface roughness of the samples. Plasma cleaner (TERGEO, PIE Scientific) was used to pre-treat the polydimethylsiloxane (PDMS) and polyethylene terephthalate (PET)T|H Docket: 222105-2260 ID: 2024-048-02 substrates. Attenuated total reflection Fourier Transform Infrared spectra was recorded using Thermo Fischer Nicolet spectrometer 6700 (Waltman, MA) at ambient conditions. The transparency of the solid samples was measured using UV-Spectrophotometer CARY 60, AGILENT Technologies. The cells were imaged using Advanced Microscopy Group’s EVOS FL Fluorescence Imaging Microscope (AMG, Mill Creek, WA). Images (n = 5) per sample were acquired and number of cells per frame were quantified to assess the cell adhesion using ImageJ (Wayne Rasband, National Institute of Health, USA) software’s Cell Counter Plugin from the blue channel (DAPI stained). Cell spread area and circumference measurements were done by tracing cell boundaries manually using ImageJ software. Quantification of adsorbed protein on surfaces were measured using a BioTek Cytation 5 plate reader in area scanning mode (Ex: 490 / 20 nm, Em: 525 / 20). Digital images were captured using iPhone 14.

[0091] Fabrication of the ‘Liquid-Like’ Omniphobic Solid Coating on DifferentSubstrates:Primarily, glass slides were subjected to piranha treatment (7 mL H2SO4and 3mL H2O2) for24 hours to induce surface hydroxyl groups for further chemical modifications.All cautions pertaining to handling of piranha solution was exercised. The piranha treated glass substrates were washed with DI water thoroughly and thereafter placed in a solution of (3- aminopropyl) trimethoxysilane (APTMS) for half an hour to functionalize the surface with sufficient amine groups. The APTMS-coated glass substrates were washed thoroughly with DI water and oven dried for 5 mins. Meanwhile, 0.78 mmoles perfluorooctyl triethoxysilane (PFOTS) and 1.06 mmoles (3-Glycidyloxypropyl)trimethoxysilane) (GPTMS) were mixed together (in 1 mL ethanol) and kept on a shaker plate for 15 mins. The resulting ‘reactive’ solution was applied on the APTMS-coated glass substrates following doctor blading method to obtain ‘liquid-like’ omniphobic solid coatings on glass denoted as LL-OSC. The reaction solution can also be applied using spray or dip coating method with the same results. Subsequently, the substrates were subjected to heat treatment (100°C) for 3 hours to facilitate the amine-epoxy ring opening reaction.

[0092] For coating on PDMS and PET substrates, plasma treatment (at 75 W, 10 SCCM for 2 min in air) was performed to induce the surface hydroxyl groups. Aluminium and stainless steel was etched following previously reported methods.1,2Briefly, aluminium sheets were cleaned thoroughly with acetone and ethanol to remove any surface impurities. Next, the substrates were placed in a solution of sodium hydroxide (1 M) at 55°C for 10 mins followed by immersion in DI water for 10 mins. In case of adherence of brown powder on the surface,thesubstrates were rinsed with acetone. Stainless steel was etched using a solution of HCl,HNO3,and glycerol in the ratio 1:3:1, wherein the substrates were placed in this solution for1 min followed by thorough rinsing with DI water. Thereafter, the APTMS-treatment of substrates followed by application of the ‘reactive’ solution and heat curing were the same asT|H Docket: 222105-2260 ID: 2024-048-02 described above for glass substates to obtain ‘liquid-like’ omniphobic solid coatings on different substrates.

[0093] Durability Analysis

[0094] Physical Durability: To examine the robustness of the as-obtained ‘liquid-like’ omniphobic coating on different substrates, a few standard physical durability tests were performed as discussed in detail below.

[0095] Sandpaper Abrasion: To examine the robustness of the as-obtained ‘liquid-like’ omniphobic coating on different substrates, a few standard physical durability tests were performed as discussed in detail below.

[0096] Adhesive Tape Test: For this test, an adhesive tape was fixed onto the surface of the ‘liquid-like’ omniphobic glass, PDMS, aluminium and stainless steel individually with a 500 g load on top to ensure uniform contact between the tape and the underlying substrate. After 5 mins, the tape was peeled off from the surface and the sliding behaviour of liquids with different surface tensions was examined through sliding angle measurements. The tape peeling was repeated for several cycles and the tape was replaced after every 5thcycle.

[0097] Knife Scratch Test: In knife scratch test, the slippery omniphobic glass substrate was scratched multiple times with a knife in arbitrary directions to induce damage to the surface coating. Afterwards, the sliding behaviour of liquids with different surface tensions was examined at regular intervals through sliding angle measurements.

[0098] Pencil Hardness Test: In an attempt to further scratch the surface of the slippery omniphobic coating on the glass substrate, a standard pencil hardness test (ASTM D 3363) was performed using the VETUS INSTRUMENTS manufactured pencil hardness kit. A 6H pencil inclined at ~ 45° with 1 kg load on top was used to scratch the substrate. Thereafter, the liquid sliding behaviour was examined through sliding angle measurements for water, diiodomethane and hexadecane.

[0099] Chemical Durability: Glass substrates coated with the ‘liquid-like’ omniphobic coating was exposed to various chemically contaminated aqueous phases such as pH 1, pH 12, surfactant contaminated water (SDS, CTAB 1mM each), river (tap) water and artificial seawater for 48 hours continuously. The artificial sea water was prepared using 0.32 g MgSO4, 0.22 g MgCl2, 2.67 g NaCl and 0.11 g CaCl2was dissolved in 100 mL DI water. Thereafter, the liquid sliding behaviour was examined through sliding angle measurements at regular intervals for water, diiodomethane and hexadecane.

[0100] Heat treatment, UV irradiation, Air Stability: Glass substrates coated with the ‘liquid-like’ omniphobic coating was exposed to continuous heat (100°C) for 30 days, UV irradiation (354 nm) for 30 days and kept in air for 6 months. Thereafter, the liquid sliding behaviour was examined at regular intervals through sliding angle measurements for water, diiodomethane and hexadecane.T|H Docket: 222105-2260 ID: 2024-048-02

[0101] Drip Flow Bioreactor Studies: The bacteriostatic properties of the different samples groups under dynamic conditions were analysed by quantifying the biofilm formation on the surface (glass substrates were used). A BioSurface Technologies DFR-110-6 drip flow bioreactor was used for the biofilm formation and supplementation. For testing, an overnightculture of E. coli(ATC 25922) was inoculated in LB media and diluted to 0.1 OD600(107 CFUmL-1). Upondilution, the bacterial culture was exposed to a 2 g / L LB solution in reactorchannels loaded with the different sample types i.e. uncoated glass surface, APTMS coated glass surface and LL-OSC on glass (n = 3 for each sample type) for the batch phase biofilm formation for 6 hours. After completion of the batch phase, the continuous phase commenced for a duration of 48 hours at 37°C with LB media supplementation at a rate of 0.8 + / - 0.03 mL min-1across the same reactor channels tilted at 10°. Similarly, for the gram-positive bacterial strain, S. aureus (ATCC 6538), an overnight culture of S. aureus in tryptic soy broth(TSB) was dilutedto 0.1 OD600(107 CFU mL -1) and exposed to a 3g / L TSB solution in thesample loaded reactorchannels for a 6-hour batch phase biofilm accumulation. After the batchphase, the same continuous phase protocol as gram-negative studies were conducted for 48 h at 37°C.

[0102] Cytocompatibility Analysis: The cytocompatibility of the ‘liquid-like’ omniphobic coating on glass substrates was assessed through an in vitro cytotoxicity experiment with 3T3 mouse fibroblast cells. Yellow 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay was used to quantify the cytocompatibility of the samples following the ISO 10993 standard.67The glass samples namely__uncoated surface, AS coated surface, ‘liquid-like’ omniphobic solid surface (denoted as LL-OSS) were tested to assess the relative cytocompatibility of the different glass sample types normalized to the surface area. The leachates from each sample type (n = 6) were collected in DMEM for 24 hours at 37°C and exposed to cells grown in a 96-well plate. The sample leachate was allowed to interact with cells in the well plate for 24 h and then MTT solution was added to the well plate and incubated for 3 h. Next, the supernatant was removed from each well and MTT crystals were dissolved in DMSO. The absorbance in the wells was read at 570 nm using a plate reader which indicated the viability of the cells.

[0103] Thereafter, the samples were removed from their respective channels and rinsed with PBS in order to remove the excess unadhered bacterial cells. The samples were dried in the oven at 60°C for 8 hours. To account for the biomass accumulated on the respective surfaces, the dry weight of the samples before and after the drip-flow bioreactor experiment was recorded. The percentage biomass accumulation was calculated using the following formula,T|H Docket: 222105-2260 ID: 2024-048-02 Biomass accumulation (%) = [1- (Dry wt. of sample before / Dry wt. of sample after)] X 100%

[0104] Cytocompatibility Analysis

[0105] Cell Viability Using MTT Assay: The cytocompatibility of the ‘liquid-like’ omniphobic coating on glass substrates was assessed through an in vitro cytotoxicity experiment with 3T3 mouse fibroblast and and human umbilical endothelial (HUVEC) cells. Yellow 3-(4,5- dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay was used to quantify the cytocompatibility of the samples following the ISO 10993 standard.3Theglass samples namely uncoated surface, APTMS coated surface, ‘liquid-like’ omniphobicsolid coating (denoted as LL-OSC) were tested to assess the relative cytocompatibility of the different glass sample types normalized to the surface area. The leachates from each sample type (n = 6) were collected in DMEM for 24 hours at 37°C and exposed to cells grown in a 96- well plate. The sample leachate was allowed to interact with cells in the well plate for 24 h and then MTT solution was added to the well plate and incubated for 3 h. Next, the supernatant was removed from each well and formazan crystals were dissolved in DMSO. The absorbance in the wells was read at 570 nm using a plate reader which indicated the viability of the cells.

[0106] For determination of half-maximal inhibitory concentration (IC50) of PFOTS,hydrolysed wassupplemented in the desired molarity in culture media and treated to 3T3 cellsfor 24 h. Since the 0.78 mmol PFOTS (corresponds to 0.76 M of the silane) in the reactive mixture is in an ethanolic solvent system, 50% of this concentration (0.38 M) was chosen and subsequent dilutions were made in culture media for treatment on 3T3 cells. After treatment, MTT solution was added, and the formazan crystals formed were solubilized by DMSO and read at 570 nm using microplate reader.

[0107] Live / Dead Cell Assay: For assessing the distribution of live and dead cell population, they were stained with calcein-AM and ethidium homodimer (Sigma, USA).3T3 cells were seeded at a seeding density of 20000 cells / cm2in cell culture dishes (n= 4) andtreated for 24 h with culture media supplemented with (i) 1mM H2O2(negative control), (ii)19mM PFOTS (cytotoxic concentration comparable to negative control used), (iii) 9.5 mM PFOTS, or the leachates from (iv) uncoated, (v) APTMS surface, (vi) LL-OSC surface. Non- treatment group with normal culture media remained as positive control. Concentrationdependency for H2O2sensitivity on 3T3 cells (data not shown) was done to determine thecytotoxic 1 mM concentration used here for negative control treatment. After treatment, the cells were stained with 40 nM calcein-AM and 20 nM ethidium homodimer cocktail in 1X PBS for 20 min and visualized under fluorescence microscope. (Advanced Microscopy Group’s AMG EVOS microscope). Cytosolic esterases from live cells cleave calcein-AM to yield green fluorescent calcein while exposed nucleic acid (DNA) from dead cells bind to ethidiumT|H Docket: 222105-2260 ID: 2024-048-02 homodimer fluorescing red. Fluorescent images (at 10X magnification from at least 12 frames captured across each sample set) were assessed by Image-J using thresholding and segmentation analysis to count the live / dead cells which are presented as their relative distribution percentages.4

[0108] LDH assay for assessing percent cytotoxicity: Lactate dehydrogenase (LDH) leaks from compromised plasma membranes of dead (apoptotic or necrotic) cells.53T3 cellswere seeded at a seeding density of 20000 cells / cm2in 96 well plate and exposed to theaforementioned treatment regimen as in section 8.2. After 24 h, the spent media were collected. The total LDH content within control cells were lysed by 5 % (v / v) triton X-100 to determine the maximum LDH release. The percentage cytotoxicity was determined using the following equation using the Roche LDH cytotoxicity assessment kit (Millipore-Sigma, USA) following manufacturer’s protocol.

[0109] Assessment of Cell Adhesion and Cytoskeletal Architecture of the Adhered Cells

[0110] For assessing the extent of cell adhesion rectangular glass coverslips (22 mm x 30 mm, thickness 0.16 to 0.19 mm; made from Corning® 0211 float glass) were used. The glass coverslips were modified to obtain the APTMS-coated surface and LL-OSC. To enable seeding of cells, wells (inner diameter = 0.87 cm; height = 1 cm) were made on top of these surfaces by using cut Eppendorf® 1.5 mL microfuge tubes and sticking them to coverslips using poly- dimethoxysilane glue (Sylgard 184 silicone elastomer 10:1 ratio with DOWSIL 184 silicone elastomer curing agent) on the outer edges of the tube and curing for 4 h at 60 ºC. The effective seeding surface per well was 0.594 cm2and the effective volume was 0.5 mL. NIH / 3T3 fibroblasts were maintained in DMEM with 10% fetal bovine serum supplemented with 1% (v / v) Pen-Strep.

[0111] Prior to cell seeding, the wells made on the coverslip’s samples namely, uncoated surface, APTMS coated surface, and LL-OSC were sterilized by UV sterilization for 30 min. Cells were seeded in these wells (in triplicates) at a seeding density of 10,000 cells / well. After 24 h, the cells were fixed with 4% paraformaldehyde for 15 min at room temperature and permeabilized with 0.1% (v / v) Triton-X100 for 10 min at room temperature. The samples were then blocked with 5% (w / v) bovine serum albumin in 1X PBS, followed by staining of F-actin (cytoskeleton) with 1 μM Alexafluor® 488 conjugated to Phalloidin for 20 min, and nucleus were stained with 1 μg / mL DAPI for 2 min. The cells were imaged using fluorescence microscopy with actin filament stained green and nucleus stained blue.T|H Docket: 222105-2260 ID: 2024-048-02

[0112] Fibrinogen Adsorption Studies

[0113] The glass samples namely, uncoated surface, APTMS coated surface, and LL- OSC were evaluated for resistance to plasma protein adsorption under physiological conditions (PBS (1x) at 37°C) via incubation with human fibrinogen (Fg) following our previously reported method.6Purified human Fg fluorescently tagged with fluorescein isothiocyanate (FITC-Fg) was mixed 1:10 by mass with unlabelled Fg to a final concentration of 4 mg mL-1. All the sample types were incubated in PBS (1x) at 37°C for 30 min at a standardized surface area-to- volume (SA:V) ratio of 1 cm2 / mL in 12-well glass-bottom black polystyrene well plates. Following equilibration, the samples were treated with the Fg working solution to achieve a final exposure concentration of 2 mg / mL. All the substrates were incubated for 90 min at 37°C with further protection from light. Afterward, wells were sequentially washed with PBS (1x) for a total of ten steps on a basis of 1 mL per step. These washing steps diluted out solution-phase Fg and removed non-adsorbed Fg from the substrates. The resulting Fg-treated substrates were finally suspended in 1 mL of PBS (1x) for analysis.

[0114] Fluorescence measurements were recorded before Fg treatment and following treatment, with standardization against the neat working solution. Final results are reported as the mean mass of adsorbed Fg normalized to exposed surface area (mg m-2) (n = 8). Further fluorescence microscopy imaging of the surfaces was performed to investigate surface coverage and corroborate fluorometric findings.

[0115] Blood Compatibility Analysis

[0116] Collection and Processing of Porcine Whole Blood

[0117] All protocols relating to the use of porcine whole blood (WB) and its products were approved by the University of Georgia’s Institutional Animal Care and Use Committee. Porcine WB was drawn into 3.2% sodium citrate through blind draws. WB samples were assessed for hematological parameters including cell counts and hemoglobin (Hg) levels. WB was centrifuged (280 rcf, 2 min) to fractionate platelet-rich plasma (PRP). PRP was further evaluated for hematological parameters, with the remaining sample further fractionated (3,000 rcf, 20 min) to obtain platelet-poor plasma (PPP). All samples were processed within 4 h of the draw.

[0118] In Vitro Studies of Platelet Adhesion

[0119] Platelet adhesion on the glass samples namely, uncoated surface, APTMS coated surface, and LL-OSC was studied following our previously reported methods with slight modification.6,7Collected PRP was diluted with PPP to achieve a normalized platelet count (2 × 108platelets mL-1) and treated with calcium chloride (2.5 mM) to achieve a platelet working solution with reversed anticoagulation. All the samples with normalized surface area (1 cm2) were incubated in the platelet working solution (SA / V ratio of 1 cm2mL-1) for 90 min with gentle rocking. Following incubation, the samples were removed from the platelet solution and gentlyT|H Docket: 222105-2260 ID: 2024-048-02 washed with sterile PBS (1x) to remove nonadherent platelets. Adherent platelets were then lysed with 2% v / v Triton-X-100 in PBS (1x, 200 µL). Lysates were then processed with the Roche® Cytotoxicity Detection Kit, which measures the activity of released lactate dehydrogenase in the lysate via redox cycling and conversion of a tetrazolium salt to its formazan product. Standard curves of known concentrations of platelets were prepared for assay normalization. Final results are reported as the mean number of adhered platelets per unit surface area (platelets cm-2) ± SD (n = 8).

[0120] Hemolysis: The hemolytic index of the sample groups was assessed following the modified NAMSA protocol.8Herein, PDMS as the substrate was used for ease of experiment thus, the sample groups were uncoated PDMS, APTMS coated PDMS and LL-OSC- PDMS (n = 8). Briefly, porcine whole blood was diluted with calcium and magnesium-free (CMF-PBS) to a total hemoglobin concentration of 10 ± 1.0 mg / mL. Next, 1 mL of porcine whole blood was diluted with 7 mL of sterile deionized water as the positive control, or 7 mL CMF-PBS as the blank, and incubated for 3 h. Thereafter, 1 cm2high-density polyethylene (HDPE) coupons were incubated with dilute whole blood according to the NAMSA ASTM F756 protocol surface area to volume ratio as the negative control. Each of the sample groups with CMF-PBS as the solvent were incubated at 37°C for 3 h with inversions every 30 min. After incubation, the samples were centrifuged at 800 gravity for 15 min. The supernatant from the different sample groups were combined in 1:1 ratio with Drabkin’s reagent and incubated for 15 min at room temperature followed by quantifying the absorbance at 540 nm. Percent hemolysis was calculated using the following equation: Hemolysis (%) = [(Abssample- Absblank) / (Absdiluted blood- Absblank)] X 100

[0121] Statistical Significance: All data represented as mean ± standard deviation unless otherwise mentioned. All statistical analysis were performed using GraphPad Prism software (Version: 10.1.0). Outliers were removed using a Grub’s test and LL-OSC results were compared with respective controls using one-way Annova followed by Tukey’s test. Results with p < 0.05 were considered as statistically significant. RESULTS AND DISCUSSION

[0122] Fabrication of the ‘Liquid-Like’ Omniphobic Slippery Surface

[0123] We have introduced a strategic covalent grafting approach that utilizes a mixture of fluorinated-silane, epoxy and amine terminated silanes to obtain a highly durable, anti- biofouling solid slippery coating. The ‘reactive’ solution of perfluorooctyl triethoxysilane (PFOTS) and (3-Glycidyloxypropyl)trimethoxysilane (GPTMS) undergo random hydrolysis and condensation to yield an interconnected silane network as shown in FIG.1. The role of GPTMS is a) to act as a molecular spacer to provide an optimum distance between the rigid fluorinated chains to attain chain flexibility and b) also provide ‘reactive’ epoxy groups to covalently and robustly anchor onto a pre-functionalized amine surface to enhance theT|H Docket: 222105-2260 ID: 2024-048-02 durability of the solid slippery coatings. The current approach for covalently binding the epoxy- derived ‘reactive’ slippery formulation with chemically pre-functionalized surfaces is not just limited to the epoxy-amine ring opening reaction but can also be extended to epoxy-thiol,39epoxy-carboxylic acid reactions,40thus, opening up avenues for various applications in diagnostics, droplet transport, manipulation etc.

[0124] We investigated the optimum concentration of PFOTS required in the ‘reactive’ solution to attain solid slippery coatings on a pre-functionalized amine surface. The direct application of PFOTS on a glass substrate fails to exhibit liquid sliding property at lower sliding angles as evident from past literature reports.5,35,38Primarily, we examined the influence of varying the concentration of PFOTS on the liquid sliding behavior while the GPTMS concentration was kept constant (1.06 mmol). It was observed that the decreased concentration of PFOTS (0.4 mmol) in the ‘reactive’ solution exhibited higher liquid sliding angles (FIG.2A, 2D), well-spaced PFOTS chains in the appropriate concentration (0.78 mmol) displayed significantly lower sliding angles for liquids of varying surface tensions whereas increasing the PFOTS grafting (0.88 mmol) beyond the optimum value led to an increase in the liquid sliding angles (FIG.2C, 2D).

[0125] To understand this trend in dynamic liquid wettability, the surface morphology of the coating was investigated, and it was found that the surface roughness was ^ 0.24 nm, 3 nm and 6 nm for the reduced, optimal and excessive PFTOS grafting respectively. The AFM images indicate that on increasing the PFTOS grafting, nano-aggregation on the surface was observed that led to an increase in the surface roughness. However, the sliding angle data (FIG.2D) shows that the liquid droplets still exhibit dynamic wettability to a certain extent on the reduced and excessively grafted PFTOS surface. Thus, from the AFM analysis and the sliding angle data it can be inferred that surface roughness is not the only criteria affecting the dynamic de-wettability of the as-developed solid slippery coating. This hypothesis is evidently supported by past results that asserts the major influence of chemical (surface energy) and physical (liquid like) properties over the surface morphology of alkyl / fluoro hybrid films in determining the dynamic liquid wettability.35-36Hence, in our work the uniform distribution (chemical property) and mobility (physical property) of PFTOS play a key role in imparting the ‘liquid-like’ behaviour. When the grafting density is reduced, the ‘liquid-like’ PFTOS on the surface are widely spaced and hence, the chemical non-uniformity on the surface is the reason for the hindered dynamic wettability of the beaded liquid droplet. The optimally grafted PFTOS coating consists of chemically uniform and flexible PFTOS chains that exhibits superior ‘liquid- like’ behaviour towards the beaded liquid droplets. However, the excessively grafted PFTOS coating led to steric effect of the fluorinated chains resulting in a rigid confirmation that is moreT|H Docket: 222105-2260 ID: 2024-048-02 ‘solid-like’ rather than ‘liquid-like’. Thus, based on the above results we fabricated the solid slippery coatings in the current work using PFTOS and GPTMS in millimoles ratio 0.7:1.

[0126] The ‘liquid-like’ omniphobic coating on a glass surface displays sliding angle ~18° for water and sliding angles <15° for liquid droplets (droplet volume = 15 μL) including diiodomethane, ethylene glycol, DMSO, hexadecane, and ethanol (FIG. 2K). However, the liquid droplets (water and organic) either completely spread or do not slide on the uncoated and APTMS treated surfaces. These results demonstrate that the optimum combination of PFOTS and GPTMS on APTMS functionalized surfaces provide the desired ‘liquid-like’ solid slippery behavior. The liquid sliding angles varied on changing the liquid droplet volume wherein the sliding angles decreased on increasing the volume of the liquid droplet. The optical transparency of our solid slippery coatings > 90% with respect to normalized uncoated glass surfaces. Thus, our solid slippery coatings with high optical transparency would be desirable for medical devices.

[0127] Scanning electron micropscopy (SEM) images revealed the featureless surface morphology of LL-OSC as shown in FIG 2I. Atomic force microscopy (AFM) analysis revealed that the average surface roughness of LL-OSC was ~ 3 nm which confirmed the physical homogeneity of the surface (FIG.2J). The average thickness of LL-OSC was found to be ^ 20 ^ 5 nm. Energy dispersive X-ray spectroscopy confirmed the presence of fluorine groups on LL-OSC besides Si, O, C, N on the uncoated and APTMS substrates.

[0128] The surface pre-functionalization with amines and the subsequent epoxy-amine ring opening reaction was monitored through attentuated fourier transform spectroscopy.41The APTMS pre-functionalized surface exhibited primary amine bending peak at 1584 cm-1and Si-O-Si stretching peak at 1070 cm-1as shown in FIG.2L (green spectra).42The presence of the C-O-C stretching peak at 890 cm-1and the C-O-C ring breathing peak at 1244 cm-1confirmed the presence of epoxy groups in the ‘reactive’ solution (red spectra).43Moreover, the presence of peaks at 953 cm-1, 1165 cm-1and 1200 cm-1validated the inclusion of PFOTS in the ‘reactive’ solution.41Upon coating the APTMS surface with the ‘reactive’ solution, the peaks corresponding to the primary amine bending and epoxy rings diminished, confirming the successful ring opening reaction between the epoxy and surface amine (black spectra). The appearance of the C-OH in plane bending peak at 1453 cm-1confirmed the ring opening of the epoxy groups present in the ‘reactive’ solution.

[0129] Physical and Chemical Durability of LL-OSC: Examination of the robustness of solid slippery coatings against several physical abrasions, prolonged chemical and other challenging abrasive conditions is a necessity prior to extending the coatings for direct practical applications. There remains a gap in developing a transparent, durable, omniphobic organosilane based solid slippery coating for extended biomedical applicability with substrateT|H Docket: 222105-2260 ID: 2024-048-02 independent characteristics. In the current work, we performed different types of physical and chemical abrasions and tested the storage stability of LL-OSC for prolonged durations.

[0130] First, an abrasive sandpaper (400 grit) was rubbed back and forth on the LL-OSC with distance covered per abrasion stroke ~15 cm with a pressure of ~25 kPa on top (FIG. 3A). The sliding property remained unaltered and water, hexadecane and diiodomethane droplets (liquid droplet volume = 15 μL) slid off the tilted surface even after the severe abrasion (FIG.3B-D, 3M). The contact angle hysteresis after sandpaper abrasion reveals insignificant changes throughout the abrasion cycles. Moreover, paint contraction test was performed on LL-OSC before and after sandpaper abrasion to investigate the paint contraction pattern. The paint spread on an uncoated surface and permanently adhered onto it. However, LL-OSC exhibited paint contraction and retained the paint contraction characteristics even after the severe sandpaper abrasion, thus, revealing the durability of the as developed ‘liquid-like’ solid coating.

[0131] Next, we performed a standard pencil hardness test, wherein a 6H pencil (the hardest in the 6B-6H series) was used to scratch the LL-OSC multiple times with 1 kg load on top (FIG. 3E). However, the embedded slippery property of LL-OSC remained unperturbed towards liquids (liquid droplet volume = 15 μL) of different surface tensions (FIG.3F-H). As compared to an unabraded surface, the SEM images reveal minimal scratches on LL-OSC even after performing the 6H pencil hardness test. Thus, the as-developed ‘liquid-like’ solid coating is mechanically durable and any variation in the coating morphology after the pencil hardness test is insignificant to be able to cause considerable change in the dynamic surface wettability.

[0132] Paint contraction test was also performed on LL-OSC before and after pencil hardness test that revealed similar paint contraction patterns. Further, an adhesive tape was pressed on the surface of LL-OSC with a 500 g load (to ensure uniform contact between the tape and the substrate) followed by peeling the tape as shown in FIG.3I. The tape peeling was repeated for 100 cycles on LL-OSC without perturbing the slippery behavior (FIG.3J-L, 3N). The contact angle hysteresis after adhesive tape peeling remained consistent throughout the tape peeling cycles. We also performed a knife scratch test on LL-OSC and observed that multiple cycles of arbitrary scratching failed to deter the impeccable liquid sliding behavior. The liquid droplet volume used for analyzing slippery property after adhesive tape and knife scratch test was 15 μL.

[0133] The LL-OSC exhibited durability against a continuous water jet (with flow flux ~1.4 L / min) for 300 seconds without leaving behind any traces of water with respect to an uncoated glass surface. In addition, LL-OSC could withstand 30 days of exposure to thermal treatment (100°C) as shown in FIG. 3O, 180 days of storage at room temperature (FIG. 3P), UVT|H Docket: 222105-2260 ID: 2024-048-02 irradiation and DI water exposure without any noticeable change in liquid sliding behavior (liquid droplet volume = 15 μL).

[0134] Exposure to harsh chemical conditions is inevitable at practical settings. Thus, we subjected our LL-OSC to multiple cycles of dipping in different aqueous medi and did not observe any traces of left-over liquid stains. We exposed LL-OSC to different chemically contaminated aqueous media such as pH 1, pH 12, tap water, artificial sea water and surfactant contaminated (SDS, CTAB 1 mM each) water for 48 hours continuously and noted no observable change in the liquid sliding behavior (FIG.3Q).

[0135] In the past, epoxy resins in the presence of an amine functional molecule that serves as the coating hardener, have been widely used to develop mechanically durable and scratch resistant coatings.44-45The heat mediated amine-epoxy ring opening reaction results in a durable covalent linkage that resists severe abrasions.46Thus, the remarkable durability of the amine-epoxy bond is widely known in literature as well as at practical settings. Furthermore, GPTMS has been used to develop abrasion and scratch resistant hybrid coatings47-48wherein the durability provided by GPTMS was attributed to the presence of the inorganic silica network.13,17,26Thus, in the current work, we capitalized both on the robust epoxy-amine bond and the inorganic silica network to develop mechanically durable solid slippery coatings. Herein, GPTMS (along with PFTOS) provides the a) silica co-condensed network and b) the presence of residual epoxy groups in the GPTMS-PFTOS mixture ensures the covalent binding of the silica co-condensed network to the underlying amine functionalized substrate through the amine-epoxy ring opening reaction. Thus, the LL-OSC is durably embedded onto the underlying substrate exhibiting impeccable abrasion resistance.

[0136] Assessment of Anti-Biofouling Characteristics: Protein adsorption followed by platelet activation on blood-contacting medical devices lead to thrombosis and a host of associated infections and it remains a burning issue that requires immediate attention and resolution.49-50In the past, solid slippery coatings have been explored for its anti-biofouling properties against bacteria, proteins, and cells.18-23These reported coatings lack extensive physical and chemical durability, and remains unexplored for its hemolytic response and platelet repellence property. In our current work, we have developed a highly robust ‘liquid- like’ omniphobic solid coating for the first-time investigation of platelet repellence and hemolytic activity as well as examination of biofilm inhibition, cyctocompatibility, fibrinogen and cell repellent characteristics.

[0137] Biomass Accumulation on LL-OSC:

[0138] Over 60% of hospital acquired infections are a consequence of biofilm formation on implantable medical devices which forms the major basis for device associated complications and even fatalities in patients.51Biofilms are an irreversible and structured cumulation of bacterial cells that colonize on foreign surfaces and reproduce to form anT|H Docket: 222105-2260 ID: 2024-048-02 extracellular polymeric substance (EPS) which provides a protective barrier against the conventional antimicrobial therapies.52-53Compared to planktonic bacteria, biofilms possess immune evasion mechanisms in addition to increased cell density within the EPS and require extensive treatments that have the potential to develop complications such as antibiotic resistance, chronic inflammation, and uncontrolled sepsis. Table S1 summarizes the reported solid slippery coatings that have been investigated in the past for its anti-bacterial behaviour however, concerns relating to a) lack of prolonged physical or chemical durability of the coating and b) lack of other overall anti-biofouling data limit the practical utility. In the current work, we investigated the biofilm formation and eradication efficacy of E. coli and S. aureus (FIG.4A- B) on our solid slippery coating. First, we exposed the different sample types i.e. uncoated, APTMS coated and LL-OSC to static (6 hours) followed by dynamic bacterial conditions for 48 hours. The E. coli biomass accumulation on an APTMS functionalized surface was found to be ~79% with respect to the normalized uncoated surface (considered to be 100%). The slight reduction of biomass on APTMS surface can be attributed to the presence of the positively charged amine groups that inhibit the biofilm formation via electrostatic interactions.54-55Interestingly, the E. coli biomass accumulation on LL-OSC was found to be only ~11% with respect to the normalized uncoated surface as shown in FIG.4C. Similarly, our solid slippery coating exhibited only ~20% S. aureus biofilm accumulation with respect to the normalized uncoated surface (FIG.4D).

[0139] Further, we analyzed the morphology and biofilm coverage of E. coli and S. aureus on the uncoated surface and our solid slippery coating through SEM imaging wherein it was observed that biofilm coverage on LL-OSC is very scarce as compared to the uncoated and APTMS coated surfaces (FIG.4E-F). Thus, the bacteriostatic properties of our solid slippery coating promotes its biological efficacy in vitro to prevent medical devices associated infections and demonstrates its potential in vivo applicability.

[0140] Cytocompatbility Analysis: To classify any biomaterial as cyctocompatible and safe for biological applications, cell viability greater than 70% is desirable.56The cytotoxicity analysis of the uncoated surface, APTMS-coated surface, and LL-OSC was performed following the Yellow 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay using 3T3 mouse fibroblast cells. The interaction of the leachates collected from each sample type with MTT resulted in the formation of purple formazan in the metabolically active cells owing to the enzymatic degradation of MTT. This was used as the metric for cytocompatibility assessment.57The cells incubated with the sample leachates were found to have relative cell viability greater than 90% (FIG. 5B), thus, indicating cytocompatiblity and safe for relevant biological applications.

[0141] To overrule the effect of any unreacted / residual PFOTS present in the leachate of the LL-OSC, relative cell viability to determine the half-maximal inhibitory concentration (IC50)T|H Docket: 222105-2260 ID: 2024-048-02 was performed and it was found to be 9.5 mM. Thus, this infers that any unreacted or leached PFOTS present in the leachates (in the MTT assay) had no deleterious effect on cells and it is possibly below 0.002375 M which did not have any cytotoxic effect as it was on par with the cell control. We further performed the Calcein-AM and ethidium homodimer based semi- quantitative analysis of live / dead population on 3T3 cells with different treatment conditions. This assay relies on live cell’s cytosolic esterases to cleave calcein-AM to fluoresce in green while ethidum homodimer binds to exposed nucleic acid (DNA) of dead cells. Fluorescent microscopic images revealed that the negative control group (1 mM H2O2treated group) and 19 mM PFOTS exhibited morphology typical of dead (apoptotic / necrotic) cells, becoming rounded with >70% of population stained red. The half-maximal inhibitory concentration of PFOTS (9.5 mM) had 60 / 40 % live / dead cell population respectively. However, the LL-OSC leachate group had the same population distribution comparable to cell control group maintaining the same levels of healthy live cells.

[0142] We also tested the cytotoxicity by measuring the relative LDH (lactate dehydrogenase) released into the media when cell plasma membrane is compromised during cell death. Cytotoxic concentration of PFOTS (19 mM) and 0.1 mM H2O2, recorded highest the cytotoxicity of ~27%, while IC50concentration had ~21%. LL-OSC exhibited cytotoxicity < 10% which establishes the consensus that LL-OSC is cytocompatible. For blood contacting applications, endothelial cells cytocompatibility is essential. Hence, we assessed the cytocompatibility of human umbilical vein endothelial cells (HUVECs) against the collected leachates wherein cell viability was > 90 % was recorded for LL-OSC. Based on these conclusive in vitro tests, the as-developed solid slippery coating can be a prospective non- cytotoxic biomaterial for applications in implantable non-resorbable medical devices and blood contacting devices.

[0143] Investigation of Plasma Protein Adsorption and Cell Adhesion on LL-OSC: Surface morphology and chemistry has been well established to play a vital role in promoting or preventing protein and cell adhesion.58Blood-contacting biomaterials primarily experience non-specific protein adsorption.59-60Cells are incapable of directly sensing any surface. In the first step, an adsorbed protein layer (serum / plasma proteins in vitro or proteins in blood / interstitial fluid present in vivo) forms over the biomaterial surface through Van der Waals forces and ionic interactions.61-62The second phase of interaction involves the cell- biomaterial interaction via the adsorbed proteins, followed by the third phase i.e., cytoskeletal interactions which lead to cell spreading. Protein adsorption is the precursor step to subsequent platelet adhesion and activation that leads to thrombosis; thus, the protein repellence ability of any biomaterial is extremely important for in vivo applicability.63

[0144] Superhydrophobic coatings and biomaterials with a metastable air layer trapped within the hierarchal surface topography have been explored as prospective functionalT|H Docket: 222105-2260 ID: 2024-048-02 materials to combat thrombosis and infections in blood-contacting medical devices.64-65The susceptibility of the metastable trapped air layer to external factors such as harsh temperatures, extremes of pressure etc. limits the practical utility. Similarly, SLIPS have also been explored as potential protein and cell repellent surfaces,66-68but, the lubricant leaching over time remains a concern. In that context, the current work on robust and cytocompatible ‘liquid-like’ solid coatings that rules out the dependency of the surface on any trapped external third phase can emerge to be a promising avenue for preventing overall biofouling.

[0145] As shown in FIG.5C, 5I, the uncoated glass surfaces exhibited higher cell adhesion (nucleus per frame) as well as higher fibrinogen adsorption which can be attributed to the Vroman effect (FIG. 5K).69-70The APTMS coated surface was observed to exhibit higher affinity for cell and fibrinogen adhesion (FIGS.5D, I, K), which is in agreement with previous literature that states that amine-terminated self-assembled monolayers (SAMs) exhibit higher fibrinogen adhesion.71Interestingly, LL-OSC exhibited a significant reduction in cell adhesion compared to control samples as shown in FIG.5E, 5I. LL-OSC demonstrated ~78% reduction in fibrinogen adsorption in comparison to uncoated and APTMS coated surfaces (FIG.4K). The decrease in the interaction forces between the adsorbed proteins and LL-OSC that were hypothesized to be governed by Lifshitz-van der waals (LW) force, Lewis acid-base (AB) force and electrostatic double-layer (EL) force,72-73aided in exhibiting impeccable anti-fouling characteristics. Furthermore, the fibrinogen adsorption data were corroborated by fluorescence imaging of the fibrinogen treated surfaces, showing reduced surface coverage with LL-OSC.

[0146] The adhered cells were studied for their cytoskeletal architecture by staining the F- actin, which gives insights on how the focal adhesion complexes have matured. In the uncoated and APTMS surfaces, due to increased protein adhesion, the cells have more focal points to adhere, and the cells tend to spread out more as depicted by the presence of mature actin filaments (FIGS.5F, 5G). Microscopic images on LL-OSC display rounded cells with low cell spread-out area with notable cell-clustering as shown in FIG.5H which can be accounted to cell-cell interactions being favored over cell-material interactions. FIG.5J accounts for the cytoskeleton area per cell for each of the sample groups where LL-OSC exhibited negligible cell spreading area as compared to the controls.

[0147] Platelet Adhesion Examination on LL-OSS:

[0148] Platelet adhesion on blood-contacting medical devices that lead to thrombosis, hampers the practical use of biomaterials.74Anti-coagulant drugs such as heparin,75neoendothelialization,76bio-inspired anti-biofouling coatings77-78etc have been extensively explored to combat platelet assisted thrombosis on medical devices. Heparin related thrombocytopenia, hyperkalemia and so on,79the associated durability, biocompatibility, andT|H Docket: 222105-2260 ID: 2024-048-02 facile fabrication of the anti-biofouling coatings are some of the major concerns that limit the application of the currently available combative approaches.61,65

[0149] The current work is the first-time investigation of platelet adhesion on a ‘liquid-like’ omniphobic solid coating that opens a new and promising avenue for utility of solid slippery coatings in blood-contacting medical devices. To analyse the hemocompatibility, we exposed all sample groups to platelet-normalized PRP (2 × 106platelets mL-1) for 90 min followed by measurement of the platelet adhesion behaviour. FIG. 5L shows that LL-OSC decreases platelet adherence by ~50% as compared to the uncoated and APTMS coated glass surfaces. These results are complementary to our fibrinogen adsorption studies (~78% reduction) wherein the decreased fibrinogen adsorption (which is the primary step for platelet adhesion) is an obvious indication towards reduced platelet adhesion and thus, can prevent possible medical device associated thrombosis.63To translate any technology for biomedical applications, examining the associated hemolytic response is an essential criterion. According to NAMSA ASTM F756 (SI section 11.3), 2-5% hemolytic index is considered to be slightly hemolytic and >5% is considered to be hemolytic and thus, unfit for practical applications. Our solid slippery coating with hemolytic index ~0.2% can therefore, be classified as a non- hemolytic coating. These results pave a novel way for extending our solid slippery coating for resisting platelet deposition without any associated fabrication, durability, or morbidity concerns, thus, conferring added benefit for blood-contacting medical device applications.

[0150] Substrate Independent Applicability: In the past, different chemical approaches have been adopted to develop organo-silane based omniphobic solid slippery coatings mainly on glass or silicon wafer substrates for various applications. There are a few reports of organo- silane based slippery coatings on polymers that have been reported but the lack of associated durability was a limiting factor. Thus, there still exists a need to develop a solid slippery formulation that coats on a wide range of substrates to obtain durable, transparent, omniphobic solid slippery surfaces.

[0151] Uncoated substrates such as PDMS, stainless steel and aluminum either hindered the sliding of water and ethanol or exhibited trailing droplets after tilting the surface (FIG.6A- B). However, coating the same substrates i.e., PDMS, aluminum and stainless steel with the ‘reactive’ solution (pre-treated the substrates with APTMS) embedded solid slippery behavior on the substrates (FIG.6C-I) with liquid droplet volume = 15 μL. To ascertain the durability of the LL-OSC on different substrates, sandpaper abrasion was performed covering a total distance of ^ 300 cm with an applied load of 25 kPa on top and it was observed that the sliding behavior of water (polar liquid) and diiodomethane (non-polar liquid) remained unperturbed (FIG.6J, droplet volume = 15 ^L). Repetitive cycles of adhesive tape test were also performedT|H Docket: 222105-2260 ID: 2024-048-02 on the different LL-OSC-substrates to reveal the superior durability of the as-developed slippery formulation irrespective of the underlying substrate.

[0152] We demonstrated the anti-inking performance of the ‘liquid-like’ omniphobic coating on polyethylene terephthalate (PET) films wherein the ink marks adhered permanently on the uncoated surface even after multiple cycles of wiping (FIGS. 6K-M) whereas the permanent marker writing barely adhered on LL-OSC-PET and could be completely wiped off from the surface (FIGS. 6N-P), thus, paving way for the use of LL-OSC as stain-protective coatings, display screens etc. The flexibility of the solid slippery coating was elucidated by subjecting the LL-OSC-PET film to multiple cycles of bending around a 4 mm metal tube followed by subsequent investigation of the liquid sliding characteristics that indicated minimal difference in sliding behavior of water, diiodomethane and hexadecane. Thus, the ‘liquid-like’ extremely robust, omniphobic solid coating developed in the current work can be applied onto any appropriately pre-functionalized substrate ranging from polymers to metals, therefore, exhibiting the potential for a wide range of practical applications. CONCLUSION

[0153] The current work adopts a strategic chemical approach to design a robust, transparent, substrate-independent omniphobic solid slippery coating following the hydrolysis and condensation between fluorinated and epoxy terminated silane molecules. The epoxy silane imparts the optimum spacing for mobility of the fluorine-terminated silane and provides a point of covalent, durable anchorage with an amine pre-functionalized surface following the epoxy-amine ring opening reaction. The as-developed ‘liquid-like’ omniphobic solid coating (LL-OSC) was capable of repelling water and liquids of various surface tensions with sliding angles less than 18°. Standard physical durability and chemical stability tests, heating at 100°C, UV irradiation (365 nm) and DI water exposure for 30 days, room temperature storage stability for 180 days revealed the uncompromised liquid sliding behaviour on LL-OSC. The current work demonstrates the excellent cytocompatibility of LL-OSC and biofilm inhibition, fibrinogen, and cells repellence along with the first-time investigation of the anti-platelet adhesion (~50% reduction) and hemolytic response of a ‘liquid-like’ omniphobic solid coating. Furthermore, the as-developed, robust slippery formulation was successfully applied to different substrates including PDMS, PET, stainless steel and aluminium. We also demonstrated the anti-inking performance and bendability on a ‘liquid-like’ omniphobic PET substrate wherein the permanent marker writing barely adhered on LL-OS-PET whereas it adhered permanently on the uncoated PET surface, thus, paving way for the use of LL-OSC as stain-protective coatings, display screens etc. Thus, the reported chemical approach for developing an organosilane derived highly durable solid slippery coating can be successfully extended for different prospective biomedical, energy and environmental applications.T|H Docket: 222105-2260 ID: 2024-048-02

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Claims

T|H Docket: 222105-2260 ID: 2024-048-02 CLAIMS 1. An article comprising of a perfluoroalkylsiloxane covalently bonded to a surface of the article, wherein the article is produced by the method comprising: (a) functionalizing a surface of the article with a plurality of nucleophilic groups to produce a pre-functionalized surface, and (b) contacting the pre-functionalized surface with a perfluorolkylsiloxane comprising an electrophilic group, wherein the plurality of nucleophilic groups on the surface of the article react with the electrophilic group on the perfluoroalkylsiloxane to covalently bond the perfluoroalkylsiloxane to the surface of the article.

2. The article of claim 1, wherein the nucleophilic group is a hydroxyl group, a thiol group, an amino group, or any combination thereof.

3. The article of claim 1, wherein at least the surface of the article is functionalized with a silane compound comprising a nucleophilic group.

4. The article of claim 1, wherein at least the surface of the article is functionalized with a silane compound comprising at least one hydroxyl group, thiol group, or amino group.

5. The article of claim 1, wherein at least the surface of the article is functionalized with an aminosilane.

6. The article of claim 1, wherein at least the surface of the article is functionalized with a compound having the structure I I wherein each R1is independently an alkoxy group, cycloalkoxy group, or aryloxy group, and o is an integer from 1 to 10.

7. The article of claim 1, wherein the electrophilic group comprises a substituted or unsubstituted epoxide group, a substituted or unsubstituted acrylate group, an ester, or a carboxylic acid group.

8. The article of claim 1, wherein the electrophilic group comprises an unsubstituted epoxide group.

9. The article of claim 1, wherein the perfluoroalkylsiloxane comprising an electrophilic group comprises the reaction product between aT|H Docket: 222105-2260 ID: 2024-048-02 perfluorolkylsiloxane and a silane compound comprising at least one electrophilic group.

10. The article of claim 9, wherein the perfluoroalkylsiloxane has the formula R3-Si(OR2)3, wherein R2is a substituted or unsubstituted C1-C20alkyl group, and R3is a C1-C20perfluoroalkyl group.

11. The article of claim 10, wherein R2is a C1to C4alkyl group.

12. The article of claim 10, wherein R3is a C1to C10perfluoroalkyl group.

13. The article of claim 10, wherein each R2is methyl or ethyl, and R3is a C8perfluoroalkyl group.

14. The article of claim 9, wherein the silane compound comprising at least one epoxide group comprises a glycidyl silane compound.

15. The article of claim 9, wherein the silane compound comprising at least one epoxide group is a compound having the structure IIwherein an group, group, or aryloxy group, Y is O or S; n is an integer from 1 to 10; and m is an integer from 1 to 10.

16. The article of claim 15, wherein n is 3 and m is 1.

17. The article of claim 15, wherein n is 3, m is 1, and Y is O.

18. The article of claim 15, wherein n is 3, m is 1, Y is O, and each R4is a C1 to C5 alkoxy group.

19. The article of claim 9, wherein the reaction product between the perfluoroalkylsiloxane and the silane compound comprising at least one electrophilic group is performed in the absence of a solvent.

20. The article of claim 9, wherein the molar ratio of the perfluoroalkylsiloxane to the silane compound comprising at least one electrophilic group is from about 1:1 to about 1:

3.

21. The article of claim 1, wherein prior to step (a), the at least one surface of the article is cleaned to remove substantially all impurities.T|H Docket: 222105-2260 ID: 2024-048-02 22. The article of claim 1, wherein prior to step (a), the at least one surface of the article is contacted with an acid or base.

23. An article comprising a perfluorolkylsiloxane covalently bonded to at least one surface of the article, wherein the article has at least one structural unit comprising the structure III wherein Surface is the A is a residue of anB is a residue of a silane compound comprising at least one epoxide group; and C is a residue of a perfluorolkylsiloxane.

24. The article of claim 23, wherein A is wherein each R1is cycloalkoxy group, oraryloxy group, and o is an integer from 1 to 10.

25. The article of claim 23, wherein B is wherein each R4is independently an alkoxy group, cycloalkoxy group, or aryloxy group, wherein at least one of R4is a residue of the perfluorolkylsiloxane; Y is O or S; n is an integer from 1 to 10; and m is an integer from 1 to 10.

26. The article of any one of claims 1-25, wherein the article comprises glass, a polymer, or a metal.T|H Docket: 222105-2260 ID: 2024-048-02 27. The article of claim 26, wherein the metal is aluminum or stainless steel.

28. The article of any one of claims 1-25, wherein the surface comprising the perfluorolkylsiloxane has a sliding angle of less than 20.0 degrees for water or an organic solvent.

29. The article of claim 28, wherein the organic solvent comprises diiodomethane, ethylene glycol, DMSO, DMF, hexadecane, or ethanol.

30. The article of any one of claims 1-25, wherein the surface comprising the perfluorolkylsiloxane is transparent.

31. The article of any one of claims 1-25, wherein the article comprises a polymeric grade material, a medical device, a surface or article in a hospital or medical facility, a surface in an automobile, boat, or aircraft, or an electronic display screen.

32. The article of any one of claims 1-25, wherein the article prevents the growth of microbes on the article.

33. The article of any one of claims 1-25, wherein the article prevents the adhesion of fibrinogen on the article.

34. The article of any one of claims 1-25, wherein the article prevents the adhesion of platelets on the article.

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