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WO2025094171A1 - Revêtement superhydrophobe - Google Patents

Revêtement superhydrophobe Download PDF

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Publication number
WO2025094171A1
WO2025094171A1 PCT/IL2024/051000 IL2024051000W WO2025094171A1 WO 2025094171 A1 WO2025094171 A1 WO 2025094171A1 IL 2024051000 W IL2024051000 W IL 2024051000W WO 2025094171 A1 WO2025094171 A1 WO 2025094171A1
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Prior art keywords
phe
film
material according
phenylalanine
nanoparticle
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Inventor
Meital Reches
Pooi See Lee
Tan HU
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Yissum Research Development Co of Hebrew University of Jerusalem
Nanyang Technological University
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Yissum Research Development Co of Hebrew University of Jerusalem
Nanyang Technological University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the invention generally relates to fluorine-free superhydrophobic coatings fabricated by amino acids on a variety of surfaces, including soft electroadhesive surfaces.
  • Superhydrophobic coatings are defined as having a static water contact angle (WCA) higher than 150° and a sliding angle (SA) lower than 10°. These coatings have broad application prospects in anti-corrosion, self-cleaning, anti-fogging, drag-reduction, anti-icing, emulsion separation, and protection of electronic devices. These coatings are typically achieved through a precise synergistic combination of suitable surface morphology and low surface energy materials.
  • nanocomposite materials including fluoropolysiloxane and TiCh, FesC nanoparticles (NPs), melanin NPs, cellulose-based derivatives, stoichiometric silanization, fluorinated nanodiamonds, polytetrafluoroethylene, polystyrene@SiO2, and fluorinated SiCh NPs.
  • fluoropolysiloxane and TiCh FesC nanoparticles (NPs), melanin NPs, cellulose-based derivatives, stoichiometric silanization, fluorinated nanodiamonds, polytetrafluoroethylene, polystyrene@SiO2, and fluorinated SiCh NPs.
  • NPs FesC nanoparticles
  • melanin NPs melanin NPs
  • cellulose-based derivatives cellulose-based derivatives
  • stoichiometric silanization fluorinated nanodiamonds
  • silica-based (SiCh) superhydrophobic materials have been widely studied due to their abundance, cost-effectiveness, and ease of surface modification compared to other nanomaterials.
  • the silica-based superhydrophobic coatings made by nonfluorinated derivatives of silane still have several disadvantages that limit their practical applications, including coating stability (mechanical instability, durability issues, sensitivity to environmental conditions, and limited chemical resistance) and potential environmental and health concerns.
  • AEROSIL®E 972 SiO2-DDS
  • DDS dimethyldichlorosilane
  • Soft robotic grippers have attracted considerable attention due to their inherent compliance and adaptability, which allows them to handle flat, soft, fragile, and deformable objects.
  • various types of soft grippers have been designed and developed, including soft bending grippers using pneumatic actuation, dielectric elastomer actuators (DEAs), jamming grippers, suction cup grippers, gecko-adhesion grippers, and electroadhesive (EA) grippers.
  • DEAs dielectric elastomer actuators
  • jamming grippers suction cup grippers
  • gecko-adhesion grippers gecko-adhesion grippers
  • electroadhesive (EA) grippers electroadhesive
  • Soft EA grippers have been utilized in robotic prototypes for anti-gravity locomotion, aerial perching, and fragile object handling.
  • Soft EA devices consist of an insulating dielectric layer and a pair of electrodes, which are critical components. Intensive studies have focused on developing soft electrodes (i.e., ionic organohydrogel) and dielectric elastomers (i.e., polydimethylsiloxane (PDMS) and polyurethane) with favorable material properties and processibility to create desirable EA devices.
  • soft electrodes i.e., ionic organohydrogel
  • dielectric elastomers i.e., polydimethylsiloxane (PDMS) and polyurethane
  • PDMS polydimethylsiloxane
  • polyurethane polyurethane
  • SiO 2 nanoparticles (NPs) associated to -Phe-Cbz were used to fabricate a superhydrophobic coating on soft electroadhesive (EA) grippers.
  • EA soft electroadhesive
  • the coated grippers showed rapid release and the ability to grasp various objects including wet objects and irregular objects.
  • a fluorine-free SiO2(np)-O- propylene-NH-Phe-Cbz coating was formed on a PDMS substrate, a water contact angle (WCA) of ⁇ 161° and a sliding angle (SA) of ⁇ 1° were measured, attesting to the superhydrophobic nature of the coating.
  • the exhibited superhydrophobic behavior is attributed to the presence of short peptides that are hydrophobic in nature and which can assemble or be assembled into a continuous and compact film that does not degrade or deteriorate upon prolonged exposures to water, humidity or generally wet environments.
  • the presence of aromatic functionalities along the film not only increases the hydrophobic behavior but also enables 7t-7t interactions along the film.
  • the use of nanoparticles to anchor and orient the short peptides increases protection of the surface on which the film is formed, increases the stability of the film and greatly contributes to the overall prolonged and robust superhydrophobic properties.
  • superhydrophobic properties may be achievable by forming thin films or coatings of short peptide-functionalized nanoparticles that comprise hydrophobic aromatic functionalities.
  • the invention concerns peptide-conjugated nanoparticles for forming superhydrophobic films on surfaces or substrates of a variety of composites and surface properties. More specifically, the invention concerns a nanoparticle-based material for forming superhydrophobic films or coatings, the material comprising a nanoparticle associating one or more short peptides, each of the one or more peptides comprising between 1 and 10 amino acids.
  • the short peptides comprise a hydrophobic aromatic amino acid and a hydrophobic amino acid or a hydrophobic functionality. Where the peptide comprises a single amino acid, this amino acid may be selected amongst hydrophobic aromatic amino acids.
  • the single hydrophobic aromatic amino acid may be associated or chemically bonded to a hydrophobic functionality that may or may not be aromatic.
  • the conjugation or association of the peptide to the nanoparticle surface may be direct or via a linker moiety.
  • the actual association to the nanoparticle surface may be by covalent or non-covalent bonding, e.g., ionic, electrostatic, metallic or by way of a complex.
  • the association to the nanoparticle surface is via covalent bonding. In other cases, the association is not covalent.
  • peptide refers to a chemical group that comprises between 1 and 10 amino acids and additional functionalities that are not amino acids.
  • the term encompasses any functional sequence of atoms, as described herein, provided that it comprises an amino acid, as known in the art and defined herein.
  • the invention concerns a nanoparticle-based material for forming superhydrophobic films or coating, the material being peptide-conjugated nanoparticles, wherein the peptide comprises between 1 and 10 amino acids, one or more of said amino acids being selected from hydrophobic aromatic amino acid; and wherein the peptide comprises one or more hydrophobic amino acid or a hydrophobic functionality.
  • the invention further concerns a nanoparticle-based material for forming superhydrophobic films or coatings, the material being of the formula NP-[P]n, wherein NP designates a nanoparticle, [P] designates a short peptide of between 1 and 10 amino acids, and n designates a number of the short peptides [P] surface-associated to the nanoparticle surface, wherein [P] is of formula -L-[AA]-X, wherein L may be absent or is a linker moiety, [AA] designates one or a plurality of hydrophobic aromatic amino acids associated to each other through peptide bonds, each ” - “ designates a chemical bond, being covalent or non-covalent, and X designates one or more hydrophobic amino acids bonded in sequence or a capping hydrophobic functionality.
  • each of designates a covalent bond.
  • n is one or more.
  • X is not an amino acid.
  • the hydrophobic functionality comprises an aromatic group (i.e., an aryl group), as defined herein.
  • the invention also provides a nanoparticle-based material of the form NP-[L- [AA]-X]n, wherein NP designates a nanoparticle, L may be absent or is a linker moiety, [AA] designates one or a plurality of hydrophobic aromatic amino acids, X designates one or more hydrophobic amino acid or hydrophobic functionalities, each of designates a chemical bond, e.g., a covalent bond, and n designates a number of -L-[AA]- X groups that are surface-associated to the NP surface, wherein the L-[AA]-X group comprises between 2 and 10 amino acids in total.
  • the invention also provides a material of the formulaNP-[L-[AA]-X] n , as defined herein.
  • the invention further provides a superhydrophobic film comprising a nanoparticle-based material of a formula NP-[P]n, as defined herein.
  • the superhydrophobic film comprising or consisting a plurality of nanoparticlebased materials according to the invention, is formed on a surface region of any substrate.
  • the film may be formed by a bonding material, such as a polymeric material, that bonds or securely associates a plurality of the nanoparticle-based materials (as a homogeneous or heterogenous mixture of nanoparticle populations) to a surface region of a substrate, as further disclosed herein.
  • the superhydrophobic film comprises a heterogenous population or a mixture of two or more populations of nanoparticle-based materials, wherein each population differs in composition (as may be reflected in the amino acids present, the number of amino acids used, the different lengths of the peptide chains, etc).
  • the term superhydrophobic film or coating is one that exhibits a very low wettability for water and other polar liquids.
  • the hydrophobic nature may be reflected in a film or a coating having a static water contact angle (WCA) higher than 150° and a sliding angle (SA) lower than 10°.
  • WCA static water contact angle
  • SA sliding angle
  • Both the WCA and SA may be measured following formation of the film or coating on a substrate or a surface by means known in the art.
  • the static contact angle may be measured at a three-phase boundary (a boundary intersection of a liquid— a water droplet, gas— air, and solid — the surface) of a droplet of water placed on the film or coating formed.
  • a sliding angle measurement determines the angle at which a droplet of water placed on the film or coating begins to slide off once the surface is tilted.
  • the sliding angle may be determined by the Inclined Plane Method, by the Tilting Plate Method, by the Rotational Method, by an Automated Optical Method or by any other method known in the art.
  • hydrophobic used in reference to certain amino acids or groups making up a material of the invention, refers to such that tend not to dissolve or interact with polar solvents, especially water, or which do not tend to be wetted by water.
  • the hydrophobic amino acids or hydrophobic functionalities may contain saturated or unsaturated, linear, branched cyclic hydrocarbon, or aromatic-based groups.
  • the nanoparticle-based material of the invention used for generating a superhydrophobic film or coating, is a peptide which comprises between 1 and 10 amino acids and which is nanoparticle-bound.
  • the nanoparticle-based material thus comprises a nanoparticle that is surface associated with a one or a plurality (n number) of short peptide groups, being all same or different (a mixture of peptides), each of the formula - L-[AA]-X, as defined herein.
  • the number (n) of peptides bound to the surface of the nanoparticle is typically not controlled and may greatly vary between few to several dozens. Without limitation, n represents at least one peptide or between 1 and 200 or more, depending inter alia on the size of the nanoparticles.
  • the actual number of the peptides bound to the nanoparticles is of no effect on the superhydrophobicity of a film formed therefrom.
  • n is 1. In other embodiments, n is between 5 and 200. In some embodiments, n is greater than several hundred. In some embodiments, n is statistically random and may vary between nanoparticles.
  • all functionalities and amino acids making up the peptides of the form -L-[AA]-X are free of fluorine and chlorine atoms, and are selected amongst hydrophobic amino acids and hydrophobic groups.
  • the nanoparticles are similarly free of such atoms and are further free of heavy metals.
  • the nanoparticles carrying the peptide [P], as defined herein, are selected of materials that are water-insoluble and which do not undergo dissolution or degradation in presence of water or organic solvents. Typically, the nanoparticles are between 1 and 900 nm in size or diameter.
  • the nanoparticles may be spherical, spheroid, oval, elongated, or of any shape and may be of a material selected amongst organic, inorganic, metallic, metal oxide, ceramic, glass, and others.
  • the nanoparticles utilized are between 1 and 500 nm in size, or between 10 and 500 nm in size, or between 30 and 550 nm in size, or between 50 and 500 nm in size, or between 50 and 400nm, or between 50 and 300nm, or between 50 and 300nm, or between 50 and lOOnm, or between 100 and 400nm, or between 100 and 300nm, or between 100 and 200nm in size.
  • Metallic nanoparticles may be purely made of metals and can be monometallic, bimetallic, or polymetallic. Bimetallic nanoparticles may be made from alloys or formed in core/shell forms.
  • Non-limiting examples of metallic nanoparticles include nanoparticles of Ag, Au, Al, Fe, Co, Ni and alloys thereof.
  • Metal oxide nanoparticles may include SiO 2 , AI2O3, CoFe2O4, FesCU, ZnO, TiCh, and others.
  • Ceramic nanoparticles may include clay, carbonates, carbides, phosphates, and oxides of metals and metalloids.
  • Organic nanoparticles may be formed of carbon dots, graphite and various polymeric materials and combinations.
  • the nanoparticles are metallic nanoparticles, selected from Ag, Au, Al, Fe, Co, Ni and alloys thereof.
  • the nanoparticles are metal oxide nanoparticles, selected from SiO2, AI2O3, CoFe2O4, Fe3O4, ZnO, and TiO2.
  • the nanoparticles are SiO2.
  • the nanoparticles may or may not be surface-decorated with reactive or unreactive ligand molecules.
  • the nanoparticles may be surface decorated with reactive ligands.
  • the ligand groups may be surface exposed thiol groups, hydroxyl groups, amine groups, aldehyde groups, acid groups, carboxyl groups, carbonyl groups and others.
  • the peptide(s) [P] may be associated to the nanoparticles’ surface through the reactive ligands.
  • the peptide(s) may be directly associated to the nanoparticles’ surface.
  • the surface thereof may be free of ligand molecules.
  • the nanoparticles are oxide particles, such as SiO 2
  • the nanoparticles surface may comprise functional ligand groups such as surface exposed hydroxyl groups.
  • a material of the form NP-[L-[AA]-X]n may or may not comprise a linker group L through which the group AA associates to the nanoparticles surface.
  • L is absent and the material is of the form NP-[AA]-X] n .
  • the group AA may be associated to the nanoparticle surface through ligands present on the nanoparticle surface.
  • group L may be a homo-bifunctional or hetero-bifunctional linker moiety or an amino acid having a nanoparticle surface associating group and an amino acid associating group (permitting association to an amino acid of group [AA]).
  • the linker L may be a hydrophobic moiety having between 1 and 5 carbon atoms or 1 or 2 amino acids.
  • the nanoparticle-surface associating group depends on the nature and composition of the nanoparticle and/or the presence or absence of surface ligands or surface functionalities that may be present on the nanoparticles surface.
  • the surface associating group may be a thiol a disulfide, an amine, an alcohol and others.
  • the surface associating group may be an ester, an aldehyde, an acid, a silyl, and others.
  • the surface associating group may be a halide, a carboxylic acid, an aldehyde, and others.
  • the nanoparticle surface associating group may be generally selected from a thiol, a sulfide, a hydroxyl, a halide, a carboxylic acid, an aldehyde, an ester, an amine, a silyl and others.
  • R and R’ may be same or different and is typically selected from H or a -Ci-Csalkyl.
  • the amino acid associating group may be any such group reactive with a carboxyl group or an amine group of the amino acid.
  • Such groups may be an amine, a carboxylic acid, an ester, a hydroxy, a halide, a thiol, an aldehyde and others.
  • the bifunctional linker L may be a linear, branched or cyclic hydrocarbon or an aromatic group or a combination of same.
  • Non-limiting examples include a -Ci- Csalkylene, -C2-Csalkenylene, -C 2 -C 5 alkenylene, -C 1 -C 5 alkylene-C 6 -Cioarylene, -C 2 - Csalkenylene-C 6 -Cioarylene, -C2-C3alkynylene-C6-Cioarylene, -C 6 -Cioarylene, -C3- Ceheteroarylene (comprising between 1 and 3 heteroatoms such as N, O and S), and others.
  • -Ci-Csalkylene refers to a divalent moiety of alkyl, comprising 1, 2, 3, 4 or 5 carbon atoms, namely 1 to 5 -CH2- groups in a linear or branched sequence.
  • an alkylene group has 2 to 5 carbon atoms (C2-C6 alkylene).
  • Examples of -Ci-C4alkylene include methylene (Cl), ethylene (C2), propylene (C3) (e.g., n-propyl, isopropyl), butylene (C4) (e.g., n-butyl, tert-butyl, sec-butyl, isobutyl), and pentylene (C5) (e.g., n-pentyl, 3-pentanyl, amyl, neopentyl, 3-methyl-2- butanyl, tert-amyl).
  • each instance of an alkylene group is independently unsubstituted or substituted with one or more substituents (e.g., not including Cl and F).
  • the linker is a -C 1 -C 5 alkylene, being in some embodiments propylene.
  • alkenylene n refers to a divalent alkenyl, comprising 2, 3, 4, or 5 carbon atoms and 1 or 2 double bonds.
  • an alkenylene group has 3 to 5 carbon atoms (Cs-Csalkenylene).
  • C2-C5alkenylene groups include ethenylene (C2), 1 -propenylene (C3), 2-propenylene (C3), 1-butenylene (C4), 2- butenylene (C4), butadienylene (C4), and the like.
  • C 2 -C 5 alkenylene n refers to a divalent alkynylene, comprising 2, 3, 4, or 5 carbon atoms and 1 or 2 triple bonds.
  • an alkynylene group has 3 to 5 carbon atoms (C 3 -C 5 alkynylene).
  • Examples of C 2 -C 5 alkynylene groups include, without limitation, ethynylene (C 2 ), 1-propynylene (C 3 ), 2- propynylene (C3), 1- butynylene (C4), 2-butynylene (C4), and the like.
  • -C 1 -C 3 alkenylene-C 6 -C 10 arylene refers to an alkylene comprising 1 to 3 carbon atoms, as defined herein, that is bonded to an aryelene group comprising 6 to 10 carbon atoms.
  • Aryelene is a divalent moiety of aryl, a monocyclic or polycyclic aromatic ring or ring system.
  • the arylene may be phenylene, 1 -naphthylene or 2-naphthylene.
  • Examples of -C 1 -C 5 alkylene-C 6 -Cioarylene include benzyl, phenylethylene, and others.
  • -C 6 -C 10 arylene refers to an arylene, as defined herein, comprising 6 to 10 carbon atoms.
  • heteroarylene refers to a divalent heteroaryl comprising between 1 and 3 heteroatoms such as N, O and S, and between 4 and 7 carbon atoms.
  • the heteroarylene is a 5-10 membered monocyclic or polycyclic aromatic ring system.
  • heteroarylene groups include indolylene, quinolinylene, carbazolylene, and the like.
  • the nanoparticle-based material is of a formula selected from
  • NP-O-L-S-[AA]-X and others, wherein each of NP, [AA], L and X is as defined herein, and wherein Si is a silicone atom, N is a nitrogen atom or a nitrogen-containing group (such as NH, or NR, wherein R is as defined herein), O is an oxygen atom, S is a sulfur atom, S-S is a disulfide group.
  • an atom directly associating the NP to the linker moiety L, or amino acid AA may be an atom of the NP or may be part of the linker L or the amino acid AA.
  • the O atom may be an atom of a hydroxylated SiO 2 nanopartcile.
  • group L is -C 1 -C 5 alkylene, namely any alkylene comprising 1 to 5 carbon atoms (inclusive). These include methylene, ethylene, propylene, iso-propylene, butylene, iso-butylene, tert-butylene, pentylene, tert-pentylene, neopentylene, and iso-pentylene.
  • group L is a -C 1 -C 5 alkylene or a -Cs-Csalkylene.
  • group L is a -C 1 -C 5 alkylene, e.g., methylene, ethylene, propylene, or iso-propylene.
  • group L is propylene
  • the nanoparticle-based material is of a formula selected from
  • NP-N-CH 2 -CH 2 -CH 2 -O-[AA]-X and others, wherein each of NP, [AA], and X is as defined herein, and wherein Si is a silicone atom, N is a nitrogen atom or a nitrogen-containing group (e.g., NH), O is an oxygen atom, S is a sulfur atom, S-S is a disulfide group.
  • Si is a silicone atom
  • N is a nitrogen atom or a nitrogen-containing group (e.g., NH)
  • O is an oxygen atom
  • S is a sulfur atom
  • S-S is a disulfide group.
  • the nanoparticle-based material is of a formula selected from
  • NP-NH-CH 2 -CH 2 -CH 2 -O-[AA]-X and others, wherein each of NP, [AA], and X is as defined herein.
  • the nanoparticle-based material is of a formula selected from
  • NP-NH-CH 2 -CH 2 -CH 2 -O-[AA]-X wherein each of NP, [AA], and X is as defined herein.
  • Group AA designates a hydrophobic aromatic amino acid or a sequence of such amino acids.
  • the group [AA] may thus comprise a single hydrophobic aromatic amino acid or between 2 and 5 such amino acids.
  • a hydrophobic aromatic amino acid is an aromatic amino acid having a low water solubility.
  • Such hydrophobic aromatic amino acids include phenylalanine (Phe), phenylalanine derivatives and tryptophan (Trp).
  • the AA is or includes between 2 and 5 phenylalanine (Phe) groups, phenylalanine derivatives and/or tryptophan (Trp) groups.
  • AA comprises or consists a single phenylalanine (Phe), a single phenylalanine derivative or a single tryptophan (Trp).
  • AA comprises or consists between 1 and 5 phenylalanine (Phe) amino acids, between 1 and 5 phenylalanine derivatives or between 1 and 5 tryptophan (Trp) amino acids.
  • the phenylalanine derivative may be selected from 4-methoxy-phenylalanine, 4- carbamimidoyl-l-phenylalanine, 3 -cyano-phenylalanine, 4-bromo-phenylalanine, 4- cyano-phenylalanine, 4-hydroxymethyl-phenylalanine, 4-methyl-phenylalanine, 1- naphthyl-alanine, 3-(9-anthryl)-alanine, 3-methyl-phenylalanine, m-amidinophenyl-3- alanine, phenylserine, benzylcysteine, 4,4- biphenylalanine, 2-cyano-phenylalanine, 3,4- dihydroxy-phenylalanine, 3, 5 -dibromot
  • AA is Phe or a phenylalanine derivative.
  • the nanoparticle-based material is NP-L-Phe-X.
  • L is a -C 1 -C 5 alkylene, e.g., methylene, ethylene, propylene, or isopropylene.
  • group L is n-propylene.
  • the nanoparticle-based material is of a formula selected from
  • NP-O-CH 2 -CH 2 -CH 2 -NH-Phe-X NP-NH-CH 2 -CH 2 -CH 2 -NH-Phe-X, NP-Si-CH 2 -CH 2 -CH 2 -NH-Phe-X, NP-S-CH 2 -CH 2 -CH 2 -NH-Phe-X, NP-S-S-CH 2 -CH 2 -CH 2 -NH-Phe-X, NP-O-CH 2 -CH 2 -CH 2 -CH 2 -O-Phe-X, NP-O-CH 2 -CH 2 -CH 2 -S-Phe-X, NP-NH-CH 2 -CH 2 -CH 2 -CH 2 -O-Phe-X, and others, wherein each of NP and X is as defined herein.
  • the nanoparticle-based material is of a formula selected from
  • Group X designates one or more hydrophobic amino acids bonded in sequence or may be a capping hydrophobic functionality.
  • X is a hydrophobic amino acid, or a sequence of hydrophobic amino acids comprising between 2 and 5 hydrophobic amino acids.
  • the hydrophobic amino acids may be selected amongst hydrophobic aromatic amino acids, as defined herein.
  • X comprises between 1 and 5 hydrophobic amino acids.
  • the hydrophobic amino acids are selected from glycine (Gly), alanine (Ala), valine (Vai), leucine (Leu), isoleucine (He), proline (Pro), phenylalanine (Phe), methionine (Met), and tryptophan (Trp).
  • X designates a hydrophobic functionality, not an amino acid.
  • the hydrophobic functionality acting as a capping group or an end group may be selected from -C 1 -C 5 alkyl, -C 2 -C 5 alkenyl, -C 2 -C 5 alkynyl, -C 1 -C 5 alkylene-C 6 -Cioaryl, -Ci- C 3 alkyl-C 6 -C 10 arylene, -C 2 -C 5 alkenlene-C 6 -Cioaryl, -C 2 -C3alkynylene-C 6 -Cioaryl, -C 6 - Cioaryl, and others.
  • X may be phenyl, benzyl, naphthyl, ethylenephenyl, propylenephenyl, butylenephenyl, or pentylenephenyl.
  • X is benzyl
  • the hydrophobic amino acid or hydrophobic functionality may be associated with the hydrophobic aromatic amino acid via a peptide bond, where relevant, or any other bonding atom or group.
  • the atoms or groups of atoms include atoms such as N, O, S, and C, or groups containing same.
  • the hydrophobic amino acid AA is bonded to benzyloxycarbonyl (Cbz).
  • the nanoparticle-based material is NP-O-CH 2 -CH 2 -CH 2 - NH-Phe-Cbz.
  • Non-limiting examples of nanoparticle-based materials of the invention include: NP-0-(CH2)y-NH-[Phe] z -X, wherein NP is a nanoparticle as defined herein, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-S-(CH2)y-NH-[Phe] z -X wherein NP is a nanoparticle as defined herein, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-S-S-(CH2)y-NH-[Phe] z -X wherein NP is a nanoparticle as defined herein, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;.
  • NP-NH-(CH2)y-NH-[Phe] z -X wherein NP is a nanoparticle as defined herein, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-0-(CH2)y-NH-[Phe] z -X wherein NP is a metal oxide nanoparticle as defined herein, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-S-(CH2)y-NH-[Phe] z -X wherein NP is a metal oxide nanoparticle as defined herein, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-NH-(CH2)y-NH-[Phe] z -X wherein NP is a metal oxide nanoparticle as defined herein, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-0-(CH2)y-NH-[Phe] z -X wherein NP is a SiO 2 nanoparticle, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-S-(CH2)y-NH-[Phe] z -X wherein NP is a SiO 2 nanoparticle as defined herein, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-NH-(CH2)y-NH-[Phe] z -X wherein NP is a SiO 2 nanoparticle as defined herein, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • C 5 alkyleneC 6 -Cioaryl is as defined herein; Si02np-0-(CH2)3-NH-[Phe]2-C 1 -C 5 alkyleneC 6 -Cioaryl, wherein -Ci-
  • C 5 alkyleneC 6 -Cioaryl is as defined herein;
  • C 5 alkyleneC 6 -Cioaryl is as defined herein;
  • C 5 alkyleneC 6 -Cioaryl is as defined herein;
  • C 5 alkyleneC 6 -Cioaryl is as defined herein;
  • C 5 alkyleneC 6 -Cioaryl is as defined herein;
  • Nanoparticle-based materials of the invention may be produced by solid state synthesis or by solution- state synthesis. Without wishing to be bound by a particular fabrication process, the materials may be produced by surface modification of preformed nanoparticles.
  • Surface functionalization of the nanoparticles may involve a first step of functionalization using a homo- or a hetero-bifunctional linker L with the aim to add an atom or an organic functional group (R-NH2, R-COOH, etc.) useful in achieving binding of the peptide [P],
  • R-NH2, R-COOH, etc. an organic functional group useful in achieving binding of the peptide [P]
  • aminosilanes may be used that introduce an amino group on the nanoparticle surface for the next conjugation.
  • the surface of the silica nanoparticles may be modified to form surface- exposed hydroxyl groups that can be substituted.
  • Metals such as gold, can be functionalized by using crosslinkers with -SH or -NH2 groups able to react with the metal and to produce a covalent bond.
  • Nanoparticles formed of metal oxides can be easily modified by using a ligand exchange strategy based on the substitution of the original surfaces with functional groups such as diol, amine, carboxylic acid, and thiol useful for the next steps.
  • halogenation techniques it is possible to obtain active surface regions that can be further modified or functionalized.
  • covalent bond strategy can be implemented to attach the peptide(s) .
  • the covalent bonding of the peptide group(s) can be achieved using various linker molecules.
  • An example is a bifunctional linker, such as L, that can be provided with specific functional groups at the ends and used as a homo-bifunctional or a heterobifunctional linker to perform a wide range of functionalization processes. Thanks to the ability to directly associate the peptide [P] to the modified or functionalized nanoparticle surface, the linker L may be pre-conjugated to the peptide [P] .
  • TEM Transmission electron microscopy
  • SEM scanning electron microscopy
  • FTIR Fourier transform infrared spectroscopy
  • DLS dynamic light scattering
  • C,- potential analysis may be used to determine shape, size, chemical composition, and superficial charge of the nanoparticles, at any stage of the synthesis and to confirm final shape, size and chemical composition of the formed nanoparticles.
  • SiO 2 particles modified by the amino acid Cbz-Phe were synthesized by coupling of the amino acid onto functionalized silica NPs, as exemplified in Fig. 1A.
  • SiO 2 -OH particles were synthesized by hydrolysis of tetraethyl orthosilicate (TEOS).
  • TEOS tetraethyl orthosilicate
  • the formed -OH modified silica nanoparticles were then reacted with a linker material aminopropyltriethoxysilane (APTES) to produce surface conjugation with propylamine (being a linker L mediating the nanoparticle surface and the amino acid AA).
  • APTES aminopropyltriethoxysilane
  • the exposed -NH2 groups were than substituted with Phe-Cbz to generate the SiO2-O-propylene-NH-Phe-Cbz nanoparticles.
  • the invention further provides a method for making or synthesizing a nanoparticle-based material of the form NP-[P], wherein NP is a nanoparticle and P is a peptide, the method comprising exposing or treating a nanoparticle having a suitable surface exposed functionality to a peptide group having a reactive functionality capable of covalently associating with the surface exposed functionality.
  • the method comprising providing a population of nanoparticle having suitable surface exposed functionalities.
  • the method comprising functionalizing a surface of a nanoparticle to form thereon a plurality of suitable surface exposed functionalities.
  • the “suitable surface exposed functionality” is any such functionality that can form a covalent or a non-covalent bond with a reactive functionality of the peptide [P],
  • the suitable surface exposed functionality may be an inherent group of the nanoparticle, e.g., -OH, - NH2 and others, or may be specifically selected based on the peptide group to be conjugated. Both the suitable surface exposed functionality and the reactive functionality on the peptide [P] may vary and be selected as disclosed herein.
  • the peptide [P] comprises at least one hydrophobic aromatic amino acid and optionally comprises a linker group L.
  • the peptide [P] is of the structure -L-[AA]-X, wherein each of L, AA and X is as defined herein.
  • the method comprises obtaining a peptide [P], as defined herein.
  • the method comprises reacting the nanoparticle having suitable surface exposed functionalities with a bifunctional linker group L capable of associating to an amino acid, e.g., AA.
  • the method comprises:
  • the invention further a method for making or synthesizing a nanoparticle-based material of the form NP-L-[AA]-X, the method comprising exposing or treating a nanoparticle having a suitable surface exposed functionality to a bifunctional linker moiety L to associate the linker L to the surface exposed functionalities and form a compound of the form NP-L and reacting said compound with a peptide group of the form -AA-X to covalently associate with the linker L, thereby obtaining the material of the form NP-L-[AA]-X.
  • the invention further provides a solution or a medium comprising a nanoparticlebased material of the invention.
  • the solution or medium may be an organic liquid that can solubilize or carry (e.g., suspension or dispersion) the nanoparticle-based material in a homogenous form.
  • the organic liquid may be an aromatic liquid such as benzene, toluene and others; or non-aromatic liquids such as methanol, ethanol, isopropanol and others.
  • the solution or medium comprising the nanoparticle-based material is a polymeric solution or medium comprising the material and at least one polymer or pre-polymer or monomer or oligomer of a polymer, as further discussed hereinbelow.
  • Films and coatings may be formed on any surface or substrate which wetting property is to be modulated or rendered superhydrophobic. Such surfaces or substrates may be of unlimited compositions, shapes and surface roughness.
  • surface materials include metallic, polymeric, glass, ceramic, paper and other fibrous materials, hybrid materials, natural materials and others.
  • the surface is a metallic surface, formed of a single metal, an alloy of metals, metal oxides, conducting metals, semiconductors, etc.
  • Non-limiting examples of metallic surfaces include a gold surface, a silver surface, an aluminum surface, a titanium surface, a silica surface, an alumina surface, a copper surface, an iron surface, a steel surface, a stainless-steel surface, a bronze surface, a brass surface and others.
  • films and coating of the invention are continuous structures that fully or partially cover a surface region of a substrate.
  • the film or coating is continuous where superhydrophobic properties are to be endowed.
  • the film may be a continuous or non-continuous structure formed of the material of the invention and as defined herein, with a thickness that is substantially monolayer, yet could also be multilayered.
  • the film or coating may be on a full surface of the substrate or object (as a coating).
  • the film or coating may be formed by direct deposition of the nanoparticle-based material on a surface region of a substrate or may be formed by using an adhesive material or a bonding layer that can associate the nanoparticle-based material to the surface.
  • the bonding layer may be a thin continuous film of an adhesive having a thickness sufficient for bonding without completely encapsulated or engulfing the nanoparticle-based material.
  • the thickness of the bonding layer may be at most 50% of the size or diameter of the nanoparticle-based material.
  • the thickness of the bonding layer is 40%, 30%, 20% or 10% of the size of the nanoparticlebased material.
  • the bonding layer may be about 10 nm.
  • the bonding layer having a thickness of between 1 and 20 nm.
  • Superhydrophobic films and coating of the invention may be characterized by water contact angles (WCA) that are higher than 150° and/or sliding angles (SA) that are lower than 10°.
  • WCA water contact angles
  • SA sliding angles
  • films and coatings of the invention are characterized by a WCA that is between 150 and 200°, or between 150 and 190°, or between 150 and 180°, or between 150 and 170°, or between 150 and 160°, or between 160 and 200°, or between 160 and 190°, or between 160 and 180°.
  • the WCA is greater than 200°.
  • films and coting of the invention are characterized by a SA between 10 and 1°, or between 9 and 1°, or between 8 and 1°, or between 7 and 1°, or between 6 and 1°, or between 5 and 1°, or between 4 and 1°, or between 3 and 1°, or between 2 and 1°.
  • the WCA is below 1°.
  • films and coatings of the invention are characterized by a water contact angle (WCA) of about 161° and a sliding angle (SA) of about 1°
  • the polymers may be selected from homopolymers, copolymers, terpolymer, block copolymers and the like, or pre-polymer forms thereof that can easily generate the polymer (such pre-polymers may be monomers, oligomers etc.).
  • the polymer or pre-polymer may be a material that can be processed by any polymerization reaction, curing, sintering, light irradiation, or thermal or chemical treatments to transform the polymer or pre-polymer into a solid or a semisolid or a geltype bonding layer that holds the nanoparticle-based material in an exposed fashion to render the coated substrate superhydrophobic.
  • the processing protocols and conditions used may vary depending, inter alia, on the coating or object to be formed.
  • the polymers may be selected amongst such polymers that can be polymerized by reactions involving formation of radicals, cations, anions; reactions involving thermal or chemical curing; extrusion reactions and others.
  • the polymeric composition may include, in addition to the at least one polymer or pre-polymer thereof, a photo initiator or a crosslinking material, each as known in the art.
  • a photo initiator or a crosslinking material each as known in the art.
  • polymerization or curing is achievable thermally or under light irradiation, optionally in absence of a photo initiator or a crosslinking agent.
  • polymers may include polyolefins, olefin copolymers with polar monomers, poly acrylates and methacrylates, styrene polymers, polyesters, polyamides, polyimines, polycarbonates, natural polymers, cellulosic materials, polysaccharides, thermoplastic elastomers, polyvinyl alcohols, polynitriles, polyacetals, polyimides, polyarylketones, polyetherketones, polyhydroxyalkanoates, polycaprolactones, polyurethanes, polysulfones, polyphenylene oxides, polyphenylene sulfides, polyacetates, liquid crystal polymers, fluoropolymers, ionomeric polymers, thermoplastic elastomers, and blends thereof.
  • Additional specific non-limiting examples include carrageenan, alginates, polysaccharides, pectin, gelatin, agar, cellulose derivatives, polyacrylate derivatives, polyacrylamide polymers, Carbopol (polyacrylat), chitosan (Poly-D-Glucosamin), Dermacryl 79 (Carboxylates Acrylpolymer), ethylcellulose, Eudragit NE (ethyl acrylate methylmethacrylate copolymer), Eudragit RL-100 (polymethacrylate polymere), Eudragit RS-100 (polymethacrylate polymer), Eudragit L30D-55 (methacrylate- ethylacrylate-copolymer), hydroxypropyl-beta-cyclodextrin, hydroxypropylmethyl cellulose (HPMC), Klucel (Hydroxypropyl cellulose), Macrogol, methyl cellulose, poloxamer (polyethylenepolypropylene glyco
  • films and coatings of the invention are polymeric films formed directly on a surface region of a subject by depositing, by any of the methods mentioned hereinabove (e.g., spraying, wetting, printing etc), a polymeric composition or formulation or solution comprising the at least one polymer or prepolymer thereof, followed by deposition on the polymeric film, yet not cured or crosslinked, a composition or formulation containing the nanoparticle-based material of the invention.
  • a solid polymeric film or coating may be obtained by allowing the polymeric film to harden, cure or polymerize.
  • the invention further provides a method of forming a superhydrophobic film containing a polymer and a nanoparticle-based material of the invention, the method comprising forming a film of a polymer composition on a surface region of a substrate, followed by deposition thereon of a composition or formulation comprising the material of the invention and curing, crosslinking or hardening the film.
  • Each of the polymeric composition and the nanoparticle-based material may be formed into films by spray coating, dipping, brushing, deposition, printing or by any other method involving contacting of the surface or substrate with a solution or a medium containing a polymer, a pre-polymer, a monomer or an oligomer of the polymer and a material or a mixture of materials according to the invention.
  • the film or coating may be cured to provide a robust, undetachable and durable film or coating that can sustain mechanical disturbances (such as searching) and maintains superhydrophobic characteristics over time. Curing of the film or coating may be achievable by thermally treating the film under preselected conditions.
  • the “preselected conditions” include thermally treating the surface at a temperature below the melting temperature of the surface or substrate, or below a temperature at which the film may detach or degrade. Such conditions my include a temperature between 60 and 150 °C. In some embodiments, the temperature is between 60 and 140 °C, 60 and 130 °C, 60 and 120 °C, 60 and 110 °C, 60 and 100 °C, 60 and 90 °C, 60 and 80 °C, 80 and 150 °C, 90 and 150 °C, 100 and 150 °C, or between 110 and 150 °C. In some embodiments, the temperature is 70, 80, 90, 100 or 110 °C.
  • the invention further provides a device, an element or an object having at least one surface region coated with a film of a superhydrophobic material of the invention.
  • the film is formed directly on the surface region.
  • the film is formed in a bonding layer, e.g., polymeric layer.
  • the device, element or object may be selected from fabrics, windshields and glass surface, maritime facilities and maritime vehicles, aircraft wings and other external regions, robotic arms, surgical tools and appliances, medical equipment, implants, lenses, wood surfaces exposed to the elements, and others.
  • the superhydrophobic films or coatings may be formed on a surface region of any apparatus, device, unit, element or feature of a machine or an object.
  • the superhydrophobic film or coating may be formed on the surface region to modulate at the coated surface region the wetting property and optionally at least one surface property, including for example corrosion resistance and long-term chemical stability.
  • the superhydrophobic coatings may be used as anti-fog coating, anti-freeze surfaces, oil and water separation, anti-bacterial surfaces, and for medical applications due to the surface compatibility with living cells.
  • a non-limiting example of a use of superhydrophobic surface is in soft robotic grippers such as soft bending grippers using pneumatic actuation, dielectric elastomer actuators (DEAs), jamming grippers, suction cup grippers, gecko-adhesion grippers, and electroadhesive (EA) grippers.
  • soft robotic grippers such as soft bending grippers using pneumatic actuation, dielectric elastomer actuators (DEAs), jamming grippers, suction cup grippers, gecko-adhesion grippers, and electroadhesive (EA) grippers.
  • DEAs dielectric elastomer actuators
  • EA electroadhesive
  • the invention thus provides:
  • a nanoparticle-based material for use in forming a superhydrophobic film on a surface region of a substrate comprising a plurality of nanoparticles, each nanoparticle being surface-associated with at least one peptide having between 1 and 10 amino acids, wherein said amino acids comprising one or more hydrophobic aromatic amino acids, and wherein said at least one peptide comprising one or more hydrophobic amino acids or hydrophobic functionalities.
  • the material is of the formula NP-[P]n, wherein NP designates the nanoparticle, [P] designates the at least one peptide and n designates a number of the peptides [P] that are surface-associated to the nanoparticle surface, wherein [P] is of a formula -L-[AA]-X, wherein L is absent or is a linker moiety, [AA] designates one or a plurality of hydrophobic aromatic amino acids associated to each other through peptide bonds, each ” - “ designates a covalent bond or a non-covalent bond, and X designates one or more hydrophobic amino acids bonded in sequence or X is a hydrophobic functionality, wherein [P] comprises a total of between 2 and 10 amino acids.
  • the material is of formula NP-[L-[AA]-X]n, wherein NP designates the nanoparticle, L is absent or is a linker moiety, [AA] designates one or a plurality of hydrophobic aromatic amino acids, X designates one or more hydrophobic amino acids or one or more hydrophobic functionalities, each of designates a covalent bond, and n designates a number of L-
  • [AA]-X groups surface-associated to the NP.
  • the material is for forming the film directly on the surface region of the substrate.
  • the material is for forming the film on a bonding layer pre-formed on the surface region of the substrate.
  • the nanoparticles carrying the at least one peptide [P] are water-insoluble and do not undergo dissolution or degradation in presence of water or organic solvents.
  • the nanoparticles are between 1 and 900 nm in size or diameter.
  • the nanoparticles are metallic nanoparticles.
  • the nanoparticles are metal oxide nanoparticles
  • the nanoparticles are formed of a metal oxide selected from SiO 2 , AI2O3, CoFe2O4, FesCU, ZnO, and TiCh.
  • the nanoparticles are SiO 2 nanoparticles.
  • the SiO 2 nanoparticles are surface decorated with -OH groups.
  • linker L is absent.
  • linker L is a homobifunctional or hetero-bifunctional linker.
  • linker L is a hydrophobic moiety having between 1 and 5 carbon atoms or 1 or 2 amino acids.
  • the linker L is a linear, branched or cyclic hydrocarbon or an aromatic group or a combination of same. In some cases concerning any material of the invention, linker L is selected from -C 1 -C 5 alkylene, -C 2 -C 5 alkenylene, -C 2 -C 5 alkenylene, -C 1 -C 5 alkylene-C 6 -Cioarylene, - C2-C3alkenylene-C6-Cioarylene, -C2-C3alkynylene-C6-Cioarylene, -C 6 -Cioarylene, and - C3-Ceheteroarylene.
  • linker L is a -Ci- Csalkylene.
  • linker L is methylene, ethylene, propylene, butylene or pentylene.
  • linker L is propylene
  • the material having a formula selected from
  • NP-N-CH2-CH2-CH 2 -O-[AA]-X wherein each of NP, [AA], and X is as defined herein.
  • the hydrophobic aromatic amino acid is phenylalanine (Phe), a phenylalanine derivative and tryptophan (Trp).
  • AA is or comprises between 2 and 5 phenylalanine (Phe) groups, phenylalanine derivatives and/or tryptophan (Trp) groups.
  • AA comprises or consists between 1 and 5 phenylalanine (Phe) amino acids, between 1 and 5 phenylalanine derivatives or between 1 and 5 tryptophan (Trp) amino acids.
  • the phenylalanine derivative is selected from 4-methoxy-phenylalanine, 4-carbamimidoyl-l-phenylalanine, 3 -cyano- phenylalanine, 4-bromo-phenylalanine, 4-cyano-phenylalanine, 4- hydroxymethyl- phenylalanine, 4-methyl-phenylalanine, 1-naphthyl-alanine, 3-(9- anthryl)-alanine, 3-methyl-phenylalanine, m-amidinophenyl-3 -alanine, phenylserine, benzylcysteine, 4,4-biphenylalanine, 2-cyano-phenylalanine, 3,4-dihydroxy- phenylalanine, 3, 5 -dibromotyrosine, 3,3-diphenylalanine, 3-ethyl-phenylalanine, 4- amino-L-phenylalanine, homopheny
  • AA is Phe.
  • any material of the invention being selected from NP-O-CH2-CH2-CH 2 -NH-Phe-X, NP-NH-CH 2 -CH2-CH 2 -NH-Phe-X, NP-Si-CH2-CH2-CH 2 -NH-Phe-X, NP-S-CH2-CH2-CH2-CH 2 -NH-Phe-X, NP-S-S-CH2-CH2-CH 2 -NH-Phe-X, NP-O-CH2-CH2-CH2-CH 2 -O-Phe-X, NP-O-CH2-CH2-CH2-CH 2 -S-Phe-X, and NP-NH-CH2-CH2-CH2-CH 2 -O-Phe-X, wherein each of NP and X is as defined herein.
  • X is between 2 and 5 hydrophobic amino acids bonded in sequence or X is a capping hydrophobic functionality.
  • the hydrophobic amino acid is selected from glycine (Gly), alanine (Ala), valine (Vai), leucine (Leu), isoleucine (He), proline (Pro), phenylalanine (Phe), methionine (Met), and tryptophan (Trp).
  • X is different from a hydrophobic aromatic amino acid.
  • X is a hydrophobic functionality, different from an amino acid, and selected from -Ci-Csalkyl, -C2-Csalkenyl, -C2-Csalkynyl, -Ci-Cralkylene-C 6 -Cioaryl, -C2-C3alkenlene-C 6 -Cioaryl, -C2- Cralkynylene-C 6 -Cioaryl, -C 6 -Cioaryl.
  • X is selected from -Ci- Csalkyl, -Ci-Cralkylene-C 6 -Cioaryl, and -C 6 -Cioaryl.
  • X is selected from ethyl, propyl, butyl, pentyl, phenyl, benzyl, naphthyl, ethylenephenyl, propylenephenyl, butylenephenyl, and pentylenephenyl. In some cases concerning any material of the invention, X is phenyl, benzyl, naphthyl, ethylenephenyl, propylenephenyl, butylenephenyl, or pentylenephenyl.
  • X is benzyl
  • AA is bonded to benzyloxycarbonyl (Cbz).
  • the material is selected from:
  • NP-O-(CH2)y-NH-[Phe] z -X wherein NP is the nanoparticle, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-S-(CH2)y-NH-[Phe] z -X wherein NP is the nanoparticle, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-S-S-(CH2)y-NH-[Phe] z -X wherein NP is the nanoparticle, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-NH-(CH2)y-NH-[Phe] z -X wherein NP is the nanoparticle, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-O-(CH2)y-NH-[Phe] z -X wherein NP is a metal oxide nanoparticle, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-S-(CH2)y-NH-[Phe] z -X wherein NP is a SiO 2 nanoparticle, y is an integer between 1 and 5, z is an integer between 1 and 5, X is as defined herein;
  • NP-O-CH2-CH2-CH2-NH-Phe-X wherein NP and X is as defined herein;
  • NP-NH-CH2-CH2-CH2-NH-Phe-X wherein NP and X is as defined herein;
  • NP-S-CH2-CH2-CH2-NH-Phe-X wherein NP and X is as defined herein;
  • NP-O-CH2-CH2-CH2-O-Phe-X wherein NP and X is as defined herein;
  • NP-O-CH2-CH2-CH2-S-Phe-X wherein NP and X is as defined herein;
  • NP-NH-CH2-CH2-CH2-O-Phe-X wherein NP and X is as defined herein;
  • NP-O-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-NH-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-Si-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-S-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-S-S-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-O-CH2-CH2-CH2-O-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-O-CH2-CH2-CH2-S-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-NH-CH2-CH2-CH2-O-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-O-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-N-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-Si-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-S-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-S-S-CH2-CH2-CH2-NH-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-O-CH2-CH2-CH2-O-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-O-CH2-CH2-CH2-S-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-N-CH2-CH2-CH2-O-[AA]-X wherein NP, AA and X is as defined herein;
  • NP-O-L-NH-[AA]-X wherein NP, L, AA and X is as defined herein;
  • NP-N-L-NH-[AA]-X wherein NP, L, AA and X is as defined herein;
  • NP-Si-L-NH-[AA]-X wherein NP, L, AA and X is as defined herein;
  • NP-S-L-NH-[AA]-X wherein NP, L, AA and X is as defined herein;
  • NP-S-S-L-NH-[AA]-X wherein NP, L, AA and X is as defined herein;
  • NP-O-L-O-[AA]-X wherein NP, L, AA and X is as defined herein;
  • NP-O-L-S-[AA]-X wherein NP, L, AA and X is as defined herein;
  • SiO2np-O-(CH2)5-NH- [Phe]i-X wherein X is as defined herein; SiO2np-O-(CH2)3-NH- [Phe]2-X, wherein X is as defined herein;
  • a solution or a medium comprising a material according to the invention comprising an organic liquid solubilizing or carrying the material in a homogenous form.
  • the organic liquid is selected from benzene, toluene methanol, ethanol, and isopropanol.
  • a superhydrophobic film or coatings comprising or consisting a material according to the invention.
  • the film or coating is formed directly on a surface region of a substrate.
  • the film or coating is formed on a bonding or an adhesive film preformed on a surface region of a substrate.
  • the bonding or adhesive film is a curable or a crosslinkable film.
  • the bonding or adhesive film is formed on the surface region prior to deposition of a film of the material according to the invention.
  • the film or coating formed by a method comprising depositing a film of a material according to the invention on a thin film of a bonding or an adhesive material preformed on a surface region of a substrate to render said surface region superhydrophobic.
  • the film or coating is formed by a method comprising
  • said causing comprises thermal curing.
  • the film or coating formed on a surface region of a substrate selected from a metallic, polymeric, glass, ceramic, paper and other fibrous materials, hybrid materials, and natural materials.
  • the bonding or the adhesive film is a thin continuous film of a thickness of at most 50% of the nanoparticle NP size or diameter.
  • the bonding or the adhesive film comprises a polymer selected from homopolymers, copolymers, terpolymer, and block copolymers; or a pre-polymer.
  • the bonding or the adhesive film is formed of a material selected from polyolefins, olefin copolymers with polar monomers, poly acrylates and methacrylates, styrene polymers, polyesters, polyamides, polyimines, polycarbonates, natural polymers, cellulosic materials, polysaccharides, thermoplastic elastomers, polyvinyl alcohols, polynitriles, polyacetals, polyimides, polyarylketones, polyetherketones, polyhydroxyalkanoates, polycaprolactones, polyurethanes, polysulfones, polyphenylene oxides, polyphenylene sulfides, polyacetates, liquid crystal polymers, fluoropolymers, ionomeric polymers, thermoplastic elastomers, and blends thereof.
  • the bonding or the adhesive film is formed of a material selected from acrylonitrile butadiene styrene (ABS), polymethyl methacrylate (PMMA), cellulose acetate, cyclic olefin copolymer (COC), ethylene-vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), polytetrafluoroethylene (PTFE), ionomers, polyoxymethylene (POM or Acetal), polyacrylonitrile (PAN), polyamide 6, polyamide 6,6, polyamide-imide (PAI), polyaryletherketone (PAEK), polybutadiene (PBD), polybutylene (PB), polybutylene terephthalate (PBT), polycaprolactone (PCL), polychlorotrifluoroethylene (PCTFE), polyethylene terephthalate (PET), polycyclohexylene dimethylene terephthalate (PCT), polycarbonate (PC), polyhydroxybutyrene (ABS), polymethyl methacryl
  • the bonding or adhesive film is formed of a material selected from carrageenan, alginates, polysaccharides, pectin, gelatin, agar, cellulose derivatives, polyacrylate derivatives, polyacrylamide polymers, Carbopol (polyacrylate), chitosan (Poly-D-Glucosamin), Dermacryl 79 (Carboxylates Acrylpolymer), ethylcellulose, Eudragit NE (ethyl acrylate methylmethacrylate copolymer), Eudragit RL-100 (polymethacrylate polymere), Eudragit RS-100 (polymethacrylate polymer), Eudragit L30D-55 (methacrylate- ethylacrylate-copolymer), hydroxypropyl-beta-cyclodextrin, hydroxypropylmethyl cellulose (HPMC), Klucel (Hydroxypropyl cellulose), Macrogol,
  • the bonding or the adhesive film comprises or consists PDMS.
  • the bonding or the adhesive film is formed of a material selected from polyester (PES); polyethylene terephthalate (PET); polyethylene (PE); high-density polyethylene (HDPE); low-density polyethylene (LDPE); polypropylene (PP); polyvinyl chloride (PVC); polyvinylidene chloride (PVDC); polystyrene (PS); high impact polystyrene (HIPS); polyamides (PA); acrylonitrile butadiene styrene (ABS); polyethylene/acrylonitrile butadiene styrene (PE/ABS); polycarbonate (PC); polycarbonate/acrylonitrile butadiene styrene (PC/ ABS); polyurethane (PU); polylactic acid (PLA); polyimide; polyetherimide (PEI); polyetheretherketone (PEEK); phenol formaldehydes (PF); polymethyl methacrylate (PMMA).
  • PET polyethylene terephthalate
  • the film or coating formed on a surface region of a substrate comprising a bonding PDMS layer and a layer of a material according to the invention formed on the PDMS layer.
  • a method of forming a superhydrophobic film containing a polymer and a nanoparticle-based material according to the invention comprising forming a bonding film of a polymer on a surface region of a substrate, and depositing thereon the material.
  • the method comprising curing, crosslinking or hardening the bonding film with the deposited material.
  • the bonding film and the film of the material is formed by spray coating, dipping, brushing, deposition, or printing.
  • the bonding film and the material deposited thereon are cured at a temperature below the melting temperature of the surface or substrate, or below a temperature at which the bonding film detaches or degrades.
  • a device, an element or an object having at least one surface region coated with a superhydrophobic film according to the invention is provided.
  • the device, element or object being selected from fabrics, windshields and glass surface, maritime facilities and maritime vehicles, aircraft wings and other external regions, robotic arms, surgical tools and appliances, medical equipment, implants, lenses, and wood surfaces.
  • the device, element or object being soft robotic grippers.
  • the film is formed on a surface of a fabric, windshield, glass surface, maritime facility, maritime vehicle, aircraft wing, robotic arm, surgical tool, surgical appliance, medical equipment, implant, lenses, or wood surface.
  • the film formed on a soft robotic gripper In some cases concerning any film of the invention, the film formed on a soft robotic gripper.
  • the film having a water contact angle (WCA) of about 161° and a sliding angle (SA) of about 1°.
  • the film having a water contact angle (WCA) of about 161° and a sliding angle (SA) of about 1°.
  • Figs. 2A-C Photographs of the synthesized SiO 2 -OH, SiO 2 -NH 2 , and SiO 2 - Phe-Cbz NPs
  • B Full FT-IR spectrum for SiO 2 -OH, SiO 2 -NH 2 , and SiO 2 -Phe-Cbz NPs.
  • C XPS (N Is) analysis of SiO 2 -NH 2 .
  • Figs. 3A-H Characterization of the coating formed by the SiO 2 -Phe-Cbz NPs on a PDMS substrate.
  • A Schematic illustration of the fabrication process for SiO 2 -Phe-Cbz coating on PDMS substrates.
  • Figs. 4A-H Optimization of the coating formed by SiO2-Phe-Cbz on PDMS substrates.
  • A WCA and SA values of the coatings formed by the different ratios of PDMS and SiO2-Phe-Cbz NPs.
  • B Representative images of uncoated (left) and 100% SiO2-Phe-Cbz coated PDMS substrates (right). SEM images of coatings with different ratios of SiO 2 -Phe-Cbz NPs (C) 20%, (D) 40%, (E) 60%, (F) 100%, (G)150%, and (H) 200%, respectively.
  • Figs. 5A-J The mechanical, thermal, and physical stability and properties of the SiO 2 -Phe-Cbz coating.
  • A WCA and SA values for the coated PDMS substrates subjected to 10 cycles of abrasion tests.
  • B WCA and SA values for the coated PDMS after physical, chemical, and thermal, and light treatments.
  • C Photographs showing the water droplets on the superhydrophobic coating fabricated by SiO 2 -Phe-Cbz NPs at 0% and 100% strain, respectively.
  • D Stress-strain curve and
  • E Young’s modulus of uncoated and coated PDMS substrates.
  • F Cyclic curves representing the hysteresis loss of coated PDMS substrates for 10 cycles.
  • Figs. 6A-B Schematic diagram of (A) sand and (B) water impinging tests.
  • FIGs. 7A-H SEM images of the treated coated PDMS by (A) Sand impinging (120 g), (B) water drop impinging (10 L), (C) 0.1 M NaOH for 12 h, (D) 0.1 M HC1 for 12 h, (E) 1%SDS for 12 h, (F) heat (150 °C for 18 h), (G) UV for 10 min, and (H) near IR for 30 min.
  • Fig. 8 Cyclic curves representing the hysteresis loss of uncoated PDMS substrates for 10 cycles.
  • FIGs. 9A-G The performance of EA grippers with a superhydrophobic coating.
  • A Schematic illustration of the fabrication process of CNT parallel-plate electrodes (2 cm x 3 cm, gap: 1 mm) for EA grippers.
  • B Representative images showing coated EA patch picking up aluminum foil, filter paper, and silicon wafer (from left to right).
  • C Recorded release time of coated EA patch releasing aluminum foil, filter paper, and silicon wafer under different working voltages.
  • F Image of coated soft EA grippers fabricated by PDMS outer layers and CNT parallel-plate electrodes.
  • G Photographs showing the coated soft EA grippers picking up a titanium cube, a wood cube, a piece of tofu, a clove of garlic, and a chocolate ball (from left to right). The orange scale bar represents 2 cm.
  • FIGs. 10A-E Representative photographs of uncoated (left) and coated patch (right).
  • B The representative shear force curve of shear forces for aluminum foil.
  • C The representative normal force curve of shear forces for aluminum foil.
  • D The photograph showing the breakdown of the uncoated outer layer (400 pm) of the EA patch after contact with wet objects.
  • E The representative image of clean coated EA grippers after grasping those objects.
  • nanoparticle-based materials may be described as nanoparticles which are surface associated with a plurality of short peptides.
  • the short peptides are unique in having a surface anchoring or surface associating groups or functionality and a hydrophobic end group that endows, in combination with the amino acid(s) making up the peptide, superhydrophobic surface properties.
  • films formed of such peptide are superhydrophobic and additionally exhibit anti-fog and other properties.
  • the nanoparticle-based material of the invention is generally depicted as having a structure NP-L-[AA]-X, as defined herein. While a great number of materials of the aforementioned structure may render superhydrophobic properties.
  • An exemplary compound SiO2-O-propylene-NH-Phe-Cbz (referred to in short in the figures as SiO 2 - Phe-Cbz) is demonstrated herein. Results and discussion
  • SiO 2 -OH particles were synthesized by the hydrolysis of tetraethyl orthosilicate (TEOS) followed by a treatment using aminopropyltriethoxysilane (APTES) to produce free amine groups, SiO2-O-propylene-NH2.
  • TEOS tetraethyl orthosilicate
  • APTES aminopropyltriethoxysilane
  • SiO2-O-propylene-NH- Phe- Cbz NPs were then synthesized by conjugating SiO2-O-propylene-NH2 with Cbz-Phe.
  • FIG. 2C show the XPS spectra of the N (Is) region of SiO 2 -NH 2 and SiO 2 -Phe-Cbz, respectively.
  • No N (Is) signal could be detected for the SiO 2 -OH NPs.
  • the N (Is) peaks for SiO 2 -NH 2 at 399.14 eV and 400.88 eV were observed (Fig. 2C).
  • the peak at 399.14 eV indicated the presence of free NH2 groups, which originated from the Si end of the APTES reaction with the silanol groups of the SiO 2 via a condensation reaction. This is in accordance with a previous study that demonstrated that APTES-functionalized SiO 2 NPs exhibited a binding energy of 399.70 eV.
  • the SiO 2 -OH NPs had an average size of 85 ⁇ 5 nm, while SiO 2 -NH 2 and SiO 2 -Phe-Cbz NPs were with an average size of 95 ⁇ 5 nm and 100 ⁇ 6 nm, respectively. This result was consistent with the observation of the particle size distribution by DLS measurements. These findings also demonstrated the functionalization of APTES and Cbz-Phe, respectively, which agrees with the findings from the FT-IR and XPS analysis.
  • a spray coating method To generate a superhydrophobic coating on a PDMS substrate, we employed a spray coating method.
  • Commercial PDMS SYLGARD 184 was first sprayed on a PDMS substrate to serve as a bonding layer, facilitating the adhesion between the PDMS substrate and SiO 2 -Phe-Cbz NPs (Fig. 3A).
  • the values of WCA and SA are shown in Fig. 3B.
  • the bare PDMS and PDMS coated with the bonding layer exhibited WCAs values of 112° ⁇ 2° and 114° ⁇ 3°, respectively, indicating that the bonding layer did not significantly affect the wettability of the PDMS substrate.
  • the WCA of the PDMS coated with SiO 2 -OH NPs, SiO 2 -NH 2 , and SiO 2 -Phe-Cbz NPs was 137° ⁇ 3°, 143° ⁇ 2°, and 160° ⁇ 2°, respectively. According to the definition of superhydrophobicity, the SiO 2 -Phe- Cbz NPs coated PDMS had an adequate WCA (above 150°) and SA (less than 10°) confirming its superhydrophobic nature.
  • SiO2-Phe-Cbz NPs different weight percentage of SiO2-Phe-Cbz NPs were applied on the surface. This percentage was defined by the ratio of SiO2-Phe-Cbz NPs/PDMS utilized as a bonding layer (w/w, 0%, 20%, 60%, 100%, 150%, and 200%, respectively). Since the SiO 2 -Phe- Cbz NPs roughened the surface, the ratio of SiO 2 -Phe-Cbz NPs/PDMS bonding layer (w/w) affected the morphology of the surface, directly influencing the superhydrophobic properties. As shown in Fig.
  • the mechanical robustness, thermal stability, and chemical resistance are critical factors determining the long-term application of superhydrophobic coatings.
  • the WCA and SA were monitored after different abrasion cycles (Fig. 5A). Even after 10 abrasion cycles, the WCA and SA remained >150° and ⁇ 5°, respectively, indicating the sustained superhydrophobicity. Although partial loss of roughness might occur due to the physical force, the NPs-based coating exhibited remarkable mechanical robustness and stability, making it suitable for practical applications.
  • the coated surface showed a comparative maximum strain value (-147%) to the uncoated substrate (-155%) (Figs. 5D-G and Fig. 8).
  • the measured Young’s modulus of uncoated and coated PDMS was 1.29 ⁇ 0.10 MPa and 1.23 ⁇ 0.20 MPa, respectively, indicating no significant change in the mechanical properties (Fig. 5E).
  • LB lysogeny broth
  • the coated superhydrophobic PDMS was kept clean upon application of distilled water to wash the polluted surfaces, while the dirt was still attached on the uncoated surfaces.
  • the dirt can be easily removed by a stream of nitrogen gas, suggesting the self-cleaning properties of the superhydrophobic coating.
  • This feature broadens the potential application of the SiO 2 -Phe-Cbz-based coating.
  • EA grippers have been widely applied as soft grippers for soft robotics due to precise control of adhesive force, fast response, quiet operation, gentle/flexible handling, and low energy consumption when compared to other existing soft gripper systems.
  • Current EA grippers still face limitations such as the inherent tackiness of the dielectric elastomer outer layer, slow release after voltage cutoff, and susceptibility to dielectric breakdown when handling wet objects.
  • Fig. 9 illustrates the fabrication of flexible EA electrodes by depositing a dispersion of carbon nanotube (CNT) on a parallelplate mask with a gap of 1mm between the electrodes.
  • CNT carbon nanotube
  • Electrodes were then transferred onto a 100 pm thick PDMS substrate and encapsulated with another 400 pm thick PDMS outer layer.
  • the PDMS substrate was coated with SiO 2 -Phe-Cbz NPs as described earlier to create a superhydrophobic coating (Fig. 10).
  • the coated EA patch was tested for adhesion capabilities with various objects. As depicted in Fig. 9B, both uncoated and coated EA patches successfully picked up aluminum foil (1 kV), filter paper (0.5 kV), and a silicon wafer (2 kV) under low voltage output ( ⁇ 2 kV). It has been reported that the electrostatic adhesion mechanism on conductors and dielectric materials was different.
  • the release ( ⁇ 1 s) of our superhydrophobic EA patches was faster than that of EA patches in previous studies in Table 1. Further analysis of shear and normal pressure using a standardized testing method according to our previous work. As shown in Figs. 9D-E and Figs. 10B- C, the coated EA patch can generate a high shear pressure (>1 kPa) for aluminum foil, filter paper, and silicon wafer under 3 kV, showing shear pressures with a magnitude equal to that in previous studies.
  • the coated EA patch measured higher normal pressure with increasing voltage input and manifested a stronger effect on conductors (aluminum, 0.7 kPa under 2 kV) than dielectrics (glass, 0.5 kPa under 2 kV, Fig. 10E). This can be attributed to the different electrostatic adhesion mechanisms.
  • Table 1 Comparison of release time of EA patch for handling objects after a voltage cutoff.
  • the fluorine-free amino acid NPs (SiO 2 -Phe-Cbz) were non-toxic (Fig. IB) and thus the SiO 2 -Phe-Cbz coating was suitable to be utilized in handling agricultural and food products.
  • Fig. 10F EA patches as soft grippers
  • obj ects such as a titanium cube, a wood cube, a piece of tofu, a clove of garlic, and a chocolate ball.
  • the coated EA gripper rapidly grasped and released various dry and wet objects under different voltage inputs, extending the practical utility of EA grippers.
  • the uncoated outer layer was easily broken down when in contact with the wet objects (tofu), indicating the limitation for the uncoated EA grippers picking up wet objects (Fig. 10D).
  • the coated flexible EA grippers could also quickly handle irregular objects (garlic) and round objects (chocolate ball) within 1 s.
  • the coated EA grippers kept clean after handling objects due to the selfcleaning properties of the superhydrophobic coating (Fig. 10E).
  • SiO 2 -NH 2 was obtained through centrifugation (10000 rpm, 10 min) followed by washing with ethanol for at least 3 cycles, and then dried for 12 h in a vacuum oven at 60 °C.
  • the synthesized SiO 2 -NH 2 NPs 5 mM described above were dispersed in DMF solvent.
  • FT-IR spectra were recorded using a Nicolet 6700 FT-IR spectrometer with a deuterated triglycine sulfate (DTGS) detector (Thermo Fisher Scientific, MA, USA) at a 4 cm' 1 resolution and averaged after 2000 scans.
  • DTGS deuterated triglycine sulfate
  • XPS X-ray photoelectron spectroscopy
  • the particle size distribution 0.5 mg/mL of SiO 2 -OH, SiO 2 -NH 2 , and SiO 2 -Phe-Cbz solution was dispersed into absolute ethanol and the size distribution was performed by a Malvern dynamic light scattering (DLS) instrument (Zetasizer Nano ZSZEN3600).
  • DLS Malvern dynamic light scattering
  • Cell cytotoxicity was measured using a human ovarian A2780 cell line by the 3- (4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. Briefly, Cells (0.6 x 10 6 ) in medium (containing 88% RPMI-1640, 10% fetal bovine serum, 1% L-glutamine, and 1% penicillin-streptomycin) were seeded in a 96-well plate in medium and allowed to attach for one day. The cells were subsequently administered with synthesized nanoparticles tested at 10 different concentrations (from 0 to 50 pg/mL).
  • MTT 5mg/mL was added, and the cells were incubated for an additional 3 h. Thereafter, the MTT solution was removed, and 200 pL of isopropanol was added. The absorbance at 550 nm was measured by a Spark 10 M Multimode Microplate Reader spectrophotometer (Tecan Group Ltd.). Each measurement was repeated 3 ⁇ 3 times, namely, three repeats per plate, all repeated 3 times on different days.
  • the SiO 2 -Phe-Cbz-based coating was prepared as depicted in Fig. 3A. Initially, a PDMS substrate (1 cm x 1cm) was washed with ethanol 3 times and dried by nitrogen. A mixture of 0.3 g PDMS and 0.3 g curing agent was dissolved in 25 mL toluene and then continuously stirred for 60 min. The mixture was sprayed onto a horizontally placed PDMS substrate using an airbrush (nozzle diameter: 0.5 mm) with 0.4 MPa air.
  • WCA Water contact angle
  • SA sliding angle
  • WCA was measured by a video optical contact system (OCA 20, Data Physics, Germany) using a sessile drop with a drop volume of 8 pL.
  • SA was measured by placing a drop of 8 pL ultrapure water (18.2 MQ cm) and then slowly rotating until the drop started to move. The corresponding angle was measured on a scale with a precision of about 0.5° and the angle from which the droplet started to move is referred to as the “SA”. Each experimental measurement was repeated five times, and the reported angles were averaged. Characterization and stability of SiOi-Phe-Cbz superhydrophobic coating
  • the superhydrophobic coating was evaluated by SEM and Atomic Force Microscope (AFM).
  • the SEM and AFM images were recorded by a JEOL field emission scanning electron microscope (JSM-7600F) and AFM (AFM Park Systems NX10), respectively.
  • JSM-7600F JEOL field emission scanning electron microscope
  • AFM AFM Park Systems NX10
  • For coating stability a standard abrasion test was performed to study the mechanical properties of the coating. The coating was brought into contact with a sandpaper (1400 mesh), Under the horizontal push of an external force, the coatings moved slowly back and forth along a ruler under a load of 200 g for 20 cm, which was defined as one cycle. WCA and SA values were recorded during 10 cycles.
  • the sand (120 g, 30-40 mesh) and water (10 L, 20 min) impinging tests were also evaluated by releasing drops of sand and water from a height of 50 cm to impact the surface of the sample inclined at 45° according to a previous study by Guo et al. with the same modification. Then, the wetting properties of the surface were evaluated.
  • the chemical stability immersing the coating into 0.1 M NaOH, 0.1 M HC1, and 1% SDS for 12 h), thermal stability (150 °C for 18 h), and sensitivity to radiation (UV light (340 nm) for 10 min and near IR for 30 min) were also evaluated.
  • the EA patch consisted of interdigital electrodes and two PDMS-based outer layers.
  • 20 mg CNT powder and 60 mg triton X-100 were added into 150 mL distilled water and then sonicated for 30 min to obtain a uniform CNT solution.
  • CNT solution was then disposed of onto a parallel-plate mask (the gap was 1mm).
  • the dried CNT electrode film was transferred onto a PDMS layer (100 pm) and then another outer layer (400 pm) encapsulated the electrodes.
  • SiO 2 -Phe-Cbz NPs were sprayed coated on the PDMS layer (100 pm) to generate the superhydrophobicity.

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Abstract

L'invention a pour objet des revêtements superhydrophobes exempts de fluor et faits de nanoparticules liées par acides aminés.
PCT/IL2024/051000 2023-11-02 2024-10-14 Revêtement superhydrophobe Pending WO2025094171A1 (fr)

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Citations (5)

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WO2006055531A2 (fr) * 2004-11-16 2006-05-26 Northwestern University Polymeres peptidomimetiques pour surfaces antisalissure
US20100143250A1 (en) * 2007-03-28 2010-06-10 Marc Port Compounds for the diagnosis of apoptosis
US20180079912A1 (en) * 2013-01-31 2018-03-22 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd Antifouling materials
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LEE DAEDU ET AL: "Adsorption of dipeptide L-alanyl-L-tryptophan on gold colloidal nanoparticles studied by surface-enhanced Raman spectroscopy", SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, ELSEVIER, AMSTERDAM, NL, vol. 247, 10 October 2020 (2020-10-10), XP086399832, ISSN: 1386-1425, [retrieved on 20201010], DOI: 10.1016/J.SAA.2020.119064 *
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