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WO2018189588A1 - Microcapsules contenant des nanoparticules métalliques, leurs procédés de fabrication et utilisations - Google Patents

Microcapsules contenant des nanoparticules métalliques, leurs procédés de fabrication et utilisations Download PDF

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Publication number
WO2018189588A1
WO2018189588A1 PCT/IB2018/000461 IB2018000461W WO2018189588A1 WO 2018189588 A1 WO2018189588 A1 WO 2018189588A1 IB 2018000461 W IB2018000461 W IB 2018000461W WO 2018189588 A1 WO2018189588 A1 WO 2018189588A1
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WIPO (PCT)
Prior art keywords
typically
microcapsules
microcapsule
shell
silver
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PCT/IB2018/000461
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English (en)
Inventor
Celine Anna Simone BUREL
Remi Dreyfus
Ahmed M. ALSAYED
Ludivine MALASSIS
Bertrand DONNIO
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Centre National de la Recherche Scientifique CNRS
Rhodia Operations SAS
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Centre National de la Recherche Scientifique CNRS
Rhodia Operations SAS
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the present disclosure relates to microcapsules comprising a hollow or non-hollow core, and a rigid or flexible shell, wherein a plurality of metallic nanoparticles, wherein each metallic nanopartide is a solid nanopartide free of transition metal oxide or a core/shell nanopartide, is embedded in said shell.
  • the applications of the microcapsules of the present disclosure are diverse. Applications may include, but are not limited to, renewable energy, such as solar energy harvesting; biology and medicine, such as cancer therapy, antibacterial therapy, and drug delivery; and sensor technology in the aerospace, automotive, and civil engineering industries.
  • Au NPs gold nanoparticles
  • a striking feature of Au NPs lies in the potential for tuning their localized plasmon resonance maximum by adjusting their shape, size, surrounding environment and interparticle distance.
  • Such strong plasmonic effects have been widely used in areas such as solar energy harvesting, cancer therapy, and drug delivery for accurate transport and delivery of medications.
  • metallic nanoparticles may be useful in controllable optical sensors. For example, a pregnancy test based on Au NPs is well-known. The test is based on the color change of the solution due to the aggregation of Au NPs mediated by components in the urine.
  • a positive is red when the nanoparticles are stabilized by human chorionic gonadotropin (hCG), a hormone produced by the embryo after implantation.
  • hCG human chorionic gonadotropin
  • a negative test turns blue upon the nanoparticles aggregation in absence of hCG.
  • Other examples of plasmonic-based sensors rely on the aggregation of nanoparticles triggered by a change in pH, temperature or even charge destabilization. However, to the inventors' knowledge, no plasmonic-based microcapsule sensors have been developed that are capable of sensing external mechanical stress.
  • the present disclosure relates to a microcapsule comprising:
  • each metallic nanoparticle is a solid nanoparticle free of transition metal oxide or a core/shell nanoparticle, is embedded in said shell.
  • the present disclosure relates to a process for manufacturing microcapsules described herein, the process comprising: a) forming an emulsion by mixing a first mixture comprising a first solvent and a plurality of metallic nanoparticles, wherein each metallic nanoparticle is a solid nanoparticle free of transition metal oxide or a core/shell nanoparticle, and a second mixture comprising a second solvent, immiscible with the first solvent,
  • first mixture and/or the second mixture comprises one or more shell precursor compounds
  • step b) recovering the microcapsules formed in step b).
  • the present disclosure relates to a film comprising a polymer matrix and a plurality of microcapsules described herein.
  • the present disclosure relates to a method for detecting an external stimulus, the method comprising:
  • the present disclosure relates to a method for inhibiting the growth of a microbe, the method comprising contacting the microbe with a plurality of microcapsules described herein, thereby inhibiting the growth of the microbe.
  • FIG. 2 shows a schematic representation of the formation of inventive gold-silica microcapsules.
  • FIG. 3 shows a) an optical microscope image of typical microcapsules at 0.02 M of gold; b) and c) SEM images of microcapsules obtained at 0.02M of gold, and d) an SEM image of a typical microcapsule surface covered by Au NPs.
  • FIG. 4 shows the position of the plasmonic peak maximum as the polymer is elongated.
  • the dashed line corresponds to the wavelength of maximum extinction of the Au NPs in water.
  • Inset shows optical response as a function of film elongation (extinction normalized at 400 nm).
  • FIG. 5 shows the optical response as a function of potential energy of impact (the extinction is normalized at 420 nm). Inset shows the position of the plasmonic peak maximum as the polymer is impacted.
  • the term “comprises” includes “consists essentially of” and “consists of.” Analogously, the term “comprising” includes “consisting essentially of” and “consisting of.”
  • Cx-Cy in reference to an organic group, wherein x and y are each integers, means that the group may contain from x carbon atoms to y carbon atoms per group.
  • the microcapsules of the present disclosure comprise a hollow or non-hollow core, and a rigid or flexible shell, wherein a plurality of metallic nanoparticles is embedded in said shell.
  • the microcapsules may be hollow or non-hollow.
  • a liquid is typically encapsulated within the microcapsule.
  • the liquid encapsulated within the microcapsule is typically a hydrophobic liquid.
  • Exemplary hydrophobic liquids include, but are not limited to, Ci -2 o straight, branched, or cyclic alkanes, such as pentane, hexane, cyclohexane, dodecane, hexadecane, and decalin; and d-2o aromatic hydrocarbons, such as benzene, xylene, and toluene; select alcohols, such as octanol; oils, such as silicon oil, animal, vegetable or other natural oils; alkyl esters, such as ethyl acetate and hexyl acetate; and mixtures thereof.
  • the core comprises toluene.
  • the core may further comprise an active agent.
  • an active agent is a material that provides a beneficial effect. Suitable active agents include, but are not limited to, drugs or other pharmaceutical agents, such as antibacterial agents; fragrances, flavoring agents, dyes, fluorophores, and spiropyran derivatives.
  • the shell of the microcapsules of the present disclosure may be rigid or flexible depending on the material used to make the microcapsule.
  • the shell typically comprises silicon.
  • the shell comprises silicon dioxide.
  • the shell typically comprises a polymer.
  • the polymer is a homopolymer or copolymer derived from ethylenically- unsaturated monomers.
  • the copolymer may be a random copolymer or a block copolymer.
  • Exemplary ethylenically-unsaturated monomers suitable for use in the shell of the microcapsules include, but are not limited to, (meth)acrylic ester monomers, including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, ethyl methacrylate, isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; (meth)acrylic amides, such as (meth)acrylamide, N-isopropyl(meth)acrylamide, and bis-acrylamide; styrene and substituted styrenes; butadiene; vinyl acetate, vinyl butyrate and other vinyl esters; vinyl monomers, such as vinyl chloride, vinyl toluen
  • the shell comprises a homopolymer or copolymer derived from ethylenically-unsaturated monomers selected from the group consisting of methyl methacrylate, butyl acrylate, methyl acrylate, N-isopropyl(meth)acrylamide, bis-acrylamide, and mixtures thereof.
  • nanoparticle refers to a particle having at least one dimension less than or equal to 1000 nm, typically less than or equal to 100 nm.
  • the metallic nanoparticles used in the present disclosure may have any shape.
  • the metallic nanoparticles are spherical or substantially spherical.
  • the mean diameter of the metallic nanoparticles is about 1 nm to about 100 nm, typically from about 1 to about 60 nm, more typically about 20 to about 60 nm, most typically about 40 nm.
  • Each metallic nanoparticle comprises or consists of a metal, or an alloy or
  • Metals include, for example, alkali metals, such as, for example, lithium, sodium, potassium, and rubidium; main group metals such as, e.g., lead, tin, bismuth, antimony and indium; transition metals, such as gold, silver, copper, nickel, cobalt, palladium, platinum, iridium, osmium, rhodium, ruthenium, rhenium, vanadium, chromium, manganese, niobium, molybdenum, tungsten, tantalum, titanium, zirconium, zinc, mercury, yttrium, iron and cadmium; as well as inner transition metals, also referred to rare earth elements, such as cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), holmium (Ho), lanthanum (La), lutetium (Lu), ne
  • alkali metals such
  • each metallic nanoparticle comprises at least one transition metal, typically gold or silver.
  • the plurality of metallic nanoparticles comprises nanoparticles having the same metal, typically the same transition metal.
  • the plurality of metallic nanoparticles comprises
  • nanoparticles having different metals typically different transition metals, more typically gold and silver.
  • the metallic nanoparticles used in the microcapsules described herein are solid nanoparticles free of transition metal oxide and/or core/shell nanoparticles.
  • Solid nanoparticles free of transition metal oxide are solid metallic nanoparticles that do not contain any metal oxides.
  • Representative metal oxides that the metallic nanoparticles do not contain include silver oxides, titanium oxides, such as titanium dioxide (Ti0 2 ), and the like.
  • core/shell nanoparticle refers to a nanoparticle having a core that is coated on the surface with another material, which forms a shell.
  • the core of a core/shell nanoparticle comprises or consists of a metal, or an alloy or intermetallic comprising a metal.
  • the thickness of the shell surrounding the core is not particularly limited. However, the shell thickness is typically from 1 nm to 40 nm.
  • the metallic nanoparticles may be in any form known to those of ordinary skill in the art.
  • the metallic nanoparticles may be in the form of nanocrystals, in which the atoms are in one or more crystalline arrangements, or in the form of nanophosphors, which may be doped or undoped. Nanophosphors make up a class of optical materials having such properties as quantum cutting and photon
  • Some doped nanophosphors such as lanthanide-doped colloidal upconverting nanophosphors, are capable of converting long-wavelength near-infrared excitation into short-wavelength visible emission through the long-lived, metastable excited states of the dopant.
  • the downconverting phosphors are capable of convert high energy photons (low wavelength) into several lower energy photons with energies above the band gap of the luminescent material.
  • the metallic nanoparticles used in the microcapsules described herein may comprise an organic capping agent.
  • Suitable organic capping agents include, for example, phosphines; phosphine oxides; alkyl phosphonic acids; polymers, such as polyalkylpolyoxyalkyl polyacrylates, polyvinylpyrrolidones, such as PVP-10K and poly(diallyldimethylammonium-nitrate-co-l -vinylpyrrolidone) (PVP-DADMAN,
  • Solvay® polyvinyl acetates, polyvinyl alcohol), polystyrene, and polymethacrylate
  • polymeric acids such as polyacrylic acid
  • alkyl thiols such as (C 4 -Ci 2 ) thiols
  • alkyl amines such as (C 4 -Ci 2 ) amines
  • carboxylic acids such as acetic acid, citric acid, and ascorbic acid
  • fatty acids such as (C 6 -C 24 ) fatty acids
  • surfactants dendrimers, and salts and combinations thereof.
  • (C 4 -Ci 2 ) thiols include, but are not limited to, ethanethiol, propanethiol, butanethiol, and dodecanethiol.
  • (C 4 -Ci 2 ) amines include, but are not limited to, butylamine, sec-butylamine, isobutylamine, tert-butylamine, 3-methoxypropylamine, (2-methylbutyl)amine, 1 ,2- dimethylpropylamine, 1 -ethylpropylamine, 2-aminopentane, amylamine,
  • fatty acids include, but are not limited to, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, oleic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pamoic acid, hexacosanoic acid, 8-methylnonanoic acid, 1 1 -methyllauric acid, 12-methyltridecanoic acid, 12- methyltetradecanoic acid, 13-methylmyristic acid, is
  • Surfactants include, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants.
  • Anionic surfactants include, for example, alkyl sulfates (eg., dodecylsulfate), alkylamide sulfates, fatty alcohol sulfates, secondary alkyl sulfates, paraffin sulfonates, alkyl ether sulfates, alkylpolyglycol ether sulfates, fatty alcohol ether sulfates, alkylbenzenesulfonates, alkylphenol ether sulfates, alkyl phosphates; alkyl or alkylaryl monoesters, diesters, and triesters of phosphoric acid; alkyl ether phosphates, alkoxylated fatty alcohol esters of phosphoric acid, alkylpolyglycol ether phosphates (for example, polyoxyethylene octadecenyl ether phosphates marketed as LUBRHOPHOS® LB-400 by Rhodia), phosphonic esters
  • Cationic surfactants include, for example, aliphatic, cycloaliphatic or aromatic primary, secondary and tertiary ammonium salts or alkanolammonium salts;
  • quaternary ammonium salts such as tetraoctylammonium halides and
  • cetyltrimethylammonium halides eg., cetyltrimethylammonium bromide (CTAB)
  • CTCAB cetyltrimethylammonium bromide
  • cationic surfactants suitable for use according to the present disclosure include cationic ethoxylated fatty amines.
  • cationic ethoxylated fatty amines include, but are not limited to, ethoxylated oleyl amine (marketed as
  • Nonionic surfactants include, for example, alcohol alkoxylates (for example, ethoxylated propoxylated Ce-C-i o alcohols marketed as ANTAROX® BL-225 and ethoxylated propoxylated C10-C16 alcohols marketed as ANTAROX® RA-40 by Rhodia), fatty alcohol polyglycol ethers, fatty acid alkoxylates, fatty acid polyglycol esters, glyceride monoalkoxylates, alkanolamides, fatty acid alkylolamides, alkoxylated alkanol-amides, fatty acid alkylolamido alkoxylates, imidazolines, ethylene oxide-propylene oxide block copolymers (for example, EO/PO block copolymer marketed as ANTAROX® L-64 by Rhodia), alkylphenol alkoxylates (for example, ethoxylated nonylphenol marketed as IGEPAL® CO
  • alkyl thio alkoxylates for example, alkyl thio ethoxylates marketed as ALCODET® by Rhodia
  • amine alkoxylates and mixtures thereof.
  • nonionic surfactants include addition products of ethylene oxide, propylene oxide, styrene oxide, and/or butylene oxide onto compounds having an acidic hydrogen atom, such as, for example, fatty alcohols, alkylphenols or alcohols.
  • Examples are addition products of ethylene oxide and/or propylene oxide onto linear or branched fatty alcohols having from 1 to 35 carbon atoms, onto fatty acids having from 6 to 30 carbon atoms and onto alkylphenols having from 4 to 35 carbon atoms in the alkyl group; (C6-C3o)-fatty acid monoesters and diesters of addition products of ethylene oxide and/or propylene oxide onto glycerol; glycerol monoesters and diesters and sorbitan monoesters, diesters and triesters of saturated and
  • unsaturated fatty acids having from 6 to 22 carbon atoms and their ethylene oxide and/or propylene oxide addition products, and the corresponding polyglycerol-based compounds; and alkyl monoglycosides and oligoglycosides having from 8 to 22 carbon atoms in the alkyl radical and their ethoxylated or propoxylated analogues.
  • Amphoteric or zwitterionic surfactants include, but are not limited to, aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, wherein the aliphatic radicals can be straight chain or branched, and wherein the aliphatic substituents contains about 6 to about 30 carbon atoms and at least one aliphatic substituent contains an anionic functional group, such as carboxy, sulfonate, sulfate, phosphate, phosphonate, and salts and mixtures thereof.
  • zwitterionic surfactants include, but are not limited to, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines, alkyl glycinates, alkyl carboxyglycinates; alkyl
  • amphopropionates such as cocoamphopropionate and caprylamphodipropionate (marketed as MIRANOL® JBS by Rhodia); alkyl amidopropyl hydroxysultaines, acyl taurates, and acyl glutamates, wherein the alkyl and acyl groups have from 6 to 18 carbon atoms, and salts and mixtures thereof.
  • each metallic nanoparticle comprises an organic capping agent, typically a polyvinylpyrrolidone, more typically poly(diallyldimethylammonium-nitrate- co-1 -vinylpyrrolidone).
  • organic capping agent typically a polyvinylpyrrolidone, more typically poly(diallyldimethylammonium-nitrate- co-1 -vinylpyrrolidone).
  • the metallic nanoparticles used in the present disclosure may be obtained from commercial sources or synthesized according to methods known to those of ordinary skill in the art.
  • the metallic nanoparticles are synthesized by reduction of a metal precursor compound with a reducing agent, optionally in the presence of an organic capping agent, such as those described herein.
  • Exemplary metal precursor compounds include silver nitrate, silver nitrite, silver oxide, silver fluoride, silver hydrogen fluoride, silver carbonate, silver oxalate, silver azide, silver tetrafluoroborate, silver acetate, silver propionate, silver butanoate, silver ethylbutanoate, silver pivalate, silver cyclohexanebutanoate, silver
  • ethylhexanoate silver neodecanoate, silver decanoate, silver trifluoroacetate, silver pentafluoropropionate, silver heptafluorobutyrate, silver trichloroacetate, silver 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate, silver lactate, silver citrate, silver glycolate, silver glyconate, silver benzoate, silver salicylate, silver
  • hexafluoroplatinate sodium tetrachloroplatinate, dihydrogen tetrachloroplatinate, potassium hexabromoplatinate, hexachloroplatinic acid, hexabromoplatinic acid, dihydrogen hexahydroxoplatinate, diammine platinum chloride, tetraammine 5 platinum chloride, tetraammine platinum hydroxide, tetraammine platinum
  • the above compounds may be employed as such or optionally as their hydrates.
  • Reducing agents include, for example, polyols, such (alkylene)glycols (e.g., ethylene glycol, propylene glycol and the butylene glycols); hydrazine and derivatives thereof; hydroxylamine and derivatives thereof, monohydric alcohols such as, e.g, methanol and ethanol, aldehydes such as, e.g., formaldehyde, ammonium formate, formic acid, acetaldehyde, and propionaldehyde, or salts thereof (e.g., ammonium formate); hypophosphites; sulfites; tetrahydroborates (such as, e.g., the tetrahydroborates of Li, Na, K); lithium aluminum hydride (LiAIH 4 ); sodium borohydride (NaBH 4 );
  • polyols such as (alkylene)glycols (e.g., ethylene glycol, propylene glycol
  • polyhydroxybenzenes such as, e.g., hydroquinone, alkyl-substituted hydroquinones, catechols and pyrogallol; phenylenediamines and derivatives thereof; aminophenols and derivatives thereof; carboxylic acids and derivatives thereof such as, e.g., ascorbic acid, ascorbate salts, citric acid, citrate salts, erythorbic acid, erythorbate salts, and ascorbic acid ketals; 3-pyrazolidone and derivatives thereof;
  • the reducing agent is ascorbic acid.
  • the reducing agent is a polyol, typically ethylene glycol.
  • the metallic nanoparticles are embedded in the shell of the microcapsules described herein.
  • the metallic nanoparticles are embedded in the shell of the microcapsules described herein.
  • the metallic nanoparticles are embedded in the shell of the microcapsules described herein.
  • nanoparticles are immobilized in the shell.
  • a portion of each metallic nanoparticle embedded in the shell is exposed on the surface of the shell.
  • the surface area covered by nanoparticles in each microcapsule is from 0% to about 99%, typically 1 % to about 90%, more typically from about 10% to 90%, more typically from about 50% to 90%.
  • the present disclosure also concerns a process for manufacturing the microcapsules described herein, the process comprising: a) forming an emulsion by mixing a first mixture comprising a first solvent and a plurality of metallic nanoparticles, wherein each metallic nanoparticle is a solid nanoparticle free of transition metal oxide or a core/shell nanoparticle, and a second mixture comprising a second solvent, immiscible with the first solvent,
  • first and/or second mixtures each comprise one or more shell precursor compounds
  • step b) recovering the microcapsules formed in step b).
  • an emulsion is formed by mixing a first mixture comprising a first solvent and a plurality of the metallic nanoparticles described herein and a second mixture comprising a second solvent, immiscible with the first solvent.
  • the first and/or second mixtures each comprise one or more shell precursor compounds.
  • the first mixture comprises one or more shell precursor compounds.
  • the second mixture comprises one or more shell precursor compounds.
  • the term "immiscible" means that no more than 1 g/L, no more than 0.9 g/L, no more than 0.6 g/L, or no more than 0.5 g/L of one solvent is dissolved in another solvent.
  • an emulsion comprises a continuous phase and a dispersed phase resulting from the mixing of two or more liquids that are immiscible.
  • the formation of emulsions is well known to those of ordinary skill in the art.
  • the continuous phase may be formed from a hydrophilic or hydrophobic liquid as long as the dispersed phase is formed from a liquid immiscible with the liquid used to form the continuous phase.
  • the dispersed phase is formed from a hydrophobic liquid, or vice versa.
  • the continuous phase is formed by the first mixture comprising a first solvent and a plurality of metallic nanoparticles.
  • the first solvent comprises water and, optionally, one or more water-miscible organic liquids. Suitable water miscible organic liquids include polar aprotic organic solvents, such as, for example, dimethyl sulfoxide and dimethyl 2- methylglutarate (marketed as Rhodiasolv® IRIS), polar protic organic solvents, such as, for example, methanol, ethanol, propanol, butanol, ethylene glycol, and propylene glycol, and mixtures thereof.
  • the plurality of metallic nanoparticles is dispersed in the first solvent to provide the first mixture.
  • the first mixture comprises a first solvent, a plurality of metallic nanoparticles, and one or more shell precursor compounds.
  • the first mixture is typically acidic (i.e., pH less than 7).
  • the first mixture further comprises an acid.
  • Suitable acids include, but are not limited to, inorganic acids, such as, for example, hydrofluoric acid (HF), hydrochloric acid (HCI), hydrobromic acid (HBr), hydroiodic acid (HI), and solutions thereof; oxo acids, such as nitric acid (HN0 3 ), phosphoric acid (H 3 P0 4 ), sulfuric acid (H 2 S0 4 ), and solutions thereof; and carboxylic acids, such as acetic acid, citric acid, trifluoroacetic acid, and solutions thereof.
  • the pH of the first mixture is less than or equal to 4.
  • the dispersed phase is formed by the second mixture comprising a second solvent, immiscible with the first solvent, and optionally one or more shell precursor compounds.
  • the second solvent typically comprises one or more hydrophobic organic liquids.
  • Exemplary hydrophobic organic liquids suitable for use as the second solvent include, but are not limited to, Ci -2 o straight, branched, or cyclic alkanes, such as pentane, hexane, cyclohexane, dodecane, hexadecane, and decalin; d-2o aromatic hydrocarbons, such as benzene, xylene, and toluene; select alcohols, such as octanol; oils, such as silicon oil, animal, vegetable or other natural oils; alkyl esters, such as ethyl acetate and hexyl acetate; and mixtures thereof.
  • the second solvent is toluene.
  • Shell precursor compounds are compounds capable of undergoing a reaction, such as a polymerization reaction, to form the shell of the microcapsule.
  • Suitable precursor compounds include, but are not limited to, siloxanes, such as, for example, tetraethyl orthosilicate (TEOS), polydiethoxysiloxane (PEOS), and ethylenically- unsaturated monomers.
  • TEOS tetraethyl orthosilicate
  • PEOS polydiethoxysiloxane
  • ethylenically- unsaturated monomers ethylenically- unsaturated monomers.
  • Exemplary ethylenically-unsaturated monomers include, but are not limited to, (meth)acrylic ester monomers, including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, ethyl methacrylate, isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate;
  • (meth)acrylic ester monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, ethyl methacrylate, isodecyl methacrylate, lauryl
  • (meth)acrylic amides such as (meth)acrylamide, N-isopropyl(meth)acrylamide, and bis-acrylamide; styrene and substituted styrenes; butadiene; vinyl acetate, vinyl butyrate and other vinyl esters; vinyl monomers, such as vinyl chloride, vinyl toluene, vinyl benzophenone; vinylidene chloride, and mixtures thereof.
  • the one or more shell precursor compounds is
  • PEOS polydiethoxysiloxane
  • an ethylenically-unsaturated monomer selected from the group consisting of methyl methacrylate, butyl acrylate, methyl acrylate, N- isopropyl(meth)acrylamide, bis-acrylamide, and mixtures thereof.
  • the first mixture and second mixture are subsequently combined and agitated to form the emulsion. Any method known to those of ordinary skill in the art may be used for agitation. For example, sonication may be used.
  • the emulsion formed according to the present disclosure is stable versus
  • Stable Pickering emulsions may be formed by satisfying the following various conditions.
  • Equation (1 ) shows the free energy of desorption of a nanoparticle at the interface, where ⁇ ⁇ ⁇ is the interfacial tension; 0 OW is the three- phase contact angle between the solid and the interface; R is the radius of the nanoparticles.
  • the adsorption of nanoparticles of radius ranging between 10 nm and 100 pm and with intermediate contact angle (40° ⁇ 0 OW ⁇ 90°) induces a decrease in the energy of order of thousands of k B T per particle, where k B is the Boltzmann constant and T is the temperature. Thermal energy is thus not large enough to desorb the nanoparticles from the interface, and a single metallic NP is strongly and irreversibly bound to the interface.
  • the metallic nanoparticles described herein may be tuned by using a suitable organic capping agent such that the particles have equal affinity for the continuous and dispersed phase.
  • the number of nanoparticles suitable for forming a stable Pickering emulsion can be estimated from Equation (2) where N p is the number of NPs needed to fully cover droplets of diameter D with particles of diameter d, w p is the total mass of the nanoparticles; p is the density of the nanoparticles; and V is the total volume of the dispersed phase.
  • the reaction step comprises a radical polymerization reaction, as in the case when ethylenically-unsaturated shell precursor compounds are used, or a
  • the metallic nanoparticles are adsorbed on the interface between the dispersed phase and the continuous phase. Following the reaction step, a shell is formed at the interface, which locks the plurality of metallic nanoparticles in the formed shell. Recovering the microcapsules formed in the reaction step may be achieved using any method. For example, the microcapsules may be recovered using
  • the process described herein may further comprise drying the recovered
  • microcapsules to remove any solvent, including solvent trapped in the core of the microcapsules. Drying may be achieved by any known method.
  • the microcapsules may be dried by subjecting the microcapsules to heat and/or low pressure atmosphere.
  • the present disclosure concerns a film comprising a polymer matrix and a plurality of microcapsules described herein.
  • the polymer matrix is not limited and may be any type of polymeric material known to those of ordinary skill in the art.
  • exemplary polymer matrices include, but are not limited to, polyesters, polysulfones, polyethersulfones, polyarylates, polyimides, polyetherimides,
  • a plurality of microcapsules may be dispersed in a solution comprising the polymer matrix. The solvent may then be removed to yield a film comprising the polymer matrix and the plurality of microcapsules. Alternatively, a plurality of microcapsules may be dispersed in a solution comprising monomers that are subsequently polymerized to form the polymer matrix, yielding a film in which the plurality of microcapsules is embedded in the polymer matrix.
  • a plurality of microcapsules is added to a solution of polymer matrix, typically polyvinyl alcohol (PVA) or acrylic polymer. Removal of the solvent results in a film comprising PVA or acrylic polymer and a plurality of microcapsules embedded therein.
  • PVA polyvinyl alcohol
  • the film may be rigid or elastic. By choosing the appropriate glass transition temperature for the polymer matrix used, the elasticity of the obtained film can be tuned.
  • the present disclosure also relates to a method for detecting an external stimulus, the method comprising:
  • incorporación of a plurality of microcapsules described herein into a substrate may be achieved according to any method known to the ordinarily-skilled artisan.
  • the plurality of microcapsules may be introduced during the manufacture of the substrate, which may subsequently be used to manufacture an article.
  • the substrate may comprise, for example, a metal, a polymer, a glass, a paper, a ceramic material, or a combination thereof.
  • Suitable polymers are polymers selected from polyesters, polysulfones, polyethersulfones, polyarylates, polyimides, polyetherimides, polytetrafluoroethylenes, poly(ether ketone)s, poly(ether ether ketone)s, poly((meth)acrylate)s, polycarbonates, polyolefins, polyvinyl alcohols, and mixtures thereof.
  • Exposure of the substrate comprising the plurality of microcapsules described herein to an external stimulus includes, but is not limited to, mechanical deformation, change in temperature; adsorption of oil, organic solvent, and/or water; and change in pH, results in a change in extinction or a change in optical fluorescence.
  • a change in extinction or a change in optical fluorescence typically manifests as a change in color or color intensity capable of being observed by the naked eye.
  • a change in extinction or a change in optical fluorescence may also be observed with the aid of devices known to be useful in detecting such changes, for example, by using a UV-vis spectrophotometer in accordance with methods known to those of ordinary skill.
  • the removal of the external stimulus results in a return to the condition before the exposure of the substrate to the external stimulus. That is to say, the change in extinction or a change in optical fluorescence due to the external stimulus, for example, mechanical deformation, change in temperature; adsorption of oil, organic solvent, and/or water; and change in pH, is reversed when the external stimulus is removed.
  • the present disclosure relates to a method for inhibiting the growth of a microbe, the method comprising contacting the microbe with a plurality of the microcapsules described herein, thereby inhibiting the growth of the microbe.
  • microbes whose growth may be inhibited include, but are not limited to, bacteria, viruses, yeast and other fungi, algae, plankton, and protozoa.
  • the microbe is bacteria, algae, or plankton.
  • the microcapsules may be used in wound care products, including, but not limited to, dressings, hydrogels, hydrocolloids, creams, gels, lotions, catheters, sutures, socks and bandages.
  • microcapsules, methods and processes, and films according to the present disclosure are further illustrated by the following non-limiting examples.
  • the Au NPs used in this procedure were synthesized by reduction of HAuCI 4 with ascorbic acid in presence of PVP-DADMAN.
  • the emulsion droplets do not appear to present a very high packing fraction of the Au NPs on their surface, and thus the droplets appear pink.
  • the pH was set below the pKa of the ascorbic acid.
  • Silver nanoparticles (Ag NPs) were synthesized by reduction of AgN0 3 using ascorbic acid in the presence of PVP-DADMAN or were obtained by reduction of AgN0 3 in ethylene glycol. Mixtures of gold and silver NPs were obtained by mixing the Au NPs and Ag NPs.
  • microcapsules dispersion in water on an electron microscopy science carbon-coated copper grid.
  • Transmission electron microscopy (TEM) was carried out on a JEOL JEM-1400 electro-microscope.
  • the accelerating voltage was set at 120kV.
  • PEOS 0.2 g of PEOS was diluted in 1 ml_ of toluene.
  • the oil and water phases were emulsified together with a Brandson 3210 ultrasonic bath at 30°C for 15 minutes. After 3 days, the silica shell was fully formed. The microcapsules were recovered, cleaned and concentrated by simple
  • FIG. 2 shows the schematic representation of the gold-silica microcapsules formed.
  • FIG. 3 shows images of the dried microcapsules formed after 3 days. The color, aspect and size of the microcapsules are analyzed by optical microscopy (FIG. 3a) and SEM (Figs. 3b-3d). The microcapsules are spherical with dimensions ranging from several hundredths of nanometers to several tenths of micrometers (4-20 pm). The microcapsules had a deep blue color, which comes from a monolayer of densely packed nanoparticles on their surface, as shown in Figure 3d. The silica shell thickness as measured from SEM images ranges between 30 and 60 nm.
  • azobisisobutyronitrile AIBN
  • 10 mg of azobisisobutyronitrile (AIBN) was dissolved in 0.5 ml_ of toluene containing diverse ratios of methylmethacrylate/methacrylate/butacrylate for a total mass of monomers equal to 0.2g.
  • the oil and water phases were emulsified together with a Brandson 3210 ultrasonic bath at 30°C for 15 minutes. After 2 hrs at 60°C under inert atmosphere, the acrylate shells were fully formed.
  • the microcapsules were recovered, cleaned and concentrated by simple
  • Example 4 Silver-silica microcapsules.
  • PEOS 0.2 g of PEOS was diluted in 1 mL of toluene.
  • the oil and water phases were emulsified together with a Brandson 3210 ultrasonic bath at 30°C for 15 minutes. After 3 days, the silica shell was fully formed. The microcapsules were recovered, cleaned and concentrated by simple sedimentation.
  • Example 5 PVA film preparation and stretching.
  • a solution of 10 wt% PVA in water was prepared and degassed. Then 1 g of the microcapsules made according to Example 1 were concentrated and dispersed in the PVA solution under gentle stirring to avoid the formation of air bubbles, which could make the final film inhomogeneous and more fragile. The final polymer- microcapsule solution was left to dry at room temperature for several days.
  • the silica crust provided blue microcapsules with enough rigidity to retain their spherical shape. Their intrinsic color confers to the resulting film a slight blue color.
  • a uni-axial stretching of the polymer film is then performed. Stretching of the dried film was achieved using a vise upon mild heating of the film. A magnified view of the elongated polymer film displays pink stretched microcapsules. This color change is noticeable by naked eye on the film. It is attributed to the deformation of the spherical microcapsules into an ellipsoid-like shape along with the increase of the interparticle distance. Indeed, during this anisotropic deformation, the distance between the Au NPs increases, thus entailing a color change.
  • FIG. 4 shows the position of the plasmonic peak maximum as the polymer was elongated, with the inset showing the UV response as a function of film elongation (the extinction is normalized at 400 nm).
  • the maximum of the extinction peak is plotted versus the potential energy of the weight at impact.
  • the plot is shown in FIG. 5.
  • the graph shows that as the potential energy of the weight at impact increases, the extinction of the plasmonic peak shifts from the red/infrared region (A ⁇ 970nm) to the green/blue visible region of the spectrum (A ⁇ 540nm).
  • the analysis using the spectrophotometer exhibits a very small shift of the maximum of the plasmonic peak that cannot be detected by the human eye (circled in black on film at top of FIG. 5).
  • the human eye is capable of seeing the area of impact by noticing a red spot at the place of the impact zone as shown in the image at the bottom of FIG. 5.
  • the second test relates to perforating the film.
  • the polymer film underwent very large strains in the vicinity of the hole. Observations under an optical microscope showed that the microcapsules lying far from the hole remain undisturbed and spherical and thus displayed a blue color, whereas those located close to the edge of the perforation were likely deformed into an ellipsoidal shape as indicated by their purple and/or pink color.
  • the PVA film comprising the microcapsules described herein were sensitive enough to enable the detection of a color change by spectrophotometry arising from very tiny deformations not detectable by the eye.
  • the underlying industrial potential applications are numerous. For instance, such mechanochromic shells mixed in paints, fabrics or polymers could be used to gather local and/or global information about the material they have been embedded in; such as the early detection of cracks or bullet/rock impact locations.
  • Example 7 Acrylate latex film preparation and stretching.
  • This example shows that the synthesis method described herein is versatile as microcapsules comprising one or more types of nanoparticles embedded in silica shell can be easily synthesized. It is also possible to reduce different metal salts into nanoparticles at high concentration in metal salt.
  • the optical response of the final gold-silica microcapsules can be finely tuned with the ratio gold/silver NPs and that, therefore, the color of the microcapsules can be tuned by changing the ratio of gold/silver NPs in the
  • the antibacterial properties of the silver-silica (AgSi) microcapsules made according to Example 4 were investigated in a disk diffusion assay and a planktonic assay.
  • the silver NPs were obtained by reduction of silver nitrate in ethylene glycol.
  • microcapsules provide an efficient way to deliver antibacterial silver because they are easy to synthesize (2 steps), their spherical shape presents increased antibacterial surface, and are environmentally friendly due to easy recovery by physical methods, such as filtration or sedimentation.
  • the gold-acrylate microcapsules made according to Example 2 were exposed to an excess of toluene. Before exposure to the toluene solvent, the gold-acrylate microcapsules exhibited a dark blue color. However, upon exposure to toluene, the dark blue microcapsules turned a blue color and then a purple-pink color over time.
  • inventive microcapsules may be used, for example, in visual detection of oil/solvent in mixture, visual detection of trapping/oil- solvent recovery, and kitchen grease trapping/detection in coatings.
  • microcapsules exhibit a change in color upon hydration.
  • inventive microcapsules may be used, for example, as a visual humidity sensor.
  • Example 11 Detection of pH Gold-acrylate microcapsules were made according to Example 2 and suspended in an acidic solution.
  • the acidic solution pH ⁇ 1
  • the acidic solution containing the inventive gold-acrylate microcapsules, was observed under an optical microscope.
  • the gold- acrylate microcapsules appeared dark blue color in color.
  • NaOH was then added to the acidic solution such that the NaOH was allowed to diffuse through the solution. As the NaOH diffused through the solution, the color of the gold-acrylate
  • microcapsules changed from dark blue to purple-pink, indicating a change in pH.
  • the color of the gold-acrylate microcapsules was purple-pink in areas where the solution was basic while the color of the gold-acrylate microcapsules was dark blue in areas where the solution was still acidic. This observation indicates that the inventive microcapsules are suitable for detecting local pH and local changes in pH.
  • the solution containing the inventive microcapsules was made completely basic (pH ⁇ 14).
  • the microcapsules appeared purple-pink.
  • HCI was added and allowed to diffuse through the solution.
  • the color of the gold-acrylate microcapsules was dark blue in areas where the solution was acidic while the color of the gold-acrylate microcapsules was purple-pink in areas where the solution was still basic. This result indicates that the color change due to pH is reversible.
  • the pH can be increased and decreased over many cycles with the result that the color of the gold-acrylate microcapsules alternates between dark blue and purple-pink.

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Abstract

La présente divulgation concerne des microcapsules comprenant un cœur creux ou non creux, et une coque rigide ou flexible, où une pluralité de nanoparticules métalliques, chaque nanoparticule métallique étant une nanoparticule solide exempte d'oxyde de métal de transition ou de nanoparticule cœur/coque, est incorporée dans ladite coque. Des procédés de fabrication desdites microcapsules et leurs utilisations sont en outre décrits.
PCT/IB2018/000461 2017-04-14 2018-04-11 Microcapsules contenant des nanoparticules métalliques, leurs procédés de fabrication et utilisations Ceased WO2018189588A1 (fr)

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US11471386B2 (en) 2017-12-29 2022-10-18 Conopco, Inc. Non-spherical microcapsule
US11642290B2 (en) * 2017-12-29 2023-05-09 Conopco, Inc. Non-spherical microcapsule
US11904287B2 (en) 2019-04-17 2024-02-20 The Procter & Gamble Company Capsules
US11446627B2 (en) 2019-04-17 2022-09-20 The Procter & Gamble Company Capsules
US11628413B2 (en) 2019-04-17 2023-04-18 The Procter & Gamble Company Methods of making capsules
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CN110506743B (zh) * 2019-07-24 2021-08-17 广州市香港科大霍英东研究院 一种导热性能优良的抗菌相变微胶囊及其制备方法
CN110506743A (zh) * 2019-07-24 2019-11-29 广州市香港科大霍英东研究院 一种导热性能优良的抗菌相变微胶囊及其制备方法
CN111398232A (zh) * 2020-04-07 2020-07-10 浙江大学 变压器油中待测离子浓度的荧光检测方法
CN111471125B (zh) * 2020-05-25 2021-11-09 哈尔滨工程大学 一种Pickering乳液制备透明导电材料的方法
CN111471125A (zh) * 2020-05-25 2020-07-31 哈尔滨工程大学 一种Pickering乳液制备透明导电材料的方法
US11912961B2 (en) 2020-10-16 2024-02-27 The Procter & Gamble Company Liquid fabric care compositions comprising capsules
US11938349B2 (en) 2020-10-16 2024-03-26 The Procter & Gamble Company Antiperspirant and deodorant compositions comprising capsules
US12077728B2 (en) 2020-10-16 2024-09-03 The Procter & Gamble Company Laundry care additive particles
US12129448B2 (en) 2020-10-16 2024-10-29 The Procter & Gamble Company Water-soluble unit dose article containing a core/shell capsule

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