WO2019191065A2 - Colloïdosome à coque poreuse accordable - Google Patents

Colloïdosome à coque poreuse accordable Download PDF

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Publication number
WO2019191065A2
WO2019191065A2 PCT/US2019/024030 US2019024030W WO2019191065A2 WO 2019191065 A2 WO2019191065 A2 WO 2019191065A2 US 2019024030 W US2019024030 W US 2019024030W WO 2019191065 A2 WO2019191065 A2 WO 2019191065A2
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micro
colloidosome
nano
shell
cross
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PCT/US2019/024030
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WO2019191065A3 (fr
Inventor
C. William GUNDLACH
Nitin Chopra
Jonathan SCHOLIN
Ihab Odeh
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Sabic Global Technologies B.V.
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Publication of WO2019191065A2 publication Critical patent/WO2019191065A2/fr
Publication of WO2019191065A3 publication Critical patent/WO2019191065A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005—Wall or coating material
    • A61K9/5021—Organic macromolecular compounds
    • A61K9/5026—Organic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyvinyl pyrrolidone, poly(meth)acrylates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005—Wall or coating material
    • A61K9/5021—Organic macromolecular compounds
    • A61K9/5031—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, poly(lactide-co-glycolide)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5089—Processes
    • 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
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • 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
    • 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
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5107—Excipients; Inactive ingredients
    • A61K9/513—Organic macromolecular compounds; Dendrimers
    • A61K9/5138—Organic macromolecular compounds; Dendrimers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyvinyl pyrrolidone, poly(meth)acrylates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5107—Excipients; Inactive ingredients
    • A61K9/513—Organic macromolecular compounds; Dendrimers
    • A61K9/5146—Organic macromolecular compounds; Dendrimers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, polyamines, polyanhydrides
    • A61K9/5153—Polyesters, e.g. poly(lactide-co-glycolide)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5192—Processes

Definitions

  • Colloidosomes are one type of microencapsulation whose shells are composed of colloidal particles.
  • colloidosomes can be used to encapsulate a variety of active materials that may be slowly released over a specific period of time through the shells.
  • Fig. 1 is a schematic of a colloidosome having two different micro- or nano-materials making up an outer shell that contains an active material.
  • Fig. 2 is optical microscopy of multiple
  • Fig. 3 is optical microscopy of a colloidosome having a non-spherical shape.
  • Microencapsulation is the process of embedding or surrounding a core of active material within a shell.
  • Microencapsulation is commonly employed for materials such as flavors, fragrances, air fresheners, lotions, creams, nutrients, textile scents, drugs, etc., with goals such as: protecting active ingredients from degradation, improving material handling, and delaying or prolonging the release of the active material.
  • Colloidosomes are one type of microencapsulation whose shells are composed of colloidal particles.
  • Nanostructured encapsulation systems e.g., colloidosomes, encapsulated nanoparticles, liposomes, and the like
  • colloidosome systems have several limitations. By way of example, these systems tend to have a more spike or burst release profile of the active material rather than a more controlled and tunable release profile.
  • the loading capacity of the colloidosomes is limited by their core volumes, and the composition of the shells can impose thermodynamic limits on the type of active materials to be stored. Also, the types of stimuli that can be used to release active agents from the core are limited.
  • colloidosomes are microcapsules whose shells are composed of colloidal particles, there are inherent interstitial spaces between the colloidal particles in the shell. These interstitial spaces provide paths for leakage of active materials from the core.
  • the active material (s) are physically large such as antibodies or live cells (and physically larger than the size of the interstitial pores, ) leakage is less of a problem.
  • the active material is a molecule with an effective size the same or less than the interstitial spaces, for example, fragrances
  • the leakage of active material (s) can be significant unless methods are used to hinder diffusion of the active materials (s) through the shell (e.g., sinter the colloidal particles into a contiguous shell, encapsulate the colloidosome in additional shell layers, or increase the length of the tortuous diffusion path) .
  • Microencapsulation of fine fragrances presents a
  • fragrance oils are relatively volatile, low molecular weight, and possess small effective sizes relative to the size of colloidosome interstitial pores.
  • the primary vehicle in fine fragrance is ethanol, which readily permeates/leaches across many shell materials.
  • Prior methods to control the leakage of active from colloidosomes include: multiple shell layers, sintering of the shell particles to form a contiguous shell, and over
  • Sintering of polymeric shell materials can be achieved, for example, by heating colloidosomes comprised of polystyrene styrene microgels to 105 °C.
  • this method is not well- suited for active materials with relatively high volatility, because the active core will expand and burst the shell during heating .
  • Sintering presents material and temperature limitations, especially with volatile (low boiling point) active materials, while multiple layers add cost and complexity to processing, and can undesirably alter the release profile.
  • sintering can result in uncontrolled fusion of shell colloidal particles that can impart characteristics of a single shell encapsulation and could be detrimental to the desired hindered diffusion phenomena that could be achieved in a
  • colloidosome architecture Limited control over colloidal particle packing leads to the following problems in colloidosome microencapsulation: poor active encapsulation; high leak rate of active material from the colloidosomes; instability of the colloidosome architecture (with respect to time, temperature, or both) ; uncontrolled filling of the colloidosomes with active materials; disintegration of the colloidosome architecture under shrinking and swelling; and difficult or time-consuming active (re) filling of colloidosomes when multiple processing steps are employed after colloidosome formation or the colloidosomes are filled with active materials in a stepwise manner.
  • a colloidosome shell can be tunable to allow desired loading of one or more active materials into the cores of the colloidosomes.
  • the tunable shells can also provide improved transport of the active
  • a colloidosome comprises: a micro- or nano-structured porous shell comprising a plurality of micro- or nano-materials and interstices located between the micro- or nano-materials; and a core that is defined by the shell, wherein the shell is tunable to allow selective filling of an active material into the core and selective transport of the active material from the core through the shell.
  • the term "colloidosome” refers to a structure that has a shell defined by a plurality of micro- or nano-materials and interstices formed between the micro- or nano-materials and a core that is defined by the nanostructure shell .
  • the colloidosome includes a micro- or nano- structured porous shell comprising a plurality of micro- or nano-materials and interstices located between the micro- or nano-materials.
  • the pore size of the micro- or nano-structured porous shell can vary depending on the application. Non- limiting examples of pore sizes range from about 0.5 nm to about 3 micrometers, about 10 nm to about 1,000 nm, or about 75 nm to about 200 nm, etc. In some embodiments, irrespective of pore size, the pore size can be tuned by surface functionality of the pore, where the surface functionalized molecule steric size can act as a pore blocking or gating tether.
  • the micro- or nano-structured porous shell can also include more than one type of micro- or nano-materials, for example, as shown in Fig. 1.
  • the shell can include a first layer of the plurality of micro- or nano-materials.
  • the first layer of the shell can define the core containing the active material.
  • the shell can further include a second layer of a plurality of different micro- or nano-materials. The first plurality and the second plurality of the micro- or nano
  • the shell can include a second micro- or nanostructured porous shell that encompasses the first shell and includes a second set of a plurality of micro- or nano-materials and interstices formed between the second set of micro- or nano-materials.
  • An overall size of the colloidosome can range from 5 to 30,000 nm, with the average size of the plurality of micro- or nano-materials being 2 nm to 15, 000 nm, and/or the size of the core being 5 nm to 2,500 nm, with the understanding that the size of the core is larger than the average size of the plurality of micro- or nano-materials that make up the shell.
  • the shape of the micro- or nano-materials can be a wire, a particle (e.g., having a substantially spherical shape), a rod, a tetrapod, a hyper-branched structure, a tube, a cube, a random structure, or mixtures thereof.
  • the colloidosome can have a substantially spherical shape.
  • Fig . 3 depicts a colloidosome having a non-spherical shape.
  • the plurality of micro- or nano-materials can be microgel particles, nanogel particles, polymer brushes,
  • the plurality of micro- or nanomaterials are micro- or nanogel particles having a gel phase that include a polymer network of hydrophilic, hydrophobic, amphiphilic, amphiphobic, lipophilic, or lipophobic polymers, or a
  • the polymer network can be cross-linked.
  • the polymeric network can include non-ionic, cationic, anionic, or zwitterionic polymers or polymers that include metal-organic frameworks or zeolitic imidazolate
  • colloidosomes are formed by cross-linking microstructures, nanostructures, or both together.
  • a polymer is a large molecule composed of repeating units, typically connected by covalent chemical bonds.
  • a polymer is formed from monomers. During the formation of the polymer, some chemical groups can be lost from each monomer.
  • the piece of the monomer that is incorporated into the polymer is known as the repeating unit or monomer residue.
  • the backbone of the polymer is the continuous link between the monomer residues.
  • the polymer can also contain functional groups connected to the backbone at various locations along the
  • Polymer nomenclature is generally based upon the type of monomer residues comprising the polymer.
  • a polymer formed from one type of monomer residue is called a homopolymer.
  • a copolymer is formed from two or more different types of monomer residues. The number of repeating units of a polymer is
  • the chain length of the polymer referred to as the chain length of the polymer.
  • the number of repeating units of a polymer can range from approximately 11 to greater than 10,000.
  • the repeating units from each of the monomer residues can be arranged in various manners along the polymer chain.
  • the repeating units can be random, alternating, periodic, or block.
  • the conditions of the polymerization reaction can be adjusted to help control the average number of repeating units (the average chain length) of the polymer.
  • the repeating units from each of the monomer residues can be arranged in various manners along the polymer chain.
  • the repeating units can be random, alternating, periodic, or block.
  • a "polymer” can include a cross-linked polymer.
  • a "cross link” or “cross linking” is a connection between two or more polymer molecules.
  • a cross-link between two or more polymer molecules can be formed by a direct interaction between the polymer molecules, or conventionally, by using a cross- linking agent that reacts with the polymer molecules to link the polymer molecules.
  • the polymers can be selected from the group consisting of poly (N-isopropylacrylamide) (pNiPAAm), N- isopropylacrylamide - (N, N' -methylenebisacrylamide ) copolymer, N-isopropylacrylamide - (N, N' -methylenebisacrylamide) -allyl amine copolymer ("Nfh-functionalized pNiPAAm", ) polyethylene glycol, functionalized pNiPAAm, polyvinyl alcohol (PVA) , hydroxylated poly (meth) acrylate, ethylene-vinyl acetate
  • polyolefin poly lactic acid (PLA) , polylactic-coglycolic acid copolymer (PLGA) , alginate, chitosan, polyesters (eg
  • poly (pentadecanolide ) polyethylene terephthalate (PET), polybutylene terephthalate (PBT) , poly (butylsuccinate ) ) , polyester copolymers (e.g., lactic acid/lysine copolymer), glycerol copolymers, polycarbonates, polyetherimides ,
  • polyphenyloxides polystyrenes, poly (methyl methacrylate)
  • the colloidosome can be formed by the addition of a cross-linking agent to form the micro- or nano-structured porous shell.
  • a cross-linking agent for example, poly lactic acid is a polymer that does not need to be cross-linked; however, an example of a polymer that can be cross-linked is bis-acrylamide cross-linked pNiPAAm.
  • a cross-linking agent can be added to help stabilize the colloidosomes formed from polymeric micro- or nano
  • the core of the micro- or nano-structured porous shell includes an active material. There can also be more than one type of active material in the core.
  • the core of the colloidosome can be a polymer emulsion, a polymer gel, an aerogel, a liquid (e.g. an oil), or a partially void space.
  • the active material can be any active material that is desirably released from the core in a desired period of time. Examples of active materials include, but are not limited to, a chemical agent, a biological agent, an oil, an ionic liquid, a
  • Chemical agents can include a drug, gaseous molecules, a cosmetic agent, a flavoring agent, a fragrance-producing chemical, a malodor agent, a reactive agent, a cross-linker, a reactive diluent, a solvent, an inorganic or organic chemical, a organometallic system, a petrochemical, a reducing or oxidizing agent, or an aqueous salt, or any combination thereof.
  • the biological agent can include a protein, a peptide, a nucleic acid, a
  • compositions include pharmaceutical
  • compositions cosmetic compositions, personal care products, fragrances, perfumes, compositions intended for inanimate objects or surfaces (e.g., cleansers, disinfectants, dish detergents, laundry detergents), etc.
  • the colloidosomes can be used in a variety of applications ranging from drug delivery, catalysis,
  • nanocomposites bioanalysis, diagnostics, sensors and markers, energy storage, bio-inhibitors (repellants pesticides,
  • herbicides urea release
  • self-repair e.g., paints, paper, textile, concrete, etc.
  • flame retardancy e.g., flame retardancy
  • personal care e.g., skin care, fragrances or perfumes, hair, teeth, etc.
  • the interstice sizes of the colloidosome are substantially uniform. That is, at least about 90%, or about 95%, or even about 100% of the interstices of the colloidosome can be about the same size.
  • interstices can, for example, have the same average diameter or vary no more than about 10%, about 5%, or about 2% of the average diameter.
  • the average diameter of a non-circular interstice is the diameter of a circle having the same surface area as that of the interstice.
  • the radius of the interstice may differ by about 50% to about 300%, resulting in interstice differing in diameter by up to a factor of about 1.5, or even by a factor up to about 4.
  • the interstice may differ in radius by up to about 50%.
  • the shell is tunable to allow selective filling of an active material into the core and selective transport of the active material from the core through the shell.
  • the active material is transportable from the core through the micro- or nano-structured porous shell. Transport of the active material can be achieved through diffusion or release.
  • the shell can also be tunable to provide an optimum release (i.e., premature release of the active material is substantially inhibited or prevented) of the active material from the core.
  • the shell is tunable by altering the normalized packing density of the micro- or nano-materials.
  • the normalized particle density can be in the range from about 0.5 to about 1.2.
  • the normalized particle density p-d n 2 is used here to characterize the colloidosome structure and obtain a relation with the number-average particle diameter d n .
  • the density p is defined as the number of particles per unit area, which is obviously different for each particle size. Therefore, it has to be normalized by multiplying with the square of the diameter in order to make a fair comparison among the different particle sizes.
  • the normalized packing density can be altered via changes to: an interaction between individual micro- or nano particles (e.g., altering the dielectric constant, short range forces, long range forces, hydrophobic interactions, and ionic interactions); inter-particle cross-linking; colloidosome morphology size and shape; reactivity and functionality of a cross-linker; extent of cross-linking (e.g., cross-linker concentration, number of cross-linking treatments, density of functional sites on the surface of the micro- or nano-materials, cross-linker reactivity, and temperature) ; or morphology of the micro- or nano-particles.
  • an interaction between individual micro- or nano particles e.g., altering the dielectric constant, short range forces, long range forces, hydrophobic interactions, and ionic interactions
  • inter-particle cross-linking e.g., altering the dielectric constant, short range forces, long range forces, hydrophobic interactions, and ionic interactions
  • inter-particle cross-linking e.g
  • a cross-linking agent can be used to tune the micro- or nano-structured porous shell to achieve desired properties.
  • the use of either multiple and/or different (with regards to length, functionality or both) cross-linking agents or multiple rounds of treatments with the same cross linker can provide tight colloidal particle packing enabling reduced leakage.
  • an active material is loaded after the step of synthesizing the colloidosomes , it can be advantageous to retain porosity in the shell.
  • a porous shell allows ingress or loading of the active material, which can subsequently be locked in place by techniques such as adding additional cross-linking agents (with the same or different cross-linkers) or by adding one or more shells.
  • the empty, porous colloidosomes can be provided as a product and encapsulation is performed by the customer at his/her premises.
  • cross linkers that are responsive/reactive to changes in reaction conditions can be utilized.
  • the cross-linking rate and density can be modulated by altering: the solution medium, pH, the polarity of the solution, temperature, pressure, etc.
  • cross linkers can be used that possess physiochemical properties that affect active transport across the shell, adjusting the
  • colloidosomes are dispersed, or directing the assembly of additional shells over the colloidosome .
  • An example is loading a colloidosome with a lipophilic oil, then performing cross-linking with cross-linker molecules that possess hydrophilic or ionically-charged regions between reactive groups, thereby providing an energetic barrier to diffusion across the shell.
  • ionically-charged "spacer" portion between the two or more reactive ends can be used to create a composite electrostatic barrier comprised of both an ionically charged medium around the colloidosome and ionically charged cross-linkers.
  • the choice of cross-linker can in this way change the transport/barrier properties of the shell. Additionally, the cross-linker
  • functionality can be used to influence the interaction of the architecture with the surrounding medium (e.g., fragrance formulation) and lead to a partially or fully stable dispersion.
  • the surrounding medium e.g., fragrance formulation
  • the shell can be tunable by using cross-linkers that can be isomerized, and thereby changing the normalized packing density upon
  • Ultraviolet light can be used to induce a trans-cis conversion, effectively shortening the cross-linker length and bringing neighboring colloidal shell particles closer together, and thus, changing the normalized packing density.
  • the cross-linker can be selected from the group consisting of bis isocyanates (e.g., lysine diisocyanate ethyl ester), bis epoxides (eg, 1 , 4-butanediol diglycidyl ether,) activated esters (e.g., N-hydroxysuccinimide esters,
  • bis isocyanates e.g., lysine diisocyanate ethyl ester
  • bis epoxides eg, 1 , 4-butanediol diglycidyl ether
  • activated esters e.g., N-hydroxysuccinimide esters
  • pentafluorophenyl esters bis or poly amines (e.g., 1,6- diaminohexane, spermidine) , bis lactones, acid anhydrides, bis carboxylic acids, and combinations thereof.
  • concentration of the cross-linker can vary and can be selected to tune the normalized packing density of the micro- or nano-materials.
  • the cross-linker is in a concentration in the range of about 0.5 mM to about 5 M.
  • one or more different cross-linkers can be used to tune the micro- or nano-structured porous shell by adjust the normalized packing density.
  • more than one cross-linker is used to form the colloidosome with the cross-linkers being the same (but with different concentrations) or different.
  • the two or more cross linkers can be added at the same time or at different times during or after manipulation or treatment of the colloidosome.
  • the shell can also be tunable by adjusting the morphology (i.e., the size and shape) of the micro- or nano materials forming the shell.
  • the physical size of the colloidal particles can be selected or controlled.
  • the micro- or nano-materials can have different sizes and the shapes of the shell can be altered to provide shells having round, oval, elliptical, etc. shapes. Examples include: using polydispersity in nano- or micro-particle sizes to enable use of non-uniform size distribution in order to achieve packed shells of colloidosomes and thus, eliminate time-consuming and/or expensive approaches to obtain narrow distribution or size control of microgels.
  • Such colloidosomes may significantly reduce thermodynamic phenomena such as the Ostwald ripening effect that can cause destabilization of the colloidosome architecture wherein the encapsulated active materials can prematurely leak out.
  • the approach of having polydisperse microgels also allows for minimizing the dynamic changes in colloidosome sizes in a specific formulation. This can be achieved in single or multi-shell architectures.
  • the morphology can also be adjusted by selecting or controlling the geometry of the colloidal particles
  • colloidosome shell comprising the colloidosome shell (s.) Examples include:
  • micro- or nano materials different or the same sizes and shapes of the micro- or nano materials; combining swollen or shrunken micro- or nano
  • the shell can be tunable by altering the
  • the dielectric constant of the colloidosome ' s surroundings can be altered by the addition of
  • dissociative additives e.g., salts such as LiCl, polyanions, or polycations such as spermidine in water at neutral pH
  • dissociative additives e.g., salts such as LiCl, polyanions, or polycations such as spermidine in water at neutral pH
  • colloidosome to either stay intact, or release the active material at a rate controlled by the charge type/density.
  • the core of the colloidosome can be re-filled after transport of the active material from the core through the shell. According to certain embodiments, after transport of the active material through the shell, the shell remains
  • the cross-linking bonds are reversible and the shell can be refilled with the same or different active material after transport of the active material through the shell. This can be achieved by using cross-linkers that are chemically reversible.
  • a reversible cross-linking bond is thiol-disulfide bonds. If a cross-linker possesses a disulfide bond, the bond can be readily cleaved to thiols with a reducing agent, thereby lowering the packing density, and later re oxidize to the disulfide, thereby restoring the normalized packing density.
  • Methods of producing the colloidosome can include combining micro- or nano-materials, a base fluid, and an active material to form a first fluid; adding a cross-linking agent to the first fluid to form a second fluid; and allowing the cross- linking agent to cross-link the micro- or nano-materials to form a micro- or nano-structured porous shell comprising a plurality of the micro- or nano-materials and interstices located between the micro- or nano-materials, and wherein the active material is located within a core that is defined by the shell.
  • the base fluid can include water, a liquid hydrocarbon, a solvent (e.g., benzene, hexane, xylene, methanol, ethanol, dichloromethane, etc.), or mineral oil, edible oils (e.g., sunflower oil), toluene, or silicone fluids.
  • a solvent e.g., benzene, hexane, xylene, methanol, ethanol, dichloromethane, etc.
  • mineral oil e.g., sunflower oil
  • toluene e.g., sunflower oil
  • the method can further include adding a second micro- or nano-material to the second fluid.
  • the methods can further include more than one addition of the cross-linking agent to form the second fluid, for example, utilizing multiple additions of the cross-linking agent over a specified period of time.
  • a method of making a colloidosome can include: combining micro- or nano materials, a solvent, and an active material to form a first fluid; adding a first cross-linking agent to the first fluid to form a second fluid; adding a second cross-linking agent to the second fluid; and allowing the cross-linking agent to cross-link the micro- or nano-materials to form a micro- or nano-structured porous shell comprising a plurality of the micro- or nano materials and interstices located between the micro- or nano materials, and wherein the active material is located within a core that is defined by the shell.
  • the first cross-linking agent and the second cross-linking agent can be different.
  • This method can also include adding a second micro- or nano-material to the second solution before, during, or after the addition of the second cross-linking agent.
  • a method for altering the dielectric constant can include: dispersing micro- or nano-materials in a working fluid; creating an emulsion by combining the working fluid with a liquid hydrocarbon; and adjusting the ionic strength of the emulsion with an electrolyte.
  • the electrolyte can be selected from the group consisting of salts (e.g., sodium chloride, potassium chloride, calcium chloride, etc.) in aqueous
  • This method can further include adding a second micro- or nano-material to the emulsion before the step of adjusting the ionic strength.
  • a surfactant or emulsifier can be added to the working base fluid and the liquid hydrocarbon to create the emulsion.
  • the surfactant or emulsifier can be selected from ionic, anionic, non-ionic, cationic, zwitterionic, or neutral surfactants, and combinations thereof. Examples
  • Example 1 50 milligrams (mg) of amino-functionalized poly(N- isopropylacrylamide ) (pNiPAAm) microgels (lyophilized NH 2 - pNiPAAm) having a diameter of approximately 0.5 to 1.1 micrometers (pm) (500 to 1,100 nanometers (nm) ) were dispersed in 5 grams (g) of water with vigorous stirring. 0.6 g of an active material of limonene was then added. Stirring was continued overnight. 84 mg of a cross-linking agent of 1,4- butanediol diglycidyl ether was then added in portions.
  • pNiPAAm amino-functionalized poly(N- isopropylacrylamide )
  • Example 2 26 mg of polylactic-coglycolic acid copolymer (PLGA) (50:50 L:G monomer ratio, 15-25 kDa) microgels (lyophilized solid) having a diameter of approximately 200 to 300 nm were added to 2.5 g of 10 mM phosphate buffer, pH 7, in a glass scintilliation vial with stirbar. The mixture was stirred at 1,000 revolutions per minute (rpm) for approximately 5 min. 129 mg of an active material of limonene was then added and the stir rate was increased to 1,200 rpm for 10 min. Stirring was
  • Example 3 After 2 days, a 1 g portion of the reaction mixture from Example 1 was removed and combined with 2 g of water and approximately 10 mg of a second type of pNiPAAm microgels, carboxylate-functionalized microgels (CCpH-pNIPAM) having a diameter of 0.2 to 0.5 pm (200 to 500 nm) and shaken on a rotary orbital shaker to produce a mixed or layered NH 2 -pNIPAM and CCpH- pNIPAM colloidosome shell surrounding the limonene core.
  • CpH-pNIPAM carboxylate-functionalized microgels
  • Example 4 50 mg of reconstituted lyophilized Nf ⁇ -functionalized pNiPAAm microgels having an approximate diameter of 0.5 to 1.0 pm were dispersed in 5 g of water. 0.6 g of an active material of limonene was then added with vigorous stirring. 84 mg of a cross-linking agent of 1 , 4-Butanediol diglycidyl ether (20 times reactive equivalents) was then added in four different time frames over a period of approximately 8 h. The solution was aged at room temperature with stirring to form colloidosomes with a cross-linked pNiPAAm polymer shell surrounding the
  • limonene core [0049] The following example illustrates a method of preparing colloidosomes with two different types of cross- linking agents and two different types of micro- or nano materials (microgels) :
  • Example 5 A 1 g portion of the intermediate reaction product (cross-linked amino-pNiPAm colloidosomes) listed in Example 1 was combined with 10 mg of a second type of microgel of
  • carboxylate-functionalized microgels (pNiPAM in 2 g water, CCpH- pNilPAAm) having a diameter of 0.2 to 0.5 pm (200 to 500 nm) .
  • Example 6 Poly (lactic acid) (PLA) microgels having a mean diameter of approximately 200 nm were dispersed in 5 milliliters of water at a concentration of 20 mg/mL. While stirring at
  • the colloidosome for the testing results shown in Fig. 4 was prepared in a vial by mixing 1 mL of pNIPAM-NH 2 nanogels (concentration 10 mg/mL) , either 1 or 10 mL of
  • the samples were then sonicated using a probe sonicator at 50% intensity for 30 seconds on ice.
  • the solutions were then heated at 60 °C for 30 minutes. After heating, the samples were then aged at room temperature for 72 hours.
  • Tenacity testing samples were prepared after blotting 20 mg of colloidosomes onto a filter paper. Tenacity was measured by a GC headspace method.
  • Sample B had a slower release of the active material (limonene) due to the greater packing density of neighboring nanogels terminated with different chemical end groups (i.e., amine and carboxylic acid groups) .
  • the release time of the active material can be controlled by changing the interaction between particles, inter-particle cross-linking, colloidosome morphology, reactivity or
  • cross-linker functionality of a cross-linker, extent of cross-linking, and/or morphology of colloidal particles.
  • Fig . 6 The following test shown in Fig . 6 was performed to show re-loading of an active material into the colloidisomal shell.
  • the test was performed by preparing a colloidosome by mixing 1 mL of rNIRAM-N3 ⁇ 4 nanogels (concentration 10 mg/mL) , 10 mL of glutaraldehyde (25%), 40 mg Dowsil 5200, 1 mL of limonene (99.5%), and 10 mL of DI water.
  • the sample was then sonicated using a probe sonicator at 50% intensity for 30 seconds on ice.
  • the solution was then heated at 60 °C for 30 minutes. After heating, the sample was then aged at room temperature for 72 hours.
  • the active material limonene was removed from the colloidosomes by immersing the colloidosomes in a IPA solution overnight. The collected precipitate was re-dispersed into a guanine solution to re-load the core with guanine. Excess guanine was removed by centrifuge. A control sample of guanine was prepared without encapsulation. Tenacity testing of the samples was prepared after blotting 20 mg of colloidosomes onto a filter paper. Tenacity was measured by a GC headspace method. The results in Fig . 6 show that guanine was re-loaded into the colloidosome shell compared to the control without
  • the samples were then sonicated using a probe sonicator at 50% intensity for 30 seconds on ice.
  • the solutions were then heated at 60 °C for 30 minutes. After heating, the samples were then aged at room temperature for 72 hours.
  • Tenacity testing samples were prepared after blotting 20 mg of colloidosomes onto a filter paper. Tenacity was measured by a GC headspace method.
  • sample S has a slower release of the active material (limonene) due to the adjustment of the ionic strength by adding an electrolyte (NaCl) .
  • the release time of the active material can be controlled by
  • compositions, systems, and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions, systems, and methods also can “consist essentially of” or “consist of” the various components and steps. It should also be understood that, as used herein, “first,” “second,” and “third, “ are assigned arbitrarily and are merely intended to differentiate between two or more particles, shell layers, etc., as the case may be, and does not indicate any sequence.

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Abstract

Cette invention concerne un colloïdosome comprenant : une coque poreuse micro- ou nanostructurée comportant une pluralité de micro- ou nanomatériaux et des interstices situés entre les micro-ou nanomatériaux ; et un cœur qui est défini par la coque, où la coque est accordable pour permettre le remplissage sélectif d'un principe actif dans le cœur et le transport sélectif du principe actif depuis le cœur à travers la coque. Les procédés de formation de colloïdosome peuvent comprendre les étapes consistant à : combiner les micro- ou nanomatériaux, un fluide de base et un principe actif pour former un premier fluide ; ajouter un agent de réticulation au premier fluide pour former un second fluide ; et laisser l'agent de réticulation réticuler les micro- ou nanomatériaux pour former une coque poreuse micro- ou nanostructurée comportant la pluralité des micro- ou nano-matériaux et des interstices situés entre les micro- ou nanomatériaux, où le principe actif se trouve à l'intérieur d'un cœur qui est défini par la coque.
PCT/US2019/024030 2018-03-26 2019-03-26 Colloïdosome à coque poreuse accordable WO2019191065A2 (fr)

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CN113999668A (zh) * 2021-08-18 2022-02-01 江苏集萃先进高分子材料研究所有限公司 一种不可逆变色微胶囊及其制备方法
CN118231732A (zh) * 2024-01-15 2024-06-21 广东派顿新能源有限公司 一种纳米胶体电池的制备方法及系统

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EP3468536A4 (fr) * 2016-06-13 2020-01-08 SABIC Global Technologies B.V. Colloïdosomes à nano-architecture pour libération régulée et déclenchée

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* Cited by examiner, † Cited by third party
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CN113999668A (zh) * 2021-08-18 2022-02-01 江苏集萃先进高分子材料研究所有限公司 一种不可逆变色微胶囊及其制备方法
CN113999668B (zh) * 2021-08-18 2023-12-19 江苏集萃先进高分子材料研究所有限公司 一种不可逆变色微胶囊及其制备方法
CN118231732A (zh) * 2024-01-15 2024-06-21 广东派顿新能源有限公司 一种纳米胶体电池的制备方法及系统

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