WO2019241138A1

WO2019241138A1 - Compositions, use and methods for tunable tenacity of active(s) encapsulated in colloidosome architectures

Info

Publication number: WO2019241138A1
Application number: PCT/US2019/036357
Authority: WO
Inventors: Jonathon SCHOLIN; C. William Gundlach Iv; Nitin Chopra; Ihab N. ODEH
Original assignee: Sabic Global Technologies, B.V.
Priority date: 2018-06-12
Filing date: 2019-06-10
Publication date: 2019-12-19

Abstract

A colloidosome composition comprising a liquid medium and a plurality of colloidosomes dispersed therein; wherein the colloidosomes are characterized by tunable tenacity, wherein the tenacity is tuned by controlling a colloidosome environment comprising the liquid medium; wherein the colloidosomes comprise (i) a micro-structured and/or nano-structured porous shell comprising micro-materials and/or nano-materials, respectively, and interstices dispersed therein, wherein the interstices are located between the micro-materials and/or nano-materials; and (ii) a core that is defined by and located inside the shell; wherein the colloidosomes encapsulate an active material, wherein the shell and/or the core comprise the active material; wherein the shell and/or the interstices allow for releasing active material from the shell and/or the core into the colloidosome environment; and wherein the tenacity is defined as the time period that the plurality of colloidosomes is releasing a given amount of active material from the shell and/or the core into the colloidosome environment.

Description

COMPOSITIONS, USE AND METHODS FOR TUNABLE TENACITY OF ACTIVE(S)

ENCAPSULATED IN COLLOIDOSOME ARCHITECTURES

TECHNICAL FIELD

[0001] The present disclosure relates to colloidosome compositions for release of active components, more specifically colloidosome compositions having tunable tenacity, and methods of making and using same.

BACKGROUND

[0002] Micro-structured and/or nano-structured encapsulation systems (e.g., colloidosomes, encapsulated nanoparticles, liposomes, etc.) can provide improved uptake and efficient transport or delivery of active agents to intended targets (e.g., a person, an animal, an inanimate object, etc.). Micro-structured and/or nano-structured encapsulation generally refers to the process of embedding or surrounding a core of “active” material in a“shell” material that is different from the core material. Microencapsulation can be applied to active materials such as fragrances, flavors, and drugs for protecting the active materials from degradation, improving material handling, or delaying/prolonging/triggering the release of an active material(s).

[0003] Colloidosomes can be typically formed such that the core is loaded with an active material. Colloidosomes can be used for the release of flavors, fragrance, air fresheners, lotions, creams, nutrients, textile scents, drugs, etc., from colloidosome cores.

[0004] Such core loaded colloidosome systems, however, have several limitations. For example, colloidosome systems tend to have a spike or burst release profile of the active material rather than a controlled and tunable release profile. This can pose an issue when the active material is a fragrance or a pharmaceutical agent.

[0005] Conventionally, a low duration of a fragrance (e.g., a volatile fragrance), or low tenacity (i.e., low duration of a scent), can be addressed via the addition of: (a) other fragrances with lower volatility and/or (b) additives to produce a fragrance formulation that meets customer demand of > 3 h tenacity. Both approaches (a and/or b) increase the complexity and cost of the final product (e.g., fragrance formulation). In the case of adding additional fragrance oils with lower volatility (“middle notes” or“base notes”), such oils are usually significantly more expensive than the highly volatile“top notes” and also have a much different scent profile, for example woody or musky.

[0006] In some applications, active materials can be blended with other chemical ingredients to create a suitable product formulation for a consumer to use. For example, fragrance oils can be mixed with ethanol to create a product formulation that, when applied to an object at room temperature, results in a burst release of fragrance oil enhanced by the ethanol environment. Thus, tuning the release kinetics for faster or slower release per application need would require encapsulating pure active and/or active diluted with the formulation components, resulting in a major challenge of balancing leakage and release profiles.

[0007] Generally, additives that can increase tenacity of volatile active materials can either alter the vapor pressure (e.g., fixatives) or slow the diffusion rate of the fragrance oil (e.g., barriers). Fixatives increase scent tenacity by slowing the evaporation of volatile fragrance compounds; and fixatives are typically relatively low volatility compounds. Fixatives can bind to or interact with a fragrance oil, lowering the vapor pressure of the bulk formulation. However, fixatives can carry distinct odors of their own, and the amount that can be used is limited by a perceptible residue or an undesirable odor or appearance in a product formulation. While tenacity can be tuned to a certain extent with a choice of a fixative or a blend of fixatives, fixatives are associated with an increased formulation cost and fixative residue after application. Non-odorous fixatives can include capsules or complexes based on dextrines, melamines or obtained by coacervation of anionic and cationic polymers; however, capsules or complexes are difficult to formulate into a fragrance composition and/or the release is little controlled but depends on variable factors like moisture or sebum amount or sweat intensity. Other examples of non-odorous fixatives can include perfume base notes such as musks; however, perfume base notes can negatively impact the fragrance character of the compositions to which they are added.

[0008] Polymer films can act as a permeable barrier to trap active materials on a surface for slower evaporation. However, polymer films can also leave behind an undesirable residue after application, which residue can be perceived both visually and tactilely. In addition, a polymer film approach does not allow for tunable release of active materials and protection of active materials. Fragrance encapsulation within polymeric single shells can be used to suppress the evaporation of volatile actives, but loading is limited by the internal volume of the individual polymer particles shells (e.g., a 80 pm diameter microcapsule with a shell thickness of 10 pm has a maximum loading volume of 40%). Such a limited“payload” requires a greater amount of polymer shells to encapsulate a large volume of active materials, raises formulation costs, creates stability issues (e.g., particle sedimentation), and becomes problematic for transparent formulations (e.g., fine perfume) by imparting turbidity. While the release of active materials from single shells can be moderated by slower diffusion out of the material, it lacks tunable tenacity. Thus, there is an ongoing need for the development of active materials encapsulation compositions that can provide for tunable tenacity.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] For a detailed description of the preferred aspects of the disclosed methods, reference will now be made to the accompanying drawing in which:

[0010] Figures 1A, IB, and 1C display a configuration of a device for the delivery of an active material;

[0011] Figure 2 displays another configuration of a device for the delivery of an active material; [0012] Figure 3 displays yet another configuration of a device for the delivery of an active material;

[0013] Figure 4 displays still yet another configuration of a device for the delivery of an active material;

[0014] Figure 5 displays an optical microscope image of colloidosomes loaded with a fragrance;

[0015] Figure 6 displays a graph of limonene tenacity with and without colloidosme encapsulation;

[0016] Figure 7 displays a schematic of colloidosome re-dispersion process;

[0017] Figure 8 displays a graph of tenacity for various colloidosome compositions;

[0018] Figure 9A displays a schematic of forming colloidosomes, and colloidosome behavior in the presence of an interstice blocking agent;

[0019] Figure 9B displays a graph of limonene tenacity without colloidosme encapsulation, and with colloidosome encapsulation in the presence and in the absence of an interstice blocking agent;

[0020] Figure 10A displays a schematic of forming colloidosomes, and colloidosome behavior in the presence of stabilizers;

[0021] Figure 10B displays a graph of limonene tenacity without colloidosme encapsulation, and with colloidosome encapsulation in the presence and in the absence of a stabilizer;

[0022] Figure 1 1A displays a schematic of forming colloidosomes, and colloidosome behavior in the presence of destabilizers; and

[0023] Figure 1 IB displays a graph of limonene tenacity with and without acetone destabilizer.

DETAILED DESCRIPTION

[0024] Disclosed herein are colloidosome compositions comprising a liquid medium and a plurality of colloidosomes dispersed therein, and methods of making and using same; wherein the plurality of colloidosomes is characterized by tunable tenacity, wherein the tenacity is tuned by controlling a colloidosome environment, and wherein the tenacity is defined as the time period that the plurality of colloidosomes is releasing a given amount of active material into the colloidosome environment.

[0025] Disclosed herein are systems of tunable-release profile colloidosomes and methods for creating colloidosomes with adjustable release kinetics of encapsulated active material(s) (i.e., tunable tenacity). Such tunable tenacity in colloidosomes can be achieved by controlling the colloidosome environment, for example via 1) controlling the medium surrounding the colloidosomes (e.g., molecular, nano, micro, and/or bulk scale) and/or 2) using of packaging and/or delivery elements that alter either colloidosome properties or the solution environment of the colloidosome composition or formulation.

[0026] In an aspect, a desired tenacity of an active material (or multiple active materials) can be achieved through one or more of the following: (i) balancing an active material concentration inside and outside of colloidosomes (i.e., encapsulated and unencapsulated active material) once the colloidosomes are dispersed into a medium, (ii) encapsulating an active material with additives that chemically and/or physically interact and/or block interstitial transport channels, (iii) altering the surface tension of the colloidosomes to control spreading and/or rupture of colloidosomes after application, (iv) partitioning of active material-filled colloidosomes from diluent in an applicator system to minimize active material leakage and diffusion prior to application, (v) using of immobilized active in a portion of a dispensing or delivery system (e.g., active material deposited on a surface) to achieve repacking of active material into colloidosomes, (vi) coextrusion of a barrier layer around colloidosomes or colloidosome composition droplets during delivery of the colloidosome composition, (vii) re-emulsification of colloidosomes to delay the release via multi-layered architectures; and (viii) combinations of (i)-(vii).

[0027] Other than in the operating examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as modified in all instances by the term“about.” Various numerical ranges are disclosed herein. Because these ranges are continuous, they include every value between the minimum and maximum values. The endpoints of all ranges reciting the same characteristic or component are independently combinable and inclusive of the recited endpoint. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations. The endpoints of all ranges directed to the same component or property are inclusive of the endpoint and independently combinable. The term“from more than 0 to an amount” means that the named component is present in some amount more than 0, and up to and including the higher named amount.

[0028] The terms“a,”“an,” and“the” do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. As used herein, the singular forms“a,”“an,” and“the” include plural referents.

[0029] As used herein,“combinations thereof’ is inclusive of one or more of the recited elements, optionally together with a like element not recited, e.g., inclusive of a combination of one or more of the named components, optionally with one or more other components not specifically named that have essentially the same function. As used herein, the term“combination” is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0030] Reference throughout the specification to“an aspect,”“another aspect,”“other aspects,”“some aspects,” and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the aspect is included in at least an aspect described herein, and may or may not be present in other aspects. In addition, it is to be understood that the described element(s) can be combined in any suitable manner in the various aspects.

[0031] As used herein, the terms“inhibiting” or“reducing” or“preventing” or“avoiding” or any variation of these terms, include any measurable decrease or complete inhibition to achieve a desired result. [0032] As used herein, the term“effective,” means adequate to accomplish a desired, expected, or intended result.

[0033] As used herein, the terms“comprising” (and any form of comprising, such as“comprise” and “comprises”),“having” (and any form of having, such as“have” and“has”),“including” (and any form of including, such as“include” and“includes”) or“containing” (and any form of containing, such as“contain” and“contains”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0034] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art.

[0035] Compounds are described herein using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash (“-”) that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through the carbon of the carbonyl group.

[0036] In an aspect, a colloidosome composition can comprise a liquid medium and a plurality of colloidosomes dispersed therein. For purposes of the disclosure herein, the terms “colloidosome composition” and“colloidosome formulation” can be used interchangeably.

[0037] In an aspect, a colloidosome can comprise (i) a micro-structured and/or nano-structured porous shell comprising a plurality of micro-materials and/or nano-materials, respectively, and a plurality of interstices dispersed therein, wherein the interstices are located between the micro-materials and/or nano materials; and (ii) a core that is defined by and located inside the shell; wherein each of the plurality of colloidosomes encapsulates an active material (e.g., encapsulated active material), wherein the shell and/or the core comprise the active material; and wherein the shell and/or the interstices allow for releasing active material from the shell and/or the core into the colloidosome environment. For purposes of the disclosure herein, the term“colloidosome” refers to a structure that has (i) a shell (e.g., a porous shell) defined by a plurality of micro-materials and/or nano-materials and interstices formed between the micro-materials and/or nano-materials; and (ii) a core that is defined by the micro-structured and/or nano-structured porous shell. Further, for purposes of the disclosure herein, and without wishing to be limited by theory, the term “colloidosome” refers to a structure composed of colloidal particles or materials; i.e., at least a portion of the plurality of micro-materials and/or nano-materials that form the colloidosome are colloidal particles or materials (e.g., can form a stable dispersion in a given liquid medium).

[0038] The plurality of micro-materials and/or nano-materials can comprise microparticles, nanoparticles, microgels, nanogels, polymer brushes, surfactants, metal oxides, inorganic polymers, organic polymers, lipids, block copolymers, cross-linked polymers, biopolymers, biomolecules, micellular/dendrimer structures, yolk/shell structures, core/shell structures, pomegranate structures, nanomaterials, functionalized microstmctures, functionalized nanostructures, hollow nanostructures, and the like, or combinations thereof. The plurality of micro-materials and/or nano-materials can have any suitable shape. Nonlimiting examples of micro-materials and/or nano-materials shapes include cylindrical, discoidal, spherical, tabular, ellipsoidal, equant, irregular, cubic, tubular, rod, acicular, wire, tetrapod, a hyper-branched structure, a random structure, and the like, or combinations thereof.

[0039] In an aspect, the plurality of micro-materials and/or nano-materials can have an average size (e.g., average particle size) of from about 1 nm to about 15,000 nm, alternatively from about 10 nm to about 5,000 nm, or alternatively from about 25 nm to about 1,000 nm. For purposes of the disclosure herein, the average size of a particle refers to an arithmetic mean of particle sizes, wherein the size of a particle (e.g., micro-materials and/or nano-materials) refers to the largest dimension of any two dimensional cross section through the particle.

[0040] In an aspect, the plurality of micro-materials and/or nano-materials can comprise microgels and/or nanogels, respectively, wherein the microgels and/or nanogels can comprise a polymer network of hydrophilic polymers, hydrophobic polymers, amphiphilic polymers, amphiphobic polymers, lipophilic polymers, lipophobic polymers, and the like, or a combination thereof. In some aspects, the polymeric network can comprise non-ionic polymers, cationic polymers, anionic polymers, zwitterionic polymers, polymers comprising metal-organic frameworks, polymers comprising zeolitic imidazolate frameworks, and the like, or a combination thereof. The polymer network can be cross-linked.

[0041] Nonlimiting examples of polymers suitable for use as micro-materials and/or nano-materials in the porous shells include polyvinyl alcohol (PVA), poly(N-isopropyl acrylamide) (pNIPAAm), cross-linked N-isopropylacrylamide, functionalized polyNIPAAm (e.g., C0₂H-NIPAAm, NH₂-NIPAAm, etc.), copolymers of NIPAAm and N,N'-methylenebisacrylamide (MBA), co-polymers of NIPAAm and allyl amine, copolymers of NIPAAm and acrylic acid, poly( ethylene glycol) (PEG), a hydroxylated poly(methyl methacrylate), an ethylene-vinyl acetate copolymer, a polymer of 2-hydroxyethyl methacrylate (HEMA), poly (maleic acid/octyl vinyl ether) (PMAOVE), a polyurethane, poly(acrylic acid), poly(stearyl acrylate) (PSA), poly(acrylamide), dipropylene glycol acrylate caprylate (DGAC), dipropylene glycol diacrylate sebacate (DGDS), starch, chitin, silicone, a polyolefin, co-polymers of N-isopropylacrylamide and glutaraldehyde, polylactic acid (PLA), polylactic-coglycolic acid copolymer (PLGA), alginate, polyesters (e.g., 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) (PMMA), derivatives thereof, copolymers thereof, and the like, or combinations thereof.

[0042] In an aspect, the plurality of micro-materials and/or nano-materials that form the colloidosome porous shell can be the same or different. [0043] In some aspects, the porous shell can comprise a single shell layer. In other aspects, the porous shell can comprise two or more shell layers. In yet other aspects, the porous shell can comprise a first shell layer (e.g., a full or complete shell layer), and at least one additional shell layer, wherein the at least one additional shell layer can be a partial layer or a complete layer. Each layer of the porous shell can comprise micro-materials and/or nano-materials that can be the same or different.

[0044] The porous shell comprises a plurality of micro-materials and/or nano-materials, and a plurality of interstices dispersed therein, wherein the interstices are located between the micro-materials and/or nano materials. For purposes of the disclosure herein, an interstice or pore is defined as an opening, space, or passage way that allows for an active material to travel from the core into the colloidosome environment (i.e., a material transport flow path that connects the core with the colloidosome environment), for example into a liquid medium contacting and surrounding the colloidosome. The interstices or pores can have any suitable dimension as necessary to provide for a desired active material release profile from the colloidosome. In an aspect, the interstices can have a size of from about 0.5 nm to about 3,000 nm, alternatively from about 10 nm to about 1,000 nm, or alternatively from about 75 nm to about 200 nm. In some aspects, irrespective of pore size, the pore function (e.g., the ability of the pore to allow for the transport of active material) can be tuned by surface functionality of the pore, wherein surface functionalized molecule can act as a pore blocking or gating tether.

[0045] In some aspects, the porous shell can comprise an active material. The active material can be (i) bound to a surface of the plurality of micro-materials and/or nano-materials, (ii) loaded or impregnated within the plurality of micro-materials and/or nano-materials, (iii) contained within the plurality of interstices formed between the micro-materials and/or nano-materials, or (iv) combinations of (i)-(iii).

[0046] The active material can be selected from the group consisting of a chemical agent, a biological agent, an oil (e.g., a plant derived oil), an ionic liquid, a suspension, a polymer, and combinations thereof. The active material can be any suitable material that is desirably released from the core and/or shell over a desired period of time. Chemical agents can comprise a drug, gaseous molecules, a cosmetic agent, a flavoring agent, a fragrance (e.g., a scent-producing chemical compound), a malodor agent, a reactive agent, a cross-linker, a reactive diluent, a solvent, an inorganic or organic chemical, an organometallic system, a petrochemical, a reducing agent, an oxidizing agent, an aqueous salt, a pesticide, a herbicide, and the like, or combinations thereof. Biological agents can comprise a protein, a peptide, an antibody, a nucleic acid, a carbohydrate, a lipid, and the like, or combinations thereof.

[0047] While the current disclosure will be discussed in detail in the context of a colloidosome comprising an active material comprising a fragrance, it should be understood that the methods disclosed herein can be used in conjunction with any suitable method of tuning the tenacity of a colloidosome composition that comprises an active material compatible with the methods and materials disclosed herein. Generally, a fragrance refers to one or more chemical compounds that gives a certain product (e.g., perfume, cologne, shower gel, bathing foam, deodorant spray, body lotion, hand washing cream, hair shampoo, shaving cream, etc.) a desired scent.

[0048] In an aspect, the active material can comprise an oil, such as an essential oil (e.g., a plant derived oil). In some aspects, the oil can be a fragrance. Nonlimiting examples of essential oils suitable for use in the present disclosure include sesame oil, macadamia nut oil, tea tree oil, evening primrose oil, Spanish sage oil, Spanish rosemary oil, coriander oil, thyme oil, pimento berries oil, rose oil, anise oil, balsam oil, bergamot oil, rosewood oil, cedar oil, chamomile oil, cinnamon oil, sage oil, clary sage oil, clove oil, cypress oil, eucalyptus oil, fennel oil, sea fennel oil, frankincense oil, garlic oil, geranium oil, ginger oil, grapefruit oil, jasmine oil, juniper oil, lavender oil, lemon oil, lemongrass oil, lime oil, mandarin oil, marjoram oil, myrrh oil, neem oil, neroli oil, orange oil, patchouli oil, pepper oil, peppermint oil, black pepper oil, petitgrain oil, pine oil, rose otto oil, rosemary oil, sandalwood oil, spearmint oil, spikenard oil, vetiver oil, wintergreen oil, ylang ylang, and the like, or combinations thereof.

[0049] Nonlimiting examples of chemical compounds suitable for use as a fragrance in the present disclosure include limonene, carvone, isoamyl benzoate, methyl heptine carbonate, triacetin, anethole, methyl isoeugenol, safrole, diphenyl oxide, benzyl propionate, eugenol acetate, phenylethyl acetate, cinnamyl acetate, propiophenone, p-cresyl acetate, p-methyl acetophenone, benzyl acetate, ethyl acetoacetate, ethyl benzoate, isosafrole, ethyl cinnamate, acetophenone, benzyl benzoate, p-methyoxy acetophenone, methyl cinnamate, benzyl formate, methyl benzoate, 2-undecanone, ethyl laurate, isoamyl isovalerate, 2-nonanone, linalyl acetate, octyl acetate, phenyl methyl carbonyl propionate, isoamyl butyrate, menthyl acetate, menthone, phenyl methyl carbonyl acetate, terpinyl acetate, thujone, ethyl caprylate, fenchone, geranyl acetate, bornyl acetate, pulegone, p-cresyl ethyl ether, methyl eugenol, piperitone, jasmine, methyl chavicol, dibenzyl ether, and the like, or combinations thereof.

[0050] The core of the colloidosome can comprise a polymer emulsion, a polymer gel, an aerogel, a liquid, an oil, a solution, an electrolyte, a biochemical agent, a void space, and the like, or combinations thereof. For example, when the active material comprises a pesticide (e.g., a solid pesticide), the pesticide could be dissolved in a solvent (e.g., thereby forming a solution) for loading into the colloidosome core. Nonlimiting example of solvents suitable for use in the present disclosure include organic solvents, such as ethanol, methyl acetate, ethyl acetate, isopropanol, butanol, and the like, or combinations thereof.

[0051] For purposes of the disclosure herein, the term“oil” refers to a liquid that is immiscible with water. Further, for purposes of the disclosure herein, the term“immiscible” when used with reference to the oil and water refers to an oil that has a solubility in water of less than about 5 wt.%, alternatively less than about 1 wt.%, or alternatively less than about 0.1 wt.%. Nonlimiting examples of oils suitable for use in the present disclosure include a synthetic oil (e.g., a synthetic hydrophobic liquid), a plant-derived oil (e.g., a plant-derived hydrophobic liquid), a vegetable oil (e.g., sunflower oil), an essential oil, a terpene-containing essential oil, a terpenoid, a hydrocarbon, an aliphatic hydrocarbon, a cyclic hydrocarbon, and the like, or combinations thereof.

[0052] In an aspect, the oil can be an oleophilic liquid, i.e., a liquid that has affinity for oils. In an aspect, the oil can be a lipophilic liquid, i.e., a liquid that has affinity for lipids, fats, etc. In some aspects, oleophilic liquids and/or lipophilic liquids can be characterized by a limited solubility (e.g., less than about 10 wt.%) in one or more of oleophilic liquids, lipophilic liquids, and hydrophilic liquids. In such aspects, the oil can have a surface coating of a non-oil substance (e.g., a hydrophilic coating).

[0053] In some aspects, the colloidosomes can encapsulate any suitable active materials, such as hydrophilic active materials, wherein the hydrophilic active materials can be solubilized, suspended, or otherwise dispersed in an aqueous medium in the colloidosome core. In other aspects, the colloidosomes can encapsulate any suitable active materials, such as hydrophobic, lipophobic, etc., active materials, wherein the active materials can be solubilized, suspended, or otherwise dispersed in an oil in the colloidosome core.

[0054] The core of the colloidosome can have an average size of from about 2 nm to 20,000 nm, alternatively from about 10 nm to about 10,000 nm, or alternatively from about 50 nm to about 5,000 nm; with the proviso that the average size of the core is larger than the average size of the plurality of micro materials and/or nano-materials that make up the shell. For purposes of the disclosure herein, the average size of the core refers to an arithmetic mean of core sizes, wherein the size of core refers to the largest dimension of any two dimensional cross section through the core. As will be appreciated by one of skill in the art, and with the help of this disclosure, the size of the micro-materials and/or nano-materials of the shell determines the colloidosome internal volume (e.g., core volume) for active material encapsulation.

[0055] In some aspects, the core of the colloidosome can comprise an active material. In aspects where the shell and the core both comprise an active material, the active material of the shell and the active material of the core can be the same or different.

[0056] In an aspect, the shell comprises an active material, and the core comprises no active material. In another aspect, the core comprises an active material, and the shell comprises no active material. In yet another aspect, both the shell and the core comprise an active material, wherein the active material of the shell and the active material of the core can be the same or different. In some aspects, there can be more than one type of active material in the shell and/or core.

[0057] In an aspect, the colloidosome can comprise the active material in an amount of from about 0.1 wt.% to about 80 wt.%, alternatively from about 1 wt.% to about 80 wt.%, or alternatively from about 10 wt.% to about 80 wt.%, alternatively from about 15 wt.% to about 75 wt.%, alternatively from about 20 wt.% to about 60 wt.%, or alternatively from about 30 wt.% to about 50 wt.%, based on the total weight of the colloidosome; wherein the active material can be present in the shell and/or the core of the colloidosome.

[0058] In an aspect, the colloidosome can have an average size of from about 5 nm to about 50,000 nm, alternatively from about 10 nm to about 25,000 nm, or alternatively from about 100 nm to about 10,000 nm. For purposes of the disclosure herein, the average size of a colloidosome refers to an arithmetic mean of colloidosome sizes, wherein the size of a colloidosome refers to the largest dimension of any two dimensional cross section through the colloidosome. In some aspects, the colloidosome can have a substantially spherical shape. In other aspects, the colloidosome can have a non-spherical shape (e.g., oblate, prolate, discoidal, tabular, ellipsoidal, irregular, equant, polygonal, etc.)

[0059] A colloidosome can be prepared by using any suitable methodology. In an aspect, a colloidosome can be formed by attaching the plurality of micro-materials and/or nano-materials to one another. Such attachment can occur through a chemical bond (e.g., covalent bond), electrostatic interaction, van der Waals interaction, ionic interaction, hydrogen bonding, dipolar interaction, or combinations thereof. In some aspects, colloidosomes can be formed by cross-linking micro-materials and/or nano-materials. For example, glutaraldehyde and/or 1 ,4-butanediol diglycidyl ether can be used to cross-link micro-materials and/or nano-materials formed from NH₂-functionalized pNIPAAm. Such cross-linking of micro-materials and/or nano-materials can provide for improved mechanical properties of the shell (e.g., a yield strength of 1 kPa to 1 MPa or 1 kPa to 50 kPa), when compared to a shell formed without cross-linking. Colloidosomes and methods of making and using same are described in more detail in Publication No. WO 2017/216667 Al ; and U.S. Provisional Application No. 62/648,001; each of which is incorporated by reference herein in its entirety.

[0060] In an aspect, the liquid medium of the colloidosome composition can comprise water, an alcohol, ethanol, propanol, isopropanol, butanol, a C₅-Ci₈ alcohol, an oil (e.g., a synthetic oil, a plant-derived oil, a vegetable oil, sunflower oil, an essential oil, a terpene-containing essential oil, a terpenoid, a hydrocarbon, an aliphatic hydrocarbon, a cyclic hydrocarbon, etc.), an organic solvent (e.g., ethanol, methyl acetate, ethyl acetate, isopropanol, butanol, etc.), a buffer, and the like, or combinations thereof. In an aspect, the buffer can comprise a phosphate (e.g., sodium phosphate, ammonium phosphate, etc.), a borate (e.g., sodium borate), an acetate (e.g., sodium acetate), a citrate (e.g., sodium citrate, potassium citrate, etc.), imidazole, 2-(N-morpholino)ethanesulfonic acid (MES), 4-(2-hydroxyethyl)-l-piperazineethanesulfonic acid (HEPES), tris(hydroxymethyl)-aminomethane (TRIS), 3-(N-morpholino)propanesulfonic acid) (MOPS), piperazine-N,N'-bis(2-ethanesulfonic acid) (PIPES), and the like, or combinations thereof. For example, the buffer can comprise an aqueous solution, such as a 0.1 M aqueous citric acid solution.

[0061] The liquid medium can further comprise any suitable additives, for example to render the colloidosome composition suitable for a desired application. In an aspect, the liquid medium can further comprise an emulsifier, a preservative, an antimicrobial agent, an antioxidant, an ultraviolet (UV) stabilizer, a surfactant, a colorant, and the like, or combinations thereof.

[0062] Nonlimiting examples of colloidosome compositions suitable for use in the present disclosure include pharmaceutical compositions, cosmetic compositions, personal care products, fragrances, perfumes, compositions intended for use on inanimate objects or surfaces (e.g., cleansers, disinfectants, dish detergents, laundry detergents, fabric refreshers), and the like, or combinations thereof. For purposes of the disclosure herein, a perfume refers to a formulation (e.g., composition, colloidosome composition, colloidosome formulation) for the delivery of a particular fragrance. In an aspect, a perfume comprises a fragrance, wherein the fragrance can be present in the perfume in any suitable amount.

[0063] The colloidosome compositions disclosed herein can be used in a variety of applications ranging from drug delivery, catalysis, nanocomposites, bioanalysis, diagnostics, sensors and markers, energy storage, bio-inhibitors (e.g., repellants, pesticides, herbicides), urea release, self-repair (e.g., paints, paper, textile, concrete, etc.), flame retardancy, personal care (e.g., skin care, fragrances, perfumes, hair care, teeth care, etc.), nutritional additives, vitamins, flavors, pigments, textile scent, detergents, softeners, animal care, lubricants, adhesives, and the like, or combinations thereof.

[0064] In an aspect, the colloidosome compositions can comprise the colloidosomes in an amount of from about 0.01 wt.% to about 95 wt.%, alternatively from about 0.1 wt.% to about 90 wt.%, alternatively from about 0.5 wt.% to about 50 wt.%, alternatively from about 1 wt.% to about 25 wt.%, or alternatively from about 1 wt.% to about 10 wt.%, based on the total weight of the composition.

[0065] In an aspect, the colloidosome compositions can comprise the liquid medium in an amount of from about 5 wt.% to about 99.9 wt.%, alternatively from about 10 wt.% to about 99.9 wt.%, alternatively from about 50 wt.% to about 99.5 wt.%, alternatively from about 75 wt.% to about 99 wt.%, or alternatively from about 90 wt.% to about 99 wt.%, based on the total weight of the composition.

[0066] In an aspect, the colloidosomes as disclosed herein can be characterized by tunable tenacity, wherein the tenacity can be tuned by controlling a colloidosome environment. For purposes of the disclosure herein, the term“colloidosome environment” refers to the surroundings of the colloidosome (i.e., the surroundings of the shell of the colloidosome) and components thereof. The colloidosome environment can be controlled: (i) at molecular scale (e.g., by controlling the type and/or amount of molecules that interact with the colloidosome, for example by blocking shell interstices, or by diffusing across the shell into the core); (ii) at nano scale (e.g., by controlling the type and/or amount of nanoparticles that interact with the colloidosome or shell of the colloidosome, for example by blocking shell interstices, by blocking a diffusion path to the colloidosome shell, etc.); (iii) at micro scale (e.g., by controlling the type and/or amount of microparticles that interact with the colloidosome or shell of the colloidosome, for example by enclosing the colloidosome in a secondary shell or a secondary partial shell, thereby by blocking shell interstices, blocking a diffusion path to the colloidosome shell, etc.); (iv) at bulk scale (e.g., by controlling the liquid medium and any components thereof, by controlling a configuration of a device comprising the colloidosome composition, etc.); or (v) combinations of (i)-(iv). Without wishing to be limited by theory, the principles of tuning tenacity as disclosed herein rely on equilibrium (e.g., concentration equilibrium), osmosis (e.g., concentration gradient), surface tension, etc., which principles are largely independent of the type of active material used, and as such the methods of tuning the tenacity as disclosed herein can be applied to a wide variety of active materials.

[0067] For purposes of the disclosure herein, the terms“tenacity of active material,”“tenacity of encapsulated active material,” “tenacity of colloidosomes” comprising active material, “tenacity of a colloidosome composition” comprising colloidosomes comprising active material, and “tenacity of a colloidosome formulation” comprising colloidosomes comprising active material, all refer to the tenacity of an active material that has been encapsulated in a colloidosome for delivery in a specific application (as opposed to the tenacity of unencapsulated active material), and can be used interchangeably.

[0068] In an aspect, the colloidosome environment comprises the liquid medium. In an aspect, the colloidosome environment comprises a device for the delivery of an active material, wherein the device comprises the colloidosome composition, wherein the colloidosome composition comprises the liquid medium and a plurality of colloidosomes dispersed therein. The colloidosome environment can further comprise a space surrounding the colloidosome composition and/or the device for the delivery of an active material, wherein the device comprises the colloidosome composition.

[0069] For purposes of the disclosure herein, the tenacity can be defined as the time period that the plurality of colloidosomes is releasing a given amount (e.g., a desired amount) of active material from the shell and/or the core into the colloidosome environment, and wherein the given amount of active material refers to the total amount of active material released by the plurality of colloidosomes of the colloidosome composition. For example, in aspects where the active material is a pesticide, the tenacity can be defined as the time period that the plurality of colloidosomes is releasing an amount of pesticide of equal to or greater than about 0.001 wt.%, alternatively equal to or greater than about 0.01 wt.%, or alternatively equal to or greater than about 0.1 wt.%, based on the total weight of the initial active material loading of the colloidosome, from the shell and/or the core into the colloidosome environment. For purposes of the disclosure herein, the initial active material loading of the colloidosome refers to the amount of active material loaded into or present in the colloidosome prior to the colloidosome releasing the active material into the colloidosome environment (e.g., releasing the active material during and/or subsequent to the delivery of the active material in a desired application). The tenacity of a colloidosome composition comprising a pesticide can be equal to or greater than about 12 hours, alternatively equal to or greater than about 1 day, alternatively equal to or greater than about 1 week, or alternatively equal to or greater than about 1 month.

[0070] As another example, in aspects where the active material is a fragrance, the tenacity can be defined as the time period that the plurality of colloidosomes is releasing an amount of fragrance of equal to or greater than about 0.1 wt.%, alternatively equal to or greater than about 1 wt.%, or alternatively equal to or greater than about 5 wt.%, based on the total weight of the initial active material loading of the colloidosome, from the shell and/or the core into the colloidosome environment. The tenacity of a colloidosome composition comprising a fragrance can be equal to or greater than about 1 hour, alternatively equal to or greater than about 2 hours, alternatively equal to or greater than about 3 hours, alternatively equal to or greater than about 4 hours, alternatively equal to or greater than about 5 hours, or alternatively equal to or greater than about 6 hours. As will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, the tenacity of a colloidosome is dependent on the type of active material, for example the state of the active material (e.g., liquid, solid, gas), the vapor pressure of the active material (i.e., whether the active material evaporates quickly or not), the chemical stability of the active material (i.e., whether the active material degrades or not once released from the colloidosome), etc.

[0071] As will be appreciated by one of skill in the art, and with the help of this disclosure, creating fragrance products with multiple hour tenacity is challenging owing to the high volatility of certain desirable scents commonly referred to as“top notes,” such as limonene, bergamot, cinnamon, peppermint, orange, and lemon. D-limonene is a widely used top note in consumer products such as fine fragrances or personal care products to impart desirable“citrus”,“clean,”“fresh,” or“bright” notes to a scent. However, and without wishing to be limited by theory, due to the high vapor pressure of limonene, the scent associated with limonene dissipates quickly, often in approximately 10 minutes or less. Colloidosome encapsulation of active materials comprising a fragrance can advantageously increase the tenacity of highly volatile fragrances.

[0072] In aspects where the active material comprises a fragrance, the tenacity of the colloidosomes comprising the active material (e.g., encapsulated active material) can be increased by from about 20% to about 10,000%, alternatively from about 50% to about 1,000%, or alternatively from about 100% to about 500%, when compared to the tenacity of the unencapsulated active material. As will be appreciated by one of skill in the art, and with the help of this disclosure, loading an active material (e.g., a fragrance) in a colloidosome can inhibit evaporation and/or degradation of the active material, thereby increasing tenacity, for example when compared with the tenacity of an unencapsulated active material.

[0073] The colloidosome compositions as disclosed herein can comprise colloidosomes having active materials in the shell and/or the core, thereby allowing for a relatively high loading of active material in the colloidosome, for example from about 10 wt.% to about 80 wt.%, alternatively from about 20 wt.% to about 60 wt.%, or alternatively from about 30 wt.% to about 50 wt.%, based on the total weight of the colloidosome. Such high loading of active material in the colloidosome can provide protection of the active material from degradation, chemical alterations (e.g., oxidation), dilution with other colloidosome composition components (e.g., liquid medium, such as ethanol), and the like, or combinations thereof; for increased tenacity over the unencapsulated active material. Without wishing to be limited by theory, the micro-materials and/or nano-materials forming the shell can provide for a tight cohesive boundary that limits the spreading of highly volatile active materials when applied to a surface, thereby resulting in a significant improvement in tenacity (e.g., colloidosome encapsulated highly volatile fragrance with a tenacity of from about 1 hour to about 5 hours versus unencapsulated highly volatile fragrance with a tenacity of less than about 30 minutes).

[0074] For purposes of the disclosure herein, tuning the tenacity refers to increasing the tenacity, decreasing the tenacity, customizing a tenacity profile that can have various periods of increased and/or decreased tenacity, or combinations thereof. Manipulation of the environment surrounding the colloidosome can provide for controlling of the rate of active material release (e.g., tuning tenacity). The tenacity of active materials can be tuned by colloidosome encapsulation and controlling the colloidosome environment, for example by adjusting the microenvironment surrounding the colloidosome (e.g., the composition of the liquid medium and/or the colloidosome formulation) and/or using packaging features (e.g., macroenvironment) that provide for controlling the delivery of the colloidosome composition in a manner that allows for tuning the tenacity. In some aspects, controlling the microenvironment (e.g. equilibrating the active material concentration inside and outside of colloidosomes) can give an initial burst of active materials, followed by a subsequent two-stage release from the core, and micro-materials and/or nano-materials forming the shell. In other aspects, packaging and delivery device designs can increase tenacity by maintaining a relatively high loading of active material in the colloidosome (e.g., from about 10 wt.% to about 80 wt.%, based on the total weight of the colloidosome), for example via compartmentalization of the active material from the bulk formulation; coating active material-containing droplets with a barrier layer during delivery to further slow active material release; etc.

[0075] In an aspect, the tenacity of the colloidosomes can be tuned by controlling the colloidosome environment, wherein the colloidosome environment is controlled by the liquid medium comprising unencapsulated active material in an amount of from about 5 wt.% to about 50 wt.%, alternatively from about 10 wt.% to about 45 wt.%, or alternatively from about 25 wt.% to about 40 wt.%, based on the total weight of the colloidosome composition. The presence of unencapsulated active material in the liquid medium can provide for slowing down the release of the active material from the colloidosome into the colloidosome environment (i.e., liquid medium), for example and without wishing to be limited by theory, by hindering the diffusion of the active material into the liquid medium. Further, and without wishing to be limited by theory, the presence of unencapsulated active material in the liquid medium allows for achieving a chemical potential balance between the interior of the colloidosome and the exterior of the colloidosome, which correlates with reducing the osmotic pressure. Furthermore, the presence of unencapsulated active material in the liquid medium can allow for an initial burst phase of active material release during application that can then be followed by the slow release of active material from the colloidosomes. As previously discussed herein, and without wishing to be limited by theory, the micro-materials and/or nano materials forming the shell can provide for a tight cohesive boundary that hinders the diffusion of the active material into the liquid medium.

[0076] In an aspect, the tenacity of the colloidosomes can be tuned by controlling the colloidosome environment, wherein the colloidosome environment is controlled by the liquid medium comprising an interstice blocking agent in an amount of from about 0.1 wt.% to about 20 wt.%, alternatively from about 0.5 wt.% to about 15 wt.%, or alternatively from about 1 wt.% to about 10 wt.%, based on the total weight of the colloidosome composition. For purposes of the disclosure herein, the term“interstice blocking agent” refers to any suitable agent that can interact with the interstices in the colloidosome shell to block or slow down the release of active material from the colloidosome into the colloidosome environment.

[0077] Nonlimiting examples of an interstice blocking agent suitable for use in the present disclosure include a chemical blocking agent, an amine, a nanoparticle, a silica nanoparticle, an anionic compound, a cationic compound, a zwitterionic compound, and the like, or combinations thereof. Without wishing to be limited by theory, certain chemical blocking agents (e.g., amines) could form strong hydrogen bonds with chemical functional groups present at interstices, thereby tuning the release kinetics of active materials by hindering diffusion through such interstices. Further, and without wishing to be limited by theory, ionic compounds (e.g., an anionic compound, a cationic compound, a zwitterionic compound) can interact with chemical functional groups present at interstices and form bonds, such as ionic bonds, thereby tuning the release kinetics of active materials by hindering diffusion through such interstices. Furthermore, and without wishing to be limited by theory, nanoparticles (e.g., silica nanoparticles) can be embedded in the interstices thereby providing a physical barrier in the diffusion path of active materials. The interstice blocking agent can be encapsulated together with active material in the colloidosome and/or can be adsorbed by the colloidosome from the surrounding colloidosome environment (e.g., liquid medium).

[0078] In an aspect, the tenacity of the colloidosomes can be tuned by controlling the colloidosome environment, wherein the colloidosome environment is controlled by the liquid medium comprising a stabilizer and/or a surface tension modifier in an amount of from about 0.1 wt.% to about 50 wt.%, alternatively from about 1 wt.% to about 25 wt.%, or alternatively from about 5 wt.% to about 15 wt.%, based on the total weight of the colloidosome composition. [0079] For purposes of the disclosure herein, the term“stabilizer” refers to a chemical compound that increases the stability of a colloidosome in the liquid medium, e.g., a chemical compound that increases the tendency of the micro-materials and/or nano-materials forming the shell to remain assembled as the shell (as opposed to diffusing out of the shell and forming larger interstices and/or unraveling or disassembling the colloidosome).

[0080] Nonlimiting examples of a stabilizer suitable for use in the present disclosure include an electrolyte; a polyelectrolyte, a polymer, polyvinylpyrrolidone (PVP), poly(vinyl alcohol) (PVA), poly(ethylene glycol) (PEG); an ionic polymer, alginate, chitosan; an ionic surfactant, sodium dodecyl sulfate (SDS), sodium lauryl ether sulfate (SLES); a non-ionic surfactant, a polyoxamer, a polysorbate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, tocopheryl polyethylene glycol succinate (TPGS), tocopheryl polypropylene glycol succinate (TPPG); and the like; or combinations thereof. For example, and without wishing to be limited by theory, in the case of ionically charged stabilizers, such as an electrolyte and/or an ionic surfactant, the stabilizer can induce a dissociation of charges on a hydrated surface (e.g., an external surface of a colloidosome shell), thereby providing for charged micro-materials and/or nano materials that form the shell, wherein the resultant dipolar repulsion stabilizes the micro-materials and/or nano-materials that form the shell.

[0081] For purposes of the disclosure herein, the term“surface tension modifier” refers to a chemical compound that can modify the surface tension of the colloidosomes. Generally, surface tension can be defined as the property of a surface that allows the surface to resist an external force (e.g., adhesion forces, which enable the wetting of a surface), due to the cohesive nature of its molecules. For example, and without wishing to be limited by theory, the surface tension allows the micro-materials and/or nano materials that form the colloidosome shell to resist coming apart (e.g., as a result of adhesion forces, for example between the micro-materials and/or nano-materials that form the colloidosome shell and the liquid medium molecules, which result in a“wetting” phenomenon) and enlarging the interstices and/or unraveling the colloidosome. In some aspects, the surface tension modifier can increase the surface tension of the colloidosomes (e.g., reduce wetting of an external surface of a colloidosome shell), thereby increasing the tenacity. In other aspects, the surface tension modifier can decrease the surface tension of the colloidosomes (e.g., enhance wetting of an external surface of a colloidosome shell), thereby decreasing the tenacity.

[0082] Nonlimiting examples of a surface tension modifier suitable for use in the present disclosure include polydimethylsiloxane (PDMS), surfactants, alkoxylated surfactants, branched alkoxylated surfactants, hyperbranched alkoxylated surfactants, organomodified silicones, sulfosuccinates, glycols, polyols, and the like, or combinations thereof. [0083] In an aspect, the tenacity of the colloidosomes can be tuned by controlling the colloidosome environment, wherein the colloidosome environment is controlled by formation of at least a portion of the plurality of colloidosomes into one or more colloidosome architectures in the liquid medium, wherein the colloidosome architectures comprise non-covalent interactions between at least a portion of the plurality of micro-materials and/or nano-materials of the shell, and wherein the non-covalent interactions can be selected from the group consisting of van der Waals interactions, dipole-dipole interactions, hydrogen bonding, ionic bonding, and combinations thereof. The formation of colloidosome architectures in the liquid medium can regulate leakage and release of the active material, for example by reducing the diffusion of the active material from the colloidosome, thereby increasing tenacity.

[0084] The colloidosome architectures exclude the formation of covalent bonds, such as covalent cross-linking between at least a portion of the plurality of micro-materials and/or nano-materials of the shell. As will be appreciated by one of skill in the art, and with the help of this disclosure, the plurality of micro materials and/or nano-materials that form the shell can be selected to promote the formation of non-covalent interactions between at least a portion of the plurality of micro-materials and/or nano-materials of the shell, thereby enabling the formation of colloidosome architectures, without the need of covalent cross-linking.

[0085] The non-covalent interactions can be formed between micro-materials and/or nano-materials of the same colloidosome, of different colloidosomes, or both.

[0086] When the non-covalent interactions are formed between micro-materials and/or nano-materials of the same colloidosome, the term“colloidosome architecture” refers to a single or individual colloidosome that has a more tightly packed shell owing to the non-covalent interactions between at least a portion of the plurality of micro-materials and/or nano-materials of the shell. Without wishing to be limited by theory, a more tightly packed shell hinders the diffusion of the active material from the colloidosome.

[0087] When the non-covalent interactions are formed between micro-materials and/or nano-materials of different colloidosomes, the term“colloidosome architecture” refers to a structure comprising two or more colloidosomes, wherein a portion of the plurality of micro-materials and/or nano-materials of the shell of a particular colloidosome forms non-covalent interactions with at least a portion of the plurality of micro materials and/or nano-materials of the shell of another colloidosome. Without wishing to be limited by theory, a colloidosome architecture comprising two or more colloidosomes hinders the diffusion of the active material from the colloidosome architecture by blocking the diffusion path of the active material into the liquid medium.

[0088] In an aspect, the colloidosome architectures can be formed in a liquid medium comprising unencapsulated active material in an amount of from about 0.5 wt.% to about 50 wt.%, alternatively from about 1 wt.% to about 40 wt.%, or alternatively from about 5 wt.% to about 25 wt.%, based on the total weight of the colloidosome composition. As will be appreciated by one of skill in the art, and with the help of this disclosure, and without wishing to be limited by theory, when the liquid medium contains unencapsulated active material, the colloidosomes (e.g., colloidosome architectures) are more stable as the active material is not driven out of the colloidosome in response to osmotic pressure. For example, when a concentrated colloidosome composition is contacted with a liquid medium to form a resulting less concentrated colloidosome composition (which process can be referred to for purposes of the disclosure herein as re-dispersion or re-emulsification); in the case of the liquid medium comprising unencapsulated active material, the amount of the unencapsulated active material in the liquid medium can balance the amount of the encapsulated active material in the colloidosome, resulting in a balancing of the chemical potential of the active material inside and outside of the colloidosome, and thereby allowing for a stable and active material loaded colloidosome architecture without the need for covalent cross-linking. Without wishing to be limited by theory, in the case of the liquid medium lacking unencapsulated active material, the colloidosome can be unstable, and unravel to release the active material owing to osmotic pressure.

[0089] In an aspect, the colloidosome architectures can be formed in a liquid medium comprising a selective containment agent in an amount of from about 0.1 wt.% to about 50 wt.%, alternatively from about 1 wt.% to about 40 wt.%, or alternatively from about 5 wt.% to about 25 wt.%, based on the total weight of the colloidosome composition. For purposes of the disclosure herein, the term“selective containment agent” refers to any suitable agent that can interact with the colloidosome and prevent the dissociation of the colloidal particles of the colloidosome, as well as prevent diffusion of the active material into the colloidosome environment (thereby containing the active material in the colloidosome).

[0090] Nonlimiting examples of a selective containment agent suitable for use in the present disclosure include a polyelectrolyte, an emulsifier, a plurality of micro-materials and/or nano-materials assembled in a partial colloidosome shell, and the like, or combinations thereof.

[0091] In the case of the liquid medium lacking unencapsulated active material, when a concentrated colloidosome composition is contacted with a liquid medium to form a resulting less concentrated colloidosome composition, the presence of a selective containment agent in the liquid medium can enable re-dispersion of active material-loaded colloidosomes into a diluted formulation and improve dispersion and stability of the resulting colloidosome composition, for example a colloidosome composition comprising colloidosome architectures such as multi-layered colloidosome architectures and/or shell into shell colloidosome architectures. As will be appreciated by one of skill in the art, and with the help of this disclosure, colloidosome architectures such as multi-layered colloidosome architectures and/or shell into shell colloidosome architectures can hinder diffusion of active material into the colloidosome environment, thereby increasing tenacity.

[0092] In an aspect, the tenacity of the colloidosomes can be tuned by controlling the colloidosome environment via a device for the delivery of the active material. [0093] A device for the delivery of the active material can comprise (i) a bulk formulation compartment having from about 0.5 wt.% to about 10 wt.%, alternatively from about 1 wt.% to about 8 wt.%, or alternatively from about 2 wt.% to about 6 wt.% active material-loaded colloidosomes, based on the total weight of the bulk formulation; and (ii) a smaller permeable compartment (from about 1 vol.% to about 10 vol.%, alternatively from about 2 vol.% to about 8 vol.%, or alternatively from about 4 vol.% to about 6 vol.% of the bulk formulation volume) containing additional active material-loaded colloidosomes, wherein the smaller permeable compartment comprises from about 10 wt.% to about 90 wt.%, alternatively from about 20 wt.% to about 80 wt.%, or alternatively from about 25 wt.% to about 75 wt.% active material- loaded colloidosomes, based on the total weight of the permeable compartment formulation. The permeable compartment can comprise pores, wherein a pore size of the smaller permeable compartment can be from about 0.1 nm to about 100 nm, alternatively from about 1 nm to about 75 nm, or alternatively from about 10 nm to about 50 nm to allow active material diffusion between the bulk formulation compartment and the smaller permeable compartment. The pore size of the permeable compartment does not allow for transport of colloidosome into the bulk formulation compartment. As shown in the configuration of Figures 1A, IB, and 1C, the active material-loaded colloidosome concentrate is confined within a smaller compartment having permeable membrane (compartment A) which allows active material to diffuse (as shown by arrows) into the bulk formulation compartment (compartment B) to maintain active material concentrations inside and outside of the colloidosomes for prolonged tenacity. The smaller compartment can be positioned in any suitable position; for example on the side (as shown in device I in Figure 1A), in the center (as shown in device II in Figure IB), or on the bottom (as shown in device III in Figure 1C), for a desired appearance and/or transparency. In some aspects, two or more active materials could be encapsulated within stimulus- responsive (e.g., thermoresponsive) colloidosome materials (e.g., poly(N-isopropylacrylamide) containing polymers) for triggered release of active materials. For example, colloidosomes made of poly(N- isopropylacrylamide) (PNIPAm) are thermoresponsive or thermosensitive. Polymeric particles containing PNIPAm can rapidly shrink in size at temperatures above the lower critical solution temperature (LCST) of the polymer (e.g., 32°C for PNIPAm), thereby enabling triggered release of active materials from the micro materials and/or nano-materials, as well as release from the core through the interstices of the colloidosome.

[0094] Figures 1A, IB, and 1C display configurations of devices 101, 102, and 103, respectively for the delivery of an active material. In an aspect, the device 101, 102, 103 for the delivery of an active material can comprise a first compartment 11, 12, 13 (compartment B, bulk formulation compartment) and a second compartment 21, 22, 23 (compartment A, smaller permeable compartment), wherein the first compartment 1 1, 12, 13 is in fluid communication (as shown by arrows) with the second compartment 21, 22, 23 via a permeable membrane, and wherein a ratio of a second compartment volume to a first compartment volume is from about 1 : 100 to about 1 : 10, alternatively from about 1 :80 to about 1 :20, or alternatively from about 1 :50 to about 1 :25; wherein the first compartment 1 1, 12, 13 comprises a first colloidosome composition comprising colloidosomes in an amount of from about 0.5 wt.% to about 10 wt.%, based on the total weight of the first colloidosome composition, and wherein the first composition optionally comprises an unencapsulated active material (e.g., from about 5 wt.% to about 50 wt.%, based on the total weight of the first composition); wherein the first compartment 11, 12, 13 is configured for the delivery of at least a portion of the first composition comprising active material outside of the device 101, 102, 103; wherein the second compartment 21, 22, 23 comprises a second composition comprising colloidosomes 15, 16, 17 in an amount of from about 10 wt.% to about 90 wt.%, based on the total weight of the second composition, and wherein the second composition optionally comprises an unencapsulated active material (e.g., from about 5 wt.% to about 50 wt.%, based on the total weight of the second composition); and wherein the device 101, 102, 103 is configured to control the colloidosome environment of the first composition by allowing the diffusion of unencapsulated active material across the permeable membrane (from the second compartment 21, 22, 23 to the first compartment 1 1, 12, 13 via the permeable membrane) and by blocking the diffusion of colloidosomes across the permeable membrane.

[0095] A sprayer device for the delivery of the active material can comprise a delivery tube having an inner surface covered with deposited unencapsulated active material, for example to achieve from about 50% to about 99%, alternatively from about 60% to about 95%, or alternatively from about 70% to about 90% surface area coverage of the inner surface of the delivery tube. The immobilized active (denoted“A” in Figure 2) can reduce active material leakage from colloidosomes before or during application of the colloidosome formulation. The active material coating the inner surface of the tube sprayer can allow for the diffusion of unencapsulated active material into the colloidosomes travelling through the tube, thereby replenishing the active material into the colloidosomes as they pass through. An inner coating of the tube could be achieved by binding the active material directly to the inner surface of the tube, by binding the active material to a polymer (e.g., a high molecular weight polymer) coating the inner surface of the tube, or both; thereby preventing or reducing active material leakage from the colloidosomes immediately prior to dispensing.

[0096] Figure 2 displays a configuration of a device 200 for the delivery of an active material. In an aspect, the device 200 for the delivery of an active material can comprise a compartment 25 and a delivery conduit 26, wherein the delivery conduit 26 is in fluid communication with the compartment 25, wherein an inner surface 26a of the delivery conduit comprises unencapsulated active material 27 deposited on from about 50% to about 99% of the inner surface area of the delivery conduit 26; wherein the compartment 25 comprises the colloidosome composition as disclosed herein; wherein the colloidosome environment further comprises the delivery conduit 26; wherein the delivery conduit 26 is configured for the delivery of at least a portion of the colloidosome composition comprising active material outside of the device; and wherein the device 200 is configured to control the colloidosome environment by allowing the diffusion of unencapsulated active material 27 into a colloidosome 28 travelling through the delivery conduit 26. In an aspect, the device 200 is a spraying device.

[0097] A device for the delivery of the active material can comprise a dual compartment container comprising from about 50 vol.% to about 95 vol.%, alternatively from about 60 vol.% to about 90 vol.%, or alternatively from about 65 vol.% to about 85 vol.% diluent; and from about 5 vol.% to about 50 vol.%, alternatively from about 10 vol.% to about 40 vol.%, or alternatively from about 15 vol.% to about 35 vol.% colloidosome formulation; based on the total volume of the dual compartment container. Separating colloidosomes from the diluent can provide for decreasing active material leakage for longer product shelf life. As shown in the configuration of Figure 3, the diluent (compartment A) can co-elute with the colloidosomes formulation (compartment B) immediately prior to exiting a delivery nozzle. In some aspects, the diluent can comprise from about 0.1 wt.% to about 10 wt.%, alternatively from about 1 wt.% to about 8 wt.%, or alternatively from about 2 wt.% to about 6 wt.% colloidosome destabilizer, based on the total weight of the diluent. For purposes of the disclosure herein, the term“colloidosome destabilizer” refers to any chemical compound or agent that interferes with the structural integrity of the colloidosome in order to disassemble the colloidosome structure for tunable tenacity. Nonlimiting examples of destabilizers suitable for use in the present disclosure include a surfactant, a solvent for micro-materials and/or nano materials of a colloidosome shell, a chemical and/or physical agent that has the ability to interfere with interparticle bonds formed between micro-materials and/or nano-materials of a colloidosome shell, a chemical and/or physical agent that has the ability to interfere with intraparticle polymer cross-linking in micro-materials and/or nano-materials of a colloidosome shell, and the like, or combinatios thereof.

[0098] Figure 3 displays a configuration of a device 300 for the delivery of an active material. In an aspect, the device 300 for the delivery of an active material can comprise a first compartment 31, a first delivery conduit 33, a second compartment 32 (e.g., formed via a container having an impermeable barrier 55), and a second delivery conduit 34; wherein the first compartment 31 is in fluid communication with the first delivery conduit 33 via an intake end of the first delivery conduit, wherein the second compartment 32 is in fluid communication with the second delivery conduit 34 via an intake end of the second delivery conduit, wherein a delivery end of the first delivery conduit is in fluid communication with a delivery end of the second delivery conduit, and wherein a ratio of a second compartment volume to a first compartment volume is from about 1 :20 to about 1 : 1; wherein the first compartment 31 comprises a diluent, wherein the diluent comprises water, an alcohol, ethanol, propanol, isopropanol, butanol, a C₅-C₁₈ alcohol, an oil, an organic solvent (e.g., ethanol, methyl acetate, ethyl acetate, isopropanol, butanol, etc.), a buffer, or combinations thereof, and wherein the diluent optionally comprises a colloidosome destabilizer in an amount of from about 0.1 wt.% to about 10 wt.%, based on the total weight of the diluent, and wherein the destabilizer comprises a surfactant, a solvent for micro-materials and/or nano-materials of a colloidosome shell, a chemical and/or physical agent that has the ability to interfere with interparticle bonds formed between micro-materials and/or nano-materials of a colloidosome shell, a chemical and/or physical agent that has the ability to interfere with intraparticle polymer cross-linking in micro-materials and/or nano materials of a colloidosome shell, and the like, or combinations thereof; wherein the first delivery conduit 33 is configured for the delivery of at least a portion of the diluent outside of the device; wherein the second compartment 32 comprises the colloidosome composition as disclosed herein, and wherein the diluent and the liquid medium can be the same or different; wherein the second delivery conduit 34 is configured for the delivery of at least a portion of the colloidosome composition comprising active material outside of the device; and wherein the device 300 is configured to control the colloidosome environment by contacting the diluent travelling through the first delivery conduit 33 with the colloidosome composition travelling through the second delivery conduit 34 prior to the delivery of colloidosome composition outside of the device.

[0099] A device for the delivery of the active material can comprise a dual compartment container comprising from about 20 vol.% to about 80 vol.%, alternatively from about 30 vol.% to about 70 vol.%, or alternatively from about 40 vol.% to about 60 vol.% barrier solution; from about 20 vol.% to about 80 vol.%, alternatively from about 30 vol.% to about 70 vol.%, or alternatively from about 40 vol.% to about 60 vol.% colloidosome formulation; based on the total volume of the dual compartment container; and a coextruding nozzle. This particular device design can advantageously reduce active material leakage by separating the barrier solution (or diluent) from the colloidosome phase. Further, this particular device design can advantageously increase tenacity by coextruding (or alternatively referred to as co-emitting or coaxial emission) an outer barrier layer around an inner core of active material-loaded colloidosomes. As shown in the configuration of Figure 4, an outer barrier layer (from compartment A) is co-extruded in the nozzle around an inner core of colloidosomes (from compartment B). The barrier solution (e.g., outer phase or barrier layer) can comprise from about 1 wt.% to about 20 wt.%, alternatively from about 2.5 wt.% to about 15 wt.%, or alternatively from about 5 wt.% to about 10 wt.% barrier agent, based on the total weight of the barrier solution. For purposes of the disclosure herein, the term“barrier agent” refers to any chemical compound or agent that hinders the diffusion of the active material from the colloidosome into the colloidosome environment (e.g., creates a“barrier” that slows the diffusion of the active material from the colloidosome into the colloidosome environment). Nonlimiting examples of barrier agents suitable for use in the present disclosure include an electrolyte, a polycation, a polyanion, an organic polymer, an inorganic polymer, an oil, and the like, or combinations thereof. Tenacity can be tuned by (1) adjusting (i.e., increasing or decreasing) the amount of barrier agent in the barrier solution; and/or (2) varying the volumetric ratio of the two coextruded phases or layers, an outer barrier solution phase, and an inner colloidosome formulation core phase. [00100] Figure 4 displays a configuration of a device 400 for the delivery of an active material. In an aspect, the device 400 for the delivery of an active material can comprise a first compartment 40, a first delivery conduit 50, a second compartment 60 (e.g., formed via a container having an impermeable barrier 55), and a second delivery conduit 70; wherein a ratio of a second compartment volume to a first compartment volume is from about 1 :4 to about 1 :0.25; wherein the first compartment 40 is in fluid communication with the first delivery conduit 50 via an intake end 51 of the first delivery conduit, wherein the second compartment 60 is in fluid communication with the second delivery conduit 70 via an intake end

71 of the second delivery conduit, wherein a delivery end 72 of the second delivery conduit is housed inside a delivery end 52 of the first delivery conduit, wherein the delivery end 72 of the second delivery conduit and the delivery end 52 of the first delivery conduit form a coextruding nozzle 80 having an annular flow space 81 and an inner flow space 82, wherein the annular flow space 81 is defined by an inner surface of the delivery end 52 of the first delivery conduit and by an outer surface of the delivery end 72 of the second delivery conduit 70, and wherein the inner flow space 82 is defined by an inner surface of the delivery end

72 of the second delivery conduit 70; wherein the second compartment 60 comprises the colloidosome composition as disclosed herein; wherein the second delivery conduit 70 is configured for the delivery of at least a portion of the colloidosome composition comprising active material outside of the device 400 via the inner flow space 82 of the coextruding nozzle 80; wherein the first compartment 40 comprises a barrier solution, wherein the barrier solution comprises a liquid medium that can be the same or different from the liquid medium of the colloidosome composition, wherein the barrier solution optionally comprises a barrier agent, and wherein the barrier agent comprises an electrolyte, a polycation, a polyanion, an organic polymer, an inorganic polymer, an oil, and the like, or combinations thereof; wherein the first delivery conduit 50 is configured for the delivery of at least a portion of the barrier solution outside of the device 400 via the annular flow space 81 of the coextruding nozzle 80; and wherein the device 400 is configured to control the colloidosome environment by delivering outside of the device 400, via the coextruding nozzle 80, the colloidosome composition 91 at least partially enclosed in the barrier solution 92.

[00101] In an aspect, a device for the delivery of an active material can comprise a first compartment, a first delivery conduit, a second compartment, and a second delivery conduit; wherein a ratio of a second compartment volume to a first compartment volume is from about 1 :4 to about 1 :0.25; wherein the first compartment is in fluid communication with the first delivery conduit via an intake end of the first delivery conduit, wherein the second compartment is in fluid communication with the second delivery conduit via an intake end of the second delivery conduit, wherein a delivery end of the second delivery conduit is housed inside a delivery end of the first delivery conduit, wherein the delivery end of the second delivery conduit and the delivery end of the first delivery conduit form a coextruding nozzle having an annular flow space and an inner flow space, wherein the annular flow space is defined by an inner surface of the delivery end of the first delivery conduit and by an outer surface of the delivery end of the second delivery conduit, and wherein the inner flow space is defined by an inner surface of the delivery end of the second delivery conduit; wherein the second compartment comprises any suitable colloidosome composition as disclosed herein; wherein the second delivery conduit is configured for the delivery of at least a portion of the colloidosome composition comprising active material outside of the device via the inner flow space of the coextruding nozzle; wherein the first compartment comprises a barrier solution, wherein the barrier solution comprises a liquid medium that can be the same or different from the liquid medium of the colloidosome composition, wherein the barrier solution optionally comprises a barrier agent, and wherein the barrier agent comprises an electrolyte, a polycation, a polyanion, an organic polymer, an inorganic polymer, an oil, or combinations thereof; wherein the first delivery conduit is configured for the delivery of at least a portion of the barrier solution outside of the device via the annular flow space of the coextruding nozzle; and wherein the device is configured to control the colloidosome environment by delivering outside of the device, via the coextruding nozzle, the colloidosome composition at least partially enclosed in the barrier solution.

[00102] In an aspect, the colloidosome compositions having tunable tenacity and methods of making and using same, as disclosed herein can advantageously display improvements in one or more composition characteristics when compared to conventional colloidosome compositions. The colloidosome structures as disclosed herein can advantageously allow for relatively high loading of active material (e.g., from about 10 wt.% to about 80 wt.%, based on the total weight of the colloidosome). The colloidosome compositions as disclosed herein can advantageously afford protection of active materials, for example active materials diluted with other formulation ingredients, such as ethanol. Manipulation of the surrounding colloidosome environment can advantageously afford control of the rate of active material release (i.e., tunable tenacity). Additional advantages of the colloidosome compositions having tunable tenacity, as disclosed herein; and methods of making and using same, can be apparent to one of skill in the art viewing this disclosure.

EXAMPLES

[00103] The subject matter having been generally described, the following examples are given as particular embodiments of the disclosure and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification of the claims to follow in any manner.

EXAMPLE 1

[00104] Polyllactic acid colloidosomes preparation to reduce active spreading. Poly(lactic) acid [PLA, Natureworks 2003 D, MW 250 kDa] was dissolved in ethyl acetate (EtOAc) up to concentrations of 50 mg/mL. Separately, a 10 mL aqueous phase was prepared by dissolving 0.03 wt.% vitamin-E tocopherol poly(ethylene glycol) succinate (TPGS-1000) in water with stirring at 1,000 rpm. The PLA/EtOAc solution (2.0 mL) was added dropwise to the stirring aqueous phase through a 21 -gauge needle. The mixture was then placed on ice and probe sonicated three times at 50% intensity for 10 seconds to create an oil-in-water emulsion. The emulsion was returned to a stir plate for mixing at 1,000 rpm overnight to simultaneously remove ethyl acetate and create hardened PLA microgels. This procedure was repeated an additional nine times to make a 100 mL aqueous dispersion of PLA microgels.

[00105] After complete solvent evaporation, PLA microgels were concentrated via centrifugation at 10,000 rpm for 5 minutes. The supernatant was discarded to recover approx. 250 mg of PLA microgels in 1 mL of water. The microgel suspension in water was then swollen with 500 mg of d-limonene by stirring at 1,200 rpm for 10 minutes. The swollen microgel mixture was probe sonicated for 10 seconds at 50% intensity after addition of 25 mg Dow Corning formulation aid 5200 (DC 5200) emulsifier to create a limonene-loaded PLA microgel cream finally, 0.5 mL of the cream was added dropwise through a 26-gauge needle to 1 mL of neat PLA microgels (25 mg/mL), and was stirred at 300 rpm for 1 hour to form limonene-loaded PLA colloidosomes. figure 5 displays an optical microscope image of PLA colloidosomes loaded with d-limonene. figure 6 displays the tenacity of d-limonene without encapsulation (orange) and encapsulated in colloidosomes (blue).

EXAMPLE 2

[00106] Colloidosomes were prepared as described in Publication No. WO 2017/216667 Al . More specifically, colloidosomes were prepared as described in Example 1 , with the difference that polylactic- coglycolic acid copolymer (PLGA, from PolySciTech, catalogue no. AP040) was used instead of PLA. Limonene-loaded colloidosome architectures were concentrated via centrifuge at 10,000 rpm for 10 min. This concentrate was re-dispersed into a formulation like medium (95% ethanol, 5% water, and variable amounts of top note or limonene 19 mg, 100 mg, 500 mg, etc.). This re-dispersion was achieved via syringe method, where one syringe filled with concentrated limonene-loaded colloidosomes was dropped into a vial containing the formulation-like medium with variable amounts of limonene. The rate of dropping concentrate could be between 1 mL/h and 1,000 mL/h. This process of re-dispersing loaded colloidosomes into an already containing limonene formulation enables chemical potential balance as described in figure 7. figure 7 displays a container on the left with colloidosomes dispersed in one kind of formulation (with no active material outside of colloidosomes); such colloidosomes can be transferred to another container (on the right) with active material in bulk formulation enabling equilibration of active materials inside and outside of the colloidosomes.

[00107] PLGA colloidosomes prepared as described above (Publication No. WO 2017/216667 Al) were demonstrated to show such characteristics, and the measured tenacity was much improved for chemically balanced formulation as compared to control formulations. The results are shown in figure 8. EXAMPLE 3

[00108] Colloidosomes were prepared as described in Publication No. WO 2017/216667 Al . More specifically, colloidosomes were prepared by dissolving poly(lactic) acid (PLA, from Natureworks, catalogue no. 6362D) in ethyl acetate (EtOAc) up to concentrations of 50 mg/mL. Separately, a 10 mL aqueous phase was prepared by dissolving 0.03 wt.% Pluronic F-127 ( from Sigma Aldrich, catalogue no. P2443) in water with stirring at 1,000 rpm. The PLA/EtOAc solution (2.0 mL) was added dropwise to the stirring aqueous phase through a 21 -gauge needle. The mixture was then placed on ice and probe sonicated three times at 50% intensity for 10 seconds to create an oil-in-water emulsion. The emulsion was returned to a stir plate for mixing at 1 ,000 rpm overnight to simultaneously remove ethyl acetate and create hardened PLA microgels. This procedure was repeated an additional nine times to make a 100 mL aqueous dispersion of PLA microgels.

[00109] After complete solvent evaporation, PLA microgels were concentrated via centrifugation at 10,000 rpm for 5 minutes. The supernatant was discarded to recover approximately 250 mg of PLA microgels, which were then re-dispersed in 5 mL of water. The microgel suspension in water was then swollen with 500 mg of d-limonene by stirring at 1,200 rpm for 10 minutes. The swollen microgel mixture was probe sonicated for 10 seconds at 50% intensity after addition of 3 mg Dow Corning formulation aid 5200 (DC 5200) emulsifier to create a limonene-loaded PLA microgel cream finally, 5 ml of the above emulsion was added to 10 ml aqueous solution of PLA microgels (2 mg/mL) and silica nanospheres (20 mg/ml) from Nanocomposix (80 nm, 10 mg/ml), and was stirred at 500 rpm for 1 hour to form limonene-loaded PLA colloidosomes.

[00110] The effect of an interstice blocking agent on colloidosome behavior with respect to active release (e.g., colloidosome tenacity) was investigated. More specifically, the effect of silica nanospheres on colloidosome tenacity was investigated according to the schematic of figure 9A, and the data are displayed in figure 9B. Sample A comprises a polylactic acid (PLA) colloidosome composition with 20 wt.% silica nanospheres (80 nm), based on the total weight of the colloidosome composition; and encapsulated limonene. Sample B comprises limonene control, with no encapsulation (i.e., no colloidosome structure). Sample C comprises PLA colloidosome with encapsulated limonene.

[00111] The limonene without encapsulation (sample B) did not last much longer than 10 minutes compared to limonene encapsulated in colloidosomes (sample C), which exhibited slow release over 3 hours. When 20 wt.% of silica nanospheres were incorporated into the colloidosome architecture (sample A), the release of limonene was decreased even further owing to slower diffusion of active (i.e., limonene) through the interstitial spaces of the colloidosome. EXAMPLE 4

[00112] Colloidosomes were prepared as described in Publication No. WO 2017/216667 Al . More specifically, colloidosomes were prepared by dissolving poly(lactic) acid (PLA, from Natureworks, catalogue no. 6362D) in ethyl acetate (EtOAc) up to concentrations of 50 mg/mL. Separately, a 10 mL aqueous phase was prepared by dissolving 0.03 wt.% Pluronic F-127 ( from Sigma Aldrich, catalogue no. P2443) in water with stirring at 1,000 rpm. The PLA/EtOAc solution (2.0 mL) was added dropwise to the stirring aqueous phase through a 21 -gauge needle. The mixture was then placed on ice and probe sonicated three times at 50% intensity for 10 seconds to create an oil-in-water emulsion. The emulsion was returned to a stir plate for mixing at 1 ,000 rpm overnight to simultaneously remove ethyl acetate and create hardened PLA microgels. This procedure was repeated an additional nine times to make a 100 mL aqueous dispersion of PLA microgels.

[00113] After complete solvent evaporation, PLA microgels were concentrated via centrifugation at 10,000 rpm for 5 minutes. The supernatant was discarded to recover approximately 250 mg of PLA microgels, which were then re-dispersed in 5 mL of water. The microgel suspension in water was then swollen with 500 mg of d-limonene by stirring at 1,200 rpm for 10 minutes. The swollen microgel mixture was probe sonicated for 10 seconds at 50% intensity after addition of 3 mg Dow Corning formulation aid 5200 (DC 5200) emulsifier to create a limonene-loaded PLA microgel cream finally, 5 ml of the above emulsion was added to 10 ml aqueous solution of PLA microgels (2 mg/mL) and sodium dodecyl sulfate (5 mg/ml) ( from Sigma Aldrich, catalogue no. 436143), and was stirred at 500 RPM for 1 hour to form limonene-loaded PLA colloidosomes.

[00114] The effect of a stabilizer on colloidosome behavior with respect to active release (e.g., colloidosome tenacity) was investigated. More specifically, the effect of sodium dodecyl sulfate (SDS) on colloidosome tenacity was investigated according to the schematic of figure 10A, and the data are displayed in figure 10B. Sample A comprises a PLA colloidosome composition with encapsulated limonene and 50 wt.% SDS, based on the total weight of the colloidosome composition. Sample B comprises limonene control, with no encapsulation (i.e., no colloidosome structure). Sample C comprises PLA colloidosomes with encapsulated limonene.

[00115] The limonene without encapsulation (sample B) did not last much longer than 10 minutes compared to limonene encapsulated in colloidosomes (sample C), which exhibiteed slow release over 3 hours. When 50 wt.% of SDS was added to the colloidosome dispersion (sample A), the release of limonene was decreased even further owing to slower diffusion of active (i.e., limonene) through the interstitial spaces of the colloidosome. EXAMPLE 5

[00116] Colloidosomes were prepared as described in Publication No. WO 2017/216667 Al . More specifically, colloidosomes were prepared by dissolving poly(lactic) acid (PLA, from Natureworks, catalogue no. 6362D) in ethyl acetate (EtOAc) up to concentrations of 50 mg/mL. Separately, a 10 mL aqueous phase was prepared by dissolving 0.03 wt.% Pluronic F-127 ( from Sigma Aldrich, catalogue no. P2443) in water with stirring at 1,000 rpm. The PLA/EtOAc solution (2.0 mL) was added dropwise to the stirring aqueous phase through a 21 -gauge needle. The mixture was then placed on ice and probe sonicated three times at 50% intensity for 10 seconds to create an oil-in-water emulsion. The emulsion was returned to a stir plate for mixing at 1 ,000 rpm overnight to simultaneously remove ethyl acetate and create hardened PLA microgels. This procedure was repeated an additional nine times to make a 100 mL aqueous dispersion of PLA microgels.

[00117] After complete solvent evaporation, PLA microgels were concentrated via centrifugation at 10,000 rpm for 5 minutes. The supernatant was discarded to recover approximately 250 mg of PLA microgels. 100 mg of PLA microgels were then re-dispersed in 5 mL of water. The microgel suspension in water was then swollen with 500 mg of d-limonene by stirring at 1,200 rpm for 10 minutes. The swollen microgel mixture was probe sonicated for 10 seconds at 50% intensity after addition of 3 mg Dow Corning formulation aid 5200 (DC 5200) emulsifier to create a limonene-loaded PLA microgel cream finally, the above emulsion was added to 10 ml aqueous solution of PLA microgels (2 mg/mL) and was stirred at 500 rpm for 1 hour to form limonene-loaded PLA colloidosomes. further, 9 grams of the prepared limonene-loaded PLA colloidosomes were transferred to a separate container and 1 g of acetone was added to destabilize the colloidosomes and release the actives.

[00118] The effect of a destabilizer on colloidosome behavior with respect to active release (e.g., colloidosome tenacity) was investigated. More specifically, the effect of acetone on colloidosome tenacity was investigated according to the schematic of figures 3 and 11 A, and the data are displayed in figure 1 IB. Sample A comprises PLA colloidosomes with encapsulated limonene. Sample B comprises a PLA colloidosome composition with encapsulated limonene and 10 wt.% acetone, based on the total weight of the colloidosome composition.

[00119] The results in figure 11B display the effect of adding 10% of acetone on PLA-limonene colloidosomes tenacity profile, by comparison with control (reference, PLA colloidosomes without a destabilizer). The disruptive effect of acetone destabilizer in Sample B is clearly demonstrated in figure 1 IB where the limonene release does not last even 10 minutes in the presence of acetone.

[00120] Lor the purpose of any U.S. national stage filing from this application, all publications and patents mentioned in this disclosure are incorporated herein by reference in their entireties, for the purpose of describing and disclosing the constructs and methodologies described in those publications, which might be used in connection with the methods of this disclosure. Any publications and patents discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.

[00121] In any application before the United States Patent and Trademark Office, the Abstract of this application is provided for the purpose of satisfying the requirements of 37 C.F.R. § 1.72 and the purpose stated in 37 C.F.R. § 1.72(b)“to enable the United States Patent and Trademark Office and the public generally to determine quickly from a cursory inspection the nature and gist of the technical disclosure.” Therefore, the Abstract of this application is not intended to be used to construe the scope of the claims or to limit the scope of the subject matter that is disclosed herein. Moreover, any headings that can be employed herein are also not intended to be used to construe the scope of the claims or to limit the scope of the subject matter that is disclosed herein. Any use of the past tense to describe an example otherwise indicated as constructive or prophetic is not intended to reflect that the constructive or prophetic example has actually been carried out.

[00122] While embodiments of the disclosure have been shown and described, modifications thereof can be made without departing from the spirit and teachings of the invention. The embodiments and examples described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention.

[00123] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the detailed description of the present invention. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference.

Claims

CLAIMS What is claimed is:

1. A colloidosome composition comprising a liquid medium and a plurality of colloidosomes dispersed therein;

wherein the plurality of colloidosomes is characterized by tunable tenacity, wherein the tenacity is tuned by controlling a colloidosome environment, and wherein the colloidosome environment comprises the liquid medium;

wherein each of the plurality of colloidosomes comprises (i) a micro-structured and/or nano- structured porous shell comprising a plurality of micro-materials and/or nano-materials, respectively, and a plurality of interstices dispersed therein, wherein the interstices are located between the micro-materials and/or nano-materials; and (ii) a core that is defined by and located inside the shell; wherein each of the plurality of colloidosomes encapsulates an active material, wherein the shell and/or the core comprise the active material; wherein the shell and/or the interstices allow for releasing active material from the shell and/or the core into the colloidosome environment; and

wherein the tenacity is defined as the time period that the plurality of colloidosomes is releasing a given amount of active material from the shell and/or the core into the colloidosome environment, and wherein the given amount of active material refers to the total amount of active material released by the plurality of colloidosomes of the colloidosome composition.

2. The colloidosome composition of claim 1, wherein the plurality of micro-materials and/or nano materials comprise microparticles, nanoparticles, microgels, nanogels, polymer brushes, surfactants, metal oxides, inorganic polymers, organic polymers, lipids, block copolymers, cross-linked polymers, biopolymers, biomolecules, micellular/dendrimer structures, yolk/shell structures, core/shell structures, pomegranate structures, nanomaterials, functionalized microstructures, functionalized nanostructures, hollow nanostructures, or combinations thereof.

3. The colloidosome composition of claim 1, wherein the active material is selected from the group consisting of a chemical agent, a biological agent, an oil, an ionic liquid, a suspension, a polymer, and combinations thereof.

4. The colloidosome composition of claim 1, wherein of each of the plurality of colloidosomes has an average size of from about 5 nm to about 50,000 nm, wherein each of the plurality of micro-materials and/or nano-materials has an average size of from about 1 nm to about 15,000 nm, wherein the core has an average size of from about 2 nm to about 20,000 nm, with the proviso that the average size of the core is greater than the average size of each of the plurality of micro-materials and/or nano-materials.

5. The colloidosome composition of claim 1, wherein the liquid medium comprises water, an alcohol, ethanol, propanol, isopropanol, butanol, a C₅-Ci₈ alcohol, an oil, an organic solvent, a buffer, or combinations thereof; and wherein the liquid medium further comprises an emulsifier, a preservative, an antimicrobial agent, an antioxidant, an ultraviolet (UV) stabilizer, a surfactant, a colorant, or combinations thereof.

6. The colloidosome composition of claim 1, wherein the colloidosome environment is controlled by the liquid medium comprising unencapsulated active material in an amount of from about 5 wt.% to about 50 wt.%, based on the total weight of the composition.

7. The colloidosome composition of claim 1, wherein the colloidosome environment is controlled by the liquid medium comprising an interstice blocking agent in an amount of from about 0.1 wt.% to about 20 wt.%, based on the total weight of the composition.

8. The colloidosome composition of claim 7, wherein the interstice blocking agent comprises a chemical blocking agent, an amine, a nanoparticle, a silica nanoparticle, an anionic compound, a cationic compound, a zwitterionic compound, or combinations thereof.

9. The colloidosome composition of claim 1, wherein the colloidosome environment is controlled by the liquid medium comprising a stabilizer and/or a surface tension modifier in an amount of from about 0.1 wt.% to about 50 wt.%, based on the total weight of the composition.

10. The colloidosome composition of claim 9, wherein the stabilizer comprises an electrolyte; a polyelectrolyte, a polymer, polyvinylpyrrolidone (PVP), poly(vinyl alcohol) (PVA), poly(ethylene glycol) (PEG); an ionic polymer, alginate, chitosan; an ionic surfactant, sodium dodecyl sulfate (SDS), sodium lauryl ether sulfate (SLES); a non-ionic surfactant, a polyoxamer, a polysorbate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, tocopheryl polyethylene glycol succinate (TPGS), tocopheryl polypropylene glycol succinate (TPPG); or combinations thereof;

and wherein the surface tension modifier comprises polydimethylsiloxane (PDMS), surfactants, alkoxylated surfactants, branched alkoxylated surfactants, hyperbranched alkoxylated surfactants, organomodified silicones, sulfosuccinates, glycols, polyols, or combinations thereof.

11. The colloidosome composition of claim 1, wherein the colloidosome environment is controlled by formation of at least a portion of the plurality of colloidosomes into one or more colloidosome architectures in the liquid medium, wherein the colloidosome architectures comprise non-covalent interactions between at least a portion of the plurality of micro-materials and/or nano-materials of the shell, and wherein the non- covalent interactions can be selected from the group consisting of van der Waals interactions, dipole-dipole interactions, hydrogen bonding, ionic bonding, and combinations thereof.

12. The colloidosome composition of claim 11, wherein the non-covalent interactions are formed between micro-materials and/or nano-materials of the same colloidosome, of different colloidosomes, or both.

13. The colloidosome composition of claim 11, wherein the liquid medium further comprises unencapsulated active material in an amount of from about 0.5 wt.% to about 50 wt.%, based on the total weight of the composition.

14. The colloidosome composition of claim 1 1, wherein the liquid medium further comprises a selective containment agent in an amount of from about 0.1 wt.% to about 50 wt.%, based on the total weight of the composition.

15. The colloidosome composition of claim 14, wherein the selective containment agent comprises a polyelectrolyte, an emulsifier, a plurality of micro-materials and/or nano-materials assembled in a partial colloidosome shell, or combinations thereof.

16. The colloidosome composition of claim 1, wherein the active material comprises a fragrance, and wherein the tenacity of the colloidosomes comprising the active material is increased by from about 20% to about 10,000% when compared to the tenacity of the unencapsulated active material.

17. A device for the delivery of an active material,

wherein the device comprises a first compartment and a second compartment, wherein the first compartment is in fluid communication with the second compartment via a permeable membrane, and wherein a ratio of a second compartment volume to a first compartment volume is from about 1 : 100 to about 1 : 10;

wherein the first compartment comprises a first composition comprising the colloidosome composition of claim 1 , wherein the first composition comprises colloidosomes in an amount of from about 0.5 wt.% to about 10 wt.%, based on the total weight of the first composition, and wherein the first composition optionally comprises an unencapsulated active material;

wherein the first compartment is configured for the delivery of at least a portion of the first composition comprising active material outside of the device;

wherein the second compartment comprises a second composition comprising the colloidosome composition of claim 1, wherein the second composition comprises colloidosomes in an amount of from about 10 wt.% to about 90 wt.%, based on the total weight of the second composition, and wherein the second composition optionally comprises an unencapsulated active material; and

wherein the device is configured to control the colloidosome environment of the first composition by allowing the diffusion of unencapsulated active material across the permeable membrane and by blocking the diffusion of colloidosomes across the permeable membrane.

18. A device for the delivery of an active material,

wherein the device comprises a compartment and a delivery conduit, wherein the delivery conduit is in fluid communication with the compartment, wherein an inner surface of the delivery conduit comprises unencapsulated active material deposited on from about 50% to about 99% of the inner surface area of the delivery conduit;

wherein the compartment comprises the colloidosome composition of claim 1 ;

wherein the colloidosome environment further comprises the delivery conduit;

wherein the delivery conduit is configured for the delivery of at least a portion of the colloidosome composition comprising active material outside of the device; and

wherein the device is configured to control the colloidosome environment by allowing the diffusion of unencapsulated active material into a colloidosome travelling through the delivery conduit.

19. The device of claim 18, wherein the device is a spraying device.

20. A device for the delivery of an active material,

wherein the device comprises a first compartment, a first delivery conduit, a second compartment, and a second delivery conduit;

wherein the first compartment is in fluid communication with the first delivery conduit via an intake end of the first delivery conduit, wherein the second compartment is in fluid communication with the second delivery conduit via an intake end of the second delivery conduit, wherein a delivery end of the first delivery conduit is in fluid communication with a delivery end of the second delivery conduit, and wherein a ratio of a second compartment volume to a first compartment volume is from about 1 :20 to about 1 : 1 ;

wherein the first compartment comprises a diluent, wherein the diluent comprises water, an alcohol, ethanol, propanol, isopropanol, butanol, a C₅-Ci₈ alcohol, an oil, an organic solvent, a buffer, or combinations thereof, and wherein the diluent optionally comprises a colloidosome destabilizer in an amount of from about 0.1 wt.% to about 10 wt.%, based on the total weight of the diluent, and wherein the destabilizer comprises a surfactant, a solvent for micro-materials and/or nano-materials of a colloidosome shell, a chemical and/or physical agent that has the ability to interfere with interparticle bonds formed between micro-materials and/or nano-materials of a colloidosome shell, a chemical and/or physical agent that has the ability to interfere with intraparticle polymer cross-linking in micro-materials and/or nano materials of a colloidosome shell, or combinations thereof;

wherein the first delivery conduit is configured for the delivery of at least a portion of the diluent outside of the device;

wherein the second compartment comprises the colloidosome composition of claim 1, and wherein the diluent and the liquid medium can be the same or different;

wherein the second delivery conduit is configured for the delivery of at least a portion of the colloidosome composition comprising active material outside of the device; and wherein the device is configured to control the colloidosome environment by contacting the diluent travelling through the first delivery conduit with the colloidosome composition travelling through the second delivery conduit prior to the delivery of colloidosome composition outside of the device.