WO2011163635A1

WO2011163635A1 - Star macromolecules as carriers of fragrance, pharmaceutical, personal care, home care and cosmetic agents

Info

Publication number: WO2011163635A1
Application number: PCT/US2011/041904
Authority: WO
Inventors: Wojciech Jakubowski; Patrick Mccarthy; Laura Mueller
Original assignee: ATRP Solutions, Inc.
Priority date: 2010-06-24
Filing date: 2011-06-24
Publication date: 2011-12-29

Abstract

A polymer composition comprising star macromolecules is provided. Each star macromolecule has a core and five or more arms, wherein the number of arms within a star macromolecule varies across the composition of star molecules. The arms on a star are covalently attached to the core of the star; each arm comprises one or more (co)polymer segments; and at least one arm and/or at least one segment exhibits a different solubility from at least one other arm or one other segment, respectively, in a reference liquid of interest.

Description

STAR MACROMOLECULES AS CARRIERS OF FRAGRANCE, PHARMACEUTICAL, PERSONAL CARE, HOME CARE AND

COSMETIC AGENTS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 61/398,306, filed June 24, 2010. This application is further a continuation-in-part of U.S. Application No. 12/926,143, filed October 27, 2010, which is a continuation-in- part of U.S. Application No. 12/799,41 1 , filed April 23, 2010, which further claims the benefit of U.S. Provisional Application No. 61/214,397, filed April 23, 2009. The foregoing related applications, in their entirety, are incorporated herein by reference.

FIELD OF THE INVENTION

[0002] The present invention relates to multi-arm star macromolecules which are used as rheology modifiers, including use in the cosmetic, personal care and home care compositions. In addition, the present invention relates to multi-arm star macromolecules which are used as carriers of functional agents in the pharmaceutical, cosmetic, fragrance, personal care and home care compositions.

BACKGROUND AND PRIOR ART

[0003] Most personal care products on the market contain many types of polymers that vary by structure, chemistry, and raw material source (synthetic or natural) that are combined to provide products with many different desired functions. One class of polymer additives is targeted at altering or modifying the rheological properties of the product that are very important for consumer appeal. Often, additives that provide sufficient viscosity are needed, especially for those formulations where the viscosity without additives is close to that of the pure solvent (water). However, merely increasing viscosity is not sufficient, and in reality, the modifiers should be selected to provide certain desired rheological properties for the formulation that depend on its nature, the mode of delivery, type of flow, and the aesthetic appeal of final application. Typically, low molecular weight surfactants are used to modify rheological properties but they have to be used at large concentrations. Resulting in relatively high cost, and an adverse impact on the environment (e.g., water pollution). [0004] The thickeners used in cosmetic and body care preparations have to meet stringent requirements. First and foremost, they have to show high compatibility and also—if possible— biodegradability so that many substances have to be ruled out from the outset for use in cosmetics. In addition, they should be universally useable in aqueous, emulsoidal, alcoholic and oil-containing bases, be readily processable and lead to a rheology which enables the product to be easily applied so that the preparations can be removed and distributed under clean and simple conditions.

[0005] Thickeners that are designed molecular level to provide the desired properties would be expected to be compatible with many other auxiliaries, more particularly with salts and surfactants. The thickener itself and the other auxiliaries should also lend themselves to ready incorporation into the formulation. The thickened preparations are also expected to show stable rheology and an unchanging physical and chemical quality even in the event of long-term storage and changes in pH and temperature. Finally, the thickeners should be inexpensive to produce without causing significant environmental pollution.

[0006] In view of this complex requirement profile, it is clear why, even today, there is still a demand for new thickeners in the cosmetics field.

SUMMARY OF THE INVENTION

[0007] Accordingly, in one aspect the invention provides a polymer composition comprising star macromolecules, each star macromolecule having a core and five or more arms, wherein the number of arms within a star macromolecule varies across the composition of star molecules; and the arms on a star are covalently attached to the core of the star; each arm comprises one or more (co)polymer segments; and at least one arm and/or at least one segment exhibits a different solubility from at least one other arm or one other segment, respectively, in a reference liquid of interest.

[0008] The use of the polymer composition in personal care products and home care products is also provided.

[0009] In one aspect of the invention, there is a sprayable, gel-forming aqueous composition, comprising:

i) one or more active ingredients; and

ii) one or more star macromolecules having a molecular weight of between

50,000 g/mol and 2,000,000 g/mol that forms a gel when dissolved in water at a concentration of at least 0.2 wt.%; wherein the gel has:

a) a dynamic viscosity of at least 20,000 cP; and/or

b) a shear-thinning value of at least 10; and

wherein at least one of the one or more active ingredients is associated with at least one of the one or more star macromolecules.

[0010] In one aspect of the invention, there is a sprayable, gel-forming aqueous composition, comprising:

i) one or more active ingredients; and

ii) one or more star macromolecules represented by Formula X:

Formula X [(Pl)_ql-(P2)_p2]_t-Core-[(P3)_q3]_r wherein:

Core represents a crosslinked polymeric segment;

PI represents a substantially hydrophobic segment comprising repeat units of monomeric residues of polymerized hydrophobic monomers; P2 represents a substantially hydrophilic segment comprising repeat units of monomeric residues of polymerized hydrophilic monomers;

P3 represents a substantially hydrophilic segment comprising repeat units of monomeric residues of polymerized hydrophilic monomers;

ql represents the number of repeat units in PI and has a value between 1 and

100;

q2 represents the number of repeat units in P2 and has a value between 30 and 1 ,000;

q3 represents the number of repeat units in P3 and has a value between 30 and 1,000;

r represents the number of arms covalently attached to the Core; and t represents the number of arms covalently attached to the Core; and wherein:

a) the molar ratio of r to t is in the range of between 40: 1 and 2: 1 ; and b) at least one of the one or more active ingredients is associated with at least one of the one or more star macromolecules.

[0011] In one aspect of the invention, there is a sprayable, gel-forming, wound treating aqueous composition, comprising:

i) one or more active ingredients; and

ii) one or more star macromolecules represented by Formula X: Formula X [(Pl)_q,-(P2)_q2]_t-Core-[(P3)_q3]_r wherein:

Core represents a crosslinked polymeric segment;

PI represents a substantially hydrophobic segment comprising repeat units of monomeric residues of polymerized hydrophobic monomers;

P2 represents a substantially hydrophilic segment comprising repeat units of monomeric residues of polymerized hydrophilic monomers;

q l represents the number of repeat units in PI and has a value between 1 and

100;

q3 represents the number of repeat units in P3 and has a value between 30 and 1 ,000;

a) the molar ratio of r to t is in the range of between 40: 1 and 2: 1 ; and

b) at least one of the one or more active ingredients associated with at least one of the one or more star macromolecules.

[0012] In one aspect of the invention, there is a composition wherein the one or more active ingredients comprises one or more: active pharmaceutical ingredients, active cosmetic ingredients, fragrance ingredients, and/or active skin-care ingredients. In another aspect of the invention, there is a composition wherein the one or more active ingredients comprises an antibacterial agent. In another aspect of the invention, there is a composition wherein the composition further comprises an anesthetic and optionally a skin soothing agent and/or an analgesic. In another aspect of the invention, there is a composition wherein the composition is a burn and/or wound treatment. In another aspect of the invention, there is a sprayable, gel-forming, wound and burn treating aqueous composition, comprising:

[0013] In one aspect of the invention, there is a composition wherein the sprayable, gel-forming aqueous composition comprises a dynamic viscosity of 60,000 cP or less at 1 rpm. [0014] In one aspect of the invention, there is a composition wherein the one or more star macromolecules has a molecular weight of between 50,000 g/mol and 2,000,000 g/mol and forms a gel when dissolved in water at a concentration of at least 0.2 wt.% having a shear-thinning value of at least 10.

[0015] In one aspect of the invention, there is a composition wherein the association of the at least one of the one or more active ingredients with the at least one of the one or more star macromolecules comprises: i) one or more van der Waals interactions; ii) one or more hydrophobic interactions; iii) one or more polar interactions; iv) one or more hydrophilic interactions; v) one or more hydrogen bonding interactions; vi) one or more ionic interactions; and/or vii) encapsulation of the at least one of the one or more active ingredients by the at least one of the one or more star macromolecules.

[0016] In one aspect of the invention, there is a composition wherein the at least one associated one or more active ingredients is associated with the arms of the at least one of the one or more star macromolecules.

[0017] In one aspect of the invention, there is a composition wherein the at least one associated one or more active ingredients is released from the at least one of the one or more star macromolecules.

[0018] In one aspect of the invention, there is a method of treating a wound, comprising applying a sprayable, gel-forming aqueous composition, as disclosed herein, to a mammal's wound.

[0019] In one aspect of the invention, there is a method of treating skin with a sprayable, gel-forming aqueous composition, as disclosed herein, by spraying a gel- forming amount on the skin.

[0020] In one aspect of the invention, there is a method the active ingredient becomes un-associated (or released) from the macromolecule and available to the skin.

[0021] In one aspect of the invention, there is a method a chemical and/or physical action triggers the release of at least a portion of the active ingredient.

[0022] In one aspect of the invention, there is a method the release of the active ingredient occurs over an extended time.

[0023] In one aspect of the invention, there is a method between 10 wt.% to 100 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, is released within 12 hours of the gel forming on the skin.

[0024] In one aspect of the invention, there is a method between 10 wt.% to 100 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, is released within 12 hours of being exposed to said chemical and/or physical trigger.

[0025] In one aspect of the invention, there is a method between 10 wt.% to 30 wt.% is released within 3 hours.

[0026] In one aspect of the invention, there is a method at least 80 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, remains associated (un-released) from the star

macromolecule after 4 to 12 hours of being exposed to said chemical and/or physical trigger.

[0027] In one aspect of the invention, there is a method between 10 wt.% to 30 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, is released within 2 hours and at least 80 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, remains associated (un-released) from the star macromolecule after 4 to 12 hours of being exposed to said chemical and/or physical trigger.

[0028] In one aspect of the invention, there is a method of making a sprayable, gel-forming aqueous composition, comprising:

i) mixing one or more active ingredients with one or more star macromolecules represented by Formula X to form a mixture; and

ii) introducing additional components to the mixture to form the sprayable, gel- forming aqueous composition;

wherein the one or more star macromolecules represented by Formula X:

Formula X [(Pl)_ql-(P2)_q2]_t-Core-[(P3)_q3]_r wherein:

Core represents a crosslinked polymeric segment;

P2 represents a substantially hydrophilic segment comprising repeat units of monomeric residues of polymerized hydrophilic monomers; P3 represents a substantially hydrophilic segment comprising repeat units of monomeric residues of polymerized hydrophilic monomers;

ql represents the number of repeat units in PI and has a value between 1 and 100;

[0029] In one aspect of the invention, there is a process of forming a mikto star macromolecule comprising:

i) creating a reaction mixture comprising a plurality of first polymeric segments having an ATRP-functional terminal group and a plurality of second monomers, wherein at least a portion of the first polymeric segments are formed by polymerizing a plurality of first monomers, non-limiting examples of first monomers include hydrophobic monomers;

ii) forming a second polymeric segment extending from said first polymeric segment by activating the ATRP-functional terminal group on said first polymeric segment to initiate polymerization of a portion of the second monomers, to form a plurality of block copolymeric arms;

iii) during the polymerization of the second monomers, introducing a plurality of second monomer initiators having an ATRP functional terminal group into the reaction mixture;

iv) activating the ATRP-functional terminal group on said second monomer

initiator to initiate polymerization of a second portion of the second monomer, to form a plurality of homopolymeric arms; and

v) crosslinking at least a portion of the block copolymeric arms and at least a portion of the homopolymeric arms to form at least one mikto star

macromolecule. [0030] In one aspect of the invention, there is a star macromolecule that forms a gel when dissolved in water at a concentration of at least 0.2 wt.% and is formed by: i) creating a reaction mixture comprising a plurality of first polymeric segments having an ATRP-functional terminal group and a plurality of second monomers, wherein at least a portion of the first polymeric segments are formed by polymerizing a plurality of first monomers;

iv) activating the ATRP-functional terminal group on said second monomer

v) crosslinking at least a portion of the block copolymeric arms and at least a portion of the homopolymeric arms;

wherein:

a) the gel has a dynamic viscosity of at least 20,000 cP; and

b) the star macromolecule has a molecular weight of 150,000 g/mol and

600,000 g/mol.

[0031] In one aspect of the invention, there is a star macromolecule polymer composition comprising one or more star macromolecules prepared by an improved, efficient arm-first living-controlled radical polymerization method, wherein the one or more star macromolecules are represented by Formula X:

Formula X [(Pl)_ql-(P2)_q2]_t-Core-[(P3)_q3]_r wherein:

Core represents a crosslinked polymeric segment;

PI represents a hydrophobic homopolymeric segment comprised of repeat units of monomeric residues of polymerized hydrophobic monomers;

P2 represents a hydrophilic homopolymeric segment comprised of repeat units of monomeric residues of polymerized hydrophilic monomers; P3 represents a hydrophilic homopolymeric segment comprised of repeat units of monomeric residues of polymerized hydrophilic monomers;

ql represents the number of repeat units in PI and has a value between 1 and 50;

q2 represents the number of repeat units in P2 and has a value between 30 and 500;

q3 represents the number of repeat units in P3 and has a value between 30 and 500;

r represents the number of copolymeric arms covalently attached to the Core; t represents the number of homopolymeric arms covalently attached to the Core; and

wherein the molar ratio of r to t is in the range of between 20: 1 and 2: 1.

[0032] In one aspect of the invention, there is a star macromolecule having a molecular weight of between 150,000 g/mol and 600,000 g/mol that forms a clear homogeneous gel when dissolved in water at a concentration of at least 0.2 wt.% wherein the gel has:

i) a dynamic viscosity of at least 20,000 cP;

ii) a salt-induced break value of at least 60%;

iii) a pH-induced break value of at least 80%>;

iv) a shear-thinning value of at least 10; and/or

v) an emulsion value of greater than 12 hours.

[0033] In one aspect of the invention, there is a clear homogeneous gel, comprising a star macromolecule having a molecular weight of between 150,000 g/mol and 600,000 g/mol, comprises the following properties:

i) a dynamic viscosity of at least 20,000 cP;

ii) a salt-induced break value of at least 60%;

iii) a pH-induced break value of at least 80%;

iv) a shear-thinning value of at least 10; and/or

v) an emulsion value of greater than 12 hours;

wherein the clear homogeneous gel is formed when the star macromolecule is dissolved in water at a concentration of at least 0.2 wt.%.

[0034] In one aspect of the invention, there is an emulsifier-free emulsion comprising:

a water-soluble star macromolecule having: i) molecular weight of at least 150,000 g/mol; and

ii) a dynamic viscosity of at least 20,000 cP at a concentration of 0.4 wt.%.

[0035] In one aspect of the invention, there is an emulsion comprising:

a water-soluble star macromolecule having:

i) a molecular weight of at least 150,000 g/mol; and

ii) a dynamic viscosity of at least 20,000 cP at a concentration of 0.4 wt.%.

[0036] In one aspect of the invention, there is a thickening agent that forms a clear homogeneous gel when dissolved in water at a concentration of at least 0.2 wt.%, wherein the gel has:

i) a dynamic viscosity of at least 20,000 cP;

ii) a salt-induced break value of at least 60%;

iii) a pH-induced break value of at least 80%;

iv) a shear-thinning value of at least 10; and/or

v) an emulsion value of greater than 12 hours.

[0037] In one aspect of the invention, the star macromolecule, emulsfier, gel, emusilfier-free emulsion, emulsion and/or thickening agent, including those formed by the one-pot process, ATRP, CRP, and/or combinations of one or more of these processes, may be used to provide a certain level of control over viscosity and consistency factors in many aqueous and oil based systems including, for example, water- and solvent-based coating compositions, paints, inks, antifoaming agents, antifreeze substances, corrosion inhibitors, detergents, oil-well drilling- fluid rheology modifiers, additives to improve water flooding during enhanced oil recovery, dental impression materials, cosmetic and personal care applications including hair styling, hair sprays, mousses, hair gels, hair conditioners, shampoos, bath preparations, cosmetic creams, cosmetic gels, lotions, ointments, deodorants, powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin wipes, sunscreens, shaving preparations, and fabric softeners.

[0038] In one aspect of the invention, there is a macromolecule, comprising: a plurality of arms comprising at least two types of arms, wherein a first-arm-type extends beyond a second-arm-type and said first-arm-type has a hydrophobic segment on its distal end, wherein at least a portion of the hydrophobic segment may extend beyond the length of the second-arm-types either by the size of the monomeric segment or segments (which may be varied by length of monomeric residue, degree of polymerization, and/or both) for which the hydrophobic segment is attached. Recognizing that the "length" of an arm or segment and the "extending beyond" limitation may be theoretical, meaning that while it is not emperically measured it is understood to "extend beyond" and/or have a longer "length"relative to the length of the second-arm-type if the degree of polymerization is greater for monomeric residues of the same type or of the same theoretical length.

[0039] In one aspect of the invention, there is a star macromolecule, comprising: a plurality of arms comprising at least two types of arms, wherein the degree of polymerization of a first-arm-type is greater than the degree of polymerization of a second-arm-type, and wherein said first-arm-type has a distal end portion that is hydrophobic. In another aspect of the invention, this star macromolecule may be formed by first forming or obtaining the hydrophobic portion and then forming the remaining portion of the first-arm-type from the end of the hydrophobic portion and the second-arm-type in a one-pot synthesis wherein the poylmerization of the second portion of the first-arm-type is commenced prior to the initialization of the second- arm-type but there is at least some point wherein portions, e.g., substantial portions, of the first-arm-type and second-arm-type are being polymerically extended

simultaneously.

[0040] In one aspect of the invention, there is an oil-soluble star macromolecule, comprising: a plurality of different arms comprising at least two types of arms, wherein a first-arm-type extends beyond a second-arm-type and said first-arm-type has a hydrophilic segment on its distal end.

[0041] In one aspect of the invention, there is an oil-soluble star macromolecule, comprising: a plurality of arms comprising at least two types of arms, wherein the degree of polymerization of a first-arm-type is greater than the degree of

polymerization of a second-arm-type, and wherein said first-arm-type has a hydrophilic segment on its distal end.

[0042] In one aspect of the invention, there is a star macromolecule, comprising: a plurality of arms comprising at least two types of arms, wherein the degree of polymerization of a first-arm-type is greater than the degree of polymerization of a second-arm-type, and wherein said first-arm-type has a distal end portion that is hydrophobic and the proximal portion of the first-arm-type and second-arm-type are the same with the only difference between the first-arm-type and the second-arm-type being that the first-arm-type has a hydrophobic portion on its distal end. In another aspect of the invention, this star macromolecule may be formed by first forming or obtaining the hydrophobic portion and then forming the remaining portion of the first- arm-type from the end of the hydrophobic portion and the second-arm-type simultaneously in a one-pot synthesis.

[0043] In an aspect of the invention, the star macromolecules may have an HLM of greater than 0.85, for example greater than 0.87. or 0.9 or 0.93 or 0.95 or 0.97 or 0.98.

[0044] In an aspect of the invention, the star macromolecules may have a calculated HLM of greater than 0.85, for example greater than 0.87. or 0.9 or 0.93 or 0.95 or 0.97 or 0.98 and a viscosity of greater than 60,000 cP at a pH between 7 to 10.5 and a molecular weight of between 200,000 g/mol and 550,000 g/mol and a shear-thinning value of at least 10 and, optionally, a salt-induced break value of at least 60%.

BRIEF DESCRIPTION OF THE DRAWINGS

[0045] The features and advantages of the present invention may be better understood by reference to the accompanying Figures, in which:

[0046] Figure 1 : Illustration of the structure of a segmented homo-arm star macromolecule and two different types of mikto-arm star macromolecules.

[0047] Figure 2: GPC curve for the polystyrene macroinitiator formed in step 1 of the synthesis of an exemplary (PSt-6-PAA) star macromolecule.

[0048] Figure 3: GPC curves for the polystyrene macroinitiator formed in step 1 of the synthesis of an exemplary (PSt-6-PAA) star macromolecule and GPC curve for block copolymer formed after chain extension with tBA in step 2 of the synthesis.

[0049] Figure 4: GPC curves of the PSt-6-tBA block copolymer and the star macromolecule formed after core formation reaction is step 3 of the formation of an exemplary (PSt-6-PAA) star macromolecule.

[0050] Figure 5: Image showing the thickening properties of (PSt- >-PAA) star macromolecule.

[0051] Figure 6: Viscosity of aqueous solution of (PSt-6-PAA) star

macromolecule vs. shear rate.

[0052] Figure 7: Viscosity of aqueous solution of (PSt-6-PAA) star

macromolecule vs. concentration.

[0053] Figure 8: Viscosity of an aqueous solution and a water/windex (1/1 v/v) solution of (PSt-6-PAA) star macromolecule vs. shear rate. [0054] Figure 9: Viscosity of an aqueous solution and a water/windex (1/1 v/v) solution of Carbopol EDT 2020 vs. shear rate.

[0055] Figure 10: GPC Curves for preparation of the precursor to a PAA star. Solid line PtBA M_n = 18,900 PDI=1.14; Dashed line (PtBA) _x star with M_n,_app 1 12,600 PD1=1.36

[0056] Figure 1 1 : Viscosity of aqueous solution of (PSt-i-PAA) star

macromolecule and (PAA) star macromolecule vs. shear rate.

[0057] Figure 12: Images demonstrating the emulsifying properties of (PSt-Z>- PAA) star macromolecule.

[0058] Figure 13 : Synthesis of [(PSt-6-PtB A) / (PtBA)] star macromolecule using arm-first method.

[0059] Figure 14: GPC curves for Cig-PtBA arm star macromolecule, Solid line C₁₈-PtBA arm with M_n =19,200 PDI=1.16; dashed line (C₁₈-PtBA)_x star

macromolecule M_n>app = 95,600 PDI=1.48.

[0060] Figure 15. GPC curves for C|₂-PtBA arm star macromolecule, Solid Line C₁₂-PtBA M_n =17,500 PDI=1.22; Dashed line (C,₂-PtBA) M_n,app 1 13,900 PDI=1.53.

[0061] Figure 16: is a graph comparing viscosity of Advantomer and Carbopol ETD 2020 at varying thickening agent weight %.

[0062] Figure 17: is a graph comparing viscosity of Advantomer and Carbopol ETD 2020 at varying shear rates.

[0063] Figure 18: is a graph comparing viscosity of Advantomer and Carbopol ETD 2020 at varying NaCl weight%.

[0064] Figure 19: is a graph comparing viscosity of Advantomer and Carbopol ETD 2020 at varying pH.

[0065] Figure 20: is a graph comparing viscosity of Advantomer and Carbopol ETD 2020 at varying H₂0₂ weight %.

[0066] Figure 21 : is a graph comparing viscosity of Advantomer and Carbopol ETD 2020 at varying temperatures.

[0067] Figure 22: is a graph comparing viscosity of Advantomer and Carbopol ETD 2020 at varying NaCl weight%.

[0068] Figure 23: GPC curves for the reaction product resulting from step 2 of Example 9.

[0069] Figure 24: GPC curves for the reaction prodcut resulting from step 3 of example 9. DETAILED DESCRIPTION OF THE INVENTION

[0070] The term "solubility" or "soluble" is understood to mean that when a component is mixed into a solvent and tested, at STP in a 1 cm cuvette, it has a light transmittance value, at a wavelength at or around a UV Vis minimum wavelength for the mixture, of at least 40%, for example, at least 50%, 70%, 85%, or at least 95%.

[0071] The term "clear" as is used to describe a homogenous gel or homogenous solution is understood to mean that when the gel or solution is tested, at STP in a 1 cm cuvette, it has a light transmittance value, at a wavelength at or around a UV Vis minimum wavelength for the gel or solution, of at least 40%, for example, at least 50%, 70%, 85%, or at least 95%.

[0072] The term "water-soluble monomer" is understood to mean a monomer having at least about 10 wt. % solubility in water at STP. For example, a water soluble monomer may have at least 15 wt.%, 20 wt.%, 25 wt. %, or at least 30 wt. % solubility in water at STP.

[0073] The term "water-insoluble monomer" is understood to mean a monomer having less water solubility than a water soluble monomer, for example, less that about 5 wt.%, such as less than 1 wt.% or 0.5 wt.% solubility in water at STP.

[0074] The term "water-soluble star macromolecule" is understood to mean a star macromolecule that is soluble in water, pH adjusted if necessary to a pH of no greater than 8 with sodium hydroxide, at a concentration of at least 5g/L, for example, between 8g/L to lOOg/L, such as, at least lOg/L, 12g/L, 15g/L, or at least 20g/L. For example, a water-soluble star macromolecule having an aqueous solubility of at least lOg/L may include the introduction of at least lOg of the star macromolecule into approximately 1 L of water, neutralizing the mixture, if necessary, by adjusting the pH of the resulting mixture to about pH 8 (e.g. , with the addition of base, such as sodium hydroxide), and vigorously stirring at a temperature no greater than 100°C for no more than about 60 minutes, to achieve dissolution of the star macromolecule, and testing the solubility at STP.

[0075] The term "oil-soluble star macromolecule" is understood to mean a star macromolecule that is soluble in mineral oil at a concentration of at least 5g/L, for example, between 8g/L to lOOg/L, such as, at least lOg/L, 12g/L, 15g/L, or at least 20g/L of mineral oil. For example, an oil-soluble star macromolecule having an oil solubility of at least lOg/L may include the introduction of at least lOg of the star macromolecule into approximately 1 L of mineral oil, and vigorously stirring at a temperature no greater than 100°C for no more than about 60 minutes, to achieve dissolution of the star macromolecule, and testing the solubility at STP.

[0076 J The term "hydrophilic" is understood to mean, in relation to a material, such as a polymeric arm, or a polymeric segment of a polymeric arm, that the material is water soluble and comprises hydrophilic segments having an HLB equal to or greater than 8, for example, an HLB equal to 16-20, or equal to or greater than 18, 19, or 19.5. In certain embodiments, the hydrophilic segment may comprise at least 75 mol% of water-soluble monomer residues, for example, between 80 mol% to 100 mol% or at least 85 mol%, 90 mol%, 95 mol%, or at least 97 mol% water-soluble monomer residues.

[0077] The term "hydrophobic" is understood to mean, in relation to a material, such as a polymeric arm, or a polymeric segment of a polymeric arm, that the material is water insoluble and comprises hydrophilic segments having an HLB less than 8, for example, an HLB less than 7. In certain embodiments, the hydrophobic segment may comprise at least 75 mol% of water-insoluble monomer residues, for example, between 80 mol% to 100 mol% or at least 85 mol%, 90 mol%, 95 mol%, or at least 97 mol% water-insoluble monomer residues.

[0078] The term "monomer residue" or "monomeric residue" is understood to mean the residue resulting from the polymerization of the corresponding monomer. For example, a polymer derived from the polymerization of an acrylic acid monomer (or derivatives thereof, such as acid protected derivatives of acrylic acid including but not limited to methyl or t-butyl ester of acrylic acid), will provide polymeric segments, identified as PAA, comprising repeat units of monomeric residues of acrylic acid, i.e. , "-CH(C0₂H)CH₂-". For example, a polymer derived from the polymerization of styrene monomers will provide polymeric segments, identified as PS, comprising repeat units of monomeric residues of styrene, i.e. , "-CH(C₆H₅)CH₂- ." For example, a polymer derived from the polymerization of monomeric

divinylbenzene monomers will provide polymeric segments comprising repeat units of monomeric residues of divinylbenzene, i.e., "-CH₂CH(C₆H₅)CHCH₂-."

[0079] The term "emulsifier" is understood to mean a component that comprises an appreciable weight percent of an amphiphilic compound having a molecular weight of less than 5,000 MW. Emulsifiers are usually linear organic compounds that contain both hydrophobic portions (tails) and hydrophilic portions (heads), i.e., are amphiphilc. Examples of emulsifiers include but are not limited to: alkyl

benzenesulfonates, alkanesulfonates, olefin sulfonates, alkylethersulfonates, glycerol ether sulfonates, .alpha.-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and

dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates,sulfotriglycerides, ether carboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, acyl lactylates, acyl tartrates, acyl glutamates, acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (particularly wheat-based vegetable products) and alkyl (ether) phosphates, alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazoliniumbetaines and sulfobetaines.

[0080] The term "emulsifier-free" is understood to mean a composition or mixture wherein the formulation is substantially deviod of any emulsifiers, for example less than 0.1 wt.% of emulsifier, relative to the total composition, or less than 0.05 wt.% of emulsifier, relative to the total composition, or less than 0.01 wt.% of emulsifier, relative to the total composition, or a formulation where there is no emulsifier.

[0081] The term "STP" is understood to mean standard conditions for temperature and pressure for experimental measurements, wherein the standard temperature is a temperature of 25°C and the standard pressure is a pressure of 1 atm.

Structure of the Polymer Composition

[0082] Multi-arm star macromolecules are shown schematically in Figure 1.

[0083] In one embodiment, the arms in a star macromolecule are comprised of two or more (co)polymer segments selected to modify the rheology of the reference liquid of interest. The star macromolecule structure is represented by the following formula [F-(Ml)_p (M2)_P2 ]_n-C wherein

i. [F-(Ml)_pi-(M2)_P2] represents an arm comprised of a segmented (co)polymer chain wherein each (co)polymer segment,

ii. (Ml)pi- and (M2)_p2- are compositionally distinct adjacent (co)polymer segments where each segment is comprised of one or more monomers with homo, random, gradient or block (co)polymer structure and where i and p2 represent the degree of polymerization of each copolymer segment,

iii. F- represents an optionally functional group or mixture of functional groups present on the arm chain-end, iv. (Ml)pi is not soluble or not fully soluble in the reference liquid of interest, v. (M2)_P2 is soluble or mostly soluble in the reference liquid of interest,

vi. and C represents the crosslinked core of the star macromolecule which is

comprised of crosslinker (Mx), crosslinker (Mx) and monomer (My), crosslinker (Mx) and (M2), or a mixture of (Mx), (My) and (M2), and

vii. n represents the average number of arms covalently attached to the core of the star macromolecule.

[0084] In another embodiment, the star macromolecule structure can be

represented by the following formula,

[F-(Ml)_pl-(M2)_p2]_n-C-[(M3)_P3-F]_m wherein

i. [F-(Ml)pi -(M2)_p2] represents an arm comprised of a segmented (co)polymer chain,

ii. (M l)_pi- and (M2)_p2- are compositionally distinct adjacent (co)polymer segments where each segment is comprised of one or more monomers with homo, random, gradient or block (co)polymer structure and where pi and p2 represent the degree of polymerization of each copolymer segment,

iii. F- represents an optionally functional group or mixture of functional groups present on the arm chain-end,

iv. (Ml)pi is not soluble or not fully soluble in the reference liquid of interest, v. (M2)p₂ is soluble or mostly soluble in the reference liquid of interest,

vi. and C represents the crosslinked core of the star macromolecule which is

viii. (M3)_P3 is a (co)polymer segment which is comprised of one or more monomers with homo, random, gradient or block (co)polymer structure with a degree of polymerization p3 and

ix. m is the number of (M3)_p3 (co)polymer arms covalently attached to the core, x. (M3)p₃ is soluble or mostly soluble in the reference liquid of interest and xi. M2 and M3 can be comprised of the same or different (co)monomers.

[0085] In a further embodiment, polymer composition comprises star

macromolecules in which the structure of a star can be represented by the following formula, [F-(M 1 )_pi ]_s-C-[(M3)_p3-F]_m wherein

i. [F-(Ml)_p]-(M2)_p2] represents an arm comprised of a segmented (co)polymer chain,

ii. (Ml)_pi- is a (co)polymer segment where each segment is comprised of one or more monomers with homo, random, gradient or block (co)polymer structure with a degree of polymerization pi ,

iv. (Ml)_pi is not soluble or not fully soluble in the reference liquid of interest, v. C represents the crosslinked core of the star macromolecule which is comprised of crosslinker (Mx), crosslinker (Mx) and monomer (My), crosslinker (Mx) and (M2), or a mixture of (Mx), (My) and (M2), and

vi. (M3)_P3 is a (co)polymer segment which is comprised of one or more monomers with homo, random, gradient or block (co)polymer structure with a degree of polymerization p3 and

vii. (M3)_P3 is soluble or mostly soluble in the reference liquid of interest and viii. m is the number of (M3)_p3 (co)polymer arms covalently attached to the core, and ix. s is the average number of (Ml)_pi (co)polymer arms covalently attached to the core.

[0086] In an embodiment, the polymer composition, the number of arms on any particular star varies across the population of star macromolecules in each

composition, due to the synthetic process used for the synthesis of the composition. This process is called "arm first" method and is described in details herein below. Due to variation in the number of arms in star macromolecules, the number of arms n, m and s are referred as an average number of arms.

[0087] Star macromolecules with a single peak in the GPC curve with a polydispersity index (PDI) above 1.0 and below 2.5 is preferred.

[0088] As used herein, the term "reference liquid of interest" means the liquid to which the polymer composition will be added. Suitable examples of reference liquids include, but are not limited to, water, oil or mixture thereof or water with additives which include but are not limited to; surfactants, oils, fats and waxes, emulsifiers, silicone compounds, UV protectors, antioxidants, various water soluble substances, biogenic agents, deodorants, odor absorbers, antiperspirants, and germ and enzyme inhibitors. Such agents are disclosed in US patents 6,663,855 and US 7,318,929 and are herein incorporated by reference to provide definitions for those terms.

[0089] Arms of a star can possess the same composition or be different (e.g. star macromolecule with formula (1) vs. (2) or (3), these star are shown in Figure 1 ). The difference can be in composition or molecular weight or both (e.g. different monomer units Ml , M2, M3 and/or different degree of polymerization pi , p2, p3).

[0090] Term "(co)polymer" is defined as a polymer derived from two (or more) monomeric species (monomer units).

[0091] More preferred specific monomer units as a building blocks of Ml , M2, M3 and My include those selected from protected and unprotected acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, .alpha.-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso- butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, iso-butyl ethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decyl ethacrylate, 2,3- dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl

monoacrylate, glyceryl monoethacrylate, glycidyl methacrylate, glycidyl acrylate, acrylamide, methacrylamide, ethacrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide, Ν,Ν-dimethyl methacrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-butyl acrylamide, N-t-butyl acrylamide, N,N-di-n-butyl acrylamide, Ν,Ν-diethylacrylamide, N-octyl acrylamide, N-octadecyl acrylamide, N,N- diethylacrylamide, N-phenyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-dodecyl methacrylamide, Ν,Ν-dimethylaminoethyl acrylamide, quaternised N,N-dimethylaminoethyl acrylamide, N,N-dimethylaminoethyl methacrylamide, quaternised Ν,Ν-dimethylaminoethyl methacrylamide, N.N- dimethylaminoethyl acrylate, Ν,Ν-dimethylaminoethyl methacrylate, quaternised Ν,Ν-dimethyl-aminoethyl acrylate, quaternised N,N-dimethylaminoethyl

methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, glyceryl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2- ethoxyethyl ethacrylate, maleic acid, maleic anhydride and its half esters, fumaric acid, itaconic acid, itaconic anhydride and its half esters, crotonic acid, angelic acid, diallyldimethyl ammonium chloride, vinyl pyrrolidone vinyl imidazole, methyl vinyl ether, methyl vinyl ketone, maleimide, vinyl pyridine, vinyl pyridine-N-oxide, vinyl furan, styrene sulphonic acid and its salts, allyl alcohol, allyl citrate, allyl tartrate, vinyl acetate, vinyl alcohol, vinyl caprolactam, vinyl acetamide, vinyl formamide and mixtures thereof.

[0092] Even more preferred monomer units as a building parts of Ml , M2, M3 and My are those selected from methyl acrylate, methyl methacrylate,. methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, n-butyl acrylate,. n- butyl methacrylate, n-butyl ethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl ethacrylate, N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, Ν,Ν-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, acrylic acid, methacrylic acid, N-t-butylacrylamide, N-sec- butylacrylamide, N,N-dimethylacrylamide, Ν,Ν-dibutylacrylamide, N,N- dihydroxyethyllacrylamide 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, 4-butoxycarbonylphenyl acrylate, butyl acrylate, 4-cyanobutyl acrylate, cyclohexyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, iso-butyl acrylate, 3-methoxybutyl acrylate, 3-methoxypropyl acrylate, methyl acrylate, N-butyl acrylamide, Ν,Ν-dibutyl acrylamide, ethyl acrylate, methoxyethyl acrylate, hydroxyethyl acrylate, diethyleneglycolethyl acrylate, styrene (optionally substituted with one or more Ci -C 12 straight or branched chain alkyl groups), alpha- methylstyrene, t-butyl styrene, p-methylstyrene, and mixtures thereof.

[0093] Monomer units within the arms may be connected with C-C covalent bonds. This is believed to make them hard to degrade so that the star macromolecule may perform as efficient thickening agent in a harsh environment (very high/low pH or in the presence of strong oxidizing agents).

[0094] When "C" represents the crosslinked core of the star macromolecule it may be comprised of crosslinker (Mx), crosslinker (Mx) and monomer (My), crosslinker (Mx) and (M2), or a mixture of (Mx), (My) and (M2).

[0095] Suitable crosslinkers (Mx) encompass all of the compounds which are capable, under the polymerization conditions, of bringing about crosslinking. These include but are not limited di-, tri-, tetra-functional (meth)acrylates, di-, tri- and tetra- functional styrenes and other multi- or poly-functional crosslinkers.

[0096] Some examples of the crosslinking agents may include but are not limited to 1,2-divinylbenzene, 1,3-divinylbenzene and 1 ,4-divinylbenzene, 1 ,2-ethanediol di(meth)acrylate, 1 ,3-propanediol di(meth)acrylate, 1 ,4butanediol di(meth)acrylate, 1 ,5-hexanediol di(meth)acrylate, divinylbenzene, ethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, butyleneglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, polypropyleneglycol di(meth)acrylate, polybutyleneglycol di(meth)acrylate, and allyl(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(rneth)acrylate, allyl methacrylate, allyl acrylate.

[0097] In one embodiment, the core of the star macromolecule is formed by divinyl monomeric units, wherein the vinyl groups are connected by a chemically stable bond or by a cleavable chemical bond or mixture thereof. Examples of the divinyl monomeric units, wherein the vinyl groups are connected by a chemically stable bond are listed above. According to certain embodiments, at least a portion of the crosslinks within the core is cleavable in a predetermined chemical environment or a predetermined biological environment. In certain embodiments, the cleavable crosslinks are reversibly cleavable crosslinks. That is, at least a portion of the cleavable crosslinks may be selectively cleaved under specific chemical or

biochemical conditions and the cleaved crosslinks may be selectively reformed under other specific chemical or biochemical conditions.

[0098] Biodegradable or cleavable crosslinkers include peptides, [ helfallah, N. S.; Decher, G.; Mesini, P. J. Macromolecular Rapid Communications 2006, 27, 1004- 1008] anhydrides, [US Application No. 10/ 034908] and oligo(lactate) esters [Huang, X.; Lowe, T. L. Biomacromolecules 2005, 6, 2131 -2139]. Disulfides of the type R-S₂- R (both linear or cyclic) present another class of (bio)degradable groups which can be cleaved to the corresponding thiols in the presence of reducing agents, such as, but not limited to, tributyl phosphine (Bu₃P), tris(2-carboxyethyl)phosphine (TCEP), and dithiothreitol (DTT). [Houk, J.; Whitesides, G. M. J. Am. Chem. Soc. 1987, 109, 6825; Tsarevsky, N. PhD Thesis CMU 2005, Chapter 6]. Other degradable links such as hydrazides, hydrazines, hydrazones, acetals, oximes, imines, Schiff bases or urethanes, while not as biologically benign may also be used to target different rates of degradation in different environments, as can crosslinking agents comprising degradable oligo/polymer segments such as a polysaccharide, polyesters, a peptide or protein, chitin, or chitosan.

[0099] Since controlled radical polymerization processes are envisioned as one process for the preparation of the star macromolecules, a series of disulfide- functional ized dimethacrylate crosslinkers have been developed. The degradation of disulfides has been utilized for the preparation of various polymeric materials, including stimulus-responsive gelators, [Li, C; Madsen, J.; Armes, S. P.; Lewis, A. L. Angew. Chem. Int. Ed. 2006, 45, 3510] reversible shell-crosslinked micelles, [Li, Y.; Lokitz, B. S.; Armes, S. P.; McCormick, C. L. Macromolecules 2006, 39, 2726] and polymer capsules. [Zelikin, A. N.; Quinn, J. F.; Caruso, F. Biomacromolecules 2006, 7, 27],

[00100] The terms 'mostly soluble', 'not fully soluble', and 'not soluble' are used to describe the extent which a composition which is capable of being dissolved in a reference liquid of interest.

[00101] The term 'mostly soluble' is used to describe a composition which is capable dissolves completely with exception of a slight cloudiness in the reference liquid of interest. The term 'not fully soluble' is used to describe a composition which disperses with a cloudiness in the reference liquid of interest. The term 'not soluble' is used to describe a composition which does not disperse and remains as a solid in the reference liquid of interest. A list of solvents and non-solvent for polymers can be found in "Polymer Handbook, 4^th Ed." edited by Brandrup J.; Immergut, Edmund H.; Grulke, Eric A.; Abe, Akihiro; Bloch, Daniel R., John Wiley & Sons: 2005.

[00102] Multi-arm stars macromolecules are the preferred topology for an embodiment of the present invention as they can adopt a globular shape wherein the inner segment, (M2)_P2 of each arm covalently attached to the core, can chain extend in a selected solvent to attain a highly swollen stable structure. The dispersant medium can be water, oil or mixture thereof. The degree of polymerization p2 of the segment (M2), should be higher than that of pi of segment (Ml) to attain a highly swollen stable structure. A star macromolecule with p2 > (3 x pi) is more preferred.

[00103] In one embodiment, a star macromolecule described with formula (2) and shown in Figure I B, comprising a fraction of segmented (co)polymer arms [F-(M l)_pi- (M2)_p2], the average number of arms, n, should be greater than two per star, preferentially greater than three, and can comprise a mole fraction between 0.5 and 100% of the arms in the average star macromolecule. The ratio of n to m is more preferably between 100 and 0.1.

[00104] In one embodiment, in a star macromolecule described with formula (3) and shown in Figure 1C comprising a fraction of arms [F-(Ml )_pi] the average number of arms, o, should be greater than two per star, preferentially greater than three, and can comprise a mole fraction between 0.5 and 100% of the arms in the average star macromolecule. The ratio of o to m is more preferably between 100 and 0.1.

[00105] An embodiment of the present invention can be exemplified by a multi- arm star macromolecule wherein the average number of arms in the star

macromolecule is between 5 and 500, preferentially between 10 and 250.

[00106] In one embodiment, the star macromolecule has a core which contains additional functionality and/or expanded free volume. 'Expanded free volume' of the core is defined as the core with lower crosslink density. The free volume in the core is generated when during the crosslinking process crosslinker Mx with monomer M2 or My is used. If M2 or My are monomers with functional groups, these groups will be incorporated in the core.

[00107] In one embodiment, the star macromolecule may store and release in controlled rate the small molecules. 'Small molecules' are fragrances, UV absorbers, vitamins, minerals, dyes, pigments, solvents, surfactants, metal ions, salts, oils, or drugs. These small molecules can be stored inside the core of the star macromolecule and next released. Each small molecule has some affinity to the core, is soluble in the core environment. Higher affinity of the small molecule to the core will result in the lower rate of release from star macromolecule. The affinity may be increased or decreased through non-covalent forces including H-bonding, electrostatic, hydrophobic, coordination and metal chelating interactions.

[00108] In one embodiment, the star macromolecule displays shear thinning behavior. 'Shear thinning' is defined as is an effect where viscosity decreases with increasing rate of shear stress. The extent of shear thinning behavior is characterized using a Brookfield-type viscometer where viscosities are measured under different shear rates.

[00109] In one embodiment, the star macromolecule comprises a functional group which exhibits H-bonding, coordination, hydrophobic, metal chelating and/or electrostatic forces. "F" represents an optionally functional group or mixture of functional groups present on the arm chain-end. Functional groups (F) encompass all of the compounds capable of interacting through non-covalent forces including H- bonding, electrostatic, hydrophobic, coordination and metal chelating.

[00110] Some examples of F end groups capable of H-bonding include but are not limited to modified bases adenine, thymine, guanine, cytosine, or derivatives thereof, peptides etc. Some examples of endgroups capable of electrostatic interactions include but are not limited to carboxylate, phosphate, sulfonate, secondary-, tertiary- and quaternary-amines. Some examples of endgroups capable of hydrophobic interactions include but are not limited to Ci-C₃₀ aliphatic groups, benzyl and aliphatic benzyl groups, saturated and unsaturated hydrophobes. Some examples of endgroups capable of coordination interactions include but are not limited to metal ions and/or metal ion ligands. Some examples of endgroups capable of metal chelating interactions include derivatives of diethylenetriamine-Ν,Ν,Ν',Ν',Ν"- pentaacetic acid (DTA), ethylenedinitrilotetraacetic acid (EDTA), or nitrilotriacetic acid (NT A).

[00111] In one embodiment, the star macromolecule comprises a functional group F which is designed to interact with small molecule surfactant micelles. 'Interacts with' is defined as any intermolecular force between two molecules. These intermolecular forces include electrostatic, hydrogen bonding, hydrophobic, steric, dipole-dipole, pi-pi, or other intermolecular forces.

[00112] Surfactants represent a class of molecules with a hydrophobic tail and a hydrophilic head. Some examples of surfactants include but are not limited to linear alkylbenzenesulfonate salts (LAS), alkyl ether sulfate salts (AEOS),

alkylpolyglycosides (APG), alcohol ethoxylates, fatty acid glucoamides, betaines, alpha-olefinsulfonate salts, polysorbates, PEGs, alkylphenol ethoxylates, esterquats, imidizolium salts, diamido quaternary ammonium salts, etc.

[00113] In one embodiment, the star macromolecule arms comprise a (co)polymer segment that exhibits an upper, or higher, critical solution temperature (UCST or HCST) whereby the star macromolecule is soluble in a liquid at higher temperature, say above 44°C, then at the lower use temperature the outer shell polymer segments become insoluble and self assemble to form a shear sensitive gel or in another embodiment the invention the outer shell of the star macromolecule arms comprise a (co)polymer segment that exhibits a lower critical solution temperature (LCST), say 5°C, whereby the star macromolecule is soluble in a liquid at lower temperature then at the use temperature the outer shell polymer segments become insoluble and self assemble to form a shear sensitive gel. In the case of a LCST it is envisioned that a copolymer segment with an LCST below 10°C, preferable below 5°C would be optimal. A non-limiting example would be a copolymerization of BuMA and DMAEMA and preparation of copolymers with designed LCST. A copolymer with 10% BuMA has a LCST close to 0°C and one would use less BuMA or a less hydrophobic monomer such as MMA to increase the LCST to ~5°C. Indeed the Tg of the segment of the star can be selected to allow dissolution of the star in room temperature aqueous media.

[00114] In one embodiment, a star macromolecule further comprise a personal care and cosmetics formulation and/or product. Personal care and cosmetic products include but are not limited to a shampoo, conditioner, hair lotion, tonic, hair spray, hair mousse, hair gel, hair dyes, moisturizer, suntan lotion, color cosmetic, body lotion, hand cream, baby skin-care product, facial cream, lipstick, mascara, blush, eyeliner, baby shampoo, baby moisturizer, baby lotion, shower gel, soap, shaving product, deodorant, bath cream, body wash, serum, cream, solid, gel, lubricant, gelly, balm, tooth paste, whitening gel, disposable towel, disposable wipe or ointment.

[00115] In one embodiment a star macromolecule further comprise a home care formulation and/or product. Home care products include but are not limited to a surface cleaner, window cleaner, laundry detergent, toilet cleaner, fabric cleaner, fabric softener, dish detergent, cleaning stick, stain stick, spray cleaners, sprayable formulations, lubricant, disposable towel or disposable wipe.

[00116] The polymer chains that comprise the arms are preferably provided with a molecular mass of greater than or equal to 500 which can range up to 2,000,000. This numbers correspond to pi, p2, p3 in the range of 5 up to 20,000 preferably in the range of 8 to 2,000.

[00117] In one example, the star macromolecules comprising segmented copolymers arms are directed at use in aqueous media. The stars comprise a crosslinked core, and arms comprising of water soluble copolymer (M2)_p2 and a hydrophobic (co)polymer (Ml)_pi. Therefore in a in a non-limiting example the stars comprise a crosslinked core, and arms comprising an water soluble (co)polymer (e.g. poly(acrylic acid), poly(2-hydroxyethyl acrylate), poly(N-isopropylacrylamide), poly(ethylene glycol) methacrylate, quaternized poly(dimethylaminoethyl

methacrylate), etc.) and a hydrophobic (co)polymer (e.g. polystyrene or substituted polystyrenes, poly(alkyl(meth)acrylate), etc.) or a hydrocarbon based segment.

Suitable hydrocarbon based segments can comprise low molecular weight a-olefin. Lower molecular weight -olefins are commercially available and higher molecular weight species can be prepared by telomerization of ethylene or ethylene propylene mixtures. [ aneyoshi, H.; Inoue, Y.; Matyjaszewski, K. Macromolecules 2005, 38, 5425-5435.] [00118] In an embodiement, the polymer compositions can self assemble in solution to provide a certain level of control over viscosity and consistency factors in many aqueous and oil based systems where control over the rheology is a concern. Applications include; water- and solvent-based coating compositions, paints, inks, antifoaming agents, antifreeze substances, corrosion inhibitors, detergents, oil-well drilling-fluid rheology modifiers, additives to improve water flooding during enhanced oil recovery, dental impression materials, cosmetic and personal care applications including hair styling, hair conditioners, shampoos, bath preparations, cosmetic creams, gels, lotions, ointments, deodorants, powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin wipes, sunscreens, shaving preparations, and fabric softeners, with the rheology modifier providing

characteristics of high gel strength, highly shear thinning characteristics, forms versatile low viscosity soluble concentrations, and synergistic interactions with added agents to adjust their rheology profile to optimize properties such as sedimentation, flow and leveling, sagging, spattering, etc.

[00119] One non-limiting field of applications that can exemplify the utility of the disclosed star macromolecules is cosmetic and personal care compositions such as hair styling sprays, mousses, gels and shampoos, frequently contain resins, gums and adhesive polymers to provide a variety of benefits, for example, film-forming ability, thickening, sensory properties and hair shaping and setting. Polymers designed for rheological control, as thickening agents, in such compositions generally focus on linear or graft copolymers which contain various monomers in an alternating, random or block configuration.

[00120] Suitable hydrophobic monomers that may be used to form an arm or segment of an arm, such as a polymeric segment of an arm, of a star macromolecule may include, but is not limited to methyl acrylate, ethyl acrylate, n-butyl acrylate, iso- butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methyl methacrylate; ethyl methacrylate; n-butyl mefhacrylate; iso-butyl

methacrylate; t-butyl methacrylate; 2-ethylhexyl methacrylate; decyl methacrylate; methyl ethacrylate; ethyl ethacrylate; n-butyl ethacrylate; iso-butyl ethacrylate; t-butyl ethacrylate; 2-ethylhexyl ethacrylate; decyl ethacrylate; 2,3-dihydroxypropyl acrylate; 2,3-dihydroxypropyl methacrylate; 2-hydroxypropyl acrylate; hydroxypropyl methacrylate; glycidyl methacrylate; glycidyl acrylate, acrylamides, styrene; styrene optionally substituted with one or more Ci - Cn straight or branched chain alkyl groups; or alkylacrylate. For example, the hydrophobic monomer may comprise styrene; alpha-methylstyrene; t-butylstyrene; p-methylstyrene; methyl methacrylate; or t-butyl-acrylate. For example, the hydrophobic monomer may comprise styrene. In certain embodiments, the hydrophobic monomer may comprise a protected functional group.

[00121] Suitable hydrophilic monomers that may be used to form an arm or segment of an arm, such as a polymeric segment of an arm, of a star macromolecule may include, but is not limited to, protected and unprotected acrylic acid, such as methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso- butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methyl methacrylate; ethyl methacrylate; n-butyl methacrylate; iso-butyl

methacrylate; t-butyl methacrylate; 2-ethylhexyl methacrylate; decyl methacrylate; methyl ethacrylate; ethyl ethacrylate; n-butyl ethacrylate; iso-butyl ethacrylate; t-butyl ethacrylate; 2-ethylhexyl ethacrylate; decyl ethacrylate; 2,3-dihydroxypropyl acrylate; 2,3-dihydroxypropyl methacrylate; 2-hydroxyethyl acrylate; 2-hydroxypropyl acrylate; hydroxypropyl methacrylate; glyceryl monoacrylate; glyceryl

monoethacrylate; glycidyl methacrylate; glycidyl acrylate; acrylamide;

methacrylamide; ethacrylamide; N-methyl acrylamide; Ν,Ν-dimethyl acrylamide; Ν,Ν-dimethyl methacrylamide; N-ethyl acrylamide; N-isopropyl acrylamide; N-butyl acrylamide; N-t-butyl acrylamide; N,N-di-n-butyl acrylamide; N,N- diethylacrylamide; N-octyl acrylamide; N-octadecyl acrylamide; N,N- diethylacrylamide; N-phenyl acrylamide; N-methyl methacrylamide; N-ethyl methacrylamide; N-dodecyl methacrylamide; Ν,Ν-dimethylaminoethyl acrylamide; quaternised Ν,Ν-dimethylaminoethyl acrylamide; N,N-dimethylaminoethyl methacrylamide; quaternised Ν,Ν-dimethylaminoethyl methacrylamide; N,N- dimethylaminoethyl acrylate; Ν,Ν-dimethylaminoethyl methacrylate; quaternised Ν,Ν-dimethyl-aminoethyl acrylate; quaternised N,N-dimethylaminoethyl

methacrylate; 2-hydroxyethyl acrylate; 2-hydroxyethyl methacrylate; 2-hydroxyethyl ethacrylate; glyceryl acrylate; 2-methoxyethyl acrylate; 2-methoxyethyl methacrylate; 2-methoxyethyl ethacrylate; 2-ethoxyethyl acrylate; 2-ethoxyethyl methacrylate; 2- ethoxyethy ethacrylate; maleic acid; maleic anhydride and its half esters; fumaric acid; itaconic acid; itaconic anhydride and its half esters; crotonic acid; angelic acid; diallyldimethyl ammonium chloride; vinyl pyrrolidone vinyl imidazole; methyl vinyl ether; methyl vinyl ketone; maleimide; vinyl pyridine; vinyl pyridine-N-oxide; vinyl furan; styrene sulphonic acid and its salts; allyl alcohol; allyl citrate; allyl tartrate; vinyl acetate; vinyl alcohol; vinyl caprolactam; vinyl acetamide; or vinyl formamide. For example, the hydrophilic monomer may comprise protected and unprotected acrylic acid, such as methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, a-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methyl acrylate; methyl methacrylate; methyl ethacrylate; ethyl acrylate; ethyl methacrylate; ethyl ethacrylate; n-butyl acrylate; n-butyl methacrylate; n-butyl ethacrylate; 2-ethylhexyl acrylate; 2-ethylhexyl methacrylate; 2- ethylhexyl ethacrylate; N-octyl acrylamide; 2-methoxyethyl acrylate; 2-hydroxyethyl acrylate; Ν,Ν-dimethylaminoethyl acrylate; Ν,Ν-dimethylaminoethyl methacrylate; acrylic acid; methacrylic acid; N-t-butylacrylamide; N-sec-butylacrylamide; N,N- dimethylacrylamide; Ν,Ν-dibutylacrylamide; N,N-dihydroxyethyllacrylamide; 2- hydroxyethyl acrylate; 2-hydroxyethyl methacrylate; benzyl acrylate; 4- butoxycarbonylphenyl acrylate; butyl acrylate; 4-cyanobutyl acrylate; cyclohexyl acrylate; dodecyl acrylate; 2-ethylhexyl acrylate; heptyl acrylate; iso-butyl acrylate; 3- methoxybutyl acrylate; 3-methoxypropyl acrylate; methyl acrylate; N-butyl acrylamide; Ν,Ν-dibutyl acrylamide; ethyl acrylate; methoxyethyl acrylate;

hydroxyethyl acrylate; or diethyleneglycolethyl acrylate. For example, the

hydrophilic monomer may comprise protected and unprotected acrylic acid, such as methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, a-butyl acrylate, iso- butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; 2- hydroxyethyl acrylate; N-isopropylacrylamide; ethylene glycol methacrylate;

(polyethylene glycol) methacrylate; or quaternized dimethylaminoethyl methacrylate. For example, the hydrophilic monomer may comprise acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, acrylamide, vinyl pyrrolidone, vinyl pyridine, styrene sulphonic acid, PEG-methacrylate, 2-(dimethylamino)ethyl methacrylate, 2- (trimethylamino)ethyl methacrylate, 2-acrylamido-2-methylpropane sulphonic acid. For example, the hydrophilic monomer may comprise acrylic acid.

[00122] Suitable monomers that may be used to form a core of a star

macromolecule may include, but are not limited to, a multifunctional monomer, for example, a hexafunctional monomer, a pentafunctional monomer, a tetrafunctional monomer, a trifunctional monomer, or a difunctional monomer. For example, a crosslinker may be a hydrophobic monomer or a hydrophilic monomer, such as a hydrophobic multifunctional monomer or a hydrophilic multifunctional monomer, for example, a hydrophobic difunctional monomer or a hydrophilic difunctional monomer. For example, the crosslinker may be a hydrophobic crosslinker, including, but not limited to, 1,2-divinylbenzene; 1 ,3-divinylbenzene; 1,4-divinylbenzene; 1 ,2- ethanediol di(meth)acrylate; 1 ,3 -propanediol di(meth)acrylate; l ,4butanediol di(meth)acrylate; 1 ,5-hexanediol di(meth)acrylate; divinylbenzene; ethyleneglycol di(meth)acrylate; di(ethylene glycol) diacrylate (DEGlyDA); propyleneglycol di(meth)acrylate; butyleneglycol di(meth)acrylate; triethyleneglycol di(meth)acrylate; polyethyleneglycol di(meth)acrylate; polypropyleneglycol di(meth)acrylate;

polybutyleneglycol di(meth)acrylate; allyl(meth)acrylate; glycerol di(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; allyl methacrylate; or allyl acrylate. For example, the crosslinker may be di(ethylene glycol) diacrylate (DEGlyDA) or divinylbenzene. For example, the crosslinker may be divinylbenzene.

[00123] In certain embodiments, the crosslinked core of a star macromolecule may further comprise one more monofunctional monomers, such as hydrophobic monomers and/or hydrophilic monomers, wherein the crosslinked core of the star macromolecule has a crosslinking dentsity in the range of between 0.2 mol.% to 100 mol.%, for example, between 0.2 mol.% to 90 mol.%; between 0.2 mol.% to 80 mol.%; between 0.2 mol.% to 70 mol.%; between 0.2 mol.%o to 60 mol.%>; between 0.2 mol.% to 50 mol.%; between 0.2 mol.% to 40 mol.%; between 0.2 mol.% to 30 mol.%; between 0.2 mol.% to 20 mol.%; between 0.2 mol.% to 10 mol.%; between 10 mol.% to 90 mol.%; between 10 mol.% to 75 mol.%; between 10 mol.% to 50 mol.%; between 10 mol.% to 25 mol.%; between 15 mol.% to 40 mol.%; between 20 mol.% to 60 mol.%; or between 75 mol.% to 100 mol.%. In certain embodiments, the crosslinked core of a star macromolecule may comprise hydrophobic crosslinker residues; hydrophilic crosslinker residues; hydrophobic monomeric residues; and/or hydrophilic monomeric residues.

[00124] In certain embodiments, a star macromolecule may have a diameter of 1 micron or less, such as 900 nm or less; 800 nm or less; 700 nm or less; 600 nm or less; 500 nm or less; 400 nm or less; 300 nm or less; 200 nm or less; 150 nm or less; 100 nm or less; 75 nm or less; 50 nm or less; 40 nm or less; 30 nm or less; 20 nm or less; 20 nm or less; or 10 nm or less. For example, a star macromolecule may have a diameter in the range of between 5 nm to 1 micron, such as between 5 nm to 900 nm; between 5 nm to 800 nm; between 5 nm to 750 nm; between 5 nm to 500 nm; between 5 nm to 250 nm; between 5 nm to 100 nm; between 5 nm to 50 nm; between 5 nm to 30 nm; between 5 nm to 10 nm; between 10 nm to 25 nm; between 10 nm to 50 nm; between 10 nm to 75 nm; between 10 nm to 100 nm; between 10 nm to 150 nm; between 50 nm to 150 nm; between 100 nm to 200 nm; between 150 nm to 250 nm; between 200 nm to 500 nm between 300 nm to 500 nm; between 400 nm to 600 nm; between 500 nm to 700 nm; between 600 nm to 850 nm; or between 750 nm to 1 micron.

[00125] In certain embodiments, the crosslinked core of a star macromolecule may have a diameter of 600 nm or less, such as 550 nm or less; 500 nm or less; 450 nm or less; 400 nm or less; 350 nm or less; 300 nm or less; 250 nm or less; 200 nm or less; 150 nm or less; 100 nm or less; 75 nm or less; 50 nm or less; 40 nm or less; 30 nm or less; 20 nm or less; 20 nm or less; or 10 nm or less. For example, the crosslinked core of a star macromolecule may have a diameter in the range of between 1 nm to 600 nm, such as between 1 nm to 600 nm; between 1 nm to 500 nm; between 1 nm to 400 nm; between 1 nm to 300 nm; between 1 nm to 200 nm; between 1 nm to 100 nm; between 1 nm to 50 nm; between 1 nm to 30 nm; between 5 nm to 10 nm; between 5 nm to 25 nm; between 5 nm to 50 nm; between 5 nm to 75 nm; between 1 nm to 100 nm; between 50 nm to 100 nm; between 75 nm to 150 nm; between 100 nm to 200 nm; between 150 nm to 250 nm; or between 200 nm to 500 nm.

[00126] Suitable star macromolecules may include, but are not limited to, a mikto star macromolecule, a water-soluble star macromolecule, a gel-forming star macromolecule, emulsifier/thickening agent star macromolecules or combinations thereof. In certain embodiments, the star macromolecule may have a molecular weight of greater than 50,000 g mol, for example, between 50,000 g/mol and

2,000,000 g/mol, such as between between 75,000 g/mol and 1 ,750,000 g/mol;

between 100,000 g/mol and 1 ,750,000 g/mol; 125,000 g/mol and 1 ,750,000 g/mol; between 150,000 g/mol and 1 ,750,000 g/mol; between 200,000 g/mol and 1 ,500,000 g/mol; between 225,000 g/mol and 1 ,250,000 g/mol; between 125,000 g/mol and 1 ,000,000 g/mol; between 125,000 g/mol and 900,000 g/mol; between 125,000 g/mol and 800,000 g/mol; between 125,000 g/mol and 700,000 g/mol; between 150,000 g/mol and 650,000 g/mol; between 200,000 g/mol and 600,000 g/mol; between 225,000 g/mol and 650,000 g/mol; between 250,000 g/mol and 550,000 g/mol;

between 350,000 g/mol and 500,000 g/mol; between 300,000 g/mol and 500,000 g/mol; or between 350,000 g/mol and 750,000 g/mol. [00127] Suitable star macromolecules may have a polydispersity index (PDI) of less than 2.5, for example, a PDI of less that 2.0, such as less than 1.7. For example, a star macromolecule may have a PDI of between 1.0 to 2.5, such as between 1.0 and 2.3; between 1.0 and 2.0; between 1.0 and 1.9; between 1.0 and 1 .8; between 1.0 and 1.7; between 1.0 and 1.6; between 1.0 and 1.5; between 1.0 and 1.4; between 1.0 and 1.3; between 1.0 and 1.2; between 1.0 and 1.1 ; between 1.05 and 1.75; between 1.1 and 1.7; between 1.15 and 1.65; or between 1 .15 and 1.55.

[00128] Suitable star macromolecules may comprise arms that are of the same type or a different type and are homopolymeric, copolymeric, comprise multiple block segment, random segments, gradient segments and or no particular segments. In certain embodiments, the star macromolecule may comprise, for example, one or more arm-types, such as, two or more, three or more, four or more, or five or more arm-types. Suitable arm types may include, but are not limited to, homopolymeric arms, copolymeric arms, such as random copolymeric arms or block copolymeric arms, or combinations thereof. For example, a star macromolecule may comprise homopolymeric arms and copolymeric arms, such as block copolymeric arms.

Suitable arm types may also include, but are not limited to, hydrophilic arms, hydrophobic arms, or amphiphilic arms. In certain embodiments, a star

macromolecule arm may comprise hydrophilic polymeric segments or substantially hydrophilic polymeric segments comprising hydrophilic monomeric residues, hydrophobic polymeric segments or substantially hydrophobic polymeric segments comprising hydrophobic monomeric residues, amphiphilic polymeric segments comprising amphiphilic monomeric residues, or combinations thereof. For example, in certain embodiments, a star macromolecule may comprise homopolymeric arms and copolymeric arms, such as hydrophilic homopolymeric arms and copolymeric arms comprising hydrophilic polymeric segments and hydrophobic polymeric segments. In certain embodiments, a star macromolecule may comprise arms having substantially hydrophilic polymeric segments and copolymeric arms comprising substantially hydrophilic polymeric segments and substantially hydrophobic polymeric segments. In certain embodiments, a star macromolecule may comprise arms having substantially hydrophobic polymeric segments and copolymeric arms comprising substantially hydrophilic polymeric segments and substantially hydrophobic polymeric segments. -

[00129] Suitable star macromolecules may also comprise arms that are covalently linked to the core of the star macromolecule. In certain embodiments, the arms of a star macromolecule may be covalently linked to the core of the star macromolecule via crosslinking, such as crosslinking with a crosslinker, for example, a hydrophobic difunctional crosslinker or a hydrophilic difunctional crosslinker. For example, arms of a star macromolecule, such as homopolymeric arms and block copolymeric arms of a mikto star macromolecule, may be covalently linked together to form a core by crosslinking an end of the arms with a crosslinker, such as with a hydrophobic difunctional crosslinker or a hydrophilic difunctional crosslinker.

[00130] Suitable star macromolecules may also comprise arms of varying length and/or degree of polymerization. In certain embodiments, for example, a star macromolecule may comprise homopolymeric arms and block copolymeric arms, wherein the homopolymeric arms of a shorter length and/or a lesser degree of polymerization in relation to the block copolymeric arms. In certain embodiments, for example, a star macromolecule may comprise homopolymeric arms and block copolymeric arms, wherein the block copolymeric arms of a longer length and/or a greater degree of polymerization in relation to the homopolymeric arms. In certain embodiments, a star macromolecule may comprise hydrophilic homopolymeric arms and block copolymeric arms, comprising hydrophobic polymeric segments distal to the star core and hydrophilic polymeric segments that are proximal to the core of the star, wherein a distal portion of the hydrophilic polymeric segments of the

copolymeric arm extends beyond a distal portion of the hydrophilic homopolymeric arms. For example, a star macromolecule may comprise hydrophilic homopolymeric arms comprising polymerized hydrophilic monomeric residues and block copolymeric arms comprising hydrophobic polymeric segments distal to the core of the star and hydrophilic polymeric segments that are proximal to the core of the star, wherein the distal hydrophobic polymeric segments extend beyond the most distal portion, in relation to the core, of the hydrophilic homopolymeric arms, and/or wherein a distal portion of the proximal hydrophilic polymeric segments of the copolymeric arm extend beyond the most distal portion, in relation to the core, of the hydrophilic homopolymeric arms. In certain embodiments, a star macromolecule may comprise hydrophilic homopolymeric arms and block copolymeric arms, comprising hydrophobic polymeric segments distal to the star core and hydrophilic polymeric segments that are proximal to the star core, wherein the degree of polymerization of the hydrophilic polymeric segments of the copolymeric arm is greater than, for example, 20% greater than, such as between 30% to 300% greater than, between 40% to 250%, between 50% to 200%, or between 75% to 250% greater than, the degree of polymerization of the hydrophilic homopolymeric arms, such that a distal portion of the hydrophilic polymeric segments of the copolymeric arm extends beyond the a distal portion of the hydrophilic homopolymeric arms.

[00131] In certain embodiments, a star macromolecule may comprise hydrophilic homopolymeric arms comprising polymerized hydrophilic monomeric residues and block copolymeric arms comprising hydrophobic polymeric segments distal to the core of the star and hydrophilic polymeric segments proximal to the core of the star, wherein the polymerized hydrophilic monomeric residues of the homopolymeric arm and the hydrophilic polymeric segments of the copolymeric arm may be derived from the same hydrophilic monomers, and may have the same or different degree of polymerization, for example, a degree of polymerization of between 30 to 1 ,000 monomeric residues, such as, between 30 to 900 monomeric residues; between 30 to 800 monomeric residues; between 30 to 700 monomeric residues; between 30 to 600 monomeric residues; between 30 to 500 monomeric residues; between 30 to 400 monomeric residues; between 30 to 300 monomeric residues; between 30 to 200 monomeric residues; between 100 to 750 monomeric residues; between 100 to 500 monomeric residues; between 500 to 1 ,000 monomeric residues; between 250 to 750 monomeric residues; between 300 to 600 monomeric residues; between 600 to 900 monomeric residues; between 100 to 400 monomeric residues; between 100 to 250 monomeric residues; between 125 to 175 monomeric residues; or between 150 to 300 monomeric residues. For example, a star macromolecule may comprise hydrophilic homopolymeric arms comprising polymerized hydrophilic monomeric residues and block copolymeric arms comprising hydrophobic polymeric segments distal to the core of the star and hydrophilic polymeric segments proximal to the core of the star, wherein the polymerized hydrophilic monomeric residues of the homopolymeric arm and the hydrophilic polymeric segments of the copolymeric arm may be derived from the same hydrophilic monomers, and may have the same degree of polymerization, and wherein the hydrophibic polymeric segments of the copolymeric arm may have a degree of polymerization of between 1 to 100 monomeric residues, such as between 1 to 90 monomeric residues; between 1 to 80 monomeric residues; between 1 to 70 monomeric residues; between 1 to 60 monomeric residues; between 1 to 50 monomeric residues; between 1 to 45 monomeric residues; between 50 to 100 monomeric residues; between 25 to 75 monomeric residues; between 60 to 90 monomeric residues; between 80 to 100 monomeric residues; between 35 to 65 monomeric residues; between 5 to 85 monomeric residues; between 5 to 55 monomeric residues; between 5 to 40 monomeric residues; between 8 to 35 monomeric residues; between 10 to 30 monomeric residues; between 12 to 25 monomeric residues; between 14 to 20 monomeric residues; between 15 to 30 monomeric residues; or between 5 to 20 monomeric residues.

[00132] Suitable star macromolecules may have a wide range of total number of arms, for example, a star macromolecule may comprise greater than 15 arms. For example, a suitable star macromolecule may comprise between 15 and 1 ,000 arms, such as between 15 and 900 arms; between 15 and 800 arms; between 15 and 700 arms; between 15 and 600 arms; between 15 and 500 arms; between 15 and 400 arms; between 15 and 300 arms; between 15 and 200 arms; between 15 and 100 arms;

between 15 and 90 arms; between 15 and 80 arms; between 15 and 70 arms; between 15 and 60 arms; between 15 and 50 arms; between 15 and 40 arms; between 20 and 50 arms; between 25 and 45 arms; between 25 and 35 arms; between 30 and 45 arms; between 30 and 50 arms; between 250 and 750 arms; between 500 and 1,000 arms; between 300 and 600 arms; between 600 and 900 arms; between 800 and 1,000 arms; between 200 and 400 arms; between 350 and 650 arms; between 100 and 200 arms; between 150 and 250 arms; between 200 and 300 arms; between 250 and 350 arms; between 300 and 400 arms; between 350 and 450 arms; or between 450 and 550 arms.

[00133] Suitable star macromolecules may have more than one arm type, such as two or more different arm types, where in a molar ratio of the different arm types may be between 40: 1 and 1:1. For example, a star macromolecule comprising two different arm types, such as a homopolymeric arm, for example, a hydrophilic homopolymeric arm, and a copolymeric arm, for example, a copolymeric arm comprising hydrophilic polymeric segments and hydrophobic polymeric segments, may have a molar ratio of the two different arm types between 40:1 to 2:1, such as between35:l to 2: 1; between 30:1 to 2:1; between 25:1 to 2:1; between 20:1 to 2:1; between 15:1 to 2: 1 ; between 10:1 to 2: 1 ; between 9:1 to 2: 1 ; between 8: 1 to 2: 1 ; between 7:1 to 2:1 ; between 6:1 to 2:1; between 5:1 to 2:1; between 4:1 to 2:1 ;

between 3:1 to 2:1; between 2:1 to 1:1; between 40:1 to 5:1; between 40:1 to 10:1; between 40:1 to 20:1; between 40:1 to 30:1; between 35:1 to 15:1; between 35:1 to 25: 1 ; between 30: 1 to 20: 1 ; between 30: 1 to 10: 1 ; between 25: 1 to 10: 1 ; between 25: 1 to 15: 1 ; between 20: 1 to 4: 1 ; between 20:1 to 10: 1 ; between 8: 1 to 3: 1 ; between 7: 1 to 2: 1 ; or between 5: 1 to 3: 1.

[00134] Suitable star macromolecules may include, but is not limited to, comprising arms having a molecular weight of greater than 10,000 g/mol. For example, a star macromolecule may comprise arms having a molecular weight of between 10,000 g/mol and 500,000 g/mol, such as between 10,000 g/mol and 450,000 g/mol; between 10,000 g/mol and 400,000 g/mol; between 10,000 g/mol and 350,000 g/mol; between 10,000 g/mol and 300,000 g/mol; between 10,000 g/mol and 250,000 g/mol; between 10,000 g/mol and 200,000 g/mol; between 10,000 g/mol and 175,000 g/mol; between 10,000 g/mol and 150,000 g/mol; between 10,000 g/mol and 125,000 g/mol; between 10,000 g/mol and 100,000 g/mol; between 10,000 g/mol and 90,000 g/mol; between 10,000 g/mol and 80,000 g/mol; between 10,000 g/mol and 70,000 g/mol; between 400,000 g/mol and 500,000 g/mol; between 350,000 g/mol and 450,000 g/mol; between 250,000 g/mol and 400,000 g/mol; between 200,000 g/mol and 300,000 g/mol; between 150,000 g/mol and 350,000 g/mol; between 100,000 g/mol and 300,000 g/mol; between 60,000 g/mol and 50,000 g/mol; between 10,000 g/mol and 40,000 g/mol; between 10,000 g/mol and 30,000 g/mol; between 10,000 g/mol and 20,000 g/mol; between 20,000 g/mol and 175,000 g/mol; between 20,000 g mol and 100,000 g mol; between 20,000 g/mol and 75,000 g/mol; between 20,000 g/mol and 50,000 g/mol; between 15,000 g/mol and 45,000 g/mol; or between 15,000 g/mol and 30,000 g/mol.

[00135] Suitable arms of a star macromolecule may include, but is not limited to, arms having an HLB value of at least 17 (wherein the HLB is calculated per the formula set forth in the test procedures). For example, suitable arms of a star macromolecule may have an HLB value of greater than 17.25, such as greater than 18.5; at least 19; between 17.5 to 20; between 17.5 to 19.5; between 18 to 20; between 18.5 to 20; between 19 to 20; between 19.5 to 20; between 18 to 19.5; between 18.5 to 19.75; between 18.2 to 19.2; or between 18.75 to 19.5.

[00136] Suitable hydrophobic polymeric segments of a copolymeric arm of a star macromolecule may include, but is not limited to, hydrophobic polymeric segments having an HLB value of less than 8. For example, suitable hydrophobic polymeric segments may have an HLB value of less than 7, such as less than 6; less than 5; less than 4; less than 3; less than 2; or about 1. [00137] Suitable arms of a star macromolecule may include, but is not limited to, arms having a polydispersity index (PDI) value of less than 2.5. For example, suitable arms of a star macromolecule may have PDI value of less than 2.25, such as less that 2.0; less than 1.7; between 1.0 to 2.5, such as between 1.0 and 2.3; between 1.0 and 2.0; between 1.0 and 1.9; between 1.0 and 1.8; between 1.0 and 1.7; between 1.0 and 1.6; between 1.0 and 1.5; between 1.0 and 1.4; between 1.0 and 1.3; between 1.0 and 1.2; between 1.0 and 1.1 ; between 1.05 and 1.75; between 1.1 and 1.7;

between 1.15 and 1.65; or between 1.15 and 1.55.

[00138] Suitable cores of a star macromolecule may be formed by or derived from, but is not limited to, crosslinking of a plurality of arms and a crosslinker. For example, a core may be formed by or derived from crosslinking of a plurality of homopolymeric arms and a plurality of copolymeric arms with a crosslinker, such as a mutlifunctional monomer crosslinker, for example, a hydrophobic difunctional monomer crosslinker. In certain embodiments, the core may be formed or derived from crosslinking a plurality of hydrophilic homopolymeric arms and a plurality of copolymeric arms, comprising block hydrophilic polymeric segments and block hydrophobic polymeric segments, with a crosslinker, such as a hydrophobic difunctional monomer crosslinker, for example divinylbenzene, wherein the molar ratio of the homopolymeric arms to the copolymeric arms may be between 20: 1 to 2: 1.

[00139] Suitable star macromolecules may include, but is not limited to, comprising a core having a molecular weight of greater than 3,000 g/mol. For example, a star macromolecule may comprise a core having a molecular weight of between 3,000 g/mol and 200,000 g/mol, such as between 3,000 g/mol and 175,000 g mol; between 3,000 g/mol and 150,000 g/mol; between 3,000 g mol and 125,000 g mol; between 3,000 g/mol and 100,000 g/mol; between 3,000 g/mol and 90,000 g/mol; between 3,000 g/mol and 80,000 g/mol; between 3,000 g/mol and 70,000 g/mol; between 3,000 g/mol and 60,000 g/mol; between 3,000 g/mol and 50,000 g/mol; between 3,000 g/mol and 45,000 g/mol; between 3,000 g/mol and 40,000 g/mol; between 3,000 g/mol and 30,000 g/mol; between 3,000 g/mol and 20,000 g/mol; between 3,000 g/mol and 15,000 g/mol; between 150,000 g/mol and 200,000 g/mol; between 100,000 g/mol and 200,000 g/mol; between 50,000 g/mol and 150,000 g/mol; between 50,000 g/mol and 100,000 g/mol; between 75,000 g/mol and 125,000 g/mol; between 50,000 g/mol and 75,000 g/mol; between 25,000 g/mol and 75,000 g/mol; between 40,000 g/mol and 80,000 g/mol; between 60,000 g/mol and 90,000 g/mol; between 5,000 g/mol and 40,000 g/mol; between 6,000 g/mol and 30,000 g/mol; between 7,000 g/mol and 25,000 g/mol; between 8,000 g/mol and 20,000 g/mol; between 5,000 g/mol and 15,000 g/mol; between 7,000 g/mol and 12,000 g/mol; between 5,000 g/mol and 9,000 g/mol; between 8,000 g/mol and 10,000 g/mol; or between 9,000 g/mol and 15,000 g/mol.

[00140] Suitable star macromolecules may be used to form a clear, homogeneous gel when dissolved in water at a concentration of at least 0.05 wt.% at a pH of about 7.5 at STP. For example, a star macromolecule may form a clear, homogeneous gel when dissolved in water at a concentration of between 0.05 wt.% to 3 wt.%, such as between 0.1 wt.% to 2.5 wt.%; between 0.1 wt.% to 2 wt.%; between 0.2 wt.% to 2.0 wt.%; between 0.2 wt.% to 1.5 wt.%; between 0.2 wt.% to 1.0 wt.%; between 0.2 wt.% to 2.5 wt.%; between 0.3 wt.% to 2.5 wt.%; between 0.4 wt.% to 2.0 wt.%; between 0.5 wt.% to 2.0 wt.%; between 0.6 wt.% to 2.0 wt.%; between 0.7 wt.% to 1.5 wt.%; between 0.8 wt.% to 1.2 wt.%; between 0.9 wt.% to 1.1 wt.%; between 0.5 wt.% to 2.5 wt.%; between 0.75 wt.% to 1.5 wt.%; or between 0.8 wt.% to 1.6 wt.%.

[00141] Suitable star macromolecules, in accordance with the pH Efficiency Range Test Procedure described below herein, may be used to form a clear, homogeneous gel, wherein the star macromolecule at a concentration of 0.4 wt.%, may have a viscosity of at least 20,000 cP, at a pH of between about 4 to about 12, for example, at a pH of between about 5 to about 1 1.5 such as at a pH of between about 5 to about 1 1 ; between about 5 to about 10.5; between about 5 to about 10; between about 5 to about 9.5; between about 5 to about 9; between about 5 to about 8.5; between about 5 to about 8; between about 6 to about 1 1 ; between about 5.5 to about 10; between about 6 to about 9; between about 6.5 to about 8.5; between about 7 to about 8; between about 7.5 to about 8.5; or between about 6.5 to about 7.5.

[00142] In certain embodiments, for example, suitable star macromolecules, in accordance with the pH Efficiency Range Test Procedure described below herein, may be used to form a clear, homogeneous gel, wherein the star macromolecule at a concentration of 0.4 wt.%, may have a viscosity of at least 20,000 cP at a pH between about 5.5 to about 1 1. For example, at a pH between about 5.5 to about 1 1 may have a viscosity of at least 30,000 cP, such as, at least 40,000 cP; between 20,000 cP to 250,000 cP; between 20,000 cP to 250,000 cP; between 20,000 cP to 225,000 cP; between 20,000 cP to 200,000 cP; between 20,000 cP to 175,000 cP; between 20,000 cP to 150,000 cP; between 20,000 cP to 125,000 cP; between 30,000 cP to 250,000 cP; between 30,000 cP to 200,000 cP; between 40,000 cP to 175,000 cP; or between 40,000 cP to 150,000 cP. For example, a gel at a pH between about 6 to about 1 1 may have a viscosity of at least 20,000 cP, such as, at least 30,000 cP; at least 40,000 cP; between 20,000 cP to 250,000 cP; between 20,000 cP to 250,000 cP; between 20,000 cP to 225,000 cP; between 20,000 cP to 200,000 cP; between 20,000 cP to 175,000 cP; between 20,000 cP to 150,000 cP; between 20,000 cP to 125,000 cP; between 30,000 cP to 250,000 cP; between 30,000 cP to 200,000 cP; between 40,000 cP to 175,000 cP; or between 40,000 cP to 150,000 cP. For example, at a pH between about 7 to about 10.5 may have a viscosity of at least 60,000 cP, such as at least 70,000 cP; between 60,000 cP to 250,000 cP; between 60,000 cP to 225,000 cP; between 60,000 cP to 200,000 cP; between 60,000 cP to 175,000 cP; between 60,000 cP to 150,000 cP; between 60,000 cP to 125,000 cP; between 60,000 cP to 1 15,000 cP; between 60,000 cP to 105,000 cP; or between 60,000 cP to 100,000 cP. For example, at a pH between about 7.5 to about 9.0 may have a viscosity of at least 95,000 cP, such as at least 100,000 cP; between 95,000 cP to 250,000 cP; between 95,000 cP to 225,000 cP; between 95,000 cP to 200,000 cP; between 95,000 cP to 175,000 cP; between 95,000 cP to 150,000 cP; between 95,000 cP to 125,000 cP; between 95,000 cP to 1 15,000 cP; or between 95,000 cP to 105,000 cP.

[00143] Suitable star macromolecules, in accordance with the Dynamic Viscosity & Shear- Thinning Test Procedure described below herein, may be used to form a clear, homogeneous gel, wherein the star macromolecule at a concentration of 0.4 wt.%, may have a viscosity of less than 5,000 cP at a shear rate of 4 sec^"1, such as a viscosity of less than 4,000 cP. For example, the star macromolecule at a

concentration of 0.4 wt.%, may have a viscosity have a viscosity of less than 5,000 cP at a shear rate of 6 sec^"1, such as a viscosity of less than 4,000 cP or less than 3,000 cP. For example, a gel may have a viscosity of less than 15,000 cP at a shear rate of 0.7 sec^"1, such as a viscosity of less than 14,000 cP or less than 13,000 cP. Suitable gels may include, but is not limited to, gels having shear-thinning value of at least 5, such as a shear-thinning value of at least 6, or between 5 to 15, such as between 5 to 15; between 7 to 12; between 8 to 10; or between 6 to 13.

[00144] Suitable star macromolecules, in accordance with the Dynamic Viscosity & Shear- Thinning Test Procedure described below herein, include those that have a shear- thinning value of at least 15, such as a shear-thinning value of between 15 to 100, such as between 15 to 90; between 20 to 80; between 25 to 70; between 25 to 50; or between 30 to 40.

[00145] Suitable star macromolecules, in accordance with the Salt-Induced Break Test Procedure described below herein, include those that have a salt-induced break value of at least 50%, such as a salt-induced break value of between 65% to 100%, such as between 75% to 100%; between 80% to 95%; between 75% to 90%; between 50% to 85%; between 70% to 95%; or between 60% to 100%.

|00146] Suitable star macromolecules, in accordance with the pH Efficiency Range Test Procedure described below herein, include those that have a pH-induced break value of at least 15%, such as a pH -induced break value of between 15% to 100%, such as between 25% to 100%; between 30% to 95%; between 40% to 90%; between 50% to 85%; between 70% to 95%; between 80% to 97%; between 90% to 99%; between 95% to 100%; or between 60% to 100%.

[00147] Suitable star macromolecules, in accordance with the Dynamic Viscosity & Shear-Thinning Test Procedure described below herein, include those that have a dynamic viscosity value, of greater than 20,000 cP at 1 rpm, such as 60,000 cP or less at 1 rpm, and at a concentration of 0.2wt.%, such as a dynamic viscosity value of greater than 24,000 cP; greater than 28,000 cP; or greater than 30,000 cP at a concentration of 0.2wt.%.

[00148] Suitable emulsions may include, but is not limited to, emulsions that are emulsifier-free and wherein the emulsion is thickened by a star macromolecule. For example, the star macromolecule that may be included in the emulsifier-free emulsion may be a water-soluble star macromolecule, wherein the water-soluble star macromolecule emulsifies the emulsifier-free emulsion.

[00149] Suitable star macromolecules, include star macromolecules that have an emulsion value of greater than 60 minutes, for example, greater than 3 hours, such as greater than 6 hours; greater than 10 hours; greater than 20 hours; greater than 40 hours; or greater than 100 hours.

[00150] Suitable star macromolecules, according to Formula X, may include star macromolecules wherein PI , P2, and/or P3 comprise hydrophobic monomeric residues, hydrophilic monomeric residues, amphiphilic monomeric residues, amphoteric monomeric residues, anionic monomeric residues, cationic monomeric residues, neutral monomeric residues, or combinations thereof. For example, PI comprises hydrophobic monomeric residues, P2 comprises hydrophilic monomeric W residues, and P3 comprises hydrophilic monomeric residues. For example, star macromolecules, according to Formula X, may include star macromolecules wherein ql may have a value of between 1 to 100, for example, between 1 to 60, such as, between 1 to 45; between 5 to 40; between 8 to 35; between 10 to 30; between 12 to 25; between 14 to 20; between 15 to 30; or between 5 to 20; and q2 and/or q3 have a value of between 50 to 1,000, for example, between 50 to 900, such as, between 50 to 800; between 50 to 700; between 50 to 600; between 50 to 500; between 50 to 400; between 50 to 300; between 50 to 200; between 100 to 250; between 125 to 175; between 150 to 300; between 150 to 1,000; between 250 to 1,000; between 500 to 1,000; between 750 to 1,000; between 200 to 800; between 200 to 600; between 200 to 400; between 200 to 300; between 300 to 800; between 300 to 600; between 400 to 750; between 450 to 650; between 500 to 600; between 600 to 900; between 700 to 900; or between 650 to 850. For example, star macromolecules, according to Formula X, may include star macromolecules wherein r or t, or the sum of r and t, may be greater than 15, such as between 15 and 1,000; between 15 and 900 arms; between 15 and 800 arms; between 15 and 700 arms; between 15 and 600 arms; between 15 and 500 arms; between 15 and 400 arms; between 15 and 300 arms; between 15 and 200 arms; between 15 and 100 arms; between 15 and 90; between 15 and 80; between 15 and 70; between 15 and 60; between 15 and 50; between 15 and 40 arms; between 20 and 50; between 25 and 45; between 25 and 35; between 30 and 45; between 30 and 50; between 250 and 750 arms; between 500 and 1,000 arms; between 300 and 600 arms; between 600 and 900 arms; between 800 and 1,000 arms; between 200 and 400 arms; between 350 and 650 arms; between 100 and 200 arms; between 150 and 250 arms; between 200 and 300 arms; between 250 and 350 arms; between 300 and 400 arms; between 350 and 450 arms; or between 450 and 550 arms. For example, star macromolecules, according to Formula X, may include star macromolecules wherein the molar ratio of r to t is in the range of between 40: 1 to 2: 1 , such as between between 35:1 to 2: 1 ; between 30: 1 to 2: 1 ; between 25: 1 to 2: 1 ; between 20: 1 to 2: 1 ; 15:1 to 2:1; between 10:1 to 2:1; between 9:1 to 2:1; between 8:1 to 2:1; between 7:1 to 2: 1 ; between 6:1 to 2: 1 ; between 5:1 to 2: 1 ; between 4:1 to 2: 1 ; between 3:1 to 2: 1 ; between 2:1 to 1:1; between 40:1 to 5:1 ; between 40:1 to 10:1; between 40:1 to 20:1; between 40:1 to 30:1; between 35:1 to 15:1; between 35:1 to 25:1; between 30:1 to 20:1; between 30:1 to 10:1; between 25:1 to 10:1; between 25:1 to 15 : 1 ; between 20:1 to 4:1; between 20:1 to 10:1; between 8:1 to 3:1; between 7:1 to 2:1; or between 5:1 to 3 : 1. For example, star macromolecules, according to Formula X, may include star macromolecules wherein the core may be derived from crosslinker monomers, such as hydrophobic crosslinker monomers. For example, star macromolecules, according to Formula X, may include star macromolecules wherein the core may comprise crosslinker monomereric residues, such as hydrophobic crosslinker monomeric residues. For example, star macromolecules, according to Formula X, may include star macromolecules wherein the arm [(Pl)_qi-(P2)_q2]t may be homopolymeric, substantially homopolymeric, or copolymeric, such as block copolymeric or random copolymeric.

[00151] Suitable star macromolecules, may include, but is not limited to, star macromolecules formed by crosslinking the arms with a crosslinker, such as crosslinking homopolymeric arms and block copolymeric arms with a hydrophobic crosslinker. For example, the homopolymeric arms and the copolymeric arms of a star macromolecule may be covalently attached to the core via crosslinkage with a crosslinker. For example, a core of a prepared star macromolecule may be prepared by crosslinking an end of a homopolymeric arm with an end of a copolymeric arm, such as an end of a hydrophilic homopolymeric arm with a hydrophilic end of a copolymeric arm. For example, the core of a prepared star macromolecules may be formed by crosslinking an ATRP-functional terminal group end of a homopolymeric arm with an ATRP-functional terminal group end of a copolymeric arm.

[00152] Suitable initiators that may be used to form the star macromolecules disclosed herein, may include, but is not limited to, nitroxide initiators, such as stable nitroxide initiators, for example, 2,2,6,6-Tetramethylpiperidine- l -oxyl, sometimes called TEMPO; transition metal complexes, such cobalt containing complexes; ATRP initiators, comprising halides, such as, bromide, chloride, or iodide, and transition metal sources, such as, copper, iron, ruthenium transition metal sources; iodide with RCTP catalysts, such as germanium or tin catalysts; RAFT initiators, such as dithioesters, dithiocarbamates, or xanthates; ITP catalysts, comprising iodides;

tellurium compounds (e.g. , TERP); stibine compounds (e.g. , SBRP); or bismuth compounds (e.g. , BIRP). For example, in certain embodiments, an initiator may further comprise a monomeric residue, a polymeric segment comprising monomeric residues, or a small-molecule. For example, in certain embodiments, an initiator may comprise an ATRP initiator, wherein the ATRP initiator serves as a terminal functional group. For example, in certain embodiments, an initiator may comprise an ATRP-functional terminal group, comprising an ATRP initiator, such as halides and transition metal sources.

[00153] Suitable materials comprising the star macromolecules disclosed herein, include, but is not limited to, sprayable formulations, such as sprayable gel-forming formulations; skin treating formulations, such as topical formulations; wound treating formulations, such as burn treating formulations; lotions, such as cosmetic lotions, personal care lotions, body lotions, emulsifier-free body lotions; serums, such as anti- aging serums; sunscreens, such as SPF 30 sunscreens, SPF 35 sunscreens, SPF 40 sunscreens, SPF 50 sunscreens; creams, such as face-creams, cosmetic creams; hair products, such as shampoos, hair styling products, hair sprays, mousses, hair gels, hair conditioners, bath preparations; gels, such as cosmetic gels or personal care gels; skin application products, such as ointments, deodorants, personal care powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin wipes, shaving preparations; fabric softeners; dental impression materials; or variations thereof.

[00154] Suitable materials comprising the one or more active ingredients

(functional agents) comprise one or more: active pharmaceutical ingredients; active cosmetic ingredients; fragrance and/or oil ingredients; active skin-care ingredients; bioactive molecules; flavors; and/or agrochemicals, such as herbicides, fungicides, or pesticides; and/or dyes.

[00155] Suitable materials comprising the active pharmaceutical ingredients may include, without limitation, any one or more of the following: hypnotics and sedatives; heterocyclic hypnotics; antidepressants; tranquilizers; benzodiazepines; anticonvulsants; muscle relaxants and anti-parkinson agents; analgesics; antipyretics and anti-inflammatory agents; anesthetics, such as local anesthetics; prostaglandins; antibacterial agents; anti-microbials; anti-malarials; hormonal agents; androgenic steroids; progestational steroids; sympathomimetic drugs; cardiovascular drugs;

diuretics; antiparasitic agents; neoplastic agents; hypoglycemic drugs; nutritional agents; eye drugs; antiviral drags; anti-nausea; anti-thrombotic agents; antiinflammatory agents; cancer agents; anesthetic agents; anti-coagulants; vascular cell growth promoters; cholesterol-lowering agents; angiopoietins; antimicrobial agents; cytotoxic agents; cytostatic agents; cell proliferation affectors; vasodilating agents; and/or agents that interfere with endogenous vasoactive mechanisms. For example, suitable materials comprising the active pharmaceutical ingredients may comprise: Hypnotics and sedatives, comprising: pentobarbital sodium, phenobarbital, secobarbital, thiopental, amides and ureas exemplified by diethylisovaleramide and alpha-bromo-isovaleryl urea, urethanes, or disulfanes; Heterocyclic hypnotics, comprising: Dioxopiperidines and glutarimides; Antidepressants, comprising:

Isocarboxazid, nialamide, phenelzine, imipramine, tranylcypromine and pargyline; Tranquilizers, comprising: Chloropromazine, promazine, fluphenazine reserpine, deserpidine and meprobamate; Benzodiazepines, comprising: Chlordiazepoxide; Anticonvulsants, comprising: Primidone, diphenylhydantoin, ethltoin, pheneturide and ethosuximide; Muscle relaxants and anti-parkinson agents, comprising:

Mephenesin, methocarbomal, trihexylphenidyl, biperiden, levo-dopa, L-dopa and L- beta-3-4-dihydroxyphenylalanine; Analgesics, comprising: Morphine, codeine, meperidine and nalorphine; Antipyretics and anti-inflammatory agents, comprising: Aspirin, salicylamide, sodium salicylamide, naproxen and ibuprofen; Local anesthetics, comprising: Procaine, lidocaine, naepaine, piperocaine, tetracaine and dibucane; Antispasmodics and antiulcer agents: Atropine, scopolamine,

methscopolamine, oxyphenonium and papaverine; Prostaglandins, comprising: PGE1 , PGE2, PGFl , PGF2a, and PGA; Anti-microbials, comprising: Penicillin, tetracycline, oxytetracycline, chlorotetracycline, chloramphenicol, sulfonamides, tetracycline, bacitracin, chlorotetracycline and erythromycin; Anti-malarials, comprising: 4-aminoquinolines, 8-aminoquinolines and pyrimethamine; Hormonal agents, comprising: Prednisolone, cortisone, Cortisol and triamcinolone; Androgenic steroids, comprising: Methyltestosterone, fluoxmesterone, estrogenic steroids, 17- beta-estradoil and thinyl estradiol; Progestational steroids, comprising: 17-alpha- hydroxyprogesterone acetate, 19-nor-progesterone and norethindrone;

Sympathomimetic drugs, comprising: Epinephrine amphetamine, ephedrine and norepinephrine; Cardiovascular drugs, comprising: Procainamide, amyl nitrate, nitroglycerin, dipyridamole, sodium nitrate and mannitol nitrate; Diuretics, comprising: Acetazolamide, chlorothiazide and flumethiazide; Antiparasitic agents, comprising: Bephenium hydroxynaphthoate, dichlorophen, enitabas and dapsone; Neoplastic agents, comprising: Mechloroethamine, uracil mustard, 5-fluorouracil, 6- thioguanine and procarbazine; Hypoglycemic drugs, comprising: Isophane insulin suspension, protamine zinc insulin suspension, globin zinc insulin, extended insulin zinc suspension, tolbutamide, acetohexamide, tolazamide and chlorpropamide;

Nutritional agents, comprising: Vitamins, essential amino acids, and essential fats; Eye drugs, comprising: Pilocarpine base, pilocarpine hydrochloride and pilocarpine - nitrate; Antiviral drugs, comprising: Disoproxil fumarate, aciclovir, cidofovir, docosanol, famciclovir, fomivirsen, foscarnet, ganciclovir, idoxuridine, penciclovir, trifluridine, tromantadine, valaciclovir, valganciclovir, vidarabine, amantadine, arbidol, oseltamivir, peramivir, rimantadine, zanamivir, abacavir, didanosine, emtricitabine, lamivudine, stavudine, zalcitabine, zidovudine, tenofovir, efavirenz, delavirdine, nevirapine, loviride, amprenavir, atazanavir, darunavir, fosamprenavir, indinavir, lopinavir, nelfinavir, ritonavir, saquinavir, tipranavir, enfuvirtide, adefovir, fomivirsen, imiquimod, inosine, podophyllotoxin, ribavirin, viramidine, fusion blockers specifically targeting viral surface proteins or viral receptors; Anti-nausea, comprising: Scopolamine, dimenhydrinate, iodoxuridine, hydrocortisone, eserine, phospholine, iodide, ondansetron, terbinafine, fluconazole, metronidazole, fentanyl, nandrolone decanoate, nestorone, norethisterone, eperisone, tolperisone, vinpocetine, ketamine, vincristine, vinblastine; Anti-thrombotic agents, comprising: Heparin, heparin derivatives, urokinase, and PPack (dextrophenyl alanine proline arginine chloromethylketone); Anti-inflammatory agents, comprising: Dexamethasone, prednisolone, corticosterone, budesonide, estrogen, acetyl salicylic acid, sulfasalazine and mesalamine; Cancer agents, comprising: Paclitaxel, 5-fluorouracil, cisplatin, methotrexate, doxorubicin, vinblastine, vincristine, epothilones, endostatin, angiostatin, angiopeptin, monoclonal antibodies capable of blocking smooth muscle cell proliferation, and thymidine kinase inhibitors; Anesthetic agents, comprising: Lidocaine, bupivacaine and ropivacaine; Anti-coagulants, comprising: D-Phe-Pro-Arg chloromethyl ketone, an RGD peptide-containing compound, heparin, hirudin, antithrombin compounds, platelet receptor antagonists, anti-thrombin antibodies, antiplatelet receptor antibodies, aspirin, prostaglandin inhibitors, platelet inhibitors and tick antiplatelet factors or peptides; Vascular cell growth promoters, comprising: Growth factors, transcriptional activators, and translational promoters, vascular cell growth inhibitors such as growth factor inhibitors (e.g., PDGF inhibitor-Trapidil), growth factor receptor antagonists, transcriptional repressors, translational repressors, replication inhibitors, inhibitory antibodies, antibodies directed against growth factors, bifunctional molecules consisting of a growth factor and a cytotoxin, bifunctional molecules consisting of an antibody and a cytotoxin; protein kinase and tyrosine kinase inhibitors (e.g., tyrphostins, genistein, quinoxalines); prostacyclin analogs; and antimicrobial agents, comprising: triclosan, cephalosporins,

aminoglycosides and nitrofurantoin. [00156] A number of the above therapeutic agents and several others have also been identified as candidates for vascular treatment regimens, for example, as agents targeting restenosis. Such agents include one or more of the following: calcium- channel blockers, including benzothiazapines (e.g., diltiazem, clentiazem);

dihydropyridines (e.g., nifedipine, amlodipine, nicardapine); phenylalkylamines (e.g., verapamil); serotonin pathway modulators, including 5-HT antagonists (e.g., ketanserin, naftidrofuryl) and 5-HT uptake inhibitors (e.g., fluoxetine); cyclic nucleotide pathway agents, including phosphodiesterase inhibitors (e.g., cilostazole, dipyridamole), adenylate/guanylate cyclase stimulants (e.g., forskolin), and adenosine analogs; catecholamine modulators, including .alpha.-antagonists (e.g., prazosin, bunazosine), .beta.-antagonists (e.g., propranolol), and .alpha./.beta.-antagonists (e.g., labetalol, carvedilol); endothelin receptor antagonists; nitric oxide donors/releasing molecules, including organic nitrates/nitrites (e.g., nitroglycerin, isosorbide dinitrate, amyl nitrite), inorganic nitroso compounds (e.g., sodium nitroprusside), sydnonimines (e.g., molsidomine, linsidomine), nonoates (e.g., diazenium diolates, NO adducts of alkanediamines), S -nitroso compounds, including low molecular weight compounds (e.g., S-nitroso derivatives of captopril, glutathione and N-acetyl penicillamine) and high molecular weight compounds (e.g., S-nitroso derivatives of proteins, peptides, oligosaccharides, polysaccharides, synthetic polymers/oligomers and natural polymers/oligomers), C-nitroso-, O-nitroso- and N-nitroso-compounds, and L- arginine; ACE inhibitors (e.g., cilazapril, fosinopril, enalapril); ATII-receptor antagonists (e.g., saralasin, losartin); platelet adhesion inhibitors (e.g., albumin, polyethylene oxide); platelet aggregation inhibitors, including aspirin and

thienopyridine (ticlopidine, clopidogrel) and GP Ilb/IIIa inhibitors (e.g., abciximab, epitifibatide, tirofiban, intergrilin); coagulation pathway modulators, including heparinoids (e.g., heparin, low molecular weight heparin, dextran sulfate, .beta.- cyclodextrin tetradecasulfate), thrombin inhibitors (e.g., hirudin, hirulog, PPACK (D- phe-L-propyl-L-arg-chloromethylketone), argatroban), FXa inhibitors (e.g., antistatin, TAP (tick anticoagulant peptide)), vitamin K inhibitors (e.g., warfarin), and activated protein C; cyclooxygenase pathway inhibitors (e.g., aspirin, ibuprofen, flurbiprofen, indomethacin, sulfinpyrazone); natural and synthetic corticosteroids (e.g.,

dexamethasone, prednisolone, methprednisolone, hydrocortisone); lipoxygenase pathway inhibitors (e.g., nordihydroguairetic acid, caffeic acid; leukotriene receptor antagonists; antagonists of E- and P-selectins; inhibitors of VCAM-1 and ICAM-1 interactions; prostaglandins and analogs thereof, including prostaglandins such as PGE1 and PGI2; prostacyclin analogs (e.g., ciprostene, epoprostenol, carbacyclin, iloprost, beraprost); macrophage activation preventers (e.g., bisphosphonates); HMG- CoA reductase inhibitors (e.g., lovastatin, pravastatin, fluvastatin, simvastatin, cerivastatin); fish oils and omega-3-fatty acids; free-radical scavengers/antioxidants (e.g., probucol, vitamins C and E, ebselen, retinoic acid (e.g., trans-retinoic acid), SOD mimics); agents affecting various growth factors including FGF pathway agents (e.g., bFGF antibodies, chimeric fusion proteins), PDGF receptor antagonists (e.g., trapidil), IGF pathway agents (e.g., somatostatin analogs such as angiopeptin and ocreotide), TGF-.beta. pathway agents such as polyanionic agents (heparin, fucoidin), decorin, and TGF-.beta. antibodies, EGF pathway agents (e.g., EGF antibodies, receptor antagonists, chimeric fusion proteins), TNF-. alpha, pathway agents (e.g., thalidomide and analogs thereof), thromboxane A2 (TXA2) pathway modulators (e.g., sulotroban, vapiprost, dazoxiben, ridogrel), protein tyrosine kinase inhibitors (e.g., tyrphostin, genistein, and quinoxaline derivatives); MMP pathway inhibitors (e.g., marimastat, ilomastat, metastat), and cell motility inhibitors (e.g., cytochalasin B); antiproliferative/antineoplastic agents including antimetabolites such as purine analogs (e.g., 6-mercaptopurine), pyrimidine analogs (e.g., cytarabine and 5- fluorouracil) and methotrexate, nitrogen mustards, alkyl sulfonates, ethylenimines, antibiotics (e.g., daunorubicin, doxorubicin, daunomycin, bleomycin, mitomycin, penicillins, cephalosporins, ciprofalxin, vancomycins, aminoglycosides, quinolones, polymyxins, erythromycins, tertacyclines, chloramphenicols, clindamycins, linomycins, sulfonamides, and their homologs, analogs, fragments, derivatives, and pharmaceutical salts), nitrosoureas (e.g., carmustine, lomustine) and cisplatin, agents affecting microtubule dynamics (e.g., vinblastine, vincristine, colchicine, paclitaxel, epothilone), caspase activators, proteasome inhibitors, angiogenesis inhibitors (e.g., endostatin, angiostatin and squalamine), and rapamycin, cerivastatin, flavopiridol and suramin; matrix deposition/organization pathway inhibitors (e.g., halofuginone or other quinazolinone derivatives, tranilast); endothelialization facilitators (e.g., VEGF and RGD peptide); and blood rheology modulators (e.g., pentoxifylline).

|00157] Other suitable examples of therapeutic agents include anti-tumor agents, such as docetaxel, alkylating agents (e.g., mechlorethamine, chlorambucil,

cyclophosphamide, melphalan, ifosfamide), plant alkaloids (e.g., etoposide), inorganic ions (e.g., cisplatin), biological response modifiers (e.g., interferon), and hormones (e.g., tamoxifen, flutamide), as well as their homologs, analogs, fragments, derivatives, and pharmaceutical salts.

[00158] Additional sutiable examples of therapeutic agents include organic-soluble therapeutic agents, such as mithramycin, cyclosporine, and plicamycin. Further examples of therapeutic agents include pharmaceutically active compounds, anti- sense genes, viral, liposomes and cationic polymers (e.g., selected based on the application), biologically active solutes (e.g., heparin), prostaglandins, prostcyclins, L-arginine, nitric oxide (NO) donors (e.g., lisidomine, molsidomine, NO-protein adducts, NO-polysaccharide adducts, polymeric or oligomeric NO adducts or chemical complexes), enoxaparin, Warafin sodium, dicumarol, interferons, chymase inhibitors (e.g., Tranilast), ACE inhibitors (e.g., Enalapril), serotonin antagonists, 5- HT uptake inhibitors, and beta blockers, and other antitumor and/or chemotherapy drugs, such as BiCNU, busulfan, carboplatinum, cisplatinum, Cytoxan, DTIC, fludarabine, mitoxantrone, velban, VP-16, herceptin, leustatin, navelbine, rituxan, and taxotere.

[00159] Suitable materials comprising the one or more active ingredients, such as one or more active cosmetic ingredients, active skin-care ingredients, and/or bioactive molecules, may include, without limitation, any one or more of the following: antiacne actives, emollients; non-steroidal anti-inflammatory actives (NSAIDS); topical anaesthetics; artificial tanning agents and accelerators; antiseptics; anti-microbial and anti-fungal actives; skin soothing agents; sunscreening agents; skin barrier repair aids; anti-wrinkle and anti-skin atrophy actives; skin repair actives; lipids; skin lightening agents; sebum inhibitors; sebum stimulators; skin sensates; protease inhibitors; skin tightening agents; anti-itch ingredients; hair growth inhibitors; desquamation enzyme enhancers; and/or anti-glycation agents. For example, suitable materials may include: Anti-Acne Actives: Anti-acne actives can be effective in treating and preventing acne vulgaris, a chronic disorder of the pilosebaceous follicles; preferred anti-acne actives include benzoyl peroxide, lactic acid, 4-methoxysalicylic acid, metronidazole, niacinamide, panthenol, retinoic acid and derivatives thereof, salicylic acid, sulphur, triclosan, zinc oxide, and mixtures thereof; Emollients: Examples of emollients useful herein include mineral oil, petrolatum, C7-C40 branched chain hydrocarbons, C 1 -C30 alcohol esters of C 1-C30 carboxylic acids, monoglycerides of C1 -C30 carboxylic acids, C 1 -C30 carboxylic acid monoesters and polyesters of sugars, for example, sefa cottonate (sucrose polycottonseedate), polydialkylsiloxanes; silicone gums, resins and elastomers; cyclomethicones having 3 to 9 silicon atoms, vegetable oils, hydrogenated vegetable oils and mixtures thereof. Preferred emollients are selected from linear and branched chain hydrocarbons, sugar polyesters and silicones, especially dimethicone and dimethiconol; Non-Steroidal Anti-Inflammatory Actives (NSAIDS): Examples of suitable NSAIDS and their esters for use herein are described in W098/18444;

Topical Anaesthetics: examples of suitable topical anaesthetic drugs for use herein are benzocaine and bupivacaine; Artificial Tanning Agents and Accelerators: Artificial tanning agents can help in simulating a natural suntan by increasing melanin in the skin or by producing the appearance of increased melanin in the skin; non-limiting examples of artificial tanning agents and accelerators include dihydroxyacetone, glucose tyrosinate and acetyl tyrosine, brazilin, caffeine, coffee extracts, DNA fragments, isobutyl methyl xanthine, methyl xanthine, PHOTOTAN (available from Laboratoires Serobiologiques located in Somerville, N.J.), prostaglandins, tea extracts, theophylline, UNIPERTAN P2002 (available from Unichem, located in Chicago, 111.) and UNIPERTAN P27 (available from Unichem, located in Chicago, 111.); and mixtures thereof; Antiseptics: Suitable antiseptics for use herein include alcohols, benzoate, sorbic acid, and mixtures thereof; Anti-microbial and Anti-fungal Actives: Anti-microbial and anti-fungal actives can be effective to prevent the proliferation and growth of bacteria and fungi; non-limiting examples of antimicrobial and antifungal actives include ketoconazole, benzoyl peroxide, tetracycline, benzalkonium chloride, benzoic acid and its salts, butyl paraben, cinnamon oil, citronella oil, echinacea, ethyl paraben, GLYDANT PLUS (available from Lonza located in Fairlawn, N.J.), grapefruit seed oil, iodopropynl butyl carbamide lemon balm oil, salicylic acid, sodium metabisulphite, sodium sulphite, sorbic acid and its salts, and tea tree oil; Skin Soothing Agents: Skin soothing agents can be effective in preventing or treating inflammation of the skin. The soothing agent enhances the skin appearance benefits of the present invention, e.g., such agents contribute to a more uniform and acceptable skin tone or colour; examples of skin soothing agents include allantoin, aloe, bisabolol, borage oil, chamomile, evening primrose, panthenol, and tocopherol; Sunscreening Agents: Sunscreens useful herein include both inorganic sunscreens such as titanium and zinc oxides, as well as the many commercially available UVA and UVB absorbing organic sunscreens; Skin Barrier Repair Aids: Skin barrier repair actives are those skin care actives which can help repair and replenish the natural moisture barrier function of the epidermis; non-limiting examples of skin barrier repair aids include ceramides, cholesterol, lanolin, lanolin alcohols, n-acetyl cysteine, n-acetyl-L-serine, niacinamide, nicotinic acid and its esters, nicotinyl alcohol, panthenol, phosphodiesterase inhibitors, trimethyl glycine, tocopheryl nicotinate, and vitamin D₃ and analogs or derivatives; Anti-Wrinkle and Anti-Skin Atrophy Actives: Anti- wrinkle and anti-skin atrophy actives can be effective in replenishing or rejuvenating the epidermal and/or dermal layer; wherein these actives generally provide these desirable skin care benefits by promoting or maintaining the natural process of desquamation and/or building skin matrix components (e.g., collagen and glycosaminoglycans); examples of antiwrinkle and anti-skin atrophy actives include niacinamide, nicotinic acid and its esters, nicotinyl alcohol, estrogens and estrogenic compounds, or mixtures thereof; Skin Repair Actives: Skin repair actives can be effective in repairing the epidermal and/or dermal layer; non-limiting examples of skin repair actives include adenosine, aloe derived lectins, ascorbyl palmitate, azaleic acid, biotin, blackberry bark extract,

catecholamines, chalcones, cis retinoic acid, citric acid esters, coenzyme Q10 (ubiquinone), dehydrocholesterol, dehydroepiandrosterone, dehydroascorbic acid and derivatives thereof, dehydroepiandrosterone sulphate, estrogen and its derivatives, farnesol, gingko bilboa extracts, ginseng extracts, lactate dehydrogenase inhibitors, magnesium ascorbyl phosphate, melatonin, N-acetyl cysteine, pantethine, phytic acid and its salts, retinal, retinol, retinyl acetate, retinyl propionate and vitamin K; Lipids: Examples of suitable lipids include cetyl ricinoleate and phytanetriol; Skin Lightening Agents: Skin lightening agents can actually decrease the amount of melanin in the skin or provide such an effect by other mechanisms; skin lightening agents suitable for use herein are described in EP-A-758,882 and EP-A-748,307, both of which are incorporated herein by reference; other skin lightening agents include arbutin, ascorbic acid, ascorbyl palmitate, azelaic acid, butyl hydroxy anisole, gallic acid and its derivatives, glycyrrhizinic acid, hydroquinine, inositol ascorbate, kojic acid, niacinamide and vitamin D₃ and its analogues; Sebum Inhibitors: Sebum inhibitors can decrease the production of sebum in the sebaceous glands; examples of suitable sebum inhibitors include dichlorophenyl imidazoldioxolan, aluminium hydroxy chloride, corticosteroids and cucumber extracts; Sebum Stimulators: Sebum stimulators can increase the production of sebum by the sebaceous glands; non- limiting examples of sebum stimulators include bryonolic acid,

dehydroepiandrosterone and orizanol; Skin Sensates: Non-limiting examples of suitable skin sensates for use herein include agents which impart a cool feel such as camphor, thymol, 1 -menthol and derivatives thereof, eucalyptus, carboxamides;

menthane ethers and menthane esters; and agents imparting a warm feel such as cayenne tincture, cayenne extract, cayenne powder, vanillylamide nonanoate, nicotinic acid derivatives (benzyl nicotinate, methyl nicotinate, phenyl nicotinate, etc.), capsaicin, nasturtium officinale extract, Zanthoxylum piperitum extract and ginger extract, or mixtures thereof; Protease Inhibitors: Protease inhibitors are compounds which inhibit the process of proteolysis, that is, the splitting of proteins into smaller peptide fractions and amino acids; examples of suitable protease inhibitors include A E COMPLEX (available from Barnet Products located in

Englewood, N.J.), BLUE ALGAE EXTRACT (available from Collaborative Labs Inc. located in East Setauket, N.Y.), and SEPICONTROL AS (available from Seppic located in Paris, France); Skin Tightening Agents: Examples of skin tightening agents include sodium polystyrene sulphonate, B IOC ARE SA (available from Amerchol located in Edison, N.J.) and egg albumen; Anti-Itch Ingredients: Examples of anti-itch ingredients include ichthyol and OXYGENATED GLYCERYL TRIESTERS

(available from Laboratoires Seporgia located in Sophia Antipolis, France.); Hair Growth Inhibitors: Suitable agents for inhibiting hair growth include 17 beta estradiol, anti angiogenic steroids, curcuma extract, cycloxygenase inhibitors, evening primrose oil, linoleic acid and 5-alpha reductase inhibitors such as ethynylestradiol and, genistine; Desquamation Enzyme Enhancers: These agents enhance the activity of endogenous desquamating enzymes; non-limiting examples of desquamation enzyme enhancers include N-methyl serine, serine, trimethyl glycine, and mixtures thereof; and/or Anti-Glycation Agents: Anti-glycation agents prevent the sugar induced crosslinking of collagen. A suitable example of an anti-glycation agent includes AMADORINE (available from Barnet Products Distributor located in Englewood, N.J.).

[00160] Suitable materials comprising the one or more active ingredients, such as one or more active cosmetic ingredients, active skin-care ingredients, and/or bioactive molecules, may include, without limitation, any one or more of the following:

ascorbic acid and derivatives thereof, salicylic acid, niacinamide, panthenol, tocopheryl nicotinate, benzoyl peroxide, 3-hydroxy benzoic acid, flavonoids (e.g., flavanone, chalcone), farnesol, phytantriol, glycolic acid, lactic acid, 4-hydroxy benzoic acid, acetyl salicylic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, cis-retinoic acid, trans-retinoic acid, retinol, retinyl esters (e.g., retinyl propionate), phytic acid, N-acetyl-L-cysteine, lipoic acid, tocopherol and its esters (e.g., tocopheryl acetate), azelaic acid, arachidonic acid, tetracycline, ibuprofen, naproxen, ketoprofen, hydrocortisone, acetaminophen, resorcinol, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 3,4,4'-trichlorocarbanilide, octopirox, lidocaine hydrochloride, clotrimazole, miconazole, ketoconazole, neomycin sulfate, theophylline, and mixtures thereof.

J00161] Suitable materials for cosmetic methods of treatment of the skin, hair or nails, the cosmetic benefit agent may include anti-wrinkle and anti-skin atrophy actives, anti-acne actives, artificial tanning agents and accelerators, emollients, humectants, skin repair actives, skin barrier repair aids, skin lightening agents, skin sensates, skin soothing agents, lipids, sebum inhibitors, sebum stimulators, sunscreening agents, protease inhibitors, skin tightening agents, anti-itch ingredients, and desquamation enzyme enhancers, or mixtures thereof.

[00162] Suitable materials comprising the fragrances and oils may include, without limitation, any one or more of the following: esters, aldehydes, alcohols, amines, thiols, ketones, lactones, terpenes, and/or aromatic compounds from natural or synthetic sources. In certain embodiments, the fragrances and oils may include oils like Agar oil, Ajwain oil, Angelica root oil, Anise oil, Asafoetida, Balsam oil, Basil oil, Bay, Bergamot oil, Black Pepper oil, Buchu oil, Birch oil, Camphor oil, Cannabis flower oil, Caraway oil, Cardamom seed oil, Carrot seed oil, Cedarwood oil,

Chamomile oil, Calamus Root, Cinnamon oil, Citronella oil, Clary Sage, Clove leaf oil, Coffee, Coriander, Costus Root, Cranberry seed oil, Cubeb, Cumin oil/Black seed oil, Cypress, Cypriol, Curry leaf, Davana oil, Dill oil, Elecampane, Eucalyptus oil, Fennel seed oil, Fenugreek oil, Fir, Frankincense oil, Galangal, Galbanum, Geranium oil, Ginger oil, Goldenrod, Grapefruit oil, Henna oil, Helichrysum, Horseradish oil, Hyssop, Idaho Tansy, Jasmine oil, Juniper berry oil, Lavender oil, Ledum, Lemon oil, Lemongrass, Lime, Litsea cubeba oil, Mandarin, Marjoram, Melaleuca See Tea tree oil, Melissa oil (Lemon balm), Mentha arvensis oil/Mint oil, Mountain Savory, Mugwort oil, Mustard oil (essential oil), Myrrh oil, Myrtle, Neem Tree Oil, Neroli, Nutmeg, Orange oil, Oregano oil, Orris oil, Palo Santo Parsley oil, Patchouli oil, Perilla essential oil, Pennyroyal oil, Peppermint oil, Petitgrain Pine oil, Ravensara, Red Cedar, Roman Chamomile, Rose oil, Rosehip oil, Rosemary oil, Rosewood oil, Sage oil, Sandalwood oil, Sassafras oil, Savory oil, Schisandra oil, Spearmint oil, Spikenard, Spruce, Star anise oil, Tangerine, Tarragon oil, Tea tree oil, Thyme oil, Tsuga, Turmeric, Valerian, Vetiver oil (khus oil), Western red cedar, Wintergreen, Ylang-ylang and Zedoary.

[00163] In certain embodiments, the esters, aldehydes, alcohols, amines, thiols, ketones, lactones, terpenes, and/or aromatic compounds, of the fragrances and oils may comprise: Esters, comprising: Methyl formate; Methyl acetate; Methyl butyrate; Methyl butanoate; Ethyl acetate; Ethyl butyrate; Ethyl butanoate; Isoamyl acetate; Pentyl butyrate; Pentyl butanoate; Pentyl pentanoate; Octyl acetate; Fructone; Hexyl acetate; and/or Ethyl methylphenylglycidate; Aldehydes, comprising: Acetaldehyde; Hexanal; cis-3-Hexenal eugenol; citral; citronellal; campholenic aldehyde; cinnamic aldehyde; hexylcinnamic aldehyde; formyl pinane; hydroxycitronellal; cuminic aldehyde; vanilline; ethyl vanilline; [3-(4-tert-butylphenyl)-2-methylpropanal; [4- and 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-l-carbaldehyde; [3-(4-tert- butylphenyl)propanal; heliopropanal [3-(l ,3-benzodioxol-5-yl)-2-methylpropanal; Zestover (2,4-dimethyl-3-cyclohexene-l -carbaldehyde); (3-phenylbutanal); (4- methylphenoxy)acetaldehyde; 1 ,3-benzodioxol-5-carboxaldehyde; [8(9)-methoxy- tricyclo[5.2.1.0.(2,6)]decane-3(4)-carbaldehyde; (4R)-l -p-menthene-9-carbaldehyde;

[3-(4-isopropylphenyl)]-2-methylpropanal; ortho- and para-anisaldehyde; 3-methyl-5- phenylpentanal; [4-(4-methyl-3-pentenyl)]-3-cyclohexene-l -carbaldehyde; (3,7- dimethyl-6-octenyl)acetaldehyde; 2,6-dimethyl-5-heptanal; [l-methyl-4-(4-methyl-3- pentenyl)-3-cyclohexen- l-carbaldehyde; and/or (2,4,6-trimethyl-3-cyclohexene-l - carbaldehyde); Alcohols, comprising: Furaneol; 1-Hexanol; cis-3-Hexen- l -ol and Menthol; 2-cyclohexyl-l -propanol; 1 -decanol; geraniol; nerol; 3,7-dimethyl-l - octanol; citronellol; 1-dodecanol; ethyl vanillin; 2-ethyl- l -hexanol; 1 -hexanol; pipol; vegetol; 4-hydroxy-3-methoxybenzaldehyde; 4-(4-hydroxy-l-phenyl)-2-butanone; 7- p-menthan-l -ol; anisic alcohol; guaiacol; 2-methoxy-2-phenyl- l -ethanol; isoeugenol; cyclomethylene citronellol; 2-methyl-4-phenyl-l -pentanol; 2-methyl-5-phenyl-l- pentanol; 3 -methyl-5-phenyl-l -pentanol; 6-nonen-l-ol; 2,6-nonadien-l-ol; l-octanol;

2- phenoxy-l -ethanol; 1 -phenyl-l -ethanol; 2-phenyl-l -ethanol; 2-phenyl-l-propanol;

3 - phenyl -1-propanol; cinnamic alcohol; salicylates; 2,4,6-trimethyl-3-cyclohexene- l - methanol; farnesol; 3,5, 5-trimethyl- 1 -hexanol; 1-undecanol; 10-undecen-l -ol;

patchone; 2-tert-butyl-4-methyl-l-cyclohexanol; 6,8-dimethyl-2-nonanol; 4,8- dimethyl-7-nonen-2-ol; (E)-3,3-dimethyl-5-(2^,,2',3'-trimethyl-3'-cycl-openten-r-yl)-4- penten-2-ol; ethyl 3-hydroxy hexanoate; 5-ethyl-2-nonanol; dartanol; 3-hydroxy-2- butanone; l -(4-isopropyl-l -cyclohexyl)-l -ethanol; menthol; 8-p-menthen-2-ol;

isopulegol; 7-methoxy-3,7-dimethyl-2-octanol; 2-methoxy-4-propyl- 1 -cyclohexanol; 4-methyl-3-decen-5-ol; l -(4-rnethylphenyl)-l -ethanol; 4-methyl-l-phenyl-2-pentanol; l ,2,3,4,4a,5,8,8a-octahydro-2,2,6,8-tetramethyl-l-naphthalenol; 3-methyl-5-(2,2,3- trimethyl-3-cyclopenten-l-yl)-2-pentanol; 2-octanol; 3-octanol; l-octen-3-ol;

3,4,5, 6,6-pentamethyl-2-heptanol; 2-pentyl-l-cyclopentanol; 4-phenyl-2-butanol; 4- phenyl-3-buten-2-ol; l-phenyl-2-hexanol; l -phenyl-2-pentanol; l-phenyl-2-propanol; limbanol; fenchol; borneol; 3-(5,5,6-trimethyl-bicyclo[2.2. l ]hept-2-yl)-l - cyclohexanol; vebanol; 4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-3-butenol; alpha-ionol; norlimbanol; 2-undecanol; 3-benzyl-3-pentanol; 4-cyclohexyl-2-methyl-2-butanol; 2,6-dimethyl-2-heptanol; ethyl linalool; 3,7-dimethyl-l ,6-octadien-3-ol; 3,7-dimethyl- 3-octanol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol; hydroxycitronellal; 8-p- menthanol; terpinenol; alpha- terpineol; methyl-4-phenyl-2-butanol; 2-methyl-l- phenyl-2-propanol; 2-(4-methylphenyl)-2-propanol; perhydro-4,8a-dimethyl-4a- naphthalenol; tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol; linalyl oxide; 2,6,10, 10- tetramethyl-l -oxaspiro[4.5]decan-6-ol; 2,6,6,8-tetramefhyl- tricyclo[5.3.1.0(l ,5)]undecan-8-ol; nerolidol; pinanol; and/or Furfural; Amines, comprising: Trimethylamine; Ammonia; Putrescine; Diaminobutane; Cadaverine; Pyridine; Indole; and/or Skatole; Thiols, comprising: Ethanethiol; Grapefruit mercaptan; Methanethiol; and/or 2-Methyl-2-propanethiol; Ketones, comprising: Dihydrojasmone; 1 -(5,5-dimethyl- 1 -cyclohexen- 1 -yl)-4-penten- 1 -one; 7-methyl- 2H,4H- 1 ,5-benzodioxepin-3-one; [( 1 R,4R)-8-mercapto-3-p-menthanone; [4-( 1 ,1- dimethylpropyl)-l -cyclohexanone; 2-pentyl-l-cyclopentanone; 2-naphthalenyl-l - ethanone; 2,2,5-trimethyl-5-pentyl- 1 -cyclopentanone; 4-isopropyl-2-cyclohexen- 1 - one; l-(octahydro-2,3,8,8-tetrame-2-naphthalenyl)-l-ethanone; 5-methyl-exo- tricyclo[6.2.1.0(2,7)]undecan-4-one; cyclopentadecanone; 3-methyl-4- cyclopentadecen- 1 -one; 3-methyl-5-cyclopentadecen- 1 -one; 3-methyl- 1 - cyclopentadecanone; oct-l -en-3-one; 2-Acetyl-l-pyrroline; camphor; carvone;

menthone; ionones; irones; damascenones; damacones; benzyl acetone (4-phenyl-2- butanone); 1 -carvone; 4-(4-hydroxy-l-phenyl)-2-butanone; and/or methyl

dihydrojasmonate; Lactones, comprising: gamma-Decalactone; gamma-Nonalactone; delta-Octal actone; Massoia lactone; and/or Sotolon; Terpenes, comprising: Myrcene; Verbena; Geraniol Rose; Geranium; Lemon; Geranial; Pelargonium; Lavender; Coriander; Jasmine; Limonene; Camphor; Terpineol; and/or Juniper; Aromatic compounds, comprising: Benzaldehyde; Eugenol; Cinnamaldehyde; Ethyl maltol; Vanillin; Anisole; Anethole; and/or Estragole; and/or miscellaneous compounds, comprising: Methylphosphine; dimethylphosphine; Nerolin; Tetrahydrothiophene; 2,4,6-Trichloroanisole; 6-Acetyl-2,3,4,5-tetrahydropyridine; andor substituted pyrazines.

[00164] In certain embodiments, at least one of the one or more active ingredients may associate with at least one of the one or more star macromolecules. For example, at least two or at least three types of active ingredients may associate with at least one of the one or more star macromolecules; or at least one or more active ingredients may associate with at least two or at least three types of star macromolecules; or combinations thereof. In certain embodiments, at least one of the one or more active ingredients may associate with the arms and/or the crosslinked core of at least one of the one or more star macromolecules. For example, at least one of the one or more active antibacterial agents may associate with the arms and/or the crosslinked core of at least one of the one or more star macromolecules. The association of the at least one of the one or more active ingredients with the at least one of the one or more star macromolecules may involve (or be achieved) or otherwise comprise, for example: one or more van der Waals interactions; one or more hydrophobic interactions; one or more polar interactions; one or more hydrophilic interactions; one or more hydrogen bonding interactions; one or more ionic interactions; one or more physical

entanglements; and/or encapsulation of the at least one of the one or more active ingredients by the at least one of the one or more star macromolecules. For example, at least one of the one or more active ingredients may be encapsulated within the crosslinked core of at least one of the one or more star macromolecules. For example, at least one of the one or more active antibacterial agents may encapsulate within the crosslinked core of at least one of the one or more star macromolecules.

[00165] In certain embodiments, a method of treating a wound may comprise applying a sprayable, gel-forming aqueous composition, as disclosed herein, to a mammal's wound. The wound, for example, may be a flesh wound, such as a cut or gash, and/or may be a burn, such as a sunburn, a chemical bum, a rash, and/or an abrasion. For example, the method of treating may comprise treating a mammal having a wound and a bum. Suitable methods for treating such a wound, may include applying a gel-forming amount of a sprayable, gel-forming aqueous composition (or further formulation thereof) onto the skin of a wounded mammal. Suitable mammals may include, but are not limited to humans, such as patients or individuals in need (or desirous) of cosmetics, fragrances, or skin-care products.

[00166] In certain embodiments, the method may include an associated active ingredient becoming un-associated (or released) from the star macromolecule and being available, such as being available to the skin of a mammal, for example a wounded mammal. For example, at least one type, such as at least two or at least three types, of associated active ingredients may become un-associated (or released) from the one, such as at least two or at least three types, of star macromolecules. In certain embodiments, the method of releasing the active ingredient may facilitate penetration of the active ingredient into skin and/or a wound. The release of the active ingredient may be triggered by a chemical and/or physical action (or an internal or external stimuli). For example, exposure to (or application of) a chemical and/or physical action may trigger the release of at least a portion of the associated active ingredient. The physical action to release the active ingredient may comprise: a mechanical action, such as a movement or rubbing action; an electrical action; an magnetic action; a photo (light) action; a photodynamic action; and/or thermal action. The chemical action to release the active ingredient may comprise: an electrochemical action; a pH action; an ionic strength action; a salt-induced action; an exchange action, such as ion-exchange or applying a second composition; a degradation action; and/or a biological action.

[00167] For example, the release of an active ingredient via a mechanical action may comprise (or be achieved by) a physical movement of the mammal or by applying or exerting a rubbing action on the treated area of skin, the formed gel, or the area to which the composition has been sprayed. For example, the release of an active ingredient via a mechanical action may comprise (or be achieved by) incorporating any one or more mechanically activated components or techniques known in the art. For example, the mechanical activity may be achieved by incorporating at least one mechanically active (i.e., a moiety, monomer, monomeric residue or component) that responds to a mechanical trigger. For example, the release of an active ingredient via an electrical or magnetic action may comprise (or be achieved by) exposure of the treated area to a low to moderate electric or electro-magnetic field. For example, the release of an active ingredient via an electrical or magnetic action may comprise (or be achieved by) incorporating any one or more electrically or magnetically activated components or techniques known in the art. For example, the electrical or magnetic activity may be achieved by incorporating at least one electrically or magnetically active (i.e., a moiety, monomer, monomeric residue or component) that responds to an electrical or magnetic trigger. For example, the release of an active ingredient via a photo action or photodynamic action may comprise (or be achieved by) incorporating any one or more photo activated components or techniques known in the art. For example, the photo activity may be achieved by incorporating at least one photo active (i.e., a moiety, monomer, monomeric residue or component) that responds to a photo trigger. For example, the release of an active ingredient via a thermal action may comprise (or be achieved by) applying or exerting a cooling or low to moderate heating to or on the treated area of skin, the formed gel, or the area to which the composition has been sprayed. For example, the thermal activity may be achieved by employing an ice pack or a common heating pad. For example, the release of an active ingredient via a thermal action may comprise (or be achieved by) incorporating any one or more thermally activated components or techniques known in the art. For example, the thermal activity may be achieved by incorporating at least one thermally active (i.e., a moiety, monomer, monomeric residue or component) that responds to a thermal trigger. For example, the release of an active ingredient via an

electrochemical action may comprise (or be achieved by) applying a conductive material to or on the treated area of skin, the formed gel, or the area to which the composition has been sprayed. For example, the release of an active ingredient via an electrochemical action may comprise (or be achieved by) incorporating any one or more electrochemically activated components or techniques known in the art. For example, the electrochemical activity may be achieved by incorporating at least one electrochemically active (i.e., a moiety, monomer, monomeric residue or component) that responds to an electrochemical trigger. For example, the release of an active ingredient via a pH action may comprise (or be achieved by) applying altering the pH of the treated area of skin, the formed gel, or the area to which the composition has been sprayed. For example, the alteration of the pH may comprise (or be achieved by) diet, physical activity, exposure to slightly acidic solutions, such as white vinegar or citric solutions, or slightly basic solutions, such as dilute ammonia or basic inorganic salt solutions. For example, the release of an active ingredient via a pH action may comprise (or be achieved by) incorporating any one or more pH activated components or techniques known in the art. For example, the pH activity may be achieved by incorporating at least one pH active (i.e., a moiety, monomer, monomeric residue or component) that responds to a pH trigger. For example, the release of an active ingredient via an ionic strength action or a salt-induced action may comprise (or be achieved by) applying an aqueous solution having a high, moderate, or low concentration of salt, such as sodium chloride or other pharmaceutically acceptable salt, or applying a distilled water solution to or on the treated area of skin, the formed gel, or the area to which the composition has been sprayed. For example, the release of an active ingredient via an ionic strength or salt-induced action may comprise (or be achieved by) incorporating any one or more ionic strength activated or salt-induced activating components or techniques known in the art. For example, the ionic strength or salt-induced activity may be achieved by incorporating at least one ionic strength or salt-inducing active (i.e., a moiety, monomer, monomeric residue or component) that responds to an ionic strength or salt-induced trigger. For example, the release of an active ingredient via an exchange action may comprise (or be achieved by) an ion-exchange by applying an aqueous solution having a high, moderate, or low concentration of an inorganic salt, such as sodium chloride or other pharmaceutically acceptable salt, or an organic pharmaceutically acceptable salt, to or on the treated area of skin, the formed gel, or the area to which the composition has been sprayed. For example, the exchange action may comprise (or be achieved by) application of another composition, such as another spray formualation to or on the treated area of skin, the formed gel, or the area to which the composition disclosed herein has been sprayed. For example, the release of an active ingredient via an exchange action may comprise (or be achieved by) incorporating any one or more exchange activated components or techniques known in the art. For example, the exchange activity may be achieved by incorporating at least one exchangably active (i.e., a moiety, monomer, monomeric residue or component) that responds to an exchange trigger. For example, the release of an active ingredient via a degradation action may comprise (or be achieved by) applying a physical and/or chemical action to or on the treated area of skin, the formed gel, or the area to which the composition has been sprayed, whereby the star macromolecule degrades to release the active ingredient. In certain embodiments, the active ingredient may be a degradable precursor that, upon a physical and/or chemical action, degrades to an active form that is then released from the star macromolecule. For example, the precursor may include a photo-labile group, that degrades upon exposure to light, thereby resulting in the release of the active form of the active ingredient to be released from the star macromolecule. For example, the release of an active ingredient via a degradation action may comprise (or be achieved by) incorporating any one or more degradation activated components or techniques known in the art. For example, the degradation activity may be achieved by incorporating at least one degradation active (i.e., a moiety, monomer, monomeric residue or component) that responds to an exchange trigger. For example, the release of an active ingredient via a biological action may comprise (or be achieved by) a biological mechanism that is triggered upon applying the treatment composition to the skin. For example, the star macromolecule composition may trigger a biological response from the mammal, such as a cytokine release, that results in altering the local environment of the star macromolecule, thereby releasing the active ingredient. For example, the release of an active ingredient via a biological action may comprise (or be achieved by) incorporating any one or more biologically activated components or techniques known in the art. For example, the biological activity may be achieved by incorporating at least one biologically active (i.e., a moiety, monomer, monomeric residue or component) that responds to a biological trigger.

[00168] In certain embodiments, the release of the active ingredient may occur over an extended period of time, for example, between 5 minutes to 72 hours, such as between 5 minutes to 60 hours; between 5 minutes to 48 hours; between 5 minutes to 36 hours; between 5 minutes to 24 hours; between 5 minutes to 12 hours; between 5 minutes to 8 hours; between 5 minutes to 6 hours; between 5 minutes to 4 hours; between 5 minutes to 3 hours; between 5 minutes to 2 hours; between 5 minutes to 1 hours; between 5 minutes to 30 minutes; between 30 minutes to 48 hours; between 30 minutes to 24 hours; between 30 minutes to 12 hours; between 30 minutes to 8 hours; after spraying, between 1 hour to 12 hours; or between 1 hour to 24 hours; after forming a gel, and/or exposure to a chemical and/or physical action.

[00169] In certain embodiments, the release of the active ingredient may occur such that between 10 wt.% to 100 wt.%, such as between 10 wt.% to 90 wt.%, between 10 wt.% to 80 wt.%, between 10 wt.% to 70 wt.%, between 10 wt.% to 60 wt.%, between 10 wt.% to 50 wt.%, between 10 wt.% to 40 wt.%, between 10 wt.% to 30 wt.%, between 10 wt.% to 20 wt.%, between 25 wt.% to 75 wt.%, between 50 wt.% to 100 wt.%, or between 25 wt.% to 50 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, is released within 12 hours, such as within 10 hours, within 8 hours, within 6 hours, within 4 hours, within 2 hours, within 1 hour, within 30 minutes, or within 15 minutes, of the gel forming on the skin.

[00170] In certain embodiments, the release of the active ingredient may occur such that between 10 wt.% to 100 wt.%, such as between 10 wt.% to 90 wt.%, between 10 wt.% to 80 wt.%, between 10 wt.% to 70 wt.%, between 10 wt.% to 60 wt.%, between 10 wt.% to 50 wt.%, between 10 wt.% to 40 wt.%, between 10 wt.% to 30 wt.%, between 10 wt.% to 20 wt.%, between 25 wt.% to 75 wt.%, between 50 wt.% to 100 wt.%, or between 25 wt.% to 50 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star

macromolecules, is released within 12 hours, such as within 10 hours, within 8 hours, within 6 hours, within 4 hours, within 2 hours, within 1 hour, within 30 minutes, or within 15 minutes, of being exposed to said chemical and/or physical trigger.

[00171] In certain embodiments, the release of the active ingredient may occur such that at least 80 wt.%, such as at least 85%, at least 90%, or at least 95%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, remains associated (un-released) from the star

macromolecule after 4 to 12 hours, such as after 4 to 8 hours, or 8 to 12 hours, of being exposed to said chemical and/or physical trigger.

[00172] In certain embodiments, the release of the active ingredient may occur such that between 10 wt.% to 30 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, is released within 2 hours, such as within 1 hour, within 30 minutes, or within 15 minutes, and at least 80 wt.%, such as at least 85%, at least 90%, or at least 95%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, remains associated (un-released) from the star macromolecule after 4 to 12 hours, such as after 4 to 8 hours, or 8 to 12 hours, of being exposed to said chemical and/or physical trigger.

[00173] In certain embodiments, the method of making a sprayable, gel-forming aqueous composition, comprising: i) mixing one or more active ingredients with one or more star macromolecules, such as the one or more star macromolecules represented by Formula X, to form a mixture; and ii) introducing additional components to the mixture to form the sprayable, gel-forming aqueous composition. [00174] Suitable materials comprising an emulsifier-free emulsion, wherein the emulsion is thickened by a star macromolecule disclosed herein, may include, but is not limited to, lotions, such as cosmetic lotions, personal care lotions, body lotions, emulsifier-free body lotions; serums, such as anti-aging serums; sunscreens, such as SPF 30 sunscreens, SPF 35 sunscreens, SPF 40 sunscreens, SPF 50 sunscreens; creams, such as face-creams, cosmetic creams; hair products, such as shampoos, hair styling products, hair sprays, mousses, hair gels, hair conditioners, bath preparations; gels, such as cosmetic gels or personal care gels; skin application products, such as ointments, deodorants, personal care powders, skin cleansers, skin conditioners, skin emollients, skin moisturizers, skin wipes, shaving preparations; fabric softeners; dental impression materials; or variations thereof.

[00175] In an embodiment, examples of suitable lotion formulations include body lotion formulations, comprising an emulsifier-free emulsion, wherein the emulsion is thickened by a star macromolecule disclosed herein, may include, but is not limited to, formulations comprising one or more of the following: Deionized Water;

Disodium EDTA; 1 ,3-Butylene Glycol; Glycerin; Allantoin; Urea; TEA 99%; Edible Olive Oil (N.F.); Shea Butter; Wickenol 171 ; Squalane; Crodamol CAP; Crodamol STS; Crodacol C; Tween 20; Lipo GMS 470; PEG 100 Stearate; Cetyl Palmitate; Crodamol PTIS; Crodafos CES; DC 1401 ; Evening Primrose Oil; Vitamin E Acetate; D-Panthenol; Distinctive HA2; Diocide; or derivatives or combinations thereof.

[00176] In an embodiment, examples of suitable lotion formulations include emulsifier-free personal care lotion formulations, comprising an emulsifier-free emulsion, wherein the emulsion is thickened by a star macromolecule disclosed herein, may include, but is not limited to, formulations comprising one or more of the following: Deionized Water; Disodium EDTA; 1 ,3-Butylene Glycol; Glycerin;

Allantoin; Urea; TEA 99%; Edible Olive Oil (N.F.); Wickenol 171 ; Myritol 318; Squalane; Crodamol PTIS; Isododecane; Evening Primrose Oil; Vitamin E Acetate; D-Panthenol; Distinctive HA2; Diocide; or derivatives or combinations thereof.

[00177] In an embodiment, examples of suitable formulations include serum formulations, such as anti-aging serum formulations, comprising an emulsifier-free emulsion, wherein the emulsion is thickened by a star macromolecule disclosed herein, may include, but is not limited to, formulations comprising one or more of the following: Deionized Water; Disodium EDTA; Glycerin; 1 ,3-Butylene Glycol;

Caffeine; Allantoin; Triethanolamine 99%; Crodamol STS; Myritol 318; Wickenol 171 ; Tween 20; Crodaphos CES; BVOSC; Vitamin E Acetate; Vitamin A Palmitate; Vitamin D3; Gransil IDS; D-Panthenol; DC Upregulex; DC Skin Bright MG;

Actiphyte ofJapanese Green Tea G; Actiphyte of Grape Seed G; DC Hydroglide; Diocide; or derivatives or combinations thereof.

[00178] In an embodiment,suitable formulations include sunscreen formulations, comprising an emulsifier-free emulsion, wherein the emulsion is thickened by a star macromolecule disclosed herein, may include, but is not limited to, formulations comprising one or more of the following: Deionized Water; Disodium EDTA;

Glycerin; Triethanolamine 99%; Homomethyl Salicylate; Ethylhexyl Salicylate; Avobenzone; Benzophenone 3; Myritol 318; Lexfeel 7; Octocrylene; Cetyl Alcohol; PEG- 15 Cocamine; Lipo GMS 470; Crodafos CS-20; Vitamin E Acetate; Aloe Vera Leaf Juice; Diocide; or derivatives or combinations thereof.

[00179] In an embodiment, examples of suitable formulations include face cream formulations, comprising an emulsifier-free emulsion, wherein the emulsion is thickened by a star macromolecule disclosed herein, may include, but is not limited to, formulations comprising one or more of the following: Deionized Water;

Disodium EDTA; 1,3 Butylene Glycol; Glycerin; Caffeine; Allantoin;

Triethanolamine 99%; Myritol 318; Octyl Palmitate; Wickenol 171 ; Crodaphos CES; Cetyl Alcohol; Pationic SSL; Cetyl Palmitate; Vitamin E Acetate; BVOSC; Lexfeel 7; Lipo GMS 470; Vitamin A/D3 in Corn Oil; DC 1401 ; Actiphyte ofJapanese Green Tea G; Actiphyte of Grape Seed G; DC Hydroglide; Diocide; or derivatives or combinations thereof.

[00180] SYNTHESIS OF THE RHEOLOGY MODIFIER

[00181] Although any conventional method can be used for the synthesis of the multi-arm star macromolecules of the invention, free radical polymerization is the preferred and living/controlled radical polymerization (CRP) is the most preferred process.

[00182] CRP has emerged during the past decade as one of the most robust and powerful techniques for polymer synthesis, as it combines some of the desirable attributes of conventional free radical polymerization (e.g., the ability to polymerize a wide range of monomers, tolerance of various functionality in monomer and solvent, compatibility with simple industrially viable reaction conditions) with the advantages of living ionic polymerization techniques (e.g., preparation of low polydispersity index (PDI = M M_n) polymer and chain-end functionalized homo- and block (co)polyniers). The basic concept behind the various CRP procedures is the reversible activation of a dormant species to form the propagating radical. A dynamic and rapid equilibrium between the dormant and the active species minimizes the probability of bimolecular radical termination reactions and provides an equal opportunity for propagation to all polymer (or dormant) chains.

[00183] CRP procedures can be classified into three main groups based on the mechanism of reversible activation: (a) stable free radical polymerization (SFRP, Scheme la), (b) degenerative chain transfer polymerization (DT, Scheme lb), and (c) atom transfer radical polymerization (ATRP, Scheme lc).

(a) Stable free radical polymerization (SFRP)

(b) Degenerative chain transfer polymerization (DT)

^~ ^Λ , Initiator _/-~-Λ_>

Pn-X + Pn . ^■ -■ - Pn*. ⁺ Pn^'

(c) Atom transfer radical polymerization (ATRP)

P_n-X + Cu(l)-X / L - ^— ρ_η· + Cu(ll)-X₂ / L

k^<ia k *

Scheme 1. Three main groups of controlled radical polymerization based on the mechanism of reversible activation: (a) stable free radical polymerization (SFRP), (b) degenerative chain transfer polymerization (DT), and (c) atom transfer radical polymerization (ATRP).

[00184] As shown in Scheme 1 various capping agents, X, are used for the different CRP procedures and they are summarized in Scheme 2. They include stable nitroxides (Scheme 2a), transition metal complexes (Scheme 2b), halides with transition metal catalysts (Scheme 2c), iodine with catalysts (Scheme 2d), sulfur compounds (Scheme 2e), iodine (Scheme 2f), and organometal compounds (Scheme 2g). (a) Nitroxides (NMP)

X = -O- ( TEMPO ) etc.

(b) Transition metal complexes

(c) Halides with transition metals (ATRP)

X = -Br, CI, 1 + Metal (Cu, Fe, Ru, etc.)

(d) Iodide with catalysts (RCTP)

X = H + Ge, Sn, etc.

(e) Dithioester, dithiocarbamate, and xanthate (RAFT)

X = -so=S

Z ( Z = Ph, CH₃, NE«₂, OEt, etc. )

(f) Iodine (ITP)

X = -I

(g) Tellurium, stibine, and bismuth compounds

(TERP, SBRP, and BIRP)

X = -RR'

( R = Te, Sb, or Bi, R' = CH₃, etc. )

Scheme 2. Examples of capping agent X.

[00185] Star polymers are nano-scale materials with a globular shape. As illustrated in Figure 1 , stars formed by the "arm first" procedure, discussed in detail below, can have a crosslinked core and can optionally possess multiple segmented arms of similar composition. Stars can be designed as homo-arm stars or mikto-arm stars. Figure 1 A represents a homo-arm star with block copolymer arms. Mikto-arm stars have arms with different composition or different molecular weight; Figure 1 B and 1 C. Both homo-arm stars and mikto-arm stars can optionally possess a high- density of peripheral functionality.

[00186] Synthesis of star polymers of the invention can be accomplished by "living" polymerization techniques via one of three strategies: 1) core-first" which is accomplished by growing arms from a multifunctional initiator; 2) "coupling-onto" involving attaching preformed arms onto a multifunctional core and the 3) arm-first" method which involves cross-linking preformed linear arm precursors using a divinyl compound

[00187] While all above controlled polymerization procedures are suitable for preparation of an embodiment of the disclosed self assembling star macromolecules. Other embodiments are also exemplified, for example, the preparation of the self assembling multi-arm stars with narrow MWD, in contrast to prior art using ATRP. The reason for the use of the Controlled Radical Polymerization process (CRP) known as ATRP; disclosed in U.S. Patents 5,763,546; 5,807,937; 5,789,487;

5,945,491 ; 6,1 1 1 ,022; 6,121 ,371 ; 6,124,41 1 : 6,162,882: and U.S. Patent Applications 09/034,187; 09/018,554; 09/359,359; 09/359,591 ; 09/369,157; 09/126,768 and 09/534,827, and discussed in numerous publications listed elsewhere with

Matyjaszewski as co-author, which are hereby incorporated into this application, is that convenient procedures were described for the preparation of polymers displaying control over the polymer molecular weight, molecular weight distribution, composition, architecture, functionality and the preparation of molecular composites and tethered polymeric structures comprising radically (co)polymerizable monomers, and the preparation of controllable macromolecular structures under mild reaction conditions.

[00188] An aspect of the present invention relates to the preparation and use of multi-arm star macromolecules by an "arm first" approach, discussed by Gao, H.; Matyjaszewski, K. JACS; 2007, 129, 1 1828. The paper and cited references therein are hereby incorporated by reference to describe the fundamentals of the synthetic procedure. The supplemental information available within the cited reference provides a procedure for calculation of the number of arms in the formed star macromolecule.

[00189] It is expected that biphasic systems such as a miniemulsion or an ab initio emulsion system would also be suitable for this procedure since miniemulsion systems have been shown to function as dispersed bulk reactors [Min, K.; Gao, H.; Matyjaszewski, K. Journal of the American Chemical Society 2005, 127, 3825-3830] with the added advantage of minimizing core-core coupling reactions based on compartmentalization considerations.

[00190] In one embodiment star macromolecules are prepared with composition and molecular weight of each segment predetermined to perform as rheology modifiers in aqueous based solutions. The first formed segmented linear (co)polymer chains are chain extended with a crosslinker forming a crosslinked core.

[00191] In another embodiment a simple industrially scalable process for the preparation of star macromolecules is provided wherein the arms comprise segments selected to induce self assembly and wherein the self assemblable star

macromolecules are suitable for use as rheology control agents in waterborne and solvent-borne coatings, adhesives, cosmetics and personal care compositions. [00192] The invention is not limited to the specific compositions, components or process steps disclosed herein as such may vary.

[00193] It is also to be understood that the terminology used herein is only for the purpose of describing the particular embodiments and is not intended to be limiting.

[00194] The procedure for the preparation of star macromolecules may be exemplified by (co)polymerization of linear macromolecules, including

macroinitiators (MI) and macromonomers (MMs), with a multi-vinyl cross-linker, a divinyl crosslinker is employed in the exemplary examples disclosed herein, to form a core of the star. The formation of the core of the star can also be formed through a copolymerization reaction wherein a monovinyl monomer is added to expand the free volume of the core to allow incorporation of additional arms into the congested core forming environment or to provide sufficient free volume within the core of the star to encapsulate functional small molecules. A molecule that functions as an initiator and a monomer, an inimer, can also be employed in the preparation of the core of the star macromolecule. When added to the reaction it functions to form a three arm branch in the core of the molecule and hence acts in a manner similar to the added monomer to increase the free volume within the star core.

[00195] The volume fraction of the core of the star can be controlled by appropriate selection of the crosslinker molecule or by conducting a copolymerization between the crosslinker and a vinyl monomer or an inimer. The composition of the core can be selected to provide an environment to encapsulate small molecules, such as fragrances, and control the rate of diffusion of the fragrance from the self assembled thickening agent after deposition on a part of the human body.

[00196] The core of the star polymers may contain additional functionality. This additional functionality can be of direct utility in certain applications or can be employed to tether or encapsulate further functional materials such as fragrances, stimuli responsive molecules or bio-responsive molecules to the core of the star by chemical or physical interactions.

[00197] The star macromolecules can be prepared in dilute solution when reaction conditions and crosslinker are chosen to avoid or reduce star-star coupling reactions.

[00198] The synthesis of multi-arm star polymers where the periphery of the star polymers contains additional functionality is possible. This functionality can be introduced by use of an initiator comprising the desired a-functionality in the residue of the low molecular weight initiator remaining at the a-chain end of each arm. [00199] An embodiment of the present invention can be exemplified by the preparation of a multi-arm star macromolecule wherein the number of arms in the star macromolecule is between 5 and 500, preferentially between 10 and 250, with segments selected to induce self assembly when the star macromolecule is dispersed in a liquid wherein the self assemblable star macromolecules are suitable for use as thickening agents or rheology modifiers in cosmetic and personal care compositions at low concentrations of the solid in the thickened solution, preferably less than 5 wt%, and optimally less than 1 wt%. The dispersion medium can comprise aqueous based systems or oil based systems.

[00200] The structure of an exemplary new thickening agent, or rheology modifier, of one embodiment, is a multiarm segmented star macromolecule wherein the core is prepared by controlled radical polymerization using an arm-first method. Scheme 3 provides a simple four step procedure that can be employed for preparation of an initial non-limiting exemplifying case the procedure is an atom transfer radical polymerization arm first macroinitiator method. In this approach the precursor of the arm(s) comprise a linear copolymer chain with a single terminal activatable group, as will be understood by one skilled in the art, having this disclosure as a guide, the activatable arm precursor will have a co-terminal functionality that under the conditions of the polymerization procedure can reversibly generate a radical. Scheme 3 illustrates the concept by sequential polymerization of styrene and tBA. These monomers are purely exemplary monomers and should not limit the applicability of the procedure in any manner since other monomers of similar phylicity can be employed. In Scheme 3 the polystyrene segment can be considered the outer shell of the star and the final poly(acrylic acid) segments the inner water soluble shell and the segment formed by chain extending the linear copolymer macroinitiators by reaction with the divinylbenzene crosslinker the core of the star.

Star Star PSt-b-PtBA PSt-b-PAA

Step 1 Step 2 Step 3 S Step 4

Scheme 3. Multistep synthesis of PSt-6-PAA block copolymer stars [00201] Similar structures can also be prepared using the macromonomer method or a combination of the macromonomer and macroinitiator method in a controlled polymerization process, or even through free radical copolymerization conducted on macromonomers, as known to those skilled in the art.fGao, H.; Matyjaszewski, K. Chem.-Eur. J. 2009, 75, 6107-61 1 1.]

[00202] Both the macromonomer and macroinitiator procedures allow

incorporation of polymer segments prepared by procedures other than CRP [WO 98/01480] into the final star macromolecule. Polymer segments can comprise segments that are bio-degradable of are formed from monomers prepared from biological sources.

[00203] As noted above the first formed ATRP macroinitiator can be prepared by conducting a sequential ATRP (co)polymerization of hydrophobic and hydrophilic monomers or precursors thereof or can be prepared by other polymerization procedures that provide a functional terminal atom or group that can be converted into an ATRP initiator with a bifunctional molecule wherein one functionality comprises a transferable atom or group and the other functionality an atom or group that can react with the functionality first present on the (co)polymer prepared by a non-ATRP procedure. [WO 98/01480]

[00204] In aqueous solutions, the composition and molecular weight of the outer shell of hydrophobes, or agents that participate in molecular recognition, can be selected to induce self-assembly into aggregates and act as physical crosslinkers. Above a certain concentration, corresponding to the formation of a reversible three dimensional network, the solutions will behave as physical gels thereby modifying the rheology of the solution.

[00205] In one embodiment, the polymer compositions of the invention have significantly lower critical concentration for network (gel) formation compared to networks formed with block copolymers, graft and stars with a low specific number of attached arms due to:

• multi-arm structure (many transient junctions possible between hydrophobic parts of the stars)

• very high molecular weight of each star (5 thousand to 5 million or higher) allows high swelling ratio of the molecules in solution

• molecular organization on larger scales (>1 μηι) [00206] Whereas the examples above and below describe the preparation and use of block copolymers as arms with a well defined transition from one segment to the adjoining segment a segmented copolymer with a gradient in composition can also be utilized. The presence of a gradient can be created by addition of a second monomer prior to consumption of the first monomer and will affect the volume fraction of monomer units present in the transition form one domain to another. This would affect the shear responsiveness of the formed star macromolecule.

[00207] Star macromolecules with narrow polydispersity comprising arms with block copolymer segments can be formed with as few as 5 arms by selecting appropriate concentration of reagents, crosslinker and reaction temperature.

[00208] Star macromolecules can be prepared in a miniemulsion or reverse miniemulsion polymerization system. The first formed block copolymers are used as reactive surfactants for star synthesis by reaction with a selected crosslinker in miniemulsion.

[00209] EXAMPLES

Abbreviation Name Form Purity Commercial So

St styrene liquid 99% Sigma Aldrich tBA tertiary-butyl acrylate liquid 98% Sigma Aldrich

AA acrylic acid (formed by deprotection) NA NA NA

HEA hydroxyethyl acrylate liquid 96% Sigma Aldrich

DEBMM diethyl 2-bromo-2-methylmalonate liquid 98% Sigma Aldrich

TPMA tris(2-pyridylmethyl)amine solid 95% ATRP Solutions

AIBN 2,2'-Azobis(2-methylpropionitrile) solid 98% Sigma Aldrich

Sn(EH)₂ tin(ll) 2-ethylhexanoate liquid 95% Sigma Aldrich

DVB divinylbenzene liquid 80% Sigma Aldrich

TFA trifluroacetic acid liquid 99% Sigma Aldrich

THF tetrahydrofuran liquid 99.9% Sigma Aldrich

NaOH sodium hydroxide solid 98% Sigma Aldrich

EBiB Ethyl a-bromoisobutyrate liquid 98% Sigma Aldrich

Methylene chloride liquid 99.6% Sigma Aldrich

Acetonitrile liquid 99.8% Sigma Aldrich

NaCI Sodium chloride solid 99.7% Fisher Chemical

DMAEMA 2-(dimethylamino)ethyl methacrylate

PEGMA (polyethylene glycol) methacrylate

NIPAM N-isopropylacrylamide

[00210] Synthesis, purification and properties of star thickening agent. [00211] The initial examples of a star thickening agents with the structure shown below in Figure 1 as structure A, are star macromolecules with PSt-A-PAA arms or PSt-6-P(HEA) arms.

(00212] Example 1 : Preparation of a (PSt-b-PAA)x Star Macromolecule.

[00213] The simple four step procedure was developed for the preparation of a poly(acrylic acid) based star macromolecule is described in Scheme 3. 1 kg of the star macromolecule with PSt-^-P BA arms was prepared as follows.

[00214] STEP 1 : Synthesis of a polystyrene macroinitiator using ICAR ATRP. The reaction conditions are St / DEBMM / CuBr₂ / TPMA / AIBN = 50 / 1 / 0.002 / 0.003 / 0.05 in bulk at T = 60 °C, t = 10.2 h. The reaction was run to -30%

conversion resulting in the molecular weight of the hydrophobic, polystyrene segment = 1600 which is equivalent to an average degree of polymerization (DP) of 16.

[00215] The GPC trace obtained for the macroinitiator is shown in Figure 2.

[00216] STEP 2: Synthesis of polystyrene-&-poly(t-butyl acrylate) segmented block copolymer macroinitiator. The reaction conditions for the synthesis of PSt-b- PtBA macroinitiator arm are: tBA / PSt / CuBr₂ / TPMA / Sn(EH)₂ = 200 / 1 / 0.01 / 0.06 / 0.008 in anisole (0.5 volume eq. vs. tBA), T=55 °C, t=18.0 h. A higher molecular weight precursor of the water soluble segment was targeted to allow significant degree of swelling of the inner shell of the final functional star

macromolecule. The final molecular weight of the poly(t-butyl acrylate) segment in the block copolymer was -15,400 which is equivalent to a DP =120. The GPC curves of the polystyrene macroinitiator and the formed block copolymer macroinitiator is shown in Figure 3 and clearly indicates that a clean chain extension had occurred.

[00217] STEP 3: Synthesis of the (PSt-6-PtBA)x star macromolecule.

[00218] A multi-arm star macromolecule was prepared by conducting a further chain extension reaction with the block copolymer macroinitiator formed in step 2. The reaction was conducted with a mole ratio of block copolymer to divinylbenzene of 1 : 12 in anisole. The reaction conditions are: DVB / PSt-b-PtBA / CuBr₂ / TPMA / Sn(EH)₂ = 12 / 1 / 0.02 / 0.06 / 0.1 in anisole (38 volume eq. vs. DVB), T = 80 °C, t = 21.0 h). The GPC curves and results of the star forming reaction are provided in Figure 4. It can be seen that a multi-arm star macromolecule with a crosslinked core was formed. The GPC molecular weight of the star was 102,700 with a PDI 1.29, which would indicate an average of six arms but this is an underestimate of the actual number of arms since the star molecule is a compact molecule. Indeed in this situation the number of arms in the star molecule is close to 30.

[00219] The number of arms can be modified by conducting the core forming reaction with a different ratio of crosslinking agent to arm precursor or by running the reaction with a different concentration of reagents.

[00220] STEP 4: Deprotection of the (PSt-b-PtBA)x star macromoleeule to (PSt-b- PAA)x star block copolymer to provide water soluble poly(acrylic acid) segments in the multi-arm star macromoleeule. The PSt-6-P/BA arms of the star macromoleeule were transformed to PSt-6-PAA arms using a new procedure. Polymer was dissolved in methylene chloride and trifluoroacetic acid to deprotect tBu groups, the reaction was performed at room temperature for 60.0 h. Then polymer was decanted and washed 3 times with acetonitrile. Polymer was then solubilized in THF and precipitated into acetonitrile. The star macromoleeule was dried in vacuum oven for 3 days at 50 °C. The amount of polymer obtained after purification was 550 g, which would correspond to full conversion of PtBA to PAA.

[00221] Example 2: Properties of (PSt-b-PAA) star macromoleeule as a thickening agent

[00222] The thickening properties of the final star macromoleeule were investigated in aqueous solution. 100 mg of (PSt-b-PAA) star macromoleeule was dissolved in 0.5 ml of THF and transferred to 10 ml of water. Solution was then neutralized with 2 ml of basic water (with NaOH). After few minutes of stirring gel was formed, see image in Figure 5.

[00223] The rheological properties of the multi-arm star built with a longer poly(acrylic acid (PAA) hydrophilic internal core segment and a short hydrophobic polystyrene (PSt) peripherial segment were then investigated. The viscosity of aqueous solutions containing different concentrations of the star macromoleeule vs. shear rate were measured; using a Brookfield LVDV-E, Spindle #3 l(or #34, #25) at a T = 25 °C, and the results are presented in Figure 6. It is clear that even very low concentrations of the star macromoleeule in water (<0.6 weight%) the apparent viscosity of the sample is very high (in the range of 50,000 to 100,000 centipoise (cP)).

[00224] In comparison, leading thickening agents on the market for personal care products (e.g. natural nonionic vegetable derived liquid thickener Crothix Liquid by CRODA or synthetic aery late based copolymer DOW CORNING RM 2051) are used at the level of 2-5 weight% and only increase the viscosity of a water based solution up to 5,000 - 20,000 cP.

[00225] Figure 7 presences the viscosity of aqueous solution of a (PSt-6-PAA) star macromolecule vs. concentration. The measurement was conducted on a Brookfield LVDV-E with spindle #31 (or #34, #25) at a temperature = 25 °C and rate = 1 RPM. It can be seen that for this particular star macromolecule 0.3 weight% concentration of star macromolecule in water is a minimum amount for gel formation and that higher concentrations significantly increase the viscosity of the resulting solution.

[00226] Tests indicated that the thickening agent provided formulations that exhibited a lack of tackiness, a very pleasant feel on the skin.

[00227] Example 3: Properties of (PSt-b-PAA) star macromolecule as thickening agents in harsh environments

[00228] The thickening properties of the final star macromolecule were

investigated in aqueous solution in the presence of an oxidizing agent and at high pH. Figure 8 presents the viscosity of an aqueous solution of (PSt-b-PAA) star

macromolecule and the viscosity of water/windex (1/1 v/v) solution of (PSt-b-PAA) star macromolecule and Figure 9 presents the results obtained with Carbopol EDT 2020 in the same media. The pH of the aqueous solution was 6-7 while for the water/Windex solution pH = 9-10. (Measurement of viscosity was conducted using a Brookfield LVDV-E, Spindle #31 (or #34, #25), T = 25 °C.) It can be seen that viscosity of water/windex solution is higher than that of water solution. The performance of (PSt-b-PAA) star macromolecule as thickening agent is not diminished in this harsh environment presented by the windex/water solution with a pH = 9-10 resulting from the presence of high amount of ammonia-D. In comparison, the thickening properties of the leading thickener on the market, Carbopol EDT 2020, were decreased in similar conditions and Figure 9 shows that the viscosity of water/windex solution is lower than that of pure aqueous solution.

[00229] It is envisioned that the poor performance of Carbopol vs. (PSt-b-PAA) star macromolecule as thickening agent in water/Windex solution is a consequence of the high amount of ester bonds in its structure which can interact with the ionic species present in such harsh environment or can be even degraded. On the other side (PSt-b-PAA) star macromolecule has only C-C bonds, which make this thickening agent stable in water/Windex solution and overall thickening performance is not decreased. [00230] Example 4: Properties of (PSt-b-PAA) star macromolecule vs. (PAA) star macromolecule as thickening agents.

[00231] A (PAA) star macromolecule was synthesized in order to compare its properties to those determined for the (PSt-b-PAA) star macromolecule. Synthesis of (PAA) star was performed in similar way as for synthesis of (PSt-b-PAA) star macromolecule but starting with pure PtBA arms.

[00232] The final (PAA) star had similar molecular weight, number of arms and molecular weight distribution to the (PSt-b-PAA) star macromolecule, Figure 10. The only one difference between two star macromolecules is the outer shell which comprises of PSt with degree of polymerization 16 in (PSt-b-PAA) star

macromolecule whereas this star macromolecule posses pure PAA homo-polymeric arms. Figure 1 1 presents the viscosity of aqueous solutions of (PSt-b-PAA) star and (PAA) star macromolecules. The measurement was conducted using a Brookfield LVDV-E fitted with a #31 spindle at a temperature = 25 °C and pH = 7. It can be seen that viscosity of star macromolecule with a hydrophobic outer shell has very strong thickening properties, where the pure (PAA) star has low thickening effect on water.

[00233] Therefore one can conclude that in order to thicken aqueous based media the proposed multi-arm star macromolecules have to have a blocky structure, with a hydrophilic inner shell and a hydrophobic outer shell. Without wishing to be limited by a proposed mechanism we believe these results in aqueous media can be explained by the induced self-assembly of the hydrophobic segments into aggregates, the hydrophobes act as "junctions" between aggregates, and above a certain

concentration, a three-dimensional reversible physical network is formed with a behavior similar to conventional gels.

[00234] Above described star macromolecules will not only differ by mechanical properties in water solution but also by the encapsulation and release of functional agent. As discussed earlier, two different compositions of the arms of star

macromolecules will have strong effect on the release characteristic of functional agents. If functional agent will have affinity to and will be stored in hydrophobic core C, its release will be faster from pure (PAA) star macromolecule. Hydrophobic PSt shell on (PSt-b-PAA) star macromolecule will slow down the release of hydrophobic functional agent via hydrophobic-hydrophobic affinity. The above stated rates of release and extended release may be achieved in a number of ways, including, for example, by tuning in this case by changing amount of hydrophobic PSt in the outer shell and/or the characteristic of the arms and core (for example the amount of cross- linking and/or overall number and/or size of the arms or size of the core).

[00235] Example 5: (PSt-b-PAA) star macromolecule as thickening and

emulsifying agent.

[00236] Due to its very well-defined structure, (PSt-b-PAA) multi-arm star macromolecule may act not only as a thickening agent but also as efficient emulsifying agent. Figure 12 presents images demonstrating the emulsifying properties of (PSt-b-PAA) star macromolecule. First photograph shows mixture of water with 2 volume % of pure lemon oil. After vigorous mixing, water and oil quickly separated into two phases. The second photograph presents water with 2 volume % of lemon oil and 0.6 weight % of thickening agent. After vigorous mixing, the phase separation did not occur and thicken properties did not decrease. Solutions were shaken for 1 min and photographs were taken 2 h after mixing.

[00237] Its hydrophobic core (as well as hydrophobic outer shell) may act as a storage place for small organic molecules (e.g. vitamins, fragrances, sunblock agents, etc.). This provides for the possibility for delivery of functional organic molecules, e.g. fragrance for slow release or UV absorbing molecules in sunscreens to any part of the body in a pleasant feeling emulsion.

[00238] In order to provide an equivalent response for non-polar media the phylicity of the inner and outer shells would have to be reversed.

[00239] Example 6: Mikto-arm star macromolecules

[00240] A multi-arm star macromolecule was synthesized. The procedures for forming the arms PSt-b-PtBA and PtBA were similar to that described in Example 1. Next, two different arms were crosslinked together to form a star macromolecule. Reaction conditions for core forming crosslinking reaction: DVB / [PSt-b-PtBA / PtBA] / CuBr2 / TPMA / Sn(EH)2 = 17 / 1 / 0.02 / 0.06 / 0.2 in anisole (38 volume eq. vs. DVB), (1667 ppm of Cu) T=95 °C, t= 53.0 h, PSt-b-PtBA / PtBA = 1 / 4. Next, PtBA was transformed to PAA by deprotection with acid as described in Step 4 in Example 1.

[00241] Figure 13 shows the GPC curves of the arms and the formed mikto-arm star macromolecule before and after purification by precipitation. Schematic 13B shows a representation of such a mikto-arm star macromolecule. [00242] Synthesis of stars with lower amounts of the outer PSt block was successfully performed. Two stars were synthesized, one with 50% and one with 20% of PSt-b-PAA arms and 50% and 80% pure PAA arms (WJ-08-006-234 and WJ- 06-235) by the procedures detailed above. Studies show that these star

macromolecules can be dispersed directly in warm water. Thickening properties of these two new stars were as good as first exemplary star with 100% of PSt-b-PAA arms.

[00243] Stars with different outer hydrophobic shells can be prepared. One example that provides an outer shell which exhibits a Tg below use temperature is a star prepared with a PnBA outer shell.

[00244] Another approach which can reduce the cost of the preparing an outer hydrophobic shell is conversion of commercially available α-olefins to an ATRP initiator by reaction with a halo-alky(meth)acrylylhalide.

[00245] Example 7: Stars with different hydrophobic segments

[00246] One parameter which may significantly change viscosity of thickening agent as well as its interaction with surfactant in shampoo formulations is the type of hydrophobic unit capped at the peripheral end of a fraction of the arms of the star macromolecule. Two additional stars were synthesized in order to compare to (PSti₆- PAAi2o)x (before deprotection: M_n,app= 102,700 g/mol, PDI=1.29) star macromolecule.

[00247] These stars include:

A) C, 8-PAA₁₄₆)x: M_n,app = 95,600 g/mol, PDI=1.48,

B) C,2-PAAi34) x: M_n,_app = 1 13,900 g/mol, PDI=1.53,

[00248] Each star was prepared in three steps:

i) preparation of PtB A arm,

ii) crosslinking arms into star macromolecule,

iii) deprotection of tBu groups. All of the stars had relatively low PDI with low amount of unreacted arms (<15 wt%).

[00249] A) A new PtBA macroinitiator was prepared from an initiator containing a linear C)₈ alkyl chain for preparation of the (C i 8-PAAi4₆)x star. The synthesis of this arm precursor C_{] 8}-P?BA-Br was accomplished using ARGET ATRP of tBA using Ci₈ alkyl chain functionalized EBiB. The conditions and properties of synthesized polymer are shown in Table 1. Table 1. Experimental conditions and properties of Ρ/ΉΑ prepared by ARGET

ATRP.^a

Molar ratios Cu Time Conv. MJ

Entry _ _^ _ M_{n, thc0} M_n> GPC

tBA 1 CuBr₂ L RA [ppm] (min) (%) M„

08-006- 300 1 0.015 0.06 0.1 50 1380 47 18200 19700 1.19 160 TPMA

a I- Cig-EBiB, L= Ligand, RA = reducing agent = Sn(EH)₂; [zBA]₀=4.67 M; T-60 °C, in anisole (0.5 volume equivalent vs. monomer); ^b M_{n t}heo⁼([M]o/[Ci 8-EBiB]o) x conversion

[00250] This macroinitiator was than crosslinked using DVB into a star

macromolecule. After deprotection of tBu groups by stirring the reaction for 3 days in the presence of TFA resulting in transformation to PAA units star was precipitated from CH₂CI2. The viscosity of resulting (Cig-PAA)x star and the (Ci₂-PAA)x star can be compared to (PSt-b-PAA)x in water and shampoo formulations.

[00251] Example 8: Stars with an inner P(HEA) shell

[00252] P(HEA) star macromolecules that comprise water soluble non-ionizable hydrophilic segments selected to make the star macromolecules compatible with solutions further comprising dissolved/dispersed salts that are additionally stable over a broad range of pH.

[00253] The PSt-έ-ΡΗΕΑ arm precursor was prepared using ICAR ATRP.

Conditions for the polymerizations and characterization of the resulting polymer are shown in Table 2. Polymerization was well controlled and well-defined block copolymer was prepared with relatively low (PDI=1.26 and 1.20) . This is the first example of successful ICAR ATRP for acrylate type monomer. PSt-6-PHEA arm precursor was purified by precipitation into ethyl ether and dried under vacuum over two days at 50 °C. Table 2. Experimental conditions and properties of PSt-A-PHEA prepared by ICAR ATRP.^a

Molar ratios Cu Time Conv. _h M

Entry Mn, theo M„, ore

HEA I CuBr₂ L RA [ppm] (min) (%) M„

08-006- 200 1 0.04 0.04 0.1 200 1200 63 16100 30400 1.26

155 TPMA

08-006- 300 1 0.05 0.05 0.05 167 1230 54 20300 42300 1.20

158 TPMA

" I=PSt (08-006-29, M„=1600 g/mol, PDI=1.20), L= Ligand, RA = reducing agent = AIBN

[HEA]o=5.44 M; T=65 °C, in DMF (0.7 volume equivalent vs. monomer);

* M_n>

x conversion.

[00254] Different crosslinking agents were investigated, including DVB and in run 08-006-159 di(ethylene glycol) diacrylate (DEGlyDA) and in run 08-006-161

DEGlyDA with small amount of HEA monomer. The reaction was not fully

controlled when conversion of the added divinyl crosslinker was driven to high conversion as a consequence of star-star core coupling reactions resulted in gel formation. However at lower conversion of the crosslinker and under more dilute conditions star macromolecules were formed.

[00255J Example 9: Preparation of a (PSti₅-b-PAA₂9o / PAAi₅o)=30 Miktoarm Star Macromolecule (referenced herein as Advantomer).

[00256] The simple four step procedure was developed for the preparation of a poly(acrylic acid) based miktoarm star macromolecule and is described in Scheme 4. 1 kg of the miktoarm star macromolecule with PSt-&-PAA and PAA arms (molar ratio of arms 4/1) was prepared as follows.

STEP 1 STEP 2

ICAR ATRP ARGET ATRP ARGET ATRP """^^W

►_► ^y, „ +

tBA at certain conversion

+ EtBiB

PSt PSt-b-PfBA PSt-ft-PfBA

and PfBA

STEP 3 STEP 4

Controlled

crosslinking

Star Star

[(PSt-/>-PfBA)_x / (PtBA)J -DVB [(PSt-fe-PAA)_x / (PAA)J -DVB

Scheme 4. Multistep synthesis of [PSt-6-PAA / PAA] miktoarm stars copolymers

[00257] STEP 1 : Synthesis of a Polystyrene Macroinitiator (PSt) having 15 DP

[00258] A polystyrene macroinitiator was formed using ICAR ATRP by introducing the following components into the reaction vessel at the following molar ratio: St / DEBMM / CuBr₂ / TPMA / AIBN = 50 / 1 / 0.002 / 0.003 / 0.05 in bulk at T = 60 °C, t = 10.2 h. The reaction was run to -30% conversion. The resulting reaction product was purified to obtain the PSt in powder form. A portion of the PSt powder was dissolved in THF and passed through the GPC column. The GPC trace obtained for the macroinitiator is shown in Figure 2. The measured molecular weight of the hydrophobic, polystyrene segment = 1600 which is equivalent to an average degree of polymerization (DP) of about 15-16 and the PDI was measured to be 1.24.

[00259] STEP 2: One-Pot Synthesis of Polystyrene-6-Poly(t-Butyl Acrylate) and Poly(/-Butyl Acrylate) Macroinitiator

[00260] The following components were introduced into the reaction vessel in the following molar ratio: tBA / PSt (from stepl)/ CuBr₂ / TPMA / Sn(EH)₂ = 200 / 0.2 / 0.01 / 0.06 / 0.1, in anisole (0.5 volume eq. vs. tBA), T=55 °C. About 2.0 hours after the reaction was initiated, the conversion of the tBA reached about 6 % and a portion of the PSt-b-PtBA was recovered and measured by GPC with the following results M_r = 19,800 g/mol; PDI = 1.16. It was determiend that the following PSti₅-b-PtBAi₄₀ copolymeric block was obtained. Then, 0.8 molar ratio amount, relative to the initially introduced components, of Ethyl 2-bromoisobutyrate (EBiB) was injected into the polymerization mixture. The reaction was continued and stopped after about 19.8 h. The reaction product was purified and the product was analyzed by GPC. Based on the GPC measured values the final molecular weight of the product was determined to be poly(t-butyl acrylate) segment in the block copolymer was -37,200 g/mol (PSti5-b-PtBA₂9o) and the molecular weight of poly(t-butyl acrylate) initiated from EBiB was 19,200 g/mol which is equivalent to a DP =150. The overall molecular weight of mixture of arms resulted in M_n = 20,800 g/mol and PDI = 1.27. The GPC curves of the polystyrene macroinitiator and the mixture of formed block copolymer arms PSti5-b-PtBA₂9o and poly(t-butyl acrylate) arms PtBAiso are shown in Figure 23. The signal from block copolymer is overlapping with signal from homopolymer but this result clearly indicates that a clean chain extension from PSt had occurred.

[00261] STEP 3: Synthesis of the (PSt-6-PtBA / PtBA)_¾30 Miktoarm Star

Macromolecule.

[00262] A mikto multi-arm star macromolecule was prepared by conducting a further chain extension reaction with the block copolymer and homopolymer macroinitiators formed in step 2. The reaction was conducted with a mole ratio of macroinitiators to divinylbenzene of 1 : 16 in anisole. The following components were introduced into the reaction vessel in the following molar ratio: DVB / [PSt-b-PtBA / PtBA] (from step 2) / CuBr₂ / TPMA / Sn(EH)₂ = 16 / 1 / 0.02 / 0.07 / 0.15 in anisole (38 volume eq. vs. DVB), T = 95 °C, t = 20.6 h. The reaction product was purified and the product was analyzed by GPC. The GPC curves and results of the star forming reaction are provided in Figure 24. It can be seen that a multi-arm star macromolecule with a crosslinked core was formed. The GPC apparent molecular weight of the star was 109,400 with a PDI 1.52, which would indicate an average of six arms but this is an underestimate of the actual number of arms since the star molecule is a compact molecule. Indeed in this situation, the number of arms in the star molecule is close to 30.

[00263] The number of arms can be modified by conducting the core forming reaction with a different ratio of crosslinking agent to arm precursor or by running the reaction with a different concentration of reagents.

[00264] STEP 4 : Deprotection of the (PSt-6-PtB A / PtBA) to (PSt-6-P AA / P AA)

[00265] Deprotection of the (PSt-6-PtB A / PtB A)_s30 star macromolecule to (PSt-6- PAA / PAA)_¾3o star block copolymer to provide water soluble poly(acrylic acid) segments in the mikto multi-arm star macromolecule. The PSt-^-PtBA / PtBA arms of the miktoarm star macromolecule were transformed to PSt-/?-PAA / PAA arms with the following procedure. Polymer was dissolved in methylene chloride and trifluoroacetic acid to deprotect Bu groups, the reaction was performed at room temperature for 60.0 h. Then polymer was decanted and washed 3 times with acetonitrile. Polymer was then solubilized in THF and precipitated into acetonitrile. The star macromolecule was dried in vacuum oven for 3 days at 50 °C. The amount of polymer obtained after purification was 550 g, which would correspond to full conversion of P/BA to PAA.

[00266] Test Results Table - comparing the star macromolcule formed in example 9 (Advantomer) against commerically available thickening agent, Carbopol ETD 2020.

[00267] Test Procedures:

[00268] SAMPLE PREPARATION

[00269] Aqueous gel compositions were prepared at various concentrations (e.g.,

0.2 wt.%, 0.25 wt%, 0.4 wt.% 0.6 wt.%, 0.7 wt.% and 1.0 wt.%) by heating and stirring, as necessary (e.g., vigorously mixing at a temperature of about 60 °C) the sample material (e.g., a star macromolecular powder or Carbopol ETD 2020) into water pH adjusted, as necessary, (e.g., a pH of about 7.5 with addition of sodium hydroxide) to obtain a homogenous mixture.

[00270] Dynamic Viscosity & Shear- Thinning Test Procedure

[00271] A portion of the sample preparation was introduced into a Brookfield

LVDV-E Digital Viscometer, using spindle #25 or #31 , depending on anticipated viscosity, for mixing, at STP, over a wide range of rates (e.g, 0.3-100 rpm) and the shear rate and viscosity was recorded. Viscosity measurements were taken in the following sequence without stopping the instrument, 0.3, 0.5, 1 , 2, 5, 10, 20, 30, 50, and l OOrpm. Unless otherwise stated, the dynamic viscosity in centipoise (cP) was determined at a concentration of 0.2 wt.% of star macromolecules at STP, pH 7.5 (for anionic) and pH 5.0 (for cationic) and a shear rate of 0.3 rpm, using spindle #25.

[00272] Shear-Thinning Value

[00273] A shear-thinning value was determined by dividing the dynamic viscosity value at 0.3 rpm by the dynamic viscosity value at 20rpm.

[00274] Salt-Induced Break Test Procedure

[00275] A portion of the sample preparation was introduced into 20 ml glass scintillation vial. A measured portion of NaCl was added into the vial (e.g., 0.05 wt.% relative to the total weight of the sample in the vial. After the NaCl addition was complete, the vial was closed and shaken for 10 min. Then, the viscosity of the sample was measured in accordance with the Dynamic Viscosity & Shear-Thinning Test Procedure, above, and the dynamic viscosity at 1 rpm was recorded. This procedure was repeated for differing concentrations of NaCl. The results are presented in Figures 18 & 22. The salt-induced break value, in percent, is determined by the following equation:

[00276J Initial Dynamic Viscosity (0% NaCl) -Dynamic Viscosity (0.05 wt.% NaCiyinitial Dynamic Viscosity (0% NaCl) x 100%. [00277] pH Efficiency Range Test Procedure

[00278] An aqueous gel composition at 0.4 wt.% was prepared for the star macromolecule of Example 9, at a starting pH of around 5 and a separate aqueous gel composition at 0.2 wt.% aqueous gel composition of Carbopol ETD 2020, at a starting pH of around 3, was prepared by mixing and heating , as necessary (e.g., vigorous mixing at a temperature of about 60 °C). Then, the viscosity of the sample was measured in accordance with the Dynamic Viscosity & Shear-Thinning Test

Procedure, above, and the dynamic viscosity at 1 rpm was recorded. This procedure was repeated for differing pH values, adjusted by addition of sodium hydroxide. The results are presented in Figure 19. The ph-induced break value, in percent, is determined by the following equation:

[00279] Dynamic Viscosity (at 1 rpm) at pH 7.5 -Dynamic Viscosity (at 1 rpm) at pH 5/ Dynamic Viscosity (at l rpm) at pH 7.5 x 100%.

[00280] Emulsion Test Procedure

[00281] 340mL of water was added to a 500ml beaker and stirred vigorously with an overhead stirrer. 1.6 g of the material to be tested for emulsifying effect was added and heated to 80C. The solution was pH adjusted with 400 mg of NaOH and stirring continued until a homogeneous gel was obtained. 60ml sunflower oil was added while vigorous stirring was continued with an overhead stirrer at 80C for l Omin or until homogenous emulsion is obtained. The mixture was allowed to cool to room temperature. Once the system cools to room temperature start timer. The emulsion value is the time, in minutes, it takes for the system to form two visible layers (phase separation).

[00282] Strong Gel Test Procedure

[00283] 10 ml portion of the sample preparation material was introduced into a 20 ml glass scintillation vial. After the transfer was complete, the vial was placed on a surface and remained undisturbed for about 20 minutes at STP. The vial was then gently inverted (turned-upside down) and placed on the surface and a timer started. If after 5 minutes, there is no visible flow then the sample is said to be a strong gel.

[00284] Hydrophilic-Lipophilic (HLB) Arm/Segment Calculation

[00285] HLB = 20 * Mh / M

where Mh is the molecular mass of the hydrophilic portion of the polymeric arm or segment, and M is the molecular mass of the whole polymeric arm or segment. [00286] Hydrophilic-Lipophilic Macromolecule Calculation

∑ MWnXHLB* / 20 o _3MWem + \ MW_n

HLM = divided by *-ⁱ

where

MW„ is the molecular weight for the respective arm,

HLB_n is the HLB, as calculated from the HLB arm calculation, for the respective arm, and

Wcore is the molecular weight for the core, and

M is the total number of arms.

[00287] The disclosed star macromolecules can find utility in a spectrum of applications including, but not limited to; personal care: including

shampoos/conditioners, lotions, serums, creams, solids, gelly, cosmetics: including mascara, blush, lip stick, powders, perfumes and home care: including cleaners for windows, household and work surfaces, toilet areas, laundry, and in dish and dishwasher applications.

WAI-3012503v2

Claims

What is claimed is:

1. A sprayable, gel-forming aqueous composition, comprising:

i) one or more active ingredients; and

ii) one or more star macromolecules having a molecular weight of between

50,000 g/mol and 2,000,000 g/mol that forms a gel when dissolved in water at a concentration of at least 0.2 wt.%;

wherein the gel has:

a) a dynamic viscosity of at least 20,000 cP; and/or

b) a shear- thinning value of at least 10; and

2. A sprayable, gel-forming aqueous composition, comprising:

i) one or more active ingredients; and

ii) one or more star macromolecules represented by Formula X:

Formula X [(Pl)_ql-(P2)_q2]_rCore-[(P3)_q3]_r wherein:

Core represents a crosslinked polymeric segment;

P2 represents a substantially hydrophilic segment comprising repeat units of monomeric residues of polymerized hydrophilic monomers; P3 represents a substantially hydrophilic segment comprising repeat units of monomeric residues of polymerized hydrophilic monomers; ql represents the number of repeat units in PI and has a value between 1 and 100;

3. A sprayable, gel-forming, wound treating aqueous composition, comprising: i) one or more active ingredients; and

ii) one or more star macromolecules represented by Formula X:

Formula X [(Pl)_qi-(P2)_q2]rCore-[(P3)_q3]r wherein:

Core represents a crosslinked polymeric segment;

a) the molar ratio of r to t is in the range of between 40: 1 and 2: 1 ; and

4. The composition of any one of claims 1 -3, wherein the one or more active ingredients comprises one or more: active pharmaceutical ingredients, active cosmetic ingredients, fragrance ingredients, and/or active skin-care ingredients.

5. The composition of any one of claims 1-4, wherein the one or more active ingredients comprises an antibacterial agent.

6. The composition of any one of claims 1-5, wherein the composition further comprises an anesthetic and optionally a skin soothing agent and/or an analgesic.

7. The composition of any one of claims 1 -6, wherein the composition is a burn and/or wound treatment.

8. The composition of any one of claims 1 -7, wherein the sprayable, gel-forming aqueous composition comprises a dynamic viscosity of 60,000 cP or less at 1 rpm.

9. The composition of any one of claims 2-8, wherein the one or more star maeromolecules has a molecular weight of between 50,000 g/mol and 2,000,000 g/mol and forms a gel when dissolved in water at a concentration of at least 0.2 wt.% having a shear-thinning value of at least 10.

10. The composition of any one of claims 1-9, wherein the association of the at least one of the one or more active ingredients with the at least one of the one or more star maeromolecules comprises:

i) one or more van der Waals interactions;

ii) one or more hydrophobic interactions;

iii) one or more polar interactions;

iv) one or more hydrophilic interactions;

v) one or more hydrogen bonding interactions;

vi) one or more ionic interactions; and/or

vii) encapsulation of the at least one of the one or more active ingredients by the at least one of the one or more star maeromolecules.

1 1. The composition of any one of claims 1 -10, wherein the at least one associated one or more active ingredients is associated with the arms of the at least one of the one or more star maeromolecules.

12. The composition of any one of claims 1-1 1 , wherein the at least one associated one or more active ingredients is released from the at least one of the one or more star macromolecules.

13. A method of treating a wound, comprising applying the sprayable, gel-forming aqueous composition of any one of claims 1-12 to a mammal's wound.

14. A method of treating skin with the composition of any one of claims 1 -12, by spraying a gel-forming amount on the skin.

15. The method of claim 14, wherein the active ingredient becomes released from the macromolecule and available to the skin.

16. The method of claim 15, wherein a chemical and/or physical action triggers the release of at least a portion of the active ingredient.

17. The method of any one of claims 15- 16, wherein the release of the active ingredient occurs over an extended time.

18. The method of any one of claims 14- 17, wherein between 10 wt.% to 100 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, is released within 12 hours of the gel forming on the skin.

19. The method of any one of claims 16-18, wherein between 10 wt.% to 100 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, is released within 12 hours of being exposed to said chemical and/or physical trigger.

20. The method of any one of claims 18-19, wherein between 10 wt.% to 30 wt.% is released within 3 hours.

21. The method of any one of claims 18-19, wherein at least 80 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, remains associated from the star macromolecule after 4 to 12 hours of being exposed to said chemical and/or physical trigger.

22. The method of any one of claims 18-19, wherein between 10 wt.% to 30 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, is released within 2 hours and at least 80 wt.%, relative to the amount of the one or more active ingredients initially associated with the one or more star macromolecules, remains associated from the star macromolecule after 4 to 12 hours of being exposed to said chemical and/or physical trigger.

23. A method of making a sprayable, gel-forming aqueous composition, comprising:

wherein the one or more star macromolecules represented by Formula X:

Formula X [(Pl)_ql-(P2)_£)2],-Core-[(P3)_q3]_r wherein:

Core represents a crosslinked polymeric segment;

q3 represents the number of repeat units in P3 and has a value between 30 and 1 ,000; r represents the number of arms covalently attached to the Core; and t represents the number of arms covalently attached to the Core; and wherein: