Oral care compositions and methods

Abstract

The present disclosure provides star polymers and methods of using the same. Also provided are oral compositions comprising the star polymers and an orally acceptable carrier and methods of using the same. The star polymers provided herein have a structure according to formula (I):

Description

Technical Field

[0001] The present disclosure generally relates to oral care compositions comprising star polymers and methods of using the same. More specifically, the present disclosure relates to oral care compositions for inhibiting bacterial attachment to teeth, comprising a star polymer and an orally acceptable carrier. Background Art

[0002] Oral hygiene is one of the most important aspects of consumer personal care. As part of maintaining dental hygiene, consumers around the world use different types of oral care products. People typically brush their teeth at least twice a day with a toothbrush and a dentifrice (including toothpaste or tooth powder or mouthwash). The purpose of such toothbrushing is to ensure good oral hygiene by minimizing oral bacteria that accumulate in the mouth during the night while sleeping or during the day when people eat and drink beverages. Thus, regular toothbrushing can minimize problems such as tooth decay, tartar, gingivitis, dental caries, and bad breath (also known as halitosis).

[0003] Despite brushing teeth twice a day, many people suffer from various forms of one or more of the above diseases related to dental hygiene and it is believed that this is partly caused by the formation of oral biofilm or dental plaque on the tooth surface.

[0004] Teeth are composed of an inner dentin layer and an outer hard enamel layer that serves as a protective layer for the teeth. The enamel layer is composed of hydroxyapatite (HAP) mineral crystals, which can form a slightly porous surface. Dental plaque appears as a film on almost all tooth surfaces, such as on the enamel layer containing HAP. Dental plaque is a byproduct of microbial growth and contains a dense layer of microorganisms composed of a large number of microorganisms embedded in a polysaccharide matrix. Dental plaque itself adheres firmly to the tooth surface, such as on enamel, and is difficult to remove even by a rigorous toothbrushing regimen. In addition, dental plaque reforms rapidly on the tooth surface after removal. Dental plaque can form on any part of the tooth surface, especially at the gum margins, in enamel cracks, and on the surface of dental calculus. The danger associated with the formation of dental plaque on teeth is that dental plaque will accumulate and eventually cause gingivitis, periodontitis, and other types of periodontal diseases, as well as dental caries and dental calculus. Summary of the Invention

[0005] There is provided herein an oral care composition comprising a star polymer and an orally acceptable carrier, wherein the star polymer has a structure according to formula (I):

[0006]

[0007] wherein each R 1Independently contains H or an acrylate polymer, each n is independently from 5 to 500, such as from 10 to 400, or from 15 to 300, and each X is independently O, NR 4 or S, where R 4 contains H or C 1-6 alkyl, and R 2 includes H, C 1-8 alkyl or a functionalized acrylate polymer, and each R 3 independently includes H, C 1-8 alkyl or a phosphoric acid C 1-8 alkyl ester.

[0008] The present disclosure also provides a method for inhibiting bacterial attachment to teeth, the method comprising administering to a subject an oral care composition comprising a star polymer having the structure of formula (I) and an orally acceptable carrier.

[0009] There is also provided a star polymer having the structure according to formula (I).

[0010] There is further provided a method for forming a layer on a tooth surface, the method comprising administering to a subject an oral care composition comprising a star polymer having the structure of formula (I) and an orally acceptable carrier.

[0011] Those of ordinary skill in the art will appreciate other aspects and advantages from a reading of the following detailed description. While the compositions and methods are susceptible to various forms of embodiments, the following description includes specific embodiments, and it should be understood that the present disclosure is illustrative and not intended to limit the present disclosure to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 Displays a Mayo diagram showing the polymerization and synthesis of the star polymer via a chain transfer process.

[0013] Figure 2 A illustrates the maximum adsorption (q max ) of the star polymer of the present disclosure to the HAP surface.

[0014] Figure 2 B illustrates the dissociation constant (K d ) of the star polymer of the present disclosure to the HAP surface.

[0015] Figure 2 C illustrates the effect of the polymer arm length (DP) on the adsorption (q max ) of the star polymer to the HAP surface.

[0016] Figure 2 D illustrates the effect of the polymer arm length (DP) on the dissociation constant (Kd ) influence

[0017] Figure 3 Illustrate the influence of the hydrophobic monomer composition on the HAP adsorption of the 4-arm star polymers according to the present disclosure.

[0018] Figure 4 Illustrate the antibacterial attachment activity of the star polymers according to the present disclosure.

[0019] Figure 5 Illustrate the influence of the star polymers according to the present disclosure on the contact angle. Detailed Description

[0020] The present disclosure provides a star polymer. The present disclosure also provides an oral care composition comprising the star polymer and an orally acceptable carrier, wherein the star polymer has a structure according to formula (I):

[0021]

[0022] wherein the substituents are described in detail below.

[0023] The star polymers described herein can be used in oral care compositions to inhibit the attachment and growth of microbial biofilms on tooth surfaces. For example, when the polymers are used in oral care compositions, they bind to the hydroxyapatite (HAP) surface, thereby promoting repulsion and / or preventing bacteria from attaching to the tooth surface, making the use of these polymers in oral care compositions particularly advantageous.

[0024] Star Polymer

[0025] Provided herein is a star polymer. Also provided is an oral care composition comprising the star polymer and an orally acceptable carrier. The star polymer has a structure according to formula (I):

[0026]

[0027] wherein,

[0028] each R 1 independently comprises H or an acrylate polymer;

[0029] each n is independently from 5 to 500, such as from 10 to 400, or from 15 to 300

[0030] each X is independently O, NR 4 or S, other embodiments wherein R 4 comprises H or C 1-6 alkyl;

[0031] R 2 comprises H, C 1-8An alkyl or functionalized acrylate polymer; and,

[0032] Each R 3 independently comprises H, C 1-8 alkyl or C 1-8 alkyl phosphate.

[0033] As provided herein, each R 1 independently comprises H or an acrylate polymer. The various R 1 moieties throughout the star polymer can be the same or different. In some embodiments, each R 1 comprises H. In other embodiments, each R 1 comprises an acrylate polymer.

[0034] As used herein, "acrylate polymer" refers to any polymer formed by the polymerization of a reaction mixture comprising acrylate monomers. Thus, "acrylate polymer" can refer to a homopolymer formed by the polymerization of a single type of acrylate monomer (e.g., polyacrylic acid), or a copolymer formed by the polymerization of two or more types of monomers, wherein at least one type of monomer is an acrylate monomer. Acrylate polymers can be linear homopolymers, linear copolymers, branched homopolymers, or branched copolymers. Suitable acrylate monomers that can be used to prepare acrylate polymers can include, for example, acrylic acid or its derivatives, methacrylic acid or its derivatives, and combinations of the foregoing. Acrylic acid derivatives include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and 2-ethylhexyl acrylate. Methacrylic acid derivatives include, but are not limited to, methyl methacrylate, ethyl methacrylate, butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, and 2-ethylhexyl methacrylate. Other suitable acrylic acid derivatives include phosphates of acrylic acid or its derivatives and phosphates of methacrylic acid and its derivatives, including, but not limited to, ethylene glycol monomethacrylate phosphate (also known as 2-hydroxyethyl methacrylate phosphate) and other acrylic alkyl ester phosphates and methacrylic alkyl ester phosphates. Other monomers suitable for acrylate copolymers include, but are not limited to, other phosphate-containing monomers, phosphonate-containing monomers, acrylamide, methacrylamide, and styrene monomers. In embodiments, R 1 comprises a linear acrylate polymer. In embodiments, R 1 comprises a branched acrylate polymer. In embodiments, the acrylate polymer is selected from the group consisting of polymethacrylate, poly(ethyl acrylate), poly(propyl acrylate), poly(butyl acrylate), and poly(C 1-8 alkyl phosphate acrylate). In some embodiments, R 1Comprises an acrylate copolymer, wherein the copolymer is prepared by polymerization of a reaction mixture comprising a combination of methacrylate with any one or more monomers, as provided above. For example, in some cases, the molar percentage of methacrylate in the star polymer of the oral care composition according to the present disclosure is from about 5 to about 70 mol%, from about 25 to about 65 mol% or from about 40 to about 60 mol%, for example, about 5, 10, 15, 20, 25, 30, 34, 35, 40, 45, 50, 56, 57, 60, 65 or 70 mol%. The molar percentage of methacrylate or any other monomer used to prepare the star polymer can be determined by analyzing the 1 1H NMR spectrum.

[0035] In an embodiment, R 1 can be selected taking into account other molecular formula parameters such that the star polymer as a whole remains substantially water-soluble. The ability of the polymer to bind to HAP and thereby repel or prevent bacterial attachment while remaining water-soluble is particularly advantageous for use in oral care compositions as provided herein because it allows for easy formulation of the composition and application of the composition to the oral cavity of a human or mammalian subject.

[0036] As provided herein, each R 3 independently comprises H, C 1-8 alkyl or phosphoric acid C 1-8 alkyl ester. In some embodiments, R 3 comprises H. In some embodiments, R 3 comprises C 1-8 alkyl. In some embodiments, R 3 comprises phosphoric acid C 1-8 alkyl ester. The various R 3 moieties can be the same or different in a given segment of the star polymer and more generally can also be the same or different throughout the star polymer. As used herein, the term "alkyl" refers to straight-chain and branched-chain saturated hydrocarbon groups containing from one to thirty carbon atoms, for example from one to twenty carbon atoms or from one to ten carbon atoms. The term C n means that the alkyl has "n" carbon atoms. For example, C4 alkyl refers to an alkyl having 4 carbon atoms. C 1-8An alkyl group refers to an alkyl group having a full range of carbon atom numbers (i.e., 1 to 8 carbon atoms) and all subgroups (such as 1-7, 2-7, 1-6, 2-6, 1-5, 2-5, 3-5, 3-6, 4-8, 4-7, 5-8, 1, 2, 3, 4, 5, 6, 7, and 8 carbon atoms). Non-limiting examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), tert-butyl (1,1-dimethylethyl), n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2,2-dimethylheptyl, 2-ethylhexyl, 3-ethylhexyl, 3,4-dimethylhexyl, 3,4-diethylbutyl, or 2-methyl-3-ethylpentyl. Unless otherwise specified, the alkyl group can be a substituted alkyl group or an unsubstituted alkyl group. In some cases, each R 3 is methyl. In some cases, each R 3 is n-butyl. In some embodiments, each R 3 is C 1-8 alkyl phosphate. As used herein, the term "alkyl phosphate" refers to a phosphate group in which one or more O atoms of the phosphate ester are substituted by an alkyl group. Non-limiting examples of alkyl phosphate groups include, but are not limited to, monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, hexyl phosphate, or diethylhexyl phosphate.

[0037] As provided herein, each X is independently O, NR 4 or S, where R 4 comprises H or C 1-6 alkyl. In some embodiments, X is O. In some cases, X is NH. In some cases, X is NC 1-6 alkyl. For example, X can be N, where N is substituted by methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), tert-butyl (1,1-dimethylethyl), n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, or 2-ethylbutyl. In certain cases, X is S. In a given segment of the star polymer and more generally throughout the star polymer, the various X moieties can be the same or different.

[0038] As provided herein, R 2 comprises H, C 1-8 alkyl or a functionalized acrylate polymer. In some embodiments, R 2 comprises H. In some embodiments, R 2 comprises C 1-8 alkyl. In some embodiments, R 2 comprises a functionalized acrylate polymer. As used herein, "functionalized acrylate polymer" is similar to "acrylate polymer" as described above, but also includes moieties that can facilitate chain transfer and chain elongation. For example, an acrylate polymer that also contains a thiol or an amine (e.g., an acrylate homopolymer or acrylate copolymer as described above) can provide a functionalized acrylate polymer in a star polymer. In various cases, R 2 comprises a functionalized acrylate homopolymer. In some cases, R 2 comprises a functionalized acrylate copolymer. For example, in some cases, R 2 comprises a functionalized acrylate copolymer having a structure according to formula (IA), (IB), (IC), (ID), or (IE): (IA), (IB), (IC), (ID), or (IE):

[0039]

[0040]

[0041] where each substituent is as described above. In embodiments where R 2 is of formula (IA), the star is referred to as a 4-arm star polymer (4Star). In embodiments where R 2 is of formula (IB), the star is referred to as a 6-arm star polymer (6Star). In embodiments where R 2 is of formula (IC), the star is referred to as an 8-arm star polymer (8Star). In embodiments where R 2 is of formula (ID), the star is referred to as a 10-arm star polymer (10Star). In embodiments where R 2 is of formula (IE), the star is referred to as a 12-arm star polymer (12Star). Thus, the star polymers according to the present disclosure can have as few as three arms (where R 2 is H) and as many as 12 arms.

[0042] In an embodiment, R 2Selection can be made taking into account other molecular formula parameters such that the star polymer remains substantially water-soluble as a whole. As described above, the ability of the polymer to bind HAP and thereby repel or prevent bacterial attachment while maintaining water solubility is particularly advantageous for the formulation, application, and use of oral care compositions according to the present disclosure.

[0043] As provided herein, each n is independently from 5 to 500, 10 to 400, or 15 to 300, such as 5, 10, 15, 20, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500.

[0044] In some embodiments, the star polymer has a structure selected from Formula (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), and (XII):

[0045]

[0046]

[0047]

[0048] wherein each n and each m are independently in the range of 5 to 500, 10 to 400, or 15 to 300, such as 5, 10, 15, 20, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500.

[0049] The molecular weight of the star polymer is not particularly limited. In an embodiment, the number-average molecular weight (M n) ranging from about 1,000 g / mol to about 700,000 g / mol, about 1500 g / mol to about 500,000 g / mol, about 1750 g / mol to about 250,000 g / mol, or about 2000 g / mol to about 200,000 g / mol, such as about 1000, 1250, 1500, 1750, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8000, 9000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 125,000, 150,000, 175,000, 200,000, 225,000, 250,000, 275,000, 300,000, 325,000, 350,000, 375,000, 400,000, 425,000, 450,000, 475,000, 500,000, 525,000, 550,000, 575,000, 600,000, 625,000, 650,000, 675,000 or 700,000 g / mol

[0050] The molecular weight of the star polymer can also be described by its weight-average molecular weight (M w )). In an embodiment, the weight-average molecular weight (M w)Ranging from about 1,000 g / mol to about 700,000 g / mol, about 1,500 g / mol to about 500,000 g / mol, about 1,750 g / mol to about 250,000 g / mol, or about 2,000 g / mol to about 200,000 g / mol, such as about 1,000, 1,250, 1,500, 1,750, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 125,000, 150,000, 175,000, 200,000, 225,000, 250,000, 275,000, 300,000, 325,000, 350,000, 375,000, 400,000, 425,000, 450,000, 475,000, 500,000, 525,000, 550,000, 575,000, 600,000, 625,000, 650,000, 675,000, or 700,000 g / mol. In an embodiment, the weight-average molecular weight of the polymer ranges from about 10,000 to about 150,000 g / mol.

[0051] The molecular weight of the star polymer can be adjusted by changing the ratio of CTA to monomer. Generally, as the ratio of CTA to monomer increases, the molecular weight of the star polymer decreases. The molar ratio of CTA to monomer can range from about 1:1000 to about 1:20, such as about 1:500 to about 1:25, about 1:200 to about 3:100 or about 1:100 to about 1:50, such as 1:1000, 1:500, 1:200, 1:100, 1:50, 3:100, 1:25 or 1:20.

[0052] The star polymer can be a hydrophobic star polymer, and the content of its hydrophobic monomers is at least about 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, about 40 mol%, about 45 mol%, about 50 mol%, about 55 mol% or about 60 mol%. Suitable examples of hydrophobic monomers can include those described herein for acrylate polymers, such as acrylic acid or its derivatives, methacrylic acid or its derivatives, and combinations of the foregoing. Acrylic acid derivatives include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and 2-ethylhexyl acrylate. Methacrylic acid derivatives include, but are not limited to, methyl methacrylate, ethyl methacrylate, butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, and 2-ethylhexyl methacrylate.

[0053] The hydrophobic star polymers of the present disclosure can have a water contact angle of at least about 60°, such as at least about 60°, 65°, 70°, 75° or 80° and / or up to about 95°, 90°, 85°, 80° or 75°. A water contact angle of at least about 60° is generally desirable because it has been found to correspond to improved antibacterial properties of the star polymer. Methods for measuring the water contact angle, for example, on the surface of hydroxyapatite, are well known in the field of oral care and are described in the examples provided herein.

[0054] The star polymer is characterized by its dissociation constant (K d ) with HAP. In an embodiment, the polymer has a K d of less than about 5 μmol / L, such as about 5 μmol / L, about 4.5 μmol / L, about 4 μmol / L, about 3.5 μmol / L, about 3 μmol / L, about 2.5 μmol / L, about 2 μmol / L, about 1.5 μmol / L or about 1 μmol / L. Advantageously, the star polymers of the present disclosure can have a lower dissociation constant than the corresponding linear polymers, which corresponds to improved binding to the hydroxyapatite surface.

[0055] The star polymer can be used in oral care compositions, as described in more detail below. Generally, star polymers can be used to inhibit bacterial attachment to surfaces. Advantageously, the star polymers of the present disclosure can effectively bind to hydroxyapatite. Thus, the star polymers of the present disclosure can be used to inhibit bacterial attachment to surfaces, where the surface contains hydroxyapatite.

[0056] Oral composition

[0057] The star polymers as described herein can be used in oral compositions. The oral composition according to the present disclosure comprises a star polymer and an orally acceptable carrier.

[0058] The amount of the star polymer in the oral composition can range from about 0.1 wt% to about 10 wt% based on the total weight of the composition. For example, the oral composition can contain from about 0.5 wt% to about 7.5 wt%, from about 1.0 wt% to about 5 wt%, from about 0.5 wt% to about 4 wt%, from about 0.5 wt% to about 3 wt%, from about 0.5 wt% to about 2 wt%, from about 1 wt% to about 10 wt%, from about 1 wt% to about 7 wt%, from about 1 wt% to about 6 wt%, or from about 2 wt% to about 4 wt% of the star polymer, such as about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 wt% of the star polymer.

[0059] The oral composition further comprises an orally acceptable carrier. As used herein, "orally acceptable carrier" refers to a material or combination of materials that can be safely used in an oral composition, commensurate with a reasonable risk / benefit ratio. The term "orally acceptable carrier" also refers to any carrier that can be used to formulate any oral care composition described herein. An orally acceptable carrier is harmless to a mammal when retained in the mouth in the amounts disclosed herein without swallowing for a time sufficient to allow effective contact with the tooth surfaces as required herein. Typically, an orally acceptable carrier is harmless even if inadvertently swallowed.

[0060] In an embodiment, the oral composition contains the star polymer and an orally acceptable carrier in a product, such as a mouthwash, oral rinse, toothpaste, dentifrice, dental gel, periodontal gel, dental powder, non-abrasive gel, mousse, foam, oral spray, lozenge, chewing gum, soluble or insoluble film or strip, dental floss, oral tablet, dental tool or pet care product. In various embodiments, the oral composition according to the present invention is not intended to be swallowed, but is retained in the mouth for a time sufficient to achieve the desired utility. In other portable embodiments (such as lozenges, mints, beads, wafers, liquids formulated from a small portable nebulizer for oral administration, liquids formulated from a small portable dropper bottle for oral administration or soft flexible tablets) the composition is intentionally swallowed, optionally after being retained in the mouth for a time sufficient to achieve the desired utility.

[0061] Suitable orally acceptable carriers include, for example, water, aqueous solubilizers, thickeners, buffers, wetting agents, surfactants, abrasives, sweeteners, flavoring agents, edible flavors, colorants, anti-caries agents, antibacterial or antimicrobial agents, anti-plaque agents, cleaning agents, adhesives, foam regulators, whitening agents, tartar control (anti-tartar) agents, saliva stimulants, desensitizing agents, antioxidants, nutrients, preservatives, enzymes, or any combination thereof. Generally, the carrier provides the desired properties to the composition to maintain or promote contact with the enamel layer and / or otherwise allow the star polymer to contact, coat, and / or adsorb to the enamel layer.

[0062] In an embodiment, the oral care composition comprises water. The water used to prepare the oral care compositions disclosed herein should be deionized and free of organic impurities. The water can constitute the balance of the oral care composition. In some embodiments, the oral care compositions disclosed herein comprise up to about 90 wt%, about 0.1 wt% to about 90 wt%, about 1 wt% to about 80 wt%, about 2 wt% to about 70 wt%, about 5 wt% to about 60 wt%, about 5 wt% to about 50 wt%, about 20 wt% to about 60 wt% or about 10 wt% to 40 wt% water, based on the total weight of the composition. This amount of water includes the added free water plus the amount introduced with other components of the oral care composition such as sorbitol (which may be provided, for example, as a 70% active solution, the balance including water).

[0063] Thickeners provide a desirable consistency and / or stabilize and / or enhance the properties of the oral care composition (e.g., provide desirable active release characteristics upon use). Suitable thickeners for the oral compositions of the present disclosure include, but are not limited to, carboxyvinyl polymers, carrageenan (also known as Irish moss), hydroxyethyl cellulose (HEC), natural and synthetic clays (such as Veegum and synthetic hectorite), soluble salts of water cellulose ethers (such as sodium carboxymethyl cellulose (CMC) and sodium carboxymethyl hydroxyethyl cellulose), natural gums (such as karaya gum, xanthan gum, gum arabic, and tragacanth gum), colloidal magnesium aluminum silicate, silica (e.g., finely divided silica), polyvinylpyrrolidone, carbowax, fatty acids and their salts, and mixtures thereof. In some embodiments, the oral care compositions disclosed herein comprise from about 0.01 wt% to about 15 wt%, from about 0.1 wt% to about 15 wt%, from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 5 wt%, from about 0.5 wt% to about 10 wt%, from about 0.5 wt% to about 5 wt%, from about 1 wt% to about 4 wt%, from about 2 wt% to about 5 wt%, from about 2 wt% to about 4 wt%, or from about 3 wt% to about 4 wt% of a thickener, based on the total weight of the composition. Higher weight percentages can be used for chewing gums, lozenges and mints, sachets, non-abrasive gels, and subgingival gels. In some embodiments, a mixture of thickened silica and carrageenan is used as a thickener in the oral care compositions disclosed herein. In some embodiments, the oral care compositions disclosed herein comprise from about 0.01 wt% to about 15 wt%, from about 0.1 wt% to about 15 wt%, from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 5 wt%, from about 0.5 wt% to about 10 wt%, from about 0.5 wt% to about 5 wt%, from about 1 wt% to about 4 wt%, from about 2 wt% to about 5 wt%, from about 2 wt% to about 4 wt%, or from about 3 wt% to about 4 wt% of thickened silica and carrageenan, based on the total weight of the composition.

[0064] Buffers adjust the pH value of the oral care composition to a range of, for example, from about pH 4.0 to about pH 6.0. Buffers that can be used in the oral care compositions disclosed herein include, but are not limited to, sodium bicarbonate, sodium phosphate (e.g., monosodium phosphate (NaH2PO4), disodium phosphate (Na2HPO4), trisodium phosphate (Na3PO4)), sodium hydroxide, sodium carbonate, sodium acid pyrophosphate, citric acid, sodium citrate, and mixtures thereof. In some embodiments, the oral care compositions disclosed herein contain from about 0.5 wt% to about 10 wt%, from about 0.5 wt% to about 5 wt%, from about 0.5 wt% to about 4 wt%, from about 0.5 wt% to about 3 wt%, from about 0.5 wt% to about 2 wt%, or from about 1 wt% to about 2 wt% of a buffer, based on the total weight of the composition. In some embodiments, sodium hydroxide is used as a buffer in the oral care compositions disclosed herein. In some embodiments, the oral care compositions disclosed herein contain from about 0.5 wt% to about 10 wt%, from about 0.5 wt% to about 5 wt% of sodium hydroxide, from about 0.5 wt% to about 4 wt%, from about 0.5 wt% to about 3 wt%, from about 0.5 wt% to about 2 wt%, or from about 1 wt% to 2 wt% sodium hydroxide.

[0065] Humectants prevent the oral care composition from hardening upon exposure to air. Certain humectants can also impart the desired sweetness or flavor to the oral care composition. Humectants that can be used in the oral care compositions disclosed herein include, but are not limited to, glycerin, sorbitol, xylitol, butylene glycol, polyethylene glycol, propylene glycol, trimethylglycine, and mixtures thereof. In some embodiments, the oral care compositions disclosed herein contain up to about 70 wt% of a humectant, based on the total weight of the composition, e.g., from about 10 wt% to about 70 wt%, from about 10 wt% to about 65 wt%, from about 10 wt% to about 60 wt%, from about 10 wt% to about 50 wt%, from about 20 wt% to about 50 wt%, from about 30 wt% to about 50 wt%, or from about 40 wt% to about 50 wt% of a humectant, based on the total weight of the composition. In some embodiments, a mixture of glycerin, sorbitol, and propylene glycol is used as a humectant in the oral care compositions disclosed herein. In some embodiments, the oral care compositions disclosed herein contain up to about 70 wt% of glycerin, sorbitol, and propylene glycol, e.g., from about 10 wt% to about 70 wt%, from about 10 wt% to about 65 wt%, from about 10 wt% to about 60 wt%, from about 10 wt% to about 50 wt%, from about 20 wt% to about 50 wt%, from about 30 wt% to about 50 wt%, or from about 40 wt% to about 50 wt% of glycerin, sorbitol, and propylene glycol.

[0066] In some embodiments, the oral care compositions disclosed herein comprise a surfactant. The surfactant can be selected from anionic, cationic, zwitterionic, and nonionic surfactants, and mixtures thereof. In some embodiments, the surfactant is fairly stable over a wide pH range. Surfactants are described, for example, in U.S. Patent No. 3,959,458 to Agricola et al.; U.S. Patent No. 3,937,807 to Haefele; and U.S. Patent No. 4,051,234 to Gieske et al. In some embodiments, the oral care compositions disclosed herein comprise from about 0.01 wt% to about 10 wt%, about 0.05 wt% to about 5 wt%, about 0.1 wt% to about 10 wt%, about 0.1 to about 5 wt%, about 0.1 to about 2 wt%, or about 0.5 wt% to about 2 wt% of the surfactant, based on the total weight of the composition.

[0067] In some embodiments, the oral care compositions disclosed herein comprise an anionic surfactant. Anionic surfactants useful in the oral care compositions disclosed herein include, but are not limited to, (i) water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of the monosulfated monoglyceride of hydrogenated coconut oil fatty acid, such as sodium N-methyl-N-cocoyl taurate, sodium cocomonoglyceride sulfate; (ii) higher alkyl sulfates, such as sodium lauryl sulfate; (iii) higher alkyl ether sulfates, such as the higher alkyl ether sulfate of the formula CH3(CH2) m CH2(OCH2CH2) n OSO3X, where m is 6-16 (e.g., 10), n is 1-6 (e.g., 2, 3, or 4), and X is Na or K, such as sodium laureth-2 sulfate (CH3(CH2) 10 CH2(OCH2CH2)2OSO3Na); (iv) higher alkyl aryl sulfonates, such as sodium dodecylbenzenesulfonate (sodium laurylbenzenesulfonate); (v) higher alkyl sulfonacetates, such as sodium lauryl sulfonacetate (sodium dodecyl sulfonacetate), higher fatty acid esters of 1,2-dihydroxypropane sulfonic acid, sulfolaurate (potassium N-2-ethyllaurylsulfonylacetamide), and sodium lauroyl sarcosine. As used herein, "higher alkyl" means C 6-30Alkyl. In some cases, the oral care compositions disclosed herein comprise from about 0.01 wt% to about 10 wt%, from about 0.05 wt% to about 5 wt%, from about 0.1 wt% to about 10 wt%, from about 0.1 to about 5 wt%, from about 0.1 to about 2 wt%, or from about 0.5 wt% to about 2 wt% of an anionic surfactant, based on the total weight of the composition. In some embodiments, the anionic surfactant is a water-soluble salt of an alkyl sulfate having 10 to 18 carbon atoms in the alkyl group or a water-soluble salt of a sulfonated monoglyceride of a fatty acid having 10 to 18 carbon atoms. Sodium lauryl sulfate, sodium lauroyl sarcosinate, and sodium coco monoglyceride sulfonate are examples of this type of anionic surfactant. In some embodiments, the oral care compositions disclosed herein comprise sodium lauryl sulfate, sodium laureth ether sulfate, or a mixture thereof. In some embodiments, the oral care compositions disclosed herein comprise sodium lauryl sulfate. In some embodiments, the oral care compositions disclosed herein comprise from about 0.01 wt% to about 10 wt%, from about 0.05 wt% to about 5 wt%, from about 0.1 wt% to about 10 wt%, from about 0.1 to about 5 wt%, from about 0.1 to about 2 wt%, or from about 0.5 wt% to about 2 wt% of sodium lauryl sulfate, based on the total weight of the composition.

[0068] The compositions of the present invention may comprise an abrasive that can be used, for example, as a polishing agent. Any orally acceptable abrasive can be used, but the type, fineness (particle size), and amount of the abrasive should be selected such that enamel is not overly worn during normal use of the composition. Suitable abrasives include, but are not limited to, silica, for example in the form of precipitated silica or in a form mixed with alumina, insoluble phosphates, calcium carbonate, and mixtures thereof. Insoluble phosphates that can be used as abrasives include orthophosphates, poly metaphosphates, and pyrophosphates. Illustrative examples are dicalcium phosphate dihydrate, calcium pyrophosphate, calcium metaphosphate, tricalcium phosphate, calcium poly metaphosphate, and insoluble sodium poly metaphosphate. Some embodiments provide an oral care composition comprising from about 5 to about 15 wt% abrasive, based on the total weight of the composition. When an abrasive is present, the average particle size is generally from about 0.1 to about 30 microns, such as from about 1 to about 20 or from about 5 to 15 microns.

[0069] In some embodiments, the oral care compositions disclosed herein comprise a sweetening agent. Sweetening agents that can be used in the oral care compositions disclosed herein include, but are not limited to, sucrose, glucose (i.e., dextrose), ribose, galactose, saccharin, sucralose, polydextrose, lactose, mannose, mannitol, sorbitol, erythritol, fructose (e.g., levulose), maltose, maltitol, xylose, xylitol, isomaltulose, saccharin salts (e.g., sodium saccharin), thaumatin, aspartame, D-tryptophan, dihydrochalcones, acesulfame potassium, neotame, cyclamate salts, dextrin, partially inverted sugar dry, corn syrup hydrolyzed starch, hydrogenated starch hydrolyzates, dipeptide-based high-intensity sweeteners, and mixtures thereof. In some embodiments, the oral care compositions disclosed herein comprise from about 0.005 to about 10 wt%, from about 0.01 wt% to about 10 wt%, from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 5 wt%, from about 0.1 wt% to about 3 wt%, from about 0.1 wt% to about 1 wt%, or from about 0.1 wt% to about 0.5 wt% of a sweetening agent, based on the total weight of the composition. In some embodiments, sodium saccharin is used as the sweetening agent in the oral care compositions disclosed herein. In some embodiments, the oral care compositions disclosed herein are from about 0.005 wt% to about 10 wt%, from about 0.01 wt% to about 10 wt%, from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 5 wt%, from about 0.1 wt% to about 3 wt%, from about 0.1 wt% to about 1 wt%, or from about 0.1 wt% to about 0.5 wt% sodium saccharin, based on the total weight of the composition. Some components, such as sorbitol, can be included in an amount sufficient to function as both a sweetening agent and a humectant. Generally, when provided in a relatively large amount suitable for a humectant, the presence of sorbitol is also sufficient to act as a sweetening agent in the composition.

[0070] Flavorings or flavoring agents useful herein include any material or mixture of materials that can be used to enhance the taste of a composition. Any orally acceptable natural or synthetic flavoring agent can be used, such as flavor oils, flavor aldehydes, esters, alcohols, similar materials, and combinations thereof. Flavoring agents include vanillin, sage, marjoram, parsley oil, spearmint oil, cinnamon oil, wintergreen oil (methyl salicylate), peppermint oil, clove oil, laurel oil, anise oil, eucalyptus oil, citrus oils, fruit oils, and essences (including those from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, pineapple, etc.), bean and nut essences such as coffee, cocoa, cola, peanut, almond, etc., adsorbed encapsulated flavorings, and mixtures thereof. Also included among the flavoring agents herein are mouthfeel agents. Mouthfeel agents include materials that impart a desired texture or other sensation during the use of the composition. Ingredients that can provide flavor and / or other sensory effects in the oral cavity, including cooling or warming effects, include but are not limited to menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cinnamon, xanthone, α-ionone, allyl guaiacol, thymol, linalool, benzaldehyde, cinnamaldehyde, N-ethyl-p-menthan-3-amine, N,2,3-trimethyl-2-isopropylbutyramide, 3-1-menthoxypropane-1,2-diol, cinnamaldehyde glycerol acetal (CGA), methyl ketone glycerol acetal (MGA), and mixtures thereof. One or more edible flavorings can be present in an amount of about 0.01 wt% to about 5 wt%, about 0.05 to about 2 wt%, about 0.1 wt% to about 2.5 wt%, or about 0.1 to about 0.5 wt% of the total weight of the composition based on the total weight of the edible flavorings.

[0071] In some embodiments, the oral care compositions disclosed herein contain colorants or coloring agents, including but not limited to pigments, dyes, specks, beads, stripes, pearlescent agents, and mixtures thereof. These colorants can impart a specific gloss or reflectivity to the oral surface or to the oral composition itself. In various embodiments, the colorants are operable to provide a white or light-colored coating on the tooth surface as an indicator of the location on the tooth surface that has been effectively contacted by the oral composition, and / or to alter the appearance of the oral composition, particularly the color and / or opacity, to enhance consumer appeal. Any orally acceptable colorant can be used, including FD&C dyes and pigments, talc, mica, magnesium carbonate, calcium carbonate, magnesium silicate, magnesium aluminum silicate, silica, titanium dioxide, zinc oxide, red, yellow, brown, and black iron oxides, ammonium ferric ferrocyanide, manganese violet, ultramarine, titanium mica, bismuth oxychloride, and mixtures thereof. One or more colorants can be present in an amount of about 0.001 wt% to about 20 wt%, such as about 0.01 wt% to about 10 wt% or about 0.1 wt% to about 5 wt% of the total weight of the composition based on the total weight of the pigments.

[0072] In some embodiments, the oral care compositions disclosed herein comprise an anti-caries agent. In some embodiments, the oral care compositions disclosed herein comprise from about 0.001 wt% to about 10 wt%, from about 0.01 wt% to about 10 wt%, from about 0.01 wt% to about 5 wt%, from about 0.01 wt% to about 1 wt%, from about 0.01 wt% to about 0.3 wt%, from about 0.1 wt% to about 5 wt%, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, from about 0.1 wt% to about 0.8 wt%, from about 0.1 wt% to about 0.6 wt%, from about 0.1 wt% to about 0.5 wt% or from about 0.1 wt% to about 0.3 wt% of an anti-caries agent, based on the total weight of the composition. In some embodiments, the anti-caries agent is a fluoride ion source. In some embodiments, the oral care compositions disclosed herein comprise from 0.001 wt% to about 10 wt%, from about 0.01 wt% to about 10 wt%, from about 0.01 wt% to about 5 wt%, from about 0.01 wt% to about 1 wt%, from about 0.01 wt% to about 0.3 wt%, from about 0.1 wt% to about 5 wt%, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, from about 0.1 wt% to about 0.8 wt%, from about 0.1 wt% to about 0.6 wt%, from about 0.1 wt% to about 0.5 wt% or from about 0.1 wt% to about 0.3 wt% of a fluoride ion source, based on the total weight of the composition. Examples of fluoride ion sources that can be used in the oral compositions disclosed herein can be found in U.S. Patent No. 3,535,421 to Briner et al.; U.S. Patent No. 4,885,155 to Parran, Jr. et al. and U.S. Patent No. 3,678,154 to Widder et al. Other examples of fluoride ion sources include, but are not limited to, stannous fluoride, sodium fluoride, potassium fluoride, sodium monofluorophosphate, sodium fluorosilicate, ammonium fluorosilicate, amine fluorides (e.g., N'-octadecyltrimethylenediamine-N,N,N'-tris(2-ethanol)-dihydrofluoride), ammonium fluoride, titanium fluoride, hexafluorosulfate, and combinations thereof. In some embodiments, the fluoride ion source comprises stannous fluoride, sodium fluoride and sodium monofluorophosphate, and mixtures thereof. In some embodiments, the anti-caries agent comprises sodium fluoride. In some embodiments, the oral care compositions disclosed herein are from 0.001 wt% to about 10 wt%, from about 0.01 wt% to about 10 wt%, from about 0.01 wt% to about 5 wt%, from about 0.01 wt% to about 1 wt%, from about 0.01 wt% to about 0.3 wt%, from about 0.1 wt% to about 5 wt%, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, from about 0.1 wt% to about 0.8 wt%, from about 0.1 wt% to about 0.6 wt%, from about 0.1 wt% to about 0.5 wt% or from about 0.1 wt% to about 0.3 wt% sodium fluoride, based on the total weight of the composition.

[0073] In some embodiments, the oral care compositions disclosed herein comprise an anticaries agent as a source of fluoride ions in an amount sufficient to provide from about 25 ppm to about 25,000 ppm, from about 100 ppm to about 20,000 ppm, from about 300 ppm to about 15,000 ppm, from about 500 ppm to about 10,000 ppm, from about 500 ppm to about 8,000 ppm, from about 500 ppm to about 6,000 ppm, from about 500 ppm to about 4,000 ppm, from about 500 ppm to about 2,000 ppm, from about 500 ppm to about 1,800 ppm, or from about 1,000 ppm to about 1,600 ppm fluoride ions, such as about 1,450 ppm fluoride ions. The appropriate level of fluoride ions depends on the particular application. It should be understood that the weight of the fluoride salt providing the appropriate level of fluoride ions will vary according to the weight of the counterion in the salt, and one of ordinary skill in the art can readily determine such amounts. In some embodiments, toothpaste for consumer use comprises an anticaries agent as a source of fluoride ions in an amount sufficient to provide from about 1,000 ppm to about 1,500 ppm fluoride ions, while pediatric toothpaste contains a slightly lower amount. In some embodiments, dentifrices or coatings for professional applications comprise an anticaries agent as a source of fluoride ions in an amount sufficient to provide from about 5,000 ppm to about 25,000 ppm fluoride ions.

[0074] In some embodiments, the oral care compositions disclosed herein comprise an antibacterial or antimicrobial agent. Examples of antibacterial or antimicrobial agents that can be used in the oral compositions of the present disclosure include, but are not limited to, halogenated diphenyl ethers (e.g., triclosan), herbal extracts and essential oils (e.g., rosemary extract, tea extract, magnolia extract, honokiol, butylhonokiol, thymol, menthol, cineole, geraniol, carvacrol, citral, hinokitiol, obovatol, catechol, methyl salicylate, epigallocatechin gallate, epigallocatechin, gallic acid, tartary buckwheat extract, seabuckthorn extract), biguanide preservatives (e.g., chlorhexidine, alexidine or octenidine), quaternary ammonium compounds (e.g., cetylpyridinium chloride (CPC), benzalkonium chloride, tetradecylpyridinium chloride (TPC), N-tetradecyl-4-ethylpyridinium chloride (TDEPC)), phenolic preservatives, hexetidine, octenidine, sanguinarine, povidone iodine, delmopinol, salifluor, metal ions (e.g., zinc salts such as zinc citrate, zinc lactate or zinc chloride; stannous salts such as stannous chloride and stannous fluoride; copper salts; iron salts), sanguinarine, propolis and oxygenating agents (e.g., hydrogen peroxide, buffered sodium perborate or sodium percarbonate), phthalic acid and its salts, monoperphthalic acid and its salts and esters, ascorbyl stearate, oleoyl sarcosine, alkyl sulfates, dioctyl sulfosuccinate, salicylanilide, domiphen bromide, delmopinol, cinprazide and other piperidinyl derivatives, niacin preparations, chlorites, methylparaben and mixtures thereof. In some embodiments, the oral care compositions disclosed herein comprise from about 0.01 wt% to about 10 wt%, from about 0.1 wt% to about 10 wt%, from about 0.5 wt% to about 5 wt%, from about 0.01 wt% to about 5 wt%, from about 0.03 wt% to about 4 wt%, from about 0.05 wt% to about 3 wt%, from about 0.07 wt% to about 2 wt%, from about 0.09 wt% to about 1 wt%, from about 0.1 wt% to about 0.9 wt%, from about 0.1 wt% to about 0.8 wt%, from about 0.1 wt% to about 0.7 wt%, from about 0.1 wt% to about 0.6 wt%, from about 0.1 wt% to about 0.5 wt%, from about 0.1 wt% to about 0.4 wt%, from about 0.2 wt% to about 0.4 wt% of an antibacterial or antimicrobial agent based on the total weight of the composition. The amount of the antibacterial agent will vary depending on the type of oral care composition. For example, the level used in a toothpaste oral care composition such as toothpaste is 5 to 15 times the level used in a solution-based oral care composition for coating the enamel layer, such as a mouthwash. For example, a mouthwash containing triclosan can contain, for example, about 0.03 wt% of triclosan, while a toothpaste containing triclosan can contain, for example, about 0.3 wt% of triclosan.In some embodiments, the antimicrobial agent is selected from triclosan, cetylpyridinium chloride, magnolia extract, magnolol, honokiol, butyl magnolol, propyl honokiol, zinc chloride, zinc lactate, zinc citrate, stannous fluoride, and stannous chloride. Some components, such as stannous fluoride, may be included in an amount sufficient to function as an antibacterial and anti-caries agent. For example, stannous fluoride may be present in an amount of from about 0.01 wt% to about 1 wt%, and provides antibacterial and anti-caries properties to the composition.

[0075] The oral composition may also include a tooth whitening agent or a tooth bleaching agent. Suitable whitening and bleaching agents include peroxides, metal chlorites, and / or persulfates. Peroxides include hydrogen peroxide, hydrogen peroxide, peroxides of alkali metals and alkaline earth metals, organic peroxides, peroxyacids, and mixtures thereof. Peroxides of alkali metals and alkaline earth metals include lithium peroxide, potassium peroxide, sodium peroxide, magnesium peroxide, calcium peroxide, barium peroxide, and mixtures thereof. Other peroxides include perborates, carbamide peroxide, and mixtures thereof. Suitable metal chlorites may include calcium chlorite, barium chlorite, magnesium chlorite, lithium chlorite, sodium chlorite, and potassium chlorite. Depending on the reagent selected, such reagents may be added in an effective amount based on the total weight of the composition, e.g., from about 1 wt% to about 20 wt% by weight.

[0076] The compositions of the present disclosure may also include a tartar control (anti-tartar) agent. Tartar control agents useful herein include salts of any of these reagents, such as their alkali metal salts and ammonium salts: phosphates and polyphosphates (e.g., pyrophosphates), polyaminopropanesulfonic acid (AMPS), polyolefin sulfonates, polyolefin phosphates, diphosphonates such as azacycloalkane-2,2-diphosphonates (e.g., azacycloheptane-2,2-diphosphonic acid), N-methylazacyclopentane-2,3-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid (EHDP), and ethane-1-amino-1,1-diphosphonic acid esters, phosphonatoalkanecarboxylic acids. Useful inorganic phosphates and polyphosphates include sodium dihydrogen phosphate, disodium hydrogen phosphate, and trisodium phosphate, sodium tripolyphosphate, tetrapolyphosphoric acid, mono-, di-, tri-, and tetrasodium pyrophosphate, sodium trimetaphosphate, sodium hexametaphosphate, and mixtures thereof. Other useful tartar control agents include polycarboxylate polymers and polyvinyl methyl ether / maleic anhydride (PVM / MA) copolymers, such as In some embodiments, the tartar control agent is a polycarboxylate polymer or a polyvinyl methyl ether / maleic anhydride (PVM / MA) copolymer.

[0077] The compositions of the present disclosure may include a saliva stimulant, for example, for improving dry mouth. Any orally acceptable saliva stimulant may be used, including but not limited to edible acids, such as citric acid, lactic acid, malic acid, succinic acid, ascorbic acid, adipic acid, fumaric acid, and tartaric acid, and mixtures thereof. One or more saliva stimulants are optionally present in a saliva-stimulating effective total amount.

[0078] The compositions of the present disclosure may contain one or more desensitizing or anti-sensitivity agents, such as potassium salts, such as potassium nitrate, potassium bicarbonate, potassium chloride, potassium citrate, and potassium oxalate; capsaicin; eugenol; strontium salts; zinc salts; chloride salts, and combinations thereof. Depending on the reagent selected, such reagents may be added in an effective amount, for example, from about 1 wt% to about 20 wt%, based on the total weight of the composition. The oral compositions according to the present disclosure may also treat hypersensitivity by blocking dentinal tubules when applied to teeth.

[0079] In some embodiments, the oral compositions of the present disclosure contain antioxidants. Any orally acceptable antioxidant may be used, including butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), vitamin A, carotenoids, vitamin E, flavonoids, polyphenols, ascorbic acid, herbal antioxidants, chlorophyll, melatonin, and mixtures thereof.

[0080] In some embodiments, the compositions of the present disclosure contain nutrients. Suitable nutrients include vitamins, minerals, amino acids, and mixtures thereof. Vitamins include vitamins C and D, thiamine, riboflavin, calcium pantothenate, niacin, folic acid, nicotinamide, pyridoxine, cyanocobalamin, para-aminobenzoic acid, bioflavonoids, and mixtures thereof. Nutritional supplements may include amino acids (such as L-tryptophan, L-lysine, methionine, threonine, L-carnitine, and L-carnitine), lipotropics (such as choline, inositol, betaine, and linoleic acid), and mixtures thereof.

[0081] Suitable enzymes for the oral compositions of the present disclosure are described in U.S. Patent No. 7,939,306, which is incorporated by reference. These enzymes include proteinaceous substances in the class of proteases, which break down or hydrolyze proteins (proteases). These proteolytic enzymes are obtained from natural sources or by the action of microorganisms having a nitrogen source and a carbon source. Examples of proteolytic enzymes useful in the practice of the present invention include papain, bromelain, chymotrypsin, ficin, and alkaline protease.

[0082] Papain obtained from the latex of the papaya tree is a proteolytic enzyme suitable for the compositions of the present disclosure and can be incorporated into oral care compositions in an amount of about 0.1 wt% to about 10 wt% or about 0.5 wt% to about 5 wt% of the total weight of such papain having an activity of 150 to 300 MCU / mg as determined by the Milk Clot Assay Test of Biddle Sawyer Group (see J. Biol. Chem., Vol. 121, pp. 737 - 745).

[0083] Another enzyme that can be included in the compositions of the present disclosure is a carbohydrase. Suitable examples of carbohydrases include, but are not limited to, glucoamylase, α- and β-amylases, dextranase, and mutanase. Glucoamylase is glucoamylase derived from Aspergillus niger cultured by fermentation. This enzyme can hydrolyze the α-D-1,6 glycosidic branch points and α-1,4 glycosidic bonds of oligosaccharides. The oral composition can contain about 0.001 wt% to about 2 wt% of the carbohydrase, or about 0.01 wt% to about 0.55 wt% of the carbohydrase, based on the total weight of the composition.

[0084] The composition may also include a lipase, such as a plant lipase, gastric lipase, or pancreatic lipase. The lipase can be derived from a selected strain of Aspergillus niger and exhibits random cleavage at the 1,3 positions of fats and oils. The enzyme has maximum lipolytic activity at pH 5.0 to 7.0 when assayed with olive oil. The lipase can be included in the oral composition in an amount in the range of about 0.010 wt% to about 5.0 wt% or about 0.02 wt% to about 0.10 wt% based on the total weight of the composition.

[0085] The presence of tannase is also beneficial for promoting the decomposition of extrinsic staining. Tannase has been purified from Aspergillus niger and Aspergillus sydowii and can be used to hydrolyze tannins, which are known to discolor the tooth surface.

[0086] Other suitable enzymes that can be included in the oral compositions of the present disclosure include lysozyme derived from egg white, which comprises a single polypeptide chain crosslinked by four disulfide bonds and has a molecular weight of 14,600 daltons. The enzyme can exhibit antibacterial properties by promoting the hydrolysis of the bacterial cell wall and cleaving the glycosidic bond between carbon 1 of N-acetylmuramic acid and carbon 4 of N-acetyl-D-glucosamine, which polymerize in vivo to form the cell wall polysaccharide. In addition, pectinase is an enzyme present in most plants that promotes the hydrolysis of the polysaccharide pectin into sugars and galacturonic acid.

[0087] In some embodiments, the enzyme is one or more enzymes selected from proteases, carbohydrases, lipases, tannases, lysozymes, pectinases, and combinations thereof. In certain cases, the protease is selected from papain, bromelain, chymotrypsin, ficin, alkaline protease, and combinations thereof. In some cases, the carbohydrase is selected from glucoamylase, α - amylase, β - amylase, dextranase, allosteric enzyme, and combinations thereof.

[0088] The compositions of the present disclosure may also include other conventional reagents commonly included in oral care compositions, such as anti - plaque agents, detergents, binders, foam regulators, whitening agents (e.g., abrasive silica or peroxide), or any combination thereof. Each of the anti - plaque agent, detergent, binder, and foam regulator can be included in any amount suitable for the oral composition in which it is present.

[0089] General synthesis of star polymers

[0090] The star polymers of the present disclosure can be synthesized using conventional techniques known to those skilled in the art and readily available starting materials. Generally, the compounds provided herein are conveniently obtained via standard organic and polymer chemistry synthetic methods. The following description of the synthetic methods is intended to illustrate but not limit the general procedures for preparing the polymers of the present disclosure.

[0091] Typically, the star polymers of formula (I) can be synthesized as shown in the following examples. For example, the polymer can be prepared by mixing a monomer with a chain - transfer agent (CTA) and a radical initiator (e.g., AIBN) in a suitable solvent (e.g., acetonitrile and / or DMF). The CTA can be appropriately selected to obtain relatively linear polymers or 3 - arm, 4 - arm, 6 - arm, 8 - arm, 10 - arm, or 12 - arm star polymers. For example, to obtain relatively linear polymers, the CTA can be methyl 3 - mercaptopropionate (MMP). To obtain 4 - arm star polymers, the CTA can be pentaerythritol tetra(3 - mercaptopropionate) (PETMP). To obtain 6 - arm star polymers, the CTA can be dipentaerythritol hexa(3 - mercaptopropionate) (DPEHMP). Given the above description and the following examples, determining the appropriate CTA to prepare 3 - arm, 8 - arm, 10 - arm, and 12 - arm star polymers will be within the ability of those of ordinary skill in the art.

[0092] The monomer used in the reaction is not restricted and can be selected based on the desired properties of the final star polymer.

[0093] Method of use

[0094] The present disclosure also provides methods of using the oral compositions of the present disclosure. The compositions according to the present disclosure can be administered to human or other mammalian subjects or applied to human or other mammalian subjects. The composition can be suitable for oral administration or application to a human or mammalian subject. Generally, the composition can be used to inhibit microbial biofilm formation on the enamel layer and / or degrade microbial biofilms.

[0095] In various embodiments, the present disclosure provides a method of forming a layer on a tooth surface, comprising administering to a subject an oral care composition according to the present disclosure.

[0096] In various embodiments, the present disclosure provides a method of inhibiting bacterial attachment to teeth, comprising administering to a subject an oral care composition according to the present disclosure. In particular, it has been found that the star polymers of the present disclosure effectively bind to the HAP surface (e.g., tooth surface), thereby providing a protective layer and preventing and / or inhibiting the attachment of various bacteria to the HAP surface. Advantageously, compared to a comparative linear polymer, the star polymer shows an increased binding affinity for the HAP surface. This is particularly surprising given the ability of the comparative linear polymer to more easily stretch through the HAP surface. Similarly, the star polymers of the present disclosure have surprisingly been shown to significantly reduce the attachment of bacteria such as Actinomyces viscosus and Streptococcus oralis to the HAP surface.

[0097] In various embodiments, the present disclosure provides the use of star polymers in inhibiting bacterial attachment to a surface. In an embodiment, the surface comprises hydroxyapatite (e.g., a tooth). In an embodiment, the bacteria can include Actinomyces viscosus and / or Streptococcus oralis.

[0098] The foregoing description is given for clarity of understanding only, and should not be construed as an undue limitation therefrom, since modifications within the scope of the present disclosure will be apparent to those of ordinary skill in the art.

[0099] The oral compositions and methods according to the present disclosure can be better understood in light of the following examples, which are intended to illustrate the compositions and methods only and are not intended to limit their scope in any way.

[0100] Example

[0101] Materials

[0102] 2,2'-Azobisisobutyronitrile (AIBN) and pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) were purchased from Sigma-Aldrich Co., LLC. Dipentaerythritol hexa(3-mercaptopropionate) (DPEHMP) was purchased from TCI America. Methacryloyloxyethylthiocarbamyl rhodamine B was purchased from Polysciences. Trifluoroacetic acid (TFA) and solvents were purchased from ThermoFisher Scientific, Inc. tert-Butyl acrylate (t-BuA), methyl acrylate, and methyl 3-mercaptopropionate (MMP) were purchased from Acros Organics, respectively. The inhibitors of these monomers were removed by alumina before use. Other chemicals and solvents were used without further purification. 1 1H NMR was performed using a Varian MR400 (400 MHz) and analyzed using VNMRJ 3.2 and MestReNova. Gel permeation chromatography (GPC) analysis was carried out using a Waters 1515 HPLC instrument with THF as the eluent, equipped successively with Waters Styragel (7.8×300 mm) HR 0.5, HR 1, and HR 4 columns, and detected by a differential refractometer (RI). Sintered HAP disks (0.5 cm in diameter) were purchased from Himed, Inc.

[0103] Example 1: Synthesis of Polymer

[0104] Synthesis of tert-Butyl Poly(acrylate) (tBu PAA) Homopolymer

[0105] Under the conditions provided in Table 1 below, tert-butyl acrylate (t-BuA), AIBN, and a chain transfer agent (CTA) (MMP, PETMP, or DPEHMP) were mixed in a flask in acetonitrile. To prepare a comparative linear polymer, MMP was used as the CTA. To prepare 4-arm star polymers, PETMP was used as the CTA. To prepare 6-arm star polymers, DPEHMP was used as the CTA. Oxygen was removed by bubbling nitrogen for 10 minutes, and the solution was stirred at 70 °C for 16 hours. The reaction was cooled to room temperature. The solvent was removed by evaporation under reduced pressure. The resulting residue was dissolved in diethyl ether, and the polymer was separated by precipitation in a methanol:water [50:50 (v / v)] mixture. The polymer arm length (DP) was calculated by comparing the integral peaks of the -OCH2- group of the chain transfer agent with the -CH- polymer backbone. The number-average molecular weight (M n ) was calculated using the DP and molecular weight of the monomer and CTA. Gel permeation chromatography molecular weight results were determined using a calibration curve based on polystyrene standard samples. 11H NMR (CDCl3, 400 MHz) δ: 4.21 - 4.06 (s, 2H, -OCH2- of PETMP), 2.85 - 2.51 (brs, 4H, -SCH2CH2-), 2.37 - 2.07 (brs, 1H, -CH-), 1.97 - 1.14 (brs, 11H, -CH3 and -CH2-).

[0106] The tert-butyl groups of the polymer were then removed by adding trifluoroacetic acid (TFA) (5 mL per 1 g of polymer). After stirring for 30 minutes, the TFA was removed by purging with nitrogen. The residue was dissolved in methanol and the deprotected polymer was isolated by precipitation in excess diethyl ether. Subsequently, the precipitate was dissolved in distilled water and lyophilized to yield the desired product. 1 1H NMR (DMSO, 400 MHz) 2.4 - 2.0 (brs, 1H, -CH-), 1.8 - 1.2 (brs, 2H, -CH2-).

[0107] The synthesis of star polymers generally follows the following protocol; while a 4-arm star polymer protocol is shown, other essentially similar protocols using essentially similar reactants can be used to synthesize star polymers with different numbers of arms, different chain lengths, etc.:

[0108]

[0109] Table 1. Polymerization conditions for tBu PAA homopolymers

[0110]

[0111] Linear, 4-arm, and 6-arm star polymers are denoted as Lin-X, 4Star-X, and 6Star-X, respectively, where X represents the DP of each arm determined for the protected t-BuA polymer.

[0112] Not determined.

[0113] The characterization data of the resulting polymers are provided in Table 2.

[0114] Table 2. Characterization of tBu PAA homopolymers

[0115]

[0116] As shown in Table 2, as the ratio of CTA to monomer increases, the molecular weight of the polymer (measured by GPC and NMR) decreases, yielding a series of star and control linear polymers with Mn and Mw of approximately 2,000 to approximately 200,000 g / mol.

[0117] To detect chain transfer polymerization, the relationship between the ratio of the thiol group (present in the exemplary chain transfer agent for chain transfer, although other moieties can also be used) to the monomer and the polymer chain length was examined. Mayo plots (1 / DP or 1 / Mn versus [SH] / [monomer]) for comparing linear polymers, as well as 4-arm and 6-arm star polymers, showed a linear correlation based on Equation (1)( Figure 1 ) and the C tr value (i.e., the chain transfer constant) for each CTA was determined as the slope of the fitted line in the Mayo plot (C tr = 0.91 (Lin), 1.06 (4Star), 0.97, (6Star)).

[0118]

[0119] Furthermore, the plot of 1 / Mn (determined by GPC) versus [SH] / [monomer] (i.e., [number of thiol groups in CTA] x [CTA] / [M]) also showed a linear correlation( Figure 1 ). These results indicate that the polymerization is driven by an independent chain transfer process initiated by each thiol group of the CTA, thus supporting the formation of star polymers. These results further suggest that polymer chains grow from each CTA arm and that the average polymer chain arm length can be controlled by changing the ratio of CTA to monomer.

[0120] Synthesis of tert-Butyl Poly(acrylic acid) / Methacrylate (t-Bu PAA / MA) Copolymers

[0121] Under the conditions provided in Table 3 below, a random t-Bu PAA copolymer with methacrylate (MA) was synthesized using the same method as in Example 1. The CTA (i.e., PETMP) was used in an amount of 0.098 g (0.2 mmol), AIBN was used in an amount of 1.56 mmol, and acetonitrile was used in an amount of 40 g. The ratio of CTA to monomer was 0.001.

[0122] Table 3. Polymerization Conditions for tBu PAA / MA Copolymers

[0123]

[0124] The 4-arm star polymer is denoted as 4Star y -X, where X represents the DP of each arm and y represents the molar percentage of MA in the polymer.

[0125] As shown in Table 3, the molar percentage of methacrylate in the polymer was close to the initial feed ratio, indicating that the MA monomer was quantitatively incorporated into the polymer chain.

[0126] Table 4. Characterization of tBu PAA / MA Copolymers

[0127]

[0128] Therefore, Example 1 demonstrates the synthesis of star polymers according to the present disclosure.

[0129] Example 2: HAP Binding Assay

[0130] The binding behavior of rhodamine-labeled polymers to hydroxyapatite (HAP) (as a model of tooth enamel surface) was investigated. Under the conditions provided in Table 5 below, rhodamine B-labeled copolymers were synthesized by the same method as in Example 1, using methacryloyloxyethylthiocarbamoyl rhodamine B (0.1 mol% of the total monomers). For the comparative linear polymer, 0.156 mmol (0.0256 g) of AIBN was used. For the star polymer, 0.078 mmol (0.013 g) of AIBN was used. The components were mixed in a 2:1 acetonitrile:DMF solution.

[0131] Table 5. Polymerization Conditions of Rhodamine B-Labeled Polymers

[0132]

[0133] Polymer solutions with different concentrations (pH 7, adjusted with aqueous NaOH, 0.5 mL, 0.04, 0.08, 0.16, 0.31, 0.63, and 1.25 g / L) were incubated with HAP (30 mg / mL) in a 1.5 ml tube in a buffer solution. The solution was gently shaken using a mechanical shaker at room temperature for 2 hours and then centrifuged at 10,000 rpm for 10 minutes. The fluorescence emission intensity of the supernatant (excitation wavelength = 553 nm, emission wavelength = 627 nm) was measured and compared with the fluorescence emission intensity of the same concentration polymer sample without HAP to calculate the amount of free polymer (C eq ) in the supernatant at equilibrium, and the amount of polymer adsorbed on the HAP surface (q). As the polymer concentration increased, the amount of polymer adsorbed on the HAP surface increased and seemed to level off at high concentrations. The adsorption isotherm of the Langmuir adsorption model is represented by Equation 2:[[]]

[0134]

[0135] Or its linear form, as shown in Equation 3:[[]]

[0136]

[0137] Where q max and K dThey are the maximum amount of adsorbed polymer and the dissociation constant, respectively.

[0138] The data are linear and well fitted by Equation 2, except for the data points at the highest polymer concentrations. Without being bound by theory, this may be due to polymer aggregation in solution, which has been reported to occur due to the adsorption of acrylate polymers onto HAP. q max and K d values were calculated from these data and are shown in Table 6 below along with other polymer characterization data. The number-average molecular weight (M n ) of the deprotected acrylic polymer that could not be measured by NMR was estimated based on the DP of the protected tBu polymer and the molecular weights of the CTA and acrylic acid.

[0139] Table 6. Polymer Characterization and HAP Binding

[0140]

[0141] As shown in Table 6 and Figure 2 A, the q max values (i.e., adsorption onto the HAP surface) of the 4-arm and 6-arm star polymers are lower than the q max values of the comparative linear polymers. Without being bound by theory, this may be due to the larger molecular size of the star polymers, which occupy a larger area on the hydroxyapatite surface compared to the comparative linear polymers, and thus fewer star polymers can bind to the hydroxyapatite surface. However, in contrast, the dissociation constant K d values of the star polymers are significantly smaller than those of the comparative linear polymers ( Figure 2 B), indicating that the star polymers have a stronger adsorption force onto the hydroxyapatite surface than the comparative linear polymers. Without being bound by theory, this is believed to be due to the larger polymer size of the star polymers, which have more contact points for binding on the hydroxyapatite surface. The 4-arm and 6-arm star polymers show similar q max and K d , indicating that these polymers occupy similar regions on the HAP surface and have similar binding affinities.

[0142] The q max and K d values of the 4-star and comparative linear polymers appear to flatten out at large DPs ( Figure 2C, 2D). These results indicate that once the size of the polymer becomes large enough, the maximum number of adhered polymers and their binding affinity do not increase. Without being bound by theory, it is believed that this balance in the HAP-binding behavior of the polymer occurs because the anionic carboxyl groups of the polymer side chains bind ligands to the HAP surface through electrostatic interactions. Thus, as the polymer chain grows longer and has more carboxyl side chains, the binding affinity of the polymer for HAP increases. However, the binding of the carboxyl side chains to the HAP surface requires the polymer chain to flatten and / or stretch on the HAP surface, which is unfavorable due to a large entropy loss. Therefore, the binding of the polymer depends on the balance between two driving forces to maximize the number of binding sites for carboxyl groups on the HAP surface (enthalpy gain) and minimize the strain on the polymer chain (entropy penalty). As the polymer DP increases, the number of carboxyl side chain groups increases, thereby increasing their binding. However, once the polymer is long enough, it is difficult to confine the polymer chain to the HAP surface due to entropy loss, resulting in the flattening of q max and K d .

[0143] In addition, random copolymers with the hydrophobic monomer MA (which is more hydrophobic than acrylate and even alkylated acrylates such as tert-butyl acrylate) show a change in binding with increasing MA composition ( Figure 3 ). Without being bound by theory, this binding behavior can be explained by the interaction between the electrostatic binding of carboxylate groups to HAP and the intra- and intermolecular associations of MA groups. Increasing the MA composition reduces the number of carboxyl side chains, which in turn decreases the binding affinity of the polymer for HAP (higher K d ). On the other hand, the hydrophobic groups may associate intramolecularly (within the same star polymer), which may prevent the extension of the polymer chain for binding and also result in a low binding affinity (higher K d ). Thus, the increase in the K d value at a low percentage of MA may indicate that intramolecular association and / or a decrease in the number of acidic groups dominate. However, the high affinity (low K d ) value of the polymer with 55% MA indicates that intermolecular hydrophobic association between star polymers may play an important role in stabilizing the polymer layer. On the other hand, q max also increases slightly, indicating a more compact conformation of the bound polymer chains (occupying a smaller surface area). The polymer with 55% MA content shows a lower q max , indicating that the polymer chains are more likely to swell due to the increased intermolecular association of MA groups between star polymers, which is in good agreement with the low K d value. These results indicate that the binding behavior of the polymer to the HAP surface can be controlled by their hydrophobicity.

[0144] Example 2 demonstrates that, compared to the comparative linear polymers, the star polymers of the present disclosure can bind to the HAP surface and have a higher binding affinity. Example 2 further demonstrates that hydrophobic interactions caused by the methacrylate monomers can help stabilize the polymers on the HAP surface.

[0145] Example 3: Antibacterial Adhesion Assay

[0146] A variety of comparative linear and star polymers with a DP in the range of 100 to 200 and different degrees of hydrophobicity were selected to examine the effect of the polymer composition and shape on the antibacterial attachment activity.

[0147] HAP-coated MBECs were treated with a polymer solution (1 wt%, pH 6.5, adjusted with NaOH or HCl) TM coverslips and allowed to shake in an incubator at 37 °C for 1 hour. After treatment, the excess polymer solution was removed from the MBEC TM coverslips by soaking in tryptic soy broth (TSB) for 10 - 15 seconds for three cycles, with the TSB broth replaced in each new cycle. Then the untreated and polymer-treated MBEC TM coverslips were incubated with an overnight culture of freshly prepared mixed viscous Actinomyces viscosus (ATCC#43146) and Streptococcus oralis (ATCC#35037) at 37 °C for 3 hours. After incubation, the MBEC TM coverslips were immersed in TSB and sonicated twice for 2 minutes each to detach the bacteria bound to the HAP into the TSB. BacTiter-Glo Microbial Cell Viability Assay was used for the resuspended TSB to determine the percent reduction. The percent reduction was calculated by the following equation: percent reduction = 100 x (bacteria attached to the untreated surface - bacteria attached to the polymer-treated surface) / bacteria on the untreated surface. One-way analysis of variance (ANOVA) was used to evaluate the treatment effects. Tukey's multiple comparison test was used to evaluate pairwise treatment differences. p < 0.05 was used to indicate significant statistical differences.

[0148] As Figure 4 shown, relative to the untreated control, all polymers reduced the attachment of oral bacteria to the HAP surface by 17 - 54%. Compared to the comparative linear and star homopolymers, the hydrophobic random linear copolymer (LinMA48-194) and the 4-arm star copolymers (4StarMA34-171 and 4StarMA56-215) showed higher percent reductions in bacterial attachment (43 - 54%), indicating that the hydrophobic monomer groups enhance the ability of the polymers to reduce bacterial attachment.

[0149] Therefore, Example 3 further demonstrates that introducing hydrophobic groups into the star polymers of the present disclosure results in a reduced improvement in bacterial attachment to the HAP surface compared to relatively more hydrophilic star polymers.

[0150] As shown in Examples 2 and 3, these data further indicate that while the hydrophobicity of the polymers results in an enhanced antibacterial adhesion effect, the enhanced effect is not due to differences in the inherent binding properties of the polymers to the HAP surface, but rather is related to the physicochemical properties of the polymers or the conformation of the polymers on the HAP surface.

[0151] The ability of the polymer to provide an antibacterial attachment effect to the oral surface only occurs when the polymer can sufficiently bind to the oral surface (e.g., the K of the copolymer d is less than about 5 μmol / L). The multi-arm star polymers bind significantly better to HAP. Similarly, the hydrophobicity of the polymers significantly reduces bacterial attachment, even if it does not significantly affect K d . Therefore, the data of Examples 2 and 3 indicate that hydrophobic star polymers will provide the most effective oral compositions because such star polymers exhibit significantly improved binding to HAP as well as improved antibacterial properties.

[0152] Example 4: Contact Angle Measurement

[0153] Contact angles were measured on an Attension Theta instrument from Biolin Scientific. Data were analyzed using OneAttension software v 2.9. Briefly, 1.0 wt% polymer solutions were prepared and their pH was adjusted to 6.5 with concentrated NaOH or HCl. Since the solution droplets would immediately be absorbed into the hydroxyapatite, surface modification was required prior to treatment with the polymer solution to obtain stable droplets for comparison. Sintered HAP was first treated with modified artificial saliva 47 for 1 h (see Supporting Information). Thereafter, the discs were soaked in 2 mL of the polymer solution on an orbital shaker for 3 h. The discs were removed and rinsed slightly to remove excess or loosely bound material and then dried overnight. Contact angle measurements were collected and averaged using four individual measurements of 3 μL droplets.

[0154] As Figure 5 shown, for most of the polymer samples, an increase in contact angle greater than 7° was observed, indicating that most of the polymer-treated surfaces were more hydrophobic than the untreated controls. The magnitude of this difference also reflected compositional variations in the polymers themselves. For example, the highest contact angle for 4StarMA 56 -171 was 87.6°, which was due to the 56% MA concentration in the polymer.

[0155] Example 4 demonstrates that the star polymers of the present disclosure are effective in modulating the properties and functions of the HAP surface, even in the presence of a protein layer, which can lead to preventing oral bacteria attachment.

[0156] The results of the above examples indicate that surface attachment may depend more on the polymer shape (e.g., linear vs. star), while antibacterial attachment may depend more on the polymer composition (e.g., hydrophobicity).

Claims

1. An oral care composition comprising a star polymer and an orally acceptable carrier, wherein the star polymer has a structure according to formula (I): Wherein: Each R 1 independently contains H or an acrylate polymer, Each n is independently from 5 to 500, Each X is independently O, NR 4 or S, where R 4 comprises H or C 1-6 alkyl R 2 comprising H, C 1-8 an alkyl or functionalized acrylate polymer, and Each R 3 independently contains H, C 1-8 alkyl or C 1-8 alkyl phosphate ester.

2. The oral care composition according to claim 1, wherein each n is independently from 10 to 400.

3. The oral care composition according to claim 1, wherein each n is independently from 15 to 300.

4. The oral care composition according to claim 1, wherein X is O.

5. The oral care composition according to claim 1, wherein X is S.

6. The oral care composition according to claim 1 or 2, wherein R 1 is an acrylate polymer selected from polymethacrylate, poly(ethyl acrylate), poly(propyl acrylate), poly(butyl acrylate), and poly(C 1-8 alkyl ester acrylate).

7. The oral care composition according to claim 1 or 2, wherein R 2 is a functionalized acrylate copolymer having a structure according to one of the following formulas:

8. The oral care composition according to claim 1 or 2, wherein the number average molecular weight of the star polymer is from 1,000 to 700,000 g / mol, from 1,500 to 500,000 g / mol, from 1,750 to 250,000 g / mol, or from 2,000 to 200,000 g / mol.

9. The oral care composition according to claim 1 or 2, wherein the weight average molecular weight of the star polymer is from 1,000 to 700,000 g / mol, from 1,500 to 500,000, from 1,750 to 250,000 or from 2,000 to 200,000 g / mol.

10. The oral care composition according to claim 9, wherein the weight average molecular weight of the star polymer is from 10,000 to 150,000 g / mol.

11. The oral care composition according to claim 1 or 2, wherein the molar percentage of methacrylate repeating units in the star polymer is from 5 to 70 mol%, from 25 to 65 mol% or from 40 to 60 mol%.

12. The oral care composition according to claim 1 or 2, wherein the composition comprises from 0.1 wt.% to 10 wt.%, from 0.5 wt.% to 7.5 wt.%, from 1.0 wt.% to 5 wt.%, from 0.5 wt.% to 4 wt.%, from 0.5 wt.% to 3 wt.%, from 0.5 wt.% to 2 wt.%, from 1 wt.% to 10 wt.%, from 1 wt.% to 7 wt.%, from 1 wt.% to 6 wt.%, or from 2 wt.% to 4 wt.% by weight of the star polymer, based on the total weight of the composition.

13. The oral care composition according to claim 1 or 2, wherein the composition is a mouthwash, toothpaste, tooth gel, tooth powder, non-abrasive gel, mousse, foam, oral spray, lozenge, or pet care product.

14. The oral care composition according to claim 1 or 2, wherein the orally acceptable carrier comprises water, a thickening agent, a buffering agent, a humectant, a surfactant, an abrasive, a sweetening agent, a flavoring agent, a food flavor, a coloring agent, an anti-caries agent, an antibacterial or antimicrobial agent, an anti-plaque agent, a cleansing agent, an adhesive, a foam regulator, a whitening agent, a tartar control agent, a saliva stimulant, an anti-sensitivity or desensitizing agent, an antioxidant, a nutrient, a preservative, an enzyme, or any combination thereof.

15. The composition according to claim 14, wherein the antimicrobial agent is selected from triclosan, cetylpyridinium chloride, magnolia bark extract, magnolol, honokiol, butylmagnolol, propylene glycol, zinc chloride, zinc lactate, zinc citrate, stannous fluoride, and stannous chloride.

16. The composition according to claim 14, wherein the tartar control agent is a polycarboxylate polymer or a polyvinyl methyl ether / maleic anhydride (PVM / MA) copolymer.

17. The composition according to claim 14, wherein the enzyme is one or more enzymes selected from protease, carbohydrase, lipase, tannase, lysozyme, pectinase, and combinations thereof.

18. The composition according to claim 17, wherein the protease is selected from papain, bromelain, chymotrypsin, ficin, alkaline protease, and combinations thereof.

19. The composition according to claim 17, wherein the carbohydrase is selected from glucoamylase, α - amylase, β - amylase, dextranase, mutanase, and combinations thereof.

20. Use of the oral care composition according to any one of claims 1 - 19 in the manufacture of a medicament for inhibiting bacterial attachment to teeth.

21. Use of the oral care composition according to any one of claims 1 - 19 in the manufacture of a medicament for forming a layer on the tooth surface.

22. A star polymer having the structure of formula (I): Wherein: Each R 1 independently contains H or an acrylate polymer, Each n is independently from 5 to 500, Each X is independently O, NR 4 or S, where R 4 comprises H or C 1-6 alkyl R 2 containing H, C 1-8 an alkyl or functionalized acrylate polymer, and Each R 3 independently contains H, C 1-8 alkyl or C 1-8 alkyl phosphate.

23. The star polymer according to claim 22, wherein each n is independently from 10 to 400.

24. The star polymer according to claim 22, wherein each n is independently from 15 to 300.

25. The star polymer according to claim 22, wherein X is O.

26. The star polymer according to claim 22, wherein X is S.

27. The star polymer according to claim 22 or 23, wherein R 1 is an acrylate polymer selected from polymethacrylate, poly(ethyl acrylate), poly(propyl acrylate), poly(butyl acrylate), and poly(C 1-8 alkyl ester acrylate).

28. The star polymer according to claim 22 or 23, wherein R 2 is a functionalized acrylate copolymer having a structure according to one of the following formulas:

29. The star polymer according to claim 22 or 23, wherein the number average molecular weight of the star polymer is from 1,000 to 700,000 g / mol, 1500 to 500,000 g / mol, 1750 to 250,000 g / mol, or 2000 to 200,000 g / mol.

30. The star polymer according to claim 22 or 23, wherein the weight average molecular weight of the star polymer is from 1,000 to 700,000 g / mol, 1500 to 500,000, 1750 to 250,000, or 2000 to 200,000 g / mol.

31. The star polymer according to claim 30, wherein the weight average molecular weight of the star polymer is from 10,000 to 150,000 g / mol.

32. The star polymer according to claim 22 or 23, wherein the star polymer has a hydrophobic monomer content of at least 5 mol%.

33. The star polymer according to claim 22 or 23, wherein the molar percentage range of methacrylate repeating units in the star polymer is from 5 to 70 mol%, 25 to 65 mol%, or 40 to 60 mol%.

34. The star polymer according to claim 22 or 23, wherein the star polymer has a water contact angle of at least 60° on the surface of hydroxyapatite.

35. The star polymer according to claim 22 or 23, wherein the dissociation constant of the star polymer is less than 5 μmol / L.

36. The star polymer according to claim 22 or 23, wherein the dissociation constant of the star polymer is 5 μmol / L, 4.5 μmol / L, 4 μmol / L, 3.5 μmol / L, 3 μmol / L, 2.5 μmol / L, 2 μmol / L, 1.5 μmol / L, or 1 μmol / L.

37. The star polymer according to claim 22 or 23, wherein the star polymer has a structure selected from the group consisting of: wherein each n and each m are independently in the range of 5 to 500, 10 to 400, or 15 to 300.

38. The star polymer for inhibiting the attachment of bacteria to a surface according to claim 22 or 23, wherein the surface comprises hydroxyapatite.

39. The star polymer according to claim 38, wherein the surface is a tooth.

40. The star polymer according to claim 38, wherein the bacteria include Actinomyces viscosus, Streptococcus oralis, or a combination thereof.

41. The star polymer for an oral care composition according to claim 22 or 23.

42. The star polymer according to claim 41, wherein the oral care composition comprises an orally acceptable carrier.

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