Dentin tubule occlusion using catechol-based compounds

Abstract

The present invention provides methods for occluding dentin tubules including contacting the tooth enamel with material comprising catechol, semi-quinone, or quinone. Advantageously, the catechol or catechol-containing material can include poly-catechol styrene (PCS).

Description

DENTIN TUBULE OCCLUSION USING CATECHOL-BASED COMPOUNDSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 551,585, filed February 9, 2024, which is incorporated by reference herein in its entirety for any and all purposes.FIELD OF INVENTION

[0002] The present invention relates to the field of dental and hard tissue treatment, including but not limited to tooth surface restoration and hard tissue modification. More specifically, the present invention relates to occlusion of dentin tubules of the tooth the catecholcontaining materials used for such dentin tubule occlusion.BACKGROUND

[0003] Dental enamel is the hardest and most mineralized tissue in extinct and extant vertebrate species and provides maximum durability that allows teeth to function as weapons and / or tools as well as for food processing. Enamel development and mineralization is an intricate process tightly regulated by cells of the enamel organ called ameloblasts. These heavily polarized cells form a monolayer around the developing enamel tissue and move as a single forming front in specified directions as they lay down a proteinaceous matrix that serves as a template for crystal growth. Ameloblasts maintain intercellular connections creating a semi-permeable barrier that at one end (basal / proximal) receives nutrients and ions from blood vessels, and at the opposite end (secretory / apical / distal) forms extracellular crystals within specified pH conditions. In this unique environment, ameloblasts orchestrate crystal growth via multiple cellular activities including modulating the transport of minerals and ions, pH regulation, proteolysis, and endocytosis. In many vertebrates, the bulk of the enamel tissue volume is first formed and subsequently mineralized by these same cells as they retransform their morphology and function. Cell death by apoptosis and regression are the fates of many ameloblasts following enamel maturation, and what cells remain of the enamel organ are shed during tooth eruption or are incorporated into the tooth’s epithelial attachment to the oral gingiva.

[0004] Dental enamel is the hardest substance in the human body and serves as the wear-resistant outer layer of the dental crown. It forms an insulating barrier that protects thetooth from physical, thermal, and chemical forces that would otherwise be injurious to the vital tissue in the underlying dental pulp. Because the optical properties of enamel are also derived from its structure and composition, developmental defects or environmental influences affecting enamel structure are typically visualized as changes in its opacity and / or color. The impact of developmental insults on enamel is critical because, unlike bone, once mineralized, enamel tissue is acellular and hence does not remodel.

[0005] The process of enamel formation is referred to as amelogenesis. Enamel matrix proteins are secreted by ameloblasts into the enamel space, and are later degraded and proteolytically removed, also by ameloblasts. It is with a high level of precision that ameloblasts regulate the formation of a de novo hydroxyapatite-based (Hap-based) inorganic material within the enamel space. The formed enamel has a characteristic prismatic appearance composed of rods, each formed by a single ameloblast and extending from the dentin-enamel junction (DEJ) to the enamel surface, and the interrod enamel located around the enamel rods. Traces of EMP peptides are included in the fully formed enamel and are believed to contribute to the final structure, such that the fully formed (mature) enamel has unique morphological and biomechanical properties. By weight, mature enamel is -95% mineral, ~1- 2% organic material, and -2-4% water.

[0006] The health and appearance of a one's teeth is one of the main factors determining one's general health and self-image, which is important for digestion, psychological, social and sexual well-being. Generally, the condition of the teeth depends upon genetic, lifestyle, dietary, environmental and other factors. Human teeth are exposed to mechanical and chemical processes associated with food and beverage consumption, as well as the impact of bacteria and other natural and artificial substances and objects on a daily basis. In the modern world with its processed foods and sugary diets, teeth can be rapidly discolored, damaged, worn, eroded and even lost without daily oral hygiene and regular inspection and maintenance. Unlike other human tissues, the tooth enamel does not contain mechanisms for self-protection and restoration. The enamel normally can restore itself by a remineralization process with the necessary minerals and action obtained from saliva. There is a continuous demineralization / remineralization process, which restores the health of the enamel tissue, damaged by the actions described above. The past several decades have seen the introduction of many new methods improving strength of the enamel and aiding its restoration. Such methods include, but are not limited to, fluoridation of water, using fluoridated toothpastes containing amorphous calcium phosphate, using more effective toothbrushes, including electrical brushes, using new types of rinses, adding various agents to chewing gum, and the like.In recent years, cosmetic whitening of teeth using peroxide-based agents has become increasingly popular. As a result, there has been a significant decrease in tooth loss due to caries and an improvement of teeth appearance in the countries where such methods are available.

[0007] In the United States, however, 85% of population still suffers from caries and over 30% of adults are not satisfied with the cosmetic appearance of their teeth. This situation is significantly worse in the countries with no water fluoridation. Therefore, the development of new treatment for tooth protection and restoration is a very desirable objective. Tooth Structure

[0008] Human teeth serve several functions, including chewing, aiding in speech, and the perception of beauty and facial harmony. A human tooth consists of three sequential layers of tissues: (1) the hard, highly mineralized tissue, the "enamel", supported by the less mineralized and vital connective tissue, (2) the "dentin", which is formed from and supported by soft, connective tissue, and (3) the "dental pulp" or the "pulp". The pulp consists of sensitive tissue containing blood vessels, nerve fibers, specialized cells and pulpal fluid. The dentin, which surrounds the dental pulp, forms the major part of the tooth. It is dense bonelike tissue consisting of 70% inorganic material, 20% organic material, and 10% water by weight. The enamel, which surrounds coronal dentine, consists of 96% inorganic, 1% organic material and 3% water by weight. The inorganic material is called hydroxyapatite, a substance also found in bone and dentine. A tightly packed mass of apatite crystals forms the basic structural unit of enamel, called the "enamel rod" or "enamel prism." It is shaped like a keyhole and has an average width of 5 pm. Its width is determined by the local enamel thickness, with a maximum of approximately 2.5 mm. Rods run from the dentin-enamel junction perpendicularly to the outer enamel surface and are maintained in rows. Neighboring rods are separated from each other by 0.1-0.2 pm wide prism sheaths. The enamel rod consists almost entirely of hydroxyapatite, whereas the prism sheaths are made up largely of organic material comprised of amelogenin polypeptide and non-amelogenin proteins. The mineral component of enamel is an apatite like crystal, which has the formula of Aio(B04)eX2, where A is Ca, Cr, Ba, Cd, B is P, As, Si, and X is F, OH, CICO2. The dominant formula of enamel apatite is an ideal hydroxyapatite CalO(P04) 6(OH)2 with the Ca / P ratio of 1.67. In addition to hydroxyapatite, carbide apatite, chlorine apatite, fluorine apatite are also present in enamel. Apatite is formed in hexagonal micro crystals. These crystals have the typical crystal defect in the lattice arrangement including shifted, disrupted, and curved lattice planes. Defective lattices in the boundary between crystals are fused with each other. In carious lesions, mineral dissolution begins in the crystal lattice defects. The micro crystals in enamel are surrounded by awater shell, which makes enamel transparent for some ions. The main requirements for healthy enamel are mechanical hardness, wear resistance, and caries resistance (which is essentially acid resistance). In addition, the esthetic appearance of especially the anterior teeth has become of significant importance in today's appearance conscious society.

[0009] Unlike other types of hard tissue, such as cementum, dentine and bone, there are no living cells in the mature enamel, as the ameloblast cells die after the enamel is formed. Accordingly, the tooth enamel does not contain mechanisms for self-protection and regeneration and, therefore, is essentially a dead tissue. Restoration of Hard Tissue

[0010] The process of the dissolution of enamel is called demineralization. It is the result of the interaction of the enamel components with the acid, produced by the bacterial action of plaque and various foods, as well as by the consumption of acidic beverages, such as fruit juices, wine and some sports and carbonated drinks. The decrease in a pH results in the dissolution of Ca and P ions into the saliva. The solubility in acid of different types of the apatite found in the enamel varies significantly. For example, the solubility of carbonate apatite in an acid with a given pH is approximately an order of magnitude greater than that of hydroxyapatite, which, in turn, is an order of magnitude greater than that of fluorapatite.

[0011] The reverse process is called remineralization, which is facilitated by some or all of the following mechanisms. Human saliva contains calcium and phosphate in a supersaturated state, which can restore hydroxyapatite crystals lost during demineralization. This is the fundamental process in the prevention of enamel loss. Under normal conditions, there is a balance between demineralization and remineralization. The restoring and rejuvenating ability of saliva is a typical example of the natural tooth restoration mechanism. The remineralization process can also be initiated by controlling an oral fluid. The resistance of teeth to an acid attack can be increased and such methods as the use of fluoride in toothpastes and community water supplies have been known for many years. F ions from compounds, such as NaF and SnF2, replace some of the OH- ions in apatite during the remineralization process. The modified enamel substance, called fluorapatite, is more resistant to acid than hydroxyapatite. Amorphous calcium phosphate (CaPO4) or ACP, is another compound used to promote enamel remineralization. As the pH falls, ACP dissociates to form calcium and phosphate ions, thereby minimizing the drop in the pH and limiting demineralization. Since ACP can act as a reservoir for calcium and phosphate ions and maintain these ions in a state of supersaturation with respect to enamel, ACP decreases the process of demineralization andpromotes remineralization. Remineralized complexes consisting of Ca and F have been suggested as additives to strips and filling material.

[0012] Given the shortcomings of the traditional fluoride-based and calcium phosphate systems, methods and materials that aid regeneration or renewal and / or repair of lost or damaged hard tissue is needed. Acid Etching

[0013] Acid etching or enamel conditioning has a widespread use in clinical practice. It is most frequently used in bonding of resin materials. Different types and concentrations of acid may be used. Of these, 30-40% phosphoric acid with an application time of up to 60 seconds is the one most frequently used. Another, less frequent acid application is the removal of the superficial enamel stains resulting from the developmental disturbances of the enamel, such as excessive intake of fluoride. Reported uses involve 18% and 37% hydrochloric acid applied for up to 25 seconds.

[0014] Acid etching and partial demineralization of apatite crystals leads to the high porosity of exposed surfaces, which makes such surfaces better suited for bonding of the restorative and adhesive materials. Three distinct acid etching patterns can be distinguished. A type I pattern is the one where the enamel rod cores are preferentially removed. In the type II pattern mostly prism sheaths are removed, while the rod cores remain intact. The type III pattern is characterized by irregular and indiscriminate etching.

[0015] Acid etching of hard tissue is a cause of the enamel loss and the decrease of mechanical hardness and wear resistance. In addition, acid etching of the superficial enamel layer, which is the most resistant to acid attack, can accelerate the growth of a carious lesion. For this reason, acid is used in dentistry mainly for the treatment of hard tissues to facilitate adhesion of tooth colored restorative materials to such hard tissues. In low concentrations, an acid is used as an addition to peroxide bleaching agents and some rinses and toothpastes for the stabilization of various ingredients. Dentists recommend limiting the use of acidic beverages and foods. Most foods and beverages have a pH of 2.5 or more, usually between 4 and 7.Tooth Rejuvenation

[0016] Tooth restoration is one of the most important parts of preventive and esthetic dentistry. As explained above, it can be a part of the natural process, facilitated by the saliva. However, in many cases the natural role of the saliva may not be enough to keep a tooth from degradation. Several methods aimed to enhance tooth restoration exist. Most are focused on the improvement of one the components of tooth restoration, and do not provide acomplete solution. Such methods are: water fluoridation, mouth rinses, gels and strips, tooth brushing, professional oral cleaning, tooth whitening, tooth coating, tooth surface laser modification. These methods are described below in more detail.

[0017] Water fluoridation contributes to the formation of fluorapatite in the external layer of the enamel. Fluoride in water plays several roles in the prevention of dental caries, such as the inhibition of acid production in plaque, the enhancement of restoration of carious lesions and strengthening the enamel against an acid attack through the formation of the fluorapatite (Cal0(PO4)6F2). This effect takes place at low concentrations of fluoride. High concentrations of fluoride can cause the formation of CaF2 and the destruction of tooth structure.

[0018] Mouth rinses are mainly used for bacterial reduction. Some additives, such as the casein phosphopeptide-amorphous calcium phosphate nano-complexes, have been proven to be effective in the restoration process.

[0019] Different types of gels and strips and have been shown to provide an antibacterial effect. A gel, containing fluoride, calcium and phosphate ions, has been shown to be effective in the restoration process. Preliminary treatment of enamel with low acid concentrations enhances the effect of the fluoride treatment. Gels or strips may also include peroxide for tooth whitening.

[0020] Tooth brushing and flossing are the most important forms of preventing tooth stains and destruction of teeth since they are daily regimens. The mechanical cleaning of the teeth removes a biofilm, prevents / decreases the build-up of tartar and decreases acid production by bacteria. It also enhances the access of saliva to the enamel, in the process improving the chances for remineralization. In addition, toothpastes often contain antibacterial, restoration and whitening components.

[0021] Professional oral cleaning in the dental office provides additional benefits to the methods of tooth brushing and flossing, such as the removal of supra and subgingival plaque and calculus, plaque detection, and application of caries-preventing agents. The treatment typically involves the procedures, such as scaling and polishing of teeth and subgingival currettage, resulting in a more effective method of preventing of periodontal or other dental decreases, as well as an overall aesthetic improvement in the appearance of teeth and gums. Plaque detection and the application of the caries-preventing agents may also be performed by the health professional as an aid to home care and restoration. However, this treatment is not capable of removing intrinsic and deep extrinsic stains.

[0022] Teeth function in an environment of mechanical, chemical and thermal stress. With normal chewing, a modest stress of 20 MPa is applied to the tooth more than 1000 times a day. Occasional stress can be up to 100 MPa. This cyclic loading occurs in a water-based fluid environment that can have a pH from 0.5 to 8 and the temperature variations of 50°C. Many different restorative materials have been developed, designed to retain their strength and properties in an aggressive environment (for example, ceramic-based porous alumina infiltrated with lanthanum aluminosilicate glass, or porous zirconia later infiltrated with glass). Porcelain, the most popular material, has excellent color properties, but is brittle and relatively easily fractured unless it is reinforced or strengthened. Porcelain restoration treatment also destroys the tooth structure since it usually requires tooth preparation and is expensive and time consuming. These restorative materials are used for crowns or veneers and, if done properly, provide excellent esthetic appearance and prevent caries. However, the risk of recurrent caries still exists. Since any destruction of the tooth substance is harmful, clinicians have been attempting to develop non-destructive, or minimally destructive methods for tooth restoration.BRIEF DESCRIPTION OF THE DRAWINGSFIG. l is a schematic of exemplary interactions of catechols with different types of surfaces. FIG. 2 is a micrograph showing restoration of enamel and dentin tubule occlusion with 0% PCS.FIG. 3 is a micrograph showing restoration of enamel and dentin tubule occlusion with 1% PCS.DETAILED DESCRIPTITION OF THE INVENTION

[0023] The goal of the present invention is the development of a new method for tooth / enamel restoration and tooth protection and to provide a solution for the improvement of the mechanical and chemical resistance of tooth substance and to improve its esthetic appearance. Tooth restoration is defined as the changing of the tooth structure leading to an increase in some or all of the following parameters: wear resistance (mechanical resistance), resistance to chemical and / or bacterial attack, and the restoration and improvement of tooth appearance and other tooth improvements. Dentin tubule occlusion may promote tooth protection and tooth restoration.

[0024] One of the embodiments of the present invention is a method for tooth restoration comprising applying a layer catechol styrene-based composition to a tooth.

[0025] In one embodiment, the tooth enamel can be restored using catechol containing compound such as poly(catechol-styrene).

[0026] In the first experimental step, the sample, that is enamel from sectioned human tooth was embedded in acrylic resin. The samples were initially acid-etched, and then treated with PCS. The concentration was 1% in acetone. Then the sample was submerged in 1.5x simulated body fluid or SBF for 72 hours. In the next step, the sample was acid etched again, and is then resubmerged in 1.5x SBF for 72 hours. All acid etchings were 2 min in length with a 40% phosphoric acid gel. As shown in the FIG. 2, minimal restoration of enamel was visible in the control sample not containing any PCS. As shown in FIG. 3, a clearly, visible enamel restoration was seen in the sampled section was treated with 1% PCS. In the figures, ‘Z>’ = dentin, ‘AR’ = acrylic resin, and ‘E’ = enamel.

[0027] In the present disclosure the singular forms “a”, “an,” and “the” include the plural reference, and reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to “a material” is a reference to at least one of such materials and equivalents thereof known to those skilled in the art, and so forth.

[0028] In the present disclosure, the term “subject” includes any human or nonhuman animal. In certain embodiments, the subject is a human or non-human mammal. In certain embodiments, the subject is a human.

[0029] When a value is expressed as an approximation by use of the descriptor “about” or “substantially” it will be understood that the particular value forms another embodiment. In general, use of the term “about” or “substantially” indicates approximations that can vary depending on the desired properties sought to be obtained by the disclosed subject matter and is to be interpreted in the specific context in which it is used, based on its function. The person skilled in the art will be able to interpret this as a matter of routine. In some cases, the number of significant figures used for a particular value may be one nonlimiting method of determining the extent of the word “about” or “substantially”. In other cases, the gradations used in a series of values may be used to determine the intended range available to the term “about” or “substantially” for each value. Where present, all ranges are inclusive and combinable. That is, references to values stated in ranges include every value within that range.

[0030] When a list is presented, unless stated otherwise, it is to be understood that each individual element of that list and every combination of that list is to be interpreted as a separate embodiment. For example, a list of embodiments presented as “A, B, or C” is to beinterpreted as including the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,” or “A, B, or C ”

[0031] It is to be appreciated that certain features of the disclosure which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. That is, unless obviously incompatible or excluded, each individual embodiment is deemed to be combinable with any other embodiments and such a combination is considered to be another embodiment. Conversely, various features of the disclosure that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as “solely,” “only” and the like in connection with the recitation of claim elements, or use of a “negative” limitation. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step may also be considered an independent embodiment in itself.

[0032] Catechol is able to form a wide range of reversible bonds with surfaces, such as hydrogen bonding, cation-7t interaction, and metal ion complexation. Catechol can also form covalent bonds with certain bonding surfaces, for example protein surfaces, as well as cross-linking with itself. (FIG. 1).

[0033] Catechol groups are susceptible to oxidation into a semi -quinone or quinone. Several studies have documented that oxidation reduces significantly binding to inorganic surfaces. During the process of catechol oxidation into quinones, reactive oxygen species (ROS) are generated as by-products.

[0034] While strong attachment to inorganic surfaces requires catechol (reduced), quinones (oxidized) can bind covalently to organic materials via a Schiff base addition or Michael Reaction. Mussel-inspired biomimetic adhesives can be considered bifunctional “cate- chol-quinone” mixtures.

[0035] Catechol containing materials of the present invention are used for restoration of enamel and dentin tubule occlusion.

[0036] In an aspect, the disclosure is directed to a process of dentin tubule occlusion wherein the catechol containing material comprises a catechol containing monomer, polymer, or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone with or without the presence of a primary amine or a secondary amine; and wherein the polymeric layer also comprises a reactive material that is not reactive with catechol or quinone.

[0037] In an aspect, the present invention is directed to a polymeric layer for occluding dentin tubules, comprising a catechol containing monomer, polymer, or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of a primary amine or a secondary amine; and wherein the polymeric layer optionally comprises a reactive material that is not reactive with catechol or quinone.

[0038] In some embodiments, the catechol containing monomer, polymer, or oligomer in the polymeric layer is monomeric. In some embodiments, the catechol containing monomer, polymer, or oligomer in the polymeric layer is oligomeric. In some embodiments, the catechol containing monomer, polymer, or oligomer in the polymeric layer is polymeric.

[0039] In some embodiments, the catechol -containing material comprises the reactive species separate from the catechol or catechol containing material; and the reactive species is an acrylic such as 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (BisGMA), ethoxylated bisphenol-A dimethacrylate (EBPADMA), triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), tert -butylphenoxy BisGMA (MtBDMA), modified urethane dimethacrylate, amide modified bisphenol-A, CEEBisGMA, acidic bisphenol-A dimethacrylate, dimethacrylate from cycloaliphatic epoxide, aromatic urethane dimethacrylate, urethane modified BisGMA, acid aromatic dimethacrylate, oxydiphthalic-acid dimethacrylate, phenyl dihydroxymethacrylate diphosphonate, Acidic Bisphenol- A dimethacrylate, morpholine carbonyl methacrylate, phenyl carbonate methacrylate.

[0040] In some embodiments, the catechol -containing material includes free radical polymerization initiators such as acrylate polymerization initiators, including those that are light activated, such as benzoyl peroxide (BPO), 2,3-bomanedione (Camphorquinone), Ethyl - 4-(dimethylamino) benzoate (EDMAB), 2-(Ethylhexyl)-4-(dimethylamino) benzoate (OD- MAB), 2-(Ethylhexyl)-4-(dimethylamino) benzoate (TPO), Diphenyl(2,4,6- trimethylbenzoyl)-phosphineoxide or combinations thereof.

[0041] In some embodiments, the acrylate is an acrylate monomer comprising a vinyl group and at least one of a carboxylic acid ester and a carboxylic acid nitrile; and wherein the acrylate is linear or branched. In some embodiments, the acrylate is ethyl acrylate, eth- ylene-methyl acrylate, methyl methacrylate, 2-chloroethyl vinyl ether, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, butyl acrylate, trimethylolpropane triacrylate (TMPTA) or combinations thereof.

[0042] In an aspect, the catechol -containing material has a thickness of from about10 nanometers to about 100 microns. In some embodiments, the catechol -containing material has a thickness of from about 15 nanometers to about 50 microns. In some embodiments, ther polymeric layer has a thickness of from about 15 nanometers to about 15 microns. In some embodiments, the polymeric layer has a thickness of from about 150 nanometers to less than about 15 microns. In some embodiments, polymeric layer has a thickness of from about 150 nanometers to about 1.5 microns.

[0043] In some embodiments, the dentin tubule-occluding polymeric layer has a thickness of from about 10 nanometers to about 100 microns; or from about 10 nanometers to about 100 nanometers; or from about 100 nanometers to about 150 nanometers; or from about 150 nanometers to about 200 nanometers; or from about 200 nanometers to about 250 nanometers; or from about 250 nanometers to about 300 nanometers; or from about 300 nanometers to about 350 nanometers; or from about 350 nanometers to about 400 nanometers; or from about 400 nanometers to about 450 nanometers; or from about 450 nanometers to about 500 nanometers; or from about 500 nanometers to about 550 nanometers; or from about 550 nanometers to about 600 nanometers; or from about 600 nanometers to about 650 nanometers; or from about 650 nanometers to about 700 nanometers; or from about 700 nanometers to about 750 nanometers; or from about 750 nanometers to about 800 nanometers; or from about 800 nanometers to about 850 nanometers; or from about 850 nanometers to about 900 nanometers; or from about 900 nanometers to about 950 nanometers; or from about 950 nanometers to about 1000 nanometers.

[0044] In some embodiments, the dentin tubule-occluding polymeric layer has a thickness of from about 1 micron to about 1.5 microns; or from about 1.5 microns to about 5 microns; or from about 5 microns to about 10 microns; or from about 10 microns to about 15 microns; or from about 15 microns to about 20 microns; or from about 20 microns to about 25 microns; or from about 25 microns to about 30 microns; or from about 30 microns to about 35 microns; or from about 35 microns to about 40 microns; or from about 40 microns to about 45 microns; or from about 45 microns to about 50 microns; or from about 50 microns to about 55 microns; or from about 55 microns to about 60 microns; or from about 60 microns to about 65 microns; or from about 65 microns to about 70 microns; or from about 70 microns to about 75 microns; or from about 75 microns to about 80 microns; or from about 80 microns to about 85 microns; or from about 85 microns to about 90 microns; or from about 90 microns to about 95 microns; or from about 95 microns to about 100 microns.

[0045] In an aspect, the catechol containing monomer, polymer, or oligomer in the dentin tubule-occluding polymeric layer comprises poly-catechol styrene (PCS).

[0046] In some embodiments, the PCS is prepared in one or more suitable solvents. For example, the PCS may be prepared as a solution in acetone, tert-butyl alcohol, ethanol,isopropyl alcohol, or a combination thereof, or one or more other suitable solvents as understood in the art. In some embodiments, the PCS is prepared as a solution in acetone. In some embodiments, the PCS is prepared as a solution in tert -butyl alcohol. In some embodiments, the PCS is prepared as a solution in isopropyl alcohol. In some embodiments the PCS is prepared as a solution in ethanol.

[0047] In some embodiments, the PCS comprises a solution containing from about 0.001% to 10% PCS, from about 0.05% to about 5% PCS, from about 0.01% to about 2% PCS, from about 0.5% to about 1% PCS, from about 0.1% to about 0.5% PCS and any and all increments therebetween. In some embodiments, the PCS comprises about 0.1% catechol.

[0048] In some embodiments, the PCS comprises from about 20% catechol to about 22% catechol; or from about 22% catechol to about 24% catechol; or from about 24% catechol to about 26% catechol; or from about 26% catechol to about 28% catechol; or from about 28% catechol to about 30% catechol; or from about 30% catechol to about 32% catechol; or from about 32% catechol to about 34% catechol; or from about 34% catechol to about 36% catechol; or from about 36% catechol to about 38% catechol; or from about 38% catechol to about 40% catechol.

[0049] In some embodiments, the dentin tubule-occluding polymeric layer comprises a reactive material that is not reactive with catechol or quinone. In some embodiments, the reactive material is not reactive at ambient temperature with catechol or quinone. In some embodiments, the reactive material is not reactive at low temperature with catechol or quinone.

[0050] In some embodiments, the reactive material that is not reactive with catechol or quinone is a resin, an oligomer, a polymer, or a monomer. In some embodiments, the reactive material an oligomer. In some embodiments, the reactive material a polymer. In some embodiments, the reactive material a monomer.

[0051] In an aspect, the dentin tubule-occluding polymeric layer is a continuous layer. In an aspect, the dentin tubule-occluding polymeric layer is a non-continuous layer. In an aspect, the dentin tubule-occluding polymeric layer is a patterned layer or a textured layer.

[0052] In some embodiments, the dentin tubule-occluding polymeric layer includes one or more additives. In some embodiments, the one or more additives include one or more catalysts, for example one or more photo-initiators. The one or more photo-initiators may include one or more of camphorquinone (CQ), azobisisobutyronitrile (AIBN), benzoyl peroxide, 2, 2-dimethoxy-2 -phenyl acetophenone, and one or more combinations thereof. In some embodiments, the photo-initiator may include one or more additional photosensitizers or co-initiators including for example one or more peroxides, aliphatic azo compounds and the like. In some embodiments, the catalyst, co-catalyst or accelerator; and the catalyst, co-catalyst or accelerator is an acrylate catalyst that promotes an acrylate polymerization reaction, or combinations thereof.

[0053] In some embodiments, the photo-initiator is CQ. The CQ may be used at a concentration of from about 0.01% to about 1%, from about 0.05% to about 0.75% from about 0.1% to about 0.5%, and any and all increments therebetween. In some embodiments the CQ is used at a concentration of 0.1%.

[0054] In some embodiments, the catechol containing monomer, oligomer, or polymer comprises PCS.

[0055] In some embodiments, the dentin tubule-occluding polymeric layer is applied as a solution. In some embodiments, the solution comprises from about 0.001% by weight to about 10% by weight of the catechol containing monomer, polymer, or oligomer. In some embodiments, the solution comprises from about 0.01% by weight to about 5% by weight of the catechol containing monomer, polymer, or oligomer. In some embodiments, the solution comprises from about 0.01% by weight to about 1% by weight of the catechol containing monomer, polymer, or oligomer. In some embodiments, the solution comprises from about 0.1% by weight to about 1% by weight of the catechol containing monomer, polymer, or oligomer.

[0056] In some embodiments, the solution comprises from about 0.001% by weight to about 0.005% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.005% by weight to about 0.01% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.01% by weight to about 0.02% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.02% by weight to about 0.03% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.03% by weight to about 0.04% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.04% by weight to about 0.05% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.05% by weight to about 0.06% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.06% by weight to about 0.07% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.07% by weight to about 0.08% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.08% by weight to about 0.09% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.09% by weight to about 0.1% by weight of the catechol containing monomer, polymer, or oligomer; or from about0.1% by weight to about 0.11% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.11% by weight to about 0.12% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.12% by weight to about 0.13% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.13% by weight to about 0.14% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.14% by weight to about 0.15% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.15% by weight to about 0.2% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.2% by weight to about 0.25% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.25% by weight to about 0.3% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.3% by weight to about 0.35% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.35% by weight to about 0.4% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.4% by weight to about 0.45% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.45% by weight to about 0.5% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.5% by weight to about 0.75% by weight of the catechol containing monomer, polymer, or oligomer; or from about 0.75% by weight to about 1% by weight of the catechol containing monomer, polymer, or oligomer; or from about 1.25% by weight to about 1.5% by weight of the catechol containing monomer, polymer, or oligomer; or from about 1.5% by weight to about 1.75% by weight of the catechol containing monomer, polymer, or oligomer; or from about 1.75% by weight to about 2% by weight of the catechol containing monomer, polymer, or oligomer.

[0057] In some embodiments, the catechol containing monomer, polymer, or oligomer used in the solution is poly-catechol styrene (PCS). In some embodiments, the solution comprises from about 0.001% by weight to about 10% by weight of PCS. In some embodiments, the solution comprises from about 0.01% by weight to about 5% by weight of PCS. In some embodiments, the solution comprises from about 0.01% by weight to about 1% by weight of PCS. In some embodiments, the solution comprises from about 0.1% by weight to about 1% by weight of PCS.

[0058] In some embodiments, the solution comprises from about 0.001% by weight to about 0.005% by weight of PCS; or from about 0.005% by weight to about 0.01% by weight of PCS; or from about 0.01% by weight to about 0.02% by weight of PCS; or from about 0.02% by weight to about 0.03% by weight of PCS; or from about 0.03% by weight to about 0.04% by weight of PCS; or from about 0.04% by weight to about 0.05% by weight ofPCS; or from about 0.05% by weight to about 0.06% by weight of PCS; or from about 0.06% by weight to about 0.07% by weight of PCS; or from about 0.07% by weight to about 0.08% by weight of PCS; or from about 0.08% by weight to about 0.09% by weight of PCS; or from about 0.09% by weight to about 0.1% by weight of PCS; or from about 0.1% by weight to about 0.11% by weight of PCS; or from about 0.11% by weight to about 0.12% by weight of PCS; or from about 0.12% by weight to about 0.13% by weight of PCS; or from about 0.13% by weight to about 0.14% by weight of PCS; or from about 0.14% by weight to about 0.15% by weight of PCS; or from about 0.15% by weight to about 0.2% by weight of PCS; or from about 0.2% by weight to about 0.25% by weight of PCS; or from about 0.25% by weight to about 0.3% by weight of PCS; or from about 0.3% by weight to about 0.35% by weight of PCS; or from about 0.35% by weight to about 0.4% by weight of PCS; or from about 0.4% by weight to about 0.45% by weight of PCS; or from about 0.45% by weight to about 0.5% by weight of PCS; or from about 0.5% by weight to about 0.75% by weight of PCS; or from about 0.75% by weight to about 1% by weight of PCS; or from about 1.25% by weight to about 1.5% by weight of PCS; or from about 1.5% by weight to about 1.75% by weight of PCS; or from about 1.75% by weight to about 2% by weight of PCS.

[0059] In some embodiments, the solution also comprises an aqueous or organic solvent for dissolving the catechol containing monomer, polymer, or oligomer. In some embodiments, the organic solvent is acetone, tert-butyl alcohol, ethanol, isopropyl alcohol, or a combination thereof.

[0060] In some embodiments, the organic solvent is acetone. In some embodiments, the organic solvent is tert-butyl alcohol. In some embodiments, the organic solvent is ethanol. In some embodiments, the organic solvent is isopropyl alcohol. In some embodiments, the organic solvent is a combination of one or more of acetone tert -butyl alcohol, ethanol, isopropyl alcohol. In some embodiments, the organic solvent is acetone and the catechol or catechol containing material is PCS. In some embodiments, the organic solvent is tert-butyl alcohol and the catechol or catechol containing material is PCS. In some embodiments, the organic solvent is ethanol and the catechol or catechol containing material is PCS. In some embodiments, the organic solvent is isopropyl alcohol and the catechol or catechol containing material is PCS. In some embodiments, the organic solvent is a combination of one or more of acetone tert-butyl alcohol, ethanol, isopropyl alcohol, and the catechol or catechol containing material is PCS. In some embodiments, the organic solvent further comprises one or more oxidizing agents or acidifying agents. For example, in some embodiments the organic solvent further comprises acetic acid.

[0061] The pH of the solution is not particularly limited. In some embodiments, the pH of the solution is about 3; or about 3.5; or about 4; or about 4.5; or about 5; or about 5.5; or about 6; or about 6.5; or about 7; or about 7.5; or about 8; or about 8.5; or about 9; or about 9.5; or about 10; or about 10.5; or about 11.

[0062] In some embodiments, the pH of the solution is from about 3 - 3.5; or about 3.5 - 4; or about 4 - 4.5; or about 4.5 - 5; or about 5 - 5.5; or about 5.5 - 6; or about 6 - 6.5; or about 6.5 - 7; or about 7 - 7.5; or about 7.5 - 8; or about 8 - 8.5; or about 8.5 - 9; or about 9 - 9.5; or about 9.5 - 10; or about 10 - 10.5; or about 10.5 - 11.

[0063] Aspects

[0064] The following Aspects are illustrative only and do not limit the scope of the present disclosure or the appended claims. Any part or parts of any one or more Aspects can be combined with any part or parts of any one or more other Aspects.

[0065] Aspect 1. A method for occluding dentin tubules comprising contacting the tooth enamel to material comprising catechol, semi-quinone, or quinone.

[0066] Aspect 2. The method of Aspect 1, wherein the catechol -containing material comprises monomeric, oligomeric, or polymeric catechol or catechol containing material, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of an amine; and wherein the polymeric layer optionally comprises at least one of: a) a reactive species separate from the catechol or catechol containing material; and b) a catalyst, co-catalyst or an accelerator.

[0067] Aspect 3. The method of Aspect 2, wherein the catechol -containing material comprises the reactive species separate from the catechol or catechol containing material; and the reactive species comprises an acrylic, a silane, a silicone, a methacrylate, a polyvinyl alcohol (PVA) or a combination thereof.

[0068] Aspect 4. The method of Aspect 3, wherein the catechol -containing material comprises the reactive species separate from the catechol or catechol containing material; and the reactive species is an acrylic such as 2,2-bis[4-(2-hydroxy-3- methacryloyloxypropoxy)phenyl]propane (BisGMA), ethoxylated bisphenol -A dimethacrylate (EBPADMA), triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), tert-butylphenoxy BisGMA (MtBDMA), modified urethane dimethacrylate, amide modified bisphenol-A, CHiBisGMA, acidic bisphenol-A dimethacrylate, dimethacrylate from cycloaliphatic epoxide, aromatic urethane dimethacrylate, urethane modified BisGMA, acid aromatic dimethacrylate, oxydiphthalic-acid dimethacrylate, phenyl dihydroxymethacrylatediphosphonate, Acidic Bisphenol-A dimethacrylate, morpholine carbonyl methacrylate, phenyl carbonate methacrylate.

[0069] Aspect 5. The method of Aspect 1 further comprising free radical polymerization initiators such as acrylate polymerization initiators, including those that are light activated, such as benzoyl peroxide (BPO), 2,3-bomanedione (Camphorquinone), Ethyl -4- (dimethylamino) benzoate (EDMAB), 2-(Ethylhexyl)-4-(dimethylamino) benzoate (OD- MAB), 2-(Ethylhexyl)-4-(dimethylamino) benzoate (TPO), Diphenyl(2,4,6- trimethylbenzoyl)-phosphineoxide or combinations thereof.

[0070] Aspect 6. The method of Aspect 3, wherein the reactive species is the acrylate.

[0071] Aspect 7. The method of Aspect 1, wherein the catechol -containing material is disposed upon a tooth enamel.

[0072] Aspect 8. The method of Aspect 1, wherein the catechol -containing material has a thickness of from about 10 nanometers to about 500 microns.

[0073] Aspect 9. The method of Aspect 1, wherein the catechol or catecholcontaining material comprises poly-catechol styrene (PCS).

[0074] Aspect 10. The method of Aspect 9, wherein the PCS comprises a 0.1% solution of PCS.

[0075] Aspect 11. The method of Aspect 1 further comprising one or more photoinitiators comprising one or more of camphorquinone (CQ), azobisisobutyronitrile (AIBN), benzoyl peroxide, 2, 2-dimethoxy-2 -phenyl acetophenone, and one or more combinations thereof.

[0076] Aspect 12. The method as recited in Aspect 1 wherein the catechol containing compound is in a dissolved form.

[0077] Aspect 13. A dentin tubule-occluding polymer layer comprising a catecholcontaining polymer containing catechol, semi -quinone, or quinone.

[0078] Aspect 14. The dentin tubule-occluding polymer layer of Aspect 13, wherein the catechol-containing polymer comprises monomeric, oligomeric, or polymeric catechol or catechol containing material, wherein said catechol presents as a catechol and / or as a semiquinone and / or as a quinone, each without the presence of an amine; and wherein the dentin tubule-occluding polymer optionally comprises at least one of: a) a reactive species separate from the catechol or catechol containing material; and b) a catalyst, co-catalyst or an accelerator.

[0079] Aspect 15. The dentin tubule-occluding polymer layer of Aspect 13, wherein the catechol-containing material comprises the reactive species separate from the catechol or catechol containing material; and the reactive species comprises an acrylic, a silane, a silicone, a methacrylate, a polyvinyl alcohol (PVA) or a combination thereof.

[0080] Aspect 16. The dentin tubule-occluding polymer layer of Aspect 15, wherein the catechol-containing material comprises the reactive species separate from the catechol or catechol containing material; and the reactive species is an acrylic such as 2,2-bis[4-(2- hydroxy-3-methacryloyloxypropoxy)phenyl]propane (BisGMA), ethoxylated bisphenol-A dimetharylate (EBPADMA), triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), tert-butylphenoxy BisGMA (MtBDMA), modified urethane dimethacrylate, amide modified bisphenol-A, CEEBisGMA, acidic bisphenol-A dimetharylate, dimethacrylate from cycloaliphatic epoxide, aromatic urethane dimethacrylate, urethane modified BisGMA, acid aromatic dimethacrylate, oxydiphthalic-acid dimethacrylate, phenyl dihydroxymethacrylate diphosphonate, Acidic Bisphenol-A dimethacrylate, morpholine carbonyl methacrylate, phenyl carbonate methacrylate.

[0081] Aspect 17. The dentin tubule-occluding polymer layer of Aspect 13, further comprising free radical polymerization initiators such as acrylate polymerization initiators, including those that are light activated, such as benzoyl peroxide (BPO), 2,3-bornanedione (Camphorquinone), Ethyl-4-(dimethylamino)benzoate (EDMAB), 2-(Ethylhexyl)-4- (dimethylamino)benzoate (ODMAB), 2-(Ethylhexyl)-4-(dimethylamino)benzoate (TPO), Di- phenyl(2,4,6-trimethylbenzoyl)-phosphineoxide or combinations thereof.

[0082] Aspect 18. The dentin tubule-occluding polymer layer of Aspect 13, wherein the reactive species is the acrylate.

[0083] Aspect 19. The dentin tubule-occluding polymer layer of Aspect 13, wherein the catechol-containing material is disposed upon a tooth enamel.

[0084] Aspect 20. The dentin tubule-occluding polymer layer of Aspect 13, wherein the catechol-containing material has a thickness of from about 10 nanometers to about 500 microns.

[0085] Aspect 21. The dentin tubule-occluding polymer layer of Aspect 13, wherein the catechol or catechol-containing material comprises poly-catechol styrene (PCS).

[0086] Aspect 22. The dentin tubule-occluding polymer layer of Aspect 21, wherein the PCS comprises a 0.1% solution of PCS.

[0087] Aspect 23. The dentin tubule-occluding polymer layer of Aspect 13, further comprising one or more photo-initiators comprising one or more of camphorquinone (CQ),azobisisobutyronitrile (AIBN), benzoyl peroxide, 2, 2-dimethoxy-2 -phenyl acetophenone, and one or more combinations thereof.

[0088] Aspect 24. The dentin tubule-occluding polymer layer of claim 13, wherein the catechol containing compound is in a dissolved form.

Claims

What is Claimed:

1. A method for occluding dentin tubules comprising contacting the tooth enamel with material comprising catechol, semi-quinone, or quinone.

2. The method of claim 1, wherein the catechol -containing material comprises monomeric, oligomeric, or polymeric catechol or catechol containing material, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of an amine; and wherein the polymeric layer optionally comprises at least one of: a) a reactive species separate from the catechol or catechol containing material; and b) a catalyst, co-catalyst or an accelerator.

3. The method of claim 2, wherein the catechol -containing material comprises the reactive species separate from the catechol or catechol containing material; and the reactive species comprises an acrylic, a silane, a silicone, a methacrylate, a polyvinyl alcohol (PVA) or a combination thereof.

4. The method of claim 3, wherein the catechol -containing material comprises the reactive species separate from the catechol or catechol containing material; and the reactive species is an acrylic such as 2,2-bis[4-(2-hydroxy-3- methacryloyloxypropoxy)phenyl]propane (BisGMA), ethoxylated bisphenol-A dimethacrylate (EBPADMA), triethylene glycol dimethacrylate (TEGDMA), urethane dimethacrylate (UDMA), tert-butylphenoxy BisGMA (MtBDMA), modified urethane dimethacrylate, amide modified bisphenol-A, CHsBisGMA, acidic bisphenol-A dimethacrylate, dimethacrylate from cycloaliphatic epoxide, aromatic urethane dimethacrylate, urethane modified BisGMA, acid aromatic dimethacrylate, oxydiphthal- ic-acid dimethacrylate, phenyl dihydroxymethacrylate diphosphonate, Acidic Bisphenol-A dimethacrylate, morpholine carbonyl methacrylate, phenyl carbonate methacrylate.

5. The method of claim 1 further comprising free radical polymerization initiators such as acrylate polymerization initiators, including those that are light activated, such as benzoyl peroxide (BPO), 2,3-bornanedione (Camphorquinone), Ethyl-4- (dimethylamino) benzoate (EDMAB), 2-(Ethylhexyl)-4-(dimethylamino) benzoate (ODMAB), 2-(Ethylhexyl)-4-(dimethylamino) benzoate (TPO), Diphenyl(2,4,6- trimethylbenzoyl)-phosphineoxide or combinations thereof.

6. The method of claim 3, wherein the reactive species is the acrylate.

7. The method of claim 1, wherein the catechol -containing material is disposed upon a tooth enamel.

8. The method of claim 1, wherein the catechol -containing material has a thickness of from about 10 nanometers to about 500 microns.

9. The method of claim 1, wherein the catechol or catechol -containing material comprises poly-catechol styrene (PCS).

10. The method of claim 9, wherein the PCS comprises a 0.1% solution of PCS.

11. The method of claim 1 further comprising one or more photo-initiators comprising one or more of camphorquinone (CQ), azobisisobutyronitrile (AIBN), benzoyl peroxide, 2, 2-dimethoxy-2 -phenyl acetophenone, and one or more combinations thereof.

12. The method as recited in claim 1 wherein the catechol containing compound is in a dissolved form.

13. A dentin tubule-occluding polymer layer comprising a catechol-containing polymer containing catechol, semi-quinone, or quinone.

14. The dentin tubule-occluding polymer layer of claim 13, wherein the catecholcontaining polymer comprises monomeric, oligomeric, or polymeric catechol or catechol containing material, wherein said catechol presents as a catechol and / or as a semi-quinone and / or as a quinone, each without the presence of an amine; and wherein the dentin tubule-occluding polymer optionally comprises at least one of: a) a reactive species separate from the catechol or catechol containing material; and b) a catalyst, co-catalyst or an accelerator.

15. The dentin tubule-occluding polymer layer of claim 13, wherein the catecholcontaining material comprises the reactive species separate from the catechol or catechol containing material; and the reactive species comprises an acrylic, a silane, a silicone, a methacrylate, a polyvinyl alcohol (PVA) or a combination thereof.

16. The dentin tubule-occluding polymer layer of claim 15, wherein the catecholcontaining material comprises the reactive species separate from the catechol or catechol containing material; and the reactive species is an acrylic such as 2,2-bis[4-(2- hydroxy-3-methacryloyloxypropoxy)phenyl]propane (BisGMA), ethoxylated bi- sphenol-A dimetharylate (EBPADMA), triethylene glycol dimethacrylate (TEGD- MA), urethane dimethacrylate (UDMA), tert-butylphenoxy BisGMA (MtBDMA), modified urethane dimethacrylate, amide modified bisphenol -A, CEEBisGMA, acidic bisphenol-A dimetharylate, dimethacrylate from cycloaliphatic epoxide, aromatic urethane dimethacrylate, urethane modified BisGMA, acid aromatic dimethacrylate, oxydiphthalic-acid dimethacrylate, phenyl dihydroxymethacrylate diphosphonate, Acidic Bisphenol-A dimethacrylate, morpholine carbonyl methacrylate, phenyl carbonate methacrylate.

17. The dentin tubule-occluding polymer layer of claim 13, further comprising free radical polymerization initiators such as acrylate polymerization initiators, including those that are light activated, such as benzoyl peroxide (BPO), 2,3-bornanedione (Camphorquinone), Ethyl-4-(dimethylamino)benzoate (EDMAB), 2-(Ethylhexyl)-4-(dimethylamino)benzoate (ODMAB), 2-(Ethylhexyl)-4-(dimethylamino)benzoate (TPO), Diphenyl(2,4,6-trimethylbenzoyl)-phosphineoxide or combinations thereof.

18. The dentin tubule-occluding polymer layer of claim 13, wherein the reactive species is the acrylate.

19. The dentin tubule-occluding polymer layer of claim 13, wherein the catecholcontaining material is disposed upon a tooth enamel.

20. The dentin tubule-occluding polymer layer of claim 13, wherein the catecholcontaining material has a thickness of from about 10 nanometers to about 500 microns.

21. The dentin tubule-occluding polymer layer of claim 13, wherein the catechol or catechol-containing material comprises poly-catechol styrene (PCS).

22. The dentin tubule-occluding polymer layer of claim 21, wherein the PCS comprises a 0.1% solution of PCS.

23. The dentin tubule-occluding polymer layer of claim 13, further comprising one or more photo-initiators comprising one or more of camphorquinone (CQ), azobisisobu- tyronitrile (AIBN), benzoyl peroxide, 2, 2-dimethoxy-2 -phenyl acetophenone, and one or more combinations thereof.

24. The dentin tubule-occluding polymer layer of claim 13, wherein the catechol containing compound is in a dissolved form.

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