Catechol-containing materials for dental applications

Abstract

The present disclosure is directed to a polymer layer comprising a catechol-containing monomer, polymer, or oligomer, where the catechol is present as a catechol and / or as a semi-quinone and / or as a quinone without the presence of a primary amine or secondary amine, and the polymer layer optionally comprises a reactive material that does not react with the catechol or quinone. The present disclosure is also directed to a polymer layer comprising a catechol-containing monomer, polymer, or oligomer disposed adjacent and in contact with a bulk adhesive layer. The present disclosure is also directed to a method of coating a substrate with the layer described herein.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 245,959, filed September 20, 2021, and U.S. Provisional Application No. 63 / 287,124, filed December 8, 2021, both of which are incorporated by reference in their entireties. [Technical field]

[0002] The present disclosure relates to thin layers comprising catechol-containing monomers, polymers, or oligomers for use in dental applications. Catechol-containing materials have been shown to improve adhesion between two materials without substantial modification of the adhesive matrix. The present disclosure also relates to methods of making and using thin layers comprising the catechol-containing polymer or oligomer, poly(catechol-styrene) (PCS). [Background technology]

[0003] Strong, durable adhesives between tooth surfaces and composite filling materials, orthodontic devices, and restorative ceramics are a long-standing, challenging, and costly problem in dentistry that impacts health, safety, and well-being. Dental adhesives must bond strongly to wet tooth surfaces and maintain strength in the wet oral environment. Formulated acrylic resins are the most commonly used adhesive chemicals in dentistry. These resins are applied in liquid monomer form and polymerized in situ. Polymerization of acrylic resins is often light activated, although self-polymerizing chemicals are also used.

[0004] Acrylic adhesives bond poorly to wet surfaces, so the patient's tooth surface is usually first etched with phosphoric acid and air-dried. To further enhance bond strength, the substrate may be treated with a primer. For ease of application, dentists may use multi-part adhesive systems that consist of a combination of etchant, adhesive, and primer in a single formulation. Upon application, most of this bond strength comes from micromechanical bonding (or interlocking). Although the chemical bond between the dental adhesive and the tooth tissue is relatively limited, some studies suggest that chemical bonding is the primary factor determining bond longevity.

[0005] However, even if the initial attachment is strong, acrylic adhesives steadily lose bond strength over time. The progressive loss of bond strength has been extensively studied and is understood to be the result of several factors (e.g., hydrolysis of the acrylic adhesive, degradation of dentin collagen by activated matrix metalloproteinases, and poor initial adhesion of acrylic adhesives to moist dentin and enamel).

[0006] Furthermore, removal of hydroxyapatite by etching permanently damages tooth enamel and increases the likelihood of future caries. The liquid etchant can flow onto the gums and irritate tissue. Patients may have allergic reactions to the etchant.

[0007] Thus, a need exists for the convenient use of catechol-containing materials that improve the adhesive strength and longevity of dental adhesives in the wet conditions of the oral cavity. Summary of the Invention

[0008] In one aspect, the present invention relates to a polymer layer comprising a catechol-containing film comprising a polymer containing a catechol, semi-quinone, or quinone that improves the adhesive strength of a dental adhesive. In some embodiments, the catechol-containing film comprises a monomeric, oligomeric, or polymeric catechol or catechol-containing material, where the catechol exists as a catechol and / or as a semi-quinone and / or as a quinone without the presence of an amine, and the polymer layer optionally comprises at least one of a) a reactive species other than the catechol or catechol-containing material, and b) a catalyst, co-catalyst, or accelerator.

[0009] In some embodiments, the polymer layer comprises a reactive species other than catechol or a catechol-containing material, the reactive species comprising an acrylic, a silane, a silicone, a methacrylate, polyvinyl alcohol (PVA), or a combination thereof.

[0010] In some embodiments, the polymer layer comprises a reactive species other than catechol or a catechol-containing material, the reactive species being selected from the group consisting of 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 dimethacrylates, amide modified bisphenol-A, CH 3 These acrylics include BisGMA, acidic bisphenol-A dimethacrylate, dimethacrylates from cycloaliphatic epoxides, aromatic urethane dimethacrylates, urethane modified BisGMA, acidic aromatic dimethacrylates, oxydiphthalic acid dimethacrylate, phenyl dihydroxymethacrylate diphosphonate, acidic bisphenol-A dimethacrylate, morpholine carbonyl methacrylate, and phenyl carbonate methacrylate.

[0011] In some embodiments, the invention contemplated herein further comprises a free radical polymerization initiator, such as an acrylate polymerization initiator (including, for example, photoactivated ones 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)-phosphine oxide, or combinations thereof).

[0012] In some embodiments, the reactive species is an acrylate.

[0013] In some embodiments, the polymer layer is disposed on a dental substrate. In some embodiments, the dental substrate comprises one or more of a ceramic, a polymer, a composite, and a metal. In some embodiments, the ceramic comprises zirconia or porcelain, the polymer comprises acrylic, polypropylene, poly(methyl methacrylate), or one or more combinations thereof, the composite comprises one or more of enamel, dentin, or combinations thereof, and the metal comprises one or more of titanium, stainless steel, gold, chromium, or one or more combinations thereof.

[0014] In some embodiments, the polymer layer comprises one or more of a primer layer, an adhesive layer, or a layered restorative. In some embodiments, the polymer layer has a thickness of about 10 nanometers to about 500 microns. In some embodiments, the catechol or catechol-containing material comprises poly-catechol styrene (PCS). In some embodiments, the PCS comprises a 0.1% solution of PCS.

[0015] In some embodiments, the invention contemplated herein further comprises one or more photoinitiators including one or more of camphorquinone (CQ), azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-dimethoxy-2-phenylacetophenone, and one or more combinations thereof. In some embodiments, the adhesive life of the dental adhesive is improved over a dental adhesive that does not include a catechol-containing material.

[0016] In one aspect, the invention provides a method of coating a substrate, comprising disposing a polymer layer of claim 1 on a surface of the substrate.

[0017] In some embodiments, the substrate comprises a dental substrate including one or more of ceramic, polymer, composite, and metal, wherein the ceramic comprises zirconia or porcelain, the polymer comprises acrylic, polypropylene, poly(methyl methacrylate), or one or more combinations thereof, the composite comprises one or more of enamel, dentin, or one or more combinations thereof, and the metal comprises one or more of titanium, stainless steel, gold, chromium, or one or more combinations thereof.

[0018] In some aspects of the method, the substrate is wet, dry, semi-wet, or moist. In some aspects of the method, the substrate is within the oral cavity of the subject. In some aspects, the bond longevity of the dental adhesive is improved over a dental adhesive that does not include a catechol-containing material. [Brief description of the drawings]

[0019] [Figure 1] FIG. 1 depicts a schematic diagram of an exemplary procedure for placing a dental restoration with a composite filling. This schematic diagram, obtained from Jain, A., 2016, depicts an exemplary technique for placing a light-cured composite restoration.

[0020] [Diagram 2] FIG. 2 is a schematic diagram showing the application of a composite filler.

[0021] [Diagram 3] FIG. 3 is a schematic diagram showing the use of ceramics for bridgework and dental implants.

[0022] [Figure 4] FIG. 4 is a schematic diagram of exemplary interactions of catechol with various types of surfaces.

[0023] [Diagram 5] FIG. 5 is a schematic diagram showing the auto-polymerization and structure of polydopamine.

[0024] [Figure 6] Figure 6 shows that poly(catechol-styrene) (PCS) enamel priming promotes adhesion between dental acrylic and dental brackets. The primer (0.1% PCS in acetone) improves the adhesion of brackets to the enamel surface using a general-purpose (or all-purpose) self-etching dental adhesive (Henry Schein Natural Elegance Universal One). Samples were cured in water for 48 hours and the force required to displace the brackets was measured. Error bars are standard error of the mean.

[0025] [Figure 7] FIG. 7 shows that PCS priming enhances adhesive strength to wet zirconia. After priming with PCS or a silane-based / 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP)-containing dental primer, dental adhesive was applied to the zirconia samples in either a dry or pre-wet state. The left figure depicts a schematic of the experimental setup. The right figure depicts the results showing that PCS priming improves adhesion to wet ceramic surfaces.

[0026] [Figure 8] Figure 8 shows results indicating that PCS priming provides long term adhesion to dentin. The left image depicts a schematic of how the adhesive is applied. Wet or dry zirconia was primed with either Silane / MDP or PCS. A general purpose dental adhesive was then applied and light cured. The displacement force was then measured. The right image depicts flexural strength. PCS improves strength when applied to wet zirconia.

[0027] [Figure 9] Figure 9 shows the conversion of UDMA in the presence of PCS. The conversion of UDMA with 0.5 w / w% camphorquinone / co-initiator was measured over time using FTIR-ATR. Formulations with different concentrations of PCS were irradiated in situ on the ATR crystal.

[0028] [Figure 10] Figure 10 shows the bond strength data using PCS as a primer with photoinitiator loading as adhesion promoter for dental acrylic on dentin surface. The results show that a 0.1% PCS primer layer with 0.1% camphorquinone (CQ) photoinitiator loading is sufficient to improve and promote adhesion of dental acrylic (FILTEK®, CR) to dentin surface. Samples were cured for 24 hours and then shear tested. Error bars are standard deviation of the mean.

[0029] [Figure 11] Figure 11 shows that reduction of bulk PCS increases adhesion to aluminum. PCS was dissolved in 100% acetone or 90% acetone and 10% acetic acid. Acidification significantly increased adhesion strength. Error bars are standard error.

[0030] [Figure 12]Figure 12 shows that dental acrylic is fully polymerized after 48 hours when using 0.1% PCS primer as an adhesion promoter. The left figure shows that 48 hours is the optimum cure time for dental acrylic (Clearfil SE Bond) to be fully polymerized using PCS as an adhesion promoter. Samples were shear tested after 48 hours and show that the bond is fully cured and remains stable for at least 24 hours. The right figure shows that the optimum PCS percentage is approximately 0.1% in acetone. Samples were cured dry. Error bars represent standard error of the mean. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] In this disclosure, the singular forms "a," "an," and "the" include plural references and a reference to a particular numerical value includes at least that particular value unless the context clearly dictates otherwise. Thus, for example, a reference to "a material" is a reference to at least one of such materials and other equivalents known to those of skill in the art.

[0032] In this disclosure, the term "subject" includes either a human or a non-human animal. In some aspects, a subject is a human or a non-human mammal. In some aspects, a subject is a human.

[0033] When expressing values ​​as approximations, it will be understood that the particular value constitutes another embodiment by using the description "about" or "substantially". In general, the use of the term "about" or "substantially" indicates approximations that may vary depending on the desired properties sought to be obtained by the disclosed subject matter and should be interpreted in the particular context in which it is used based on its function. Those 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 non-limiting way of determining the scope of the term "about" or "substantially". In other cases, the scale used for the continuous values ​​may be used to determine the intended range that can be used for the term "about" or "substantially" for each value. All ranges are inclusive and combinable herein. That is, reference to values ​​described in ranges includes all values ​​within that range.

[0034] When presenting a list, it is to be understood that each individual member of that list and every combination of that list is to be construed as a separate embodiment unless otherwise stated. For example, a list of embodiments presented as "A, B, or C" is to be construed as including the embodiments "A", "B", "C", "A or B", "A or C", "B or C", or "A, B, or C".

[0035] It is to be understood that certain features of the disclosure that are described for clarity herein in the context of separate embodiments may also be provided in combination in a single embodiment. That is, each individual embodiment is considered combinable with any other embodiment, and such combination is considered a separate embodiment, unless expressly incompatible or excluded. Conversely, various features of the disclosure that are described for brevity in the context of a single embodiment may also be provided separately or in any subcombination. It is further noted that the claims may be drafted to exclude any optional element. Accordingly, this statement is intended to serve as a prerequisite for using exclusive terminology such as "solely," "only," and the like in connection with the recitation of claim elements, or for using "negative" limitations. Finally, an embodiment may be described as part of a series of steps or part of a more general structure, and each of the steps described above may also be considered an independent embodiment in itself.

[0036] Marine mussel adhesive proteins have attracted considerable research interest, at least in part because they adhere strongly to a wide range of substrates in the presence of water.

[0037] Mussels secrete mussel foot proteins (Mfps) that enable them to attach to a variety of surfaces (e.g., rocks, wood, metal surfaces, sea creature shells, etc.) in wet environments. One of the key components of Mfps is the relatively abundant rare amino acid 3,4-dihydroxy-L-phenylalanine (DOPA). DOPA contains a catechol side chain, and this catechol group has been shown to be the main contributor to the remarkable adhesive properties of Mfps. Catechol can form a wide range of reversible bonds with surfaces (e.g., hydrogen bonds, cation-π interactions, and metal ion complexation). Catechol can also form covalent bonds with certain adhesive surfaces (e.g., protein surfaces) as well as self-crosslink (Figure 4).

[0038] This remarkable understanding of catechol chemistry can be used in a wide range of applications and has stimulated the development of catechol-containing bioadhesives and biomaterials.

[0039] Catechol groups are easily oxidized to semi-quinones or quinones. Several studies have reported in the literature that oxidation significantly reduces adhesion to inorganic surfaces. During the oxidation process of catechol to quinones, reactive oxygen species (ROS) are produced as by-products.

[0040] While catechols (reduced forms) are required for strong adhesion to inorganic surfaces, quinones (oxidized forms) can covalently bond with organic materials via Schiff base addition or Michael reactions. Mussel-inspired biomimetic adhesives can be considered as bifunctional "catechol-quinone" mixtures.

[0041] The catechol-containing material of the present invention can be used as a restorative material, such as a primer, adhesive, or sealant for teeth or other dental substrates. The catechol-containing material can be used as an adhesive, a part of a restorative material for a restoration, or a sealant, etc. The catechol-containing material can be used with one or more dental materials (including, for example, one or more commercial adhesives, fillings, etc.) to improve the adhesion or performance of the dental material. The catechol-containing material can be used, for example, as a primer. In some embodiments, the dental substrate includes a dental implant, such as an artificial tooth having, for example, a ceramic surface, such as zirconia or porcelain, a tooth substrate including natural tooth substance, such as enamel, dentin, or a combination of the two, a fixed orthodontic device including an oral bracket (e.g., titanium, stainless steel, gold, chromium, polypropylene, acrylic, poly(methyl methacrylate) (PMMA), or other stable material), and / or a ceramic restorative device (e.g., zirconia crown, etc.).

[0042] In one aspect, the present disclosure is directed to a polymer layer, as shown in FIG. 6 as a PCS primer layer, comprising a catechol-containing monomer, polymer, or oligomer, where the catechol is present as a catechol and / or as a semi-quinone and / or as a quinone without the presence of a primary amine or secondary amine, and the polymer layer also comprises a reactive material that does not react with the catechol or quinone.

[0043] In one aspect, the present invention is directed to a polymer layer, comprising a catechol-containing monomer, polymer or oligomer, as shown in FIG. 6 as a PCS primer layer, wherein the catechol is present as catechol and / or semi-quinone and / or quinone without the presence of a primary amine or secondary amine, the polymer layer optionally comprising a reactive material that does not react with the catechol or quinone, the polymer layer further comprising a bulk adhesive layer, shown in FIG. 6 as a universal adhesive layer, which is disposed adjacent to and in contact with the polymer layer.

[0044] In one aspect, the present disclosure is directed to a polymer layer comprising a catechol-containing monomer, polymer, or oligomer, wherein the catechol is present as a catechol and / or semi-quinone and / or quinone without the presence of a primary amine or a secondary amine, the polymer layer further comprising a bulk adhesive layer disposed adjacent or in contact with the polymer layer.

[0045] 6 depicts a general schematic diagram of one embodiment of a polymer layer comprising a catechol-containing monomer, polymer, or oligomer and a layered article comprising a polymer layer as described herein. The layered article may have a substrate on which the polymer layer is disposed in contact. The layered article may also have a bulk adhesive layer disposed on and in contact with the polymer layer.

[0046] In some aspects, the catechol-containing monomer, polymer, or oligomer in the polymer layer is a monomer. In some aspects, the catechol-containing monomer, polymer, or oligomer in the polymer layer is an oligomer. The catechol-containing monomer, polymer, or oligomer in the polymer layer is a polymer.

[0047] In some embodiments, the polymer layer comprises a reactive species other than catechol or a catechol-containing material, such as, for example, 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, CH 3 These acrylics include BisGMA, acidic bisphenol A dimethacrylate, dimethacrylates from cycloaliphatic epoxides, aromatic urethane dimethacrylates, urethane modified BisGMA, acidic aromatic dimethacrylates, oxydiphthalic acid dimethacrylate, phenyl dihydroxymethacrylate diphosphonate, acidic bisphenol-A dimethacrylate, morpholine carbonyl methacrylate, and phenyl carbonate methacrylate.

[0048] In some embodiments, the polymer layer comprises a free radical polymerization initiator, such as an acrylate polymerization initiator (including, for example, photoactivated ones 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)-phosphine oxide, or combinations thereof).

[0049] In some embodiments, the acrylate is an acrylate monomer containing a vinyl group and at least one of a carboxylic acid ester and a carboxylic acid nitrile, and the acrylate is linear or branched. In some embodiments, the acrylate is ethyl acrylate, ethylene methyl acrylate, methyl methacrylate, 2-chloroethyl vinyl ether, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, butyl acrylate, trimethylolpropane triacrylate (TMPTA), or a combination thereof.

[0050] In one aspect, the polymer layer has a thickness of about 10 nanometers to about 100 microns. In some embodiments, the polymer layer has a thickness of about 15 nanometers to about 50 microns. In some embodiments, the polymer layer has a thickness of about 15 nanometers to about 15 microns. In some embodiments, the polymer layer has a thickness of less than about 150 nanometers to about 15 microns. In some embodiments, the polymer layer has a thickness of about 150 nanometers to about 1.5 microns.

[0051] In some embodiments, the polymer layer is 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 about 500 nanometers to about 550 nanometers, or about 550 nanometers to about 600 nanometers, or about 600 nanometers to about 650 nanometers, or about 650 nanometers to about 700 nanometers, or about 700 nanometers to about 750 nanometers, or about 750 nanometers to about 800 nanometers, or about 800 nanometers to about 850 nanometers, or about 850 nanometers to about 900 nanometers, or about 900 nanometers to about 950 nanometers, or about 950 nanometers to about 1000 nanometers.

[0052] In some embodiments, the polymer layer has a thickness of about 1 micron to about 1.5 microns, or about 1.5 microns to about 5 microns, or about 5 microns to about 10 microns, or about 10 microns to about 15 microns, or about 15 microns to about 20 microns, or about 20 microns to about 25 microns, or about 25 microns to about 30 microns, or about 30 microns to about 35 microns, or about 35 microns to about 40 microns, or about 40 microns to about 45 microns, or about 45 microns to about 50 microns, or about 50 microns to about 55 microns, or about 55 microns to about 60 microns, or about 60 microns to about 65 microns, or about 65 microns to about 70 microns, or about 70 microns to about 75 microns, or about 75 microns to about 80 microns, or about 80 microns to about 85 microns, or about 85 microns to about 90 microns, or about 90 microns to about 95 microns, or about 95 microns to about 100 microns.

[0053] In one aspect, the catechol-containing monomer, polymer, or oligomer in the polymer layer comprises poly-catecholstyrene (PCS).

[0054] 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 combinations thereof, or one or more 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.

[0055] In some embodiments, the PCS comprises a solution containing about 0.001% to 10% PCS, about 0.05% to about 5% PCS, about 0.01% to about 2% PCS, about 0.5% to about 1% PCS, about 0.1% to about 0.5% PCS, and any percentage and percentage range therebetween.

[0056] In some embodiments, the PCS contains about 20% to about 22% catechol, or about 22% to about 24% catechol, or about 24% to about 26% catechol, or about 26% to about 28% catechol, or about 28% to about 30% catechol, or about 30% to about 32% catechol, or about 32% to about 34% catechol, or about 34% to about 36% catechol, or about 36% to about 38% catechol, or about 38% to about 40% catechol.

[0057] In some embodiments, the polymer layer comprises a reactive material that does not react with catechol or quinone. In some embodiments, the reactive material does not react with catechol or quinone at ambient temperatures. In some embodiments, the reactive material does not react with catechol or quinone at low temperatures.

[0058] In some aspects, the reactive material that does not react with the catechol or quinone is a resin, an oligomer, a polymer, or a monomer. In some aspects, the reactive material is an oligomer. In some aspects, the reactive material is a polymer. In some aspects, the reactive material is a monomer.

[0059] In one aspect, the polymer layer is a continuous layer. In one aspect, the polymer layer is a discontinuous layer. In one aspect, the polymer layer is a patterned or textured layer.

[0060] In some embodiments, the polymer layer includes one or more additives. In some embodiments, the one or more additives include one or more catalysts (e.g., one or more photoinitiators). The one or more photoinitiators may include one or more of camphorquinone (CQ), azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-dimethoxy-2-phenylacetophenone, and one or more combinations thereof. In some embodiments, the photoinitiator 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; the catalyst, co-catalyst, or accelerator is an acrylate catalyst or combinations thereof that accelerate the acrylate polymerization reaction.

[0061] In some embodiments, the photoinitiator is CQ. CQ may be used in a range of about 0.01% to about 1%, about 0.05% to about 0.75%, about 0.1% to about 0.5%, and any percentage or range of photoinitiators therebetween. In some embodiments, CQ is used at a concentration of 0.1%.

[0062] In one aspect, the bulk adhesive layer comprises one or more suitable dental resins. In some embodiments, the bulk adhesive layer comprises one or more methacrylates. In some embodiments, the bulk adhesive layer comprises a catechol-containing monomer, oligomer, or polymer. In some embodiments, the catechol-containing monomer, oligomer, or polymer comprises PCS.

[0063] In one aspect, the bulk adhesive layer is a self-cure adhesive and a catalyst is activated during application. In some embodiments, the bulk adhesive layer is a light-cure adhesive. In some embodiments, the bulk adhesive layer is a dual-cure adhesive that includes or has the properties of both a self-cure adhesive and a light-cure adhesive. In some embodiments, the bulk adhesive layer is a moisture-cure adhesive.

[0064] In one aspect, the present disclosure is directed to a polymer layer as described herein disposed on a substrate surface. In some embodiments, the substrate comprises a dental implant, such as an artificial tooth having a ceramic surface or the like (e.g., zirconia or porcelain), a dental substrate (e.g., enamel, dentin, or a combination of the two), a fixed orthodontic device including an orthodontic bracket (e.g., titanium, stainless steel, gold, chromium, polypropylene, or other suitable material), and / or a ceramic restorative device (e.g., zirconia crown, etc.). In some embodiments, the substrate is wet, dry, semi-wet, or moist.

[0065] In some embodiments, the substrate is a dental implant, such as an artificial tooth having a ceramic surface, such as zirconia or porcelain. In some embodiments, the substrate is a tooth substrate, such as enamel, dentin, or a combination of the two. In some embodiments, the substrate is one or more fixed orthodontic devices, such as one or more orthodontic brackets or mounting posts, such as titanium posts, for mounting artificial teeth. In some embodiments, the one or more fixed orthodontic devices are orthodontic brackets made of one or more suitable materials, including, for example, titanium, stainless steel, gold, chromium, polypropylene, PMMA, or other suitable materials. In some embodiments, the substrate is one or more ceramic restorative devices, such as, for example, zirconia crowns.

[0066] In some embodiments, the substrate is a polymeric compound. In some embodiments, the substrate is dentin. In some embodiments, the substrate is enamel. In some embodiments, the substrate is a ceramic (e.g., zirconia or porcelain). In some embodiments, the substrate is a metal (e.g., titanium).

[0067] In some embodiments, the substrate has a smooth surface. In some embodiments, the substrate has a rough surface. In some embodiments, the substrate has a flat surface. In some embodiments, the substrate has an uneven surface.

[0068] In some embodiments, the substrate is wet. In some embodiments, the substrate is dry. In some embodiments, the substrate is semi-wet. In some embodiments, the substrate is moist.

[0069] In some embodiments, the substrate is a rigid substrate. In some embodiments, the substrate is a semi-rigid substrate. In some embodiments, the substrate is a flexible substrate.

[0070] In some embodiments, the adhesive strength is improved by including a catechol-containing polymer. For example, in some embodiments, when a catechol-containing primer coating layer is applied to a substrate in combination with an adhesive layer, as shown in Figure 6, the adhesive strength is improved as compared to the adhesive strength of a substrate coated with only the adhesive.

[0071] In some embodiments, the adhesive durability is improved by including a catechol-containing polymer. For example, in some embodiments, as shown in Figure 8, when a catechol-containing primer coating layer is combined with an adhesive layer and applied to a substrate, the adhesive strength is improved over a sustained period of time compared to the adhesive strength of a substrate coated with only the adhesive. In some embodiments, the adhesive strength is improved over the adhesive alone for periods of up to 1 day, from about 1 to about 7 days, from about 1 to about 14 days, from about 7 to about 28 days, from about 28 to about 60 days, from about 30 to about 90 days, from about 60 to about 120 days, from about 90 to about 180 days, from about 120 to about 240 days, from about 180 to about 360 days, from about 240 to about 480 days, from about 360 to about 720 days, and any number of days in between.

[0072] In one aspect, the present disclosure is directed to a method of coating a substrate comprising disposing a polymer layer described herein on a surface of the substrate. In some embodiments, the substrate is a dental substrate, such as a tooth substrate (e.g., enamel, dentin, or a combination of the two), a fixed orthodontic device (e.g., an orthodontic bracket), a ceramic restorative device (e.g., a zirconia crown), etc. The coating may be applied to the dental substrate in situ. For example, the coating may be applied to an intact tooth inside the oral cavity of a subject. The coating may be applied ex vivo. For example, the coating may be applied to a dental device prior to placement in the oral cavity. The method of disposing the polymer layer described herein is not particularly limited, as would be recognized by one of ordinary skill in the art.

[0073] In some embodiments, the method of coating the substrate comprises disposing a polymer layer on the substrate by spin coating, dip coating, spray coating, ink jet printing, or a similar method. In some embodiments, the method comprises disposing a polymer layer on the substrate by spin coating. In some embodiments, the method comprises disposing a polymer layer on the substrate by dip coating. In some embodiments, the method comprises disposing a polymer layer on the substrate by spray coating. In some embodiments, the method comprises disposing a polymer layer on the substrate by ink jet printing.

[0074] In some embodiments, the method of coating a substrate comprises disposing a polymer layer on the substrate, the polymer layer being applied to the substrate as a solution. In some embodiments, the solution comprises from about 0.001% to about 10% by weight of a catechol-containing monomer, polymer, or oligomer. In some embodiments, the solution comprises from about 0.01% to about 5% by weight of a catechol-containing monomer, polymer, or oligomer. In some embodiments, the solution comprises from about 0.01% to about 1% by weight of a catechol-containing monomer, polymer, or oligomer. In some embodiments, the solution comprises from about 0.1% to about 1% by weight of a catechol-containing monomer, polymer, or oligomer.

[0075] In some embodiments, the solution comprises from about 0.001% to about 0.005% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.005% to about 0.01% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.01% to about 0.02% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.02% to about 0.03% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.03% to about 0.04% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.04% to about 0.05% by weight of a catechol-containing monomer, polymer, or oligomer. monomers, polymers, oligomers; about 0.05% by weight to about 0.06% by weight of a catechol-containing monomer, polymer, oligomer; about 0.06% by weight to about 0.07% by weight of a catechol-containing monomer, polymer, oligomer; about 0.07% by weight to about 0.08% by weight of a catechol-containing monomer, polymer, oligomer; about 0.08% by weight to about 0.09% by weight of a catechol-containing monomer, polymer, oligomer; about 0.09% by weight to about 0.1% by weight of a catechol-containing monomer, polymer, oligomer; about 0.1% by weight to about 0.11% by weight of a catechol-containing monomer, polymer, oligomer polymers, oligomers; about 0.11% by weight to about 0.12% by weight of a catechol-containing monomer, polymer, oligomer; about 0.12% by weight to about 0.13% by weight of a catechol-containing monomer, polymer, oligomer; about 0.13% by weight to about 0.14% by weight of a catechol-containing monomer, polymer, oligomer; about 0.14% by weight to about 0.15% by weight of a catechol-containing monomer, polymer, oligomer; about 0.15% by weight to about 0.2% by weight of a catechol-containing monomer, polymer, oligomer; about 0.2% by weight to about 0.25% by weight of a catechol-containing monomer, polymer, Oligomers; from about 0.25% to about 0.3% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.3% to about 0.35% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.35% to about 0.4% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.4% to about 0.45% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.45% to about 0.5% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.5% to about 0.75% by weight of a catechol-containing monomer, polymer, or oligomer; from about 0.75% to about 1% by weight of a catechol-containing monomer, polymer, or oligomer; about 1.25% to about 1.5% by weight of a catechol-containing monomer, polymer, or oligomer; about 1.5% to about 1.75% by weight of a catechol-containing monomer, polymer, or oligomer; about 1.75% to about 2% by weight of a catechol-containing monomer, polymer, or oligomer.

[0076] 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 about 0.001% to about 10% by weight PCS. In some embodiments, the solution comprises about 0.01% to about 5% by weight PCS. In some embodiments, the solution comprises about 0.01% to about 1% by weight PCS. In some embodiments, the solution comprises about 0.1% to 1% by weight PCS.

[0077] In some embodiments, the solution contains about 0.001% to about 0.005% by weight PCS, or about 0.005% to about 0.01% by weight PCS, or about 0.01% to about 0.02% by weight PCS, or about 0.02% to about 0.03% by weight PCS, or about 0.03% to about 0.04% by weight PCS, or about 0.04% to about 0.05% by weight PCS, or about 0.05% by weight PCS. about 0.06% by weight of PCS, or about 0.06% by weight to about 0.07% by weight of PCS, or about 0.07% by weight to about 0.08% by weight of PCS, or about 0.08% by weight to about 0.09% by weight of PCS, or about 0.09% by weight to about 0.1% by weight of PCS, or about 0.1% by weight to about 0.11% by weight of PCS, or about 0.11% by weight to about 0.12% by weight of PCS, or about 0.12% by weight to about 0. 0.13% by weight PCS, or about 0.13% to about 0.14% by weight PCS, or about 0.14% to about 0.15% by weight PCS, or about 0.15% to about 0.2% by weight PCS, or about 0.2% to about 0.25% by weight PCS, or about 0.25% to about 0.3% by weight PCS, or about 0.3% to about 0.35% by weight PCS, or about 0.35% to about 0.4% by weight PCS. % PCS, or about 0.4% to about 0.45% by weight PCS, or about 0.45% to about 0.5% by weight PCS, or about 0.5% to about 0.75% by weight PCS, or about 0.75% to about 1% by weight PCS, or about 1.25% to about 1.5% by weight PCS, or about 1.5% to about 1.75% by weight PCS, or about 1.75% to about 2% by weight PCS.

[0078] In some embodiments, the solution also comprises an organic solvent for dissolving the aqueous or catechol-containing monomers, polymers, oligomers, hi some embodiments, the organic solvent is acetone, tert-butyl alcohol, ethanol, isopropyl alcohol, or a combination thereof.

[0079] 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 one or more combinations 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 one or more combinations 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 or acidifying agents. For example, in some embodiments, the organic solvent further comprises acetic acid.

[0080] 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.

[0081] In some embodiments, the pH of the solution is 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 8.5-9, or about 9-9.5, or about 9.5-10, or about 10-10.5, or about 10.5-11.

[0082] In some embodiments, the method of coating a substrate comprises disposing a polymer layer on a substrate, the substrate comprising a polymeric compound, dentin, enamel, ceramic, metal, or a combination thereof, and the substrate is wet, semi-wet, or moist. In some embodiments, the method of coating a substrate comprises performing within the oral cavity of a subject.

[0083] In some embodiments, the method of coating a substrate comprises disposing a polymer layer on a substrate comprising a polymeric compound. In some embodiments, the method comprises disposing a polymer layer on a substrate comprising dentin. In some embodiments, the method comprises disposing a polymer layer on a substrate comprising enamel. In some embodiments, the method comprises disposing a polymer layer on a substrate comprising a ceramic (e.g., zirconia or porcelain). In some embodiments, the method comprises disposing a polymer layer on a substrate comprising a metal (e.g., titanium, stainless steel, gold, chromium, or other suitable metal). In some embodiments, the method comprises disposing a polymer layer on a substrate comprising poly(methyl methacrylate) (PMMA), polypropylene, or other suitable plastic.

[0084] In some embodiments, the method of coating a substrate comprises disposing a polymer layer on a wet substrate. In some embodiments, the method comprises disposing a polymer layer on a dry substrate. In some embodiments, the method comprises disposing a polymer layer on a semi-wet substrate. In some embodiments, the method comprises disposing a polymer layer on a wet substrate.

[0085] In some embodiments, the method of coating a substrate comprises disposing a polymer layer on a substrate in a dry environment. In some embodiments, the method of coating a substrate comprises disposing a polymer layer on a substrate in an ambient environment. In some embodiments, the method of coating a substrate comprises disposing a polymer layer on a substrate in a moist environment. In some embodiments, the method of coating a substrate comprises disposing a polymer layer on a substrate in an aqueous environment. In some embodiments, the environment comprises the oral cavity of a subject.

[0086] In some embodiments, the method of making a substrate comprises disposing a polymer layer on a substrate as a continuous layer. In some embodiments, the method of making a substrate comprises disposing a polymer layer on a substrate as a non-continuous layer. In some embodiments, the method of making a substrate comprises disposing a polymer layer on a substrate as a patterned or textured layer.

[0087] In some embodiments, the method of coating the substrate comprises disposing the polymer layer on the substrate by spin coating, dip coating, spray coating, flood coating, brushing, wiping, or a similar method. In some embodiments, the method comprises disposing the polymer layer on the substrate by spin coating. In some embodiments, the method comprises disposing the polymer layer on the substrate by dip coating. In some embodiments, the method comprises disposing the polymer layer on the substrate by spray coating. In some embodiments, the method comprises disposing the polymer layer on the substrate by ink jet printing. In some embodiments, the method comprises disposing the polymer layer on the substrate by flood coating. In some embodiments, the method comprises disposing the polymer layer on the substrate by brushing. In some embodiments, the method comprises disposing the polymer layer on the substrate by wiping.

[0088] In one aspect, the present disclosure is directed to a method of manufacturing a substrate comprising disposing a polymer layer described herein on a surface of the substrate, and further comprising disposing a bulk adhesive layer on the polymer layer. The method of disposing the bulk adhesive layer described herein is not particularly limited, as would be recognized by one of ordinary skill in the art.

[0089] In some embodiments, the method of manufacturing a substrate comprises disposing a bulk adhesive layer on the polymer layer by spin coating, dip coating, spray coating, ink jet printing, flood coating, brushing, wiping, or a similar method. In some embodiments, the method comprises disposing the bulk adhesive layer on the polymer layer by spin coating. In some embodiments, the method comprises disposing the bulk adhesive layer on the polymer layer by dip coating. In some embodiments, the method comprises disposing the bulk adhesive layer on the polymer layer by spray coating. In some embodiments, the method comprises disposing the bulk adhesive layer on the polymer layer by ink jet printing. In some embodiments, the method comprises disposing the bulk adhesive layer on the polymer layer by flood coating. In some embodiments, the method comprises disposing the bulk adhesive layer on the polymer layer by brushing. In some embodiments, the method comprises disposing the bulk adhesive layer on the polymer layer by wiping.

[0090] In some embodiments, the method of making a substrate comprises disposing a bulk adhesive layer on a polymer layer in a dry environment. In some embodiments, the method comprises disposing a bulk adhesive layer on a polymer layer in an ambient environment. In some embodiments, the method comprises disposing a bulk adhesive layer on a polymer layer in a humid environment (e.g., within the oral cavity of a subject). In some embodiments, the method comprises disposing a bulk adhesive layer on a polymer layer in an aqueous environment.

[0091] In some embodiments, the method of making a substrate comprises disposing a bulk adhesive layer as a continuous layer on a polymeric layer on a substrate. In some embodiments, the method comprises disposing a bulk adhesive layer as a discontinuous layer on the polymeric layer. In some embodiments, the method comprises disposing a bulk adhesive layer as a patterned or textured layer on the polymeric layer.

[0092] In some embodiments, the method for disposing the bulk adhesive layer as a non-continuous layer or disposing the polymer layer as a non-continuous layer comprises disposing the layer in a regular pattern or a stochastic (or random) pattern.

[0093] In some embodiments, the regular pattern comprises stripes, a grid, concentric circles, or a dot pattern. In some embodiments, the method comprises disposing the bulk adhesive layer and / or the polymer layer as stripes. In some embodiments, the method comprises disposing the bulk adhesive layer and / or the polymer layer as a grid. In some embodiments, the method comprises disposing the bulk adhesive layer and / or the polymer layer as concentric circles. In some embodiments, the method comprises disposing the bulk adhesive layer and / or the polymer layer as a dot pattern.

[0094] In some embodiments, the method comprises randomly disposing the bulk adhesive layer and / or the polymer layer.

[0095] The bulk adhesive layer and / or polymer layer can be arranged in a specific shape or in a random shape, hi some embodiments, the method comprises arranging the bulk adhesive layer and / or polymer layer as a dot, a circle, a square, a rectangle, a pentagon, a hexagon, or in a random shape.

[0096] In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as a dot. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as a circle. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as an ellipse. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as a triangle. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as a square. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as a rectangle. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as a pentagon. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as a hexagon. In one embodiment, the bulk adhesive layer and / or polymer layer is irregular.

[0097] In some embodiments, the method comprises arranging the bulk adhesive layer and / or the polymer layer as grid lines, crosshairs, random lines, concentric circles, eccentric circles, spaghetti patterns, and flat strips.

[0098] In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as grid lines. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as cross lines. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as random lines. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as concentric circles. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as eccentric circles. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as a spaghetti pattern. In one embodiment, the bulk adhesive layer and / or polymer layer is shaped as flat strips.

[0099] In one aspect, the present disclosure is directed to a layered structure comprising a polymer layer as described herein. In some embodiments, the layered structure comprises a plurality (or multiple) of the polymer layers as described herein. In some embodiments, the layered structure comprises two polymer layers as described herein. In some embodiments, the layered structure comprises three polymer layers as described herein. In some embodiments, the layered structure comprises four polymer layers as described herein. In some embodiments, the layered structure comprises five polymer layers as described herein.

[0100] In one aspect, the present disclosure is directed to a layered construction comprising a polymer layer described herein disposed adjacent and in contact with a bulk adhesive layer.

[0101] In some embodiments, the layered construction comprises a plurality of bulk adhesive layers as described herein. In some embodiments, the layered construction comprises two bulk adhesive layers as described herein. In some embodiments, the layered construction comprises three bulk adhesive layers as described herein. In some embodiments, the layered construction comprises four bulk adhesive layers as described herein. In some embodiments, the layered construction comprises five bulk adhesive layers as described herein.

[0102] The following examples are provided to illustrate some of the concepts described within this disclosure and are intended to provide examples, but should not be construed as limiting the more general aspects described herein. EXAMPLES

[0103] Example 1 - PCS Primed Enamel Promotes Adhesion of Dental Brackets with Dental Acrylic

[0104] Some aspects of the invention contemplated herein relate to a process for enhancing the adhesion of a fixed orthodontic device, a composite resin, or a ceramic restorative material to a dental surface (e.g., enamel or dentin). The adhesion is achieved using an adhesive, such as an acrylic adhesive, and a primer layer, such as PCS. The primer layer may contain other chemical components, such as catalysts, co-catalysts, or accelerators. To evaluate the effect of the PCS primer layer on the bond strength, the fracture strength of dental brackets bonded with an acrylic dental adhesive was tested.

[0105] material

[0106] CUSP-LOK™ I dental brackets (Xemax; Pasadena, Calif.) were used to bond to the tooth structures for testing. Briefly, non-caries extracted molars (age 17 years < age < 33 years) were obtained, cleaned, and stored in Chloramine-T at 4° C. prior to use. The brackets consisted of 3 / 4 inch 14K gold chain attached to stainless steel orthodontic brackets. The brackets had a bonding area of ​​3 mm x 4 mm on the surface.

[0107] The brackets were bonded to the teeth using NATURAL ELEGANCE® Universal One (Henry Schein; Melville, NY) dental adhesive, which is a light-cured, self-etching (pH 2.8) bisphenol A glycidyl methacrylate (bis-GMA) adhesive. Ultramarine Etching Gel (40% phosphoric acid) (Henry Schein; Melville, NY) was used and the adhesive was cured using a 5W LED curing light lamp (ORILAO®, China).

[0108] The teeth were embedded and attached to the test devices using Amazing Casting Resin (ALUMILITE™; Galesburg, Mich.), a two-part epoxy-based resin.

[0109] 22-gauge copper wires (Hillman Group; Cincinnati, Ohio) were attached onto the dental brackets.

[0110] The fused teeth were primed with PCS primer. The primer used was a 0.1% solution of PCS polymer diluted in acetone. PCS was synthesized in the laboratory of Professor Jon Wilker (Purdue University) using an established synthesis approach.

[0111] Adhesion strength measurements were performed using an Instru-Met Model 15k lb (Instru-Met; Union, NJ) adhesion strength tester. The device was equipped with a 10 lb tension load cell (INSTRON®; Norwood, MA).

[0112] Adhesion to zirconia

[0113] method

[0114] KATANA™ Zirconia STML specimens were sectioned, sintered, and embedded in acrylic resin. The specimen surfaces were water-cooled with 600-grit silicon carbide abrasive and air-particle abraded with 50 μm aluminum oxide. A total of 100 (n=25) samples were prepared and divided into four test groups, with the first two serving as comparative controls: ceramic primer (CLEARFIL™ Ceramic Primer Plus) on dry surface, ceramic primer on wet surface, experimental primer on dry surface, and experimental primer on wet surface. After 10 seconds of primer application, the surface was air-sprayed, micro-brushed with adhesive (OPTIBOND™ Solo Plus), and light-cured for 20 seconds. Cylindrical composite samples (2.1 mm diameter, 3 mm height) were bonded to the zirconia surface by packing the material into a cylindrical plastic matrix and light-curing for 40 seconds. The specimens were stored for 48 hours at room temperature (24°C) and then mounted on a universal testing machine. SBS was measured at a crosshead speed of 0.5 mm / min and expressed in MPa. Analysis of variance (ANOVA) and pairwise comparisons using Tukey's test were used for statistical analysis.

[0115] result

[0116] The mean SBS values ​​were 33.6 MPa and 25.4 MPa for the dry and wet control groups, respectively. The mean SBS values ​​were 32.1 MPa and 32.7 MPa for the dry and wet experimental groups, respectively. The results for the dry groups were not different (p>0.05), but were statistically significantly different (p<0.05) between the wet experimental and wet control groups. As shown in Figure 7, the wet surface did not change the adhesion performance of the experimental primer.

[0117] conclusion

[0118] Pretreatment of zirconia surfaces with a mussel-biomimetic primer can improve adhesion strength to the surface in wet surface conditions.

[0119] Example 2 - Improving the durability of acrylic adhesives by priming dentin with PCS

[0120] To test the hypothesis that PCS primers may not only have the ability to increase initial bond strength but may also increase the durability of acrylic / dentin bonds, the bond durability to dentin was tested using micromechanical fatigue testing as described above. Without being bound by theory, it was hypothesized that the oxidized catechol moieties (quinones) may covalently bond to exposed collagen via Michael addition to Schiff bases or free -NH2 and -SH groups (Guvendiren et al., 2009; LaVoie et al., 2005; Burzio et al., 2000).

[0121] material

[0122] Non-carious extracted molars (age 17 years < age < 33 years) were obtained and divided into dentin blocks measuring 2 × 2 × 2 mm. 3 The dentin was cut into pieces. DENTSPLY SIRONA® (York, PA) caulk, a 34% phosphoric acid gel, was used to etch the dentin. A primer-adhesive that combines SCOTCHBOND® Universal Adhesive (3M®; St. Paul, MN) total etching, self-etching, and selective etching adhesives was used. G-aenial SCULPT™ (Tokyo, Japan) composite, a light-cured, universal nano-hybrid compactable composite resin material used for fillings, was used as the composite.

[0123] method

[0124] The effect of PCS primer on the adhesion of dental adhesives to dentin was evaluated using a resin-dentin interface fatigue test as described by Mutluay et al. in 2013. Briefly, the process involves acid etching the dentin blocks for 15 seconds, followed by rinsing with water and air drying. PCS (0.1% in acetone) was then brushed onto the dentin bonding surface and allowed to air dry for 10 seconds. SCOTCHBOND® (3M® primer + adhesive combination, St. Paul, MN) was then added and light cured for 15 seconds. G-aenial SCULPT™ composite material was added and light cured for 30 seconds. The samples were then immersed in water for 24 hours and the initial bond strength measurements were read. The remaining samples were then incubated in HBSS (Hank's Balanced Solution) at 37°C for aging. After 10 days of incubation, bond strength measurements were reassessed.

[0125] result

[0126] As shown in Figure 8, the adhesive strength of the control sample decreased significantly (~40%) over the assay period, while the PCS-primed sample showed virtually no loss in strength over the 10 day aging period. The PCS-primed sample initially had lower strength than the control, which may have been due to PCS inhibiting polymerization of the acrylic adhesive through free radical scavenging of catechol, resulting in incomplete polymerization.

[0127] Example 3 - Adhesion promotion of dental acrylic on dentin surfaces by adding PCS as a primer and photoinitiator

[0128] Bond strength measurements were performed to evaluate the effect of using photoinitiator addition in the PCS primer. Flat bonding sites were prepared on the buccal surfaces of human extracted teeth by grinding the teeth with a 600 grit surface of a water-cooled abrasive wheel (ECOMET III™ Grinder, Inc.) to expose dentin. Each test group was performed on 12 to 15 teeth.

[0129] Each adhesive pretreatment was applied to the dentin with acid conditioning, rinsing, and blot drying to prevent drying. First, the primer solution was added to the dentin and allowed to dry in air for a short time. The priming solution was 0.1 w / w% PCS in acetone. In one set of samples, a photo-crosslinker was added to the primer; for example, camphorquinone (CA) and a tertiary amine coinitiator were used.

[0130] A ULTRADENT™ shear bond tester was used to create 2.37 mm diameter cylinders to form the bonded assemblies. After extrusion into a Teflon former, the composite material specimens were photopolymerized for 30 seconds using a VALO™ Grand LED light cure. The specimens were then removed from the specimen mold and the samples were allowed to cure for 24 hours before shear testing. During shear testing, the bonded assemblies were mounted in an MTS INSIGHT™ test frame equipped with a ULTRADENT™ notched chisel. The specimens were then aligned in the chisel shape so that they were parallel to the bond site. Each cylinder was placed under a continuous load of 1 mm / min until fracture occurred. The shear bond strength was recorded in MPa.

[0131] The results shown in FIG. 10 indicate that the inclusion of a photoinitiator in the PCS primer provides improved adhesive strength.

[0132] To evaluate the conversion of urethane dimethacrylate (UDMA), the UDMA conversion of the photoinitiator was measured with increasing PCS concentration.

[0133] To assess UDMA (urethane dimethacrylate) conversion, camphorquinone (CQ) consumption was measured over time in methacrylate resins using 0.5% w / w CQ. Briefly, UDMA was mixed and CQ was used as a visible light sensitizer. The resins were photoactivated with a dental light source and Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) was used to assess the percent conversion in sample specimens. The results, shown in Figure 9, indicate that the conversion decreases with increasing amounts of PCS.

[0134] Example 4 - Reduction of bulk PCS to increase adhesion to aluminum

[0135] The effect of acid treatment on PCS adhesion to metal surfaces was evaluated to determine whether the oxidized functional group (quinone) in PCS plays a role in enhancing the durability of dentin bonding. Because quinones bond poorly to metal and catechols bond strongly, the conversion of quinones to catechols by acid was evaluated to determine whether increased bond strength to metal could be achieved.

[0136] Briefly, aluminum samples were glued with 80% bulk PCS. The solvents used were 100% acetone or 90% acetone and 10% acetic acid, respectively. To evaluate whether the acid promotes the reduction of quinones to hydroxyl groups, a 10% glacial acetic acid solution was used. The samples were left unclamped at room temperature for 1 hour, kept in a 55 °C oven for 22 hours, cooled at room temperature for 1 hour, and then tensile strength tested. The results are shown in Figure 11. Error bars represent standard error of the mean.

[0137] A consistent increase in bond strength to metal was observed in the presence of acid, suggesting that PCS was partially oxidized to quinones. These quinones were shown to promote durable covalent bonding to dentin.

[0138] Example 5 - Optimization of sample preparation

[0139] To determine the optimal cure time, fracture strength of samples prepared as described above with 0.1% PCS primer was tested for adhesion strength at extended times up to 48 hours. The results shown in Figure 12 indicate that maximum adhesion strength was achieved at 24 hours of cure time and maintained up to 48 hours.

[0140] Additionally, the optimal percentage of PCS primer concentration was evaluated by measuring the bond strength with increasing concentrations of PCS. The results shown in Figure 12 also show that the maximum bond strength was achieved at about 0.01% to about 0.1% PCS, and was most stable at 0.1% PCS in acetone. Therefore, 0.1% PCS in acetone or other stable solvent was used in the experiments presented herein.

Claims

1. A polymer layer comprising a catechol-containing thin film, comprising a polymer containing catechol, semi-quinone, or quinone; the catechol-containing thin film comprises a monomeric, oligomeric, or polymeric catechol or catechol-containing material; the catechol is present as a catechol and / or as a semi-quinone and / or as a quinone without the presence of an amine, and The polymer layer comprises: a) a reactive species other than catechol or a catechol-containing material; and b) at least one of a catalyst, a co-catalyst, or an accelerator.

2. 10. The polymer layer of claim 1, wherein the polymer layer comprises a reactive species other than catechol or a catechol-containing material, the reactive species comprising an acrylic, a silane, a silicone, a methacrylate, polyvinyl alcohol (PVA), or a combination thereof.

3. The polymer layer comprises a reactive species other than catechol or a catechol-containing material, and the reactive species is an acrylic, optionally 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, CH ３ 3. The polymer layer of claim 2, which is BisGMA, acidic bisphenol-A dimethacrylate, dimethacrylates from cycloaliphatic epoxides, aromatic urethane dimethacrylate, urethane-modified BisGMA, acidic aromatic dimethacrylate, oxydiphthalic acid dimethacrylate, phenyl dihydroxymethacrylate diphosphonate, acidic bisphenol-A dimethacrylate, morpholine carbonyl methacrylate, or phenyl carbonate methacrylate.

4. 10. The polymer layer of claim 1, further comprising a free radical polymerization initiator, optionally an acrylate polymerization initiator, optionally 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)-phosphine oxide, or combinations thereof, including those that are photoactivated.

5. The polymer layer of claim 3 wherein the reactive species is an acrylate.

6. The polymer layer of claim 1 , wherein the polymer layer is disposed on a dental substrate comprising one or more of ceramic, polymer, composite, and metal.

7. 7. The polymer layer of claim 6, wherein the ceramic comprises zirconia or porcelain, the polymer comprises acrylic, polypropylene, poly(methyl methacrylate), or one or more combinations thereof, the composite comprises one or more of enamel, dentin, or combinations thereof, and the metal comprises one or more of titanium, stainless steel, gold, chromium, or one or more combinations thereof.

8. The polymer layer of claim 1 , wherein the polymer layer comprises one or more of a primer layer, an adhesive layer, or a layered restorative.

9. The polymer layer of claim 1 , wherein the polymer layer has a thickness of from about 10 nanometers to about 500 microns.

10. 10. The polymer layer of claim 1, wherein the catechol or catechol-containing material comprises poly-catecholstyrene (PCS).

11. 10. The polymeric layer of claim 1, further comprising one or more photoinitiators comprising one or more of camphorquinone (CQ), azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-dimethoxy-2-phenylacetophenone, and one or more combinations thereof.

12. 1. A method of coating a substrate, comprising: disposing the polymer layer of claim 1 on a surface of a substrate; The coating is applied ex vivo, the substrate comprises a dental substrate including one or more of ceramic, polymer, composite, and metal; the ceramic comprises zirconia or porcelain; the polymer comprises acrylic, polypropylene, poly(methyl methacrylate), or one or more combinations thereof; The composite comprises one or more of enamel, dentin, or a combination thereof; and The method wherein the metal comprises one or more of titanium, stainless steel, gold, chromium, or one or more combinations thereof.

13. The method of claim 12, wherein the substrate is wet, dry, semi-wet or moist.

14. The method of claim 12, wherein the catechol or catechol-containing material comprises poly-catecholstyrene (PCS), and the PCS comprises a 0.1% solution of PCS.

15. The polymer layer of claim 1, 1. For use in a method of coating a substrate, comprising: disposing the polymer layer of claim 1 on a surface of a substrate; the substrate comprises a dental substrate including one or more of ceramic, polymer, composite, and metal; the ceramic comprises zirconia or porcelain; the polymer comprises acrylic, polypropylene, poly(methyl methacrylate), or one or more combinations thereof; the composite comprises one or more of enamel, dentin, or a combination thereof; and the metal comprises one or more of titanium, stainless steel, gold, chromium, or one or more combinations thereof; and The coating is a polymer layer that is applied in situ to a dental substrate.

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