Curable dental compositions with extended calcium, hydroxide, and enhanced fluoride release

Abstract

Dental compositions having an organofluoride salt and a calcium silicate-containing cement are described. Methods for preventing demineralization of a tooth surface by way of releasing calcium ions, hydroxyl ions, and fluoride ions from said dental compositions are also described.

Description

CURABLE DENTAL COMPOSITIONS WITH EXTENDED CALCIUM, HYDROXIDE, AND ENHANCED FLUORIDE RELEASE BACKGROUND

[0001] Dental enamel and dentin are comprised of a type of hydroxyapatite that includes calcium, phosphate, and hydroxyl ions arranged in a crystalline form. Hydroxyapatites are prone to demineralization and / or degradation due to contact with acid. Not only can acidic foods and beverages lead to the breakdown of hydroxyapatite, but also acids generated by bacteria, particularly in pits and fissures within enamel, can also weaken hydroxyapatite and lead to localized decay.

[0002] Replenishing teeth with calcium, phosphate, and hydroxyl ions can prevent and arrest demineralization, as well as restore the hydroxyapatite mineral. Treating teeth with fluoride ions is also beneficial in that fluoride may replace some hydroxyl ions within hydroxyapatite leading to structures that may be less prone to demineralization.

[0003] It has been challenging to formulate compositions that simultaneously treat teeth with calcium ions and fluoride ions since insoluble CaF2typically forms in the presence of water and / or saliva. Calcium fluoride (CaF2) is unable to penetrate tooth structures and unable to dissociate / dissolve so that the respective ions can be incorporated within hydroxyapatite.

[0004] What is needed are dental compositions for simultaneously delivering calcium ions, hydroxyl ions, and fluoride ions to tooth structures. SUMMARY

[0005] In one embodiment, a dental composition is described. The dental composition includes a polymerizable resin having one or more di(meth)acrylate monomer. The polymerizable resin excludes monomers having a moiety represented by Formula I: . The dental compositionby Formula II: (R1)4-N+X- (II), wherein: each R1may be independently selected from a C1-12straight or branched alkyl and a C7-12straight or branched alkaryl or alkaralkyl; and X may be F or BF4. The dental composition further includes a cement comprising calcium silicate.

[0006] In one embodiment, a dental composition is described. The dental composition includes a polymerizable resin having one or more di(meth)acrylate monomer, and excluding any monomerscharacterized by an octanol-water partition coefficient of greater than 5.5. The dental composition further includes an organofluoride salt represented by Formula II: (R1)4-N+X- (II), wherein: each R1may be independently selected from a C1-12straight or branched alkyl and a C7-12straight or branched alkaryl or alkaralkyl; and X may be F or BF4. The dental composition further includes a cement comprising calcium silicate.

[0007] In one embodiment, a dental composition is described. The dental composition includes a polymerizable resin having one or more di(meth)acrylate monomer, and excluding any monomers characterized by a refractive index greater than 1.500. The dental composition further includes an organofluoride salt represented by Formula II: (R1)4-N+X- (II), wherein: each R1may be independently selected from a C1-12straight or branched alkyl and a C7-12straight or branched alkaryl or alkaralkyl; and X may be F or BF4. The dental composition further includes a cement comprising calcium silicate.

[0008] In one embodiment, a cured dental composition is described. The cured dental composition is derived from any (curable) dental composition of the present disclosure.

[0009] In one embodiment, a method for preventing demineralization of a tooth surface is described. The method includes contacting a dental composition described herein to a tooth surface.

[0010] In one embodiment, a kit is described. The kit includes a dental composition of the present disclosure and a set of instructions directing a user to contact the dental composition to a tooth surface. BRIEF DESCRIPTION OF DRAWINGS

[0011] FIG.1 is a graph showing fluoride release over time for a dental composition of the present disclosure (EX.1) compared with other dental compositions.

[0012] FIG.2 is a graph showing calcium release over time for a dental composition of the present disclosure (EX.1) compared with other dental compositions.

[0013] FIG.3 is a graph showing pH over time for a dental composition of the present disclosure (EX.1) compared with other dental compositions.

[0014] FIG.4 is a graph showing fluoride release over time for a commercial dental composition (CE.6) including a bisphenol monomer and TBATFB, as well as similar dental compositions further including Portland cement (CE.7, CE.8).

[0015] FIG. 5 is a graph showing pH over time for a commercial dental composition (CE.6) including a bisphenol monomer and TBATFB, as well as similar dental compositions further including Portland cement (CE.7, CE.8).

[0016] FIG.6 is a graph showing shear adhesion for a dental composition of the present disclosure (EX.1) compared to a commercial dental composition including bisphenol monomer (CE.6).

[0017] FIG. 7 is a graph showing changes to integrated reflectivity after demineralization challenge for a dental composition of the present disclosure (EX.1) compared to a commercial dental composition (CE.6) including bisphenol monomer.

[0018] FIG.8 is a graph showing greyscale changes after demineralization challenge for a dental composition of the present disclosure (EX.1) compared to a commercial dental composition (CE.6) including bisphenol monomer. DETAILED DESCRIPTION

[0019] The present disclosure is directed toward dental composition that release calcium ions, hydroxyl ions, and fluoride ions to a tooth surface after having been cured. The dental compositions may be a sealant composition, a restorative composition, a primer composition, an adhesive composition, a composition for coating orthodontic appliances (e.g., liner), or the like. Furthermore, the present dental compositions avoid the use of bisphenol-type monomers that are commonly used in similar dental compositions.

[0020] It was discovered that dental compositions having a combination of organofluoride salt (i.e., quaternary ammonium fluoro salts) in the presence of a cement containing calcium silicate (source of calcium ions and hydroxyl ions) surprisingly release fluoride ions in a significantly higher amount compared to dental compositions with an organofluoride salt without cement, as well as a higher amount of fluoride release compared to dental compositions having an inorganic fluoride source (e.g., sodium fluoride) with or without cement. It is unknown why the dental compositions of the present disclosure afford uniquely high release levels of fluoride ions and calcium ions. Further, current understanding cannot explain why CaF2does not appear to form, as would normally be expected.

[0021] The dental compositions of the present disclosure are unlike anything previously known. Said dental compositions provide a means to prevent demineralization of tooth surfaces and potentially restore mineralization by way of releasing fluoride ions, calcium ions, and hydroxyl ions.

[0022] FIG.1 is a graph showing fluoride release over time for dental compositions of the present disclosure. The dental composition having tetrabutylammonium tetrafluoroborate (“TBATFB”) and Portland cement (EX.1) provided the greatest amount of fluoride release over time, much higher than the comparable dental composition having TBATFB without Portland cement (CE.2). EX.1 is also shown to have higher fluoride release than a dental composition having sodium fluoride and Portland cement (CE.1), as well as higher fluoride release than a dental composition having sodium fluoride without cement (CE.3).

[0023] FIG.2 is a graph showing calcium release over time for dental compositions of the present disclosure. The amount of calcium released for a dental composition of the present disclosure (EX.1) is comparable to similar dental composition having sodium fluoride instead of TBATFB (CE.1), eachhaving Portland cement as a calcium source. EX.1 and CE.1 show somewhat less calcium release as a dental composition having neither TBATFB nor NaF (CE.4).

[0024] FIG.3 is a graph showing pH over time for dental compositions of the present disclosure. A dental composition of the present disclosure (EX.1) is shown to increase in pH over a period of 14 days, followed by a decrease in pH over a subsequent 14+ day period. Portland cement releases hydroxyl ions owing to the observed decrease in pH. Formulations without Portland cement (CE.2, CE.3, and CE.5) are shown to steadily decrease in pH over a 35 day period.

[0025] FIG. 4 is a graph showing fluoride release over time for CE.6 (commercially-available sealant) compared with dental compositions similar to CE.6 but further including Portland Cement (CE.7 and CE.8). Adding Portland Cement to compositions having bisphenol monomer and TBATFB drastically reduced the amount of fluoride released.

[0026] FIG. 5 is a graph showing pH over time for CE.6 (commercially-available sealant) compared with dental compositions similar to CE.6 but further including Portland Cement (CE.7 and CE.8). Adding Portland cement to compositions having bisphenol monomer and TBATFB does not appear to increase the pH, which is indicative of hydroxyl ion release.

[0027] FIG.6 is a graph showing that the shear adhesion for a dental composition of the present disclosure (EX.1) is better than CE.6 (commercially-available sealant).

[0028] FIG. 7 is a graph showing changes to integrated reflectivity after demineralization challenge for a dental composition of the present disclosure (EX.1) compared to CE.6 (commercially- available sealant). EX.1 is better at preventing demineralization than is CE.6.

[0029] FIG.8 is a graph showing greyscale changes after demineralization challenge for a dental composition of the present disclosure (EX.1) compared to CE.6. Definitions

[0030] As used herein, “about” means ± 10 percent of a given value. For example, about 10 means 9 to 11.

[0031] As used herein, “acidic monomers” means a polymerizable compound with a group having one or more hydrogen characterized by a pKa ≤ 5 (e.g., groups such as -CO2H, -S(O)2OH, and -P(O)(OH)2). As used herein, “acidic polymer” means a polymer having one or more hydrogen characterized by a pKa ≤ 5.

[0032] As used herein, “alkaryl” means a bivalent alkylene group terminated with an aryl group. An alkaryl may be represented as follows: –alkylene–aryl. For example, a C7alkaryl group may be benzyl, i.e., –CH2Ph.

[0033] As used herein, “alkaralkyl” means a bivalent alkylene group bonded to a bivalent arylene group, which in turn is bonded to a monovalent alkyl group. An alkaralkyl is represented as follows: –alkylene–arylene–alkyl.

[0034] As used herein, “alkenyl” means a monovalent unsaturated hydrocarbon chain having one or more alkene (i.e., –C(Ra)2=C(Ra)2–, wherein Rais -H, alkyl, alkenyl, or a substituent as indicated). The unsaturated hydrocarbon chain may be straight or branched as indicated. As used herein, “alkenylene” means a bivalent unsaturated hydrocarbon chain having one or more alkene, straight or branched as indicated.

[0035] As used herein, “alkyl” means a monovalent saturated hydrocarbon chain, straight or branched as indicated. For example, straight C1-6alkyl includes C1alkyl (i.e., methyl), a C2alkyl (i.e., ethyl), C3alkyl (i.e., propyl –(CH2)2CH3), C4alkyl (e.g., butyl –(CH2)3CH3), C5alkyl (i.e., pentyl – (CH2)4CH3), or C6(i.e., hexyl –(CH2)5CH3). For example, a branched C3-6alkyl includes C3alkyl (i.e., isopropyl –CH(CH3)2), C4alkyl (e.g., secbutyl –CH(CH3)CH2CH3), C5alkyl (e.g., neopentyl – CH2C(CH3)3). An “alkylene” means a bivalent saturated hydrocarbon chain, straight or branched as indicated. For example, a C2alkylene is ethylene, i.e., –CH2CH2–; a C3alkylene is propylene, i.e., – CH2CH2CH2–, or isopropylene, i.e., –CH2(CH3)CH2–.

[0036] As used herein, “aryl” describes an aromatic group that is free of heteroatoms (e.g., N, O, S) within the ring. An aromatic group is cyclic, planar, fully conjugated, and follows Hückle’s Rule (i.e., having 4n + 2 π-electrons, wherein n is an integer). For example, phenyl is a C6aryl, naphthyl and azulenyl are C10aryls, and anthracenyl and phenanthrenyl are C14aryls. As used herein, “arylene” describes a bivalent aryl group. For example, a C6arylene is phenylene, i.e., –Ph–, the connectivity may be ortho, meta, or para, unless otherwise as indicated.

[0037] As used herein, “coated” means encapsulated. A coated material is a material that is surrounded by, or otherwise encapsulated by, a layer of another material.

[0038] As used herein, “cycloalkyl” describes a monovalent saturated cycloaliphatic group. For example, a C5-6cycloalkyl group includes C5cycloalkyl (i.e., cyclopentyl –C5H9) and C6cycloalkyl (i.e., cyclohexyl –C6H11). A “cycloalkylene” is a bivalent saturated cycloaliphatic group. For example,a C5-6cycloalkylene group includes C5cycloalkylene (i.e., cyclopentylene–C5H8–) and C6cycloalkylene (i.e., cyclohexylene –C6H10–), including all modes of connectivity (e.g., 1,2-, 1,3-, or the like) unless otherwise indicated.

[0039] As used herein, “exclude” means that the referenced substance is not present, i.e., 0 wt.%.

[0040] As used herein, “filler” refers to a component that increases the viscosity of a dental composition. As used herein, an “unreactive filler” is inert toward components within the dental composition, water, acid, and saliva. As used herein, a “reactive filler” is not inert toward components within the dental composition, water, acid, and / or saliva.

[0041] As used herein, “di(meth)acrylate monomer” means a compound having two (meth)acrylate units. As used herein, “(meth)acrylate” means an acrylate or a methacrylate, i.e., an α,β-unsaturated ester wherein the α-carbon is unsubstituted or substituted with -CH3. (e.g., –OC(O)C(R)=CH2, wherein R is –H or –CH3).

[0042] As used herein, “polyaryl moiety” means any moiety with more than one aromatic ring (i.e., following Huckel’s rule: a cyclic, planar ring with 4n+2π electrons) separated by 4 or less atoms / bonds, or fused aromatic rings. A polyaryl moiety is also intended to include polycyclic aromatic hydrocarbon moieties, or in other words, fused aromatic rings.

[0043] As used herein, “dental article” means any article used in a dental or orthodontic field, e.g., dental restorations, tooth models, orthodontic devices, or the like.

[0044] As used herein “inorganic fluoride source” refers to a water-soluble compound or salt represented by MoYpor Mo+Yp-, wherein M is any alkali metal, alkaline earth metal, transition metal, or even nonmetals without any carbon-containing substituents; and Y is fluorine, tetrafluoroborate, or some other species having a displaceable fluoride ion (i.e., liberates fluoride ion upon dissolution or reaction with a reactant). Variables o and p are chosen based on the appropriate valency, identifiable to one skilled in the art. M may have other ligands, substituents, or counterions so long as at least one fluorine is present. Example inorganic fluoride sources that are encompassed by the term include NaF, AgF, NH4F, and the like. Compounds such as ytterbium fluoride (YbF3), yttrium fluoride (YF3), cryolite (Na3AlF6), calcium fluoride (CaF2) are not encompassed by the term since they are insoluble in water.

[0045] As used herein, “filler” describes any inorganic additive that does not include calcium oxide. Indeed, portions of a cement described herein may fall under the definition of a filler, e.g., silicon dioxide. For the purpose clarity, compounds included within a cement are not to be considered a filler in terms of wt.% of fillers added, unless otherwise indicated. For example, a dental composition that may include a silica filler in X wt.% is not meant to include any amount of silica derived from the cement.

[0046] As used herein, “glyceryl di(meth)acrylate monomer” means a monomer having at least one glyceryl moiety (i.e., –OCH2CH(OH)CH2O– or –OCH(CH2OH)CH2O–) and two (meth)acrylate moieties.

[0047] As used herein, “glycol di(meth)acrylate monomer” means a monomer having at least one glycol moiety (i.e., –O(CHR3)n–O–, wherein each R3is independently -H or C1-4alkyl, n is 2-10) and two (meth)acrylate moieties.

[0048] As used herein, the phrase “one or more of” such as used in the phrase “one or more of A and B” or “one or more of at least one A and at least one B” means a composition may include at least one A, more than one A, at least one B, more than one B, at least one A and at least one B, more than one A and more than one B. In other words, the phrase does not mean the composition must have at least one of each of A and B.

[0049] As used herein, “octanol-water partition coefficient” (Log P) is a partition coefficient for the two-phase system of octanol and water. It serves as a measure of the relationship between lipophilicity and hydrophilicity substance. Lipophilic substances have greater solubility in the octanol portion of the two-phase system and are represented by greater Log P values. Substances that are more hydrophilic have smaller Log P values and negative Log P values. Octanol-water partition coefficients may be measured or may be estimated, for example, via quantitative structure-activity relationships (QSAR) or linear free energy relationships (LFER).

[0050] As used herein, “organic” defines a compound having carbon, whereas “inorganic” defines a compound without carbon. An “organic phase” includes all organic compounds. An “inorganic phase” includes all inorganic compounds.

[0051] As used herein, “photobleachable dye’ is a compound subject to photochemical alteration, wherein a color change is observed upon exposure to actinic radiation.

[0052] As used herein, “polymerizable resin” encompasses all polymerizable components within the dental composition. Polymerizable components are compounds that may be incorporated into a polymer under the conditions described herein.

[0053] As used herein, “silane-treated silica” means silica that is reacted with an organofunctional alkoxysilane, commonly known as a silane coupling agent. The terms organofunctional alkoxysilane and silane are used interchangeably herein.

[0054] As used herein, “urethane di(meth)acrylate monomer” refers to a monomer having at least one urethane moiety (i.e., –OC(O)–NR– or –NR–C(O)O–, wherein R is -H or C1-8alkyl) and two (meth)acrylate moieties.

[0055] As used herein, “viscosity” is a property measured using a ThermoHaake Rotovisco 1 device with a plate / plate system (diameter 20 mm) and a slit of 0.2 mm. The viscosity values for each shear rate (e.g., 101 / s to 1001 / s in 101 / s steps), with a delay of 5 seconds before collecting data. This method of measurement corresponds to DIN 53018-1. The viscosity values described herein are reported at 20 °C at a shear rate of 1 / s, unless otherwise stated.

[0056] As used herein, “soluble” refers to at least 1 g of a component A completely dissolved (no visible cloudiness, precipitate, or phase separation) in 30 mL or less component B (e.g., water) at a temperature range of about 20 ⁰C to about 23 ⁰C and at atmospheric pressure (i.e., 760 mm / Hg). It is to be understood that the conditions to determine solubility only include the component A and the component B, i.e., no added salts, or the like. Thus, a “water-soluble compound” describes a compound in which at least 1 g of said compound that dissolves completely in 30 mL water, or less.DENTAL COMPOSITIONS

[0057] In various embodiments, a dental composition is described. The dental composition may include a polymerizable resin having one or more di(meth)acrylate monomer. The polymerizable resin may exclude monomers having a moiety represented by Formula I: . The dental composition may by Formula II:, wherein: each R1may be independently selected from a C1-12straight or branched alkyl and a C7-12straight or branched alkaryl or alkaralkyl; and X may be F or BF4. The dental composition may further include a cement comprising calcium silicate.

[0058] In various embodiments, a dental composition is described. The dental composition may include a polymerizable resin having one or more di(meth)acrylate monomer, and excluding any monomers characterized by an octanol-water partition coefficient of greater than 5.5. The dental composition may include an organofluoride salt represented by Formula II above, and a cement comprising calcium silicate.

[0059] In various embodiments, a dental composition is described. The dental composition may include a polymerizable resin having one or more di(meth)acrylate monomer, and excluding any monomers characterized by a refractive index greater than 1.500. The dental composition may include an organofluoride salt represented by Formula II above, and a cement comprising calcium silicate.

[0060] In some embodiments, the dental composition may be characterized in wt.% with respect to an organic phase and an inorganic phase of the dental composition, wherein the sum of the organic phase and the inorganic phase equal 100%. For example, the polymerizable resin and the organofluoride salt (and any further organic additives, e.g., photobleachable dyes, initiators, preservatives, or the like) contribute to an organic phase whereas the cement (and any further inorganic filler) contributes to an inorganic phase. In some embodiments, the dental composition may include an organic phase present in an amount of about 20 wt.% to about 99 wt.%, and an inorganic phase present in an amount of about 1 wt.% to about 80 wt.% with respect to the weight of the dental composition. For example, the organic phase may be present in the dental composition, in wt.%, of about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99, or a value within a range between any of the preceding values, e.g., between about 40 and about 60; and the inorganic phase may be present in the dental composition in an amount, in wt.%, of about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80, or a value within a range between any of the preceding values, e.g. between about 50 toabout 70, or the like. The amount of inorganic phase may depend upon the type of dental composition, e.g., sealant, restoration, or the like.

[0061] In many embodiments, the dental composition may further include one or more filler described herein.

[0062] In many embodiments, the dental composition may further include a cure initiator system described herein. The cure initiator system may be a light-cure initiator system, a redox initiatory system, or a combination thereof.

[0063] In some embodiments, the dental composition may further include a photobleachable dye described herein.

[0064] In some embodiments, the dental composition may further include (or exclude) water, as described herein.

[0065] In some embodiments, the dental composition may further include (or exclude) an inorganic fluoride source(s) described herein.

[0066] In some embodiments, the dental composition may further include (or exclude) acidic monomers, acidic polymers, or a combination thereof. Acidic monomers are polymerizable compounds having one or more acid moieties (e.g., -CO2H, -OP(O)(OH)2, -OS(O)2OH, or the like). Acidic polymers are simply polymers having one or more acid moieties.

[0067] In some embodiments, the dental composition may further exclude monomers characterized by an octanol-water partition coefficient of greater than 5.5.

[0068] In some embodiments, the dental composition may further exclude monomers characterized by a refractive index of greater than 1.500.

[0069] In some embodiments, the dental composition may further exclude monomers characterized by an octanol-water partition coefficient of greater than 5.5 and exclude monomers characterized by a refractive index of greater than 1.500.

[0070] In some embodiments, the dental composition may be a one-part composition. In other embodiments, the dental composition may be a two-part composition. In other embodiments, the dental compositions described herein may be a one-part composition intended for use in a two-part composition.

[0071] In many embodiments, the dental composition may be a sealant, a primer, an adhesive, a restorative, a cement, or a liner for dental or orthodontic applications. The nature of the dental composition may be determined by incorporating more filler material or less filler material (e.g., fillers described herein) within the dental composition. The dental compositions may be used for dental purposes or orthodontic purposes. For example, a dental composition of the present closure may be formulated as an orthodontic adhesive or orthodontic cement for bonding orthodontic brackets to tooth structures, such as those described in Int. Pat. Pub. No. WO 2022 / 144843, which is incorporated herein by reference in its entirety.

[0072] The present disclosure further includes cured dental compositions derived from the (curable) dental compositions described herein. For example, restorative dental articles, such as crowns, that are prepared with the dental compositions described herein would allow for providing calcium ions, hydroxyl ions, and fluoride ions to underlying tooth structures.

[0073] Components of the dental composition are described in further detail below. Polymerizable Resin

[0074] Features of the polymerizable resin described below may be present alone or in combination with any other features of the dental composition(s) described herein.

[0075] In many embodiments, the polymerizable resin, and thereby the entire dental composition, may exclude monomers having a moiety represented by Formula I above. Example monomers having a moiety represented by Formula I include bisphenol-A-diglycidylmethacrylate (“Bis-GMA”), ethoxylated bisphenol A dimethacrylate (“Bis-EMA”), and ethoxylated bisphenol A diacrylate (“EBPADA”). In some embodiments, the polymerizable resin may further exclude any monomers having a polyaryl moiety.

[0076] In some embodiments, the polymerizable resin may consist essentially of monomers that are characterized by an octanol-water partition coefficient of no greater than about 5.5. In some embodiments, the polymerizable resin may consist essentially of monomers that are characterized by an octanol-water partition coefficient of no greater than about 5.5, 5.4, 5.3, 5.2, or no greater than 5.1. Example monomers having an octanol-water partition coefficient of greater than 5.5 include bisphenol- A-diglycidylmethacrylate (“Bis-GMA”), which has a calculated Log P of about 5.53; ethoxylated bisphenol A dimethacrylate (“Bis-EMA”), which has a calculated Log P of about 6.99, and ethoxylated bisphenol A diacrylate (“EBPADA”), which has a calculated Log P of about 5.89, according to Alshali, R. Z et al., Dental Materials 2015, 31, 711-720, incorporated herein by reference in its entirety. Each of the Bis-GMA, Bis-EMA, and EBPADA monomers include a moiety represented by Formula I above.

[0077] In some embodiments, the polymerizable resin may consist essentially of monomers that are characterized by a refractive index of no greater than 1.500. Example monomers having a refractive index of greater than 1.500 include bisphenol-A-diglycidylmethacrylate (“Bis-GMA”), which has an RI of 1.552, ethoxylated(6) bisphenol A dimethacrylate (“Bis-EMA-6”), which has an RI of 1.523, and ethoxylated(4) bisphenol A dimethacrylate (“Bis-EMA-4”), which has an RI of 1.531.

[0078] In some embodiments, each of the one or more di(meth)acrylate monomer present in the dental composition may be characterized by a molecular weight of no greater than about 500 Da. In other embodiments, each of the one or more di(meth)acrylate monomer present in the dental composition may be characterized by a molecular weight of no greater than about 475 Da. For example, each one or more di(meth)acrylate monomer may be characterized by a molecular weight of no greaterthan about 500, 495, 490, 485, 480, or 475. However, in other embodiments the polymerizable resin may include monomers of any kind (other than monomers of Formula I) that are characterized by a molecular of greater than about 500 Da, but only present in an amount of no more than 15 wt.% with respect to the weight of the polymerizable resin, e.g., less than 15 wt.%, 12 wt.%, 10 wt.%, 8 wt.%, 6 wt.%, 4 wt.%, 2 wt.%, 1 wt.%, 0.05 wt.%, or a value within a range between any of the preceding values, e.g., between about 5 wt% and about 10 wt%, or the like.

[0079] In some embodiments, each of the one or more di(meth)acrylate monomer may be characterized by a viscosity of no greater than 500 Pa*s at 20 °C at a shear rate of 1 / s. For example, the one or more di(meth)acrylate monomer may be characterized by a viscosity of no greater than about 500, 475, 450, 400, 350, 300, 250, 200, 150, or 100 Pa*s at 20 °C at a shear rate of 1 / s. However, in other embodiments the polymerizable resin may include monomers of any kind (other than monomers of Formula I) that are characterized by a viscosity greater than 100, 150, 200, 250, 350, 400, 450, or 500 Pa*s at 20 °C at a shear rate of 1 / s, or a value within a range between any of the preceding values (e.g., between about 200 and about 400, or the like) present in an amount of no more than 15 wt.% with respect to the weight of the polymerizable resin, e.g., less than 15 wt.%, 12 wt.%, 10 wt.%, 8 wt.%, 6 wt.%, 5 wt%, 4 wt.%, 2 wt.%, 1 wt.%, 0.05 wt.%, or a value within a range between any of the preceding values, e.g., between about 5 wt% and about 10 wt%, or the like. For example, an embodiment may include a polymerizable resin including monomers characterized by a viscosity of greater than 100, 200, 300, or the like, present in an amount less than 10 wt%, less than 5 wt%, or the like, or present in the an amount between 2 wt% and 5 wt%, or the like. In other embodiments, the polymerizable resin may exclude any monomer characterized by a viscosity of greater than 500, 475, 450, 400, 350, 300, 250, 200, 150, or 100 Pa*s at 20 °C at a shear rate of 1 / s, or exclude monomers within a range between any of the preceding values, e.g., exclude monomers characterized by a viscosity of between about 200 and about 500, or the like.

[0080] In some embodiments, the polymerizable resin may be characterized by an overall viscosity of about 0.1 to about 500 Pa*s at 20 °C at a shear rate of 1 / s. For example, the polymerizable resin may be characterized by an overall viscosity of about 0.1, 0.5, 1, 5, 10, 15, 20, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500 Pa*s at 20 °C at a shear rate of 1 / s, or a value within a range between any of the preceding values, e.g., between about 200 and about 400, or the like. In some embodiments, the dental composition of the disclosure (i.e., including any fillers or the like) may be characterized by an overall viscosity of about 1 to about 1500 Pa*s at 20 °C at a shear rate of 1 / s. For example, the dental composition may be characterized by an overall viscosity of about 1, 5, 10, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, or 1500 Pa*s at 20 °C at a shear rate of 1 / s, or a value within a range between any of the preceding values, e.g., between about 800 and about 1000, or the like.

[0081] In many embodiments, the one or more di(meth)acrylate monomer may be present in a total amount (i.e., total amount of di(meth)acrylate monomers) of at least 60 wt.% with respect to the weight of the polymerizable resin. In some embodiments the one or more di(meth)acrylate monomer may be present in a total amount of up to 100 wt.% with respect to the weight of the polymerizable resin. In other words, the polymerizable resin may be made up of at least 60 wt.% of di(meth)acrylate monomers. For example, the one or more di(meth)acrylate monomer may be present in a total wt.% amount, with respect to the weight of the polymerizable resin, of about 60, 62, 65, 68, 70, 72, 75, 78, 80, 82, 85, 88, 90, 92, 95, 98, or 100, or a value within a range between any of the preceding values, e.g., between about 60 and about 75, or the like. In some embodiments, the one or more di(meth)acrylate monomer may be present in a total amount of at least 90 wt.% with respect to the weight of the polymerizable resin.

[0082] In some embodiments, the one or more di(meth)acrylate monomer may be represented by Formula III: CH2=CR1C(O)–R2–C(O)CR1=CH2(III) wherein: each R1is independently –H or –CH3; R2is –[O(CHR3)n]m–OC(O)–R4–C(O)O–[(CHR3)nO]m–, –[O(CHR3)n]m–O–, –OCH2CH(OH)CH2O–, –OCH2CH(CH2OH)O–, or –O–R5–O–; each R3is independently –H or –CH3; R4is –NR6–R5–NR6–, –O–R5–O–, or –R5–; R5is a C2-12straight or branched alkylene, a C2-12straight or branched alkenylene, a C5-6cycloalkylene, or phenylene; each R6is independently –H, –CH3; each n is independently an integer selected from 2-10; and each m is independently an integer selected from 1-10.

[0083] In some embodiments, the polymerizable resin may include one or more di(meth)acrylate present in an amount of about 60 wt.% to about 100 wt.% wherein at least a portion of the one or more di(meth)arylate may be one or more di(meth)acrylate represented by Formula III above. In some embodiments, one or more di(meth)acrylate represented by Formula III may be present in an amount of about 60 to about 100 wt.%. For example, one or more di(meth)acrylate represented by Formula III may be present within the polymerizable resin in an amount (wt.%) of about 60, 62, 65, 68, 70, 72, 75, 78, 80, 82, 85, 88, 90, 92, 95, 98, or 100, or a value within a range between any of the preceding values, e.g., between about 65 and about 70, or the like. For example, a polymerizable resin may include 60- 100 wt.% (e.g., 80-95 wt.%) di(meth)acrylate monomers and 60-100 wt.% (e.g., 65-70 wt.%) of thedi(meth)acrylate monomers may be of one or more di(meth)acrylate monomer represented by Formula III.

[0084] In some embodiments, the polymerizable resin may include at least 50 wt.% of one or more di(meth)acrylate monomer having at least one urethane moiety, i.e., a urethane di(meth)acrylate monomer. In some embodiments, a urethane di(meth)acrylate monomer may include two urethane moieties. In some embodiments, the polymerizable resin may include up to 95 wt.% of one or more urethane di(meth)acrylate monomer. For example, the urethane di(meth)acrylate monomer may be represented by Formula III above, wherein R2is –[O(CHR3)n]m–OC(O)–R4–C(O)O–[(CHR3)nO]m– and R4is –NR5–R6–NR5–. The polymerizable resin may include one or more urethane di(meth)acrylate monomer (e.g., represented by Formula III) present in an amount in wt.% with respect to the polymerizable resin of about 50, 52, 55, 58, 60, 62 ,65, 68, 70, 72, 75, 78, 80, 82, 85, 88, 90, 92, or 95, or a value within a range between any of the preceding values, e.g., between about 55 and about 60, or the like. In some embodiments, the polymerizable resin may include at least 50 wt.% (e.g., 50-65 wt.%, or the like) of one or more urethane di(meth)acrylate of Formula III, wherein R6is a branched C8-10 alkylene (e.g., C9 alkylene, or the like). In some embodiments, the polymerizable resin may include urethane dimethacrylate (“UDMA”) present in an amount of 50-65 wt.% with respect to the weight of the polymerizable resin, UDMA being represented by the following formula: .

[0085] of one or more glyceryl di(meth)acrylate monomer. In some embodiments, the polymerizable resin may include up to 50 wt.% of one or more glyceryl di(meth)acrylate monomer. For example, the glyceryl di(meth)acrylate monomer may be represented by Formula III, wherein R2is –OCH2CH(OH)CH2O–. The polymerizable resin may include one or more glyceryl di(meth)acrylate monomer (e.g., represented by Formula III) present in an amount in wt.% with respect to the weight of the polymerizable resin of about 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, or 50, or a value within a range between any of the preceding values, e.g., between about 25 and about 35, or the like. In some embodiments, the polymerizable resin may include at least 15 wt.% (e.g., 25-30 wt.%, or thelike) of a glyceryl di(meth)acrylate monomer of Formula III, wherein R2is –OCH2CH(OH)CH2O–. In some embodiments, the polymerizable resin may include glyceryl dimethacrylate (“GDMA”) present in an amount of 15-50 wt.% with respect to the weight of the polymerizable resin, GDMA being represented by the following formula: .

[0086] In some embodiments, the polymerizable resin may include at least 5 wt.% of one or more glycol di(meth)acrylate monomer. In some embodiments, the polymerizable resin may include up to 35 wt.% of one or more glycol di(meth)acrylate monomer. For example, the glycol di(meth)acrylate monomer may be represented by Formula III, wherein R2is –[O(CHR3)n]m–O–. The polymerizable resin may include one or more glycol di(meth)acrylate monomer (e.g., represented by Formula III) present in an amount in wt.% with respect to the weight of the polymerizable resin of about 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, or 35, or a value within a range between any of the preceding values, e.g., between about 10 and about 18, or the like. In some embodiments, the polymerizable resin may include at least 15 wt.% (e.g., 12-15 wt.%, or the like) of a glycol di(meth)acrylate monomer of Formula III, wherein R2is –[O(CHR3)n]m–O–, n is 2 and m is 3. In some embodiments, the polymerizable resin may include triethylene glycol dimethacrylate (“TEGDMA”) present in an amount of 5-35 wt.% with respect to the weight of the polymerizable monomer, TEGDMA represented by the following formula: .

[0087] In someor consist essentially of, one or more urethane di(meth)acrylate monomer, one or more glycerol di(meth)acrylate monomer, one or more glycol di(meth)acrylate monomer, or a combination thereof.

[0088] In some embodiments, the polymerizable resin may include, or consist essentially of, one or more urethane di(meth)acrylate monomer present in a total amount of 50-65 wt.%, one or more glycerol di(meth)acrylate monomer present in a total amount of 15-45 wt.%, and one or more glycoldi(meth)acrylate monomer present in an amount of 5-35 wt.%, with respect to the weight of the polymerizable resin.

[0089] In some embodiments, the polymerizable resin may include, or consist essentially of, urethane dimethacrylate (“UDMA”), glycerol dimethacrylate (“GDMA”), and triethylene glycol dimethacrylate (“TEGDMA”).

[0090] In some embodiments, the polymerizable resin may include, or consist essentially of, 50- 65 wt.% UDMA, 15-45 wt.% GDMA, 5-35 wt.% TEGDMA with respect to the weight of the polymerizable resin.

[0091] In other embodiments, the polymerizable resin may include, or consist essentially of, UDMA, GDMA, and TEGDMA present in a wt.% ratio of about 4:2:1.

[0092] In some embodiments, the polymerizable resin may further include one or more acrylate- based monomer other than the di(meth)acrylate monomers. Acrylate-based monomers may include mono(meth)acrylates, tri-(meth)acrylates, or tetra(meth)acrylates. Example mono-(meth)acrylates include non-functionalized alkyl(meth)acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, or the like; crosslinkable alkyl(meth)acrylates such as allyl acrylate, glycidyl methacrylate (“GMA”), or the like; and functionalized alkyl(meth)acrylates such as (hydroxyethyl)methacrylate (“HEMA”), (2- hydroxypropyl)methacrylate (“HPMA”), 2-(dimethylamino)ethyl acrylate (“DMAEA”), or the like. Example tri-(meth)acrylate monomers may include glycerol triacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, or the like. Example tetra-(meth)acrylates monomers may include pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate. In some embodiments, acrylate-based monomers that are not di(meth)acrylate monomers, if present, may be present in an amount of about 1 wt.% to about 20 wt.% with respect to the weight of the polymerizable resin. For example, the polymerizable resin may include acrylate-based monomers other than di(meth)acrylate monomers in an amount, in wt.%, of about 1, 2, 5, 8, 10, 12, 15, 18, or 20, or a value within a range between any of the preceding values, e.g., between about 5 and 10, or the like. In some embodiments, the polymerizable resin may include less than 1, 2, 5, 8, or 10 wt.% acrylate-based monomers other than the one or more di(meth)acrylate monomers. In other embodiments, the polymerizable resin may exclude acrylate- based monomers other than di(meth)acrylate monomers.

[0093] In some embodiments, the polymerizable resin may be present in an amount of at least 20 wt.% based on the weight of the dental composition. In some embodiments, the polymerizable resin may be present in an amount of up to 95 wt.% based on the weight of the dental composition. For example, the polymerizable resin may be present within the dental composition at a wt.% of 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, 50, 52, 55, 58, 60, 62, 65, 68, 70, 72, 75, 78, 80, 82, 85, 88, 90, or 95 or a value within a range between at of the preceding values, e.g., between about 40 and about 60,between about 20 and about 80, or the like. The amount of polymerizable resin may be selected based on the intended use of the dental composition. For example, a sealant composition would have a greater amount of polymerizable resin (and less amount of filler) than would a restorative composition (less polymerizable resin and more filler, comparatively). For example, a sealant composition may include about 50 wt% to about 95 wt.% wt.% polymerizable resin. For example, a restorative composition may include about 20 wt.% to about 50 wt.% polymerizable resin.

[0094] In some embodiments, the polymerizable resin may be present in an amount, relative to an amount of the organofluoride salt (e.g., TBATFB) present, in a wt.% ratio of about 1000:1 to about 10:1. For example, the polymerizable resin and the organofluoride salt may be present in a wt.% ratio of about 1000:1, 950:1, 900:1, 850:1, 800:1, 750:1, 700:1, 650:1, 600:1, 550:1, 500:1, 450:1, 400:1, 350:1, 300:1, 250:1, 200:1, 150:1, 100:1, 90:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 15:1, or 10:1, or a value within range between any of the preceding values, e.g., between about 50:1 and about 15:1, or the like.

[0095] In some embodiments, the polymerizable resin may be present in an amount, relative to an amount of the cement (e.g., Portland cement), in a wt.% ratio of about 90:1 to about 0.5:1. For example, the polymerizable resin and the cement may be present in a wt.% ratio of about 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1, 35:1, 30:1, 25:1, 20:1, 15:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, or 0.5:1, or a value within a range between any of the preceding values, e.g., between about 10:1 to about 5:1, or the like. Organofluoride Salt

[0096] In many embodiments, the organofluoride salt(s) described below may be present alone or in combination with any other features of the dental composition(s) described herein. In some embodiments, the dental composition may include only one organofluoride salt of Formula II. In other embodiments, the dental composition may include more than one organofluoride salt of Formula II.

[0097] In some embodiments, the organofluoride salt may be represented by Formula II, and each R1may be independently selected from a C1-12straight or branched alkyl. In some embodiments, each R1may be independently selected from a C4-8straight or branched alkyl. In some embodiments, each R1may be a C4alkyl.

[0098] In some embodiments, the organofluoride salt may be represented by Formula II, and at least one R1may be a C7-12straight or branched alkaryl. For example, at least one R1may be benzyl (i.e., -CH2Ph).

[0099] In some embodiments, the organofluoride salt may be represented by Formula II, and each R1may be independently selected from a C1-12straight or branched alkyl and X may be BF4.

[0100] In some embodiments, the organofluoride salt may be represented by Formula II, and each R1may be independently selected from a C4-8straight or branched alkyl and X may be BF4.

[0101] In some embodiments, the organofluoride salt may be represented by Formula II, and each R1may be independently selected from a C1-12straight or branched alkyl and X may be F.

[0102] In some embodiments, the organofluoride salt may be represented by Formula II, and each R1may be independently selected from a C4-8straight or branched alkyl and X may be F.

[0103] In some embodiments, the organofluoride salt may be selected from tetrabutylammonium fluoride (“TBAF”), tetrabutylammonium tetrafluoroborate (“TBATFB”), and a combination thereof.

[0104] In some embodiments, the organofluoride salt (e.g., TBATFB) may be present in an amount of about 0.005 wt.% to about 15 wt.% with respect to the weight of the dental composition. For example, the organofluoride salt may be present in an amount in wt.% of about 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3.3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or 15, or a value within a range between any of the preceding values, e.g., between about 2 and about 6, or the like.

[0105] In some embodiments, the organofluoride salt (e.g., TBATFB) may be present in a molar amount of about 0.02 mmol to about 50 mmol. For example, the organofluoride salt may be present in a molar amount, in mmol, of about 0.02, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, or 50, or a value within a range between any of the preceding values, e.g., between about 8 and about 16, or the like.

[0106] In some embodiments, the organofluoride salt (e.g., TBATFB) may be present in an amount, relative to an amount of the cement present, in a wt.% ratio of about 1:200 to about 1:1. For example, the organofluoride salt and the cement may be present in a wt.% ratio of about 1:200, 1:190, 1:180, 1:170, 1:160, 1:150, 1:140, 1:130, 1:120, 1:110, 1:100, 1:90, 1:80, 1:70, 1:60, 1:50, 1:40, 1:30, 1:20, 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, or a value within a range between any of the preceding values, e.g., between about 1:5 and about 1:2, or the like. In other embodiments, the organofluoride salt to cement ratio may be upwards of about 1:6000 (e.g., 0.005 wt% organofluoride to 30 wt% cement).

[0107] In some embodiments, the organofluoride salt (e.g., TBATFB) may be present in an amount, relative to an amount of calcium oxide (within the cement, i.e., calcium silicate includes calcium oxide and silicon dioxide), in wt.% ratio of about 1:150 to about 1:0.1. For example the organofluoride salt and the calcium oxide may be present in a wt.% ratio of about 1:150, 1:140, 1:130, 1:120, 1:110, 1:100, 1:90, 1:80, 1:70, 1:60, 1:50, 1:40, 1:30, 1:20, 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 1:0.9, 1:0.8, 1:0.7, 1:0.6, 1:0.5, 1:0.4, 1:0.3, 1:0.2 or 1:0.1, or a value within a range of any of the preceding values, e.g., between about 1:3 to about 1:0.8, or the like. Cement

[0108] In many embodiments, the cement described below may be present alone or in combination with any other features of the dental composition(s) described herein.

[0109] The cement of the present disclosure includes calcium silicate, i.e., CaO and SiO2. Calcium silicate can describe compounds derived from limestone and diatomaceous earth that are composed of calcium oxide and silicon dioxide (i.e., silica) in various ratios, e.g., CaO•SiO2(“wollastonite”), 2CaO•SiO2(“belite”), 3CaO•SiO2(“alite”), and 3CaO•2SiO2. As used herein, “calcium silicate” may include any of the ratio forms, unless specifically indicated otherwise. Example cements include Portland cement, bioactive glass, and the like.

[0110] The cements of the present disclosure release calcium oxide (i.e., CaO), which in turn forms calcium hydroxide (hydroxide ions) upon contact with water or saliva. In some embodiments, the cement may include at least 20 wt.% calcium oxide. For example, the cement may include calcium oxide in an amount, in wt.%, of at least about 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or at least 95, or a value within a range between any of the preceding values, e.g., between about 20 and about 30, between about 60 and about 75, or the like. In some embodiments, the cement may include less than about 70 wt.% silicon dioxide. For example, the cement may include silicon dioxide in an amount, in wt.%, of less than about 70, 65, 60, 55, 50, 45, 40, 30, 25, 20, 15, 10, or less than 5, or a value within a range between any of the preceding values, e.g., between about 15 and about 25, between about 40 and about 50, or the like.

[0111] In some embodiments, the cement may further include aluminum oxide (Al2O3), ferric oxide (Fe2O3), magnesium oxide (MgO), potassium oxide (K2O), sodium oxide (Na2O), boric oxide (B2O3), zinc oxide (ZnO), and strontium oxide (SrO), or any combination thereof.

[0112] In many embodiments, the cement may be or include Portland Cement. The main components of Portland cement are tricalcium silicate (3CaO•SiO2), dicalcium silicate (2CaO•SiO2), tricalcium aluminate (3CaO•Al2O3), and tetracalcium aluminoferrite (4CaO•Al2O3•Fe2O3). Portland cement may include about 25-50% tricalcium silicate (3CaO•SiO2), about 20-45% dicalcium silicate (2CaO•SiO2), about 5-12% tricalcium aluminate (3CaO•Al2O3), about 6-12% tetracalcium aluminoferrite (4CaO•Al2O3•Fe2O3) and may further include about 2-10% gypsum (CaSO4•H2O), and about 1.5-5 wt.% other. In other terms, Portland cement may include 61-69% calcium oxide (CaO), 18-24% silicon dioxide (SiO2), 2.5-7% aluminum oxide (Al2O3), 1-6% ferric oxide (Fe2O3), and may further include sulfur(VI) oxide (SO3), magnesium oxide (MgO), potassium oxide (K2O), and / or sodium oxide (Na2O).

[0113] In other embodiments, the cement may be or include a bioactive glass. Bioactive glasses typically have some combination of phosphorus pentoxide (P2O5) and sodium oxide (Na2O) in addition to calcium oxide (CaO) and silicon dioxide (SiO2) and may further include one or more of potassium oxide (K2O), magnesium oxide (MgO), boric oxide (B2O3), aluminum oxide (Al2O3), zinc oxide (ZnO), and strontium oxide (SrO). Example bioactive glasses may be found in J. Nazanin et al. Biomaterials Research 2022, 26, 1-15, incorporated by reference herein in its entirety. Bioglass® 45S5 or NovaMinTM(GlaxoSmithKline; London, England) is one example of a bioactive glass that may becharacterized as a calcium sodium phosphosilicate composed of about 22.5-26.5% calcium oxide (CaO), 43-47% silica (SiO2), 5-7% phosphorus pentoxide (P2O5), and 22.5-26.5% sodium oxide (Na2O).

[0114] In some embodiments, the cement may be characterized by an average (i.e., mean) particle size of about 0.2 µm to about 1000 µm. For example, the cement may be characterized by a particle size of about 0.2, 0.5, 1, 5, 10, 25, 50, 75, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000 or a value within a range between any of the preceding values, e.g., between about 250 and about 300, or the like.

[0115] In many embodiments, the cement (e.g., Portland cement) may be present in an amount of about 1 wt.% to about 30 wt.% with respect to the weight of the dental composition. For example, the cement may be present in an amount, in wt.%, of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 112, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, or a value within a range between any of the preceding values, e.g., between about 5 and about 15, between about 8 and about 12, or the like.

[0116] In some embodiments, the cement (e.g., Portland cement) may be coated, uncoated, or partly coated with a metal oxide shell. A suitable metal oxide coating dissociates or otherwise dissolves upon contact with water, saliva, and / or acidic medium, thereby releasing the cement. Coated cements may provide a delayed release of the cement since the metal oxide shell must first dissociate; thus, coated cements may be used to modulate rates of fluoride release (i.e., slow the rate of fluoride release). Example metal oxides include oxides of aluminum, silicon, titanium, zirconium, magnesium, and zinc. In some embodiments, the cement may be coated with aluminum oxide. In some embodiments, the cement may be coated with titanium oxide. In some embodiments, the cement may be coated with silicon dioxide. Any metal oxide coating that may be present is not considered a filler as described below, i.e., it is not meant to be included in any wt.% of added filler. Further details regarding coated cements and preparations thereof may be found in the following documents, each of which are incorporated herein by reference in their entireties: U.S. Pat. Pub. No.2019-0388355, U.S. Pat. Pub. No.2023-0134622, and U.S. Pat. Pub. No.2021-0228315.

[0117] In some embodiments, the cement may be uncoated (i.e., no metal oxide shell).

[0118] In some embodiments, at least a portion of the cement may be at least partly coated with a metal oxide shell. In some embodiments, at least a portion of the cement may be coated with a metal oxide shell (i.e., uncoated cement and coated cement present within the dental composition). For example, the cement in a dental composition may be present in an uncoated:coated ratio of about 100:0, 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 40:60, 35:65, 30:70, 25:75, 20:80, 15:85, 10:90, 5:95, or 0:100, or a value within a range between any of the preceding values, e.g., between about 80:20 and about 50:50, or the like.

[0119] In some embodiments, a coated cement may be useful in dental compositions for sustained or otherwise slower release of ions (e.g., calcium ions, fluoride ions, and hydroxyl ions) as compared to compositions having an uncoated cement. In other embodiments, a coated cement may be useful indental composition configured to be used in combination (e.g., a two-part composition) with an acidic polymer (e.g., a polyacid, e.g., polyacrylic acid), e.g., a resin-modified glass ionomer, wherein it is desired to have a lower pH upon mixing of the dental composition (e.g., having an acid-reactive filler, such as FAS) and the acidic polymer, and wherein overtime the coating dissolves or otherwise releases the cement therein and effectively raises the pH due to the formation of calcium hydroxide. In some embodiments, a dental composition may include a combination of coated and uncoated cements. The release-profile of ions may further be tailored depending on one or more the thickness of the metal oxide coating and / or number of metal oxide coatings and the surface area (particle size) of the coated cement. However, most embodiments described herein utilize uncoated cement (e.g., dental sealants and composite restoratives) and exclude coated cements. Filler

[0120] In many embodiments, the filler(s) described below may be present alone or in combination with any of the dental composition features described herein.

[0121] In many embodiments, the dental composition may include an inorganic filler(s), an organic filler(s), or a combination thereof. In some embodiments, the dental composition may only include an inorganic filler(s), i.e., exclude organic filler(s).

[0122] The nature of the dental composition may depend upon the presence of filler and the amount present thereof. For example, dental compositions having a smaller amount of filler present may be suitable as a sealant or a liner. For example, dental compositions having higher amount of filler present may be suitable as a restorative. In some embodiments, the dental composition may include a total amount of filler (i.e., all fillers combined) present in an amount of about 0 wt.% to about 75 wt.% with respect to the weight of the dental composition. For example, the dental composition may include a total amount of filler (e.g., only inorganic fillers) present in an amount, in wt.%, of about 0, 0.1, 0.5, 1, 2, 3, 4, 5, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, 45, 48, 50, 52, 55, 58, 60, 62, 65, 68, 70, 72, or 75, or a value within a range between any of the preceding values, e.g., between about 5 and about 30, between about 55 and about 70, or the like. In some embodiments, a dental composition may be a sealant composition having one or more filler present in a total amount of about 0 wt.% to about 50 wt%. For example, a sealant composition may include one or more filler present in a total amount of 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50, or a value within a range between any of the preceding values, e.g., 5-25 wt.%, or the like, with respect to the weight of the dental composition. In other embodiments, a dental composition may be a restorative composition having one or more filler present in a total amount of about 30 wt% to about 75 wt.% with respect to the weight of the dental composition. For example, a restorative composition may include one or more filler present in a total amount of 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75, or a value within a range between any of the preceding values, e.g., 40-65 wt.%, or the like.

[0123] In some embodiments, the dental composition may include one or more (inorganic) filler selected from silica glass, silane-treated silica, fumed silica, fused silica, quartz, colloidal silica, feldspar, borosilicate glass, zirconia silica, pyrogenic silica, submicron silica, silicon nitride glass, fluoroaluminosilicate glass, kaolin, talc, titania, zinc glass, and a combination thereof. In some embodiments, the dental composition may include fumed silica. In some embodiments, the dental composition may include a silane-treated silica. In some embodiments, the dental composition may include fumed silica and a silane-treated silica.

[0124] In some embodiments, the dental composition may include one or more (organic) filler selected from pulverized polycarbonate, polyepoxides, or a combination thereof. In other embodiments, the dental composition may include one or more (organic) filler selected from silane-treated silica, silane-treated fluoroaluminosilicate glass, or a combination thereof. Example silanes for silane- treatment include alkyl silanes such as propyltrimethoxysilane (“PTMS”), aryl silanes such as trimethoxyphenylsilane (“TMPS”), vinyl silanes such as vinyltrimethoxysilane (“VTMS”), aminoalkyl silanes such as aminopropyltriethoxysilane (“APTES”), and orthosilicates such as tetramethyl orthosilicate (“TMOS”). In some embodiments, the surface area of the silica may be silanized in an amount of about 50% to about 100%. For example, the silica surface may be silanized with a silane that covers 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100, or a value within a range between any of the preceding values, e.g., between about 60 and about 75, or the like.

[0125] In some embodiments, the dental composition (e.g., a sealant composition) may include a fumed silica present in an amount of about 0.1 wt.% to about 10 wt.% with respect to the weight of the dental composition. For example, the dental composition may include a silane-treated silica in an amount, in wt.%, of about 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, or 10, or a value within a range between any of the preceding values, e.g., between about 0.5 and about 3, or the like. In other embodiments, the dental composition may exclude fumed silica.

[0126] In some embodiments, the dental composition (e.g., a sealant composition) may include a silane-treated silica in an amount of about 0.1 wt.% to about 25 wt.% with respect to the weight of the dental composition. For example, the dental composition may include a silane-treated silica in an amount, in wt.%, of about 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 or a value within a range between any of the preceding values, e.g., between about 10 and about 14, or the like.

[0127] In some embodiments, the dental composition (e.g., a sealant composition) may include a fumed silica and a silane-treated silica. In some embodiments, the fumed silica and the silane-treated silica may be present in a wt.% ratio of about 10:1 to 1:15. For example, the dental composition may include a fumed silica and a silane-treated silica present in a wt.% ratio of about 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, or 1:15, or a value within a range between any of the preceding values, e.g., between about 1:5 and about 1:10, or the like.Further, for example, a dental composition may include a fumed silica present in an amount of about 1 wt.% to about 3 wt.% and a silane-treated silica present in an amount of about 5 wt.% and about 15 wt.%. Initiator Systems

[0128] In many embodiments, the dental composition may include a light-cure initiator system, a portion of a redox initiator system, or a combination thereof. The initiator systems described below may be present in combination with any of the dental composition features described herein.

[0129] In some embodiments, the dental composition may include a light-cure initiator system having a photoinitiator (e.g., Norrish Type I photoinitiators). In other embodiments, the dental composition may include a light-cure initiator system having a photoinitiator (e.g., Norrish Type II photoinitiators) and a co-initiator (i.e., electron / hydrogen donor). Norrish Type I photoinitiators produce radicals by way a bond cleavage when exposed to sufficient light, whereas Norrish Type II photoinitiators produce radicals by way of electron and hydrogen abstraction from a co-initiator while in an excited state.

[0130] Some photoinitiators cannot produce free radicals under visible light (i.e., ≥ 400 nm) and therefore need to be accompanied by a photosensitizer that is excitable under visible light if it is desired to cure a composition under visible light rather than, say, ultraviolet light. Photosensitizers that absorb visible light can then activate photoinitiators through intramolecular electron transfer to yield active free radicals. In some embodiments, the dental composition may include a light-cure initiator system having a photoinitiator and a photosensitizer. In some embodiments, the dental composition may include a light-cure initiator system having a photoinitiator, a photosensitizer, and a co-initiator. In situations where a photoinitiator and a photosensitizer are not required, the photosensitizer may be considered a photoinitiator since many photosensitizers (Norrish Type II) can initiate a polymerization reaction.

[0131] Skilled artisans can readily identify photoinitiators, photosensitizers, and co-initiators that are suitable for use in dental compositions and appropriate for selected polymerizable components and / or methods of production (e.g., 3D printing a restorative dental article, filling a cavity with a syringe, or the like).

[0132] Example photoinitiators that require a photosensitizer for visible light curing may include diphenyl iodonium salts known in the art, such as diphenyl iodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, diphenyliodonium chloride, or (7-ethoxy-4-methylcoumarin-3-yl) phenyliodonium hexafluoroantimonate (“P3C-SB”). Other suitable iodonium salt photoinitiators include those in U.S. Pat. Nos. 3,729,313, 3,741,769, 3,808,006, 4,250,053 and 4,394,403, the disclosures of each of which are incorporated herein by reference in their entireties.

[0133] Further example photoinitiators / photosensitizers may include camphorquinone (“CQ”), 9,10-phenanthrenequinone (“PQ”), acetophenone, triphenylene, fluorenone, anthraquinone, triphenylamine, phenanthrene, benzophenone (“BP”), 1-phenyl-1,2-propanedione (“PPD”), 2,4,6- trimethylbenzoyl-diphenylphosphine oxide (“TPO”), bisacylphosphine oxide (“BAPO”), 9-(2,4,6- trimethylbenzoyl)-9-oxytho-9-phosphafuluorene (“TMBOPF”), 9-(p-toluyl)-9-oxytho-9- phosphafuluorene (“TOPF”), benzoyltrimethylgermane (“BTMGe”), dibenzoyldiethylgermane (“DBDEGe”), ivocerin-dibenzoyl germanium (“IVO”), (7-ethoxy-4-methylcoumarin-3- yl)phenyliodonium hexafluoroantimonate (“P3C-SB”), 4,4’-bis(N,N-diethylamino)benzophenone (“DEABP”), benzoyl peroxide, or the like. Broadly, photosensitizers may be selected from classes of compounds having one or more of the following functional groups or scaffolds: ketone, diarylketone, alpha-diketone, coumarin, ketocoumarin, xanthene, acridine, thiazole, thiazine, oxazine, azine, aminoketone, aminotriaryl methane, merocyanine, squaraine, pyridinium.

[0134] Co-initiators are compounds with heteroatoms having a lone pair of electrons (e.g., nitrogen (e.g., tertiary amines), oxygen, phosphorus, sulfur); and a carbon or silicon atom that is alpha to the heteroatom having an abstractable hydrogen. Example co-initiators may include aromatic tertiary amines such as ethyl-4-(dimethylamino)benzoate (“EDMAB”), ethyl-2-(dimethylamino)benzoate, toluidines such as N,N-dimethyl-p-toluidine (“DMPT”), N-phenylglycine, dimethylanilines, or the like; polymerizable amines such as 2-N,N-dimethylamino ethyl methacrylate (“DMAEMA”); non-aromatic tertiary amines such as methyldiethanolamine, triethylamine, triethanolamine; non-aromatic amines such as methylamine, ethylamine, propylamine, butylamine, or the like.

[0135] Further examples and information on photoinitiators / photosensitizers / co-initiators may be found in U.S. Pat. Nos.3,729,313, 4,071,424, 6,444,725, and 5,545,676, the contents of each of which are incorporated herein by reference in their entireties.

[0136] In some embodiments, the dental composition may include a light-cure initiator system having diphenyl iodonium hexafluorophosphate, camphorquinone, and ethyl-4- (dimethylamino)benzoate.

[0137] In other embodiments, the dental composition may include a redox initiator system (in lieu of a light-cure initiator system, or in combination with a light-cure initiator system) having a reducing agent and an oxidizing agent. Dental compositions having a redox initiator system would require the composition to be a multi-part composition (e.g., two-part system), wherein the oxidizing agent and the reducing agent are contained in different parts. Dental compositions of the present disclosure may have a portion (i.e., a reducing agent or an oxidizing agent) of a redox initiator system therein. Photobleachable Dye

[0138] In some embodiments, a dental composition may further include a photobleachable dye. In many embodiments, the photobleachable dye(s) described below may be present alone or in combination with any of the dental composition features described herein.

[0139] Suitable photobleachable dyes have an initial color that is in contrast with natural tooth such that a user may have a visual aid for adequate placement of the dental composition. Upon exposure to actinic radiation, a photobleachable dye changes color, preferably to color that matches surrounding tooth color and / or transmits the color of the underlying tooth. A dental composition having a particular photobleachable dye, or combination of dyes, may be selected according to the post-radiation color that most-closely matches a subject’s tooth color as compared to the VitaTMShade System. Alternatively, a dental composition having a particular photobleachable dye, or combination of dyes, may be selected to provide a post-radiation color that is decorative or otherwise cosmetic, e.g., a color other than typical tooth shades. Non-photobleachable dyes may also be used alone or in combination with a photobleachable dye depending upon the desire aesthetic. In some embodiments, the photobleachable dye may be selected according to compatible parameters within the dental composition or surrounding environment, e.g., acidity, dielectric constant, presence of water, or the like.

[0140] Example photobleachable dyes include methylene blue, amaranth, erythrosine, floxine, Rose Bengal, Acid Red, tartrazine, Sunset Yellow FCF, Fast Green FCF, Brilliant Blue FCF, Indigo carmine, phenolphthalein, sulfonephthalein, Yale Violet, methyl orange, fluorescein, methyl viologen, indophenol, dimuro betaine, bromeosin Y, laudamine B, thionine, neutral red, toluidine blue O, indocyanine green, sulfobromophthalein, uranin, lithol rubine B, lake red C, lithol red, tetrachloro tetrabromofluorescein, brilliant lake red R, deep maroon, toluidine red, tetrabromofluorescein, fast acid magenta, permanent red, dibromofluorescein, permanent orange, uranine, quinoline yellow, WS, alizarin cyanine green F, quinizarine green SS, light green SF yellow, patent blue NA, carbathrene blue, resorcinol brown, alizarine purple SS, brilliant fast scarlet, permanent red F5R, Ponceau SX, fast red S, oil orange SS, poral yellow 5G, fast light yellow 3G, naphthol green B, Guinea Green B, Sudan Blue B, alizarol purple, naphthol blue black, crocin, crocin blue, orange paprika, chlorophyl, cartamine, safflower yellow, beet red, direct fast yellow GC, direct fast orange, direct fast scarlet 4BS, fast red 6BLL, direct sky blue SB, direct fast turquoise blue GL, direct copper blue 2B, coprantine green G, direct fast black D, milling yellow O, acid brilliant scarlet 3R, acid violet 5B, azaline direct blue A2G, acid cyanine 6B, acid cyanine 5R, acid cyanine green G, milling brown 3G, acid fast black VLG, acid black WA, cation yellow 3G, cation golden yellow GL, cation flavin 10G, cation yellow 5GL, cation orange R, cation brown 3GL, cation pin FG, cation brilliant red 4G, cation red GTL, cation red BLH, cation red 6B, cation red SB, cation blue GLH, cation navy blue RHL, alizarine, chrome fast blue MB, chrome fast brown KE, chrome black P2B, chrome black T, fast scarlet G base, naphthol AS, naphthol AS-G, vat yellow GCN, vat orange RRTS, indigo, vat blue RSN, vat blue BC, vat brilliant green FFB, vat olive green B, vat olive T, vat brown R, vat gray M, disperse fast yellow G, disperse pink RF,disperse blue FFR, disperse blue green B, disperse yellow 5G, disperse golden yellow GG, disperse yellow RL, disperse yellow 3G, disperse orange B, disperse yellow brown 2R, disperse fast ruby 3B, disperse fast red FB, disperse red FL, disperse red GFL, disperse brilliant pink REL, disperse violet HFRL, disperse blue FB, disperse turquoise blue GL, disperse navy blue 2GL, fluorescent brightener WG, fluorescent brightener ERN, fluorescent brightener AT, fluorescent brighter SA, solvent orange G, solvent fast yellow 3RE, solvent fast red B, solvent fast blue HFL, reactive yellow 3G, reactive orange 2R, reactive red 3B, reactive scarlet 2G, reactive blue 3G, reactive blue R, reactive blue BR, reactive turquoise GF, reactive brilliant blue R, reactive black B, fast yellow G, fast yellow 10G, diazo yellow AAA, diazo yellow AAMX, flavane yellow, chromophtal yellow GR, methine yellow GR, methine yellow, sunset yellow lake, anthrapyrimidine yellow, isoindolinone yellow R, quinophthalone yellow, dinitroaniline orange, pyrazolone orange, dianisidine orange, persian orange lake, benzimidazolone orange HL, perinone orange, pyranthrone orange, para red, naphthol red FRR, toluidine red, naphthol carmine FB, naphthol red M, naphthol red BS, naphthol red RN, pyrazolone red, permanent red 2B, lithol red, bon lake red C, lake red C, brilliant carmine 6B, brilliant carmine 3B, Bordeaux 10B, von maroon M, brilliant scarlet G, rhodamine 6G lake, madder lake, thioindigo Bordeaux, naphthol red FGR, brilliant carmine BS, quinacridone magenta, perylene vermillion, naphthol carmin FBB, perylene red BL, chromophtal scarlet, anthrone red, naphthol red F5RK, erythrosine lake, dianthraquinolyl red, perylene red, perylene maroon, benzimidazolone carmine HF4C, perylene scarlet, amaranth lake, quinacridone red E, pyranthrone red, rhodamine B lake, methyl violet lake, alizarine maroon lake, quinacridone red, dioxazine violet, thioindigo magenta, Victoria blue lake, Victoria blue 6G lake, phthalocyanine blue, alkali blue G, indanthrone blue, brilliant green lake, malachite green lake, phthalocyanine green, pigment green B, phthalocyanine green 6Y, benzimidazolone brown HFR, aniline black, diarylide yellow H10G, diarylide yellow HR, carbazole violet, metacresol purple, bromophenol blue, crystal violet, gentian violet, bromocresol green, and bromothymol blue.

[0141] In some embodiments, the photobleachable dye may be selected from Rose Bengal, methylene violet, methylene blue, fluorescein, eosin yellow, eosin Y, ethyl eosin, eosin bluish, eosin B, erythrosine B, erythrosine yellowish blend, toluidine blue, dibromofluorescein, and a combination thereof.

[0142] In some embodiments, the photobleachable dye may be Rose Bengal. Rose Bengal is a particular photobleachable dye that may be sensitive to the pH of the dental composition.

[0143] In other embodiments, any of the photobleachable dyes (e.g., Rose Bengal) may be present in the dental composition in a total amount of about 0.005 wt.% to about 0.1 wt.%, e.g., 0.005, 0.008, 0.01, 0.015, 0.02, 0.0.25, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1, or a value within a range between any of the preceding values, e.g., between about 0.008 and about 0.015, or the like.

[0144] A dental curing light, which emits visible or near infrared (IR) light, is sufficient to induce a color change in the photobleachable dyes of the present disclosure. Dental compositions that may be cured upon exposure to light will concurrently induce a color change, but this does not ensure that the photobleachable dye will necessarily act as a cure indicator unless the rates of reaction are comparable. Dental compositions that may be cured upon redox initiation may then further be exposed to light to induce the color change in the photobleachable dye. Antioxidant Preservative

[0145] In many embodiments, the antioxidant preservatives(s) described below may be present alone or in combination with any of the dental composition features described herein.

[0146] In some embodiments, a dental composition may include an antioxidant preservative of butylated hydroxytoluene (“BHT”).

[0147] In some embodiments a dental composition may include an antioxidant preservative (e.g., BHT) present in an amount of about 0.005 wt.% to about 0.5 wt.% with respect to the weight of the dental composition. For example, the dental composition may include an antioxidant preservative present in an amount in wt.% of about 0.005, 0.01, 0.02, 0.05, 0.08, 0.1, 0.015, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or 0.5, or a value within a range between any of the preceding values, e.g., between about 0.1 and about 0.3, or the like. Water

[0148] In some embodiments, the dental composition may further include water in an amount no greater than 2 wt.% with respect to the weight of the dental composition. For example, the dental composition may include water in wt.% of less than 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.08, 0.05, 0.02, 0.01, 0.008, 0.005, 0.002, or less than 0.001, or a value within a range between any of the preceding values, e.g., between about 0.01 and about 0.05, or the like. In some embodiments, the dental composition may exclude water (i.e., 0 wt.%). Absent some mechanism from shielding the cement from reacting with water, it is necessary to limit any water present in the dental compositions to prevent hydration / hydrolysis reactions with the cement.

[0149] In some embodiments, a dental composition may include water within a separate component, i.e., a two-part composition. Inorganic fluoride Source

[0150] In many embodiments, the inorganic fluoride source(s) described below may be present alone or in combination with any of the dental composition features described herein.

[0151] In some embodiments, the dental composition may further include an inorganic fluoride source, e.g., sodium fluoride.

[0152] In some embodiments, the dental composition may further include an inorganic fluoride source(s) in an (total) amount no greater than 0.05 wt.% with respect to the weight of the dental composition. For example, the dental composition may include an inorganic fluoride source in wt.% no greater than 0.05, 0.04, 0.03, 0.02, 0.01, 0.009, 0.008, 0.007, 0.006, 0.005, 0.004, 0.003, 0.002, or less than 0.001, or a value within a range between any of the preceding values, e.g., between about 0.02 and about 0.04, or the like. In other embodiments, the dental composition may exclude inorganic fluoride sources (i.e., 0 wt.%). Example inorganic fluoride sources may include sodium fluoride, silver fluoride, ammonium fluoride, or the like. Ion-Release

[0153] In some embodiments, a dental composition may be characterized by an amount of ion release over a period. Any of the values below may be combined for a single dental composition of the present disclosure.

[0154] In some embodiments, the dental composition may be characterized by an amount of fluoride ion release of at least 0.5 ppm after 7 days according to the Fluoride Ion Release Test. For example, the dental composition may be characterized by an amount of fluoride ion release, in ppm, according to the Fluoride Ion Release Test after 7 days, of at least 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, or more, or a value within a range between any of the preceding values, e.g., between about 0.8 and about 1.1, or the like.

[0155] In some embodiments, the dental composition may be characterized by an amount of fluoride ion release of at least 1.0 ppm after 14 days according to the Fluoride Ion Release Test. For example, the dental composition may be characterized by an amount of fluoride ion release, in ppm, according to the Fluoride Ion Release Test after 14 days, of at least 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, or more, or a value within a range between any of the preceding values, e.g., between about 1.9 and about 2.2, or the like.

[0156] In some embodiments, the dental composition may be characterized by an amount of fluoride ion release of at least 1.3 ppm after 21 days according to the Fluoride Ion Release Test. For example, the dental composition may be characterized by an amount of fluoride ion release, in ppm, according to the Fluoride Ion Release Test after 21 days, of at least 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, or more, or a value within a range between any of the preceding values, e.g., between about 2.5 and about 2.9, or the like.

[0157] In some embodiments, the dental composition may be characterized by an amount of fluoride ion release of at least 1.6 ppm after 28 days according to the Fluoride Ion Release Test. For example, the dental composition may be characterized by an amount of fluoride ion release, in ppm, according to the Fluoride Ion Release Test after 28 days, of at least 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, or more,or a value within a range between any of the preceding values, e.g., between about 3.6 and about 4.3, or the like.

[0158] In some embodiments, the dental composition may be characterized by an amount of fluoride ion release of at least 1.8 ppm after 35 days according to the Fluoride Ion Release Test. For example, the dental composition may be characterized by an amount of fluoride ion release, in ppm, according to the Fluoride Ion Release Test after 35 days, of at least 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, or more, or a value within a range between any of the preceding values, e.g., between about 4.5 and about 5.0, or the like.

[0159] In some embodiments, the dental composition may be characterized by an amount of calcium ion release of at least 1 ppm after 7 days according to the Calcium Ion Release Test. For example, the dental composition may be characterized by an amount of calcium ion release, in ppm, according to the Calcium Ion Release Test after 7 days, of at least 1.0, 1.3, 1.5, 1.8, 2.0, 2.2, 2.5, 2.8. 3.0, 3.2, 3.5, 3.8, 4.04.2, 4.5, 4.8, 5.0, 5.2, 5.5, 5.8, 6.0, 6.2, 6.5, 6.8, 7.0, 7.2, 7.5, 7.8, 8.0, or more, or a value within a range between any of the preceding values, e.g., between about 7.0 and about 7.5, or the like.

[0160] In some embodiments, the dental composition may be characterized by an amount of calcium ion release of at least 10 ppm after 14 days according to the Calcium Ion Release Test. For example, the dental composition may be characterized by an amount of calcium ion release, in ppm, according to the Calcium Ion Release Test after 14 day, of at least 10.0, 10.2, 10.5, 10.8, 11.0, 11.2, 11.5, 11.8, 12.0, 12.2, 12.5, 12.8, 13.0, 13.2, 13.5, 13.8, 14.0, 14.2, 14.5, 14.8, 15, 15.2, 15.5, 15.8, 16.0, or more, or a value within a range between any of the preceding values, e.g., between about 12 and about 15, or the like.

[0161] In some embodiments, the dental composition may be characterized by an amount of calcium ion release of at least 15 ppm after 21 days according to the Calcium Ion Release Test. For example, the dental composition may be characterized by an amount of calcium ion release, in ppm, according to the Calcium Ion Release Test after 21 days, of at least 15.0, 15.2, 15.5, 15.8, 16.0, 16.2, 16.5, 16.8, 17.0, 17.2, 17.5, 17.8, 18.0, 18.2, 18.5, 18.8, 19.0, 19.2, 19.5, 19.8, 20.0, 20.2, 20.5, 20.8, 21, 21.2, 21.5, 21.8, 22.0, or more, or a value within a range between any of the preceding values, e.g. between about 18 and about 21, or the like.

[0162] In some embodiments, the dental composition may be characterized by an amount of calcium ion release of at least 22 ppm after 28 days according to the Calcium Ion Release Test. For example, the dental composition may be characterized by an amount of calcium ion release, in ppm, according to the Calcium Ion Release Test after 28 days, of at least 22.0, 22.2, 22.5, 22.8, 23.0, 23.2, 23.5, 23.8, 24.0, 24.2, 24.5, 24.8, 25.0, 25.2, 25.5, 25.8, 26, 26.2, 26.5, 26.8, 27, or more, or a value within a range between any of the preceding values, e.g., between about 22 and about 25, or the like.

[0163] In some embodiments, the dental composition may be characterized by an amount of calcium ion release of at least 25 ppm after 35 days according to the Calcium Ion Release Test. For example, the dental composition may be characterized by an amount of calcium ion release, in ppm, according to the Calcium Ion Release Test after 35 days, of at least 25.0, 25.2, 25.5, 25.8, 26, 26.2, 26.5, 26.8, 27.0, 27.2, 27.5, 27.8, 28.0, 28.2, 28.5, 28.8, 29.0, 29.2, 29.5, 29.8, 30.0, 30.2, 30.5, 30.8, 31.0, 31.2, 31.5, 31.8, 32, or more, or a value within a range between any of the preceding values, e.g., between about 26 and about 29, or the like. pH

[0164] In many embodiments, a dental composition of the present disclosure may be characterized by a pH in relation to a Water Immersion Test described herein.

[0165] In some embodiments, a dental composition may be characterized by a pH of greater than about 7 and less than 10 in view of the Water Immersion Test for a period of at least 7 days. In some embodiments, the dental composition may be characterized by a pH of greater than about 7 and less than 10 in view of the Water Immersion Test for a period of at least 14 days. In some embodiments, the dental composition may be characterized by a pH of greater than about 7 and less than 10 in view of the Water Immersion Test for a period of at least 21 days. In some embodiments, the dental composition may be characterized by a pH of greater than about 7 and less than 10 in view of the Water Immersion Test for a period of at least 28 days. In some embodiments, a dental composition may be characterized by a pH that is never below 7 in view of the Water Immersion Test.

[0166] In some embodiments, a dental composition (e.g., including TBATFB) may be characterized by a pH between 9 and 10 in view of the Water Immersion Test for a period of at least 1 day and no greater than about 14 days. For example, a dental composition may be characterized by a pH between 9 and 10 in view of the Water Immersion Test for a period, in days, of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, or a value within a range between any of the preceding values, e.g., between about 5 and about 11, or the like. Dental compositions of the present disclosure characterized by a pH of 9-10 for a period are typically those that include uncoated cement. Properties RE Demineralization

[0167] In some embodiments, a tooth surface treated with a dental composition of the present disclosure may be characterized by a Delta Integrated Reflectivity (“ΔIR”) as obtained by the 3D optical computed tomography (“OCT”), described further below in The Demineralization Challenge Tests, FIG.7, and Table 10.

[0168] In some embodiments, a treated tooth surface may be characterized by an ΔIR of no greater than 75 at a depth of 50 microns. In some embodiments, a treated tooth surface may be characterized by an ΔIR of no greater than 50 at a depth of 50 microns. In some embodiments, a treated tooth surfacemay be characterized by an ΔIR of 30 to 75 at a depth of 50 microns, e.g., 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75, or a value within a range between any of the preceding values, e.g., between about 40 and about 50, or the like.

[0169] In some embodiments a treated tooth surface may be characterized by an ΔIR of no greater than 125 at a depth of 75 microns. In some embodiments a treated tooth surface may be characterized by an ΔIR of no greater than 75 at a depth of 75 microns. In some embodiments, a treated tooth surface may be characterized by an ΔIR of 30 to 125 at a depth of 75 microns, e.g., 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, or 125, or a value within a range between any of the preceding values, e.g., between about 60 and about 75, or the like.

[0170] In some embodiments, a treated tooth surface may be characterized by an ΔIR of no greater than 175 at a depth of 100 microns. In some embodiments, a treated tooth surface may be characterized by an ΔIR of no greater than 150 at a depth of 100 microns. In some embodiments, a treated tooth surface may be characterized by an ΔIR of 30 to 175 at a depth of 100 microns, e.g., 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, or 175, or a value within a range between any of the preceding values, e.g., between about 50 and about 100, or the like.

[0171] In some embodiments, a tooth surface treated with a dental composition of the present disclosure may be characterized by a greyscale value at a given depth, as measured by microscopic computed x-ray tomography (“microCT’), described further below in The Demineralization Challenge Tests, FIG. 8, and Table 11. Higher greyscale values correspond to higher whiteness on an x-ray image, which further correlated to higher mineral density. Adhesion

[0172] In some embodiments, a dental composition of the present disclosure may be characterized by a shear adhesion value of at least 10 MPa on etched enamel, as outlined in the Adhesion Test herein. In other embodiments, a dental composition of the present disclosure may be characterized by a shear adhesion value of at least 20 MPa. METHODS FOR PREVENTING DEMINERALIZATION

[0173] In various embodiments, a method for preventing demineralization of a tooth surface is described. The method may include contacting a dental composition of the present disclosure to the tooth surface.

[0174] In some embodiments, the method may further include exposing the dental composition to light effective to cure the dental composition.

[0175] In many embodiments, the dental composition in contact with the tooth surface may release calcium ions, hydroxyl ions, and fluoride ions to the tooth surface.

[0176] In some embodiments, the dental composition may release calcium ions and fluoride ions to the tooth surface for a period of at least 5 weeks.

[0177] In many embodiments, the dental composition may be a sealant composition and the method may involve sealing a tooth surface.

[0178] In many embodiments, the dental composition may be a restorative composition and the method may involve restoring a tooth surface, e.g., filling a cavity. KITS

[0179] In various embodiments, a kit is described. A kit may include a dental composition of the present disclosure and a set of instructions directing a user to contact the dental composition to a tooth surface.

[0180] In some embodiments, the kit may further include an applicator for applying the dental composition.

[0181] In some embodiments, the kit may further include a second dental composition. For example, the second dental composition may include a portion of a redox initiator system that is complementary to a portion of a redox initiator system that may be present within the dental composition of the present disclosure.

[0182] In some embodiments, the kit may further include a second dental composition including an acidic monomers, and acidic polymer, or a combination thereof (with or without a redox initiator component). Acidic monomers and / or polymers include organic acid moieties, e.g., carboxylic acids, phosphate acids, or the like, such as those that are commonly used in resin-modified glass ionomer compositions. Dental compositions of the present disclosure that may be intended to be used as resin- modified glass ionomer compositions may further include an acid-reactive filler such as fluoroaluminosilicate glass.EXAMPLES Methods

[0183] The formulations in Tables 2 and 6 were tested according to the test procedures provided below. The results of said test procedures are provided in Tables 3-5 and 7-8.

[0184] Sample preparation for the Fluoride Ion Release Test, Calcium Ion Release Test, and Water Immersion Test (i.e., pH testing) involved light-curing the Example compositions in a 1 mm thick x 15 mm diameter mold using a 3M ESPE Elipar S10 curing light for 20 seconds on both sides of the disks. Each sample disk was weighed on a Mettler AT261 DeltaRange Analytical balance, and its dimensions were measured with a digital caliper (Mitutoyo). Individual disks were suspended in conical 50 mL centrifuge tubes (VWR) using springs and 25 mL of DI water was added to each tube. Samples were stored in a process oven (VWR) set to 37 °C and ion concentrations were measured at pre-determined intervals over 6 weeks. At each measurement time point, the water from each Example tube was decanted into a new plastic 50 mL centrifuge tube (VWR) and replaced with 25 mL fresh DI water. Fluoride Ion Release Test (3M OCSD TM-11-825469)

[0185] A Thermo Electron Orion 4Star Meter was used in conjunction with a fluoride-selective electrode (Thermo Scientific Combination Fluoride Electrode), to quantify the amount of fluoride ion released from the polymerized specimens in water. The fluoride electrode was first calibrated with parts per million (ppm) fluoride standards mixed with TISAB II (Total Ionic Strength Adjustment Buffer, Ricca Chemical) before measuring samples each day. Each Example composition was extracted into 25 mL DI water (Milli-Q Biocel System, Millipore), and a portion of this water was mixed 1:1 with TISAB II prior to measuring fluoride ion concentrations. The ion selective electrode was immersed into the liquid, and under light stirring, a value in ppm was obtained after equilibration. Each Example composition had an n = 3 samples per group, and ion concentrations were measured at pre-determined intervals over 6 weeks. Calcium Ion Release Test (3M OCSD TM-11-825469)

[0186] A Thermo Scientific Orion Versa Star Pro Meter was used in conjunction with a calcium- selective electrode (Thermo Scientific Combination Calcium Electrode), to quantify the amount of calcium ion released from the polymerized specimens in water. The calcium electrode was first verified for nominal electrode operation with a solution of Calcium ISA (Ionic Strength Adjuster, Thermo Scientific) and water. The electrode was calibrated with standards of 0.4 ppm, 4.0 ppm, 40 ppm and 400 ppm calcium content which were diluted from a concentrate of a 4000-ppm standard (0.1 M Ca2+ Standard, Thermo Scientific). Each composition was extracted into 25 mL DI water (Milli-Q BiocelSystem, Millipore), and a portion of this water was mixed with Calcium ISA (Ionic Strength Adjuster, Thermo Scientific) at a ratio of 2% (100 microliters for every 5 mL of sample) prior to measuring calcium ion concentrations. The ion selective electrode was immersed into the liquid and a value in ppm was obtained after equilibration. Each composition had an n = 3 samples per group, and ion concentrations were measured at pre-determined intervals over 6 weeks. Water Immersion Test (pH Test) (3M OCSD TM-11-825572)

[0187] A Fisher Scientific Accumet Model 15 pH Meter was used in conjunction with a pH probe (Orion ROSS Ultra Combination pH Probe, Thermo Scientific), to measure the pH of the water that the polymerized specimens were stored in. The pH electrode was calibrated with pH 4.0, 7.0 and 10.0 buffers (VWR) prior to use. Each composition was extracted into 25 mL DI water (Milli-Q Biocel System, Millipore), and the pH electrode was immersed into the water and under light stirring, a pH value was obtained after equilibration. Each composition had an n = 3 samples per group, and the pH was measured at pre-determined intervals over 6 weeks. Adhesion Test

[0188] Bovine crowns were cut from the roots, potted in acrylic, and finished / polished to cut enamel with 120 (3M sandpaper Wet or Dry product 21368 ) and 320 (3M Wet or Dry product 431Q) grit sandpaper. Adhesion testing was performed per ISO 29022 Adhesion: Notched edge shear bond strength test. A 2.3798 mm diameter Teflon mold (Ultradent) was placed on the top of a freshly exposed region of enamel and locked into place with thumb screws. Sealant was delivered to the mold via a syringe with a 27 gauge needle tip. Sealant was light cured for 20 seconds (3M Elipar DeepCure-S) and the jig was carefully removed. Prepared samples were stored in DI water at 37 °C for 24 hours before debonding. Debonding was done on an Instron 5944 testing machine with a 1 mm / minute crosshead speed. N=5 for the adhesion testing to calculate the adhesion mean and standard deviation. Demineralization Challenge Test

[0189] A 6 mm x 6 mm strip of bovine dental enamel was divided into three 2 mm sections. One section was etched with phosphoric acid etching gel (e.g., Example 1 or Comparative Example 1 Sealant) and a sealant was applied over the etched surface. One section was not etched, and a sealant was applied. One section was not etched and did not receive sealant application. The strip of bovine dental enamel was analyzed via 3D optical computed tomography (“OCT”) and microscopic computed x-ray tomography (microCT) prior to demineralization challenge.

[0190] The strip of bovine dental enamel having the three 2 mm sections was immersed in lactic acid (pH = 4.5) for 3 d (i.e., demineralization challenge). The strip of bovine dental enamel was analyzed via OCT and microCT post demineralization challenge.

[0191] OCT data was analyzed to determine the Delta Integrated Reflectivity (“ΔIR”) at depths of 50, 70, and 100 microns, according to the following formula: (ΔIR) = IRT1- IRT0wherein: ΔIR is the change in mineral content after exposure to lactic acid, IRT1is the measured mineral content at time T1 (e.g., 3 d), IRT0is the measured mineral content at time T0 (i.e., prior to demineralization challenge). Table 1. Chemical List. Acronym Name Source Di(meth)acrylate Monomer Urethane Dimethacrylate ROHAMERE 6661-0 (CAS No.41137-60-4) Rohm Tech, Inc., UDMA (Malden, MA) GDMA Glycerol Dimethacrylate Sigma-Aldrich(St. Louis, MO)TEGDMA Triethylene Glycol Dimethacrylate Arkema Inc.(King of Prussia, PA)BISGMA bisphenol A-glycidyl methacrylate 3M(Maplewood, MN)Fluoride Source TBATFBTetrabutylammonium TetrafluoroborateSigma-Aldrich (CAS No. 429-42-5)(St. Louis, MO) NaF Sodium fluoride Cement PC (uncoated) Fine Portland CementCemstone (sieved through 20 µm screen)(Mendota Heights, MN) Initiator BHT Butylated Hydroxytoluene Sigma-Aldrich(St. Louis, MO)CPQ Camphorquinone Sigma-Aldrich(St. Louis, MO)EDMAB Ethyl-4-(dimethylamino)benzoate Sigma-Aldrich(St. Louis, MO)DPIPF6 Diphenyliodonium Hexafluorophosphate Alfa Aesar(Ward Hill, MA)Filler R812S Evonik™ Aerosil™ R812S treated fumed silica Evonik 70nm S / T silica Silane-treated 70nm silica 3M(Maplewood, MN)Photobleachable Dye ROSE BENGAL (4,5,6,7-tetrachloro-2',4',5',7'-tetraiodofluoresceinMP Biomedical LLC(Solon, OH)EXAMPLE 1

[0192] The monomers, photoinitiator, inhibitor, organic soluble fluoride, and dye were mixed well to form a solution with a magnetic stirring bar mixing at room temperature. The resulting activated resin was weighed into a speed mixing cup with insoluble ingredients (e.g., silica, Portland cement) and mixed at 3000 rpm for 2 minutes and 2 cycles to form a uniform sealant paste.

[0193] The components of Example 1 are tabulated below in Table 2. All values are parts by weight (pbw). COMPARATIVE EXAMPLES 1-5

[0194] These monomers, photoinitiator, inhibitor, fluoride, and dye were mixed well to form a solution with magnetic stirring bar mixing at room temperature. The resulting activated resin was weighed into a speed mixing cup with other insoluble ingredients (e.g., silica, Portland cement) and mixed at 3000 rpm for 2 minutes and 2 cycles to form a uniform sealant paste.

[0195] The components of Comparative Examples 1-5 are tabulated below in Table 2. All values are parts by weight (pbw). Table 2. Formulations for Example 1 and Comparative Examples 1-5. EX.1 CE.1 CE.2 CE.3 CE.4 CE.5 UDMA 41.39 41.39 41.39 41.39 41.39 41.39 GDMA 20 20 20 20 20 20 TEGDMA 10 10 10 10 10 10 TBATFB 4 -- 4 -- -- -- NaF -- 4 -- 4 -- -- PC (uncoated) 10 10 -- -- 10 -- BHT 0.05 0.05 0.05 0.05 0.05 0.05 CPQ 0.15 0.15 0.15 0.15 0.15 0.15 EDMAB 0.3 0.3 0.3 0.3 0.3 0.3 DPIPF6 0.6 0.6 0.6 0.6 0.6 0.6 ROSE BENGAL0.01 0.01 0.01 0.01 0.01 0.01R812S 1.5 1.5 1.5 1.5 1.5 1.5 70nm S / T silica12 12 12 12 12 12

[0196] Example 1 and Comparative Examples 1-5 were tested for fluoride ion release according to the Fluoride Ion Release Test. The results are tabulated in Table 3 below (all values reported in ppm), and graphically represented in Figure 1.

[0197] Example 1, employing both TBATFB and Portland Cement, showed significantly greater fluoride release than Comparative Examples 1-5, i.e., a two-fold increase in fluoride release over Comparative Example 1, employing NaF rather than TBATFB as fluoride source in the presence of Portland Cement; and a two-fold increase in fluoride release over Comparative Examples 2 and 3, employing either TBATFB or NaF in the absence of Portland Cement. No formation of CaF2was observed. It is not clear by what mechanism the Portland Cement is promoting fluoride release or why the Portland Cement aids in more fluoride release for TBATFB than NaF, especially given that more moles of fluoride are present in NaF-containing composition. These results are surprising. However, it is hypothesized that an anionic component within Portland cement (e.g., hydroxyl) may ion exchange with fluoride thereby releasing free fluoride. Table 3. Fluoride ion release data for Example 1 and Comparative Examples 1-5. EX.1 CE.1 CE.2 CE.3 CE.4 CE.5 Day 1 0.118 0.255 0.109 0.143 0.042 0.042 Day 3 0.337 0.344 0.164 0.173 0.069 0.052 Day 7 0.582 0.552 0.248 0.209 0.095 0.058 Day 14 1.007 0.773 0.424 0.281 0.117 0.064 Day 21 1.382 0.845 0.559 0.339 0.12 0.064 Day 28 1.635 0.908 0.694 0.647 0.143 0.069 Day 35 1.868 0.953 0.815 0.849 0.152 0.069

[0198] Example 1 and Comparative Examples 1-5 were tested for calcium ion release according to the Calcium Ion Release Test. The results are tabulated in Table 4 below (all values reported in ppm), and graphically represented in Figure 2.

[0199] Example 1 and Comparative Example 1, each including Portland Cement and a fluoride source, showed relatively equal calcium release over the course of a week, but Example 1 showed more calcium was released over the course of 35 days. Surprisingly, Example 1 and Comparative 1 showed greater calcium release than did Comparative Example 4, having Portland Cement without a fluoride source. It is not clear by what mechanism that the presence of fluoride contributes to the release of calcium, let alone what mechanism affords TBATFB to have greater influence on calcium release than does NaF. These results are surprising. Table 4. Calcium ion release data for Example 1 and Comparative Examples 1-5. EX.1 CE.1 CE.2 CE.3 CE.4 CE.5 Day 1 0.010 0.007 0.006 0.002 0.014 0.001 Day 3 0.221 0.048 0.014 0.002 0.157 0.001 Day 7 1.488 0.845 0.033 0.013 1.768 0.009 Day 14 3.988 3.028 0.054 0.026 3.445 0.044 Day 21 4.548 4.388 0.234 0.196 5.155 0.087 Day 28 5.348 4.818 0.254 0.226 6.605 0.117 Day 35 5.668 4.891 0.259 0.229 6.826 0.119

[0200] Example 1 and Comparative Examples 1-5 were tested for pH according to the Water Immersion Test. The results are tabulated in Table 5 below, and graphically represented in Figure 3.

[0201] Each formulation including Portland cement (i.e., Example 1 and Comparative Examples 1 and 4) showed an increase in pH over a period of 14 days, followed by a decrease in pH during subsequent 14+ days – beginning and ending over a 35 day period at a neutral pH. Formulations without Portland Cement (i.e., Comparative Examples 2, 3, and 5) were shown to steadily decrease in pH over the course of 35 days. The transient increase in pH is due to release of hydroxyl ions, which is favorable for remineralization and preventing demineralization of tooth structures. Table 5. pH data for Example 1 and Comparative Examples 1-5. EX.1 CE.1 CE.2 CE.3 CE.4 CE.5 Day 1 7.11 7.00 6.43 6.49 7.02 6.41 Day 3 9.20 8.60 6.90 6.60 8.60 6.90 Day 7 9.60 9.40 5.60 6.00 9.70 5.80 Day 14 9.20 9.40 5.60 6.00 9.20 5.80 Day 21 7.10 8.30 5.60 5.80 8.00 5.70 Day 28 7.15 7.24 5.39 5.73 7.24 5.79 Day 35 7.30 7.30 5.70 6.00 7.20 5.90 COMPARATIVE EXAMPLES 6-8

[0202] Comparative Example 6 is commercially-available sealant, which includes BisGMA, which is a (i.e., a monomer of Formula I).

[0203] Comparative Examples 7 and 8. The monomers, photoinitiator, inhibitor, organic soluble fluoride, and dye were mixed well to form a solution with a magnetic stirring bar mixing at room temperature. The resulting activated resin was weighed into a speed mixing cup with other insoluble ingredients (e.g., silica, Portland cement) and mixed at 3000 rpm for 2 minutes and 2 cycles to form a uniform sealant paste.

[0204] Comparative Examples 7 and 8 are similar to Comparative Example 6 (i.e., include BisGMA, which is a monomer of Formula I), but further include Portland Cement.

[0205] The components of Comparative Examples 6-8 are tabulated below in Table 6. All values are parts by weight (pbw). Example 1 and Comparative Example 2 are provided within Table 6 for comparison.Table 6. Formulations of Comparative Examples 6-8 compared with Example 1 and Comparative Example 2. EX.1 CE.2 CE.6 CE.7 CE.8 UDMA 41.39 41.39 -- -- -- GDMA 20 20 -- -- -- TEGDMA 10 10 43.5 40.3 41.25 BisGMA -- -- 43.5 40.3 41.25 PC (uncoated) 10 -- -- 10.4 10 TBATFB 4 4 3.9 3.9 4 BHT 0.05 0.05 0.05 0.05 0.05 CPQ 0.15 0.15 0.15 0.15 0.15 EDMAB 0.3 0.3 0.3 0.3 0.3 DPIPF6 0.6 0.6 0.6 -- -- ROSE BENGAL0.01 0.01 0.006 -- --R812S 1.5 1.5 -- 4.6 3 70nm S / T silica12 12 -- -- --Aerosil R-972 -- -- 6.1 -- -- Pigment -- -- 2 -- --

[0206] Comparative Examples 6-8 were tested for fluoride ion release according to the Fluoride Ion Release Test and compared with Example 1. The results are tabulated in Table 7 below (all values reported in ppm), and graphically represented in Figure 4.

[0207] It shown that Comparative Example 6 releases more fluoride than does Example 1; however, it is widely known that there are various pressures to avoid monomers of Formula I (e.g., BisGMA) in commercial products. Reformulating Comparative Example 6 to avoid monomers of Formula I, i.e., Comparative Example 2, is shown to be relatively ineffective at releasing a suitable amount of fluoride. In other words, substituting monomers of Formula I for monomers such as UDMA is insufficient for fluoride release. Likewise, the addition of Portland cement to formulations similar to Comparative Example 6 (i.e., Comparative Examples 7 and 8) reduces the fluoride release profile compared to Comparative Example 6. Current understanding cannot explain why formulations without monomers of Formula I and with Portland Cement (i.e., Example 1) releases substantially more fluoride than compositions with monomers of Formula I and without Portland Cement (i.e., Comparative Examples 7 and 8). The results are surprising. Without wishing to be bound by theory, it is presumed that bisphenol-based monomers (RI > 1.500 and high Tg) are more rigid due to the phenyl ring system and said rigidity results in less mobility thereby impacting the release of ions in the presence of cement. Thus, one cannot simply add cement to Comparative Example 6 in an effort to achieve a dental composition that releases calcium ions and hydroxyl ions with any expectation of maintaining suitable fluoride release.Table 7. Fluoride ion release data for Example 1, Comparative Example 2, and Comparative Examples 6-8. EX.1 CE.2 CE.6 CE.7 CE.8 Day 1 0.118 0.109 0.325 0.030 0.032 Day 2 -- -- 0.534 0.057 0.061 Day 3 0.337 0.164 -- -- -- Day 4 -- -- 0.733 0.084 0.098 Day 7 0.582 0.248 1.010 0.116 0.130 Day 14 1.007 0.424 1.521 0.167 0.186

[0208] Comparative Examples 6-8 were tested for pH according to the Water Immersion Test and compared with Example 1 and Comparative Example 2. The results are tabulated in Table 8 below, and graphically represented in Figure 5.

[0209] Surprisingly, adding Portland cement to compositions having bisphenol-based monomer and TBATFB does not appear increase in the pH. Comparative Example 6 becomes relatively acidic over the course of 14 days. Comparative Examples 7 and 8, which include Portland cement, do not increase in pH, unlike Example 1. In other words, compositions having bisphenol-based monomer and Portland cement do not appear to effectively release hydroxyl ions that are beneficial for remineralization and preventing demineralization of tooth structures. Table 8. pH data for Example 1, Comparative Example 2, and Comparative Examples 6-8. EX.1 CE.2 CE.6 CE.7 CE.8 Day 1 7.11 6.43 -- -- -- Day 2 -- -- 6.08 6.87 7.00 Day 3 9.20 6.90 -- -- -- Day 4 -- -- 5.57 6.64 6.80 Day 7 9.60 5.60 6.00 6.58 6.93 Day 14 9.20 5.60 4.51 5.90 6.12

[0210] Example 1 was tested for adhesion according to the Adhesion Test. Comparative Example 6 was also tested for adhesion according to the Adhesion Test. The results are tabulated in Table 9 below, and graphically represented in Figure 6.

[0211] Example 1 shows better adhesion than Comparative Example 6. The reason for this observation is not fully understood.Table 9. Adhesion Test data for Example 1 and Comparative Example 6. EX.1 CE.6 Shear Adhesion (MPa) 20.37 ± 6.83 18.10 ± 6.08

[0212] Example 1 and Comparative Example 6 were subjected to the Demineralization Challenge Test (T1 = 3 d). The results are tabulated in Table 10 (OCT data) and Table 11 (microCT data) below, and graphically represented in Figure 7 and Figure 8, respectively.

[0213] RE Table 10 and Figure 7: ΔIR values indicate the increase in demineralization after 3 days of exposure to lactic acid. Lactic acid is often prevalent in the oral environment due to the presence of lactic acid-producing bacteria. It is shown that the ΔIR value at all depths is greater for Comparative Example 6 than it is for Example 1. In fact, the ΔIR value for Comparative Example 6 is 3X larger than Example 1 at 100 microns. Example 1 is far superior in preventing demineralization than is Comparative Example 6.

[0214] RE Table 11 and Figure 8: Higher grayscale versus depth on microCT images correspond to higher whiteness on an x-ray image, which further correlates to higher mineral density. The results show that lower mineral density (i.e., higher demineralization) for Comparative Example 6 than Example 1. Table 10. Demineralization Challenge OCT data for Example 1 / Comparative Example 6. ΔIR EX.1 CE.6 (etched) (etched) 50 microns 40 ± 10 80 ± 45 75 microns 65 ± 15 165 ± 40 100 microns 80 ± 12 230 ± 35 Table 11. Demineralization Challenge microCT data for Example 1 / Comparative Example 6. Greyscale EX.1 CE.6 (etched) (etched) 50 microns 0.3 0.3 100 microns 0.68 0.59 150 microns 0.85 0.82 200 microns 0.88 0.88 250 microns 0.9 0.9 300 microns 0.9 0.9 350 microns 0.9 0.9 400 microns 0.9 0.9EQUIVALENTS Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, numerous equivalents to the specific embodiments described specifically herein. Such equivalents are intended to be encompassed in the scope of the following claims.

Claims

What is claimed is:

1. A dental composition comprising: a polymerizable resin comprising: one or more di(meth)acrylate monomer, wherein the polymerizable resin excludes monomers having a moiety represented by Formula I: (I); an organofluoride salt(R1)4–N+X- (II), wherein: each R1is independently selected from a C1-12straight or branched alkyl and a C7-12straight or branched alkaryl or alkaralkyl, and X is F or BF4; and a cement comprising calcium silicate.

2. A dental composition comprising: a polymerizable resin comprising: one or more di(meth)acrylate monomer, wherein the polymerizable resin excludes monomers characterized by an octanol / water partition coefficient of greater than 5.5; an organofluoride salt represented by Formula II: (R1)4–N+X- (II), wherein: each R1is independently selected from a C1-12straight or branched alkyl and a C7-12straight or branched alkaryl or alkaralkyl, and X is F or BF4; and a cement comprising calcium silicate.

3. A dental composition comprising: a polymerizable resin comprising: one or more di(meth)acrylate monomer,wherein the polymerizable resin excludes monomers characterized by a refractive index greater than 1.500; an organofluoride salt represented by Formula II: (R1)4–N+X- (II), wherein: each R1is independently selected from a C1-12straight or branched alkyl and a C7-12straight or branched alkaryl or alkaralkyl, and X is F or BF4; and a cement comprising calcium silicate.

4. The dental composition of any one of claims 1-3, wherein the polymerizable resin consists essentially of monomers that are characterized by a molecular weight of no greater than 500 Da.

5. The dental composition of any one of claims 1-4, wherein the polymerizable resin consists essentially of monomers than are characterized by a viscosity of no greater than 500 Pa*s at 20 °C at a shear rate of 1 / s.

6. The dental composition of any one of claims 1-5, the one or more di(meth)acrylate monomer present in an amount of at least 60 wt.% with respect to the weight of the polymerizable resin.

7. The dental composition of any one of claims 1-6, the one or more di(meth)acrylate monomer present in an amount of at least 90 wt.% with respect to the weight of the polymerizable resin.

8. The dental composition of any one of claims 1-7, the one or more di(meth)acrylate monomer being represented by Formula III: CH2=CR1C(O)–R2–C(O)CR1=CH2(III), wherein: each R1is independently –H or –CH3; R2is –[O(CHR3)n]m–OC(O)–R4–C(O)O–[(CHR3)nO]m–, –[O(CHR3)n]m–O–, –OCH2CH(OH)CH2O–, –OCH2CH(CH2OH)O–, or –O–R5–O–; each R3is independently –H or –CH3; R4is –NR6–R5–NR6–, –O–R5–O–, or –R5–; R5is a C2-12straight or branched alkylene, a C2-12straight or branched alkenylene, a C5-6cycloalkylene, or phenylene; each R6is independently –H, –CH3; each n is independently an integer selected from 2-10; and each m is independently an integer selected from 1-10.

9. The dental composition of claim 8, wherein one or more di(meth)acrylate monomer represented by Formula III is present in the polymerizable resin in an amount of at least 60 wt.% with respect to the weight of the polymerizable resin.

10. The dental composition of claim 8, wherein one or more di(meth)acrylate monomer represented by Formula III is present in the polymerizable resin in an amount of at least 90 wt.% with respect to the weight of the polymerizable resin.

11. The dental composition of claim 8, wherein the polymerizable resin consists essentially of one or more di(meth)acrylate monomer represented by Formula III.

12. The dental composition of claim 8, the polymerizable resin comprising at least 50 wt.% of one or more di(meth)acrylate monomer represented by Formula III, wherein: R2is –[O(CHR3)n]m–OC(O)–R4–C(O)O–[(CHR3)nO]m–, and R4is –NR5–R6–NR5–.

13. The dental composition of claim 8, the polymerizable resin comprising at least 15 wt.% of one or more di(meth)acrylate monomer represented by Formula III, wherein: R2is –OCH2CH(OH)CH2O–.

14. The dental composition of claim 8, the polymerizable resin comprising at least 5 wt.% of one or more di(meth)acrylate monomer represented by Formula III, wherein: R2is –[O(CH2)n]m–O–.

15. The dental composition of any one of claims 114, the polymerizable resin comprising one or more urethane di(meth)acrylate monomer, one or more glyceryl di(meth)acrylate monomer, one or more glycol di(meth)acrylate monomer, or a combination thereof.

16. The dental composition of any one of claims 1-15, the polymerizable resin comprising urethane dimethacrylate, glycerol dimethacrylate, and triethylene glycol dimethacrylate.

17. The dental composition of any one of claims 1-16, the polymerizable resin comprising urethane dimethacrylate, glycerol dimethacrylate, and triethylene glycol dimethacrylate present in a wt.% ratio of about 4:2:1.

18. The dental composition of any one of claims 1-17, the polymerizable resin consisting essentially of urethane dimethacrylate, glycerol dimethacrylate, and triethylene glycol dimethacrylate.

19. The dental composition of any one of claims 1-18, the polymerizable resin consisting essentially of 50-65 wt.% urethane dimethacrylate, 15-45 wt.% glycerol dimethacrylate, and 5-35 wt.% triethylene glycol dimethacrylate.

20. The dental composition of any one of claims 1-19, the polymerizable resin excluding acidic monomers and acidic polymers.

21. The dental composition of any one of claims 1-20, wherein the polymerizable resin is present in an amount of least 20 wt.% based on the weight of the dental composition.

22. The dental composition of any one of claims 1-21, wherein the polymerizable resin is present in an amount of about 20 wt% to about 80 wt% based on the weight of the dental composition.

23. The dental composition of any one of claims 1-22, wherein the polymerizable resin is present in an amount of about 40 wt.% to about 60 wt.% based on the weight of the dental composition.

24. The dental composition of any one of claims 1-23, wherein polymerizable resin and organofluoride salt are present in a wt.% ratio of about 1000:1 to about 10:

1.

25. The dental composition of any one of claims 1-24, wherein the polymerizable resin and the cement are present in a wt.% ratio of about 90:1 to about 0.5:

1.

26. The dental composition of any one of claims 1-25, wherein each R1is independently selected from a C4-8alkyl.

27. The dental composition of any one of claims 1-26, wherein X is BF4.

28. The dental composition of any one of claims 1-27, wherein the organofluoride salt is selected from tetrabutylammonium tetrafluoroborate, tetrabutylammonium fluoride, and a combination thereof.

29. The dental composition of any one of claims 1-28, wherein the organofluoride salt is tetrabutylammonium tetrafluoroborate.

30. The dental composition of any one of claims 1-29, wherein the organofluoride salt is present in an amount of about 0.005 wt.% to about 15 wt.% with respect to the weight of the dental composition.

31. The dental composition of any one of claims 1-30, wherein the organofluoride salt is present in an amount of about 0.02 mmol to about 50 mmol.

32. The dental composition of any one of claims 1-31, wherein the organofluoride salt and cement are present in a wt.% ratio of about 1:200 to about 1:

1.

33. The dental composition of any one of claims 1-32, wherein the organofluoride salt and calcium oxide are present in a wt.% ratio of about 1:150 to about 1:0.1, wherein calcium oxide is a component of calcium silicate.

34. The dental composition of any one of claims 1-33, the cement comprising at least 20 wt.% calcium oxide.

35. The dental composition of any one of claims 1-34, the cement comprising 60-75 wt.% calcium oxide.

36. The dental composition of any one of claims 1-35, the cement further comprising aluminum oxide, ferric oxide, magnesium oxide, potassium oxide, sodium oxide, sodium oxide, boric oxide, zinc oxide, strontium oxide, or a combination thereof.

37. The dental composition of any one of claims 1-36, the cement characterized by an average particle size of about 0.2 µm to about 1000 µm.

38. The dental composition of any one of claims 1-37, the cement being uncoated.

39. The dental composition of any one of claims 1-38, at least a portion of the cement being at least partly coated with a metal oxide shell.

40. The dental composition of any one of claims 1-39, wherein the cement is present in an amount from about 1 wt.% to about 30 wt.% with respect to the weight of the dental composition.

41. The dental composition of any one of claims 1-40, further comprising one or more inorganic filler, one or more organic filler, or a combination thereof.

42. The dental composition of any one of claims 1-40, further comprising one or more inorganic filler and excluding organic fillers.

43. The dental composition of any one of claims 1-42, further comprising fumed silica.

44. The dental composition of any one of claims 1-43, further comprising fumed silica present in an amount of about 0.1 wt.% to about 10 wt.% with respect to the weight of the dental composition.

45. The dental composition of any one of claims 1-44, further comprising a silane-treated silica.

46. The dental composition of any one of claims 1-45, further comprising a silane-treated silica present in an amount of about 0.1 wt.% to about 25 wt.% with respect to the weight of the dental composition.

47. The dental composition of any one of claims 1-46, further comprising fumed silica and a silane-treated silica.

48. The dental composition of any one of claims 1-47, further comprising fumed silica and a silane-treated silica, the fumed silica and the silane-treated silica being present in a wt.% ratio of about 10:1 to about 1:

15.

49. The dental composition of any one of claims 1-48, further comprising one or more filler present in a total amount of about 0.1 wt.% to about 75 wt.% with respect to the weight of the dental composition.

50. The dental composition of any one of claims 1-49, further comprising a light-cure initiator system, a portion of a redox initiator system, or a combination thereof.

51. The dental composition any one of claims 1-50, further comprising a light-cure initiator system comprising a photoinitiator, a co-initiator, and a photosensitizer.

52. The dental composition of any one of claims 1-51, further comprising a light-cure initiator system comprising diphenyl iodonium hexafluorophosphate, ethyl-4-(dimethylamino)benzoate, and camphorquinone.

53. The dental composition of any one of claims 1-52, further comprising a photobleachable dye.

54. The dental composition of claim 53, wherein the photobleachable is Rose Bengal.

55. The dental composition of any one of claims 53-54, wherein the photobleachable dye is present in an amount of about 0.005 wt.% to about 0.1 wt.% with respect to the weight of the dental composition.

56. The dental composition of any one of claims 1-55, further comprising an antioxidant preservative.

57. The dental composition of claim 56, wherein the antioxidant preservative is butylated hydroxytoluene.

58. The dental composition of any one of claims 56-57, wherein the antioxidant preservative is present in an amount from about 0.005 wt.% to about 0.5 wt.% with respect to the weight of the dental composition.

59. The dental composition of any one of claims 1-58, further comprising water in an amount no greater than 2 wt.% with respect to the weight of the dental composition.

60. The dental composition of any one of claims 1-59, further comprising one or more inorganic fluoride source in an amount no greater than 0.05 wt.%.

61. The dental composition of any one of claims 1-60, excluding inorganic fluoride sources.

62. The dental composition of any one of claims 1-61, being a sealant, a primer, an adhesive, a restorative, a cement, or a liner.

63. A cured dental composition derived from a dental composition of any one of claims 1-62.

64. A method for preventing demineralization of a tooth surface, the method comprising: contacting a dental composition of any one of claims 1-62 to the tooth surface.

65. The method of claim 64, wherein the dental composition releases calcium ions, hydroxyl ions, and fluoride ions.

66. The method of any one of claims 64-65, wherein the dental composition releases calcium ions and fluoride ions for a period of at least 5 weeks.

67. The method of any one of claims 68-70, further comprising exposing the dental composition on the tooth surface to a light effective to cure the dental composition.

68. A kit comprising: a dental composition of any one of claims 1-62; and a set of instructions directing a user to contact the dental composition to a tooth surface.

69. The kit of claim 68, further comprising an applicator.

70. The kit of any one of claims 68-69, further comprising a second dental composition for use in combination with the dental composition, the second dental composition comprising an acidic monomer, acidic polymer, or a combination thereof.

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