Light-cured dimethacrylate-based resins and their composites: comparative study of mechanical strength, water sorption and ion release.

This study explored how resin type affects selected physicochemical properties of complex methacrylate copolymers and their amorphous calcium phosphate (ACP)-filled and glass-filled composites. Two series of photo-polymerizable resin matrices were formulated employing 2,2-bis[p-(2'-hydroxy-3'-methacryloxypropoxy)phenyl]propane (Bis-GMA) or an ethoxylated bisphenol A dimethacrylate (EBPADMA) as the base monomer, Unfilled copolymers and composites filled with a mass fraction with 40 %, 35 % and 30 %, respectively, of ACP or the un-silanized glass were assessed for biaxial flexure strength (BFS), water sorption (WS) and mineral ion release upon immersion in HEPES-buffered saline solution for up to six months. Substituting EBPADMA for Bis-GMA significantly reduced the WS while only marginally affected the BFS of both dry and wet copolymers. Independent of the filler level, both dry and wet ACP composites formulated with either BTHM or ETHM resins were mechanically weaker than the corresponding copolymers. The BFS of ACP composite specimens after 1 month in saline did not further decrease with further aqueous exposure. The BFS of glass-filled composites decreased with the increased level of the glass filler and the time of aqueous exposure. After 6 months of immersion, the BFS of glass-filled BTHM and ETHM composites, respectively, remained 58 % and 41 % higher than the BFS of the corresponding ACP composites. Ion release data indicated that a minimum mass fraction of 35 % ACP was required to attain the desired solution supersaturation with respect to hydroxyapatite for both the BTHM and ETHM derived composites.

Ionic Dimethacrylates for Antimicrobial and Remineralizing Dental Composites.

Two ionic dimethacrylates (IDMA1 and IDMA2) intended for utilization in multifunctional, antibacterial and remineralizing dental resins and composites were synthesized by nucleophilic substitution reactions. Crude IDMAs were purified by multi-step extraction from ethanol-diethyl ether-hexane solvent system. Their structures were validated by nuclear magnetic resonance and mass spectrometry. As evidenced by the water contact angle measurements ((63.2-65.5)0), IDMAs did not affect the wettability of urethane dimethacrylate (UDMA)- based copolymers (average contact angle ((60.8±5.1)0).The attained degrees of vinyl conversion increased from 88.1% (no-IDMA control) up to 93.0% (IDMA2 series). Flexural strength (FS) of copolymers was reduced from 94.8 MPa (control) to (68.9-71.8) MPa (IDMA counterparts) independent of monomer type and/or its concentration. This reduction in FS should not disqualify IDMAs from consideration as viable antibacterial agents in multifunctional restoratives. Tested at concentrations exceeding the expected leachability of unreacted monomers from cured copolymers and/or composites, IDMAs had no deleterious effect on viability and/or metabolic activity of fibroblasts. The remineralization potential of amorphous calcium phosphate IDMA/UDMA composites was confirmed by calcium and phosphate ion release kinetic experiments. Results of this study warrant in-depth biological, physicochemical, mechanical and antibacterial assessments of IDMA resins and composites to identify prototype(s) suitable for clinical testing.

Effect of particle size of an amorphous calcium phosphate filler on the mechanical strength and ion release of polymeric composites.

The random clustering of amorphous calcium phosphate (ACP) particles within resin matrices is thought to diminish the strength of their polymerized composites. The objective of this study was to elucidate the effect of ball-milling on the particle size distribution (PSD) of ACP fillers and assess if improved dispersion of milled ACP in methacrylate resin sufficiently enhanced filler/matrix interactions to result in improved biaxial flexure strength (BFS), without compromising the remineralizing potential of the composites. Unmilled and wet-milled zirconia-hybridized ACP (Zr-ACP) fillers were characterized by PSD analysis, X-ray diffraction, thermogravimetric and chemical analysis, infrared spectroscopy, and scanning electron microscopy. Composite specimens made from a photoactivated, ternary methacrylate resin admixed with a mass fraction of 40% of un-milled or milled Zr-ACP were evaluated for the BFS (dry and wet) and for the release of calcium and phosphate ions into saline solutions. While having no apparent effect on the structure, composition, and morphology/topology of the fillers, milling significantly reduced the average size of Zr-ACP particulates (median diameter, d(m) = 0.9 +/- 0.2 microm) and the spread of their PSD. Better dispersion of milled Zr-ACP in the resins resulted in the improved BFS of the composites, even after aqueous soaking, and also gave a satisfactory ion release profile. The demonstrated improvement in the mechanical stability of anti-demineralizing/remineralizing ACP composites based on milled Zr-ACP filler may be beneficial in potentially extending their dental utility.

Dental composites based on amorphous calcium phosphate - resin composition/physicochemical properties study.

This study explores how the resin composition/structure affects the physicochemical properties of copolymers and their amorphous calcium phosphate (ACP)-filled composites. A series of photo-polymerizable binary and ternary matrices are formulated utilizing 2,2-bis[ p-(2(')-hydroxy-3(')methacryloxypropoxy)phenyl]propane, 2,2-bis[ p-(2(')-methacryloxypropoxy)phenyl]-propane (EBPADMA), or a urethane dimethacrylate as base monomers, and triethylene glycol dimethacrylate or hexamethylene dimethacrylate (HmDMA) with or without 2-hydroxyethyl methacrylate (HEMA) as diluent monomer. Unfilled copolymers and composites filled with 40% by mass zirconia-hybridized ACP are evaluated for biaxial flexure strength (BFS), degree of conversion (DC), mineral ion release, polymerization shrinkage (PS), and water sorption (WS). The average DC values are 82-94% and 74-91% for copolymers and composites, respectively. Unrelated to the resin composition, the PS values of composites are up to 8.4 vol. % and the BFS values of wet composite specimens are on average 51 +/- 8 MPa. The maximum WS values attained in copolymers and composites reach 4.8 mass%. Inclusion of hydrophobic HmDMA monomer in the matrices significantly reduces the WS. The levels of Ca and PO(4) released from all types of composites are significantly above the minimum necessary for the re-deposition of apatite to occur. Elevated Ca, and to a lesser extent PO(4) release, is observed in HEMA-containing, ternary EBPADMA formulations. Further resin reformulations may be needed to improve the PS of composite specimens. Poor dispersion of ;as-synthesized' ACP within the composite contributes to their inferior mechanical performance.

Nano DCPA-whisker composites with high strength and Ca and PO(4) release.

The main challenges facing composite restorations are secondary caries and bulk fracture. The objective of this study was to develop nano DCPA (dicalcium phosphate anhydrous)-whisker composites with high strength and Ca and PO(4) ion release to combat caries. Flexural strength for the nano DCPA-whisker composites at a nano DCPA:whisker mass ratio of 1:2 ranged from (148 +/- 9) MPa to (167 +/- 23) MPa, significantly higher than the (103 +/- 32) MPa of an inlay/onlay commercial control composite without Ca-PO(4) release. The nano DCPA-whisker composite released PO(4) to a concentration of (1.95 +/- 0.13) mmol/L and Ca of (0.68 +/- 0.05) mmol/L. Compared with previous conventional Ca- and PO(4)-releasing composites, the nano DCPA-whisker composites had strengths two-fold higher, and released comparable or higher levels of Ca and PO(4). In conclusion, combining nano-DCPA with whiskers yielded novel composites that released high levels of Ca and PO(4) requisite for remineralization. These high-strength composites may provide a unique combination of stress-bearing and caries-inhibiting capabilities.

Amorphous calcium phosphate composites with improved mechanical properties.

Hybridized zirconium amorphous calcium phosphate (ACP)-filled methacrylate composites make good calcium and phosphate releasing materials for anti-demineralizing/remineralizing applications with low mechanical demands. The objective of this study was to assess the effect of the particle size of the filler on the mechanical properties of these composites. Photo-curable resins were formulated from ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and methacryloxyethyl phthalate. Camphorquinone and ethyl-4-N,N-dimethylaminobenzoate were utilized as components of the photoinitiator system. After 2 h of mechanical milling in isopropanol, an approximate 64 % reduction in the median particle diameter was observed [27.48 µm vs. 9.98 µm] for unmilled and milled wet ACP, respectively. Dry ACP showed a 43 % reduction in particle size from pre- to post-milling. As well as dry composites, those that had been immersed in aqueous media were evaluated for their Young's Modulus, water sorption, biaxial tensile, three-point flexural and diametral tensile strength. Mechanically milling the filler increased the volume of fine particles in the composite specimens, resulting in a more homogeneous intra-composite distribution of ACP and a reduction in voids. In turn, less water diffused into the milled composites upon aqueous exposure, and they showed a marked improvement in biaxial flexure strength and a moderate improvement in flexural strength over composites with unmilled ACP. The demonstrated improvement in the mechanical stability of milled Zr-ACP composites may help in extending their dental applicability.

Volumetric contraction and methacrylate conversion in photo-polymerized amorphous calcium phosphate/methacrylate composites.

Because of its relatively high solubility in aqueous media and its rapid transformation to hydroxyapatite, amorphous calcium phosphate (ACP) has been utilized as the filler phase of resin-based bioactive composites that have remineralization potential. The objectives of this study were to determine how various methacrylate resins and various types of ACP fillers affect acrylic vinyl conversion and polymerization shrinkage (PS). Several types of photo-crosslinkable resin systems were prepared and admixed with a mass fraction of 40% of either unhybridized, silica- or zirconia-hybridized ACP. After visible light-activated photo-polymerization ACP composites were assessed by near infrared spectroscopy for degree of vinyl conversion and by mercury dilatometry for PS. It was found for these composites that vinyl conversion was independent of filler type but strongly dependent on the type and composition of the resin phase. PS, on the other hand, showed more complex dependence both on the resin type and composition and, in some cases, on the type of ACP. In order to obtain ACP/methacrylate-based composites with maximal vinyl conversion, resin type and composition are of primary importance. However, in order to minimize volume contraction on polymerization it appears necessary to consider both the resin and filler type of these bioactive composites.

Dental composites based on hybrid and surface-modified amorphous calcium phosphates.

The objectives of this study were to prepare hybrid and surface-modified amorphous calcium phosphates (ACPs) as fillers for mineral-releasing dental composites, and determine whether the mechanical strength of the composites could be improved without decreasing their remineralization potential. ACP was hybridized with tetraethoxysilane or zirconyl chloride and surface-treated with 3-methacryloxypropoxytrimethoxy silane (MPTMS) or zirconyl dimethacrylate (ZrDMA). Composites fabricated with unmodified ACP (u-ACP), hybrid or surface-modified ACP filler and photo-activated Bis-GMA, TEGDMA and 2-hydroxyethyl methacrylate (HEMA) (BTH resin), Bis-GMA, TEGDMA, HEMA and MPTMS (BTHS resin) or Bis-GMA, TEGDMA, HEMA and ZrDMA (BTHZ resin) were tested for their remineralizing potential and biaxial flexure strength (BFS). Ion releases from all composites were significantly above the minimum necessary for reprecipitation of apatite. The BFS of unfilled polymers was not adversely affected by immersion in saline solutions. The BFS of BTH and BTHS composites deteriorated upon soaking. However, BTHZ composites were practically unaffected by exposure to saline solutions. Filler hybridization resulted in a modest, but significant, improvement in the BFS (up to 24%) of BTHZ composites. Heterogeneous distribution of the ACP on disk surfaces was detected by the FTIR microspectroscopy analyses. This might have been caused by uncontrolled aggregation of ACP particles that appeared to hinder interfacial filler/resin interactions and diminish the mechanical strength of composites.

Effect of powder grinding on hydroxyapatite formation in a polymeric calcium phosphate cement prepared from tetracalcium phosphate and poly(methyl vinyl ether-maleic acid).

The primary aim of this study was to determine if cements based on poly(methyl vinyl ether-maleic acid) (PMVE-Ma) and tetracalcium phosphate resulted in hydroxyapatite formation. In addition, the mechanical strength of this type of polymeric calcium phosphate cement was evaluated. Cements were prepared by mixing, in a powder/liquid mass ratio of 3.0, an aqueous solution of PMVE-Ma (mass fraction = 25%) and tetracalcium phosphate powders ground for various periods of time. The tetracalcium phosphate powders and set cements were characterized by means of X-ray powder diffraction and scanning electron microscopy. Mechanical strengths of the cements were tested 24 h after mixing. Prolonged grinding of tetracalcium phosphate powder decreased particle size and/or crystallite size and increased lattice distortion. This enhanced the reactivity of the tetracalcium phosphate powder and elevated the extent of crosslinking between PMVE-Ma molecules, resulting in improved mechanical strength. Hydroxyapatite formation was detected in the cement prepared with the most finely ground tetracalcium phosphate powder. The conversion of residual tetracalcium phosphate particles to more thermodynamically stable hydroxyapatite crystals will reduce the solubility of the polymeric cement and increase its biocompatibility.

Aldehyde methacrylates derived from hydroxybenzaldehydes.

Three crystalline aldehyde methacrylates with low melting points were synthesized from the readily available, isomeric hydroxybenzaldehydes and 2-bromoethyl methacrylate. These monomers can be purified by recrystallization and liquified by admixture in various proportions to obtain polymerizable liquids having workable viscosities at room temperature. These monomers may be used alone or as blends with other methacrylates since they are miscible and copolymerizable with the usual dental monomers. Also, they should be studied with other functional methacrylates designed to promote adhesion via the mineral phase to determine if this synergistic approach can improve the adhesion of dental resins to dentin. These aldehyde methacrylates, their mixtures, polymers and copolymers merit evaluation as adhesion-promoting agents for proteinaceous substrates such as bone and dentin.

Adhesive bonding of various materials to hard tooth tissues: XIII Synthesis of a polyfunctional surface-active amine accelerator.

Surface-active amine polymerization accelerators can be prepared by the reaction of polyepoxy resins with the sodium salt of N-phenylglycine and N-methyl-p-toluidine. These materials are expected to promote adhesion through complexation with surface calcium (or other metal ions), utilizing several chelating groups per molecule, and by functioning as polymerization accelerators for dental resins; they can also function as catalysts for the anionic polymerization of cyanoarylate monomers.

Dimethacrylates derived from hydroxybenzoic acids.

Since the color stabilities and durabilities of current composite and pit and fissure sealant resins need improvement, it is worthwhile to evaluate innovations that might accomplish this goal. Accordingly, three crystalline dimethacrylate monomers with low melting points were prepared from the isomeric hydroxybenzoic acids and 2-bromo-ethyl methacrylate. These monomers can be purified by crystallization and liquified by admixture in various proportions to obtain a polymerizable liquid of suitable viscosity at room temperature. In contrast to the analogous dimethacrylate monomers that were derived from the phthalic acid isomers, these aromatic ether-ester dimethacrylates do not form colored charge-transfer complexes with tertiary aromatic amine accelerators. These monomers and their polymers should be elevated for use in composites and pit and fissure sealant formulations.

Extent of polymerization of dental resins by differential scanning calorimetry.

The traditional infrared spectroscopic methods for assessing the degree of polymerization of dental monomers are often hampered by the difficulties of sample preparation and, in the case of composites, by interference from the filler component. These difficulties may be circumvented by the use of another technique, differential scanning calorimetry (DSC). In this preliminary investigation, DSC was used to ascertain the degree of vinyl polymerization of an experimental monomer system consisting of seven parts BIS-GMA and three parts TEGDMA (triethylene glycol dimethacrylate). Thermally-activated polymerizations of this monomer system were studied using benzoyl peroxide (BP) as the initiator. Both the heating rate and the concentration of BP affected the percent of reacted vinyl groups. For a BP concentration of 0.39% and heating rates of 10 degrees/min and 2.5 degrees/min, conversions were 73 and 38%, respectively. Chemically-activated polymerizations using BP and fast-acting amine accelerators (e.g., p-t-butyl-N,N-dimethylaniline) gave approximately the same results (e.g., 50% conversion) as those obtained with slower-acting promoters (e.g., ascorbyl palmitate). Experimental difficulties are encountered in observing an exotherm with the very reactive accelerators unless the other parameters (e.g., BP or inhibitor content) involved in the reaction are adjusted accordingly. As a method for evaluating the performance of various dental monomers, initiator systems, and inhibitors, DSC has great potential utility.

New initiator systems for dental resins based on ascorbic acid.

Several promising initiator systems for the ambient polymerization of dental monomers were developed utilizing the oxidation-reduction reactions of certain organic peroxides and certain transition metal compounds with L(+) ascorbic acid and its derivatives.

Wear and microhardness of a silver-sintered glass-ionomer cement.

Knoop Hardness and pin-and-disc-wear measurements were made on a commercial silver-sintered glass-ionomer cement. The objective was to determine whether the incorporation of a bonded-metal-to-glass filler would enhance durability as determined by the above measurements. As with the previous work on conventional (non-metalized) glass-ionomer cements, the specimens were preconditioned at 37 degrees C in air, water, 0.02 mol/L lactic acid (pH 2.67), and heptane. The influence of these media on the microhardness of the silver-sintered material was about the same as that on the conventional materials. Storing in air produced dehydration, which increased the hardness considerably. Heptane storage increased the hardness less, but this increase is attributed to continued curing during storage. After storage in water, the hardness was essentially unchanged; the influence of increased cure is believed to be offset by softening or plasticization from water uptake. Lactic acid produced a decrease in hardness from chemical dissolution as seen from the SEM observations. In most cases, in particular for the air-stored specimens, the wear resistance was enhanced markedly over that of the conventional materials evaluated previously. The exception was the lactic acid-stored specimens for which little, or no, improvement was observed during early periods of wear. The incorporation of silver appeared to provide lubrication, thus reducing wear. However, catastrophic failure from brittle fracture was still a problem, but its occurrence was less frequent.

Isocyanato urethane methacrylates derived from hydroxyethyl methacrylate.

Isocyanato urethane methacrylates were synthesized from five diisocyanates and hydroxyethyl methacrylate. They may be homopolymerized or copolymerized with other methacrylates by the usual free radical methods of initiation and have potential as adhesion-promoting agents for dentin.

Wear and microhardness of glass-ionomer cements.

Pin-and-disc wear and Knoop Hardness measurements were made on three commercial glass-ionomer cements having slightly different compositions. The specific objective was to determine whether these cements have potential for use in posterior teeth, and, if not, what modifications in composition and structure would be appropriate to enhance their performance. The specimens were pre-conditioned in air, water, or lactic acid at 37 degrees C for one week prior to being wear-tested. Although differences among the samples were noted, some common trends were observed. From changes in hardness, before and after storage, two opposing trends were observed. One trend involved continued cross-linking and possible dehydration, resulting in a substantial increase in hardness. The other trend involved softening from penetrant liquid absorption and a concomitant decrease in hardness. The wear resistances compared favorably with those for resin-based composites except for the lactic-acid-stored specimens, for which changes in microstructure were revealed by SEM. All specimens were very brittle, and catastrophic failure during wear was frequent. Although our conclusion is that glass-ionomer cements with composition similar to those evaluated here are not acceptable for posterior occlusal application, some compositional changes may enhance their performance in stress-bearing applications.

Reinforced polycarboxylate cements.

Mechanical properties of polycarboxylate cements are greatly improved by incorporation of high modulus fibers such as potassium titanate into acrylic-itaconic acid and acrylic-itaconic-acronitic acid copolymers. Other desirable properties of the cements are not changed by the addition of fibers.

Quantitative assessment of the efficacy of amorphous calcium phosphate/methacrylate composites in remineralizing caries-like lesions artificially produced in bovine enamel.

Recent studies show that methacrylate-based composites with amorphous calcium phosphate (ACP) as a filler can release supersaturating levels of calcium and phosphate ions in proportions favorable for apatite formation. These findings suggest that such composites could be effectively used as coatings for remineralizing teeth damaged by tooth decay. To examine this hypothesis, we tested composites in vitro for their efficacy to remineralize artificially formed caries-like lesions in extracted bovine incisors. Single 120-microns-thick sagittal tooth sections were placed in holders that exposed only the carious enamel surface. The exposed surfaces were coated with a 1-mm- to 1.5-mm-thick layer of the composite containing, by mass, 40% apatite, silica, or P2O7(-4)-stabilized ACP and 60% photoactivated resin comprised of Bis-GMA, TEGDMA, HEMA, and ZrM. The photocured composite-coated sections were immersed either in a remineralizing solution for 4 weeks at 37 degrees C (static model) or cyclically immersed in demineralizing (0.5 h) and remineralizing solutions (11.5 h) for 2 weeks (dynamic model). Quantitative digital image analysis of matched 102 microns x 220 microns areas from contact microradiographs taken of the sections before and after immersion showed that lesions coated with ACP-filled composites fractionally recovered 71% +/- 33% of their lost mineral compared with 14% +/- 13% for apatite controls in the static model and 38% +/- 16% compared with -6% +/- 24% in the dynamic model. The results suggest that sealants based on ACP-filled methacrylate composites have the potential to remineralize carious enamel lesions.

N-phenyliminodiacetic acid as an etchant/primer for dentin bonding.

Effective composite-to-dentin bonding has been achieved by the sequential use of dilute aqueous nitric acid (HNO3) and acetone solutions of N-phenylglycine and a carboxylic acid monomer, e.g., p-PMDM. Both the HNO3 pre-treatment and the surface-initiated polymerization that results from reaction of infused N-phenylglycine and PMDM have been identified as key elements of this bonding system. In this study, N-phenyliminodiacetic acid, a unique imino acid derivative with acidic and chelating potential, was evaluated as a dual etchant/primer for dentin bonding. A randomized, 2(3) factorial design was used to study the effects of 3 factors on tensile bond strength (TBS): conditioner (HNO3 vs. no HNO3), primer (N-phenylglycine vs. N-phenyliminodiacetic acid), and primer solvent (acetone vs. acetone:H2O). The three-step protocol consisting of HNO3, N-phenylglycine in acetone, and PMDM in acetone served as the control. The hypothesis tested was that N-phenyliminodiacetic acid could act as both an effective conditioner (i.e., etchant) and as a primer. Two-step protocols that included only N-phenyliminodiacetic acid and PMDM were compared with the control. TBS (n = 10 per group) were determined after 24-hour storage in H2O and analyzed by ANOVA and Duncan's Multiple Range test. Primer solvent was critical for obtaining significant bonding to dentin when HNO3 was omitted. N-phenyliminodiacetic acid in acetone without prior HNO3 etching gave the lowest ranking mean TBS (95% CI, 3.8 +/- 1.9 MPa). In contrast, the mean TBS obtained from samples treated with N-phenyliminodiacetic acid in acetone:H2O without prior HNO3 etching was not statistically different (p > 0.05) from the mean TBS for the control (95% CI, 9.3 +/- 1.8 and 9.8 +/- 1.9 MPa, respectively). Due to its dual function as etchant and primer, N-phenyliminodiacetic acid in acetone:H2O provides for a simplified bonding technique that yields strong, PMDM-mediated adhesion to dentin.