Methacrylate saccharide-based monomers for dental adhesive systems.

The aim of this in vitro study was to synthesize three new methacrylate monomers based on the modification of saccharides structures (glucose-Gluc, sucrose-Sucr and chitosan-Chit) with glycidyl methacrylate, and to use them in the composition of dental adhesives. Three methacrylate saccharide monomers were synthesized and characterized by mid-IR, 1H and 13C NMR, antioxidant activity and cytotoxic effect. Monomers included: one monosaccharide - Gluc-MA; one disaccharide - Sucr-MA; and one polysaccharide - Chit-MA. Primers containing HEMA, methacrylate saccharide monomers at concentrations of 0 (control), 1, 2 or 4 wt%, 60 wt% ethanol aqueous solution (pH3.0) and initiator system were formulated. Primers were used in conjunction with a bond step and composite paste to restore caries-free third molars, and dentin bond strength (24 hours and 6 month of storage in water), and antimicrobial activity (Alamar Blue test) were tested. Degree of conversion (DC) and maximum rate of polymerization (Rpmax) of the primers themselves were also analyzed. The mid-IR, 1H and 13C spectrum confirmed the presence of vinyl group on the structure of saccharides. Chit-MA showed low antioxidant activity and did not present a cytotoxic effect. Gluc-MA and Sucr-MA possess antioxidant and cytotoxic activity, concentration dependent. In the presence of methacrylate saccharide monomers, the primers showed DC comparable to the control group, except Gluc-MA4%, Sucr-MA4% and Chit-MA1%, which showed a range of 64.6 from 58.5 %DC. Rpmax was not statistically different for all the groups (p = 0.01). The bond strength of Sucr-MA1% increased from 25.7 (±2.8) to 40.6 (±5.3) MPa after 6 months of storage. All the synthesized monomers showed some antimicrobial activity after polymerization. Gluc-MA and Chit-MA 4% and Sucr-MA 1, 2 and 4% led to decrease bacterial metabolism. Sucr-MA 1% showed better results regarding the decrease in bacterial metabolism and increasing the bond strength after 6 months of storage.

Novel urethane-based polymer for dental applications with decreased monomer leaching.

The aim of this study was to synthesize and characterize new multifunctional-urethane-methacrylate monomers to be used as the organic matrix in restorative dental composites, and evaluate the main physical-chemical properties of the resulting material. Bis-GMA (bisphenol-A-diglycidylmethacrylate) and GDMA (glycerol dimethacrylate) were modified by reacting the hydroxyl groups with isocyanate groups of urethane-methacrylate precursors to result in the new monomeric systems U-(bis-GMA)-Mod and U-(GDMA)-Mod, U=Urethane and Mod=Modified. The modifications were characterized by FTIR and 1H NMR. The final monomeric synthesized system was used to prepare dental resins and composites. The physical-chemical properties were evaluated and compared with those of bis-GMA composites with varying filler contents or unfilled resins. U-(bis-GMA)-Mod and U-(GDMA)-Mod can be used to prepare dental restorative composites, with some foreseeable advantages compared with bis-GMA composites. One significant advantage is that these composites have the potential to be less toxic, once they presented a reduction of 50% in leaching of unreacted monomers extracted by solvent.

Thio-urethane oligomers improve the properties of light-cured resin cements.

Thio-urethanes were synthesized by combining 1,6-hexanediol-diissocyante (aliphatic) with pentaerythritol tetra-3-mercaptopropionate (PETMP) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (aromatic) with trimethylol-tris-3-mercaptopropionate (TMP), at 1:2 isocyanate:thiol, leaving pendant thiols. Oligomers were added at 10-30 phr to BisGMA-UDMA-TEGDMA (5:3:2, BUT). 25 wt% silanated inorganic fillers were added. Commercial cement (Relyx Veneer, 3M-ESPE) was also evaluated with 10-20 phr of aromatic oligomer. Near-IR was used to follow methacrylate conversion (DC) and rate of polymerization (Rpmax). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM, and toughness), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Volumetric shrinkage (VS, %) was measured with the bonded disk technique. Results were analyzed with ANOVA/Tukey's test (α=5%). In general terms, for BUT cements, conversion and mechanical properties in flexure increased for selected groups with the addition of thio-urethane oligomers. The aromatic versions resulted in greater FS/FM than aliphatic. Fracture toughness increased by two-fold in the experimental groups (from 1.17 ± 0.36 MPam(1/2) to around 3.23 ± 0.22 MPam(1/2)). Rpmax decreased with the addition of thio-urethanes, though the vitrification point was not statistically different from the control. VS and PS decreased with both oligomers. For the commercial cement, 20 phr of oligomer increased DC, vitrification, reduced Rpmax and also significantly increased KIC, and reduced PS and FM. Thio-urethane oligomers were shown to favorably modify conventional dimethacrylate networks. Significant reductions in polymerization stress were achieved at the same time conversion and fracture toughness increased.

A urethane-based multimethacrylate mixture and its use in dental composites with combined high-performance properties.

OBJECTIVES: To synthesize and characterize different molar weight urethane multimethacrylates with a single stage (one-pot) procedure. To prepare and characterize the properties of related composites. METHODS: Two methacrylate precursors were initially synthesized. Then, these precursors and the multimethacrylate system formed by their coupling were characterized by FTIR and (1)H NMR. The final product was used as a matrix (with TEGDMA and SiO2 silanized microparticles) in the preparation of composites and their physical and mechanical properties were compared to those of a bis-GMA-based resin. Water sorption and solubility measurements of the composites were also performed. RESULTS: FTIR and NMR suggested that the proposed synthesis route yields a mixture of mainly urethane-di, -tri, and tetramethacrylates. The composites presented low polymerization shrinkage (e.g. 1.88±0.08% for a resin with 70% of SiO2) and high flexural strength (e.g. 124.74±9.68 MPa for a resin with 65% of SiO2) when compared to the bis-GMA based resin and other composites found to date. Water sorption and solubility results show that the composites were deemed compliant with ISO 4049 requirements. SIGNIFICANCE: The mixture containing different molar weight of urethane multimethacrylates showed to be an excellent substitute for bis-GMA, achieving an equilibrium of properties (unlike reports elsewhere which show the enhancement of some parameters in detriment to others) and composites with low polymerization shrinkage, suitable microhardness and degree of conversion, and up to standard water sorption/solubility and flexural strength.