2-(methacryloyloxy)ethyl-phosphate and hydroxyethyl-methacrylate

To investigate the correlation of the chemical interaction between model self-etching adhesives and dentine with the degree of conversion (DC) of the adhesives.. The model self-etching adhesives contained bis[2-methacryloyloxy)ethyl] phosphate (2MP) and 2-hydroxyethyl methacrylate (HEMA) with a mass ratio of 1/1, and 0-40% water contents, respectively. The adhesives were applied either onto the prepared dentine surface or unreactive substrates (such as glass slides), agitated for 15s, then light-cured for 40s. The DCs of the adhesives were determined using micro-Raman spectral and mapping analysis.. The DCs of the adhesives cured on the dentine substrate were found to be significantly higher than those on the unreactive glass substrate. Moreover, the DCs of the adhesives displayed a decreasing trend as the distance from the dentine surface became greater. The chemical interaction of the acidic 2MP/HEMA adhesives with the mineral apatite in dentine was proposed to play a significant role for the observations. The chemical interaction could be validated by the spectral comparison in the phosphate regions of 1100 cm(-1) and 960 cm(-1) in the Raman spectra. The results also revealed a notable influence of water content on the DC of adhesives. The DCs of the adhesive at 10% water content exhibited the highest DC level for both substrates.. Interaction with dentine dramatically improved the degree of conversion of self-etching adhesives. Our ability to chemically characterise the a/d interface including in situ detection of the DC distribution is very important in understanding self-etching adhesive bonding under in vivo conditions.

Topics: Acid Etching, Dental; Adhesives; Analysis of Variance; Combinatorial Chemistry Techniques; Dental Bonding; Dentin; Dentin-Bonding Agents; Glass; Humans; Light-Curing of Dental Adhesives; Materials Testing; Methacrylates; Photoinitiators, Dental; Polymerization; Resin Cements; Spectrum Analysis, Raman; Water

The effect of hydroxyapatite (HAp) content on photopolymerization of a model self-etching adhesive was studied by using attenuated total reflectance Fourier transform infrared (ATR/FT-IR) spectroscopy.. The model adhesive contained two monomers: bis[2-(methacryloyloxy)ethyl] phosphate (2MP) and 2-hydroxyethyl methacrylate (HEMA) using a 1:1 mass ratio, representing an acidic formulation. Camphorquinone and ethyl 4-dimethylaminobenzoate were added to enable visible light photopolymerization in a constant concentration of 0.022 mmol per gram monomer. HAp [Ca(10)(OH)(2)(PO(4))(6)] powder were added to the test solutions to obtain mass fraction of 0, 1, 2, 3, and 4 wt%. The degree of conversion (DC) and the polymerization rate (PR) with/without HAp were determined using ATR/FT-IR with a time-based spectrum analysis.. Monomer DC and PR were significantly enhanced by addition of HAp. Incorporation of 4 wt% of HAp increased DC from 20.8 (±0.3) % to 93.4 (±1.1) %, and PR from 0.42 (±0.01) %/s to 3.21 (±0.07) %/s. The pH of adhesive solutions was measured and correlated with DC and PR. The pH of test solutions was also controlled using a base (sodium hydroxide, NaOH) to similar values as when using HAp. Results indicated that both the DC and PR increased with increasing pH, regardless of additive, confirming the role of pH on polymerization. From the IR spectral comparison, changes in molecular structures of the self-etching adhesive after the addition of HAp were observed, which were correlated with the specific interaction between 2MP and HAp. The effect of viscosity was also proposed to be another possible reason for the improved polymerization.. The photopolymerization of a self-etching adhesive was enhanced/accelerated in the presence of HAp. The results provide the critical information for understanding the interactions/bonding between self-etching adhesives and tooth substrates.

Topics: Dental Etching; Durapatite; Hardness; Hydrogen-Ion Concentration; Light-Curing of Dental Adhesives; Methacrylates; Polymerization; Resin Cements; Spectroscopy, Fourier Transform Infrared

To determine the effectiveness and efficiency of non-thermal, atmospheric plasmas for inducing polymerization of model dental self-etch adhesives.. The monomer mixtures used were bis-[2-(methacryloyloxy)ethyl] phosphate (2MP) and 2-hydroxyethyl methacrylate (HEMA), with mass ratios of 70/30, 50/50 and 30/70. Water was added to the above formulations: 10-30wt%. These monomer/water mixtures were treated steadily for 40s under a non-thermal atmospheric plasma brush working at temperatures from 32 to 35°C. For comparison, photo-initiators were added to the above formulations for photo-polymerization studies, which were light-cured for 40s. The degree of conversion (DC) of both the plasma- and light-cured samples was measured using FTIR spectroscopy with an attenuated total reflectance attachment.. The non-thermal plasma brush was effective in inducing polymerization of the model self-etch adhesives. The presence of water did not negatively affect the DC of plasma-cured samples. Indeed, DC values slightly increased, with increasing water content in adhesives: from 58.3% to 68.7% when the water content increased from 10% to 30% in the adhesives with a 50/50 (2MP/HEMA) mass ratio. Conversion values of the plasma-cured groups were higher than those of light-cured samples with the same mass ratio and water content. Spectral differences between the plasma- and light-cured groups indicate subtle structural distinctions in the resultant polymer networks.. This research if the first to demonstrate that the non-thermal plasma brush induces polymerization of model adhesives under clinical settings by direct/indirect energy transfer. This device shows promise for polymerization of dental composite restorations having enhanced properties and performance.

Topics: Argon; Atmospheric Pressure; Camphor; Composite Resins; Dental Materials; Deuterium Oxide; Humans; Light-Curing of Dental Adhesives; Methacrylates; para-Aminobenzoates; Photoinitiators, Dental; Plasma Gases; Polymerization; Spectroscopy, Fourier Transform Infrared; Temperature; Time Factors; Water

The application of an electric field has been shown to positively influence the bonding of dentin bonding systems (DBS) by improving adhesive impregnation into dentin. However, the mechanism responsible for this phenomenon has not been completely elucidated. The aim of this study was to clarify the effects of pH, matrix ionic strength, and applied voltage on the migration of commonly used DBS monomers in a model matrix (agarose gel).. Some common monomers examined were bis-GMA (2,2-bis[4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane); HEMA (2-hydroxyethyl methacrylate); 2-MP (bis[2-(methacryloyloxy) ethyl] phosphate); TCDM [di(hydroxyethyl methacrylate) ester of 5-(2,5,-dioxo tetrahydrofurfuryl)-3-methyl-3-cyclohexenyl-1,2-dicarboxylic acid]; and TEGDMA (triethylene glycol dimethacrylate). Agarose gels poured into a horizontal 10-well electrophoretic cell were used to mimic the collagen fibrils of the dentin organic matrix. The role of pH, matrix ionic strength, and voltage on monomer migration was assayed by modifying the experimental conditions.. Results of experiments performed at pH 3.1, 6.3, 8.5, and 12.3; at low, medium, and high ionic strength; and at 50 and 100 V clearly showed that DBA monomer migration toward both the anode and the cathode can be affected by each of these parameters.. Migration of acrylic monomers toward the anode or cathode can be achieved as desired by selective choice of pH, ionic strength, and applied voltage. Additional studies are needed to evaluate the synergistic effects of DBS monomer blends on migration in an electric field.

Topics: Bisphenol A-Glycidyl Methacrylate; Carboxylic Acids; Dentin Permeability; Dentin-Bonding Agents; Electricity; Electrophoresis, Agar Gel; Hydrogen-Ion Concentration; Materials Testing; Methacrylates; Molecular Structure; Osmolar Concentration; Polyethylene Glycols; Polymethacrylic Acids

Two different monoliths, both containing phosphoric acid functional groups and polyethylene glycol (PEG) functionalities were synthesized for cation-exchange chromatography of peptides and proteins. Phosphoric acid 2-hydroxyethyl methacrylate (PAHEMA) and bis[2-(methacryloyloxy)ethyl] phosphate (BMEP) were reacted with polyethylene glycol diacrylate (PEGDA) and polyethylene glycol acrylate (PEGA), respectively, in 75-mum i.d. UV-transparent fused-silica capillaries by photo-initiated polymerization. The hydrophobicities of the monoliths were evaluated using propyl paraben under reversed-phase conditions and synthetic peptides under ion-exchange conditions. The resulting monoliths exhibited lower hydrophobicities than strong cation-exchange monoliths previously reported using PEGDA as cross-linker. Dynamic binding capacities of 31.2 and 269mg/mL were measured for the PAHEMA-PEGDA and BMEP-PEGA monoliths, respectively. Synthetic peptides were eluted from both monoliths in 15min without addition of acetonitrile to the mobile phase. Peak capacities of 50 and 31 were measured for peptides and proteins, respectively, using a PAHEMA-PEGDA monolith. The BMEP-PEGA monolith showed negligible hydrophobicity. A peak capacity of 31 was measured for the BMEP-PEGA monolith when a 20-min salt gradient rate was used to separate proteins. The effects of functional group concentration, mobile phase pH, salt gradient rate, and hydrophobicity on the retention of analytes were investigated. Good run-to-run [relative standard deviation (RSD)<1.99%] and column-to-column (RSD<5.64) reproducibilities were achieved. The performance of the monoliths in ion-exchange separation of peptides and proteins was superior to other polymeric monolithic columns reported previously when organic solvents were not added to the mobile phase.

Topics: Acetonitriles; Cation Exchange Resins; Chromatography, Ion Exchange; Drug Stability; Hydrogen-Ion Concentration; Hydrophobic and Hydrophilic Interactions; Methacrylates; Microscopy, Electron, Scanning; Peptides; Permeability; Phosphoric Acids; Polyethylene Glycols; Polymers; Proteins; Salts

This study evaluated different initiator systems in self-etching model adhesives, in which camphorquinone (CQ) or [3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-2-hydroxylpropy] trimethylammonium chloride (QTX) was employed as a photoinitiator (dye). N-phenylglycine (NPG), ethyl 4-dimethylaminobenzoate (4E) or 2-(dimethylamino) ethyl methacrylate (DMAEMA) was used as the coinitiator (CI). The role of diphenyliodonium hexafluorophosphate (DPIHP) in the polymerization process was also studied. The concentrations of dye, CI, and DPIHP in model adhesives were all maintained at 0.022 mmol per gram monomer. The model adhesive contained two monomers: (bis[2-(methacryloyloxy)ethyl] phosphate) (2MP) and 2-hydroxyethyl methacrylate (HEMA) whose mass ratio was 1:1, thus representing an acidic and hydrophilic formulation. The polymerization rate and the degree of conversion (DC) of the model adhesives with 5, 15, or 25% water content were determined using FTIR/ATR with a time-based spectrum analysis. The results indicated that with CQ as the photoinitiator, 4E appeared to be the most efficient CI, whereas the CQ-DMAEMA combination led to very low radical generation efficiency (DC < 5%). DPIHP exhibited little effect on the polymerization process. With QTX as the photoinitiator, however, DPIHP played an essential role. Without DPIHP, all three QTX-CI systems failed to initiate polymerization (DC < 5%). The QTX-DPIHP combination, on the other hand, was found to be a viable initiator system. The above results provide the critical information for the development of self-etching adhesive systems.

Topics: Acids; Biphenyl Compounds; Coloring Agents; Dental Cements; Methacrylates; Onium Compounds; Photochemical Processes; Water