Norihiro Nishiyama

Water Concentration in Self-etching Primers Affects their Aggressiveness and Bonding Efficacy to Dentin

Water is required to ionize acid resin monomers for demineralization of tooth substrates. We tested the null hypothesis that altering the water concentration in two-step self-etching primers has no effect on their aggressiveness and bonding efficacy to dentin. Five experimental self-etching primers were prepared with resin-water-ethanol volume ratios of 9-0-1, 8-1-1, 7-2-1, 5-4-1, and 3-6-1. They were applied to smear-layer-covered dentin, followed by a bonding resin and composite build-ups for microtensile bond testing and TEM examination of tracer penetration. Increasing water concentration from 0–60 vol% improved acidic monomer ionization that was manifested as increasing hybrid layer thickness. However, significantly higher bond strength was observed in the 7-2-1 group, with minimal nanoleakage in the corresponding hybrid layer. When self-etching primers are formulated, a balance must be achieved to provide sufficient water for adequate ionization of the acidic monomers, without lowering the resin concentration too much, to optimize their bonding efficacy to dentin.

Hydrolytic stability of methacrylamide in acidic aqueous solution

In order to develop a more effective self-etching primer, with a longer lasting shelf life, we designed a self-etching primer comprised of methacrylamide, N-methacryloyl glycine, NMGly. In this study, the hydrolytic stability of the amide portion in the NMGly was examined. The difference in the hydrolytic stability between the methacrylamide and the methacrylate, 2-hydroxyethyl methacrylate, HEMA was then discussed. The addition of an acid to an aqueous solution allows for the hydrolysis of the ester portion in the methacrylate and for the production of methacrylic acid, MA and ethylene glycol, EG. From our study, the data clearly demonstrated that, if the storage duration of a commercially available self-etching primer is prolonged, then the functional methacrylates constituting the self-etching primer will be altered upon use. However, the hydrolytic stability of the amide portion in the methacrylamide, NMGly, designed as an acidic and/or hydrophilic monomer for the self-etching primer, was greater than the results achieved with the methacrylate, HEMA.

Adsorption behavior of a silane coupling agent onto a colloidal silica surface studied by 29Si NMR spectroscopy

Abstract The adsorption mechanisms of a silane coupling agent onto a colloidal silica surface are investigated by means of 29 Si NMR and compared with previous spin-labeled ESR data. The dimer species are found to be the predominant species adsorbed onto a colloidal silica surface in silane solution. The adsorption behavior shows a dependence on the concentration of the silane coupling agent used. At low concentrations, the silane coupling agent appears to be adsorbed in regular fashion, while at higher concentrations, it is adsorbed in random fashion.

Hydrolysis of Functional Monomers in a Single-bottle Self-etching Primer—Correlation of 13C NMR and TEM Findings

Self-etching primers/adhesives that combine acidic methacrylate monomers with water in a single bottle are hydrolytically unstable and require refrigeration to extend their shelf-lives. This study tested the null hypothesis that one year of intermittent refrigeration of a 4-MET-containing simplified self-etching primer does not result in hydrolytic changes that are identifiable by transmission electron microscopy and 13C NMR spectroscopy. Human dentin was bonded with UniFil Bond immediately after being unpacked, or after one year of intermittent refrigeration at 4°C. Fresh and aged primers were analyzed by NMR for chemical changes. Ultrastructural observations indicated that there was an augmentation in etching capacity of the aged adhesive that was not accompanied by resin infiltration or effective polymerization. New NMR peaks detected from the aged ethanol-based primer confirmed that degradation occurred initially via esterification with ethanol, followed by hydrolysis of both ester groups in the 4-MET. Hydrolysis of functional methacrylate monomers occurs despite intermittent refrigeration.

Effects of particle size of silica filler on polymerization conversion in a light-curing resin composite

OBJECTIVES The effect of visible light passing through a resin composite with different particle sizes of spherical silica filler on the curing depth and Knoop hardness of the resin composite was examined. The null hypotheses tested were that the particle size of silica filler has no effect on (1) the transmitted amount of visible light passing through the resin composite, (2) the curing depth of the resin composite, and (3) the ratio of the Knoop hardness of the hardened resin composite. METHODS A series of different experimental resin composite pastes with different particle sizes of silica filler were prepared. The amount of visible light passing through each of the experimental resin pastes during the hardening process was determined. The curing depth and Knoop hardness of the resin composites were measured. Further, to characterize the polymerization conversion, the ratio of the Knoop hardness of the bottom surface against the irradiated surface of the hardened resin composites was determined. RESULTS Increases in the particle size of the silica filler resulted in decreases in the transmitted amount of visible light, curing depth, and ratio of the Knoop hardness of the resin composite. The rate of polymerization conversion of the resin composite occurring deep within the cavity was found to be less than the rate of polymerization conversion occurring at the upper surface. SIGNIFICANCE To increase the rate of polymerization conversion deep within the resin composite, it is important to reduce the particle size of the silica filler.

Regeneration of the femoral epicondyle on calcium-binding silk scaffolds developed using transgenic silk fibroin produced by transgenic silkworm.

Genetically modified silk fibroin containing a poly-glutamic acid site, [(AGSGAG)4E8AS]4, for mineralization was produced as fibers by transgenic silkworms through systematic transformation of the silkworms. The Ca binding activity and mineralization of the transgenic silk fibroin were examined in vitro, showing that this transgenic silk fibroin had relatively high Ca binding activity compared with native silk fibroin. Porous silk scaffolds were prepared with the transgenic and native silk fibroins. Healing of femoral epicondyle defects in rabbit femurs treated with the scaffolds was examined by observing changes in images of the defects using micro-computed tomography. Earlier mineralization and bone formation were observed with scaffolds of transgenic silk fibroin compared with those of native silk fibroin. Thus, this study shows the feasibility of using genetically modified silk fibroin from transgenic silkworms as a mineralization-accelerating material for bone repair.

Effect of Reacted Acidic Monomer with Calcium on Bonding Performance

We determined the number of reacted and unreacted 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) molecules with calcium during the demineralization process of hydroxyapatite or dentin by 10-MDP-based one-step (Clearfil Tri-S Bond, TS) or two-step self-etch adhesive (Clearfil SE Bond Primer, SE). We then examined the effects of the number of reacted and/or unreacted 10-MDP molecules on the initial bond strength and bond durability of the resultant adhesive layer. The null hypotheses were that (1) the etching efficacy of tooth apatite by 10-MDP used in TS was the same as that in SE, and (2) the unreacted 10-MDP polymer included within the adhesive layer does not affect bond durability. Addition of hydroxyapatite or dentin to the TS and SE resulted in decreases in the NMR peak intensities for 10-MDP. The peak intensity for 10-MDP showed a greater reduction in SE than in TS, consistent with the observation that SE provided significantly higher initial mean bond strengths than TS. Further, the unreacted 10-MDP polymer within the adhesive layer did not decrease the mean bond strength, despite the application of 20,000x thermo-cycling.

A 13C NMR Study on the Adsorption Characteristics of HEMA to Dentinal Collagen

To develop a more effective primer, we must understand how 2-hydroxyethylmethacrylate, the HEMA primer, enhances bonding at the resin-dentin interface. In this study, to obtain an insight into the adhesion mechanisms of adhesive resin to etched dentin through HEMA, we examined the adsorption characteristics of HEMA to dentinal collagen by using the 13C NMR technique. The addition of dentinal collagen to the HEMA solution resulted in a decrease in T 1 values of carbons attributed to the HEMA, thus reflecting an interaction between HEMA and collagen. Specifically, a reduction in the T 1 value in the ester carbonyl carbon attributed to HEMA greater than that in the other carbons suggested the formation of a hydrogen bond between the ester carbonyl group in HEMA and the dentinal collagen.

Adhesion of N-Methacryloyl-ω-Amino Acid Primers to Collagen Analyzed by 13C NMR

Previously, we reported that the strength of the interaction between N-methacryloyl-w-amino acid (NMωA) primers and dentinal collagen exhibited a strong correlation with the bond strength of the resin to etched dentin. To determine the pertinent functional groups of the amino acid residues in the dentinal collagen, to which the amide and/or the carboxylic acid groups of the NMwAs are adsorbed, we used 13C NMR techniques-primarily through the observation of spin-lattice relaxation times, T i—to investigate the adsorption characteristics resulting from the interaction of NMwAs with a model oligopeptide for collagen, (PPG)5. The addition of NMωAs to a collagenous solution resulted in a decrease in the T 1 values of the carbonyl carbons attributed to the carboxylic acid of the C-terminal Gly and to the third amide of the N-terminal Pro residues in the (PPG)5 molecule, thus reflecting the formation of hydrogen-bonded interactions.

Adhesion mechanisms of resin to etched dentin primed with N‐methacryloyl glycine studied by 13C‐NMR

The origin of the pH-dependent bond strength of the resin to etched dentin treated with N-methacryloyl glycine (NMGly) primer was studied by 13C-nuclear magnetic resonance (NMR) including spin-lattice relaxation time, T1, observation. When the dentinal collagen was suspended in the NMGly solution at pH = 1.6, the T1 values of all the carbons attributed to the NMGly species were significantly decreased. This indicated the presence of an interaction between the NMGly and the dentinal collagen. To obtain detailed information of this interaction, the 13C-NMR spectra of the NMGly were measured in the presence of the model compound for the collagen, (Pro-Pro-Gly)5 at pH = 1.7. The 13C-NMR peaks of the carbonyl carbons of the amide and carboxylic acid in the NMGly species shifted to a higher field and the T1 values decreased. Furthermore, when the molar ratio of (Pro-Pro-Gly)5 to NMGly was decreased from 1:1 to 1:3, the T1 values of the carbonyl carbon attributed to the carboxylic acid in the C-terminal Gly residue of the oligopeptide decreased dramatically. It can be construed that this indicated the formation of a hydrogen bond between the amide, -NH and the carboxylic acid of the NMGly species and the carboxylic acid of the C-terminal Gly residue of the oligopeptide.