Assessment of cytotoxicity and DNA damage exhibited by siloranes and oxiranes in cultured mammalian cells.

The potential reactivity and structural properties of oxiranes (epoxides) are advantageous when considering polymers for medical devices. However, epoxy compounds are widely known to have genotoxic properties. The objective of the study was to evaluate the cytotoxicity and primary DNA damage effects induced by oxiranes and siloranes, silicon containing oxiranes. The siloranes, Ph-Sil, Tet-Sil, and Sil-Mix and the oxiranes Cyracure UVR-6105 and 1,3-bis[2-(2-oxiranylmethyl) phenoxy]pentane (OMP-5) were dissolved in organic solvents and dilutions containing less than 0.5% solvent were used in biological assays. The concentration that reduced the viability of 50% (TC(50)) of L929 cells was measured using the MTT assay and guided the selection of subtoxic doses for evaluation of DNA damage. Ph-Sil was more cytotoxic than OMP-5, Cyracure UVR-6105 and Sil-Mix. However, the TC(50) value of Tet-Sil could not be determined due to its poor solubility. DNA damage was evaluated in the sister chromatid exchange (SCE) assay with CHO cells, and the alkaline comet assay with L929 cells. In contrast to the siloranes, the oxiranes exhibited significant increases (p>0.05) in SCE frequencies and DNA migration relative to their solvent controls. Our findings support previous reports that siloranes have low genotoxic potential and can be suitable components for development of biomaterials.

Mechanism by which MLO-A5 late osteoblasts/early osteocytes mineralize in culture: similarities with mineralization of lamellar bone.

The mechanisms whereby bone mineralizes are unclear. To study this process, we used a cell line, MLO-A5, which has highly elevated expression of markers of the late osteoblast such as alkaline phosphatase, bone sialoprotein, parathyroid hormone type 1 receptor, and osteocalcin and will mineralize in sheets, not nodules. In culture, markers of osteocytes and dendricity increase with time, features of differentiation from a late osteoblast to an early osteocyte. Mineral formation was examined using transmission electron microscopy, scanning electron microscopy with energy-dispersive X-ray analysis, and atomic force microscopy. At 3-4 days of culture, spheres of approximately 20-50 nm containing calcium and phosphorus were observed budding from and associated with developing cellular projections. By 5-6 days, these calcified spheres were associated with collagen fibrils, where over time they continued to enlarge and to engulf the collagen network. Coalescence of these mineralized spheres and collagen-mediated mineralization were responsible for the mineralization of the matrix. Similar calcified spheres were observed in cultured fetal rat calvarial cells and in murine lamellar bone. We propose that osteoid-osteocytes generate spherical structures that calcify during the budding process and are fully mineralized on their developing cellular processes. As the cellular process narrows in diameter, these mineralized structures become associated with and initiate collagen-mediated mineralization.

Assessment of the relative skin sensitization potency of siloranes and bis-GMA using the local lymph node assay and QSAR predicted potency.

Siloranes are silicon and oxirane (epoxy) containing monomers used for new dental composite development. The siloranes 3,4-epoxycyclohexylethyl-cyclopolymethylsiloxane (Tet-Sil) and bis-3,4-epoxycyclohexylethyl-phenyl-methylsilane (Ph-Sil) have in common cycloaliphatic epoxy moieties. The epoxy group is of concern in their biocompatibility since most epoxy compounds are known skin sensitizers. The objective of this study was to determine the in vivo skin sensitization potency of the siloranes in the local lymph node assay. A comparison was made with well-known chemical allergens, bis-GMA and DNCB. Female mice (CBA/CaJ) were exposed topically (dorsum of both ears) to several doses of acetone:olive oil in the ratio of 4:1 v/v. Doses were defined by a predictive structure-activity model (QSAR) for contact sensitization. Lymph node cell (LNC) proliferation was measured on the sixth day by incorporation of radioactive thymidine into DNA of lymph node cells. The effective concentration (EC3) that produced a 3-fold stimulation in LNC proliferation relative to controls was extrapolated from dose-response curves. DNCB was a strong sensitizer (EC3 = 0.06%). The EC3 values of Ph-Sil and bis-GMA were 19% and 45%, respectively, making these weak contact sensitizers. Tet-Sil did not increase lymph node proliferation when compared with controls. In contrast to Tet-Sil, the unpolymerized monomers Ph-Sil and bis-GMA have the capacity to induce LNC proliferation, characteristic of a T-cell mediated skin contact sensitization.

Correlation of apoptotic potential of simple oxiranes with cytotoxicity.

The measurement of primary DNA damage caused by oxirane chemicals can be confounded by apoptotic-generated DNA autolysis. The apoptogenic potential of oxiranes requires knowledge of the relationship between the apoptotic threshold dose and cytotoxic dose for interpretation of DNA damage assays. This research determined the relationship between cytotoxic and apoptotic doses for seven simple oxiranes of varying structure. This relationship between cytotoxic and apoptotic thresholds was determined simultaneously in in vitro cell culture. L929 cells in log-phase growth were exposed to the oxiranes for 24 h in 25 cm(2) and then assayed fluorometrically in 96-well plates for Caspase 3. Viability was assessed using Trypan Blue exclusion and loss of Caspase 3 activity. Ranked apoptotic potency was: diepoxybutane (DEB)>styrene oxide (SO)>phenyl glycidyl ether (PGE)>epichlorhydrin (EPI)>glycidol (GLY)>epoxybutane (EB)>epoxycyclohexane (ECH). Relative cytotoxicity was significantly correlated (r(s)=0.86, p=0.02) with potencies: DEB>EPI>PGE>SO>GLY>EB>ECH. These structurally-diverse, simple oxiranes were all capable of inducing apoptosis at doses several-fold below their cytotoxic concentrations. Difunctionality and aromaticity were key predictors of potency for both. Caspase 3 activity was an accurate indicator of necrosis which correlated with Trypan Blue results.

Resin-infiltrated-dentine--a FE-ESEM microscopy investigation.

The formation of a hybrid layer is essential for bonding of dental composites to dentine. The objective of this study was to examine the effects of various etchants/conditioners and dentine bonding systems on dentine surfaces utilising a Field Emission Environmental SEM (FE-ESEM). Twenty one, freshly extracted human molar teeth were utilised. Dentine without resin application was initially observed both wet and dried in the following conditions: (1) fractured surface, (2) smear layer, and (3) smear layer removed with 37% phosphoric acid. Resin infiltration into dentine was then studied after applying Scotchbond 1, Optibond Solo, Prime & Bond NT, or Prompt L-Pop systems. Scotchbond 1, Optibond Solo, and Prime & Bond NT resins penetrated the dentine tubules and created hybrid layers; although, in some cases Prime & Bond NT only created a partially filled hybrid layer. No polymerised resin or hybrid layer was observed for Prompt L-Pop. The FE-ESEM permitted observation of specimens at near in-vivo wet conditions.

Effect of simulated resin-bonded fixed partial denture clinical conditions on resin cement mechanical properties.

The purpose of this study was to determine changes in flexural properties of resin cement under simulated resin-bonded fixed partial denture (RBFPD) clinical conditions using aqueous ageing and cyclic loading. Panavia F flexural modulus and strength were measured by static loading to failure after 48-h and 60-day aqueous ageing at 37 degrees C with and without simulated cyclic occlusal loading. Panavia F sorption and solubility were also measured. Scanning electron microscopy (SEM) was used to characterize the morphology of the fractured surfaces. A two-factor anova (P

Biocompatibility of hydroxylated metabolites of BISGMA and BFDGE.

Unpolymerized dental monomers can leach out into the oral biophase and are bioavailable for metabolism. We hypothesize that metabolites would be less toxic than parent monomers. We first identified the formation of metabolites from bisphenol F diglycidyl ether (BFDGE) and Bisphenol A glycidyl methacrylate (BISGMA) after their exposure to liver S9 fractions. Then, the metabolites and parent compounds were subjected to in vitro cytotoxicity, mutagenicity, and estrogenicity studies. Bisphenol A bis(2,3-dihydroxypropyl) ether and bisphenol F bis(2,3-dihydroxypropyl) ether were the hydroxylated metabolites of BISGMA and BFDGE, respectively. Cytotoxicity against L929 cells showed that the metabolites were significantly (p < 0.05) less cytotoxic than the parent monomers. Only BFDGE was mutagenic in the Ames assay with strain TA100 of Salmonella typhimurium. Parent and metabolite compounds did not stimulate estrogen-dependent MCF-7 cell proliferation above solvent controls. These results indicated that the hydroxylated metabolites were non-mutagenic, non-estrogenic, and less cytotoxic than their parent monomers.

In vitro biocompatibility of oxirane/polyol dental composites with promising physical properties.

OBJECTIVES: Visible light cure oxirane/polyol resins of Cyracure UVR-6105 with pTHF-250 has been previously shown useful for development of dental composites. This oxirane/polyol (4016) in combination with other oxiranes were formulated into composites (4016E, 4016G and 4016GB) containing 72.9-74.9% quartz filler. The main objective of the study was to evaluate some of the physical properties and the biocompatibility of the composites. RESULTS: PhotoDSC analysis of composites demonstrated twice the enthalphy values of Z100 (31J/g). Composites 4016E and 4016G showed compressive strengths similar to Z100 (337+/-35Mpa), P>0.05. Discs of composite 4016E, containing Epon 825 oxirane (E), and composite 4016G containing Araldite GY 281 oxirane (G) were non-cytotoxic (-) while the composite 4016GB, containing G and Ebecryl 1830 (B), was mildly (+) cytotoxic to L929 cells in the agar diffusion assay. Seven-day extracts of 4016GB composite were cytotoxic while extracts of 4016E and 4016G were less cytotoxic to L929 cells in the MTT assay. Extracts were obtained from 7 day incubations of composite (3 cm(2) surface area/ml) in acetone or ethanol/saline (1:20) at 37 degrees C. All composite extracts were non-mutagenic to Ames strains TA100, TA98, TA97a and TA1535. The overall results with composite 4016GB suggest that leachable components were cytotoxic but non-mutagenic. With the exception of oxirane components, G and E, the oxirane Cyracure UVR-6105 and other components were non-mutagenic. From cytotoxicity studies, the photoinitiator, Sarcat CD 1012, was the most cytotoxic (TC(50)=14 microM) component. Components G (TC(50)=17 microM), E (TC(50)=50 microM) and B (TC(50)=151 microM) were significantly (p < 0.05) more cytotoxic than Cyracure UVR-6105 (1488 microM) and the polyol, pTHF-250 (TC(50)=6072 microM). SIGNIFICANCE: Favorable results obtained with composites 4016G and 4016E indicates that suitable oxirane/polyol formulations can be designed and optimized for development of dental composites with acceptable mechanical properties and biocompatibility. However, leachable analysis of extracts obtained from longer incubation periods is needed before final conclusions could be drawn about the leachability of oxirane components.

Evaluation of demineralized dentin contraction by stereo measurements using environmental and conventional scanning electron microscopy.

Numerous investigations of etched human dentin are performed using scanning electron microscopy (SEM). Usually specimens are fractured and cross sections of etched layers with underlying unaffected dentin are observed. Results from this study showed that the edge of the etched layer contracted and became curved after fracture of wet specimens and that tensile stresses were developed in this layer by acid etching. The degree of contraction was determined utilizing profiles of the specimen edges obtained with the help of stereo measurements. Fixation in glutaraldehyde decreased the contraction in wet specimens prepared for environmental scanning electron microscopy (ESEM). Fixation also decreased shrinkage of the demineralized layer due to gradual desiccation in the ESEM during observation. For conventional SEM, the contraction was minimized if specimens of etched and fixed dentin were fractured in the dry condition after dehydration.

Aromatic dental monomers affect the activity of cholesterol esterase.

The dental restorative monomer, BISGMA (2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane), and bisphenol A diglycidyl ether (BADGE) increase the velocity of the reaction catalyzed by pancreatic cholesterol esterase (CEase, bovine). The metabolite of these monomers, bisphenol A bis(2,3-dihydroxypropyl) ether, and a common plasticizer, di-2-ethylhexyl phthalate (DEHP), also increase the velocity of CEase-catalyzed ester hydrolysis. BISGMA at concentrations of 1.5-8.0 microM increases the velocity to 126-169% of its value in the absence of BISGMA. Increasing BISGMA above 8 microM caused no further increase in velocity. BADGE at 7-25 microM increases the velocity to 112-205% of its value without BADGE. The metabolite of BISGMA and BADGE at concentrations of 2.0-7.1 microM increases the velocity to 103-113% of its value without metabolite. DEHP at concentrations of 0.52-4.3 microM increases the velocity to 108-187% of its value without DEHP. On the other hand, bisphenol A dimethacrylate is a competitive inhibitor of CEase, with a K(i) of 3.1 microM.

The stability of methacrylate biomaterials when enzyme challenged: kinetic and systematic evaluations.

This study addressed whether methacrylate monomers and polymers used in dentistry might degrade from enzymolysis by acetylcholinesterase (ACHE), cholesterol esterase (CHE), porcine liver esterase (PRLE), and a pancreatic lipase (PNL). Short (hour) and long-term (day) exposures were performed. Product ratios were used to determine surface hydrolysis of the polymeric materials. Enzyme kinetics were studied for the monomers when challenged by ACHE, CHE, and PRLE. In the case of PRLE, the V(max) for the dimethacrylate substrates varied slightly, but amounted to as much as 10% of that of p-nitrophenylacetate. The K(m) for triethylene glycol dimethacrylate (TEGDMA) was 197 microM for ACHE and 1107 microM for CHE. The V(max) was 2.7 nmol/min for ACHE and 3.5 nmol/min for CHE. TEGDMA was converted by CHE at 2% the rate of cholesteryl oleate. Long-term incubations of monomers with CHE and ACHE produced degrees of hydrolysis that evidenced structure dependency in the ability of the enzymes to effect hydrolysis. Particularly resistant were aromativ derivatives and those with branching in methacrylate linkages. Overall, the study confirms the ability of physiologically important esterases to catalyze the hydrolysis of biomaterial methacrylates.

Effects of dental resins on TNF-alpha-induced ICAM-1 expression in endothelial cells.

Many reports have demonstrated inflammation after the placement of dental restorations. To explain this side-effect, we studied a biomarker in the inflammatory response. The intercellular adhesion molecule-1 (ICAM-1) is a key mediator for recruitment of leukocytes to the site of inflammation. Therefore, we investigated whether methacrylates (a BISGMA-based dental resin, BISGMA, and MAA) and Cyracure UVR 6105, an epoxy monomer, could alter ICAM-1 expression in unstimulated and TNF-alpha-stimulated endothelial cells. Six-well plates with monolayers of human umbilical vein cells, ECV 304 (ATCC CRL 1998), were exposed to TNF-alpha (1 ng/mL) in the presence and absence of subtoxic and TC50 doses of chemicals for 24 hrs at 37 degrees C/5% CO2. Several doses of TNF-alpha (0.5-2 ng/mL) were coincubated with 100 microL of undiluted aqueous dental resin extracts. Cells were harvested and stained with mAB FITC-conjugated anti-human ICAM-1 (CD54). ICAM-1 expression was measured by flow cytometry. Cells expressed basal levels of ICAM-1, which was up-regulated by TNF-alpha but was not changed by all samples studied. Except for UVR 6105, the methacrylates significantly decreased ICAM-1 expression in TNF-alpha-stimulated cells. These findings suggest that methacrylates may decrease the recruitment of leukocytes to sites of inflammation.

Tensile properties of the physis vary with anatomic location, thickness, strain rate and age.

The variable outcome of physeal distraction has raised questions as to the mechanism by which bone lengthening is achieved. Is it by stretching of the matrix or does it stimulate growth? In order to explore the contribution of matrix stretching, we sought to answer the following questions in an animal model: (a) Are the tensile properties of the lateral side of the proximal tibial physis different from the medial? (b) Are the tensile properties strain-rate dependent? (c) Does the growth plate fracture through any preferred zone in tension? (d) Are the tensile properties of the bovine growth plate a function of age? (e) Are thicker growth plates weaker in tension? (f) Are the tensile properties of the bovine growth plate comparable to those of a child's? We compared bone-cartilage-bone specimens (0.5 x 2.5 mm2 in cross-section) from the lateral, central and medial regions of the proximal tibial growth plates of 12- to 18-month heifers. 70 specimens were tested to failure in tension at 0.0004, 0.004 and 0.04 mm/s. Tensile strength and tangent modulus were 33% and 25% greater, respectively, on the lateral side compared with the medial, and both were increased at the higher strain rates. We found no difference in the ultimate strains by region or strain rate. Thicker growth plates were weaker. Scanning electron microscopy revealed a three-dimensional fracture pattern extending from the upper columnar into the reserve zone. Bundles of intact chondrons remained intact, but only on the metaphyseal side, having been torn from an interterritorial matrix which remained mostly on the epiphyseal side of the fracture. We compared 21 specimens of 12- to 18-month and 19 specimens of 5-month calves from similar regions of the proximal tibia. These were tested to failure in tension at 0.004 mm/s. The older bovine growth plate was 25% thinner, 34% stronger and failed at 65% greater strain. For comparison, we tested eight samples from the femoral capital growth plate of two cerebral palsy patients. These were twice as thick as our bovine samples and about half as strong, but with similar ultimate strain values.

A comparison of palatal adaptation in acrylic resin denture bases using conventional and anchored polymerization techniques.

PURPOSE: The study investigated the effects of palatal depth and a resin anchoring system on the adaptation of denture base resin to the master cast after compression molding and heat polymerization. MATERIALS AND METHODS: Forty-eight virtually identical polymethyl methacrylate dentures were fabricated on master casts with either a deep or shallow palatal vault. One half of the master casts of each palate type were altered by the addition of anchoring holes along the posterior land area, as well as perpendicularly in the midsaggital area. Anchoring holes were made with a #8 round bur to a depth of 5 mm. Twenty-four hours after polymerization, the bases on their casts were sectioned at the posterior border and evaluated for degree of adaptation using a traveling microscope. Maladaptation at the interface of the denture base and master cast was measured at predetermined mediolateral locations. A split-plot analysis of variance (alpha = 0.05) was performed followed by a post-hoc Dunn Multiple Comparison Test. RESULTS: In general, depth of the palatal vault did not significantly influence denture palatal discrepancy (p =.0780), but the use of the anchoring system significantly reduced mean gap distances (p =.000). At lateral and midpalate locations, gap distances between the denture bases and their casts were reduced from approximately 0.3 mm to approximately 0.1 mm when the anchoring system was used. CONCLUSIONS: Mean gap distances for steep palate dentures were significantly less than shallow palate dentures at vestibule and lateral palate locations, and anchoring holes placed in an edentulous master cast along the posterior land area and at the midline significantly improved the adaptation of denture bases.

A comparison of 3 alloy surface treatments for resin-bonded prostheses.

PURPOSE: The most frequent cause of clinical failure of resin-bonded fixed partial dentures is a debonding at the metal-cement interface. The purpose of this in vitro study was to compare the tensile bond strengths of 3 different alloy-surface treatments when cemented to human enamel with a resin cement. MATERIALS AND METHODS: Cylinders of a nickel-chromium-beryllium (Ni-Cr-Be) and a gold-palladium (Au-Pd) alloy were fabricated and assigned to different surface treatment groups as follows: Group 1: Ni-Cr-Be, chemically etched; Group 2: Au-Pd, airborne particle-abraded and tin-plated; and Group 3: Au-Pd, airborne particle-abraded and treated with the Alloy Primer (Kuraray Co, LTD, Osaka, Japan). The cylinders were bonded to the enamel surfaces of extracted, human third molars and stored in normal saline at 37 degrees C for 48 hours. The tensile bond strength of 21 specimens from each group was measured on a Universal Testing Machine (Instron, Canton, MA). Three failed specimens of each group were evaluated using scanning electron microscopy and energy dispersive spectroscopy. RESULTS: Statistically significant differences (p <.05) were found between all 3 treatment groups. The mean tensile bond strengths (+/- the standard error of mean) recorded as follows: Group 1: 10.6 MPa (+/-1.3), Group 2: 0.9 MPa (+/-0.2), and Group 3: 13.4 MPa (+/-1.0). Specimens from groups 1 and 3 revealed a trend towards mixture of cohesive, within the resin cement, and adhesive failures at the metal-cement interface. Group 2 specimens exhibited primarily adhesive failures at the metal-cement interface. CONCLUSIONS: The tensile bond strength of Au-Pd alloy specimens was significantly increased with the Alloy Primer.

Novel priming and crosslinking systems for use with isocyanatomethacrylate dental adhesives.

OBJECTIVES: (a) to design, formulate and evaluate prototype primers and a crosslinking agent for use with isocyanatomethacrylate-based comonomer adhesives and (b) to establish correlations between bond strength and solubility parameter differences between the adhesives and etched dentin, and the permeability coefficients of the adhesives. METHODS: Equimolar mixtures of 2-isocyanatoethyl methacrylate (IEM) and a methacrylate comonomer were formulated with tri-n-butyl borane oxide (TBBO) as the free radical initiator to have cure times of 6-10 min. Shear bond strengths to dentin were determined for each adhesive mixture (n = 7) using standard testing protocols. Shear bond strengths for the three systems were also determined after application of "reactive primers" to the dentin surface. The "reactive primers" contained 10-20 parts by weight of the respective comonomer mixture and 3.5 parts by weight TBBO in acetone. Solubility parameters difference values (delta delta) and permeability coefficients (P) were approximated for each adhesive system and correlated with shear bond strength values. Additionally, a crosslinking agent was prepared by bulk reaction of an equimolar mixture containing IEM and a methacrylate comonomer. The effects of crosslinker addition on: (a) the setting time of IEM; and (b) the setting times and initiator requirements of selected IEM/comonomer mixtures were determined. RESULTS: Shear bond strength values (MPa): IEM/HEMA 13.6 +/- 2.0 (no primer), 20.1 +/- 2.0 (with primer); IEM/HETMA 9.3 +/- 3.3 (no primer), 20.8 +/- 8.1 (with primer); IEM/AAEMA 13.6 +/- 1.9 (no primer), 17.3 +/- 3.2 (with primer). Also, approximated permeability coefficients showed a significant correlation (r = +0.867, p < 0.001) with shear bond strength values. Crosslinker addition studies with IEM/4-META: (a) at 5-9 mol% reduced the setting time of IEM polymerization by 79%; and (b) at 6 mol% reduced initiator level requirements 60-70% to achieve a comparable setting time, and decreased setting times by ca. 75% for a given initiator level with selected IEM/methacrylate adhesive systems. SIGNIFICANCE: The shear bond strengths of isocyanatomethacrylate-based dental adhesives can be enhanced by using reactive primers; their setting times and initiator requirements can be improved using a dimethacrylate crosslinker. Approximated permeability coefficients may be useful as indicators of bonding performance for dentin adhesive systems.

In vitro toxicity of spiroorthocarbonate monomers designed for non-shrinking dental restoratives.

In development of photopolymerized expanding monomers with epoxy resin systems, there is a need for reactive expanding monomers that exert a good biocompatibility profile. The objective of this study was to evaluate the in vitro toxicology of new spiroorthocarbonates designed to be expanding monomers. The expanding monomers investigated were: trans/trans-2,3,8,9-di(tetramethylene)-1,5,7,11-tetraoxaspiro[5,5] undecane (DTM-TOSU), 5,5-diethyl-19-oxadispiro-[1,3-dioxane-2,2'-1,3-dioxane-5',4'-bicy clo[4.1.0]heptane] (DECHE-TOSU); 3,9-diethyl-3,9-dipropionyloxy methyl-1,5,7,11-tetraoxaspiro[5.5]undecane (DEDPM-TOSU); and 3,9-diethyl-3,9-diacetoxy methyl-1,5,7,11-tetraoxaspiro[5.5]undecane (DAMDE-TOSU). The in vitro toxicology of these monomers measured their cytotoxicity and mutagenicity potential. Succinic dehydrogenase (SDH) activity in the MTT assay was used to assess the toxic dose that kills 50% of cells (TC50) for all the monomers. Their mutagenic potential was measured in the Ames Salmonella assay with and without metabolic activation. Two solvents, DMSO and acetone, were used to validate effects. Appropriate controls included the solvents alone. All the expanding monomers in this study were less cytotoxic than BISGMA (p < 0.01), a commercial component of dental restoratives. The relative cytotoxicity of the expanding monomers in DMSO was defined in the following order: DTM-TOSU (more toxic) > DECHE-TOSU > DEDPM-TOSU > DAMDE-TOSU. Each was significantly different from the other (p < 0.05). Overall, the TC50 values of all expanding monomers were significantly greater in DMSO than in acetone (p < 0.05). However, for BISGMA this trend was opposite. For mutagenicity results, the expanding monomers were non-mutagenic and there was no solvent effect on this outcome. The non-mutagenicity and low cytotoxicity profile of these expanding monomers suggests their potential for development of biocompatible non-shrinking composites.

Semiempirical and ab initio conformational analysis of 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane with application of GIAO-SCF methods to NMR spectrum interpretation.

The GIAO-SCF method for calculating isotropic nuclear magnetic shielding values has been utilized to explain certain features in the 1H-NMR spectrum of 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane. Population distributions of the low-energy conformers based on their ab initio energies were used to produce weighting factors for the individual calculated shielding values to calculate the weighted average of the shielding values for a complete set of conformers. The differences in 1H chemical shifts between the hydrogens of the two methyl groups and between the axial and equatorial hydrogens in 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane were shown to be due to energy differences between the chair and boat orientations of the six-membered ring and contribution from a twist-boat conformation. Results suggest a hypothesis that intramolecular differences in chemical shift might be calculated to a greater degree of accuracy than chemical shifts calculated relative to a standard.

Environmental scanning electron microscopy of hydrated conditioned/etched dentine.

Various etchants/conditioners are used during dental treatment to affect or remove the smear layer. The purpose of this study was to evaluate the effect of different treatments on moist dentine, using a field emission environmental scanning electron microscope (FE-ESEM). Twenty freshly extracted, human molar teeth were utilised. The roots and pulps were removed, and the crowns horizontally sectioned with a low speed diamond saw (Isomet) (with cooling in a saline solution) in order to expose superficial dentine. A smear layer was created on these surfaces by using 600 grit silicone carbide paper. Test surfaces were then treated in one of the following ways: 1. 37% phosphoric acid liquid 2. 37% phosphoric acid gel 3. NRC (non-rinse conditioner) without rinsing 4. NRC with rinsing. Shallow grooves were cut on the untreated sides, using a thin diamond bur. This enabled the samples to be split in half when pressure was applied in the grooves. Samples were maintained moist throughout specimen preparation. Samples were examined in the FE-ESEM (Philips XL 30) in such a way that the effect of the treatment could be viewed occlusally, as well as perpendicular to the treated interface. Phosphoric acid liquid and gel removed the smear layer, and demineralised the dentine for approximately 5-10 micrometers. NRC penetrated the smear layer and modified it to a lesser degree. However, washing of the NRC treated surface removed part of the smear layer, and opened up some dentinal tubules. Excellent resolution was possible with the FE-ESEM in both the wet and dry modes.

Design, formulation, and evaluation of isocyanatoacrylate copolymer dental adhesives.

Experiments have recently been completed to explore the development of isocyanatoacrylate copolymers as new dental adhesives. A main goal of this work was to test the utility of solubility parameter differences between the candidate adhesives and etched dentin as a predictor of relative bond strength. All candidate adhesive mixtures contained 2-isocyanatoethyl methacrylate (IEM), a selected amount of tri-n-butylborane oxide (TBBO) initiator, and one of 13 methacrylate comonomers. Reactivity ratios were computed for comonomer pairs as indicators of relative reactivity. The concentration of TBBO was optimized for each comonomer mixture to obtain working times of 2-6 min and setting times of 6-10 min. The solubility parameter difference Deltadelta (J/cm(3))(1/2) was calculated for each test mixture with respect to an etched dentin substrate, as an approximation of wetting ability. Using standard techniques for shear bond strength evaluation, mean shear bond strength values ranging between 7-15.5 MPa were obtained for comonomer adhesives in bonding Z-100 composite to treated dentin. Shear bond strength values showed a good correlation (r = -0.612, P