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Nearly 100 million of the 170 million composite and amalgam restorations placed annually in the United States are replacements for failed restorations. The primary reason both composite and amalgam restorations fail is recurrent decay, for which composite restorations experience a 2.0-3.5-fold increase compared to amalgam. Recurrent decay is a pernicious problem-the standard treatment is replacement of defective composites with larger restorations that will also fail, initiating a cycle of ever-larger restorations that can lead to root canals, and eventually, to tooth loss. Unlike amalgam, composite lacks the inherent capability to seal discrepancies at the restorative material/tooth interface. The low-viscosity adhesive that bonds the composite to the tooth is intended to seal the interface, but the adhesive degrades, which can breach the composite/tooth margin. Bacteria and bacterial by-products such as acids and enzymes infiltrate the marginal gaps and the composite's inability to increase the interfacial pH facilitates cariogenic and aciduric bacterial outgrowth. Together, these characteristics encourage recurrent decay, pulpal damage, and composite failure. This review article examines key biological and physicochemical interactions involved in the failure of composite restorations and discusses innovative strategies to mitigate the negative effects of pathogens at the adhesive/dentin interface. © 2019 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B:2466-2475, 2019.

Resin chemistries for dental composite are evolving as noted by the introduction of silorane-based composites in 2007. This shift in the landscape from methacrylate-based composites has fueled the quest for versatile methacrylate-silorane adhesives. The objective of this study was to evaluate the polymerization behavior and structure/property relationships of methacrylate-silorane hybrid systems. Amine compound ethyl-4-(dimethylamino) benzoate (EDMAB) or silane compound tris(trimethylsilyl) silane (TTMSS) was selected as coinitiators. The mechanical properties of the copolymer were improved significantly at low concentrations (15, 25, or 35 wt %) of silorane when EDMAB was used as coinitiator. The rubbery moduli of these experimental copolymers were increased by up to 260%, compared with that of the control (30.8 ± 1.9 MPa). Visible phase separation appeared in these formulations if the silorane concentrations in the formulations were 50–75 wt %. The use of TTMSS as coinitiator decreased the phase separation, but there was a concomitant decrease in mechanical properties. In the neat methacrylate formulations, the maximum rates of free-radical polymerization with EDMAB or TTMSS were 0.28 or 0.06 s−1, respectively. In the neat silorane resin, the maximum rates of cationic ring-opening polymerization with EDMAB or TTMSS were 0.056 or 0.087 s−1, respectively. The phase separation phenomenon may be attributed to differences in the rates of free-radical polymerization of methacrylates and cationic ring-opening polymerization of silorane. In the hybrid systems, free-radical polymerization initiated with EDMAB led to higher crosslink density and better mechanical properties under dry/wet conditions. These beneficial effects were, however, associated with an increase in heterogeneity in the network structure. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 841–852, 2016.

To investigate the time- and rate-dependent mechanical properties of collagen-adhesive composites, creep and monotonic experiments are performed under dry and wet conditions. The composites are prepared by infiltration of dentin adhesive into a demineralized bovine dentin. Experimental results show that for small stress level under dry conditions, both the composite and the neat adhesive have similar behavior. On the other hand, in wet conditions, the composites are significantly soft and weak compared to the neat adhesives. The behavior in the wet condition is found to be affected by the hydrophilicity of both the adhesive and the collagen. As the adhesive-collagen composites are a part of the complex construct that forms the adhesive-dentin interface, their presence will affect the overall performance of the restoration. We find that Kelvin-Voigt model with at least four elements is required to fit the creep compliance data, indicating that the adhesive-collagen composites are complex polymers with several characteristic time scales whose mechanical behavior will be significantly affected by loading rates and frequencies. Such mechanical properties have not been investigated widely for these types of materials. The derived model provides an additional advantage that it can be exploited to extract other viscoelastic properties which are, generally, time consuming to obtain experimentally. The calibrated model is utilized to obtain stress relaxation function, frequency-dependent storage and loss modulus, and rate-dependent elastic modulus.

To enhance the water miscibility and increase the mechanical properties of dentin adhesives, a new glycerol-based monomer with vinyl and carboxylic acid, 4-((1,3-bis(-methacryloyloxy)propan-2-yl)oxy)-2-methylene-4-oxobutanoic acid (BMPMOB), was synthesized and characterized. Dentin adhesive formulations containing 2-hydroxyethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]propane (BisGMA), and BMPMOB were characterized with regard to real-time photopolymerization behavior, water sorption, dynamic mechanical analysis, and microscale three-dimensional internal morphologies and compared with HEMA/BisGMA controls. The experimental adhesive copolymers showed higher glass transition temperature and rubbery moduli, as well as improved water miscibility compared to the controls. The enhanced properties of the adhesive copolymers indicated that BMPMOB is a promising comonomer for dental restorative materials.

We have developed a micromechanics based model for chemically active saturated fibrous media that incorporates fiber network microstructure, chemical potential driven fluid flow, and micro-poromechanics. The stress-strain relationship of the dry fibrous media is first obtained by considering the fiber behavior. The constitutive relationships applicable to saturated media are then derived in the poromechanics framework using Hill's volume averaging. The advantage of this approach is that the resultant continuum model accounts for the discrete nature of the individual fibers while retaining a form suitable for porous materials. As a result, the model is able to predict the influence of micro-scale phenomena, such as the fiber pre-strain caused by osmotic effects and evolution of fiber network structure with loading, on the overall behavior and in particular, on the poromechanics parameters. Additionally, the model can describe fluid-flow related rate-dependent behavior under confined and unconfined conditions and varying chemical environments. The significance of the approach is demonstrated by simulating unconfined drained monotonic uniaxial compression under different surrounding fluid bath molarity, and fluid-flow related creep and relaxation at different loading-levels and different surrounding fluid bath molarity. The model predictions conform to the experimental observations for saturated soft fibrous materials. The method can potentially be extended to other porous materials such as bone, clays, foams and concrete.

The aim of this study is to investigate the mechanical behavior of model methacrylate-based dentin adhesives under conditions that simulate the wet oral environment. A series of monotonic and creep experiments were performed on rectangular beam samples of dentin adhesive in three-point bending configuration under different moisture conditions. The monotonic test results show a significant effect of loading rate on the failure strength and the linear limit (yield point) of the stress-strain response. In addition, these tests show that the failure strength is low, and the failure occurs at a smaller deformation when the test is performed under continuously changing moisture conditions. The creep test results show that under constant moisture conditions, the model dentin adhesives can have a viscoelastic response under certain low loading levels. However, when the moisture conditions vary under the same low loading levels, the dentin adhesives have an anomalous creep response accompanied by large secondary creep and high strain accumulation.

There have been reports of the sensitivity of our current dentin adhesives to excess moisture, for example, water-blisters in adhesives placed on over-wet surfaces, and phase separation with concomitant limited infiltration of the critical dimethacrylate component into the demineralized dentin matrix. To determine quantitatively the hydrophobic/hydrophilic components in the aqueous phase when exposed to over-wet environments, model adhesives were mixed with 16, 33, and 50 wt % water to yield well-separated phases. Based upon high-performance liquid chromatography coupled with photodiode array detection, it was found that the amounts of hydrophobic BisGMA and hydrophobic initiators are less than 0.1 wt % in the aqueous phase. The amount of these compounds decreased with an increase in the initial water content. The major components of the aqueous phase were hydroxyethyl methacrylate (HEMA) and water, and the HEMA content ranged from 18.3 to 14.7 wt %. Different BisGMA homologues and the relative content of these homologues in the aqueous phase have been identified; however, the amount of crosslinkable BisGMA was minimal and, thus, could not help in the formation of a crosslinked polymer network in the aqueous phase. Without the protection afforded by a strong crosslinked network, the poorly photoreactive compounds of this aqueous phase could be leached easily. These results suggest that adhesive formulations should be designed to include hydrophilic multimethacrylate monomers and water compatible initiators. © 2012 WILEY PERIODICALS, INC.

Most of the new indole-containing pseudopeptides (V), (VIII), and (X) possess the optimal range of lipophilicity for oral absorption, cell membrane penetration and blood-brain barrier permeation.

The pulmonary biochemical response, particularly the effects on mixed-function oxidases, was investigated in rats exposed to 40 ppm furfural for 1 h daily, 5 days per week, for periods of 7, 15 and 30 days. This concentration is ca. 22% of the acute LC50 dose. Exposure to furfural increased the activities of acid and alkaline phosphatases and glutamic-pyruvic transaminase, inhibited the activities of arginase and succinic dehydrogenases and elevated the concentration of lactic acid in the lungs. In the group of mixed-function oxidases, the activities of aminopyrene-N-demethylase and aniline hydroxylase (phase I, cytochrome P-450b specific) significantly increased and the activity of Benzo[a]pyrene hydroxylase (phase I, cytochrome P-450c specific) decreased. The activity of glutathione-S-transferase (phase II component) also was increased concurrently with a decrease in the concentration of glutathione. The magnitude of biochemical alterations in most cases was related directly to the duration of exposure. Our observations indicate that furfural caused pulmonary irritation, parenchymal injury and the regenerative proliferation of type II pneumocytes. Selective (cellular and/or cytochrome P-450 isozyme specific) enhancement of pulmonary mixed-function oxidases by furfural appears to stimulate its own pulmonary biotransformation, and the excretion of oxidative metabolites was facilitated by their enzymatic conjugation with glutathione.

For discrete materials like sands, the continuum field variables, stress and strain, are defined in terms of micro-level quantities by considering the deformation mechanism of granular soils from a microscopic point of view. Under the application of load, soil is considered to deform due to the movement relative to each other of clusters of particles. Based on this deformation mechanism, the kinematics of soils are developed and a strain tensor for granular soils, in terms of local displacements and geometric measures, is introduced. A local constitutive law relating local displacements and local tractions is defined. Using the local constitutive law, the relationships between stress and strain for the media are developed. The developed model incorporates the influence of strain hardening and material anisotropy on the deformation behaviour of the media. Comparisons of the model predictions and experimental results from tests conducted in cubical and hollow cylinder devices are presented.

The stiffness characteristics of a packing of granules are influenced by the particle interactions at contacts, the void ratio, the co-ordination number and the packing structure. A stress-strain relationship for the packings of spheres is presented. The relationship explicitly includes the contact force-displacement law and the parameters characterizing the packing structure. The initial moduli computed using this relationship are compared with experimental measurements and empirical equations for sands. The theoretical results are also compared with experimental results on packings of glass balls. Closed-form solutions are derived for statistically isotropic packings under initial isotropic stress conditions. Numerical solutions for the stiffness properties are obtained for anisotropic initial stress conditions and anisotropic packing structures.