Jonggu Park

Adhesive/Dentin Interface: The Weak Link in the Composite Restoration

Results from clinical studies suggest that more than half of the 166 million dental restorations that were placed in the United States in 2005 were replacements for failed restorations. This emphasis on replacement therapy is expected to grow as dentists use composite as opposed to dental amalgam to restore moderate to large posterior lesions. Composite restorations have higher failure rates, more recurrent caries, and increased frequency of replacement as compared to amalgam. Penetration of bacterial enzymes, oral fluids, and bacteria into the crevices between the tooth and composite undermines the restoration and leads to recurrent decay and premature failure. Under in vivo conditions the bond formed at the adhesive/dentin interface can be the first defense against these noxious, damaging substances. The intent of this article is to review structural aspects of the clinical substrate that impact bond formation at the adhesive/dentin interface; to examine physico-chemical factors that affect the integrity and durability of the adhesive/dentin interfacial bond; and to explore how these factors act synergistically with mechanical forces to undermine the composite restoration. The article will examine the various avenues that have been pursued to address these problems and it will explore how alterations in material chemistry could address the detrimental impact of physico-chemical stresses on the bond formed at the adhesive/dentin interface.

In vitro Performance of Nano-heterogeneous Dentin Adhesive

Water is ubiquitous in the mouths of healthy individuals and routinely interferes with efforts to bond restorations to dental tissues. Our previous studies using tapping-mode atomic force microscopy (TMAFM) have shown that nanophase separation is a general feature of cross-linked polymethacrylates photocured in the presence of water. To explore the relationship between nanophase separation in dentin adhesives and their long-term mechanical properties, we evaluated model adhesives after 3 months of aqueous storage. The degree of contrast in the TMAFM phase image depended on the formulations used, ranging from ‘not observable’ to ‘very strong’. Correspondingly, the mechanical properties of these model adhesives varied from ‘minimal change’ to ‘significant depreciation’. The results support the hypothesis that a high degree of heterogeneity at the nano-scale is associated with poor mechanical durability in these model adhesives.

The influence of chemical structure on the properties in methacrylate-based dentin adhesives

OBJECTIVES The objective of this study was to investigate the influence of the chemical structure of methacrylate monomers used in dentin adhesives on degree of conversion (DC), water sorption, and dynamic mechanical properties. MATERIALS AND METHODS Experimental adhesives containing 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]-propane (BisGMA), 2-hydroxyethyl methacrylate (HEMA), and co-monomer, 30/45/25 (w/w) were photo-polymerized. Ethyleneglycol dimethacrylate (EGDM), diethyleneglycol dimethacrylate (DEGDM), triethyleneglycol dimethacrylate (TEGDMA), 1,3-glycerol dimethacrylate (GDM), and glycerol trimethacrylate (GTM) were used as a co-monomer. The adhesives were characterized with regard to DC, water sorption, and dynamic mechanical analysis and compared to control adhesive [HEMA/BisGMA, 45/55 (w/w)]. RESULTS DC and water sorption increased with an increase in the number of ethylene glycol units in the monomer. Experimental adhesive containing GDM showed significantly higher storage moduli (p<0.05) in both dry and wet samples than experimental adhesives containing EGDM or DEGDM. The rubbery moduli of adhesives containing GDM and GTM were found to be significantly greater (p<0.05) than that of the control. Adhesives containing GTM exhibited the widest tanδ curves, indicating the greatest structural heterogeneity. SIGNIFICANCE The hydrophilicity, functionality and size of monomers in dentin adhesives affected the water sorption, solubility, crosslink density and heterogeneity of the polymer network. The experimental adhesives containing GDM and GTM showed higher rubbery moduli, indicating higher crosslink density accompanied by a decrease in the homogeneity of the polymer network structure.

Water sorption and dynamic mechanical properties of dentin adhesives with a urethane-based multifunctional methacrylate monomer.

OBJECTIVES Our previous study showed the synthesis and characterization of a novel urethane-linked trimethacrylate monomer for use as a co-monomer in dentin adhesives. The objective of this work was to further investigate the performance of dentin adhesives containing a new monomer, with particular emphasis on the water sorption and viscoelastic behavior of the crosslinked networks. MATERIALS AND METHODS Dentin adhesives contained 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]-propane (BisGMA), 2-hydroxyethyl methacrylate (HEMA), and a new multifunctional methacrylate with urethane-linked groups-1,1,1-tri-[4-(methacryloxyethylaminocarbonyloxy)-phenyl]ethane (MPE) and were photo-polymerized in the presence or absence of water. Adhesives were characterized with regard to degree of conversion (DC), viscosity, water sorption/solubility, and dynamic mechanical analysis (DMA) and compared with BisGMA/HEMA controls. RESULTS The experimental adhesives exhibited DC and solubility comparable to that of the control, regardless of the presence or absence of water. All the experimental adhesives tested showed less water sorption, lower tandelta peak heights, and higher rubbery modulus than the control. SIGNIFICANCE Dentin adhesives containing a new multifunctional methacrylate showed better dynamic thermomechanical properties and water sorption relative to controls, without compromising DC and solubility. Thus, MPE, when included as a component of methacrylate dentin adhesives, may provide enhanced durability in the moist environment of the mouth.

Effect of photoinitiators on the in vitro performance of a dentin adhesive exposed to simulated oral environment

OBJECTIVES Our previous study showed poor mechanical durability and nano-sized heterogeneities in cross-linked dentin adhesives cured in the presence of water. To further explore the relationship between nano-scale heterogeneities and the long-term mechanical properties of dentin adhesives, the properties of model dentin adhesives polymerized using hydrophilic photoinitiators were compared with those of adhesives polymerized using hydrophobic camphorquinone-based photoinitiators. METHODS The model adhesives consisted of HEMA and bisGMA with a mass ratio of 45/55 and were photopolymerized in the presence of 8.3 mass% water. The photo-polymerization of the model adhesives during irradiation was monitored in situ using a Perkin-Elmer Spectrum One FTIR in the ATR sampling mode. The tensile properties were determined for all samples after dry storage at room temperature, or after aqueous storage in distilled deionized water. RESULTS There was a continuous decline of mechanical properties for the specimens cured in the presence of water during 3 months aqueous storage, especially for the specimens that contained hydrophobic photoinitiators. The multi-component systems containing hydrophilic photoinitiators were shown to produce superior model dental adhesives when these materials are cured in the presence of water. SIGNIFICANCE Designing initiator systems to perform in this heterogeneous environment may improve the mechanical performance of dentin adhesives, as the results presented here indicate.

Effect of photoinitiator system and water content on dynamic mechanical properties of a light‐cured bisGMA/HEMA dental resin

The selection of an appropriate photoinitiator system is critical for efficient polymerization of dental resins with satisfactory mechanical and physical properties. The purpose of this study was to evaluate the influence of adding an iodonium salt to two-component photoinitiator systems. Four photoinitiator systems were included in a model bisGMA/HEMA resin and used to prepare samples at different water contents; the dynamic mechanical properties and the final degree of conversion of the samples were then characterized. Addition of the iodonium salt to the two-component photoinitiator systems increased the final degree of conversion, glass transition temperature, rubbery modulus, and crosslink density. The photoinitiator system containing ethyl-4-(dimethylamino) benzoate as a coinitiator and the iodonium salt exhibited the highest rubbery modulus. The enhanced properties in the presence of the iodonium salt can be attributed to the production of an active phenyl radical with regeneration of the original camphorquinone, which may increase the compatibility between monomers and initiators, especially in the presence of water. The results support the hypothesis that a photoinitiator system containing an iodonium salt can increase both mechanical properties and final conversion of model resin polymerized in the presence of water.

Enzymatic Biodegradation of HEMA/BisGMA Adhesives Formulated With Different Water Content

Dentin adhesives may undergo phase separation when bonding to wet demineralized dentin. We hypothesized that adhesives exhibiting phase separation will experience enhanced biodegradation of methacrylate ester groups. The objective of this project was to study the effect of enzyme-exposure on the release of methacrylic acid (MAA) and 2-hydroxyethyl methacrylate (HEMA) from adhesives formulated under conditions simulating wet bonding. HEMA/bisGMA(2,2-bis[4(2-hydroxy-3-methacryloyloxy-propyloxy)-phenyl] propane), 45/55 w/w ratio, was formulated with different water content: 0 Wt % (A00), 8 wt % (A08), and 16 wt % (A16). After a three day prewash, adhesive discs were incubated with/without porcine liver esterase (PLE) in phosphate buffer (PB, pH 7.4) at 37 degrees C for 8 days. Supernatants were collected daily and analyzed for MAA and HEMA by HPLC. For all formulations, daily MAA release in the presence of PLE was increased compared to MAA release in PB. HEMA release in the presence of PLE was not detected while HEMA release was consistently measured in PB. A08 and A16 released significantly larger amounts of HEMA compared to A00. Analysis of the cumulative release of analytes showed that the leachables in PLE was significantly increased (p < 0.05) as compared with that released in PB indicating that MAA release was not only formed from unreacted monomers but from pendant groups in the polymer network. However, the levels of analytes HEMA in PB or MAA in PLE were increased in A08 and A16 as compared with A00, which suggests that there could be a greater loss of material in HEMA/bisGMA adhesives that experience phase separation under wet bonding conditions.

Dynamic mechanical analysis and esterase degradation of dentin adhesives containing a branched methacrylate

A study of the dynamic mechanical properties and the enzymatic degradation of new dentin adhesives containing a multifunctional methacrylate are described. Adhesives contained 2-hydroxyethyl methacrylate, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]-propane, and a new multifunctional methacrylate with a branched side chain-trimethylolpropane mono allyl ether dimethacrylate (TMPEDMA). Adhesives were photopolymerized in the presence of 0, 8, and 16 wt % water to simulate wet bonding conditions in the mouth and compared with control adhesives. The degree of conversion as a function of irradiation time was comparable for experimental and control adhesives. In dynamic mechanical analysis, broad tan delta peaks were obtained for all samples, indicating that the polymerized networks are heterogeneous; comparison of the full-width-at-half-maximum values obtained from the tan delta curves indicated increased heterogeneity for samples cured in the presence of water and/or containing TMPEDMA. The experimental adhesive showed higher T(g) and higher rubbery modulus indicating increased crosslink density when compared with the control. The improvement in esterase resistance afforded by adhesives containing the TMPEDMA is greater when this material is photopolymerized in the presence of water, suggesting better performance in the moist environment of the mouth. The improved esterase resistance of the new adhesive could be explained in terms of the densely crosslinked network structure and/or the steric hindrance of branched alkyl side chains.

Viscoelastic and fatigue properties of model methacrylate-based dentin adhesives

The objective of the current study is to characterize the viscoelastic and fatigue properties of model methacrylate-based dentin adhesives under dry and wet conditions. Static, creep, and fatigue tests were performed on cylindrical samples in a 3-point bending clamp. Static results showed that the apparent elastic modulus of the model adhesive varied from 2.56 to 3.53 GPa in the dry condition, and from 1.04 to 1.62 GPa in the wet condition, depending upon the rate of loading. Significant differences were also found for the creep behavior of the model adhesive under dry and wet conditions. A linear viscoelastic model was developed by fitting the adhesive creep behavior. The developed model with 5 Kelvin Voigt elements predicted the apparent elastic moduli measured in the static tests. The model was then utilized to interpret the fatigue test results. It was found that the failure under cyclic loading can be due to creep or fatigue, which has implications for the failure criterion that are applied for these types of tests. Finally, it was found that the adhesive samples tested under dry conditions were more durable than those tested under wet conditions.

Fatigue life prediction of dentin-adhesive interface using micromechanical stress analysis

OBJECTIVES The objective of this work was to develop a methodology for the prediction of fatigue life of the dentin-adhesive (d-a) interface. METHODS At the micro-scale, the d-a interface is composed of dissimilar material components. Under global loading, these components experience different local stress amplitudes. The overall fatigue life of the d-a interface is, therefore, determined by the material component that has the shortest fatigue life under local stresses. Multiple 3d finite element (FE) models were developed to determine the stress distribution within the d-a interface by considering variations in micro-scale geometry, material composition and boundary conditions. The results from these models were analyzed to obtain the local stress concentrations within each d-a interface component. By combining the local stress concentrations and experimentally determined stress versus number of cycle to failure (S-N) curves for the different material components, the overall fatigue life of the d-a interface was predicted. RESULTS The fatigue life was found to be a function of the applied loading amplitude, boundary conditions, microstructure and the mechanical properties of the material components of the d-a interface. In addition, it was found that the overall fatigue life of the d-a interface is not determined by the weakest material component. In many cases, the overall fatigue life was determined by the adhesive although exposed collagen was the weakest material component. Comparison of the predicted results with experimental data from the literature showed both qualitative and quantitative agreement. SIGNIFICANCE The methodology developed for fatigue life prediction can provide insight into the mechanisms that control degradation of the bond formed at the d-a interface.