Compositional design and optimization of dentin adhesive with neutralization capability

Objectives The objective of this work was to investigate the polymerization behavior, neutralization capability, and mechanical properties of dentin adhesive formulations with the addition of the tertiary amine co-monomer, 2-N-morpholinoethyl methacrylate (MEMA). Methods A co-monomer mixture based on HEMA/BisGMA (45/55, w/w) was used as a control adhesive. Compared with the control formulation, the MEMA-containing adhesive formulations were characterized comprehensively with regard to water miscibility of liquid resin, water sorption and solubility of cured polymer, real-time photopolymerization kinetics, dynamic mechanical analysis (DMA), and modulated differential scanning calorimetry (MDSC). The neutralization capacity was characterized by monitoring the pH shift of 1 mM lactic acid (LA) solution, in which the adhesive polymers were soaked. Results With increasing MEMA concentrations, experimental copolymers showed higher water sorption, lower glass transition temperature and lower crosslinking density compared to the control. The pH values of LA solution gradually increased from 3.5 to about 6.0–6.5 after 90 days. With the increase in crosslinking density of the copolymers, the neutralization rate was depressed. The optimal MEMA concentration was between 20 and 40 wt%. Conclusions As compared to the control, the results indicated that the MEMA-functionalized copolymer showed neutralization capability. The crosslinking density of the copolymer networks influenced the neutralization rate

The Effects of Herding and Word of Mouth in a Two-Period Advertising Signaling Model

In the context of increasing globalization, a new product may be sequentially released into markets in different countries and regions. The behavior of consumers in the market where a new product is first launched may have a huge impact on the purchasing behavior of consumers in later markets through the effects of herding and word of mouth (WOM). We suggest that these effects may significantly influence advertising when new products with short life cycles, such as movies, books, games, and music, are sequentially launched and not repeatedly purchased by consumers. Using a two-period advertising signaling model, this study theoretically demonstrates that the effects of herding and WOM affect the existence of separating (signaling quality) and pooling (hiding quality information) equilibria, but the number of potential consumers in different markets has no impact. Importantly, we investigate the firm\u27s strategic choices by comparing the profits generated under different equilibria and find that if the strength of WOM or the unit advertising cost increases, or if the herding effect decreases, a pooling equilibrium is likely to be the best, and a win-win, strategy before a new product is first released and consumed; otherwise, a separating equilibrium dominates. We also find that the cost of signaling decreases as WOM increases, whereas it increases with the herding effect or the mass of consumers in Period 1. Our findings provide several managerial implications relating to releasing product quality information for those industries in which products without repeat purchase are sequentially released in different markets

Visible-Light Initiated Free-Radical/Cationic Ring-Opening Hybrid Photopolymerization of Methacrylate/Epoxy: Polymerization Kinetics, Crosslinking Structure, and Dynamic Mechanical Properties

The effects of polymerization kinetics and chemical miscibility on the crosslinking structure and mechanical properties of polymers cured by visible-light initiated free-radical/cationic ring-opening hybrid photopolymerization are determined. A three-component initiator system is used and the monomer system contains methacrylates and epoxides. The photopolymerization kinetics is monitored in situ by Fourier transform infrared-attenuated total reflectance. The crosslinking structure is studied by modulated differential scanning calorimetry and dynamic mechanical analysis. X-ray microcomputed tomography is used to evaluate microphase separation. The mechanical properties of polymers formed by hybrid formed by free-radical polymerization. These investigations mark the first time that the benefits of the chain transfer reaction between epoxy and hydroxyl groups of methacrylate, on the crosslinking network and microphase separation during hybrid visible-light initiated photopolymerization, have been determined

Synthesis and evaluation of novel siloxane-methacrylate monomers used as dentin adhesives

Objectives The objectives of this study were to synthesize two new siloxane-methacrylate (SM) monomers for application in dentin adhesives and to investigate the influence of different functionality of the siloxane-containing monomers on the adhesive photopolymerization, water sorption, and mechanical properties. Materials and method Two siloxane-methacrylate monomers (SM1 and SM2) with four and eight methacrylate groups were synthesized. Dentin adhesives containing BisGMA, HEMA and the siloxane-methacrylate monomers were photo-polymerized. The experimental adhesives were compared with the control adhesive (HEMA/BisGMA 45/55 w/w) and characterized with regard to degree of conversion (DC), water miscibility of the liquid resin, water sorption and dynamic mechanical analysis (DMA). Results The experimental adhesives exhibited improved water miscibility as compared to the control. When cured in the presence of 12 wt % water to simulate the wet environment of the mouth, the SM-containing adhesives showed DC comparable to the control. The experimental adhesives showed higher rubbery modulus than the control under dry conditions. Under wet conditions, the mechanical properties of the formulations containing SM monomer with increased functionality were comparable with the control, even with more water sorption. Significance The concentration and functionality of the newly synthesized siloxane-methacrylate monomers affected the water miscibility, water sorption and mechanical properties of the adhesives. The experimental adhesives show improved water compatibility compared with the control. The mechanical properties were enhanced with an increase of the functionality of the siloxane-containing monomers. The results provide critical structure/property relationships and important information for future development of durable, versatile siloxane-containing dentin adhesives

Tris(trimethylsilyl)silane as a co-initiator for dental adhesive: Photo-polymerization kinetics and dynamic mechanical property

Objectives The purpose of this study was to evaluate the polymerization behavior of a model dentin adhesive with tris(trimethylsilyl)silane (TTMSS) as a co-initiator, and to investigate the polymerization kinetics and mechanical properties of copolymers in dry and wet conditions. Methods A co-monomer mixture based on HEMA/BisGMA (45/55, w/w) was used as a model dentin adhesive. The photoinitiator system included camphorquinone (CQ) as the photosensitizer and the co-initiator was ethyl-4-(dimethylamino) benzoate (EDMAB) or TTMSS. Iodonium salt, diphenyliodonium hexafluorophosphate (DPIHP) serving as a catalyst, was selectively added into the adhesive formulations. The control and the experimental formulations were characterized with regard to the degree of conversion (DC) and dynamic mechanical properties under dry and wet conditions. Results In two-component photoinitiator system (CQ/TTMSS), with an increase of TTMSS concentration, the polymerization rate and DC of C═C double bond increased, and showed a dependence on the irradiation time and curing light intensity. The copolymers that contained the three-component photoinitiator system (CQ/TTMSS/DPIHP) showed similar dynamic mechanical properties, under both dry and wet conditions, to the EDMAB-containing system. Significance The DC of formulations using TTMSS as co-initiator showed a strong dependence on irradiation time. With the addition of TTMSS, the maximum polymerization rate can be adjusted and the network structure became more homogenous. The results indicated that the TTMSS could be used as a substitute for amine-type co-initiator in visible-light induced free radical polymerization of methacrylate-based dentin adhesives

Effect of crosslinking density of polymers and chemical structure of amine-containing monomers on the neutralization capacity of dentin adhesives

Objectives Neutralization of the acidic micro-environment at the tooth/material interface is expected to provide enhanced durability for dental composite restorations. The objective of this study is to explore the effect of amine-containing monomer formulations and the crosslinking density of the resultant polymers on the neutralization capacity. Materials and methods The co-monomer system was varied systematically to obtain different proportions of Bisphenol A glycerolate dimethacrylate (BisGMA) and 2-hydroxyethyl methacrylate (HEMA), while maintaining a constant amount of amine-containing methacrylate monomer. A series of amine-containing monomers covering a range of pKa values were examined. Crosslinking density of formed copolymers was controlled by adjusting the weight content of the dimethacrylate monomer BisGMA. Lactic acid (LA) was used as a probe to analyze the effectiveness of the basic polymers to neutralize acid. The neutralization capacity of each amine-containing crosslinked copolymer was characterized by measuring pH as a function of time when the specimens were soaked in 1-mM LA solution, and the results were compared to the control formulations composed solely of BisGMA and HEMA. Polymer surfaces were examined using the methyl orange (MO) assay to quantify the amount of accessible amine groups. Results For each amine-containing crosslinked co-polymer, the neutralization capacity is enhanced by decreasing crosslinking density (e.g., by reducing BisGMA concentration in the formulation). In addition, more amine groups were accessible when crosslinking density was decreased. For different amine-containing polymers with the same BisGMA concentration, the neutralization capacity is higher when the amino monomers with higher pKa values were used in the formulations. Significance This is the first time that the neutralization capacity based on crosslinked dental polymers has been studied. The information is important for future development of durable dentin adhesives

Synthesis and evaluation of a novel co-initiator for dentin adhesives: polymerization kinetics and leachables study

The final publication is available at Springer via http://dx.doi.org/10.1007/s11837-015-1335-6.A new tertiary amine co-initiator (TUMA) containing three methacrylate-urethane groups was synthesized for application in dentin adhesives. The photopolymerization kinetics and leaching of unreacted components from methacrylate-based dental polymers formulated with this new co-initiator were determined. The newly synthesize co-initiator showed good chemical stability and decreased amine release from the initiator system. This study provides important information for the future development of biocompatible dentin adhesives/composites

Fabrication of hybrid crosslinked network with buffering capabilities and autonomous strengthening characteristics for dental adhesives

Ingress of bacteria and fluids at the interfacial gaps between the restorative composite biomaterial and the tooth structure contribute to recurrent decay and failure of the composite restoration. The inability of the material to increase the pH at the composite/tooth interface facilitates the outgrowth of bacteria. Neutralizing the microenvironment at the tooth/composite interface offers promise for reducing the damage provoked by cariogenic and aciduric bacteria. We address this problem by designing a dental adhesive composed of hybrid network to provide buffering and autonomous strengthening simultaneously. Two amino functional silanes, 2-hydroxy-3-morpholinopropyl (3-(triethoxysilyl)propyl) carbamate and 2-hydroxy-3-morpholinopropyl (3-(trimethoxysilyl)propyl) carbamate were synthesized and used as co-monomers. Combining free radical initiated polymerization (polymethacrylate-based network) and photoacid-induced sol-gel reaction (polysiloxane) results in the hybrid network formation. Resulting formulations were characterized with regard to real-time photo-polymerization, water sorption, leached species, neutralization, and mechanical properties. Results from real-time FTIR spectroscopic studies indicated that ethoxy was less reactive than methoxy substituent. The neutralization results demonstrated that the methoxy-containing adhesives have acute and delayed buffering capabilities. The mechanical properties of synthetic copolymers tested in dry conditions were improved via condensation reaction of the hydrolyzed organosilanes. The leaching from methoxy containing copolymers was significantly reduced. The sol-gel reaction provided a chronic and persistent reaction in wet condition-performance that offers potential for reducing secondary decay and increasing the functional lifetime of dental adhesives

Comparative Component Analysis of Exons with Different Splicing Frequencies

Transcriptional isoforms are not just random combinations of exons. What has caused exons to be differentially spliced and whether exons with different splicing frequencies are subjected to divergent regulation by potential elements or splicing signals? Beyond the conventional classification for alternatively spliced exons (ASEs) and constitutively spliced exons (CSEs), we have classified exons from alternatively spliced human genes and their mouse orthologs (12,314 and 5,464, respectively) into four types based on their splicing frequencies. Analysis has indicated that different groups of exons presented divergent compositional and regulatory properties. Interestingly, with the decrease of splicing frequency, exons tend to have greater lengths, higher GC content, and contain more splicing elements and repetitive elements, which seem to imply that the splicing frequency is influenced by such factors. Comparison of non-alternatively spliced (NAS) mouse genes with alternatively spliced human orthologs also suggested that exons with lower splicing frequencies may be newly evolved ones which gained functions with splicing frequencies altered through the evolution. Our findings have revealed for the first time that certain factors may have critical influence on the splicing frequency, suggesting that exons with lower splicing frequencies may originate from old repetitive sequences, with splicing sites altered by mutation, gaining novel functions and become more frequently spliced