LINYONG SONG - Academia.edu (original) (raw)
Papers by LINYONG SONG
Journal of Sol-Gel Science and Technology, 2011
A new strategy to fabricate teardrop-shaped silica particles is presented. Monodispersed teardrop... more A new strategy to fabricate teardrop-shaped silica particles is presented. Monodispersed teardrop-like silica particles were obtained through basic catalyzed solgel process of tetraethoxysilane by employed sodium polyacrylate as soft template. Increasing the salt concentration of solution, the morphology of silica particles can transform from teardrop-like to hollow structures, and finally formed solid particles. The morphologies of silica particles are characterized by TEM and SEM. Our finding can be scaled up for large-scale synthesis of unusual structures of inorganic or composite materials in a predictable manner. This study is expected to provide further understanding of the role of polyelectrolyte in the synthesis of inorganic materials towards design of unusual architectures and functional materials.
Polymers, 2020
The inherent degradation property of most dental resins in the mouth leads to the long-term relea... more The inherent degradation property of most dental resins in the mouth leads to the long-term release of degradation by-products at the adhesive/tooth interface. The by-products increase the virulence of cariogenic bacteria, provoking a degradative positive-feedback loop that leads to physicochemical and mechanical failure. Photoinduced free-radical polymerization and sol‒gel reactions have been coupled to produce a novel autonomous-strengthening adhesive with enhanced hydrolytic stability. This paper investigates the effect of network structure on time-dependent mechanical properties in adhesives with and without autonomous strengthening. Stress relaxation was conducted under 0.2% strain for 8 h followed by 40 h recovery in water. The stress‒time relationship is analyzed by nonlinear least-squares data-fitting. The fitted Prony series predicts the sample’s history under monotonic loading. Results showed that the control failed after the first loading‒unloading‒recovery cycle with per...
Journal of Applied Polymer Science, Apr 1, 2015
Journal of Biomedical Materials Research Part B: Applied Biomaterials
Nearly 100 million of the 170 million composite and amalgam restorations placed annually in the U... more 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, 2019.
ACS Applied Polymer Materials
Applied Sciences
The most common cause for dental composite failures is secondary caries due to invasive bacterial... more The most common cause for dental composite failures is secondary caries due to invasive bacterial colonization of the adhesive/dentin (a/d) interface. Innate material weakness often lead to an insufficient seal between the adhesive and dentin. Consequently, bacterial by-products invade the porous a/d interface leading to material degradation and dental caries. Current approaches to achieve antibacterial properties in these materials continue to raise concerns regarding hypersensitivity and antibiotic resistance. Herein, we have developed a multi-faceted, bio-functionalized approach to overcome the vulnerability of such interfaces. An antimicrobial adhesive formulation was designed using a combination of antimicrobial peptide and a ε-polylysine resin system. Effector molecules boasting innate immunity are brought together with a biopolymer offering a two-fold biomimetic design approach. The selection of ε-polylysine was inspired due to its non-toxic nature and common use as food pres...
Dental materials : official publication of the Academy of Dental Materials, Jan 7, 2018
The objective of this study was to explore the effect of lysine integration to dental adhesives w... more The objective of this study was to explore the effect of lysine integration to dental adhesives with respect to the polymerization kinetics, neutralization capacities in the acidic microenvironment, dynamic mechanical properties, and thermal properties. Lysine was incorporated into liquid resin formulations at 2.5 and 5.0wt % with additional water/ethanol co-solvents. The co-monomer system contained 2-hydroxyethyl-methacrylate (HEMA) and Bisphenol A glycerolate dimethacrylate (BisGMA) with a mass ratio of 45/55. The kinetics of photopolymerization, neutralization capacities, lysine-leaching, dynamic mechanical properties and thermal properties of the control and experimental adhesives were analyzed. The degree of conversion of the experimental adhesive was increased substantially at 2.5wt% lysine as compared to the control. The experimental polymers provided acute neutralization of the acidic microenvironment. Approximately half of the lysine was released from the polymer network wi...
Acta Biomaterialia
Resin-based composite has overtaken dental amalgam as the most popular material for direct restor... more Resin-based composite has overtaken dental amalgam as the most popular material for direct restorative dentistry. In spite of this popularity the clinical lifetime of composite restorations is threatened by recurrent decay. Degradation of the adhesive leads to gaps at the composite/tooth interface-bacteria, bacterial by-products and fluids infiltrate the gaps leading to recurrent decay and composite restoration failure. The durability of resin-dentin bonds is a major problem. We address this problem by synthesizing silyl-functionalized BisGMA (e.g., silyl-BisGMA), formulating dental adhesives with the new monomer and determining the physicochemical properties and leaching characteristics of the silyl-BisGMA adhesives. Silyl-BisGMA was synthesized by stoichiometric amounts of BisGMA and 3-isocyanatopropyl trimethoxysilane (IPTMS). The control adhesive was a mixture based on HEMA/BisGMA (45/55, w/w). In the experimental formulations, BisGMA was partially or completely replaced by silyl-BisGMA. Water miscibility, polymerization behavior (Fourier transform infrared spectroscopy, FTIR), thermal property (modulated differential scanning calorimetry, MDSC), mechanical properties in dry and wet conditions (dynamic mechanical analysis, DMA), and leached species (HPLC) were investigated. Data from all tests were submitted to appropriate statistical analysis (α = 0.05). Silyl-BisGMA-containing adhesives exhibited comparable water miscibility, lower viscosities, and significantly improved degree of conversion of CC bond as compared to the control. After 4 weeks aqueous aging, the glass transition temperature and rubbery moduli of the experimental copolymers were significantly greater than the control (p < 0.05). HPLC results indicated a substantial reduction of leached HEMA (up to 99 wt%) and BisGMA (up to 90 wt%). By introducing silyl-functional group, the new BisGMA derivative exhibited potential as a monomer that can lead to dental adhesives with improved mechanical properties and reduced leaching under conditions relevant to the oral environment. STATEMENT OF SIGNIFICANCE: The low-viscosity adhesive that bonds the composite to the tooth (enamel and dentin) is intended to seal and stabilize the composite/tooth interface, but it degrades leading to a breach at the composite/tooth margin. As the most popular crosslinking monomer in adhesives, Bisphenol A-glycerolate dimethacrylate (BisGMA) has limitations, e.g. susceptible to hydrolysis and concomitant property degradation. A methoxysilyl-functionalized BisGMA derivative (silyl-BisGMA) was introduced in this work to respond to these limitations. Our results indicated that by introducing silyl-BisGMA, higher crosslinked networks were obtained without sacrificing the homogeneity, and the leached amount of HEMA was reduced up to 99%. This novel resin offers potential benefits including prolonging the functional lifetime of dental resin materials.
Acta biomaterialia, Feb 8, 2017
Ingress of bacteria and fluids at the interfacial gaps between the restorative composite biomater... more 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 forma...
Macromolecular Chemistry and Physics
The effects of polymerization kinetics and chemical miscibility on the crosslinking structure and... more 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 ringopening 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.
Dental Materials
To investigate the polymerization kinetics, neutralization behavior, and mechanical properties of... more To investigate the polymerization kinetics, neutralization behavior, and mechanical properties of amine-functionalized dental adhesive cured in the presence of zwitterionic monomer, methacryloyloxyethyl phosphorylcholine (MPC). The control adhesive was a mixture based on HEMA/BisGMA/2-N-morpholinoethyl methacrylate (MEMA) (40/30/30, w/w/w). The control and experimental formulations containing MPC were characterized with regard to water miscibility of liquid resins, photopolymerization kinetics, water sorption and solubility, dynamic mechanical properties and leachables from the polymers (aged in ethanol). The neutralization behavior of the adhesives was determined by monitoring the pH of lactic acid (LA) solution. The water miscibility decreased with increasing MPC amount. The water sorption of experimental copolymer specimen was greater than the control. The addition of 8wt% water led to improved photo-polymerization efficiency for experimental formulations at MPC of 2.5 and 5wt%, and significant reduction in the cumulative amounts of leached HEMA, BisGMA, and MEMA, i.e. 90, 60 and 50% reduction, respectively. The neutralization rate of MPC-containing adhesive was faster than control. The optimal MPC concentration in the formulations was 5wt%. Incompatibility between MEMA and MPC led to a decrease in water miscibility of the liquid resins. Water (at 8wt%) in the MPC-containing formulations (2.5-5wt% MPC) led to higher DC, faster RPmax and significant reduction in leached HEMA, BisGMA, and MEMA. The neutralization rate was enhanced with the addition of MPC in the amine-containing formulation. Promoting the neutralization capability of dentin adhesives could play an important role in reducing recurrent decay at the composite/tooth interface.
RSC advances, 2016
A self-strengthening methacrylate-based dental adhesive system was developed by introducing an ep... more A self-strengthening methacrylate-based dental adhesive system was developed by introducing an epoxy cyclohexyl trimethoxysilane (TS) which contains both epoxy and methoxysilyl functional groups. The experimental formulation, HEMA/BisGMA/TS (22.5/27.5/50, wt%), was polymerized by visible-light. Real-time Fourier transform infrared spectroscopy (FTIR) was used to investigate in situ the free radical polymerization of methacrylate, ring-opening cationic polymerization of epoxy, and photoacid-induced sol-gel reactions. Among the three simultaneous reactions, the reaction rate of the free radical polymerization was the highest and the hydrolysis/condensation rate was the lowest. With 40s-irradiation, the degrees of conversion of the double bond and epoxy groups at 600 s were 73.2±1.2%, 87.9±2.4%, respectively. Hydrolysis of the methoxysilyl group was initially <5%, and increased gradually to about 50% after 48 h dark storage. Photoacids generated through the visible-light-induced rea...
JOM (Warrendale, Pa. : 1989), 2016
The polymerization kinetics of physically separated hydrophobic- and hydrophilic-rich phases of a... more The polymerization kinetics of physically separated hydrophobic- and hydrophilic-rich phases of a model dental adhesive have been investigated. The two phases were prepared from neat resin containing 2-hydroxyethyl methacrylate (HEMA) and bisphenol A glycerolate dimethacrylate (BisGMA) in the ratio of 45:55 (wt/wt). Neat resins containing various combinations of popular photo-initiating compounds, e.g., camphoquinone (CQ), ethyl 4-(dimethylamino)benzoate (EDMAB), 2-(dimethylamino)ethyl methacrylate (DMAEMA) and diphenyliodonium hexafluorophosphate (DPIHP) were prepared. To obtain the two phases 33 wt% of deuterium oxide (D2O) was added to the neat resins. This amount of D2O exceeded the miscibility limit for the resins. The concentration of each component of the photo-initiating system in the two phases was quantified by HPLC. When combined with CQ, DMAEMA is less efficient as a co-initiator compared to EDMAB. The addition of DPIHP as the third component into either CQ/EDMAB or CQ/D...
Acta biomaterialia, Jan 15, 2016
Chemical and enzymatic hydrolysis provoke a cascade of events that undermine methacrylate-based a... more Chemical and enzymatic hydrolysis provoke a cascade of events that undermine methacrylate-based adhesives and the bond formed at the tooth/composite interface. Infiltration of noxious agents, e.g. enzymes, bacteria, and so forth, into the spaces created by the defective bond will ultimately lead to failure of the composite restoration. This paper reports a novel, synthetic resin that provides enhanced hydrolytic stability as a result of intrinsic reinforcement of the polymer network. The behavior of this novel resin, which contains γ-methacryloxyproyl trimethoxysilane (MPS) as its Si-based compound, is reminiscent of self-strengthening properties found in nature. The efforts in this paper are focused on two essential aspects: the visible-light irradiation induced (photoacid-induced) sol-gel reaction and the mechanism leading to intrinsic self-strengthening. The FTIR band at 2840cm(-1) corresponding to CH3 symmetric stretch in -Si-O-CH3 was used to evaluate the sol-gel reaction. Resu...
In recent years, with growing contradiction between energy supply and demand, the more and more h... more In recent years, with growing contradiction between energy supply and demand, the more and more high demand of the environmental protection is needed. The work represented an environment friendly method for recycling of waste rubber and pulp sediment that a new composite material was prepared using pulp sediment as the matrix, used rubber powder as the toughening agent, and sawdust as the reinforcement. The effects of used rubber powder content on the mechanical properties of the pulp sediment and sawdust/pulp sediment were studied by measuring Shore A hardness, tensile stress, and elongationat-break. The morphology of used rubber powder/pulp sediment composites was analyzed by scanning electronic microscopy and transmission electron microscopy. The curing conditions were also discussed. The results showed when the used rubber powder/pulp sediment mass ratio was 8/100, the used rubber powder/pulp sediment sample showed smooth surface, high hardness, compact structure, uniform arrangement, and good compatibility. When the pulp sediment used as the matrix, sawdust as the reinforcement, and used rubber powder as the toughening agent, the proper recipe of the composites was 100 phr pulp sediment, 30 phr sawdust, and 10 phr used rubber powder. The mechanical properties of the used rubber powder/pulp sediment were greater than those of pure pulp sediment and used rubber powder/sawdust/pulp sediment. The best curing conditions for the used rubber powder/pulp sediment composites were at 150°C under 5 MPa for 15 min. The study on used rubber powder modified pulp sediment, exploits a new way to recycle used rubber powder and pulp sediment, not only benefit environment purification, but also reduce cost of sheet materials, and develops a new way for the economy and environment protection.
Dental materials : official publication of the Academy of Dental Materials, Jan 4, 2016
A novel tertiary amine compound containing three methacrylate-urethane groups was synthesized for... more A novel tertiary amine compound containing three methacrylate-urethane groups was synthesized for application in dentin adhesives. The synthesis, photopolymerization kinetics, and leaching were examined in an earlier study using this novel compound as the co-initiator (0.5 and 1.75wt% based on the total resin mass). The objective of this work was to investigate the potential of TUMA (8-(2-(((2-(methacryloyloxy)ethyl)carbamoyl)oxy)propyl)-6,10-dimethyl-4,12-dioxo-5,11-dioxa-3,8,13-triazapentadecane-1,15-diyl bis(2-methylacrylate)) to serve simultaneously as a co-initiator and co-monomer (15-45wt% based on the total resin mass) in dentin adhesive formulations. The polymerization kinetics, water sorption and dynamic mechanical properties of these novel formulations were determined. The monomer system contained Bisphenol A glycerolate dimethacrylate (BisGMA), 2-hydroxyethylmethacrylate (HEMA) and TUMA (synthesized in our lab) at the mass ratio of 45/(55-x)/x. Two photoinitiator (PI) sys...
Journal of dentistry, 2015
The objective of this work was to investigate the polymerization behavior, neutralization capabil... more 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). 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 1mM lactic acid (LA) solution, in which the adhesive polymers were soaked. With increasing MEMA concentrations, experimental copolymers showed higher water sorption, lower glass transition temperature and lower crosslinking density comp...
Journal of Sol-Gel Science and Technology, 2011
A new strategy to fabricate teardrop-shaped silica particles is presented. Monodispersed teardrop... more A new strategy to fabricate teardrop-shaped silica particles is presented. Monodispersed teardrop-like silica particles were obtained through basic catalyzed solgel process of tetraethoxysilane by employed sodium polyacrylate as soft template. Increasing the salt concentration of solution, the morphology of silica particles can transform from teardrop-like to hollow structures, and finally formed solid particles. The morphologies of silica particles are characterized by TEM and SEM. Our finding can be scaled up for large-scale synthesis of unusual structures of inorganic or composite materials in a predictable manner. This study is expected to provide further understanding of the role of polyelectrolyte in the synthesis of inorganic materials towards design of unusual architectures and functional materials.
Polymers, 2020
The inherent degradation property of most dental resins in the mouth leads to the long-term relea... more The inherent degradation property of most dental resins in the mouth leads to the long-term release of degradation by-products at the adhesive/tooth interface. The by-products increase the virulence of cariogenic bacteria, provoking a degradative positive-feedback loop that leads to physicochemical and mechanical failure. Photoinduced free-radical polymerization and sol‒gel reactions have been coupled to produce a novel autonomous-strengthening adhesive with enhanced hydrolytic stability. This paper investigates the effect of network structure on time-dependent mechanical properties in adhesives with and without autonomous strengthening. Stress relaxation was conducted under 0.2% strain for 8 h followed by 40 h recovery in water. The stress‒time relationship is analyzed by nonlinear least-squares data-fitting. The fitted Prony series predicts the sample’s history under monotonic loading. Results showed that the control failed after the first loading‒unloading‒recovery cycle with per...
Journal of Applied Polymer Science, Apr 1, 2015
Journal of Biomedical Materials Research Part B: Applied Biomaterials
Nearly 100 million of the 170 million composite and amalgam restorations placed annually in the U... more 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, 2019.
ACS Applied Polymer Materials
Applied Sciences
The most common cause for dental composite failures is secondary caries due to invasive bacterial... more The most common cause for dental composite failures is secondary caries due to invasive bacterial colonization of the adhesive/dentin (a/d) interface. Innate material weakness often lead to an insufficient seal between the adhesive and dentin. Consequently, bacterial by-products invade the porous a/d interface leading to material degradation and dental caries. Current approaches to achieve antibacterial properties in these materials continue to raise concerns regarding hypersensitivity and antibiotic resistance. Herein, we have developed a multi-faceted, bio-functionalized approach to overcome the vulnerability of such interfaces. An antimicrobial adhesive formulation was designed using a combination of antimicrobial peptide and a ε-polylysine resin system. Effector molecules boasting innate immunity are brought together with a biopolymer offering a two-fold biomimetic design approach. The selection of ε-polylysine was inspired due to its non-toxic nature and common use as food pres...
Dental materials : official publication of the Academy of Dental Materials, Jan 7, 2018
The objective of this study was to explore the effect of lysine integration to dental adhesives w... more The objective of this study was to explore the effect of lysine integration to dental adhesives with respect to the polymerization kinetics, neutralization capacities in the acidic microenvironment, dynamic mechanical properties, and thermal properties. Lysine was incorporated into liquid resin formulations at 2.5 and 5.0wt % with additional water/ethanol co-solvents. The co-monomer system contained 2-hydroxyethyl-methacrylate (HEMA) and Bisphenol A glycerolate dimethacrylate (BisGMA) with a mass ratio of 45/55. The kinetics of photopolymerization, neutralization capacities, lysine-leaching, dynamic mechanical properties and thermal properties of the control and experimental adhesives were analyzed. The degree of conversion of the experimental adhesive was increased substantially at 2.5wt% lysine as compared to the control. The experimental polymers provided acute neutralization of the acidic microenvironment. Approximately half of the lysine was released from the polymer network wi...
Acta Biomaterialia
Resin-based composite has overtaken dental amalgam as the most popular material for direct restor... more Resin-based composite has overtaken dental amalgam as the most popular material for direct restorative dentistry. In spite of this popularity the clinical lifetime of composite restorations is threatened by recurrent decay. Degradation of the adhesive leads to gaps at the composite/tooth interface-bacteria, bacterial by-products and fluids infiltrate the gaps leading to recurrent decay and composite restoration failure. The durability of resin-dentin bonds is a major problem. We address this problem by synthesizing silyl-functionalized BisGMA (e.g., silyl-BisGMA), formulating dental adhesives with the new monomer and determining the physicochemical properties and leaching characteristics of the silyl-BisGMA adhesives. Silyl-BisGMA was synthesized by stoichiometric amounts of BisGMA and 3-isocyanatopropyl trimethoxysilane (IPTMS). The control adhesive was a mixture based on HEMA/BisGMA (45/55, w/w). In the experimental formulations, BisGMA was partially or completely replaced by silyl-BisGMA. Water miscibility, polymerization behavior (Fourier transform infrared spectroscopy, FTIR), thermal property (modulated differential scanning calorimetry, MDSC), mechanical properties in dry and wet conditions (dynamic mechanical analysis, DMA), and leached species (HPLC) were investigated. Data from all tests were submitted to appropriate statistical analysis (α = 0.05). Silyl-BisGMA-containing adhesives exhibited comparable water miscibility, lower viscosities, and significantly improved degree of conversion of CC bond as compared to the control. After 4 weeks aqueous aging, the glass transition temperature and rubbery moduli of the experimental copolymers were significantly greater than the control (p < 0.05). HPLC results indicated a substantial reduction of leached HEMA (up to 99 wt%) and BisGMA (up to 90 wt%). By introducing silyl-functional group, the new BisGMA derivative exhibited potential as a monomer that can lead to dental adhesives with improved mechanical properties and reduced leaching under conditions relevant to the oral environment. STATEMENT OF SIGNIFICANCE: The low-viscosity adhesive that bonds the composite to the tooth (enamel and dentin) is intended to seal and stabilize the composite/tooth interface, but it degrades leading to a breach at the composite/tooth margin. As the most popular crosslinking monomer in adhesives, Bisphenol A-glycerolate dimethacrylate (BisGMA) has limitations, e.g. susceptible to hydrolysis and concomitant property degradation. A methoxysilyl-functionalized BisGMA derivative (silyl-BisGMA) was introduced in this work to respond to these limitations. Our results indicated that by introducing silyl-BisGMA, higher crosslinked networks were obtained without sacrificing the homogeneity, and the leached amount of HEMA was reduced up to 99%. This novel resin offers potential benefits including prolonging the functional lifetime of dental resin materials.
Acta biomaterialia, Feb 8, 2017
Ingress of bacteria and fluids at the interfacial gaps between the restorative composite biomater... more 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 forma...
Macromolecular Chemistry and Physics
The effects of polymerization kinetics and chemical miscibility on the crosslinking structure and... more 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 ringopening 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.
Dental Materials
To investigate the polymerization kinetics, neutralization behavior, and mechanical properties of... more To investigate the polymerization kinetics, neutralization behavior, and mechanical properties of amine-functionalized dental adhesive cured in the presence of zwitterionic monomer, methacryloyloxyethyl phosphorylcholine (MPC). The control adhesive was a mixture based on HEMA/BisGMA/2-N-morpholinoethyl methacrylate (MEMA) (40/30/30, w/w/w). The control and experimental formulations containing MPC were characterized with regard to water miscibility of liquid resins, photopolymerization kinetics, water sorption and solubility, dynamic mechanical properties and leachables from the polymers (aged in ethanol). The neutralization behavior of the adhesives was determined by monitoring the pH of lactic acid (LA) solution. The water miscibility decreased with increasing MPC amount. The water sorption of experimental copolymer specimen was greater than the control. The addition of 8wt% water led to improved photo-polymerization efficiency for experimental formulations at MPC of 2.5 and 5wt%, and significant reduction in the cumulative amounts of leached HEMA, BisGMA, and MEMA, i.e. 90, 60 and 50% reduction, respectively. The neutralization rate of MPC-containing adhesive was faster than control. The optimal MPC concentration in the formulations was 5wt%. Incompatibility between MEMA and MPC led to a decrease in water miscibility of the liquid resins. Water (at 8wt%) in the MPC-containing formulations (2.5-5wt% MPC) led to higher DC, faster RPmax and significant reduction in leached HEMA, BisGMA, and MEMA. The neutralization rate was enhanced with the addition of MPC in the amine-containing formulation. Promoting the neutralization capability of dentin adhesives could play an important role in reducing recurrent decay at the composite/tooth interface.
RSC advances, 2016
A self-strengthening methacrylate-based dental adhesive system was developed by introducing an ep... more A self-strengthening methacrylate-based dental adhesive system was developed by introducing an epoxy cyclohexyl trimethoxysilane (TS) which contains both epoxy and methoxysilyl functional groups. The experimental formulation, HEMA/BisGMA/TS (22.5/27.5/50, wt%), was polymerized by visible-light. Real-time Fourier transform infrared spectroscopy (FTIR) was used to investigate in situ the free radical polymerization of methacrylate, ring-opening cationic polymerization of epoxy, and photoacid-induced sol-gel reactions. Among the three simultaneous reactions, the reaction rate of the free radical polymerization was the highest and the hydrolysis/condensation rate was the lowest. With 40s-irradiation, the degrees of conversion of the double bond and epoxy groups at 600 s were 73.2±1.2%, 87.9±2.4%, respectively. Hydrolysis of the methoxysilyl group was initially <5%, and increased gradually to about 50% after 48 h dark storage. Photoacids generated through the visible-light-induced rea...
JOM (Warrendale, Pa. : 1989), 2016
The polymerization kinetics of physically separated hydrophobic- and hydrophilic-rich phases of a... more The polymerization kinetics of physically separated hydrophobic- and hydrophilic-rich phases of a model dental adhesive have been investigated. The two phases were prepared from neat resin containing 2-hydroxyethyl methacrylate (HEMA) and bisphenol A glycerolate dimethacrylate (BisGMA) in the ratio of 45:55 (wt/wt). Neat resins containing various combinations of popular photo-initiating compounds, e.g., camphoquinone (CQ), ethyl 4-(dimethylamino)benzoate (EDMAB), 2-(dimethylamino)ethyl methacrylate (DMAEMA) and diphenyliodonium hexafluorophosphate (DPIHP) were prepared. To obtain the two phases 33 wt% of deuterium oxide (D2O) was added to the neat resins. This amount of D2O exceeded the miscibility limit for the resins. The concentration of each component of the photo-initiating system in the two phases was quantified by HPLC. When combined with CQ, DMAEMA is less efficient as a co-initiator compared to EDMAB. The addition of DPIHP as the third component into either CQ/EDMAB or CQ/D...
Acta biomaterialia, Jan 15, 2016
Chemical and enzymatic hydrolysis provoke a cascade of events that undermine methacrylate-based a... more Chemical and enzymatic hydrolysis provoke a cascade of events that undermine methacrylate-based adhesives and the bond formed at the tooth/composite interface. Infiltration of noxious agents, e.g. enzymes, bacteria, and so forth, into the spaces created by the defective bond will ultimately lead to failure of the composite restoration. This paper reports a novel, synthetic resin that provides enhanced hydrolytic stability as a result of intrinsic reinforcement of the polymer network. The behavior of this novel resin, which contains γ-methacryloxyproyl trimethoxysilane (MPS) as its Si-based compound, is reminiscent of self-strengthening properties found in nature. The efforts in this paper are focused on two essential aspects: the visible-light irradiation induced (photoacid-induced) sol-gel reaction and the mechanism leading to intrinsic self-strengthening. The FTIR band at 2840cm(-1) corresponding to CH3 symmetric stretch in -Si-O-CH3 was used to evaluate the sol-gel reaction. Resu...
In recent years, with growing contradiction between energy supply and demand, the more and more h... more In recent years, with growing contradiction between energy supply and demand, the more and more high demand of the environmental protection is needed. The work represented an environment friendly method for recycling of waste rubber and pulp sediment that a new composite material was prepared using pulp sediment as the matrix, used rubber powder as the toughening agent, and sawdust as the reinforcement. The effects of used rubber powder content on the mechanical properties of the pulp sediment and sawdust/pulp sediment were studied by measuring Shore A hardness, tensile stress, and elongationat-break. The morphology of used rubber powder/pulp sediment composites was analyzed by scanning electronic microscopy and transmission electron microscopy. The curing conditions were also discussed. The results showed when the used rubber powder/pulp sediment mass ratio was 8/100, the used rubber powder/pulp sediment sample showed smooth surface, high hardness, compact structure, uniform arrangement, and good compatibility. When the pulp sediment used as the matrix, sawdust as the reinforcement, and used rubber powder as the toughening agent, the proper recipe of the composites was 100 phr pulp sediment, 30 phr sawdust, and 10 phr used rubber powder. The mechanical properties of the used rubber powder/pulp sediment were greater than those of pure pulp sediment and used rubber powder/sawdust/pulp sediment. The best curing conditions for the used rubber powder/pulp sediment composites were at 150°C under 5 MPa for 15 min. The study on used rubber powder modified pulp sediment, exploits a new way to recycle used rubber powder and pulp sediment, not only benefit environment purification, but also reduce cost of sheet materials, and develops a new way for the economy and environment protection.
Dental materials : official publication of the Academy of Dental Materials, Jan 4, 2016
A novel tertiary amine compound containing three methacrylate-urethane groups was synthesized for... more A novel tertiary amine compound containing three methacrylate-urethane groups was synthesized for application in dentin adhesives. The synthesis, photopolymerization kinetics, and leaching were examined in an earlier study using this novel compound as the co-initiator (0.5 and 1.75wt% based on the total resin mass). The objective of this work was to investigate the potential of TUMA (8-(2-(((2-(methacryloyloxy)ethyl)carbamoyl)oxy)propyl)-6,10-dimethyl-4,12-dioxo-5,11-dioxa-3,8,13-triazapentadecane-1,15-diyl bis(2-methylacrylate)) to serve simultaneously as a co-initiator and co-monomer (15-45wt% based on the total resin mass) in dentin adhesive formulations. The polymerization kinetics, water sorption and dynamic mechanical properties of these novel formulations were determined. The monomer system contained Bisphenol A glycerolate dimethacrylate (BisGMA), 2-hydroxyethylmethacrylate (HEMA) and TUMA (synthesized in our lab) at the mass ratio of 45/(55-x)/x. Two photoinitiator (PI) sys...
Journal of dentistry, 2015
The objective of this work was to investigate the polymerization behavior, neutralization capabil... more 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). 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 1mM lactic acid (LA) solution, in which the adhesive polymers were soaked. With increasing MEMA concentrations, experimental copolymers showed higher water sorption, lower glass transition temperature and lower crosslinking density comp...