Carbon nanofibers have revolutionized nanotechnology due to their potential applications in emerging frontiers of research and industrial sectors. This can be attributed to their superior properties such as higher mec...Carbon nanofibers have revolutionized nanotechnology due to their potential applications in emerging frontiers of research and industrial sectors. This can be attributed to their superior properties such as higher mechanical strength, unique surface characteristics, and improved adherence that is transmitted into the polymer matrix to form a nanocomposite with improved properties. Polymethyl methacrylate is a common carbon source for the synthesis of carbon nanofibres of its high mechanical strength, thermal stability, and low moisture and water absorbing capacity that allows its products to have several applications. In this work, we report the successful electrospinning of carbon nanofibres from Poly methyl methacrylate and functionalizing the resulting carbon nanofibres. The functionalized carbon nanofibres were analyzed to determine their solubility/dispersion in selected organic solvents, then characterized using Fourier transform infra-red spectroscopy, Raman spectroscopy, scanning electron microscopy combined with Energy dispersive spectroscopy and Thermalgravimetric analysis.展开更多
A series of homo and copolymers of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, tetrahydrofuran, and benzene) have been investigated by free radical polymerization method. The sa...A series of homo and copolymers of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, tetrahydrofuran, and benzene) have been investigated by free radical polymerization method. The samples obtained from the synthesis were characterized by Fourier Transform-Infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (<sup>1</sup>H NMR), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). The results show that the synthesis of the polymers is more feasible under neat conditions rather than solvent directed reaction. Moreover, the DSC data shows that the polystyrene obtained is amorphous in nature and therefore displayed only a glass transition signal rather than crystallization and melting peaks. In addition, this study indicates that homolopolymerization of styrene via free radical polymerization tends to be preferable in less polar solvents like THF than in non-polar solvents like benzene. Benzene might destabilize the formation of the reactive radicals leading to the formation of the products. In summary, the homolpolymerization of styrene is more feasible than the homopolymerization 2-hydroxyethyl methacrylate under the experimental setup used. Styrene is more reactive than 2-hydroxyethyl methacrylate than free radical polymerization reaction due in part of the generation of the benzylic radical intermediate which is more stable leading to the formation of products than alkyl radical which are less stable. Furthermore, polymerization of styrene under neat conditions is preferable in solvent-assisted environments. The choice of solvent for the synthesis of these polymers is crucial and therefore the selection of solvent that leads to the formation of a more stable reaction intermediate is more favorable. It is worth noting that the structure of the proposed copolymer consists of a highly polar and hydrophilic monomer, 2-hydroxyethyl methacrylate and a highly non-polar and hydrophobic monomer, styrene. These functionalities constitute an amphiphilic copolymer with diverse characteristics. A plausible explanation underlying our observations is that the reaction conditions employed in the synthesis of these copolymers might not be the right route required under free radical polymerization.展开更多
The viscoelastic behavior of polymer optical fibers has garnered increasing interest due to their application as fiber sensors. A common technique for determining the storage and loss modulus of optical fibers involve...The viscoelastic behavior of polymer optical fibers has garnered increasing interest due to their application as fiber sensors. A common technique for determining the storage and loss modulus of optical fibers involves fitting an exponential model to damped oscillatory motion. However, few studies address the challenge of identifying and specifying the various internal and external contributions to damping. The damping of a simple pendulum is influenced by several factors, such as the friction at the pivot and air drag on the string. In this case, the bob and the string are a coupled oscillating system, for its study, we used a bare polymethyl methacrylate optical fiber as a non-ideal, extensible, and viscoelastic string. The optical fiber was attached to a quasi-punctual support to minimize friction at the pivot. We considered the contribution to the damping of the pendulum due to air drag on the bob by varying the bob’s frontal area and extrapolating to the limit case where the frontal area of the bob tends to zero. This approach allowed us to calculate the damping coefficient solely due to the viscoelastic properties of the string. By conducting a dynamic analysis of the forces along the string and considering the interaction between the string and bob through the viscosity, we calculated the complex Young’s modulus, a key parameter in understanding the viscoelastic properties of the system.展开更多
Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Th...Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Theirchemical structures were characterized by ~1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuCl_2/bipy as the initiating system. The resultant well-definedpolymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization ofmenthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.展开更多
Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization...Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization, multi-step emulsion polymerization, and soapless polymerization. Allyl methacylate (ALMA) and ethylene glycol dimethacrylate (EGDMA) were selected as crosslinking reagents for core polymerization. Methacrylic acid (MAA) was used as functional co-monomer with methyl methacrylate as shell component. The content of vinyl groups in PBA rubbery core increased with the amount of crosslinking reagents. The core-shell ratio affected great on the morphology of the complex particles. Furthermore, the amounts of carboxyl on the surface of core-shell particles, copolymerized with acrylic acid, were determined by potentiometric titration. Results showed that methylacrylic acid was distributed mostly on the surface of particles.展开更多
Novel Mg O–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein(MAL) with methanol to methyl methacrylate(MMA). The Mg O–SBA-15 supports were synthesized with different magnesia load...Novel Mg O–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein(MAL) with methanol to methyl methacrylate(MMA). The Mg O–SBA-15 supports were synthesized with different magnesia loadings from different magnesium precursors and hydrochloric acid molar concentrations. The Mg O–SBA-15 supports and Pd–Pb/Mg O–SBA-15 catalysts were characterized by several analysis methods. The results revealed that the addition of Mg O improved the ordered structure of SBA-15 supports and provided surface alkalinity of SBA-15 supports. The average size of the Pd3 Pb particles on magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts was smaller than that on the pure silica-based Pd–Pb/SBA-15 catalysts. The experiments on catalyst performance showed that the magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts had higher activity than pure silica-based Pd–Pb/SBA-15 catalysts, showing the strong dependence of catalytic activity on the average size of active particles. The difference of activity between Pd–Pb/SBA-15 catalysts and Pd–Pb/Mg O–SBA-15 catalysts was due to the discrepant structural properties and surface alkalinity provided by Mg O, which led to the different Pd3 Pb particle sizes and then resulted in the different number of active sites. Besides magnesia loadings, other factors, such as hydrochloric acid molar concentration and magnesium precursors, had considerable influences on the catalytic activity.展开更多
Atom transfer radical polymerization （ATRP） of methyl methacrylate （MMA） employing ethyl 2-bromoisobutyrate （EBiB）/ CuBr as the initiating system was investigated at 50 ℃ in the absence of any additional ligand...Atom transfer radical polymerization （ATRP） of methyl methacrylate （MMA） employing ethyl 2-bromoisobutyrate （EBiB）/ CuBr as the initiating system was investigated at 50 ℃ in the absence of any additional ligand in the three room temperature ionic liquids （RTILs）, 1-methyl-imidazolium acetate （[mim][CH3COO]）, 1-methylimidazolium propionate （[mim][CH3CH2COO]） and 1-methylimidazolium butyrate （[mim][CH3CH2CH2COO]）, respectively. All the polymerization in the three RTILs proceeded in a well-controlled manner. The sequence of the apparent polymerization rate constants was kapp（[mim][CH3COO]） 〉 kapp（[mim] [CH3CH2COO]） 〉 kapp （[mim][CH3CH2CH2COO]）.展开更多
Antibacterial adhesives are promising to inhibit biofilms and secondary caries. The objectives of this study were to synthesize and incorporate quaternary ammonium methacrylates into adhesives, and investigate the alk...Antibacterial adhesives are promising to inhibit biofilms and secondary caries. The objectives of this study were to synthesize and incorporate quaternary ammonium methacrylates into adhesives, and investigate the alkyl chain length effects on three-dimensional biofilms adherent on adhesives for the first time. Six quaternary ammonium methacrylates with chain lengths of 3, 6, 9, 12, 16 and 18 were synthesized and incorporated into Scotchbond Multi-Purpose. Streptococcus mutans bacteria were cultured on resin to form biofilms. Confocal laser scanning microscopy was used to measure biofilm thickness, live/dead volumes and live-bacteria percentage vs. distance from resin surface. Biofilm thickness was the greatest for Scotchbond control; it decreased with increasing chain length, reaching a minimum at chain length 16. Live-biofilm volume had a similar trend. Dead-biofilm volume increased with increasing chain length. The adhesive with chain length 9 had 37% live bacteria near resin surface, but close to 100% live bacteria in the biofilm top section. For chain length 16, there were nearly 0% live bacteria throughout the three-dimensional biofilm. In conclusion, strong antibacterial activity was achieved by adding quaternary ammonium into adhesive, with biofilm thickness and live-biofilm volume decreasing as chain length was increased from 3 to 16. Antibacterial adhesives typically only inhibited bacteria close to its surface; however, adhesive with chain length 16 had mostly dead bacteria in the entire three-dimensional biofilm. Antibacterial adhesive with chain length 16 is promising to inhibit biofilms at the margins and combat secondary caries.展开更多
Synthesis and characterization of the copolymers （PAG） of α-methyl styrene （AMS） and glycidyl methacrylate （GMA） are presented. The copolymers of PAG were characterized by gel permeation chromatography （GPC）,...Synthesis and characterization of the copolymers （PAG） of α-methyl styrene （AMS） and glycidyl methacrylate （GMA） are presented. The copolymers of PAG were characterized by gel permeation chromatography （GPC）, Fourier transform infrared spectroscopy （FTIR）, nuclear magnetic resonance （^1H-NMR） and thermogravimetery （TG）. Based on the copolymer compositions determined by ^1H-NMR, the reactivity ratios of AMS and GMA were found to be 0.105 ± 0.012 and 0.883 ± 0.046 respectively by Kelen-Tudos method. TG revealed that thermal stability of the copolymers decreased with increasing the AMS content in the copolymers, which indicated that the degradation was mainly caused by the chain scission of AMS-containing structures. Under heating, the copolymers depolymerize at their weak bonds and form chain radicals, which could further initiate other chemical reactions.展开更多
Objective To evaluate the genotoxic and nongenotoxic effects of short-term exposure to glycidyl mathacrylate (GMA) on human lung fibroblast cells (2BS cells) in vitro. Methods DNA strand breakage was determined by sin...Objective To evaluate the genotoxic and nongenotoxic effects of short-term exposure to glycidyl mathacrylate (GMA) on human lung fibroblast cells (2BS cells) in vitro. Methods DNA strand breakage was determined by single cell gel electrophoresis, and DNA ladder formation assay and flow cytometric analysis were carried out to detect apoptic responses of cells to GMA exposure. The HPRT gene mutation assay was used to evaluate the mutagenicity, and the effect of GMA on gap junctional intercellular communication (GJIC) in the exposed cells was examined with the scrape loading/dye transfer technique. The ability of GMA to transform 2BS cells was also tested by an in vitro cell transformation assay. Results Exposure to GMA resulted in a dose-dependent increase in DNA strand breaks but not apoptic responses. GMA was also shown to significantly induce HPRT gene mutations and morphological transformation in 2BS cells in vitro. In contrast, GMA produced a concentration-dependent inhibition of GJIC. Conclusions GMA elicits both genotoxic and nongenotoxic effects on 2BS cells in vitro. The induction of DNA damage and gene mutations and inhibition of GJIC by GMA may casually contribute to GMA-induced cell transformation.展开更多
文摘Carbon nanofibers have revolutionized nanotechnology due to their potential applications in emerging frontiers of research and industrial sectors. This can be attributed to their superior properties such as higher mechanical strength, unique surface characteristics, and improved adherence that is transmitted into the polymer matrix to form a nanocomposite with improved properties. Polymethyl methacrylate is a common carbon source for the synthesis of carbon nanofibres of its high mechanical strength, thermal stability, and low moisture and water absorbing capacity that allows its products to have several applications. In this work, we report the successful electrospinning of carbon nanofibres from Poly methyl methacrylate and functionalizing the resulting carbon nanofibres. The functionalized carbon nanofibres were analyzed to determine their solubility/dispersion in selected organic solvents, then characterized using Fourier transform infra-red spectroscopy, Raman spectroscopy, scanning electron microscopy combined with Energy dispersive spectroscopy and Thermalgravimetric analysis.
文摘A series of homo and copolymers of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, tetrahydrofuran, and benzene) have been investigated by free radical polymerization method. The samples obtained from the synthesis were characterized by Fourier Transform-Infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (<sup>1</sup>H NMR), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). The results show that the synthesis of the polymers is more feasible under neat conditions rather than solvent directed reaction. Moreover, the DSC data shows that the polystyrene obtained is amorphous in nature and therefore displayed only a glass transition signal rather than crystallization and melting peaks. In addition, this study indicates that homolopolymerization of styrene via free radical polymerization tends to be preferable in less polar solvents like THF than in non-polar solvents like benzene. Benzene might destabilize the formation of the reactive radicals leading to the formation of the products. In summary, the homolpolymerization of styrene is more feasible than the homopolymerization 2-hydroxyethyl methacrylate under the experimental setup used. Styrene is more reactive than 2-hydroxyethyl methacrylate than free radical polymerization reaction due in part of the generation of the benzylic radical intermediate which is more stable leading to the formation of products than alkyl radical which are less stable. Furthermore, polymerization of styrene under neat conditions is preferable in solvent-assisted environments. The choice of solvent for the synthesis of these polymers is crucial and therefore the selection of solvent that leads to the formation of a more stable reaction intermediate is more favorable. It is worth noting that the structure of the proposed copolymer consists of a highly polar and hydrophilic monomer, 2-hydroxyethyl methacrylate and a highly non-polar and hydrophobic monomer, styrene. These functionalities constitute an amphiphilic copolymer with diverse characteristics. A plausible explanation underlying our observations is that the reaction conditions employed in the synthesis of these copolymers might not be the right route required under free radical polymerization.
文摘The viscoelastic behavior of polymer optical fibers has garnered increasing interest due to their application as fiber sensors. A common technique for determining the storage and loss modulus of optical fibers involves fitting an exponential model to damped oscillatory motion. However, few studies address the challenge of identifying and specifying the various internal and external contributions to damping. The damping of a simple pendulum is influenced by several factors, such as the friction at the pivot and air drag on the string. In this case, the bob and the string are a coupled oscillating system, for its study, we used a bare polymethyl methacrylate optical fiber as a non-ideal, extensible, and viscoelastic string. The optical fiber was attached to a quasi-punctual support to minimize friction at the pivot. We considered the contribution to the damping of the pendulum due to air drag on the bob by varying the bob’s frontal area and extrapolating to the limit case where the frontal area of the bob tends to zero. This approach allowed us to calculate the damping coefficient solely due to the viscoelastic properties of the string. By conducting a dynamic analysis of the forces along the string and considering the interaction between the string and bob through the viscosity, we calculated the complex Young’s modulus, a key parameter in understanding the viscoelastic properties of the system.
基金This work was supported by the National Natural Science Foundation of China (Grants 20174001, 29992590-4) and the Ministry of Education of China for the teaching and research award fund for outstanding young teacher in higher education institutions.
文摘Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Theirchemical structures were characterized by ~1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuCl_2/bipy as the initiating system. The resultant well-definedpolymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization ofmenthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.
文摘Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization, multi-step emulsion polymerization, and soapless polymerization. Allyl methacylate (ALMA) and ethylene glycol dimethacrylate (EGDMA) were selected as crosslinking reagents for core polymerization. Methacrylic acid (MAA) was used as functional co-monomer with methyl methacrylate as shell component. The content of vinyl groups in PBA rubbery core increased with the amount of crosslinking reagents. The core-shell ratio affected great on the morphology of the complex particles. Furthermore, the amounts of carboxyl on the surface of core-shell particles, copolymerized with acrylic acid, were determined by potentiometric titration. Results showed that methylacrylic acid was distributed mostly on the surface of particles.
基金Supported by the Key Program of the National Natural Science Foundation of China(21036007)the National High-Tech Project of China(2012AA062903)
文摘Novel Mg O–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein(MAL) with methanol to methyl methacrylate(MMA). The Mg O–SBA-15 supports were synthesized with different magnesia loadings from different magnesium precursors and hydrochloric acid molar concentrations. The Mg O–SBA-15 supports and Pd–Pb/Mg O–SBA-15 catalysts were characterized by several analysis methods. The results revealed that the addition of Mg O improved the ordered structure of SBA-15 supports and provided surface alkalinity of SBA-15 supports. The average size of the Pd3 Pb particles on magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts was smaller than that on the pure silica-based Pd–Pb/SBA-15 catalysts. The experiments on catalyst performance showed that the magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts had higher activity than pure silica-based Pd–Pb/SBA-15 catalysts, showing the strong dependence of catalytic activity on the average size of active particles. The difference of activity between Pd–Pb/SBA-15 catalysts and Pd–Pb/Mg O–SBA-15 catalysts was due to the discrepant structural properties and surface alkalinity provided by Mg O, which led to the different Pd3 Pb particle sizes and then resulted in the different number of active sites. Besides magnesia loadings, other factors, such as hydrochloric acid molar concentration and magnesium precursors, had considerable influences on the catalytic activity.
基金Financial support from Zhejiang Provincial Natural Science Foundation （No.R203154, Y405124） is gratefully acknowledged.
文摘Atom transfer radical polymerization （ATRP） of methyl methacrylate （MMA） employing ethyl 2-bromoisobutyrate （EBiB）/ CuBr as the initiating system was investigated at 50 ℃ in the absence of any additional ligand in the three room temperature ionic liquids （RTILs）, 1-methyl-imidazolium acetate （[mim][CH3COO]）, 1-methylimidazolium propionate （[mim][CH3CH2COO]） and 1-methylimidazolium butyrate （[mim][CH3CH2CH2COO]）, respectively. All the polymerization in the three RTILs proceeded in a well-controlled manner. The sequence of the apparent polymerization rate constants was kapp（[mim][CH3COO]） 〉 kapp（[mim] [CH3CH2COO]） 〉 kapp （[mim][CH3CH2CH2COO]）.
基金supported by NIH R01 DE17974West China School of Stomatologya Seed Grant from Department of Endodontics,Prosthodontics and Operative Dentistry,University of Maryland
文摘Antibacterial adhesives are promising to inhibit biofilms and secondary caries. The objectives of this study were to synthesize and incorporate quaternary ammonium methacrylates into adhesives, and investigate the alkyl chain length effects on three-dimensional biofilms adherent on adhesives for the first time. Six quaternary ammonium methacrylates with chain lengths of 3, 6, 9, 12, 16 and 18 were synthesized and incorporated into Scotchbond Multi-Purpose. Streptococcus mutans bacteria were cultured on resin to form biofilms. Confocal laser scanning microscopy was used to measure biofilm thickness, live/dead volumes and live-bacteria percentage vs. distance from resin surface. Biofilm thickness was the greatest for Scotchbond control; it decreased with increasing chain length, reaching a minimum at chain length 16. Live-biofilm volume had a similar trend. Dead-biofilm volume increased with increasing chain length. The adhesive with chain length 9 had 37% live bacteria near resin surface, but close to 100% live bacteria in the biofilm top section. For chain length 16, there were nearly 0% live bacteria throughout the three-dimensional biofilm. In conclusion, strong antibacterial activity was achieved by adding quaternary ammonium into adhesive, with biofilm thickness and live-biofilm volume decreasing as chain length was increased from 3 to 16. Antibacterial adhesives typically only inhibited bacteria close to its surface; however, adhesive with chain length 16 had mostly dead bacteria in the entire three-dimensional biofilm. Antibacterial adhesive with chain length 16 is promising to inhibit biofilms at the margins and combat secondary caries.
文摘Synthesis and characterization of the copolymers （PAG） of α-methyl styrene （AMS） and glycidyl methacrylate （GMA） are presented. The copolymers of PAG were characterized by gel permeation chromatography （GPC）, Fourier transform infrared spectroscopy （FTIR）, nuclear magnetic resonance （^1H-NMR） and thermogravimetery （TG）. Based on the copolymer compositions determined by ^1H-NMR, the reactivity ratios of AMS and GMA were found to be 0.105 ± 0.012 and 0.883 ± 0.046 respectively by Kelen-Tudos method. TG revealed that thermal stability of the copolymers decreased with increasing the AMS content in the copolymers, which indicated that the degradation was mainly caused by the chain scission of AMS-containing structures. Under heating, the copolymers depolymerize at their weak bonds and form chain radicals, which could further initiate other chemical reactions.
基金This work was supported by a grant from the National Natural Science Foundation of China (grant no. 39840017).
文摘Objective To evaluate the genotoxic and nongenotoxic effects of short-term exposure to glycidyl mathacrylate (GMA) on human lung fibroblast cells (2BS cells) in vitro. Methods DNA strand breakage was determined by single cell gel electrophoresis, and DNA ladder formation assay and flow cytometric analysis were carried out to detect apoptic responses of cells to GMA exposure. The HPRT gene mutation assay was used to evaluate the mutagenicity, and the effect of GMA on gap junctional intercellular communication (GJIC) in the exposed cells was examined with the scrape loading/dye transfer technique. The ability of GMA to transform 2BS cells was also tested by an in vitro cell transformation assay. Results Exposure to GMA resulted in a dose-dependent increase in DNA strand breaks but not apoptic responses. GMA was also shown to significantly induce HPRT gene mutations and morphological transformation in 2BS cells in vitro. In contrast, GMA produced a concentration-dependent inhibition of GJIC. Conclusions GMA elicits both genotoxic and nongenotoxic effects on 2BS cells in vitro. The induction of DNA damage and gene mutations and inhibition of GJIC by GMA may casually contribute to GMA-induced cell transformation.
