TiO2-seashell composites prepared via a sol-gel method were used to generate carbonate radicals(·CO3–) under solar light irradiation. ·CO3–, a selective radical, was employed to degrade the target tetracyc...TiO2-seashell composites prepared via a sol-gel method were used to generate carbonate radicals(·CO3–) under solar light irradiation. ·CO3–, a selective radical, was employed to degrade the target tetracycline hydrochloride contaminant. A series of characterizations was carried out to study the structure and composition of the synthesized TiO2-seashell composite. This material exhibits excellent solar light-driven photochemical activity in the decomposition of tetracycline hydrochloride. The possible pathway and mechanism for the photodegradation process were proposed on the basis of high-resolution electrospray ionization time-of-flight mass spectrometry experiments. Finally, we investigated the reusability of the TiO2-seashell composite. This study is expected to provide a new facile pathway for the application of ·CO3– radicals to degrade special organic pollutants in water.展开更多
A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic(PEC) oxidation system was established by o-phenanthroline-Fe(Ⅱ)(Fe(phen)3^2+) spectrophotometr...A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic(PEC) oxidation system was established by o-phenanthroline-Fe(Ⅱ)(Fe(phen)3^2+) spectrophotometry and using anion exchange membrane. Fe (phen)3^2+ can be oxidized to o-phenanthroline-Fe(Ⅲ)(Fe(phen)3^3+) by strong oxidization of hydroxyl radicals(·OH). Then the cumulate concentration of hydroxyl radicals can be calculated through determining the change of the Fe(phen)3^3+ absorbency at 509 nm. In addition, the research results showed the production rate of hydroxyl radicals was affected obviously by pH of solution, the cumulate concentration of hydroxyl radicals was the largest at nearby the initial pH 6.3 (isoelectric point), and the change direction of pH after illumination tended to nearby isoelectric point.展开更多
A new method is proposed to determine the amplification factor for 2-hydroxy ethylperoxy radicals (HOC2H4O2·) in chemical amplifier. The radical source comes from the reaction of excess ethene with HO· rad...A new method is proposed to determine the amplification factor for 2-hydroxy ethylperoxy radicals (HOC2H4O2·) in chemical amplifier. The radical source comes from the reaction of excess ethene with HO· radicals generated in the photolysis of water vapor at the wave length of 185 nm in air in a flow tube. This produces a radical source which contains equal amount of HO2·and HOC2H4O2·. The amplification factor is derived from the slopes of the lines between produced NO2 in chemical amplifier and total initial radical concentrations measured for the source of HO2· and that of the same amount of HO2· and HOC2H4O2· respectively. The amplification factor of HOC2H4O2· was similar to that of HO2·, indicating that HOC2H4O2· can be measured with the same sensitivity as HO2· by chemical amplifier.展开更多
The properties of C-H vibration softening for CH2 and CHa radicals absorbed on Cun(n=1-6) clusters have been investigated, using the density functional theory with hybrid functional. The results indicate that the ab...The properties of C-H vibration softening for CH2 and CHa radicals absorbed on Cun(n=1-6) clusters have been investigated, using the density functional theory with hybrid functional. The results indicate that the absorption of CH2 on Cu clusters is stronger than the case of CH3. The vibrational frequencies of C-H bonding agree with the experimental results obtained for CH2 and CH3 absorbed on Cu(111). With the increase of cluster size, the softening (Einstein shift) of C-H vibrational modes become stronger.展开更多
Photolysis rate (J1) and reaction rate constants (kl) for the biacetyl (butane-2,3-dione) were evaluated in aqueous phase using a continuous photolysis system with a conventional Xe-Hg arc lamp as a light source...Photolysis rate (J1) and reaction rate constants (kl) for the biacetyl (butane-2,3-dione) were evaluated in aqueous phase using a continuous photolysis system with a conventional Xe-Hg arc lamp as a light source. The OH radicals was generated by H2OE/UV process and biacetyl (CH3C(O)C(O)CH3) concentrations were monitored using 2,4-DNPH derivatization method. 2,3-butanedione molecule is widely present in the atmosphere, it have been detected in hydrometeors (fogs, rain, and clouds) and at a significant yield (up to 10μmolar). The measurements were performed at 294 K and with free pH values. Our results lead to the following obtained values: J1= 3×10^-4 S^-1 and k1 = (6.17±0.95)×10^8 M^-1·s^-1.The uncertainty listed above is ±15%.展开更多
Absorption spectra of jet-cooled PH2 radicals were recorded in the wavelength range of 465- 555 nm using cavity ringdown spectroscopy. The PH2 radicals were produced in a supersonic jet by pulsed direct current discha...Absorption spectra of jet-cooled PH2 radicals were recorded in the wavelength range of 465- 555 nm using cavity ringdown spectroscopy. The PH2 radicals were produced in a supersonic jet by pulsed direct current discharge of a mixture of PHa and SF6 in argon. Seven vibronic bands with fine rotational structures have been observed and assigned as 0 0^, 2 0^n, and 2 1^n (n=1- 3) bands of the A^2A1- X~ 2B1 electronic transition. Rotational assignments and rotational term values for each band were re-identified, and the molecular parameters including rotational constants, centrifugal distortion constants, and spin-rotation interaction constants were also improved with reasonably high precision. In addition, large perturbations observed in each quantum number of total angular momentum of the a axis level of the excited vibronic states were briefly discussed.展开更多
In an aqueous solution, normal electrolysis at high voltages switches over spontaneously to glow discharge electrolysis and gives rise to hydroxyl radical, hydrogen peroxide, and aqueous electron, as well as several o...In an aqueous solution, normal electrolysis at high voltages switches over spontaneously to glow discharge electrolysis and gives rise to hydroxyl radical, hydrogen peroxide, and aqueous electron, as well as several other active species. Hydroxyl radical directly attacks organic contaminants to make them oxidized. In the present paper, 2-naphthylamine is eventually degraded into hydrogen carbonate and carbon dioxide. The degradation process is analyzed by using an Ultraviolet (UV) absorption spectrum, high-performance liquid chromatography (HPLC) and chemical oxygen demand (COD). It is demonstrated that 2-naphthylamine (co =30 mg·1-1) is completely converted within 2h at 30℃ and 600 V by glow discharge electrolysis, and the degradation is strongly dependent upon the presence of ferrous ions. COD is ascended in the absence of ferrous ions and descended in the presence of them.展开更多
Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical p...Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.展开更多
Selective coupling of methyl radicals to produce C_(2) species(C2H4 and C2H6)is a key challenge for oxidative coupling of methane(OCM).In traditional OCM reaction systems,homogeneous transformation of methyl radicals ...Selective coupling of methyl radicals to produce C_(2) species(C2H4 and C2H6)is a key challenge for oxidative coupling of methane(OCM).In traditional OCM reaction systems,homogeneous transformation of methyl radicals in O_(2)‐containing gases are uncontrollable,resulting in limited C_(2) selectivity and yield.Herein,we demonstrate that methyl radicals generated by La_(2)O_(3)at low reaction temperature can selectively couple on the surface of 5 wt%Na2WO4/SiO_(2).The controllable surface coupling against overoxidation barely changes the activity of La_(2)O_(3)but boosts the C_(2)selectivity by three times and achieves a C_(2)yield as high as 10.9%at bed temperature of only 570℃.Structure‐property studies suggest that Na_(2)WO_(4) nanoclusters are the active sites for methyl radical coupling.The strong CH_(3)·affinity of these sites can even endow some methane combustion catalysts with OCM activity.The findings of the surface coupling of methyl radicals open a new direction to develop OCM catalyst.The bifunctional OCM catalyst system,which composes of a methane activation center and a CH_(3)·coupling center,may deliver promising OCM performance at reaction temperatures below the ignition temperature of C2H6 and C2H4(~600℃)and is therefore more controllable,safer,and certainly more attractive as an actual process.展开更多
With the physical method of micro-gap gas discharge, OH. radicals were produced by the ionization of O2 in air and H2O in the gaseous state, in order to explore more effective method totreat the ship's ballast water....With the physical method of micro-gap gas discharge, OH. radicals were produced by the ionization of O2 in air and H2O in the gaseous state, in order to explore more effective method totreat the ship's ballast water. The surface morphology of Al2O3 dielectric layer was analysed using Atomic Force Microscopy (AFM), where the size of Al2O3 particles was in the range of 2 μm to 5 μm. At the same time, the biochemical effect of hydroxyl radicals on the introduced organisms and the quality of ship's ballast water were studied. The results indicate that the main reasons of cell death are lipid peroxide and damage of the antioxidant enzyme system in Catalase (CAT), Peroxidase (POD) and Superoxide dismutase (SOD). In addition, the quality of the ballast water was greatly improved.展开更多
A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the ato...A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.展开更多
Direct chemoselective oxidation of δ-lactones via highly stable benzyl radical cyclization is reported. The one-pot conversion of premade substituted 5-aryl pentanoic acid and 8-benzyl-1-naphthoic acid in the presenc...Direct chemoselective oxidation of δ-lactones via highly stable benzyl radical cyclization is reported. The one-pot conversion of premade substituted 5-aryl pentanoic acid and 8-benzyl-1-naphthoic acid in the presence of K2S2Os--CuCl2 results to the δ-lactones in moderate to good yields. The advantages of this methodology is using water as a solvent and utilizing available starting materials.展开更多
The reaction mechanism of CH2F radical with HNCO was investigated by density functional theory (DFT) at the B3LYP/6-311++G(d,p) level. The geometries of the reactants, the intermediates, the transition states an...The reaction mechanism of CH2F radical with HNCO was investigated by density functional theory (DFT) at the B3LYP/6-311++G(d,p) level. The geometries of the reactants, the intermediates, the transition states and the products were optimized. The transition states were verified through the vibration analysis. The relative energies were calculated at the QCISD(T)/6-311++G^**//B3LYP/6-311++G(d,p) level. Seven feasible reaction pathways of the reaction were studied. The results indicate that the pathway (5) is the most favorable to occur, so it is the main pathway of the reaction.展开更多
Patient's information The patient is a 56-year-old man who visited our hospital for "repeated epigastric pain for more than two months." Physical examination showed nearly pale appearance; abdomen was soft and no m...Patient's information The patient is a 56-year-old man who visited our hospital for "repeated epigastric pain for more than two months." Physical examination showed nearly pale appearance; abdomen was soft and no mass palpable; left supraclavicular lymph node (-); and digital rectal examination (-).展开更多
Silk was grafted using 2-hydroxyethyl methacrylate(HEMA)by atom transfer radical polymerization(ATRP)method.The amino groups and hydroxyl groups on the side chains of the silk fibroin was reacted with 2-bromoisobutyry...Silk was grafted using 2-hydroxyethyl methacrylate(HEMA)by atom transfer radical polymerization(ATRP)method.The amino groups and hydroxyl groups on the side chains of the silk fibroin was reacted with 2-bromoisobutyryl bromide(BriB-Br)to obtain efficient macroinitiator for ATRP.And the macroinitiator was grafted with HEMA in water aqueous using CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine(PMDETA)as catalyst system.The effects of monomer concentration,the proportion of CuBr and PMDETA,grafting temperature and time on the silk grafting were discussed,and the optimal grafting technology was obtained.FT-IR characterization of the grafted silk showed a peak corresponding to HEMA,which indicated that HEMA was grafted onto the surface of silk.ATRP method could be applied on the silk modification and this technique provided a new way for silk grafting.展开更多
Functional monomer (MP)_2PT having tertiary aromatic amino group was systhesized from the reaction of N, N-di (2-hydroxypropyl)-p-toluidine with 2-methyl acryloyl chloride. In the presence of organic peroxide, the rad...Functional monomer (MP)_2PT having tertiary aromatic amino group was systhesized from the reaction of N, N-di (2-hydroxypropyl)-p-toluidine with 2-methyl acryloyl chloride. In the presence of organic peroxide, the radical polymerization of (MP)_2PT in toluene took place. The kinetics of (MP)_2PT polymerization and the ESR spectra of LPO-(MP)2PT-MNP systems were determined respectively.展开更多
文摘TiO2-seashell composites prepared via a sol-gel method were used to generate carbonate radicals(·CO3–) under solar light irradiation. ·CO3–, a selective radical, was employed to degrade the target tetracycline hydrochloride contaminant. A series of characterizations was carried out to study the structure and composition of the synthesized TiO2-seashell composite. This material exhibits excellent solar light-driven photochemical activity in the decomposition of tetracycline hydrochloride. The possible pathway and mechanism for the photodegradation process were proposed on the basis of high-resolution electrospray ionization time-of-flight mass spectrometry experiments. Finally, we investigated the reusability of the TiO2-seashell composite. This study is expected to provide a new facile pathway for the application of ·CO3– radicals to degrade special organic pollutants in water.
文摘A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic(PEC) oxidation system was established by o-phenanthroline-Fe(Ⅱ)(Fe(phen)3^2+) spectrophotometry and using anion exchange membrane. Fe (phen)3^2+ can be oxidized to o-phenanthroline-Fe(Ⅲ)(Fe(phen)3^3+) by strong oxidization of hydroxyl radicals(·OH). Then the cumulate concentration of hydroxyl radicals can be calculated through determining the change of the Fe(phen)3^3+ absorbency at 509 nm. In addition, the research results showed the production rate of hydroxyl radicals was affected obviously by pH of solution, the cumulate concentration of hydroxyl radicals was the largest at nearby the initial pH 6.3 (isoelectric point), and the change direction of pH after illumination tended to nearby isoelectric point.
文摘A new method is proposed to determine the amplification factor for 2-hydroxy ethylperoxy radicals (HOC2H4O2·) in chemical amplifier. The radical source comes from the reaction of excess ethene with HO· radicals generated in the photolysis of water vapor at the wave length of 185 nm in air in a flow tube. This produces a radical source which contains equal amount of HO2·and HOC2H4O2·. The amplification factor is derived from the slopes of the lines between produced NO2 in chemical amplifier and total initial radical concentrations measured for the source of HO2· and that of the same amount of HO2· and HOC2H4O2· respectively. The amplification factor of HOC2H4O2· was similar to that of HO2·, indicating that HOC2H4O2· can be measured with the same sensitivity as HO2· by chemical amplifier.
文摘The properties of C-H vibration softening for CH2 and CHa radicals absorbed on Cun(n=1-6) clusters have been investigated, using the density functional theory with hybrid functional. The results indicate that the absorption of CH2 on Cu clusters is stronger than the case of CH3. The vibrational frequencies of C-H bonding agree with the experimental results obtained for CH2 and CH3 absorbed on Cu(111). With the increase of cluster size, the softening (Einstein shift) of C-H vibrational modes become stronger.
文摘Photolysis rate (J1) and reaction rate constants (kl) for the biacetyl (butane-2,3-dione) were evaluated in aqueous phase using a continuous photolysis system with a conventional Xe-Hg arc lamp as a light source. The OH radicals was generated by H2OE/UV process and biacetyl (CH3C(O)C(O)CH3) concentrations were monitored using 2,4-DNPH derivatization method. 2,3-butanedione molecule is widely present in the atmosphere, it have been detected in hydrometeors (fogs, rain, and clouds) and at a significant yield (up to 10μmolar). The measurements were performed at 294 K and with free pH values. Our results lead to the following obtained values: J1= 3×10^-4 S^-1 and k1 = (6.17±0.95)×10^8 M^-1·s^-1.The uncertainty listed above is ±15%.
基金This work was supported by the National Natural Science Foundation of China (No.20673107), the National Key Basic Research Special Foundation of China (No.2007CB815203), and the Chinese Academy of Sciences (No.KJCX2-SW-H08).
文摘Absorption spectra of jet-cooled PH2 radicals were recorded in the wavelength range of 465- 555 nm using cavity ringdown spectroscopy. The PH2 radicals were produced in a supersonic jet by pulsed direct current discharge of a mixture of PHa and SF6 in argon. Seven vibronic bands with fine rotational structures have been observed and assigned as 0 0^, 2 0^n, and 2 1^n (n=1- 3) bands of the A^2A1- X~ 2B1 electronic transition. Rotational assignments and rotational term values for each band were re-identified, and the molecular parameters including rotational constants, centrifugal distortion constants, and spin-rotation interaction constants were also improved with reasonably high precision. In addition, large perturbations observed in each quantum number of total angular momentum of the a axis level of the excited vibronic states were briefly discussed.
基金The project supported in part by the Project of Key Science and Technology of Education Ministry (00250)the Nature Science Foundation of Gansu Province (3ZS041-A25-028)the Invention Project of Science and Technology (KJCXGC-01, NWNU), 2000
文摘In an aqueous solution, normal electrolysis at high voltages switches over spontaneously to glow discharge electrolysis and gives rise to hydroxyl radical, hydrogen peroxide, and aqueous electron, as well as several other active species. Hydroxyl radical directly attacks organic contaminants to make them oxidized. In the present paper, 2-naphthylamine is eventually degraded into hydrogen carbonate and carbon dioxide. The degradation process is analyzed by using an Ultraviolet (UV) absorption spectrum, high-performance liquid chromatography (HPLC) and chemical oxygen demand (COD). It is demonstrated that 2-naphthylamine (co =30 mg·1-1) is completely converted within 2h at 30℃ and 600 V by glow discharge electrolysis, and the degradation is strongly dependent upon the presence of ferrous ions. COD is ascended in the absence of ferrous ions and descended in the presence of them.
文摘Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.
文摘Selective coupling of methyl radicals to produce C_(2) species(C2H4 and C2H6)is a key challenge for oxidative coupling of methane(OCM).In traditional OCM reaction systems,homogeneous transformation of methyl radicals in O_(2)‐containing gases are uncontrollable,resulting in limited C_(2) selectivity and yield.Herein,we demonstrate that methyl radicals generated by La_(2)O_(3)at low reaction temperature can selectively couple on the surface of 5 wt%Na2WO4/SiO_(2).The controllable surface coupling against overoxidation barely changes the activity of La_(2)O_(3)but boosts the C_(2)selectivity by three times and achieves a C_(2)yield as high as 10.9%at bed temperature of only 570℃.Structure‐property studies suggest that Na_(2)WO_(4) nanoclusters are the active sites for methyl radical coupling.The strong CH_(3)·affinity of these sites can even endow some methane combustion catalysts with OCM activity.The findings of the surface coupling of methyl radicals open a new direction to develop OCM catalyst.The bifunctional OCM catalyst system,which composes of a methane activation center and a CH_(3)·coupling center,may deliver promising OCM performance at reaction temperatures below the ignition temperature of C2H6 and C2H4(~600℃)and is therefore more controllable,safer,and certainly more attractive as an actual process.
基金supported by the Key Project of National Support Plan from Science and Technology Ministry of China (2006BAC11B06) the Key Project of International Cooperation from the Ministry of Science and Technology of China (2005DFA20800)+1 种基金the Support Plan of National New Century Excellent Youth of China (NCET-04-0286, -05-0398) the Project of National Natural Science Foundation of China (No. 60371035)
文摘With the physical method of micro-gap gas discharge, OH. radicals were produced by the ionization of O2 in air and H2O in the gaseous state, in order to explore more effective method totreat the ship's ballast water. The surface morphology of Al2O3 dielectric layer was analysed using Atomic Force Microscopy (AFM), where the size of Al2O3 particles was in the range of 2 μm to 5 μm. At the same time, the biochemical effect of hydroxyl radicals on the introduced organisms and the quality of ship's ballast water were studied. The results indicate that the main reasons of cell death are lipid peroxide and damage of the antioxidant enzyme system in Catalase (CAT), Peroxidase (POD) and Superoxide dismutase (SOD). In addition, the quality of the ballast water was greatly improved.
文摘A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.
文摘Direct chemoselective oxidation of δ-lactones via highly stable benzyl radical cyclization is reported. The one-pot conversion of premade substituted 5-aryl pentanoic acid and 8-benzyl-1-naphthoic acid in the presence of K2S2Os--CuCl2 results to the δ-lactones in moderate to good yields. The advantages of this methodology is using water as a solvent and utilizing available starting materials.
基金Ⅵ. ACKN0WLEDGMENTS This work was supported Natural Science Foundation by the Sichuan Province (No.05JY029-038-2) and the Sichuan Province Youth Science Foundation (No.04ZQ026-043).
文摘The reaction mechanism of CH2F radical with HNCO was investigated by density functional theory (DFT) at the B3LYP/6-311++G(d,p) level. The geometries of the reactants, the intermediates, the transition states and the products were optimized. The transition states were verified through the vibration analysis. The relative energies were calculated at the QCISD(T)/6-311++G^**//B3LYP/6-311++G(d,p) level. Seven feasible reaction pathways of the reaction were studied. The results indicate that the pathway (5) is the most favorable to occur, so it is the main pathway of the reaction.
文摘Patient's information The patient is a 56-year-old man who visited our hospital for "repeated epigastric pain for more than two months." Physical examination showed nearly pale appearance; abdomen was soft and no mass palpable; left supraclavicular lymph node (-); and digital rectal examination (-).
基金National Natural Science Foundation of China(No.50673071,No.50973079)Natural Science Fund for Colleges and Universities in Jiangsu Province,China(No.07KJD540188,No.09KJA540001)
文摘Silk was grafted using 2-hydroxyethyl methacrylate(HEMA)by atom transfer radical polymerization(ATRP)method.The amino groups and hydroxyl groups on the side chains of the silk fibroin was reacted with 2-bromoisobutyryl bromide(BriB-Br)to obtain efficient macroinitiator for ATRP.And the macroinitiator was grafted with HEMA in water aqueous using CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine(PMDETA)as catalyst system.The effects of monomer concentration,the proportion of CuBr and PMDETA,grafting temperature and time on the silk grafting were discussed,and the optimal grafting technology was obtained.FT-IR characterization of the grafted silk showed a peak corresponding to HEMA,which indicated that HEMA was grafted onto the surface of silk.ATRP method could be applied on the silk modification and this technique provided a new way for silk grafting.
文摘Functional monomer (MP)_2PT having tertiary aromatic amino group was systhesized from the reaction of N, N-di (2-hydroxypropyl)-p-toluidine with 2-methyl acryloyl chloride. In the presence of organic peroxide, the radical polymerization of (MP)_2PT in toluene took place. The kinetics of (MP)_2PT polymerization and the ESR spectra of LPO-(MP)2PT-MNP systems were determined respectively.