Three kind of aryl-substituted tri-benzyl sulfonium salts [ （4-phX）phSph2 ] PF6 [ X = S, O ] were prepared by the condensation of biphenyl sulfoxide with biphenyl sulfide, biphenyl ether or 1, 1＇ -biphenyl in the p...Three kind of aryl-substituted tri-benzyl sulfonium salts [ （4-phX）phSph2 ] PF6 [ X = S, O ] were prepared by the condensation of biphenyl sulfoxide with biphenyl sulfide, biphenyl ether or 1, 1＇ -biphenyl in the presence of polyphosphoric acid which can be used as dehydrate agent. The reaction condition was mild, such as reaction temperature between 40- 50 ℃ ,reactive time 2- 3 h, the yield of 4-（phenylthio）triphenylsulfonium hexafluorophosphate was 87.6%. The three kind sulfonium salts show better curing character to epoxy resin.展开更多
To improve the solubility and bioactivity of chitosan,a new class of carboxymethyl chitosan derivatives possessing sulfonium salts was successfully designed and synthesized,including Methyl sulfi de carboxymethyl chit...To improve the solubility and bioactivity of chitosan,a new class of carboxymethyl chitosan derivatives possessing sulfonium salts was successfully designed and synthesized,including Methyl sulfi de carboxymethyl chitosan(MCMCS),Ethyl sulfi de carboxymethyl chitosan(ECMCS),Propyl sulfi de carboxymethyl chitosan(PCMCS),and Butyl sulfi de carboxymethyl chitosan(BCMCS).To determine the structure of the new class of the derivatives,methods of the Fourier transform infrared spectroscopy(FT-IR),^(1)H nuclear magnetic resonance spectrometer(^(1)H NMR),and^(13)C nuclear magnetic resonance spectrometer(^(13)C NMR)were used.Moreover,the antioxidant activity of the derivatives for three types of free radicals,i.e.,hydroxyl radical,superoxide radical,and 1,1-diphenyl-2-picrylhydrazyl(DPPH)radical was evaluated in vitro.In addition,the L929 cells were adopted to test the cytotoxicity of chitosan and its derivatives by CCK-8 assay.The class of the carboxymethyl chitosan derivatives showed a strong scavenging ability against the three free radicals at 1.6 mg/mL,with scavenging rate of over 70%and some up to 100%.At this high rate,the overall cell viability in the toxicity test reached more than 80%,indicating that the synthetic derivative had a little cytotoxicity.The results show that the introduction of carboxymethyl group to chitosan increased the water-solubility of chitosan,and the combination of sulfonate ions with diff erent chain lengths further enhanced the antioxidant activity of chitosan.Therefore,the sulfonium-containing carboxymethyl chitosan derivatives had excellent bioactivity with good application prospects in food,biomedicine,and medical fi elds.展开更多
The photochemical and photophysical behaviors of tri(4-tert-butoxycarbonyl oxyphenyl) sulphonium salts have been investigated. In argon-satureted acetonitrile, the quantum yields of Bronsted acid formed during photoly...The photochemical and photophysical behaviors of tri(4-tert-butoxycarbonyl oxyphenyl) sulphonium salts have been investigated. In argon-satureted acetonitrile, the quantum yields of Bronsted acid formed during photolysis of these compounds was abount 0.5. In the transient absorption spectrum excited by 266nm in mathanol and dioxane an evident absorption peak at 360 nm decayed in accordance with pseudo-first-order reac tion was observed. In the presence of poly-p-hydroxystyrene or diphenyl sulphide, the apparent second-order reaction decay rate constants were 107 and 108 L·mol-1 ’s-1 t re spectively. Results indicated that the transient absorption peak at 360nm was attributed to the diphenyl sulphide radicaJ cations formed in photolysis of sulphonium salts, which were proposed by abstraction of hydrogen from solvent or polymer to yield the protonic acid and diphenyl sulphide as listed in eqns. (1) and (2). The influence of non-nucleophilic anions of title compounds on their photochemical behavior was just less important.展开更多
文摘Three kind of aryl-substituted tri-benzyl sulfonium salts [ （4-phX）phSph2 ] PF6 [ X = S, O ] were prepared by the condensation of biphenyl sulfoxide with biphenyl sulfide, biphenyl ether or 1, 1＇ -biphenyl in the presence of polyphosphoric acid which can be used as dehydrate agent. The reaction condition was mild, such as reaction temperature between 40- 50 ℃ ,reactive time 2- 3 h, the yield of 4-（phenylthio）triphenylsulfonium hexafluorophosphate was 87.6%. The three kind sulfonium salts show better curing character to epoxy resin.
基金Supported by the National Key R&D Program of China(No.2019YFD0900705)the Key Deployment Projects of the Marine Science Research Center of the Chinese Academy of Sciences(No.COMS2020J04)the Natural Science Foundation of Shandong Province of China(No.ZR2019BD064)。
文摘To improve the solubility and bioactivity of chitosan,a new class of carboxymethyl chitosan derivatives possessing sulfonium salts was successfully designed and synthesized,including Methyl sulfi de carboxymethyl chitosan(MCMCS),Ethyl sulfi de carboxymethyl chitosan(ECMCS),Propyl sulfi de carboxymethyl chitosan(PCMCS),and Butyl sulfi de carboxymethyl chitosan(BCMCS).To determine the structure of the new class of the derivatives,methods of the Fourier transform infrared spectroscopy(FT-IR),^(1)H nuclear magnetic resonance spectrometer(^(1)H NMR),and^(13)C nuclear magnetic resonance spectrometer(^(13)C NMR)were used.Moreover,the antioxidant activity of the derivatives for three types of free radicals,i.e.,hydroxyl radical,superoxide radical,and 1,1-diphenyl-2-picrylhydrazyl(DPPH)radical was evaluated in vitro.In addition,the L929 cells were adopted to test the cytotoxicity of chitosan and its derivatives by CCK-8 assay.The class of the carboxymethyl chitosan derivatives showed a strong scavenging ability against the three free radicals at 1.6 mg/mL,with scavenging rate of over 70%and some up to 100%.At this high rate,the overall cell viability in the toxicity test reached more than 80%,indicating that the synthetic derivative had a little cytotoxicity.The results show that the introduction of carboxymethyl group to chitosan increased the water-solubility of chitosan,and the combination of sulfonate ions with diff erent chain lengths further enhanced the antioxidant activity of chitosan.Therefore,the sulfonium-containing carboxymethyl chitosan derivatives had excellent bioactivity with good application prospects in food,biomedicine,and medical fi elds.
文摘The photochemical and photophysical behaviors of tri(4-tert-butoxycarbonyl oxyphenyl) sulphonium salts have been investigated. In argon-satureted acetonitrile, the quantum yields of Bronsted acid formed during photolysis of these compounds was abount 0.5. In the transient absorption spectrum excited by 266nm in mathanol and dioxane an evident absorption peak at 360 nm decayed in accordance with pseudo-first-order reac tion was observed. In the presence of poly-p-hydroxystyrene or diphenyl sulphide, the apparent second-order reaction decay rate constants were 107 and 108 L·mol-1 ’s-1 t re spectively. Results indicated that the transient absorption peak at 360nm was attributed to the diphenyl sulphide radicaJ cations formed in photolysis of sulphonium salts, which were proposed by abstraction of hydrogen from solvent or polymer to yield the protonic acid and diphenyl sulphide as listed in eqns. (1) and (2). The influence of non-nucleophilic anions of title compounds on their photochemical behavior was just less important.
