The alkylation of sulfur compounds with olefine is considered to be an attractive way to attain high level of sulfur removal by raising the boiling point of sulfur-containing compounds to ease their separation from li...The alkylation of sulfur compounds with olefine is considered to be an attractive way to attain high level of sulfur removal by raising the boiling point of sulfur-containing compounds to ease their separation from lighl fractions by distillation. A series of superparamagnetic supported catalysts, used for alkylation of thiophene with 1-octene, were prepared by loading H3PW12040 （HPW） onto commercially available nanoparticles γ-Fe2O3 through incipient wet impregnation method. The catalysts were characterized by X-ray diffraction （XRD）, Fourier transform infra-red （FT-IR）, thermo gravimetric analysis （TG）, N2-adsorption and vibrating sample magnetometer （VSM）. The physicochemical characterization reveals that 7-Fe203 could be accommodated to immobilize and disperse HPW. Moreover, possessing high magnetization of 26.1 A.mZ.kg-1 and with mesoporous structure with specific surface area of 35.9 m2·g^-1, the 40% （by mass） HPW loading catalyst is considered the proper catalyst for olefinic alkylation of thiophenic sulfur （OATS） and can be separated in an external magnetic field. The catalytic activity was investigated in the alkylation reaction of thiophene with 1-octene, and the conversion of thiophene is up to 46% at 160 ℃ in 3 h. The 40% （by mass） H3PW12O40/γ-Fe2O3 catalyst can be reused 6 times without too much loss of activit and keeps its property of superparamagnetism.展开更多
The medium band gap donor-acceptor （D-A） copolymer J61 based on bi（alkylthio-thienyl）benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit and thiophene as n-bridge has demonstrated excellent pho...The medium band gap donor-acceptor （D-A） copolymer J61 based on bi（alkylthio-thienyl）benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit and thiophene as n-bridge has demonstrated excellent photovoltaic performance as donor material in nonfullerene polymer solar cells （PSCs） with narrow bandgap n-type organic semiconductor ITIC as acceptor. For studying the effect of n-bridges on the photovoltaic performance of the D-A copolymers, here we synthesized a new D-A copolymer J61-F based on the same donor and acceptor units as J61 but with furan n-bridges instead of thiophene. J61-F possesses a deeper the highest occupied molecular orbital （HOMO） level at -5.45 eV in comparison with that （-5.32 eV） of J61. The non-fullerene PSCs based on J61-F：ITIC exhibited a maximum power conversion efficiency （PCE） of 8.24% with a higher open-circuit voltage （Voc） of 0.95 V, which is benefitted from the lower-lying HOMO energy level of J61-F donor material. The results indicate that main chain engineering by changing n-bridges is another effective way to tune the electronic energy levels of the conjugated D-A copolymers for the application as donor materials in non-fullerene PSCs.展开更多
文摘目的研究新化合物4-硫-5-(2-噻吩基)尿嘧啶核苷酸在近紫外UVA辅助下,体外抑制人黑色素瘤A375细胞增殖的作用机制。方法利用MTT法筛选4-硫-5-(2-噻吩基)尿苷和近紫外UVA的协同作用剂量;采用Annexin V-FITC/PI形态学染色法和流式细胞术对协同作用引起的细胞死亡类型做以定性判断;通过蛋白免疫印迹法,探讨协同作用在细胞内的信号传递途径。结果无毒剂量的4-硫-5-(2-噻吩基)尿苷(100μmol·L^(-1))在无害剂量的UVA(15 k J·m-2)辅助下,通过降低p38蛋白和Akt蛋白的表达及磷酸化,下调Bcl-2、pro-caspase-9和pro-caspase-3蛋白的表达量,促进Bad蛋白表达及claved-PARP蛋白的活化,诱导细胞凋亡抑制人黑色素瘤A375细胞增殖。结论 4-硫-5-(2-噻吩基)尿苷在近紫外UVA的辅助下,通过诱导细胞凋亡,抑制人黑色素瘤A375细胞增殖。
基金Supported by the National Natural Science Foundation of China(21076047)
文摘The alkylation of sulfur compounds with olefine is considered to be an attractive way to attain high level of sulfur removal by raising the boiling point of sulfur-containing compounds to ease their separation from lighl fractions by distillation. A series of superparamagnetic supported catalysts, used for alkylation of thiophene with 1-octene, were prepared by loading H3PW12040 （HPW） onto commercially available nanoparticles γ-Fe2O3 through incipient wet impregnation method. The catalysts were characterized by X-ray diffraction （XRD）, Fourier transform infra-red （FT-IR）, thermo gravimetric analysis （TG）, N2-adsorption and vibrating sample magnetometer （VSM）. The physicochemical characterization reveals that 7-Fe203 could be accommodated to immobilize and disperse HPW. Moreover, possessing high magnetization of 26.1 A.mZ.kg-1 and with mesoporous structure with specific surface area of 35.9 m2·g^-1, the 40% （by mass） HPW loading catalyst is considered the proper catalyst for olefinic alkylation of thiophenic sulfur （OATS） and can be separated in an external magnetic field. The catalytic activity was investigated in the alkylation reaction of thiophene with 1-octene, and the conversion of thiophene is up to 46% at 160 ℃ in 3 h. The 40% （by mass） H3PW12O40/γ-Fe2O3 catalyst can be reused 6 times without too much loss of activit and keeps its property of superparamagnetism.
基金supported by the National Basic Research Program,Ministry of Science and Technology of China(2014CB643501)Beijing Nova program(Z171100001117074)+1 种基金the National Natural Science Foundation of China(91633301,91433117,21374124)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB12030200)
文摘The medium band gap donor-acceptor （D-A） copolymer J61 based on bi（alkylthio-thienyl）benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit and thiophene as n-bridge has demonstrated excellent photovoltaic performance as donor material in nonfullerene polymer solar cells （PSCs） with narrow bandgap n-type organic semiconductor ITIC as acceptor. For studying the effect of n-bridges on the photovoltaic performance of the D-A copolymers, here we synthesized a new D-A copolymer J61-F based on the same donor and acceptor units as J61 but with furan n-bridges instead of thiophene. J61-F possesses a deeper the highest occupied molecular orbital （HOMO） level at -5.45 eV in comparison with that （-5.32 eV） of J61. The non-fullerene PSCs based on J61-F：ITIC exhibited a maximum power conversion efficiency （PCE） of 8.24% with a higher open-circuit voltage （Voc） of 0.95 V, which is benefitted from the lower-lying HOMO energy level of J61-F donor material. The results indicate that main chain engineering by changing n-bridges is another effective way to tune the electronic energy levels of the conjugated D-A copolymers for the application as donor materials in non-fullerene PSCs.
