通过表面交换反应,以多巴胺为偶联剂,将三苯基膦担载到磁性纳米氧化铁表面制得磁性纳米三苯基膦配体,其结构通过红外光谱、元素分析以及热重分析进行了表征。初步考察了表面交换反应条件对三苯基膦在纳米粒子表面担载量的影响;提高多巴...通过表面交换反应,以多巴胺为偶联剂,将三苯基膦担载到磁性纳米氧化铁表面制得磁性纳米三苯基膦配体,其结构通过红外光谱、元素分析以及热重分析进行了表征。初步考察了表面交换反应条件对三苯基膦在纳米粒子表面担载量的影响;提高多巴胺-三苯基膦衍生物与磁性纳米氧化铁粒子比例以及延长超声时间有助于提高三苯基膦的担载量。在优化后的反应条件下,即苯乙烯1.25 m L,30 mg磁性纳米三苯基膦,1.8 mg Rh(OAc)2,12 m L无水四氢呋喃,3 MPa合成气VCO∶VH2=1∶1,纳米三苯基膦配体中的三苯基膦含量为0.21μmol/mg,该配体能够与Rh(OAc)2一起催化苯乙烯的氢甲酰化反应并能重复使用4次,且仅有4.8%的三苯基膦配体从纳米粒子表面脱落。展开更多
Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichlo...Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris(2-chloroethyl)amine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ? b = 105.823(6)? V = 675.7(2) 3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, m(MoKa) = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ? b = 99.505(1)? V = 2383.5(3) ?, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, m(MoKa) = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 (dialdehyde) is located at the crystallographic inversion center nearby the midpoint of C(8)C(8A) single bond. The three chains in the molecule of compound 2 (trialdehyde) are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.展开更多
Although the antiestrogen agent tamoxifen has long been used to treat women with hormone receptor positive inva-sive breast carcinoma, the mechanisms of its action and acquired resistance to tamoxifen during treatment...Although the antiestrogen agent tamoxifen has long been used to treat women with hormone receptor positive inva-sive breast carcinoma, the mechanisms of its action and acquired resistance to tamoxifen during treatment are largelyunknown. A number of studies have revealed that over-activation of some signaling pathways can cause tamoxifenresistance; however, very little information is available regarding the genes whose loss-of-function alternation contrib-ute to tamoxifen resistance. Here we used a forward genetic approach in vitro to generate tamoxifen resistant cells fromthe tamoxifen sensitive breast cancer cell line ZR-75-1, and further identified the disrupted gene in different tamoxifenresistant clones. Retinol binding protein 7, DNA polymerase-transactivated protein 3, γ-glutamyltransferase-like activity 1,slit-robo RhoGTPase-activating protein, tetraspan NET-4, HSPC194, amiloride-sensitive epithelial sodium channel gene,and Notch2, were the eight mutated genes identified in different tamoxifen resistant clones, suggesting their requirementfor tamoxifen sensitivity in ZR-75-1 cells. Since the functions of these genes are not related to each other, it suggeststhat multiple pathways can influence tamoxifen sensitivity in breast cancer cells.展开更多
A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes...A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.展开更多
A pyrazoline-containing starburst molecule, 4,4’,4"-tris[(1,3-diphenyl-4,5-dihydro-1H- pyrazol)-5-yl]-triphenylamine (Tris-5-DPP), was synthesized in a facile way, which can form amorphous thin films with glass ...A pyrazoline-containing starburst molecule, 4,4’,4"-tris[(1,3-diphenyl-4,5-dihydro-1H- pyrazol)-5-yl]-triphenylamine (Tris-5-DPP), was synthesized in a facile way, which can form amorphous thin films with glass transition temperature as high as 136 °C.展开更多
Photovoltaic performance of the organic solar cells （OSCs） based on 2-（（5＇-（4-（（4-（（E）-2-（5＇-（2,2-dicyanovinyl）-3＇,4-dihexyl- 2,2＇-bithiophen-5-yl）vinyl） phenyl）（phenyl）amino）styryl）-4~4＇-dihe...Photovoltaic performance of the organic solar cells （OSCs） based on 2-（（5＇-（4-（（4-（（E）-2-（5＇-（2,2-dicyanovinyl）-3＇,4-dihexyl- 2,2＇-bithiophen-5-yl）vinyl） phenyl）（phenyl）amino）styryl）-4~4＇-dihexyl-2,2＇-bithiophen-5-yl）methylene）malononitrile （L（TPA- bTV-DCN）） as donor and PC70BM as acceptor was optimized using 0.25 vol% high boiling point solvent additive of 1-chloronaphthalene （CN）, 1,6-hexanedithiol （HDT）, or 1,8-diodooctane （DIO）. The optimized OSC based on L（TPA-bTV- DCN）-PC70BM （1：2, w/w） with 0.25 vol% CN exhibits an enhanced power conversion efficiency （PCE） of 2.61%, with Voc of 0.87 V, Jsc of 6.95 mA/cm2, and FF of 43.2%, under the illumination of 100 mW/cm2 AM 1.5 G simulated solar light, whereas the PCE of the OSC based on the same active layer without additive is only 1.79%. The effect of the additive on absorption spectra and the atomic force microscopy images of L（TPA-bTV-DCN）-PCv0BM blend films were further investigated. The improved efficiency of the device could be ascribed to the enhanced absorption and optimized domain size in the L（TPA-bTV-DCN）-PC70BM blend film.展开更多
文摘通过表面交换反应,以多巴胺为偶联剂,将三苯基膦担载到磁性纳米氧化铁表面制得磁性纳米三苯基膦配体,其结构通过红外光谱、元素分析以及热重分析进行了表征。初步考察了表面交换反应条件对三苯基膦在纳米粒子表面担载量的影响;提高多巴胺-三苯基膦衍生物与磁性纳米氧化铁粒子比例以及延长超声时间有助于提高三苯基膦的担载量。在优化后的反应条件下,即苯乙烯1.25 m L,30 mg磁性纳米三苯基膦,1.8 mg Rh(OAc)2,12 m L无水四氢呋喃,3 MPa合成气VCO∶VH2=1∶1,纳米三苯基膦配体中的三苯基膦含量为0.21μmol/mg,该配体能够与Rh(OAc)2一起催化苯乙烯的氢甲酰化反应并能重复使用4次,且仅有4.8%的三苯基膦配体从纳米粒子表面脱落。
基金The authors thank the financial support of the Natural Science Foundation of Fujian Province (No. E0110010)
文摘Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris(2-chloroethyl)amine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ? b = 105.823(6)? V = 675.7(2) 3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, m(MoKa) = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ? b = 99.505(1)? V = 2383.5(3) ?, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, m(MoKa) = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 (dialdehyde) is located at the crystallographic inversion center nearby the midpoint of C(8)C(8A) single bond. The three chains in the molecule of compound 2 (trialdehyde) are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.
基金supported in part by US Army BreastCancer Research Program Idea Award No. DAMD17-01-1-0389.
文摘Although the antiestrogen agent tamoxifen has long been used to treat women with hormone receptor positive inva-sive breast carcinoma, the mechanisms of its action and acquired resistance to tamoxifen during treatment are largelyunknown. A number of studies have revealed that over-activation of some signaling pathways can cause tamoxifenresistance; however, very little information is available regarding the genes whose loss-of-function alternation contrib-ute to tamoxifen resistance. Here we used a forward genetic approach in vitro to generate tamoxifen resistant cells fromthe tamoxifen sensitive breast cancer cell line ZR-75-1, and further identified the disrupted gene in different tamoxifenresistant clones. Retinol binding protein 7, DNA polymerase-transactivated protein 3, γ-glutamyltransferase-like activity 1,slit-robo RhoGTPase-activating protein, tetraspan NET-4, HSPC194, amiloride-sensitive epithelial sodium channel gene,and Notch2, were the eight mutated genes identified in different tamoxifen resistant clones, suggesting their requirementfor tamoxifen sensitivity in ZR-75-1 cells. Since the functions of these genes are not related to each other, it suggeststhat multiple pathways can influence tamoxifen sensitivity in breast cancer cells.
文摘A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.
基金This work was financially supported by NNSFC and the Ministry of Science and Technology of China(Grant No.20272065 and G2000028204).
文摘A pyrazoline-containing starburst molecule, 4,4’,4"-tris[(1,3-diphenyl-4,5-dihydro-1H- pyrazol)-5-yl]-triphenylamine (Tris-5-DPP), was synthesized in a facile way, which can form amorphous thin films with glass transition temperature as high as 136 °C.
基金supported by the National Basic Research Program of China(2014CB643501)the National Natural Science Foundation of China(91333204)the support from Ministry of Education and Jiangsu Province(20100092120037,XNY-48-037)
文摘Photovoltaic performance of the organic solar cells （OSCs） based on 2-（（5＇-（4-（（4-（（E）-2-（5＇-（2,2-dicyanovinyl）-3＇,4-dihexyl- 2,2＇-bithiophen-5-yl）vinyl） phenyl）（phenyl）amino）styryl）-4~4＇-dihexyl-2,2＇-bithiophen-5-yl）methylene）malononitrile （L（TPA- bTV-DCN）） as donor and PC70BM as acceptor was optimized using 0.25 vol% high boiling point solvent additive of 1-chloronaphthalene （CN）, 1,6-hexanedithiol （HDT）, or 1,8-diodooctane （DIO）. The optimized OSC based on L（TPA-bTV- DCN）-PC70BM （1：2, w/w） with 0.25 vol% CN exhibits an enhanced power conversion efficiency （PCE） of 2.61%, with Voc of 0.87 V, Jsc of 6.95 mA/cm2, and FF of 43.2%, under the illumination of 100 mW/cm2 AM 1.5 G simulated solar light, whereas the PCE of the OSC based on the same active layer without additive is only 1.79%. The effect of the additive on absorption spectra and the atomic force microscopy images of L（TPA-bTV-DCN）-PCv0BM blend films were further investigated. The improved efficiency of the device could be ascribed to the enhanced absorption and optimized domain size in the L（TPA-bTV-DCN）-PC70BM blend film.
