[Cu(C8H4F3O2S)2(C12H8N2)]·C3H6O的合成及其晶体结构

标题配合物 [Cu(C8H4 F3O2 S) 2 (C12 H8N2 ) ]·C3H6 O属于三斜晶系 ,空间群为P1,并测得如下晶胞参数a =10 .5 77(3) ,b =15 .72 2 (4) ,c =10 .133(2 ) ,α =94 .5 3(2 ) ,β =10 0 .81(2 ) ,γ =96 .18(2 )° ,V =16 37.0 3 3,Z =2 ,Mr =74 4.18,Dx =1.5 1× 10 6 g·m- 3,F(0 0 0 ) =5 2 6 ,μ =8 2 4cm- 1,最终偏差因子为R =0 .0 83,Rw=0 .0 74。Cu(II)与 2个 4 ,4 ,4 三氟 1 (2 噻吩基 )丁二酮 1,3中的四个氧原子和菲咯啉中的两个氮原子 ,组成了一个畸变的八面体构型。     

Tin Mediated Allylation of Aldimines with Allyl Bromide

SyntheticinterestsinhighlyfunctionalizedacyclicandcyclicamineshavecontributedtothewealthofexPerimentalmethodologydeveloPedfortheadditionofcarbanionstothecarbon-nitrogendoublebondofimines.Generally,organometallicreagentsorilltermedi-atesareusedascarbanionsandadditionofallylicorganometallicspeciestothenieconshtutesavaluablemethodforthesynthesisofhomoallylamines.'Amongthese,allyLlithium,'-magnesium,'-zinc,'-boraneandboronate,'-silaneand-stannane'havebeenusedforallylationofdriines.Ontheotherhand,…     

Mononuclear and dinuclear copper(I) complexes with a particularly bulky phosphine ligand. Unusual synthesis and crystal structure characterizations

Summary The addition of NPm (diphenylaminodiphenylphosphinomethane) to CuI or the addition of KI to (NPm)₂CuNO₃ leads to the same P-bonded Cu^I complex, (NPm)₂CuI, presenting a trigonal geometry around the Cu atom. The reaction of this new complex (or of its chloro analogue) with a Cu^II salt yields dinuclear species of general formula [(NPm)Cu(-X)₂Cu(NPm)] (X = Cl or I). X-ray analysis of these complexes show that they are isostructural and retain the trigonal geometry around the metal atom. The Cu···Cu distances are 2.775(1)Å for X = Cl and 2.642(1) Å for X = I. The Cu-(-X)-Cu angle is more acute for the iodide [61.48(3)°] than for the chloride [74.17(8)°] complex. These values are discussed in terms of Cu···Cu interactions induced by the electron donor ability of X and the bulk of the phosphine L.     

Synthesis of an isomer of the germacranolide isoaristolactone

Photocycloadditlon of (+)-isoplperltenone and cyclobutene-1-carboxylic acid gives an adduct which upon reduction with NaCNBH₃ followed by thermolysis yields an isomer of isoaristolactone in an overall yield of 26%.     

Large-scale synthesis of TiO2 nanorods via nonhydrolytic sol-gel ester elimination reaction and their application to photocatalytic inactivation of E. coli

A simple method of synthesizing a large quantity of TiO(2) nanorods was developed. A nonhydrolytic sol-gel reaction between titanium(IV) isopropoxide and oleic acid at 270 degrees C generated 3.4 nm (diameter) x 38 nm (length) sized TiO(2) nanocrystals. The transmission electron microscopic image showed that the particles have a uniform diameter distribution. X-ray diffraction and selected-area electron diffraction patterns combined with high-resolution transmission electron microscopic image showed that the TiO(2) nanorods are highly crystalline anatase crystal structure grown along the [001] direction. The diameters of the TiO(2) nanorods were controlled by adding 1-hexadecylamine to the reaction mixture as a cosurfactant. TiO(2) nanorods with average sizes of 2.7 nm x 28 nm, 2.2 nm x 32 nm, and 2.0 nm x 39 nm were obtained using 1, 5, and 10 mmol of 1-hexadecylamine, respectively. The optical absorption spectrum of the TiO(2) nanorods exhibited that the band gap of the nanorods was 3.33 eV at room temperature, which is 130 meV larger than that of bulk anatase (3.2 eV), demonstrating the quantum confinement effect. Oleic acid coordinated on the nanorod surface was removed by the reduction of the carboxyl group of oleic acid, and the Brunauer-Emmett-Teller surface area of the resulting naked TiO(2) nanorods was 198 m(2)/g. The naked TiO(2) nanorods exhibited higher photocatalytic activity than the P-25 photocatalyst for the photocatalytic inactivation of E. coli.     

对在建标技术报告中正确贯彻《测量不确定度表示指南》的理解

针对计量人员在贯彻《测量不确定表示指南》,尤其是在撰写“建标技术报告”时遇到的一些体问题,进行了探讨。     

Surface modification of γ-alumina membranes by silane coupling for CO2 separation

Top layers of γ-Al₂O₃ composite membranes have been modified by the silane coupling technique using phenyltriethoxysilane for improving the separation factor of CO₂ to N₂. The separation efficiency of the modified membranes was strongly dependent upon the hydroxylation tendency of the support materials and the amount of the special functional group (i.e. phenyl radical) which was coupled onto a top layer. The separation factor through the TiO₂ supported γ-Al₂O₃ membrane was found to be fairly enhanced by silane coupling, but in case of the -Al₂O₃ supported membrane was not. The CO₂/N₂ separation factor through the modified γ-Al₂O₃/TiO₂ composite membrane is 1.7 at 90°C and ΔP = 2 × 10⁵ Pa for the binary mixture containing 50 vol% CO₂. The separation factor is proportional to the CO₂ concentration in the gas mixture, and the modified membrane is stable up to 100°C. The main mechanism of the CO₂ transport through the modified γ-Al₂O₃ layer is known to be a surface diffusion.     

Baylis-Hillman reactions of N-tosyl aldimines and aryl aldehydes with 3-methylpenta-3,4-dien-2-one

The attempted Baylis-Hillman reactions of N-tosyl aldimines and aryl aldehydes with 3-methylpenta-3,4-dien-2-one gave the corresponding Baylis-Hillman adducts 3 and 6 in moderate to good yields in the presence of DMAP in DMSO, respectively. In the case of the aza-Baylis-Hillman reactions of N-tosyl aldimines with 3-methylpenta-3,4-dien-2-one catalyzed by PBu3, the corresponding aza-Baylis-Hillman derivatives 4 and 5 were formed at the same time.     

MALDI-TOF-MS法对重组人内皮抑素蛋白分子质量测定

肿瘤的生长依赖于血管的生成,新生血管不仅为肿瘤生长提供必需的营养物质,而且为肿瘤细胞扩散提供了重要的途径。1997年哈佛大学的O'Reilly等发现了一种内源性新血管生成抑制因子内皮抑素(Endoscatin),显示出特异抑制激活的血管内皮细胞增殖和肿瘤新血管生成的生物学活性,其抗肿瘤作用具有高效、低毒、无耐药性的优点。目前,内皮抑素的研究引起了国内外广泛的兴趣,在美国已进行以安全性为目的的I期临床实验,国内也有多家公司对内皮抑素进行了抗肿瘤研究并申报一类新药。内皮抑素有望成为医治肿瘤而又没有化疗和放疗的毒副作用的一种新的治疗方法,但是否能作为药物应用于临床,尚需对内皮抑素的结构特点及抑制肿瘤和内皮细胞的作用机制等方面进行许多深入的研究。     

Regioselective coupling of pentafluorophenyl substituted alkynes: mechanistic insight into the zirconocene coupling of alkynes and a facile route to conjugated polymers bearing electron-withdrawing pentafluorophenyl substituents

The reaction of Cp(2)ZrCl(2) with 2 equiv of BuLi at -78 degrees C, followed by the addition of an unsymmetrical tetra- or pentafluorophenyl substituted alkyne R(1)C[triple bond]CAr(f) (R(1), Ar(f) = (CH(2))(4)Me, p-C(6)F(4)H; Me, p-C(6)F(4)H; Ph, C(6)F(5)), resulted in regioselective couplings of these alkynes to zirconacyclopentadienes in which the Ar(f) substituents preferentially adopt the 3,4-positions (beta beta) of the zirconacyclopentadiene ring. With Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) as the zirconocene reagent, the couplings could be carried out at room temperature; however, at higher temperatures significant quantities of the 2,4-fluoroaryl substituted (alpha beta) isomers were also formed. None of the conditions employed produced the 2,5-fluoroaryl substituted (alpha alpha) isomers. These fluoroaryl-substituted zirconacyclopentadienes were readily converted to butadienes via reactions with acids. The zirconacyclopentadiene Cp(2)ZrC(4)-2,5-Ph(2)-3,4-(C(6)F(5))(2), which resulted from the coupling of PhC[triple bond]C(C(6)F(5)), was converted to the corresponding thiophene by reaction with S(2)Cl(2), and to an arene by reaction with MeO(2)CC[triple bond]CCO(2)Me/CuCl. Mechanistic studies on zirconocene couplings of (p-CF(3)C(6)H(4))C[triple bond]C(p-MeC(6)H(4)) indicate that the observed regioselectivities are determined by an electronic factor that controls the orientation of at least one of the two alkynes as they are coupled. Additionally, these studies suggest an unsymmetrical transition state for the zirconocene coupling of alkynes, and this is supported by DFT calculations. The reaction of [(C(6)F(5))C[triple bond]CCH(2)](2)CH(2) with Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) resulted in a zirconacyclopentadiene in which the pentafluorophenyl substituents have been forced into the 2,5-positions (alpha alpha). Zirconocene coupling of the diyne (C(6)F(5))C[triple bond]C-1,4-C(6)H(4)-C[triple bond]C(C(6)F(5)) provided a route to conjugated polymers bearing electron-withdrawing pentafluorophenyl groups.