HNCS与C_2H(X~2Π)反应微观动力学的理论研究

用量子化学密度泛函理论的UB3LYP/6-311 G鄢鄢方法和高级电子相关的UQCISD(T)/6-311 G鄢鄢方法研究了异硫氰酸(HNCS)与乙炔基自由基(C2H(X2Π))反应的微观机理.采用双水平直接动力学方法IVTST-M,获取反应的势能面信息,应用正则变分过渡态理论并考虑小曲率隧道效应,计算了在250～2500K温度范围内反应的速率常数.研究结果表明,HNCS与C2H(X2Π)反应为多通道、多步骤的复杂反应,共存在三个可能的反应通道,主反应通道为通过分子间H原子迁移,生成主要产物NCS C2H2.反应速率常数随温度升高而增大,表现为正温度效应.速率常数计算中变分效果很小.在低温区隧道效应对反应速率的贡献较大,反应为放热反应.     

汞(II)与牛血红蛋白相互作用的研究

本文采用紫外光谱(UV/VIS)、荧光光谱和圆二色谱等方法,对汞(II)与牛血红蛋白(BHb)的相互作用进行了研究。结果表明:Hg2 处理导致BHb紫外吸收的增加,出现LMCT带,并随Hg2 浓度的增加LMCT带强度显著增强。BHb分子中Soret带的吸收随着Hg2 作用时间的增加而持续降低,表明Hg2 使部分血红素辅基从BHb中脱离出来。蛋白内源荧光光谱显示,Hg2 与BHb的结合会影响蛋白质的三级结构和四级结构。远紫外圆二色谱表明,Hg2 处理会导致BHb蛋白的α-螺旋含量减少。     

Synthesis, Crystal Structure and Electrochemistry Properties of a (N,N'-Ethylene-bis(salicylaldiminato)) Nickel(Ⅱ) Complex, [Ni2(salen)2]·NCS-NH4

A new Ni(Ⅱ) complex [Ni2(salen)2]·(NCS)·NH4 (salen = N,N'-bis(salicylidenea-mino)ethanato) has been prepared and structurally characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 16.8725(13), b = 19.0046(15), c = 20.0583(16) (A), Z = 8, V = 6431.8(9) (A)3, C33H32N6Ni2O4S1, Mr= 726.13, Dc = 1.500 g/cm3, F(000) = 3008, μ = 1.284 mm-1, the final R = 0.0394 and wR = 0.0767 for 4449 observed reflections with Ⅰ＞2σ(Ⅰ). The complex involves a N,N'-ethylene-bis(salicylaldiminato) Schiff base, an isothiocyanato anion and an ammonium cation. The nickle(Ⅱ) ion adopts a distorted square coordination geometry with N2O2 set of Schiff base ligand. The complexes are linked into a dimmer via intermolecular hydrogen bonds and the [Ni(salen)] moieties are connected together to form a 2-D layer structure by intermolecular N-H…O hydrogen bonds and π-π stacking. Cyclic-voltammetry method was used to characterize electrochemically the complex.     

降冰片烯开环易位聚合反应的分子量及分子量分布控制

使用Grubbs催化剂催化降冰片烯单体进行开环易位聚合反应, 研究了催化剂搅拌溶解时间、聚合反应的溶剂极性和三苯基膦的加入等反应条件对降冰片烯单体ROMP反应分子量及分子量分布的影响, 从而得到降冰片烯ROMP反应的最佳条件.     

简法合成甲地孕酮

本文报道了合成甲地孕酮的简便方法,即以17α-乙酰氧基-黄体酮(3)为原料,将其烯醇醚(4)经Mannich反应,或将△~(3,5)-3,17α-二乙酰氧基-黄体酮(2)与二乙氧基甲烷反应,生成6-次甲基-17α-乙酰氧基-黄体酮(5),然后将5用钯/碳酸钙作催化剂转位得目的物甲地孕酮(6b),总收率分别为56%和50%(均以17α-羟基-黄体酮(1)为起始物)。     

Photoisomerization and photodissociation of aniline and 4-methylpyridine

Photoisomerization and photodissociation of aniline and 4-methylpyridine at 193 nm were studied separately using multimass ion imaging techniques. Photofragment translational energy distributions and dissociation rates were measured. Our results demonstrate that more than 23% of the ground electronic state aniline and 10% of 4-methylpyridine produced from the excitation by 193 nm photons after internal conversion isomerize to seven-membered ring isomers, followed by the H atom migration in the seven-membered ring, and then rearomatize to both methylpyridine and aniline prior to dissociation. The significance of this isomerization is that the carbon, nitrogen, and hydrogen atoms belonging to the alkyl or amino groups are involved in the exchange with those atoms in the aromatic ring during the isomerization.     

铂-金交替修饰的铂核纳米颗粒的制备与表征

通过吸附在铂纳米颗粒表面的氢交替还原氯金酸和氯铂酸,得到了复合型纳米颗粒Pt@Au/Pt,用UV-Vis光谱、TEM和XRD对其进行了表征.     

纳米晶复合Nd2Fe14B/α-Fe合金制备与磁性能的研究

采用熔体快淬及晶化处理工艺制备Nd11Fe71Co8V1.5Cr1B7.5纳米晶合金。经21m·s-1快淬及640℃ 4min晶化处理后,制成的粘结磁体的磁性能最佳,为:Br=0.64T,JHc=903.5kA·m-1,(BH)max=71kJ·m-3。添加Cr元素可提高内禀矫顽力,从而提高最大磁能积。     

Surface-enhanced Raman scattering (SERS) from different azobenzene self-assembled monolayers and sandwiches

Self-assembled monolayers (SAMs) of functionalized azobenzene thiols (RAzoCnSH, n=3-6 for R=H, abbreviated as AzoCnSH; and n=4 for R=CH(3)CONH, abbreviated as aaAzoC4SH) on different substrates RAzoCnSz.sbnd;z.sfnc;S (S represents substrates of vacuum-deposited gold (Au), silver foil (Ag), HNO(3) etched silver foil (EAg), and silver mirror (mAg)) have been studied by SERS in the near-infrared region. SERS of the SAMs on EAg and/or mAg exhibit SERS effects that vary with etching time and/or deposition time. The most appropriate time is 5 s for etching in 1:1 HNO(3) and 40 s for deposition in 0.1 M Ag(NH(3))(2)NO(3). Further, a layer of Ag mirror was conveniently deposited on the top of the SAMs on different substrates, yielding a more efficient SERS-active system possessing a "sandwiched" structure of mAgz.sfnc;RAzoCnS-z.sfnc;S. An appropriate surface roughness is required for the strongest SERS effect. Scanning electron microscopy (SEM) indicates that there exist a large number of projects around 100 nm on the surface showing the strongest SERS effect. When the surface roughness is decreased or increased, the SERS effect decreases sharply. The relationship between the SERS effect and the structural nature was investigated and showed that the enhancement factor decays exponentially with increasing in distances of the azobenzene group from the underlying substrate or the overlying silver mirror. This result reveals that the SERS effect may be the result of the electromagnetic coupling effect between two metal layers.     

纤维素/甲壳素共混膜的结构表征与抗凝血性能

以 6wt %NaOH 4wt%尿素为纤维素的新溶剂 ,采用溶液共混法制备出纤维素 甲壳素共混膜 ,为甲壳素在碱性溶液中制膜提供了新的方法 .红外光谱、X 射线衍射、扫描电镜和力学性能、抗凝血性能测试结果表明 ,共混膜中甲壳素含量低于 4 0wt%时 ,纤维素与甲壳素分子间具有良好的相容性 ;在纤维素中引入适量甲壳素可提高共混膜的抗张强度 ,共混膜的干、湿态抗张强度在甲壳素含量 10wt%时最大 ,其值分别为 89 1MPa和 4 3 7MPa ,比纯态纤维素膜的干、湿态抗张强度分别提高了 6 7%和 11 5 % ;甲壳素的引入可明显降低血小板在共混膜表面的粘附、凝聚与变性 ,增大共混膜的抗凝血参数 ,甲壳素含量达到 5 0wt%时 ,该共混膜具有良好的抗凝血性能