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.     

The Intelligent Properties of Micro－reactors for Preparating Nanoparticles

TiO2 nanoparticles were synthesized by using micro-reactors. The shape and size of the nanoparticles produced from the original micro-reactors and the five times recycled micro-reactorsmother liquor were investigated on transmission electron microscopy (TEM) by using the original sample, freeze prepared sample, and dyeing treated sample, respectively. UV-VIS spectrometry was used to study the growth process of TiO2 nanoparticles in main reactors. The results showed that micro-reactors with nanometer magnitude had spherical or oval structures, and could restore to their original structure after they were destroyed. The products prepared in the original micro-reactors were similar to that in the micro-reactors recycled for many times, suggesting that the micro-reactors had memory function.     

Two New Steroidal Saponins from Tacca plantaginea

Two new C27 steroidal glycosides, named taccaoside A(1) and B(2), were isolated from the traditional Chinese herb Tacca plantaginea. The spectroscopic and chemical evidences revealed their structures to be 26-O-β-D-glucopyranosyl-(25R)-3β,26-dihydroxy furost-5,20-diene-3-O-[α-L-rhamnopyranosyl(1→2)]-[α-L-rhamnopyranosyl(1→3)]-β-D-glucopyranoside(1) and 26-O-β-D-glucopyranosyl-(25R)-3β,26-dihydroxy furost-5,20-diene-3-O-[α-L-rhamnopyranosyl-(1→2)]-[β-D-glucopyranosyl(1→3)-α-L-rhamnopyranosyl(1→3)]-β-D-glucopyranoside(2),respectively.     

南药巴戟天中十二种无机元素与药效关系的进一步研究

在初步研究的基础上，进一步研究了不同产地巴戟天的无机元素含量差异，通过对比各元素含量、相关系数及TE图谱，说明地道药材与非地道药材的巴戟天，其特征元素的含量存在非常明显的差异，要使大面积扩种的药材提高药效，建议根据当地土壤含Mn、Fe、Cr、Co、Ni的含量，以旋微量元素肥料的方法来补充这些元素在土壤中的不足。但在微量元素肥料配方中，应注意巴戟天吸收土壤中的元素时的协同作用和拮抗作用。     

超声辐射下某些含官能团化合物与二氯卡宾的反应

超声辐射在有机反应中的应用日趋广泛。我们曾报道了超声辐射与相转移催化相结合产生二氯卡宾和二溴卡宾的方法及其与烯烃加成反应的结果。该法比单纯使用相转移催化剂或超声辐射更为可取。本文进一步将它用于二氯卡宾与某些含官能团化合物的反应,考察超声辐射的影响。反应是在固-液两相条件下进行的,即以粉末状氢氧化钠为碱,氯仿过量兼作溶剂。结果表明,超声辐射对各类化合物反应的影响有相当明显的差异。     

氟烷基化C_(60)与四（N，N-二甲基）氨基乙烯电荷转移复合物磁性的EPR研究

变温ERP研究揭示氟烷基化富勒烯C_(60)(R_f)_n与四(N,N-二甲基)氨基乙烯 (TDAE)间稳定的电荷转移络合物TDAE-C_(60)(R_f)_n的居里温度高达190K[R_f = C_3F_7，H（CF_2）_4]。而非氟烷基化络合物TDAE-C_(60)的相应值仅为16.1K。 这种铁磁性可能是络合物分子中氟烷基化富勒烯多价阴离子基在相应居里温度下具 有某种有序排列的缘故。     

Order from Chaos: Self‐Assembly of Nanoprism from a Mixture of Tetratopic Terpyridine‐Porphyrin Conformers

Porphyrins have been widely used in the self‐assembly of metallo‐supramolecules. In this study, we introduced 2,2':6,2"‐terpyridine (tpy) into a porphyrin core to synthesize a tetratopic building block with multiple conformers. During the self‐assembly with Zn(II), such a mixture of conformers was able to form a discrete nanoprism with all building blocks in one conformation. Detailed characterizations, including NMR, ESI‐MS and traveling‐wave ion mobility‐mass spectrometry (TWIM‐MS), all supported the formation of the desired assemblies. AFM and TEM further confirmed the dimensions of assembled nanoprisms. Moreover, the photophysical properties of the ligands and complexes were noticeably different depending upon size and metal ion center.     

Preparation and characterization of functional group gradient surfaces

Functional group gradient surfaces where the density of functional groups changes gradually along the sample length were prepared. The functional group (? COOH, ? CONH₂, and ? OH group) gradient surfaces were produced by the treatment of low-density PE sheets using a corona with gradually increasing power, followed by the graft copolymerization of acrylic acid and subsequent substitution reaction of carboxylic acid groups to amide or hydroxyl groups. The prepared gradient surfaces were characterized by the measurement of water contact angle, FTIR-ATR, and ESCA. The gradient surfaces prepared can be used to systematically investigate the interactions of biological or other species in terms of the surface functional groups and their density of polymeric materials. © 1994 John Wiley & Sons, Inc.     

尿素法合成高结晶度类水滑石

尿素的高温分解特性被用于控制层状化合物合成过程中的pH值。室温下尿素可与硝酸盐形成均一溶液，当其高温分解时可以保证溶液内部各点的pH值始终一致，因而可获得高结晶度的水滑石样品。利用该法可合成出Mg-Al、Zn-Al及Ni-Al类水滑石，但难以合成出Co-Al，Mn-Al及Co-Cr类水滑石，相信这与不同金属离子发生沉淀时所需的pH值有关。     

A New Hydroxo‐bridged Chromium(III) Dimer [Cr(saltn)OH]2·4H2O: Synthesis,Crystal Structure and Magnetic Properties

A new hydroxo‐bridged dimeric Cr(III) complex [Cr(saltn)OH]₂·4H₂O [H₂saltn=N,N′‐bis(salicylidene)trimethylenediamine] has been synthesized and its structural and magnetic properties have been investigated. The complex crystallizes in the triclinic space group P‐1 with one dimeric formula unit in a cell of dimensions a=0.95828(19) nm, b=0.95926(19) nm, c=1.0437(2) nm, α=86.77(3)°, β=82.48(3)°, and γ=64.93(3)°. The geometry around each chromium(III) center is six‐coordinate, distorted‐octahedral. The bridging Cr₂O₂ unit is strictly planar, as required by the crystallographic symmetry. The Cr? O? Cr′ bridging angle is 99.94(16)°, and the distance between Cr…Cr′ is 0.3019 nm. The magnetic susceptibility of the complex has been examined in the range of 2‐300 K. By using the spin‐spin coupled model for an S₁=S₂=3/2 dimeric system , the magnetic data were fitted to give the parameters of g=2.01(1), J=‐0.85(2) cm^‐1, and zJ' =0.18(3)cm^‐1, indicating the presence of a weak antiferromagnetic spin‐exchange interaction between the Cr(III) ions in the binuclear complex.