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.     

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.     

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.     

脱氢姜黄烯及其类似物的合成

利用苯乙酮及苯乙酮衍生物,经过傅-克乙酰化反应、偶联反应、Wittig烯化反应,合成了脱氢姜黄烯及其类似物.再经选择性催化氢化反应,可分别得到α-姜黄烯、黄根醇甲醚及姜黄氢醌甲醚.     

25,26,27-三失碳-B-高-7-氧-6-酮-5α-胆甾-3α,24-二醇的合成

本文报道以3α-羟基-6-羰基-5α-胆烷酸甲酯(3)为原料经六步反应合成了油菜甾醇类似物25,26,27-三失碳-B-高-7-氧-6-酮-5α-胆甾-3α,24-二醇(9a).总产率14%.9a的促进植物生长作用是24-表油菜甾醇内酯的60%.     

Highly Efficient Pd/C-Catalyzed Suzuki Coupling Reaction of p-（un）Substituted Phenyl Halide with （p-Substituted phenyl） Boronic Acid

A highly efficient Pd/C-catalyzed ligandless, heterogeneous Suzuki reaction of p-（un）substituted phenyl halide with （p-substituted phenyl）boronic acid in DMF/H2O solvent in a short reaction time （0.5 h） at 75 ℃ was developed. The key for such a catalytic system was the addition of 1 equivalent of tetrabutylammonium bromide. A wide variety of substituents can be tolerated and high yields of cross coupling products were achieved. The palladium catalyst can be easily recovered and reused without significantly decreasing its efficiency.     

LB膜诱导Ba(NO3)2晶体取向生长

In this work, Ba(NO₃)₂ crystals with single crystal face were induced by using the the method of bio-mimetic mineralization and double LB films of behenic acid (BA) as the template. The crystals were characterized by Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD). The crystals were observed in regular square shape with uniform size about 5～8 μm by SEM, and they were found by XRD to grow along the (111) plane. From these experiments, we can conclude that the good selection of the (111) crystal face of Ba(NO₃)₂ is due to the electrostatic interactions , the match between this crystal face and the definite lattice structure of the LB films.     

有机/无机杂化材料担载季铵盐催化剂的制备及其在相转移催化反应中的应用

利用溶胶-凝胶(S0l-gel)技术制备了新型的有机／无机杂化材料担载的季铵盐催化剂。优化了制备方法、反应条件等多种因素；考察了其作为相转移催化剂在1-溴代正庚烷与碘化钾的亲核取代反应中的应用，转化率最高可达到95％。     

均三氮苯类除草剂结构与活性的理论研究

利用Gaussian03程序包中的B3LYP方法,选择6-31G基组对均三氮苯类除草剂及类似衍生物2-(4-溴苄氨基)-4-甲基-6-三氟甲基-1,3,5-三氮苯进行了量子化学计算,从理论上讨论了它们的空间结构、电子结构特征与活性的关系.计算结果表明:三氮苯环与N(7)和N(8)原子形成了共轭结构,分子活性大小与LUMO轨道的得电子能力以及在LUMO轨道中占主要成分的原子有重要关系.N(7)和N(8)连接单个具有推电子能力的基团,有利于生物活性的提高.对于2-(4-溴苄氨基)-4-甲基-6-三氟甲基-1,3,5-三氮苯中,N(8)和C(9)是重要的活性部位,和传统的均三氮苯类除草剂分子相比,与D1蛋白上不同的氨基酸残基发生了键合作用.     

Pt3Co核-Pt壳型纳米粒子的制备及磁性

Pt₃Co alloy nanoparticles were prepared by the reduction of H₂PtCl₆ and Co(OOCCH₃)₂ using NaBH₄ as a reducing agent. The Pt₃Co core-Pt shell nanoparticles (Pt₃Co@Pt) were synthesized using hydrogen absorption reduction and characterized by plasma-atomic emission spectrometry (ICP), transmission electron microscopy (TEM), X-ray diffraction (XRD) and SQUID magnetometer. The results show that average size of Pt₃Co@Pt nanoparticles is 3.6 nm with a standard deviation of 0.9 nm. Heating Pt₃Co nanoparticles in air at 700 ℃ for 1 h, Co in Pt₃Co nanoparticles was oxidized to Co₃O₄ and CoO; while no oxidation tendency was detected for Pt₃Co@Pt nanoparticles. The crystallize structure of Pt₃Co@Pt changed from the face centered cube (fcc) to the face centered tetragonal (fct) after the heating treatment. The coercivity of the heated Pt₃Co@Pt reached to 276 Oe at room temperature.