亚微米级四方相钛酸钡低温固相法制备及晶型控制

以八水合氢氧化钡和α-钛酸为原料,在相对低的焙烧温度下,制备出近似球形、亚微米级的钛酸钡。通过XRD、SEM、Raman和FTIR等手段对钛酸钡样品进行表征,样品具有高结晶度,颗粒均一性良好。晶型转变的初步探究表明,立方相为主的钛酸钡可以在400℃发生晶相转变,成为以四方相为主的钛酸钡。     

Hydrothermal synthesis, structure and quantum chemistry of transition metal complex supported by metal-oxo cluster [(Ni(phen)22 (ξ-Mo8O26)]

A nickel-1,10-phenanthroline complex supported on an octamolybdate, [(Ni(phen)_{2 2}(ξ-Mo₈O₂₆)], has been hydrothermally synthesized with MoO₃, H₂MoO₄, Ni(OAc)₂ 6H₃O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to monoclinic P2₁/n space group,a = 1.2952(2),b = 1.6659(10),c = 1.3956(12) nm, β =106.273(8)°,V = 2.8906(5) nm³,Z = 2. 5604 observable reflections (I >2σ(I)) were used for structure resolution and refinements to converge to finalR ₁ = 0.0414,wR ₂ = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as ξ-isomer). The feature of ξ-[Mo₈O₂₆]^4- is that it is composed of Mo₆O₆ ring and two MoO₆ octahedral located at cap positions on opposite faces. The Mo₆O₆ ring contains two octahedral and four trigonal-bipyramidal Mo^VI atoms. Each ξ-[Mo₈O₂₆]^4- unit is bonded with two [Ni(phen)₂]²⁺ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo₆O₆ ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method.     

临界点二级相变的有限时间热力学逼近

应用内可逆卡诺循环的方法,导出了各种物质在临界点附近可逆与不可逆二级相变普遍适用的比热跃变公式以及广义的爱伦菲斯特方程。对简单(P,V,T)系统、超导、电介质顺电一铁电二级相变进行了应用讨论。     

Advances in late transition metal catalysts for olefin polymerization/oligomerizarion

In this review article, we have consolidated our recent studies on late transition metal catalysts (mainly Fe, Co) for olefin polymerization/oligomerization. A series of bisiminopyridyl Co(II) and Fe(II) complexes were synthesized. These catalysts when activated with MAO in aromatic or aliphatic hydrocarbon solvents, oligomerize or polymerize ethylene to α-olefins or high molecular weight polymers with exceptionally high activities and selectivities. The electronic and steric effects of allyloxy and benzyloxy substituted bisiminopyridyl Fe(II) and Co(II) complexes were also investigated. The influence of catalyst structure and temperature on the polymerization activity, thermal properties and molecular weight were discussed. The effects of heterogenization of these catalysts on silica and modified SBA-15 were analyzed. The polymerization of polar monomers such as vinyl ethers and methyl methacrylate was tested and no specific trends in activity and polymer molecular weight with changes in steric bulkiness around the metal center were observed with the same catalyst system.     

The versatility of pentalene coordination to transition metals: a density functional theory investigation

DFT calculations with full geometry optimization have been carried out on a series of real and hypothetical compounds of the type [CpM(C8H6)], [(CO)3M(C8H6)], [M(C8H6)2], [(CpM)2(C8H6)], [[(CO)3M]2(C8H6)], and [M2(C8H6)2] (M = transition metal). The bonding in all the currently known compounds is rationalized, as well as in the (so far) hypothetical stable complexes. Depending on the electron count and the nature of the metal(s), eta2 (predicted), eta3, eta5, eta8, or intermediate coordination modes can be adopted. In the case of the mononuclear species, the most favored closed-shell electron counts are 18 and 16 metal valence electrons (MVE). In the case of the dinuclear species, an electron count of 34 MVEs is most favored. However, other electron counts can be stabilized, especially in the case of dinuclear complexes. Coordinated pentalene should most often be considered as formally being a dianion, but sometimes as a neutral ligand. In the former case it can behave as an aromatic species made of two equivalent fused rings, as a C5 aromatic ring connected to an allylic anion, or even as two allylic anions bridged by a C7=C8 double bond. In the latter case, it can behave as a bond-alternating cyclic polyene or as a C5 aromatic ring connected to an allylic cation.     

酞菁配合物对锂-亚硫酰氯电池正极的催化作用

合成过渡金属酞菁配合物MPc(M=Mn(Ⅱ),Fe(Ⅱ),Co(Ⅱ),N i(Ⅱ),Cu(Ⅱ)),研究MPc及其中心离子对L i/SOC l2电池正极的催化作用,并提出相关催化机理.     

新型超支状液晶核酸传感器用于p53突变基因的检测

基于核酸杂交链式反应影响液晶取向的原理, 构建了一种新型的超支状液晶核酸传感器用于检测p53突变基因. 本文突破传统构建超支状分子的方式, 采用杂交链式反应方法, 以目标序列p53突变基因作为引发剂, 3种不同的发卡探针Hairpin A, Hairpin B和Hairpin C为单体, 在温和的条件下, 通过改变单体的浓度和反应时间自发杂交组装形成尺寸和分子量可控的超支状DNA(branched-like DNA, bDNA). 借助捕获探针将该超支状DNA连接到液晶传感基底表面, 观察液晶分子取向改变前后的光学信号, 实现了p53基因含249密码子突变序列的快速检测. 本方法有望为核酸诊断的发展提供一种新的方法和思路.     

pH响应性P(MMA-co-MAA-co-HEMA)微凝胶的制备及其性能

利用预乳化乳液法制备了不同单体配比的聚(甲基丙烯酸甲酯-co-甲基丙烯酸-co-甲基丙烯酸羟乙酯)(P(MMA-co-MAA-co-HEMA))微凝胶分散液;采用透射电子显微镜、动态光散射仪研究了微凝胶的微观形态、粒径大小及其溶胀率;利用试管倒转法对微凝胶分散液的凝胶化相转变行为进行了研究,借助椎板流变仪考察了所形成胶态凝胶的储能模量与单体配比、微凝胶分散液浓度和温度的关系.结果表明,所制备的微凝胶的数均粒径为90 nm左右,当MMA与MAA的投料质量不变时,随着HEMA含量的增加,分散液凝胶化所需的临界最小浓度增大,临界最大pH值减小,胶态凝胶的储能模量增加.当保持单体MMA与HEMA的投料质量不变时,随着单体MAA投料质量的增多,微凝胶的数均粒径和溶胀率增大,胶态凝胶的储能模量先升高后降低;当MAA占单体总摩尔数的25%时,浓度为15 wt%的微凝胶分散液在扫描频率为100 rad/s时,胶态凝胶的储能模量最高可达2×104Pa.这类微凝胶分散液在组织工程支架材料方面有潜在的应用价值.     

基底界面效应对聚苯乙烯薄膜分子运动行为的影响

本文研究了Si／Si02、Si／Si—H基底与聚苯乙烯（Ps）之间的界面相互作用对Ps薄膜的玻璃化转变及相关力学性能的影响．结果显示,无论何种基底,Ps薄膜的玻璃化转变温度（L）都随其厚度降低而降低．但相同厚度（〈110nm）下,以Si／Si-H为基底时Ps薄膜的瓦比以Si／Si02为基底的PS薄膜高．Si／Si02表面Ps薄膜疋开始下降的临界厚度为110nm,远高于以Si／Si—H为基底时的40nm．对Ps薄膜的膨胀系数和弹性模量进行研究,也得到相似的临界厚度．另外,与Si／Si02基底相比,在Si／Si-H上的Ps薄膜具有更低的膨胀系数以及较高弹性模量．可能原因是Si／Si-H与Ps具有较强的相互作用,限制了该界面分子的运动能力,导致基底／PS界面效应对薄膜分子运动的影响力增强,造成该薄膜瓦的厚度依赖性下降,并呈现出相对较硬的力学特征．     

钴(Ⅲ)-胺配合物模板导向合成系列稀土金属草酸盐化合物

水热条件下,以钴(Ⅲ)-胺配合物[Co(en)₃]³⁺,[Co(dien)₂]³⁺为模板,合成出了3例新的稀土草酸盐化合物{[Co(en)₃]·[KLa₂(C₂O₄)₅(H₂O)₆]·H₂O}_n (HNU-9)、{[Co(dien)₂][La₂(C₂O₄)₄(H₂O)₂]·xH₂O}_n (HNU-11)和{K₃[Co(dien)₂][La₄(C₂O₄)₉(H₂O)₂]·5H₂O}_n (HNU-12)。在这3个化合物中,不同的模板剂(Co(en)₃³⁺,Co(dien)₂³⁺,K⁺+Co(dien)₂³⁺)以不同的方式存在于这些化合物中,从而构筑出不同拓扑结构的三维骨架结构。有意思的是,由于中心金属原子La的配位模式不同,HNU-11和HNU-12展现出未报道过的新颖的拓扑结构。可见,具有高配位数的中心稀土金属原子较易构筑出具有新颖拓扑结构的化合物。