Structure and stabilities of (HA1NH)n (n = 2–4)

Ab initio molecular electronic structure methods have been used to study the relative stability of the planar inorganic ring (HAlNH)_n (n = 2–4) during homodesmotic and monomer polymerization reactions. Optimized geometries, frequencies and energies through restricted Hartree-Fock/6-31G* are reported, and energies at the self-consistent field optimized geometries including M?ller-Plesset fourth perturbation theory with single, double and quadruple excitation (MP4SDQ) corrections are also reported for both reactions. Homodesmotic reactions with MP4SDQ −28.5 kcal/mol for (AlN)₂, 1.9 kcal/mol for (AlN)₃ and −0.97 kcal/mol for (AlN)₄. On analysing a π-molecular orbitals diagram, only one, three and three strongly bonding π-molecular orbitals exist for the planar four-, six- and eight-membered AlN rings, respectively. Received: 9 March 1998 / Accepted: 19 March 1998 / Published online: 23 June 1998     

中国大学化学教育改革25年回顾

1中国大学化学教育历史1.1萌芽时期(1865~1910年)中国人民在长期的生产劳动过程中积累了丰富的化学知识,形成了许多成功的化学工艺,如陶瓷、酿造、炼丹、医药、火药、造纸、纺织等,但由于历史原因,这些丰富的化学知识和成功的化学工艺并没有上升为理论而形成化学学科。化学作为一门科学诞生于17世纪的西欧,其标志为1661年波义耳对“元素”提出了科学定义,继而1803年道尔顿提出了原子论,1860年康尼查罗提出原子分子论,1870年门捷列夫发现元素周期律。至19世纪中,化学已发展成一门具有坚实理论的基础学科,化学对西方物质文明的发展起了巨大的…     

高校实验教学考核模式改革探索与实践

归纳了实验教学考核模式改革的一些经验,在此基础上,针对《网络攻防技术》课程实验的考核模式进行了改革,设计了网络攻防实验考核测评指标体系,构建了网络攻防实验考核平台,提出了全过程跟踪的实验考核评价方法,取得较好的实践效果.     

弯折波导杆的超声斜入射方法*

波导杆技术是一种有效的超声辅助检测方法,在提升高温关键承压设备安全运行方面具有重要作用。现有的波导换能器因直入式发射声波,常被用来在线监测壁厚的腐蚀进程,难以对指定方向的缺陷进行有效检测。为了解决这个难题,基于斯涅耳定理以及导波的频散特性提出了一种弯折结构的波导杆来实现超声斜入射。首先分析了弯折波导杆中水平剪切波的传播特性,探究了波导杆的厚度、弯折角度对杆中声波传播的影响规律;然后,进一步研究了弯折波导杆在半无限空间内的声束指向性;最后通过一对弯折波导杆在线检测结构内部缺陷的试验证明了波导超声斜入射的应用价值。研究结果为基于斜入射技术的波导超声在线监测提供了坚实的理论基础。     

Size‐Dependent Surface Activity of Rutile and Anatase TiO2 Nanocrystals: Facile Surface Modification and Enhanced Photocatalytic Performance

The size‐dependent surface activity of titania was illustrated through the formation of ultrafine nanocrystals with clean surfaces. It was demonstrated that, when the size of the nanocrystals was small enough, their surface activity could be significantly enhanced, as evidenced by the formation of transparent macroassemblies, their increased dispersity in various solvents, the facile modification of their surface by organic molecules at room temperature, their strong visible‐light absorption through coordination with peroxide, and highly enhanced photocatalytic performance.     

Discotic liquid crystals of cucurbit[7]uril (CB[7])-functionalised Laponite clays

ABSTRACT

Here we demonstrate that in the presence of the small, barrel-shaped molecule cucurbit[7]uril (CB[7]) Laponite clay particles undergo a phase transition into a birefringent gel with lamellar structure and a fluid, Laponite-poor aqueous solution. We employ various characterisation methods and polarised light microscopy to study this transition and the system's structural and optical properties. Furthermore, when dried completely we obtain a layered, transparent composite film, still retaining some liquid-crystalline structure that can be rehydrated reversibly. We argue that this new system may be a model system for anisotropic patchy particles.     

Tetrathienylethene‐based Positional Isomers with Aggregation‐induced Emission Enabling Super Red‐shifted Reversible Mechanochromism and Naked‐eye Sensing of Hydrazine Vapor

AIE‐active positional isomers, TTE‐o‐PhCHO , TTE‐m‐PhCHO and TTE‐p‐PhCHO , tetrathienylethene ( TTE) derivates with peripherally attached ortho‐/meta‐/para‐formyl phenyl groups, were designed and synthesized. The formyl substitution position can effectively modulate their photophysical properties, mechanochromism and fluorescent response to hydrazine. TTE‐o‐PhCHO and TTE‐m‐PhCHO exhibit remarkable AIE characteristics, and TTE‐p‐PhCHO possesses aggregation‐induced emission enhancement performance. They all exhibit high contrast mechanochromism, and TTE‐m‐PhCHO shows larger red‐shift (164 nm) than TTE‐o‐PhCHO (104 nm) and TTE‐p‐PhCHO (125 nm) due to the more twisted molecular conformation and much looser molecular packing. Moreover, TTE‐o‐PhCHO with a higher contrast color change can be used as ink‐free rewritable paper. In addition, TTE‐p‐PhCHO , as a turn‐on fluorescent probe, can selectively detect hydrazine with significant color changes that are visible by the naked eye . Therefore, the position dependence of groups would be an effective method to modulate the molecular arrangement, as well as develop AIE compounds for mechano‐stimuli responsive materials, ink‐free rewritable papers and chemosensors.     

基于半互穿聚合物网络的高温质子交换膜的制备

通过构筑基于含不饱和双键的磺化聚芳醚酮(Allyl-SPAEK)与芳醚型聚苯并咪唑(PBI)的半互穿聚合 物网络(IPN), 获得综合性能优异的可用于高温质子交换膜燃料电池的PBI/Allyl-SPAEK复合膜材料. 在对 Allyl-SPAEK和PBI的分子进行设计和合成的基础上, 采用溶液共混-浇铸方法, 基于UV辐照交联, 获得了由丙烯基生成的共价键和咪唑基-磺酸基形成的强酸碱相互作用组成的IPN新体系, 并系统研究了新型复合膜的热、 机械性能和质子传导率. 结果表明, 具有PBI/Allyl-SPAEK半互穿聚合物网络的复合膜具有较高的质子 传导率和力学性能, 在同等磷酸吸附水平和测试条件下优于PBI膜. 在磷酸吸附水平为13.0左右时, PBI/ Allyl-SPAEK复合膜的最大拉伸强度达到12.1 MPa, 杨氏模量达到131.5 MPa, 是同等磷酸吸附水平下 PBI 膜的2.04倍. 在200 ℃时, 两种PBI/Allyl-SPAEK复合膜的质子传导率均达到 200 mS/cm以上, 比PBI膜传导率提高了38%.