Supramolecular hydrogen-bonded liquid–crystalline polymer complexes. Design of side-chain polymers and a host–guest system by noncovalent interaction

Supramolecular liquid–crystalline polymeric complexes based on a backbone that contains vinyl pyridine units and azobenzene or biphenyl derivatives that posses alkyl chains terminated by carboxylic acid have been obtained by the formation of intermolecular hydrogen bonds between the carboxylic acid and the pyridyl moieties. The polymeric complexes behave as side-chain liquid–crystalline polymers and exhibit smectic phases. A new type of H-bonded host-guest liquid–crystalline system is also reported. The liquid–crystalline host copolymers contain both mesogenic acrylate and 4-vinylpyridine units. The guest molecule is an azobenzene that has a carboxylic acid moiety at one of its extremities. The H-bonded polymeric host–guest complexes exhibit nematic phases. Sequential UV and visible light irradiation of the polymeric complex causes reversible photochemically induced phase transitions. The isothermal nematic–isotropic and isotropic–nematic transitions result from the trans-cis and cis-trans photoisomerization of the guest azobenzene in the host–guest system. © 1996 John Wiley & Sons, Inc.     

五氧化二钒催化环己烯烯丙位氧化

 研究了以五氧化二钒为催化剂,以过氧化氢水溶液为氧源氧化环己烯. 考察了溶剂种类、溶剂用量、催化剂用量和反应温度等因素对催化剂性能的影响. 结果表明,常温下环己烯在此催化体系中主要发生烯丙位氧化反应生成环己烯酮. 溶剂的种类对催化活性和烯丙位酮式氧化的选择性具有较大的影响,丙酮是该反应的合适溶剂. 在丙酮与环己烯的体积比为4, 五氧化二钒与环己烯的质量比为1∶40, 过氧化氢与环己烯的摩尔比为3和反应温度为20 ℃的条件下,反应24 h后的环己烯转化率可达60%以上,环己烯酮选择性可达85%. 催化反应过程中丙酮可能与过氧化氢作用生成过氧化酮,从而进行氧转移,催化剂则经过V5+/V4+物种的循环使环己烯氧化成为环己烯酮等产物.     

Comparison of electron spin resonance probe and dielectric relaxation in physically and chemically crosslinked polymers

Dielectric relaxation spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and electron spin resonance (ESR) experiments are employed to study the dynamics in chemically and physically crosslinked networks. As examples for physically crosslinked networks ortho- and para-cresol novolacs were investigated. Dielectrically these materials show low-temperature β- and high-temperature α-relaxation. Both relaxation regions differ for both types of novolacs. This is also reflected by the ESR measurements and is discussed in terms of different hydrogen bonds found to be stronger in para-cresol novolac. For the chemically crosslinked poly(triallyl isocyanurate) only a β-peak is found by the dielectric measurements. Also in the ESR experiment the slow motion regime is characterized up to high temperatures. This means that the segmental motion is strongly suppressed by chemical crosslinking. Nevertheless the obtained change in the formal T_50G value can be used to characterize the glass transition in highly crosslinked systems by the ESR method.     

146号初等元胞自动机的演化语言的复杂性

Symbolic dynamics of cellular automata is introduced by coarse-graining the temporal evolution orbits. Evolution languages are defined. By using the theory of formal languages and automata, the complexity of evolution languages of the elementary cellular automaton of rule 146 is studied and it is proved that its width 1-evolution language is regular, but for every n ≥ 2 its width n-evolution language is not context-free but context-sensitive. Also, the same results hold for the equivalent （under conjugation） elementary cellular automaton of rule 182.     

Recent Progress in Homogeneous Catalytic Dehydrogenation of Formic Acid

Recently, there has been a strong demand for technologies that use hydrogen as an energy carrier, instead of fossil fuels. Hence, new and effective hydrogen storage technologies are attracting increasing attention. Formic acid (FA) is considered an effective liquid chemical for hydrogen storage because it is easier to handle than solid or gaseous materials. This review presents recent advances in research into the development of homogeneous catalysts, primarily focusing on hydrogen generation by FA dehydrogenation. Notably, this review will aid in the development of useful catalysts, thereby accelerating the transition to a hydrogen-based society.     

Purification of Hydrogen from CO with Cu/ZSM-5 Adsorbents

The transition to a hydrogen economy requires the development of cost-effective methods for purifying hydrogen from CO. In this study, we explore the possibilities of Cu/ZSM-5 as an adsorbent for this purpose. Samples obtained by cation exchange from aqueous solution (AE) and solid-state exchange with CuCl (SE) were characterized by in situ EPR and FTIR, H₂-TPR, CO-TPD, etc. The AE samples possess mainly isolated Cu²⁺ cations not adsorbing CO. Reduction generates Cu⁺ sites demonstrating different affinity to CO, with the strongest centres desorbing CO at about 350 °C. The SE samples have about twice higher Cu/Al ratios, as one H⁺ is exchanged with one Cu⁺ cation. Although some of the introduced Cu⁺ sites are oxidized to Cu²⁺ upon contact with air, they easily recover their original oxidation state after thermal treatment in vacuum or under inert gas stream. In addition, these Cu⁺ centres regenerate at relatively low temperatures. It is important that water does not block the CO adsorption sites because of the formation of Cu⁺(CO)(H₂O)_x complexes. Dynamic adsorption studies show that Cu/ZSM-5 selectively adsorbs CO in the presence of hydrogen. The results indicate that the SE samples are very perspective materials for purification of H₂ from CO.     

微孔配位聚合物作为新型储氢材料的研究

微孔配位聚合物性质独特、结构多样,具有广泛的应用前景,它已成为近几年来一个热门的研究领域。本文简要介绍该类化合物作为一种新型的储氢材料,在合成、结构和储氢性能方面的研究进展。     

溴化二水二(皮考林酰胺)合钴配合物的合成及晶体结构

用皮考林酰胺、六水合硝酸钴和苄基溴反应制得一种新配合物[(C6H6N2O)2Co(H2O)2].B r2,通过红外光谱、元素分析及X射线晶体衍射对化合物进行了表征.结构分析结果表明,配合物属单斜晶系,P2(1)/n空间群,晶胞参数为:a=0.647 61(5)nm,b=1.026 43(9)nm,c=1.264 14(11)nm,β=93.823 0(10),°V=0.838 44(12)nm3,Z=4,Dc=1.977 g/cm3,μ=5.812 mm-1,F(000)=490,R1=0.071 0,wR2=0.251 6.配合物中,Co(Ⅱ)离子为六配位的八面体构型;相邻单元间通过N—H…B r和O—H…B r氢键相互连结而形成三维网状结构.     

基于(C-H)+…X-氢键作用的阴离子识别与传感的研究进展

对基于(C—H)+…X-氢键类型的阴离子识别以及识别过程所引起的光化学传感和电化学传感的研究进展进行了评述.     

高温高压下氧化锌纳米晶的晶粒演化动力学

用GS-1B型六面顶压机研究了ZnO纳米晶高温高压下的晶粒演化动力学, 用MDI/JADE5 X射线衍射仪(Cu靶)和XL30S-FEG场发射扫描电子显微镜对高压样品的相组成、晶粒尺寸及微观形貌进行了表征. 实验发现300 ℃(包括300 ℃)以下, ZnO纳米材料中晶粒生长速率随着压力的升高先增大后减小, 1～3 GPa烧结体晶粒尺寸随着压力的升高而增大, 4～6 GPa烧结体晶粒尺寸随着压力的升高而减小. 利用高压下晶粒生长速率方程求出1～3 GPa, 4～6 GPa的激活体积分别为－5.82, 9.66 cm³/mol. 400 ℃(包括400 ℃)以上, 1～6 GPa烧结体的晶粒尺寸随着压力的升高而不断增大.