酸、碱性条件下茜素红紫外-可见光谱的量子化学研究

茜素红(ARS)是葸醌类化合物中茜草素型的一种,被广泛应用于电化学、光谱学等领域的研究。在酸性溶液中,茜素红主要在260 nm和422 nm处出现明显的吸收峰,而在碱性溶液中吸收峰移动到272 nm和556 nm。为了分析不同溶液环境对茜素红吸收峰波长的影响,本研究在杂化密度泛函方法B3LYP/6-311+(d)水平上优化了ARS分子在酸、碱性情况时的稳定基态构型,并采用含时密度泛函(time-dependent density functional theory,TD-DFT)方法模拟了ARS分子的电子吸收光谱。计算结果与实验得到的紫外可见吸收光谱相吻合,说明密度泛函理论用来研究茜素红的紫外可见光谱是有效可靠的。通过计算还确定了每个吸收峰对应的各个电子跃迁的贡献率以及Mulliken电荷分布。该理论与实验的结合研究为茜草素型化合物的进一步应用、分子设计、药物构效关系和化学反应规律的研究提供了重要的参考依据。     

Possible use of methylbenzenes as electrolyte additives for improving the overcharge tolerances of Li-ion batteries

Based on the voltammetric behaviour of a series of methyl-substituted benzenes in 1M LiPF₆/EC-DMC electrolyte, xylene was selected and tested as an electrolyte additive for overcharge protection of Li-ion batteries. From the overcharge curves, CV behaviour and SEM observations of the cells in the presence of xylene, it was found that the additive can polymerize at the overcharged voltage to form a dense layer of isolating polymer film at the cathode surface, which blocks off further oxidation of the electroactive material and electrolyte and, therefore, improves the overcharge tolerance of the Li-ion battery. In addition, the xylene additive has shown only a slight influence on the cycling behaviour.     

K_2O－CaO－Al_2O_3－SiO_2系统自释釉瓷化学组成的研究

本文从酸度系数着手，证实了Ｋ２Ｏ－ＣａＯ－Ａｌ４Ｏ久－ＳｉＯ２系统中存在自释釉组成，限定了其组成范围，０．６７％＜Ｋ２Ｏ＜１．２８％，１０．６４％＜ＣａＯ＜１３．６２％，１１．５３％＜Ａｌ４Ｏ３＜１５．３２％，７２．７３％＜ＳｉＯ２＜７４．０４％，并讨论了自释釉瓷的性能。     

Kinetics for benzoylation of sodium 4-acetylphenoxide via third-liquid phase in the phase-transfer catalysis

In this research, the kinetics for synthesizing 4-acetylphenyl benzoate (R^*COOR) from benzoylation of sodium 4-acetylphenoxide via third-liquid phase-transfer catalysis was investigated. The reaction rate was observed to be strongly dependent on agitation speeds in the third-phase catalytic reaction. By forming the third-liquid phase, the observed reaction can be greatly enhanced to give a product yield of 100% in a duration of 3 min at 20 °C and 200 rpm. If a third-liquid phase was not formed in the liquid–liquid system, the reaction rate is very slow and the product yield is only 2% in 3 min at 20 °C. The reaction conducted in third-liquid phase-transfer catalytic system is faster than that in LLPTC system by 25–28 times. The amount of catalytic intermediate (QOR) in the third-liquid phase was about 50% of the catalyst initially added and kept about 30% of it remained after 1 min, and only small amounts of a catalytic intermediate residing in the organic phase were observed during the reaction using methyl t-butyl ether as the solvent. The concentration of catalytic intermediate slightly decreased with increasing reaction time, while the molar ratio of QOR to benzyl tri-n-butylammonium cation in the third-liquid phase remained almost constant after 1 min and increased with increasing agitation speeds. The experimental results were well described by the pseudo-first-order kinetics. The present work shows an effective method to synthesize 4-acetylphenyl benzoate.     

Soap‐free emulsion copolymerization of perfluoroalkyl acrylates in the presence of a reactive surfactant

Soap‐free emulsion copolymerization of perfluoroalkyl acrylate (FA)/methyl methacrylate (MMA)/n‐butyl acrylate (n‐BA) was carried out in the presence of sodium 2‐acrylamide‐2‐methyl propanesulfonate (AMPSNa) as a reactive surfactant and potassium persulfate (KPS) as an initiator. An analysis of the effects of concentration of AMPSNa, KPS, FA as well as polymerization temperature on the kinetic features (rate of polymerization) and colloidal characteristics (mean particle diameter, particle disperse index, particle numbers, and surface charge density) was followed. NMR, FTIR, AFM, and fluorine‐selective electrode analysis were used to characterize the composition and morphology of the FA copolymers. Both AFM analysis and contact angle measurements strongly implied that the fluorinated segments migrated to the outmost surface and created films with lower surface energy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2438–2444, 2007     

CS_2中毒法研究Pt-Al_2O_3系催化剂活性中心的性质

本文对金属催化剂活性中心性质提出了新的表征方法,即用活性频率量度活性中心的强度,用原子组合数的概念描述原子组成活性中心的方式,在此基础上提出了活性频率和活性中心原子组合数的计算公式与新的测定方法。 从测出的活性频率和活性中心原于组合数的数据,发现了Pt-Al_2O_3催化剂具有两种活性中心即α和β中心。α中心CS_2的吸附能力比β中心强,但β中心对环己烷的脱氢活性比α中心强。同时证明了不管在α中心或在β中心上环己烷的脱氢反应都是在双位中心上进行的。 本文还考察了锡和铼对铂催化剂性能的影响,实验表明锡和铼都能从结构效应和电子效应方面影响铂的催化性能。     

Raman spectroscopic study of conformational changes in the amorphous phase of poly(lactic acid) during deformation

The conformational distribution change of amorphous poly(lactic acid) (PLA) induced by deformation has been studied using Raman spectroscopy. Spectroscopic features associated with the rotational isomeric states (ttt, ttg′, tg′t, tg′g′) have been established experimentally and supported by normal coordinate analysis. Deformation induced a significant increase in the most favorable tg′t conformation. Based on the relative intensities of Raman-active skeletal modes, a quantitative method has been developed that can be used to elucidate structural changes in a variety of deformed polymer samples. For biaxially oriented PLA films, the overall tg′t conformation increased from the 76% in undeformed sample to a value as high as 92%. The change in conformational distribution in the amorphous phase follows a different trend (76-88%) as compared to the increase in sample crystallinity (0-43%). A large change in amorphous chain conformation occurred at relatively low draw ratios. In contrast, the large change in the degree of crystallinity occurred at higher draw ratios.     

油水井化学封窜堵漏新工艺

通过分析中原油田注水开发的两大问题，阐明了新型堵剂YLD-1的适应性，结合室内试验，重点分析了该堵剂的性能特点，深入探讨了封窜堵漏的选井原则和施工工艺，经过在文留油田的现场应用，展示了该技术良好的发展前景。     

浅谈企业党组织如何更加完善地为经济建设保驾护航

作为企业纪检监察组织，严格执行党章赋予的权力和职能，坚持“两手抓，两手都要硬”的方针，在积极参与和主动服务于企业经济建设的同时，大力抓好党风廉政建设，有效的发挥纪检监察在经济建设中应有的功能和作用。如何更加完善地为企业经济建设保驾护航，笔者认为可从以下几个方面去不断完善。     

农作物秸秆增强氟石膏复合材料的微观结构研究

将玉米秸秆加入改性后的氟石膏中，研究改性剂、玉米秸秆对氟石膏复合材料结构性能的影响；并用苯丙乳液对玉米秸秆纤维进行表面处理，用以改善基体材料和增强材料的界面结合状况，由此显著提高制品性能。