Mobility of water molecules in Li+, Na+ and Cs+ ionic forms of Nafion membrane studied by NMR

Correlation times and diffusion coefficients of water molecules were measured for the first time by ¹H spin relaxation and pulsed field gradient NMR in Li⁺, Na⁺ and Cs⁺ ionic forms of Nafion 117 membrane. Hydration numbers of Li⁺, Na⁺ and Cs⁺ cations were calculated. It was shown that at high humidity macroscopic transfer is controlled by the local translational motion of water molecules.     

化学类拔尖学生培养与高校青年教师成长协同发展实践*

在高等教育大众化的背景下,通过教学改革培养高素质的拔尖人才已显得非常重要。介绍一种以新入职的青年教师为实施主体的“理论课助教+实验课教学+科研训练”相结合的教学形式。通过连续、跟踪式的教学,不但可以选拔、培养出拔尖的化学类本科生,而且能够促进新入职的青年教师快速成长进步,起到“教学相长”的作用。     

Theoretical studies on the influence of metallic cations on ring opening of propylene oxide catalyzed by metal-salen complexes

We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH⁻ group [M = Al(III), Sc(III), Cr(III), Mn(III), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II), Ru(III) and Rh(III)]. The results show that the ring-opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH⁻ group and the Fukui function condensed on the OH⁻ group. The nucleophilicity ordering in the gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring-opening barriers and to screen epoxide ring-opening catalysts.     

Na原子链表面等离激元特性的含时密度泛函研究

本文用含时密度泛函理论研究了线性Na原子链的表面等离激元机理.主要在原子尺度下模拟计算了体系随着原子数增加及原子间距变化的集体激发过程.研究发现线性原子链有一个普遍的特性——存在一个纵模和两个横模.两个横模一般在实验上很难被观测到.纵模随着原子链长度增加,能量红移的同时,该纵模主峰的强度呈线性增长.随着原子个数的增加,端点模式(TE)开始蓝移,能量和偶极强度都逐渐趋向饱和.横模能量被劈裂的原因概括如下:(一)每个位置的电子受到的势不同,在两端的电子受到的势要比在中间的电子受到的势要高,因此两端的电荷积累也比中间多;(二)端点存在悬挂键,所以中间的电子-电子间相互作用与端点的不一样,这两方面又都与原子间距d有关.     

基于CEEMD的重大事件对香港住宅价格影响的实证分析

应用互补集成经验模态分解（CEEMD）方法对香港1997―2018年的住宅价格月度数据进行了分解，将经过重构后的数据分成高频序列、低频序列与残差项。将BP多断点检测应用于低频序列，并结合样本时段内的重大事件进行实证分析。结果表明：1997年亚洲金融风暴对房价的影响大于2008年金融危机；外部经济体的救市政策间接地影响香港房价；在经济不景气的大环境下“孙九招”政策没有立即见效；资本投资者入境计划、住房供给调整与按揭贷款调整对房价的影响较为显著；税收调整对房价影响不显著、对交易量影响显著；SARS爆发使住宅价格下降约1%。     

稳定分层湍流中逆梯度输运的关联分析研究

本文采用关联分析方法研究了稳定温度分层湍流中的结构特性、输运特性，以及热量、动量逆梯度输运现象的尺度效应及其参数演化．首先采用大涡模拟方法对稳定分层湍流中的结构特性和输运特性进行了分析，将逆梯度输运发生的时间尺度作为已知条件，结合关联量分析方法在波数空间中的解析解，对逆梯度输运现象的尺度效应进行了分析研究．结果发现，稳定分层强度较大的流动中发生垂向热量及动量逆梯度输运现象，发生的结构尺度与关联分析所发现垂向热量、动量逆梯度输运的波数形成了呼应．随着分层强度增加，热量、动量的输运强度均受抑制，与逆梯度输运关联的流场结构尺度减小，同样的效应也发生在流场结构向下游演化的过程中．     

砂岩方梁断裂过程区范围的实验确定方法

裂纹前端的断裂过程区是引起岩石非线性断裂及尺寸效应的主要原因。利用数字图像相关技术对砂岩开展了三点弯曲梁实验,获得观测区域高精度的全场位移和应变数据,根据断裂韧带区域水平位移和水平应变的分布特征,结合裂尖岩石颗粒变化的微观分析,提出采用裂纹尖端水平位移波动性和水平应变突变性所得到的波动系数和水平应变突变值,确定断裂过程区形状和临界尺寸的方法。结果表明:砂岩断裂过程区的形状为不规则的狭长带状区域,断裂过程区的临界长度为11~13mm,临界宽度为1.58~2.36mm。断裂过程区区域内形变在趋向裂尖时呈指数增加,但其单位区域内的形变增量呈波动状态。该方法能够更加准确判断岩石断裂过程区的范围,有助于分析岩石的非线性断裂特性。     

Assessing the nucleophilic character of 2-amino-4-arylthiazoles through coupling with 4,6-dinitrobenzofuroxan: Experimental and theoretical approaches based on structure-reactivity relationships

A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λ_max = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k₁ versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k₁) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = s_N (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. .     

Viscoelastic properties of amorphous polymers 3: low molecular weight poly(methylphenylsiloxane)

By making creep and recoverable creep measurements of a nearly monodisperse low molecular weight poly(methyl phenyl siloxane) sample, we have found on decreasing temperature towardsT _g that there is continuously a change in the viscoelastic spectrum concomitant with a decrease of the steadystate recoverable compliance. This behavior is exactly the same as previously observed in low molecular weight poly(styrene), proving that this spectacular anomaly in the viscoelasticity of low molecular weight polymers is general and deserves an explanation. Photon correlation spectroscopic measurements performed on the same sample have extended the observation of the viscoelastic response to shorter times and the result corroborates the trend of variation established by the creep data.Dedicated to Prof.Dr. E. W. Fischer on his 65th Birthday. Prof.Dr. Fischer is known for his valuable contribution to fosterine, international collaboration of research in polymer science. This work is an example of his contribution because it would not be possible without him bringing us together. One of us (KLN) would like to take this opportunity to thank Prof. Dr. Fischer for his unwaiving support of the 1st (Crete) and the 2nd (Alicante) International Discussion Meeting on Relaxations in Complex Systems     

山西省农民家庭消费水平和结构分析

本文利用统计计量学方法对山西省农民家庭消费水平和消费结构的变化及原因进行了实证分析。建立了山西省农民人均消费的消费函数和山西省农民总消费支出与食品、衣着、住房、日用品、燃料及文化生活服务支出的关系模型，并通过模型分析解释了农民的消费结构，也为决策者提供一些有效的参考资料。