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.     

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.     

Curvature investigation in tapered fibers and its application to sensing and mode conversion

Non-adiabatic tapered fibers are basic photonic components used in a wide range of applications. Here we investigate a way to increase their utility through the controllable bending of one of their tapered sections. The experiments carried out explain, for the first time, the mechanics of this approach showing how these tapers can be used to build more sensitive sensors. Their use as highly efficient mode converters is also discussed.     

Recent advances and challenges in the recovery and purification of cellular exosomes

Exosomes are nanovesicles secreted by most cellular types that carry important biochemical compounds throughout the body with different purposes, playing a preponderant role in cellular communication. Because of their structure, physicochemical properties and stability, recent studies are focusing in their use as nanocarriers for different therapeutic compounds for the treatment of different diseases ranging from cancer to Parkinson's disease. However, current bioseparation protocols and methodologies are selected based on the final exosome application or intended use and present both advantages and disadvantages when compared among them. In this context, this review aims to present the most important technologies available for exosome isolation while discussing their advantages and disadvantages and the possibilities of being combined with other strategies. This is critical since the development of novel exosome‐based therapeutic strategies will be constrained to the effectiveness and yield of the selected downstream purification methodologies for which a thorough understanding of the available technological resources is needed.     

紫色球杆菌视紫红质光谱特性的机器学习研究

近年来，机器学习等人工智能技术被应用于蛋白质工程，其在蛋白质结构、功能预测、催化活性等研究中具有独特优势。在未知蛋白质结构的情况下，将蛋白质序列和功能特性与机器学习相结合，基于序列-活性关系（innovative sequence-activity relationship，ISAR）算法，将蛋白质氨基酸序列数字化，用快速傅里叶变换（fast four transform，FFT）进行预处理，再进行偏最小二乘回归建模，可在数据集较少情况下拟合得到最佳模型。通过机器学习对紫色球杆菌视紫红质（gloeobacter violaceus rhodopsin，GR）的突变体蛋白质氨基酸序列与光谱最大吸收波长进行建模，获得了最佳模型。用最佳索引LEVM760106建模得到的确定系数R² 为0.944，均方误差E为11.64。用小波变换进行的预处理，其R² 虽也约为0.944，但E大于11.64，不及FFT进行的预处理。方法较好地解决了蛋白质序列与功能特性之间的数学建模问题，在蛋白质工程中可为预测更优的突变体提供支持。     

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。     

物体内部三维位移场分析的数字图像相关方法

提出了物体内部三维位移场的数字图像相关分析方法，对物体变形前后，或连续变形的两个相邻状态的内部三维结构的数字图像，通过相关运算获得三维位移场.文中给出了三维相关法的体搜索窗口、相关函数及亚像素运算的相关系数拟合函数.数字模拟结果证明了三维相关法的正确性及可靠性.位移计算精度为0.02像素. 关键词： 数字图像相关 三维相关 亚像素