ATR-FTIR光谱技术在聚合物膜研究中的应用

红外光谱是聚合物研究中常用的一种表征手段，而衰减全反射红外光谱（ATR-FTIR）更是由于在研究聚合物薄膜方面具有显著的优势而被广泛使用。逐层组装（layer-by-layer Assembly）技术是一种常用的组装聚合物超薄膜的方法，ATR-FTIR光谱技术的引入可以在获取膜组装过程中相应信息的同时有效地避免表征过程中对样品的损害。另一方面，ATR-FTIR方法与二维相关光谱技术（two-dimensional correlation spectroscopy, 2D correlation spectroscopy）相结合也是研究小分子（主要是水分子）在聚合物薄膜中的渗透行为的有效手段。本文对ATR-FTIR的基本原理和显著特点作了介绍，并以实例阐述该方法在逐层组装技术和水分子在薄膜内渗透行为研究两方面的应用。     

LiCoO2中锂离子固相扩散系数随循环次数的变化

The solid diffusion coefficient of lithium-ion in LiCoO₂ cathode material has been investigated by the capacity intermittent titration technique (CITT) at different voltages and at different charge/discharge cycles. By SEM, XRD and FTIR techniques, the structure of LiCoO₂ was studied before and after charge-discharge cycles, and the relationship between solid diffusion coefficient and crystal structure was further discussed. CITT results show that the value of Li⁺ solid diffusion coefficient of LiCoO₂ is about 10^-12 cm²·s^-1. During the whole charge-discharge cycles, the Li⁺ solid diffusion coefficient decreased within the voltage of 4.0～4.3 V, which is attributed to the change of the structure of LiCoO₂.     

PEMFC阴极中氧扩散和电化学反应模型研究—I．TFFA模型及其数值计算

将薄膜浸渍聚集体（TFFA）模型用于描述质子交换膜燃料电池（PEMFC）阴极中氧的扩散和反应过程，其中包括氧气在气体扩散层和反应层气体通道中的扩散，氧气在反应层薄膜中的溶解和扩散，氧在反应层浸渍聚休体中的扩散和反应以及电子和离子的传导，并根据PEMFC阴极的结构特点给出TFFA模型的数值解法。     

Suppression of red cell diffusional water permeability by lipophilic solutes

The inhibitory effect of a series of neutral lipophilic solutes (methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-amylalcohol, n-hexanol, diethylether, nitrobenzene, and pyridine) on the diffusional water permeability (Pd, tot) of bovine erythrocyte membrane at 25 degrees C was studied in comparison to that of p-chloromercuri benzoate (pCMB). Permeability data were obtained by measuring the transmembrane diffusional water exchange time tau(exch) using an 1H-T2 NMR technique. Maximal inhibition by approximately 50% of Pd, tot was produced by 2 mM pCMB which completely blocked the membrane water channels in 20 min, hence suggesting the channel-to-lipid diffusional water permeability ratio of about 1:1. Furthermore, the maximal inhibitory effect of pCMB in combination with the lipophilic solutes was lower than that of pCMB alone. As pCMB does not interfere with the lipid bilayer, and provided that it blocks the water channels in solute presence as well, this confirms that the solutes induce an increase in the lipid-mediated background water permeability contribution (Pd, lipid) by the formation of aqueous leaks in the membrane hydrophobic barrier. However, faster but less efficient in permeability inhibition than pCMB (either alone or combined with solutes) were the lipophilic solutes alone. Taken together, the results indicate that the lipophilic solutes suppress the membrane total permeability Pd, tot by two opposing effects: a reduction of its channel-mediated part (Pd, channel) to the extent exceeding that of a simultaneous Pd, lipid increase. The inhibitory potency of the solutes tested appears to be correlated with their solubility in the membrane medium.     

一个新颖三维配位聚合物Pb(1，4-napdc)(DMF)的合成、结构及热稳定性研究

A novel 3D metal-organic coordination polymer Pb(1,4-napdc)(DMF) (1,4-napdc=naphthalene-1,4-dicarboxylate) was synthesized at room temperature using slow vapor diffusion method to grow single crystal that has been analyzed by X-ray diffraction. The crystal belongs to orthorhombic with space group P2₁2₁2₁. The unit cell parameters are as fellows: a=0.701 3(2) nm, b=1.407 6(3) nm, c=1.521 5(4) nm, V=1.501 8(6) nm³ and Z=4. In the crystal structure of Pb(1,4-napdc)(DMF), the square grids constructed with paddle-wheel units of Pb(Ⅱ) and 1,4-napdc links stack over each other to generate infinite 3D network, which has square apertures (1.158×1.158 nm²) along the crystallographic a-axis. The thermal stability of compound was investigated by differential scanning calorimetry and thermogravimetric analysis. CCDC: 293617.     

微铂电极上1-酰基二茂铁动力学参数的测定

本文合成并研究了１－酰基二茂铁在ＣＨ２Ｃｌ２中的伏安行为，测定了它们在ＣＨ２Ｃｌ２中不同支持电解质浓度时的扩散系数，并分明用Ｚ．Ｇａｌｕｓ和Ｋ．Ａｏｋｉ方法计算了两种状态下的电子迁移速率常数。讨论了取代基的诱导效应和共轭效应及其链长对１－酰基二茂铁的动力学性质的影响以及支持电解质及其浓度等因素对伏安曲线的影响。     

掺杂电活性离子聚吡咯膜内的电荷传输

用循环伏安法和计时库仑法研究了掺杂亚铁氰化钾离子的聚哟咯膜内的电荷传输问题。实验结果表明，聚吡咯膜内的电荷传递可以处理成电子在膜内的扩散模型，电荷传递速度可以 用电子表观扩散系数（Ｄａｐｐ）来表征。Ｄａｐｐ的大小由聚合物膜的结构、电活怀离子之间的过及对离了在膜中的运动决定。     

Investigations of precipitates in heat treated AgPd30/CuSn6 layers

The subject of the investigations are precipitation zones, which grew as a result of chemical diffusion in AgPd30/CuSn6 bimetals. These precipitation zones have been characterized by metallography, electron probe microanalysis and x-ray diffraction. The growth of precipitation zones in the plating layer and in the substrate layer in dependence on time have been determined. The use of x-ray diffraction alone for the identification of the precipitates could not supply satisfying results in every case. This problem was solved by the application of electron probe microanalysis using a correction method, which allows the estimation of the chemical composition of small particles.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

The lion and man problem revisited

A pursuerP, whose speed is bounded by 1, wants to get closer to an evaderE, whose speed is bounded by >1.P wants to reduce his distancePE fromE below the capture radius . Both players are confined to a circular arena. This problem is equivalent to a problem discussed by Flynn, who characterized and gave numerical bounds to the least upper boundd* on the values ofPE thatE can maintain. He used direct methods and did not use Isaacs' theory.We solve our problem relying on the theory of singular surfaces in differential games. We construct and investigate barriers of the game of kind, and we replace Flynn's bounds ond* by analytical (exact) values for various speeds .The support of the TW Department of THT, Enschede, Holland, is gratefully acknowledged.