An ultramicroelectrode study of ferrocene diffusion and heterogeneous electron transfer rate in polyelectrolyte

Steady-state voltammograms at a microdisk electrode are used to measure the diffusion coefficient (D) and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG.MClO(4). The diffusion coefficient and standard heterogeneous rate constant of ferrocene are both smaller in polymer solvents than in monomeric solvents. The D and k(s) of ferrocene have been estimated in PEG containing different concentrations and cations of supporting electrolytes, and the dependencies of D and k(s) on temperature have been observed. These results show that the D and k(s) of ferrocene increase with increasing temperature in polyelectrolyte, and with increasing cation radius of supporting electrolyte, eg D and k(s) increase in the order Bu(4)NClO(4) > NaClO4 > LiClO4. On the other hand, D and k(s) increase with decreasing concentration of supporting electrolyte. The dependence of the half-wave potential (E(1/2)) on the concentration of the supporting electrolyte is also observed. E(1/2) shifts in the negative direction as the concentration of supporting electrolyte increases. (C) 1997 Elsevier Science Ltd.

Poly(epsilon-capralactone)/poly(ethylene oxide) diblock copolymer .2. Nonisothermal crystallization and melting behavior

The nonisothermal crystallization behavior and melting process of the poly(epsilon-caprolactone) (PCL)/poly(ethylene oxide) (PEG) diblock copolymer in which the weight fraction of the PCL block is 0.80 has been studied by using differential scanning calorimetry (DSC). Only the PCL block is crystallizable, the PEO block with 0.20 weight fraction cannot crystallize. The kinetics of the PCL/PEO diblock copolymer under nonisothermal crystallization conditions has been analyzed by Ozawa's equation. The experimental data shows no agreement with Ozawa's theoretical predictions in the whole crystallization process, especially in the later stage. A parameter, kinetic crystallinity, is used to characterize the crystallizability of the PCL/PEO diblock copolymer. The amorphous and microphase separating PEO block has a great influence on the crystallization of the PCL block. It bonds chemically with the PCL block, reduces crystallization entropy, and provides nucleating sites for the PCL block crystallization. The existence of the PEO block leads to the occurrence of the two melting peaks of the PCL/PEO diblock copolymer during melting process after nonisothermal crystallization. The comparison of nonisothermal crystallization of the PCL/PEO diblock copolymer, PCL/PEO blend, and PCL and PEO homopolymers has been made. It showed a lower crystallinity of the PCL/PEO diblock copolymer than that of others and a faster crystallization rate of the PCL/PEO diblock copolymer than that of the PCL homopolymer, but a slower crystallization rate than that of the PCL/PEO blend. (C) 1997 John Wiley & Sons, Inc.

Study on diffusion of electroactive species in polyelectrolyte polyethylene glycol lithium perchlorate by chronoamperometry at a microdisk electrode

The mass transport dynamics of Ferrocene in polyelectrolyte polyethylene glycol lithium perchlorate (PEG . LiClO4) was studied by using chronoamperometry at a microdisk electrode. Chronoamperometry is a powerful method for the study of mass transport in polyelectrolyte, it has many advantages over the conventional methods at a microelectrode and the steady-state method at an ultramicroelectrode. By using this method the apparent diffusion coefficient D-app and concentration C-a of the electroactive species, can be estimated from a single experiment without previous knowledge of either one. We have estimated D-app and C-a of ferrocene in PEG . LiClO4 polyelectrolyte from 25 degrees C to 75 degrees C. The dependence on the concentration of electroactive species was observed. The diffusion coefficients decrease with increasing ferrocene concentration and decreasing temperature. The mass transport mechanism is explained, by using a free volume model.

Study on ferrocene derivatives diffusion dynamics in polymer electrolyte by solid-state voltammetry

The diffusion rates of seven ferrocene derivatives have been estimated in polyelectrolyte PEG . LiClO4 by using non-steady-state chronoamperometry. The D-app of ferrocene derivatives increases with temperature, and the dependency of D-app on temperature obeys the Arrhenius equation. The D-app of ferrocene derivatives decreases with increasing size of electroactive species. The Delta D-app values of D-T>Tm and D-T T-m in the polyelectrolyte. On the other hand, the diffusion behaviour of ferrocene derivatives is qualitatively analyzed by using cyclic voltammetry. Copyright (C) 1996 Elsevier Science Ltd

Studies on water-swellable elastomer .1. Synthesis and characterization of amphiphilic polymer

A new amphiphilic polymer i.e., polyethylene glycol (PEG) grafted crystalline neoprene, which was used as compatibilizer to improve the compatibility of elastomer and water-absorbent resin, has been investigated. The synthesis was based on the reaction between chlorine in neoprene and sodium salts of PEG. PEGs with molecular weights of 600 and 2000 were used. The grafting percent and the PEG content were calculated through elemental analysis of chlorine in the resulted copolymers. The maximum grafting percent of copolymers was ca. 24.80%. The molecular parameters such as number-average molecular weight and the average number of grafting chains on one CR backbone were also calculated and discussed. (C) 1996 John Wiley & Sons, Inc.

A study of the dependence of ferrocene diffusion on electrolyte concentration and size in a polymer medium using non-steady-state chronoamperometry

This article describes a quantitative study of the diffusion rate of ferrocene(Fc) dissolved in ploy(ethylene glycol)(PEG) medium containing MClO(4)(M = Li+, Na+, Bu(4)N(+), Hx(4)N(+)). The apparent diffusion coefficient D-app and the active concentration c(a) of Fc were simultaneously measured by using non-steady-state chronoamperometry. The D-app and c(a) of Fc have been estimated in PEG containing different concentrations and sizes of supporting electrolyte, and the dependence of D-app on ferrocene concentrations has been observed. The values of D-app decrease with increasing concentrations of Fc, increasing concentrations of LiClO4 or the ratio (O:Li) and also with 4 decreasing cation radius of the electrolyte. The temperature dependencies conform to a simple free volume model. The concentration and size of the counterion dependencies of the diffusion rate are similar to the behavior of their dependencies of ionic conductivity in polyelectrolyte.

An investigation on ion solvation and ion association in a gel-type solid state polymer electrolyte

Ion salvation and ion association in polytriethylene glycol dimethacrylate (PTREGD)-LiClO4 gel-type polymer electrolytes were investigated. It was found that the fraction of solute existing as single ions (alpha(i)) decreases and that of triple ions (alpha(i)) increases linearly with increasing LiClO4 concentration, while for ion pairs, as the salt concentration increases, its fraction (alpha(p)) increases first and then falls down. The findings can be rationalized by the fact that the ionic conductance of the polymer electrolyte may be mainly contributed by triple ions and higher ionic aggregates with unequal numbers of positive and negative charges in the salt concentration range of practical significance, i.e. in the range of 0.5-1.5 mol/l. The temperature dependence of these fractions was also examined. In the case of tetraethylene glycol as the solvent, alpha(i) and alpha(p) increase as the temperature is raised, but alpha(t) decreases as the temperature increases from 25 degrees C to 85 degrees C. It seems that the increase of alpha(i) and alpha(p) results from the redissociation of triple ions at higher temperature, The same changing trend of those fractions is also observed when PEG(400) is used as the solvent.

CURE AND IONIC-CONDUCTIVITY OF A 2-COMPONENT EPOXY NETWORK POLYMER ELECTROLYTE

In order to raise the room temperature ionic conductivity and improve the mechanical strength of a PEO-based polymer electrolyte, a non-crystalline two-component epoxy network was synthesized by curing diglycidyl ether of polyethylene glycol (DGEPEG) with triglycidyl ether of glycerol (TGEG) in the presence of LiClO4 salt, which acts in this system as both a ring opening catalyst and a source of ionic carrier. The structure of the precursors, the curing process and the cured films have been characterized by C-13 NMR, IR, DSC and ionic conductivity measurement techniques. The electrolyte system exhibits an ionic conductivity as high as similar to 10(-5) S/cm at 25 degrees C and is mechanically self-supportable. The dependence of ionic conductivity was investigated as a function of temperature, salt content, MW of PEG segment in DGEPEG and the proportion of DGEPEG in DGEPEG/TGEG ratio.

IONIC-CONDUCTIVITY AND DYNAMIC MECHANICAL RELAXATION OF A 2-COMPONENT EPOXY NETWORK-LICLO4 ELECTROLYTE SYSTEM

The correlation between mechanical relaxation and ionic conductivity was investigated in a two-component epoxy network-LiClO4 electrolyte system. The network was composed of diglycidyl ether of polyethylene glycol (DGEPEG) and triglycidyl ether of glycerol (TGEG). The effects of salt concentration, molecular weight of PEG in DGEPEG and the proportion of DGEPEG (1000) in DGEPEG/TGEG ratio on the ionic conductivity and the mechanical relaxation of the system were studied. It was found that, among the three influential factors, the former reinforces the network chains, reduces the free volume fraction and thus increases the relaxation time of the segmental motion, which in turn lowers the ionic conductivity of the specimen. Conversely, the latter two increase the free volume and thus the chain flexibility, showing an opposite effect. From the iso-free-volume plot of the shift factor log at and reduced ionic conductivity, it is noted that the plot can be used to examine the temperature dependence of segmental mobility and seems to be useful to judge whether the incorporated salt has been dissociated completely. Besides, the ionic conductivity and relaxation time at constant reference temperature are linearly correlated with each other in all the three cases. This result gives an additional experimental confirmation of the coordinated motion model of the ionic hopping with the moving polymer chain segment, which is generally used to explain the ionic conduction in non-glassy amorphous polymer electrolytes.

反渗透复合膜的制备和脱盐功能

以玻璃化温度高、强度大、易磺化和耐酸碱的带酞侧基的聚芳醚酮(PEK-C)为支撑膜材料,研究了PEK-C铸膜液组成及复合液配比等对PFT反渗透复合膜(PFT ROCM)制备及其脱盐功能的影响。 试剂与材料 糠醇(FA):化学纯。用前精制,三(2-羟乙基)异氰尿酸酯(THEIC)。熔点134～136℃。聚乙二醇-400(PEG-400):化学纯。DMF,DMAc,N-甲基吡咯烷酮(NMP)为分析纯,经脱水精制。异丙醇、硫酸为分析纯。十二烷基磺酸钠(SLS)化学纯。含酞侧基的聚醚醚酮PEK-

聚苯醚磺酸锂与聚乙二醇共混体系的离子导电性

本文研究影响聚乙二醇(PEG)增塑聚苯醚磺酸锂(SPPOLi)电导率的各种因素,如摩尔比,及PEG分子量等。SPPOLi/PEG具单离子导体的特征,试样最高室温电导可达10~(-5)S/cm。

环氧乙烷--四氢呋喃无规共聚醚结构研究 Ⅰ．液体共聚醚链结构的NMR分析

环氧乙烷(EO)与四氢呋喃(TO)的端羟基液体共聚醚(ETO),其流动性好,粘结性强,易固化,燃烧完全以及热稳定性较好,是固体推进剂的优质粘合剂。本工作对M_n为2000～6000不同组份的ETO,制备30%(V/V)的CDC13溶液,用Unity—400 NMR谱仪,定量测定了ETO链结构各组成参数及其序列分布。

全新世渤海泥质区的沉积物物质组成特征及其环境意义

本文通过对渤海泥质区不同位置岩芯的粒度、矿物、化学元素等方面的分析，结合浅地层地震剖面、AMS 14C测年、微体古生物分析、稳定同位素测量、古地磁数据等，对全新世渤海泥质区中沉积物物质组成特征、物质来源、形成历史其环境响应进行了探讨。 结果显示，在早全新世期间黄河曾流经渤海南部，其携带泥沙对渤海沉积作用造成一定影响，但不同位置沉积环境及所受黄河影响的大小存在差异。 渤海泥质区的主体部分从约6000 aBP开始形成。当时沉积记录存在突变现象，不仅显示了沉积环境氧化还原条件的改变，而且温度与盐度值的变化以及沉积速率的明显偏高以及浮游有孔虫的出现说明本区开始受到黄海暖流余脉的影响。4500 aBP以来，沉积物中重矿物组合、化学成分等与黄河沉积物已较为接近，说明此时黄河物质对渤海泥质沉积的影响已经占据主导地位。渤海泥质区虽然有着离黄河口较近的特点，但并未出现明显高于陆架其它泥质沉积区的沉积速率，说明受输运机制控制，黄河物质向泥质区的输送量不大，远不如向黄海的输出量。 北部记录着全新世期间发生的两次地磁极漂移，分别发生于2800~3100 aBP（对应Starno事件）和7500~8200 aBP。漂移发生前后，气候、物质来源与海平面均有较大变化，说明地磁极漂移对气候有着重要影响。

合成孔径雷达提取海面风、浪信息研究

传统海洋测量方法例如岸基观测站、船只和浮标等方式只能对海面进行单点观测，存在很多不足之处：观测点少，只能获得有限的点的资料，无法得到大范围的海面信息；费用较高，无法大范围的密集观测；传统方法受天气影响较大，无法长时间的连续观测；星载合成孔径雷达能全天候、全天时、高分辨率对海面成像，能实现多波段、多极化、多视角得观测海面，提供大范围、高精度的实时动态海面信息。同时，这种全天候、全天时和高分辨率观测海洋的优势是可见光和红外传感器所没有的。总之研究如何从SAR影像中有效地获取海面信息具有重要的科学和实用意义。 自从1978年Seasat卫星发射以来SAR图像就广泛的应用于海洋要素的反演如海面风场、波高、平均周期。其中对海面风场的反演研究的最多，一般的方法是首先对SAR图像进行快速傅立叶变换得到SAR图像谱，通过图像谱的峰值信息能够得到具有180°模糊的风向，利用SAR图像的条纹或者浮标等外部信息来消除180°模糊确定风向，其次把风向和图像的正交后向散射截面数值(NRCS)带入经验函数CMOD4通过迭代计算得到风速。这种方法得到的海面风场需要外部信息的辅助，不利于大范围的业务化的反演海面风场。因此本文试图直接通过SAR图像来反演海面风场而不利用其他外部信息的帮助。2002年3月1日发射的ENVISAT卫星所获得的ASAR图像具有不同于ERS系列的SAR图像的新特点：不同入射角的情况下获得ASAR图片、双极化数据以及可以获得更宽的带幅的图像。双极化数据可以同时地提供同极化和交错极化的影像，两种极化的数据能够增加分辨目标的能力和提供目标更多的信息，这方面的优势也使得利用双极化的数据来消除SAR图像反演风场中的180º模糊问题提供了可能。本文推导了利用双极化的ASAR图像反演海面风场的新函数，该函数是在同极化和交错极化函数的基础上推导出来的，有效的消除了只用一副ASAR图片反演风场所固有的180º模糊现象。风速和风向的反演结果与Quikscat数据之间的均方根误差分别为0.53 m/s和2.21º。该方法与传统方法的比较可以看出新方法与浮标数据以及Quikscat数据符合的更好。 利用SAR图像来反演海浪的波高也是一个研究的比较多的领域。比较传统的方法是由SAR图像得到的海浪谱计算出波高，目前国际上比较流行的SAR图像反演海浪谱的模式有两种：一种是Hasselmann（1991）提出的在Max－Planck Institute（MPI）发展起来的方法，Hasselmann（1996）进行了改进和完善。另一种是Mastenbroek和de Valk（2000）提出的半参数化反演方法。这两种方法的最主要的缺点就是需要引进外部信息(WAM模式结果或者散射计的风的信息)来消除图像所固有的180°方向模糊问题。而本文应用的经验函数方法(CWAVE)不需要引进任何外部信息而直接得到海浪的重要参数－有效波高(Hs)，输入该经验函数的参数主要有：波模式图像的雷达截面、图像方差以及由SAR谱得到的20个参数。这些参数的选择是通过逐步回归方法进行筛选的。CWAVE经验函数的系数是通过6000幅全球分布的ERS-2波模式的图像谱拟合同时同地点的WAM模式结果得到的。利用CWAVE经验函数反演了1998年9月到2000年11月两年多的全球接近一百万的ERS-2 SAR图像的有效波高，利用NOAA浮标数据对反演结果进行了验证，他们之间的相关系数为0.83, 均方根误差为0.61m，偏差为0.02 m；反演结果也与欧洲中长期预报中心(ECMWF)的ERA-40有效波高资料和高度计资料进行了比较，结果表明该方法是通过SAR图像反演Hs的一种有效方法。 SAR的反演结果也应用于有效波高的非线性统计分布的研究。结合动力学和随机统计学原理推导了海面高度、波高和有效波高的非线性统计分布，同时利用了NOAA浮标数据、华师大的波高数据以及SAR的有效波高数据分别对推导出的非线性统计分布函数进行了检验。 SAR的结果也用来反演新的风浪成长关系： ，与已有的风浪成长关系的比较表明该成长关系与已有的结果比较一致。

四株海洋放线菌遗传转化体系的研究

作者所在的课题组，自1998年以来从胶州湾海泥中陆续分离了800株海洋放线菌，并从4株放线菌中分离出了12个新结构活性化合物。选择产生新颖抗肿瘤抗生素的海洋放线菌M045和M048，产全霉素的海洋放线菌M095和产蒽醌类化合物的海洋放线菌M097为研究材料，建立了海洋放线菌的遗传转化体系，为海洋放线菌的遗传工程操作及天然化合物组合生物合成奠定了基础。 （1）通过接合转移建立了菌株M045的遗传转化体系。用来源于蓝藻Anacystis nidulans UTEX625的别藻蓝蛋白基因验证了转化体系的有效性。通过PCR及基因组步移方法获得长度为1709bp的部分聚酮合成酶（PKS）基因，分析其同放射菌素基因具有同源性，利用基因中断插入失活该基因，但未获得突变株。因此尝试通过反向遗传学方法，克隆该菌株中新骨架抗肿瘤抗生素——中国霉素的生物合成基因簇，本研究已经构建了该菌株Fosmid基因组文库，对基因组文库的筛选工作正在进行中。 （2）利用PEG-介导的质粒pIJ702转化原生质体和接合转移两种方法均成功获得菌株M048的转化子，其中接合转移率高达10-4。菌株M048来源于高盐的海洋环境，维持原生质体所需渗透压与模式菌株—变铅青链霉菌（Streptomyces lividans）有很大差异，本研究对菌株M048原生质体形成和再生的各种因素进行了优化，获得了渗透压稳定剂蔗糖最佳浓度为0.4M。 质粒pIJ8600整合于菌株M048染色体上，对该转化株的抑菌活性、薄层层析（TLC）以及HPLC-MS进行了分析。结果表明，同野生菌株相比，该转化株对7种受试菌的抑菌活性显著增强，TLC显示差异的化合物条带，HPLC-MS显示化合物组分有差异。因此质粒pIJ8600的整合，引起菌株次级代谢产物生物合成途径的改变，使有抑菌活性的化合物大量累积。 从菌株M048染色体上克隆获得了1196bp的部分PKS基因，通过基因中断插入失活该基因，结果显示M048突变株次级代谢产物抑菌活性增强，HPLC分析发现显著差异。初步分析该PKS基因的中断使菌株体内某些生物合成途径受阻，而大量合成抗菌活性强的chandrananimycin C，或者产生了抑菌活性强的其它化合物。 （3）本研究成功建立了菌株M095的接合转移体系。M095/pIJ8600转化株的生物学活性分析并未发现差异，表明该菌株染色体上的整合位点（attB）是中性（neutral）的。通过PCR以及基因组步移的方法克隆获得了该菌株的部分糖基转移酶基因，该基因中断突变株对4株受试菌的抑菌活性增强，HPLC显示有差异，表明该糖基转移酶基因参与了菌株M095活性次级代谢产物的生物合成过程。 （4）对于菌株M097，用接合转移法成功获得了转化子。实现了别藻蓝蛋白基因的重组表达，并纯化了表达产物，体外试验表明其具有清除羟基自由基能力。结果表明来源于蓝藻的外源基因可以在海洋放线菌体内有效表达和正确折叠，初步验证了本研究所建立的海洋放线菌遗传转化体系的稳定性及有效性。对M097/pIJ8600转化株的生物学活性分析，未发现差异，表明该菌株染色体上的整合位点是中性的。 本论文首次将基因工程技术引入四株海洋放线菌，建立了海洋放线菌自身的基因转移系统，为利用基因工程技术改造海洋放线菌的天然化合物生物合成途径提供了方法。对部分PKS基因中断突变株的生物学活性及化学分析，初步揭示了通过遗传转化方法进行化合物组合生物合成的可行性。