Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Protein phosphatase inhibition assay for detection of diarrhetic shellfish poison in oyster

A method based on protein phosphatase enzyme activity inhibition for the detection of diarrhetic shellfish poison (DSP) was used to analyze the DSP toxicity in three oyster samples. Based on the standard dose-effect curve developed with a series of okadaic acid (OA) standard solutions, the DSP toxicity of the three oyster samples collected were screened, and the results showed that there were no OA and dinophysis toxins ( DTXs) in the samples without hydrolization. However, the OA toxicity could be detected in two of the hydrolyzed samples, and the OA toxicity of the two samples were 1.81 and 1.21 mu g OA eq./kg oyster, respectively.

湖南芙蓉锡多金属矿床成矿流体地球化学研究

锡的分布和成矿作用通常与花岗岩浆作用具有十分密切的联系。以往研究表明锡矿化与高度分异的S型花岗岩或陆壳改造型花岗岩具有密切的成因联系，但近年来随着大量与A型花岗岩有关的锡矿床的发现，人们开始关注A型花岗岩与锡成矿关系的研究。相对于与S型花岗岩有关的锡矿床来说，与A型花岗岩有关的锡矿床成成矿机理的研究积累少，研究程度相对较低。 湘南地区位于南岭多金属成矿带中部，是我国华南地区重要的有色金属成矿带。近年来在该成矿带上新发现的芙蓉超大型锡多金属矿床为世界瞩目，该矿床的形成与骑田岭花岗岩具有密切的时空关系。近年来研究显示骑田岭花岗岩具有A型花岗岩的特征。本文以芙蓉超大型锡多金属矿床和相关的骑田岭岩体为研究对象，在前人研究的基础上，运用岩石学、矿物学、流体包裹体、微量元素和稳定同位素地球化学等理论和方法，对芙蓉锡矿成矿流体的地球化学特征及其演化机制进行了系统的研究，并在此基础上探讨了骑田岭花岗岩体与芙蓉锡矿间的成因联系和芙蓉锡矿的成因机制。论文取得的主要认识包括以下几个方面： 1. 运用矿物学、岩石化学、微量元素地球化学以及同位素地球化学方法，进一步证实了骑田岭花岗岩体具有A型花岗岩的特征，总体具有偏铝质-弱过铝质、高硅富碱高钾的地球化学特征，早晚两期花岗岩具有同源岩浆演化特征，属于A2型花岗岩。同位素地球化学数据显示花岗岩体具有EMII型富集地幔的特征，形成于华南大陆地壳拉张减薄的构造环境，成岩过程中有地幔物质加入。 2. 通过对矿石矿物组构和成分的岩矿鉴定、扫描电镜和电子探针分析，确定了芙蓉锡多金属矿床原生夕卡岩形成于较氧化的环境，成岩作用主要与早期侵入的角闪石黑云母花岗岩密切相关，锡主要以Sn(IV)进入夕卡岩的造岩矿物晶体内。退蚀变夕卡岩、云英岩和蚀变花岗岩矿化为锡成矿主阶段，三种矿化类型的成矿流体具有相似的地球化学性质，即富Cl、Ti和Sn的特征，而锡石硫化物型矿石形成于成矿晚阶段。 3. 运用流体包裹体地球化学理论和方法以及激光拉曼分析技术，揭示了芙蓉锡矿的成矿流体组成、形成的物理化学条件和演化特征。芙蓉锡多金属矿田成矿流体为CO2-CH4-CaCl2- NaCl-KCl不混溶体系，成矿过程中发生流体不混溶作用。芙蓉锡矿成矿流体盐度为0~50.63 wt%NaCl eq.，密度为0.31~1.12g/cm3，主成矿阶段热液流体的均一温度主要集中在300-450℃，流体压力为179-1800bar，成矿晚阶段锡石硫化物型矿石中均一温度主要集中在150~300℃，流体压力为400-600bar。成矿流体特别是主成矿阶段的流体成矿过程中普遍发生了沸腾现象。从主成矿阶段到成矿晚阶段、矿化期后，热液流体盐度呈降低的趋势，流体成分也从含CO2、CH4的CaCl2-NaCl-KCl-H2O水溶液体系转化为不含CO2的简单NaCl-KCl-H2O水溶液体系。 4. 通过分析主要矿化类型矿石中脉石矿物的稀土元素和稳定同位素特征，揭示了成矿流体来源。研究表明芙蓉矿床成矿期热液脉石矿物的稀土元素地球化学和稳定同位素地球化学显示了与本区花岗岩具明显的相似性，骑田岭黑云母花岗岩形成过程中分异出的岩浆期后热液应是芙蓉矿床成矿流体的主要来源，成矿过程中有少量经过深循环的大气降水加入。 5. 在总结前人研究成果的基础上，综合上述研究，探讨了骑田岭花岗岩体与芙蓉锡矿间的成因联系和芙蓉锡矿的成因机制。本文认为骑田岭岩体中黑云母花岗岩与Sn成矿具有密切的成因联系，芙蓉锡矿田的成矿流体主要来源于黑云母花岗岩岩浆结晶期后分异出的富Cl和Sn的热液流体。芙蓉锡矿成矿流体中锡主要呈Sn(II)与氯离子形成亚锡氯络合物进行迁移，低温的大气降水与高温的岩浆热液流体混合，导致流体体系温度、盐度、压力的降低和富CO2相流体的分离（CO2去气作用），流体的氧逸度升高，使得Sn(II)与氯离子形成亚锡氯络合物解体，Sn(II)被氧化成SnO2并发生沉淀作用。这种流体的混合作用是导致锡石沉淀的最有效的机制。

塔里木西南缘塔木铅锌矿矿床特征与成因

作为铅锌金属的主要来源，赋存于沉积岩中的铅锌矿床吸引了全球范围的地质学家和矿床学家。在过去的50年内塔里木西南缘陆续发现了一批赋存于沉积岩中的铅锌矿，并开展相应的研究。但还是存在一些关键问题值得探讨，例如成矿时代、金属及硫的来源，以及成矿机制。 塔木铅锌矿床是塔里木西南缘最为重要的赋存于沉积岩中的铅锌矿床之一，其位于西昆仑和塔里木地块接触带北侧塔里木边缘，区域地层均变形或被错断。矿床赋存于下石炭统碳酸盐岩角砾岩带中，具有经济价值的矿体五个，铅锌资源量约0.2Mt。 自20世纪40年代塔木铅锌矿被发现以来，已陆续开展的研究工作有流体包裹体、铅同位素、硫同位素、碳同位素、氧同位素以及稀土元素等，但矿床成因依然困惑着众多的矿床学家。其中一部分认为矿床属密西西比河谷型，另一部分则认为应属沉积喷流型。但从前人发表的文献看，矿石结构构造、角砾和填隙物等基础研究被普遍忽视了。 在中国科学院知识创新项目(KZCX2-YW-107-6)和科技部国家科技支撑计划(2006BAB07B04-04)的资助下，本次研究以塔木铅锌矿为突破口，运用矿物学、岩石学、矿床学、地球化学方法和手段对其加以研究，以揭示成矿机制及矿床成因。以下就获得的一些新的数据、调查结论、观点作一概述： (1). 在分析矿体形态和与围岩接触关系基础上，提出塔木铅锌矿床为同生断层控制，角砾岩带为断层的组成部分；通过细致的镜下观察，深入探讨了角砾、填隙物及其结构构造，提出填隙物中沥青在成矿中的具有重要作用，并首次发现赋存于填隙物中的钡-钾长石。角砾可根据几何形态特征和角砾间接触关系分为五类：内碎屑角砾(IB)、成岩期角砾(DB)、后生角砾(EB)、崩塌角砾(FB)、断层角砾(DB)，其中断层角砾可以分为矿化断层角砾(MFB)和无矿化断层角砾(WFB)。填隙物可以根据结构划分为三种类型：同沉积-成岩作用填隙物(纹层构造)，溶蚀-交代填隙物(细粒，颗粒边缘具有溶蚀港湾结构)，以及空洞充填填隙物(粗晶结构)。塔木铅锌矿演化具有三个清晰的期次：沉积期、成岩期和后生期。矿化是成岩期和后生期的产物，主要为后生期。矿化可分为两个主要阶段：溶蚀-交代阶段和空洞充填阶段，其中溶蚀-交代阶段是矿化的主要阶段。管/脉状构造是溶蚀-交代阶段最重要的特征，其多见于后生角砾的填隙物中。 (2). 在对角砾(白云石)和填隙物(白云石)的微量元素、稀土元素、C、O同位素以及填隙物白云石流体包裹体研究基础上提出水/岩作用和TSR过程控制着流体的演化。充填阶段流体为低温(119~191°C)，盐度介于10.9~11.4wt% NaCl eq.，压强介于2~39MPa，含有少量H2S，缺乏SO42-的流体。Ca2+和HCO3-为流体主要的阳离子和阴离子。填隙物与角砾具有相似的稀土元素配分模式—海相碳酸盐岩。如果填隙物中混入钡-钾长石，其稀土元素配分模式则发生显著改变。氧同位素和碳同位素显示填隙物较角砾富集轻同位素。由于闪锌矿流体包裹体氧同位素值显著低于角砾，暗示存在大气降水的参与。根据氧同位素质量平衡方程可估计水/岩比值，封闭体系水/岩比值在0.16~0.67(119°C)或0.12~0.43(191°C)，开放体系水/岩比值在0.13~0.37(119°C)或0.10~0.28(191°C)。热化学硫酸盐还原过程(TSR)可能对沥青和H2S的形成起了重要的作用，并影响碳同位素值变化。 (3). 塔木铅锌矿硫可能来自海水或蒸发盐，存在有机物硫的加入，并受TSR过程和硫储库效应的控制，铅可能为来自淋滤结晶基底的产物。 (4). 讨论了闪锌矿流体包裹体Rb-Sr法的理论基础和应用前提，指出对定年闪锌矿必须开展细致的矿物学研究，并进行了该矿床的定年尝试。 (5). 最终得出塔木铅锌矿为赋存于碳酸盐岩受同生断层和热化学硫酸盐还原过程控制的后生铅锌矿床。

柿竹园钨、锡多金属矿田成矿流体地球化学研究

南岭地区是我国最重要的有色、稀有金属矿产资源产地，尤以钨、锡等金属的大规模爆发式成矿而闻名于世，已发现了一大批大型、超大型稀有和有色金属矿床。近年来的研究发现，这些矿床的形成很可能与华南地区中生代发生的大规模地壳拉张、岩石圈伸展减薄以及壳―幔相互作用的独特地质背景有关。本论文以与千里山花岗岩体密切相关的柿竹园钨锡钼铋铅锌矿田（以下简称柿竹园矿田）为研究对象，运用流体包裹体、稳定同位素和稀有气体同位素地球化学等方法，对其成矿流体的物理化学特征、来源及演化进行了研究，并在此基础上探讨了千里山花岗岩体与柿竹园矿田间的成因联系和矿田的成矿作用机制，获得以下主要研究成果： 1. 利用流体包裹体岩相学、显微测温学以及包裹体成分的激光拉曼分析技术，揭示了矿田中柿竹园钨锡钼铋矿床成矿流体的性质和演化特征。研究表明柿竹园钨锡钼铋矿床成矿流体为中高温、中高盐度H2O-NaCl-CaCl2-CO2-CH4-H2S-F体系。成矿流体的均一温度、盐度、密度和压力变化范围均较大，成矿早期夕卡岩阶段和云英岩阶段的流体具有较高的均一温度（239～477℃）和盐度（0～39.08 wt% NaCl eq.），云英岩网脉夕卡岩阶段和后期石英萤石脉阶段均一温度和盐度逐渐降低（分别为160～450℃，1.23～16.53 wt% NaCl eq.和156～340℃，1.23～4.49 wt% NaCl eq.）。夕卡岩阶段发生了流体沸腾作用。流体密度为0.37～1.12 g/cm3，主要集中在0.7～0.9 g/cm3；压力为10～820 bar，一般小于800 bar。野鸡尾锡铜矿床的成矿流体属于中高温度、中等盐度的H2O-NaCl-CaCl2-CO2-CH4-H2S-F型体系，柴山铅锌矿床属中温中等盐度H2O-NaCl-CaCl2-CO2-F体系，其均一温度和压力变化范围也较大。 2. 通过分析主要矿化类型矿石矿物及脉石矿物的C、H、O、S等稳定同位素特征，揭示了柿竹园矿田成矿流体的来源，并对C、O同位素的组成进行了CO2去气、流体混合和水―岩反应的理论模拟。研究表明矿田成矿流体主要来自千里山花岗岩浆，并有大气降水加入。水―岩反应在成矿过程中起着重要作用。 3. 对矿田不同矿化类型矿石矿物黄铁矿、黄铜矿、毒砂、方铅矿等进行了He、Ar同位素研究，其中3He/4He值为0.059～1.662 Ra（Ra为空气的3He/4He值，1 Ra＝1.39×10-6），40Ar/36Ar值为289.8～1071.8，表明矿田成矿流体具有壳-幔两端员混合的特征。壳源组分为获得了大量地壳放射成因4He，但获得放射成因40Ar*较少的经过地下循环的低温饱和大气水。而幔源组分来自千里山花岗岩浆流体，表明千里山花岗岩并非传统的S型花岗岩。 4. 在总结前人研究成果的基础上，结合本次研究，建立了柿竹园矿田成矿作用模式：中生代华南岩石圈发生拉张、伸展作用，地幔物质上涌，发生壳幔相互作用，形成千里山花岗岩浆。花岗岩浆充分分异演化形成富含挥发分和成矿元素的成矿流体，与泥盆系碳酸盐岩发生反应而沉淀成矿。成矿过程有大气降水的加入，并发生了流体沸腾作用。

The Dirichlet problem in convex bounded domains for operators with L^\infty-coefficients

M.Hieber, I.Wood: The Dirichlet problem in convex bounded domains for operators with L^\infty-coefficients, Diff. Int. Eq., 20, 7 (2007),721-734.

Self perceived health status of schizophrenic patients in Spain: an analysis of geog raphical differences using bayesian approach

Objectives. This paper explores the use of regression models for estimating health status of schizophrenic patients, from a Bayesian perspective. Our aims are: 1- To obtain a set of values of health states of the EQ-5D based on self-assessed health from a sample of schizophrenic patients. 2- To analyse the differences in the health status and in patients’ perceptions of their health status between four mental-health districts in Spain. Methods. We develop two linear models with dummy variables. The first model seeks to obtain an index of the health status of the patients using a VAS as a dependent variable and the different dimensions of EQ-5D as regressors. The second model allows to analyse the differences between the self-assessed health status in the different geographic areas and also the differences between the patients’ self-assessed health states, irrespective of their actual health state, in the different geographic areas. The analysis is done using Bayesian approach with Gibbs sampling (computer program WinBUGS 1.4). Data concerning self-assessed EQ-5D with VAS from four geographic areas of schizophrenic patients were obtained for the purposes of this analysis. Results. We obtained the health status index for this sample and analysed the differences for this index between the four geographic areas. Our study reveals variables that explain the differences in patients’ health status and differences in their health states assessment. We consider four possible scenarios.

Egzystencjalna teoria umysłu. Konstrukcja narzędzia pomiarowego

Wydział Nauk Społecznych: Instytut Psychologii

Functional properties of cell-seeded three-dimensionally woven poly(epsilon-caprolactone) scaffolds for cartilage tissue engineering.

Articular cartilage possesses complex mechanical properties that provide healthy joints the ability to bear repeated loads and maintain smooth articulating surfaces over an entire lifetime. In this study, we utilized a fiber-reinforced composite scaffold designed to mimic the anisotropic, nonlinear, and viscoelastic biomechanical characteristics of native cartilage as the basis for developing functional tissue-engineered constructs. Three-dimensionally woven poly(epsilon-caprolactone) (PCL) scaffolds were encapsulated with a fibrin hydrogel, seeded with human adipose-derived stem cells, and cultured for 28 days in chondrogenic culture conditions. Biomechanical testing showed that PCL-based constructs exhibited baseline compressive and shear properties similar to those of native cartilage and maintained these properties throughout the culture period, while supporting the synthesis of a collagen-rich extracellular matrix. Further, constructs displayed an equilibrium coefficient of friction similar to that of native articular cartilage (mu(eq) approximately 0.1-0.3) over the prescribed culture period. Our findings show that three-dimensionally woven PCL-fibrin composite scaffolds can be produced with cartilage-like mechanical properties, and that these engineered properties can be maintained in culture while seeded stem cells regenerate a new, functional tissue construct.

Evolutionary characters, phenotypes and ontologies: curating data from the systematic biology literature.

BACKGROUND: The wealth of phenotypic descriptions documented in the published articles, monographs, and dissertations of phylogenetic systematics is traditionally reported in a free-text format, and it is therefore largely inaccessible for linkage to biological databases for genetics, development, and phenotypes, and difficult to manage for large-scale integrative work. The Phenoscape project aims to represent these complex and detailed descriptions with rich and formal semantics that are amenable to computation and integration with phenotype data from other fields of biology. This entails reconceptualizing the traditional free-text characters into the computable Entity-Quality (EQ) formalism using ontologies. METHODOLOGY/PRINCIPAL FINDINGS: We used ontologies and the EQ formalism to curate a collection of 47 phylogenetic studies on ostariophysan fishes (including catfishes, characins, minnows, knifefishes) and their relatives with the goal of integrating these complex phenotype descriptions with information from an existing model organism database (zebrafish, http://zfin.org). We developed a curation workflow for the collection of character, taxonomic and specimen data from these publications. A total of 4,617 phenotypic characters (10,512 states) for 3,449 taxa, primarily species, were curated into EQ formalism (for a total of 12,861 EQ statements) using anatomical and taxonomic terms from teleost-specific ontologies (Teleost Anatomy Ontology and Teleost Taxonomy Ontology) in combination with terms from a quality ontology (Phenotype and Trait Ontology). Standards and guidelines for consistently and accurately representing phenotypes were developed in response to the challenges that were evident from two annotation experiments and from feedback from curators. CONCLUSIONS/SIGNIFICANCE: The challenges we encountered and many of the curation standards and methods for improving consistency that we developed are generally applicable to any effort to represent phenotypes using ontologies. This is because an ontological representation of the detailed variations in phenotype, whether between mutant or wildtype, among individual humans, or across the diversity of species, requires a process by which a precise combination of terms from domain ontologies are selected and organized according to logical relations. The efficiencies that we have developed in this process will be useful for any attempt to annotate complex phenotypic descriptions using ontologies. We also discuss some ramifications of EQ representation for the domain of systematics.

Development and validation of a shipboard system for measuring high-resolution vertical profiles of aqueous dimethylsulfide concentrations using chemical ionization mass spectrometry

A sampling and analytical system has been developed for shipboard measurements of high-resolution vertical profiles of the marine trace gas dimethylsulfide (DMS). The system consists of a tube attached to a CTD with a peristaltic pump on deck that delivers seawater to a membrane equilibrator and atmospheric pressure chemical ionization mass spectrometer (Eq-APCIMS). This allows profiling DMS concentrations to a depth of 50 m, with a depth resolution of 1.3-2 m and a detection limit of nearly 0.1 nmol L-1. The seawater is also plumbed to allow parallel operation of additional continuous instruments, and simultaneous collection of discrete samples for complementary analyses. A valve alternates delivery of seawater from the vertical profiler and the ship�s underway intake, thereby providing high-resolution measurements in both the vertical and horizontal dimensions. Tests conducted on various cruises in the Mediterranean Sea, Atlantic, Indian, and Pacific Oceans show good agreement between the Eq-APCIMS measurements and purge and trap gas chromatography with flame photometric detection (GC-FPD) and demonstrate that the delivery of seawater from the underway pump did not significantly affect endogenous DMS concentrations. Combination of the continuous flow DMS analysis with high-frequency hydrographic, optical, biological and meteorological measurements will greatly improve the spatial/temporal resolution of seagoing measurements and improve our understanding of DMS cycling.

The periodic variations of a white-light flare observed with ULTRACAM

High time resolution observations of a white-light flare on the active star EQ PegB show evidence of intensity variations with a period of ≈10 s. The period drifts to longer values during the decay phase of the flare. If the oscillation is interpreted as an impulsively-excited, standing-acoustic wave in a flare loop, the period implies a loop length of ≈3.4 Mm and ≈6.8 Mm for the case of the fundamental mode and the second harmonic, respectively. However, the small loop lengths imply a very high modulation depth making the acoustic interpretation unlikely. A more realistic interpretation may be that of a fast-MHD wave, with the modulation of the emission being due to the magnetic field. Alternatively, the variations could be due to a series of reconnection events. The periodic signature may then arise as a result of the lateral separation of individual flare loops or current sheets with oscillatory dynamics (i.e., periodic reconnection).

Strong parallel magnetic field effects on the hydrogen molecular ion

Equilibrium distances, binding energies and dissociation energies for the ground and low-lying states of the hydrogen molecular ion in a strong magnetic field parallel to the internuclear axis are calculated and refined, by using the two- dimensional pseudospectral method. High-precision results are presented for the binding energies over a wider field regime than already given in the literature (Kravchenko and Liberman 1997 Phys. Rev. A 55 2701). The present work removes a long- standing discrepancy for the R-eq value in the 1sigma(u) state at a field strength of 1.0 x 10(6) T. The dissociation energies of the antibonding 1pi(g) state induced by magnetic fields are determined accurately. We have also observed that the antibonding 1pi(g) potential energy curve develops a minimum if the field is sufficiently strong. Some unreliable results in the literature are pointed out and discussed. A way to efficiently treat vibrational processes and coupling between the nuclear and the electronic motions in magnetic fields is also suggested within a three-dimensional pseudospectral scheme.

Unusual voltammetry of the reduction of O-2 in [C(4)dmim][N(Tf)(2)] reveals a strong interaction of O-2(center dot-) with the [C(4)dmim](+) cation

Voltammetric studies of the reduction of oxygen in the room temperature ionic liquid [C(4)dmim][N(Tf)(2)] have revealed a significant positive shift in the back peak potential, relative to that expected for a simple electron transfer. This shift is thought to be due to the strong association of the electrogenerated superoxide anion with the solvent cation. In this work we quantitatively simulate the microdisc electrode voltammetry using a model based upon a one-electron reduction followed by a reversible chemical step, involving the formation of the [C(4)dmim](+)center dot center dot center dot O-2(center dot-) ion-pair, and in doing so we extract a set of parameters completely describing the system. We have simulated the voltammetry in the absence of a following chemical step and have shown that it is impossible to simultaneously fit both the forward and reverse peaks. To further support the parameters extracted from fitting the experimental voltammetry, we have used these parameters to independently simulate the double step chronoamperometric response and found excellent agreement. The parameters used to describe the association of the O-2(center dot-) with the [C(4)dmim](+) were k(f) = 1.4 x 10(3) s(-1) for the first-order rate constant and K-eq = 25 for the equilibrium constant.

Electrooxidation of the iodides [C(4)mim]I, LiI, NaI, KI, RbI, and CsI in the room temperature ionic liquid [C(4)mim][NTf2]

The electrochemical oxidation of 1-butyl-3-methylimidazolium iodide, [C(4)mim]I, has been investigated by cyclic voltammetry at a platinum microelectrode at varying concentrations in the RTIL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(4)mim][NTf2]. Two oxidation peaks were observed. The first peak is assigned to the oxidation of iodide to triiodide, in an overall two-electron process: 3I(-)- 2e(-) -> I-3(-). At higher potentials, the electrogenerated triiodide oxidizes to iodine, in an overall one-electron process: I-3(-) - e(-) -> 3/2I(2). An average diffusion coefficient, D, for I- of 1.55 x 10(-11) m(2) s(-1) was obtained. A digital simulation program was used to simulate the voltammetric response, and kinetic parameters were successfully extracted. The parameters deduced from the simulation include D for I-, I-3(-), and I-2 and K-eq,K-2, the equilibrium constant for the reaction of iodide and iodine to form triiodide. Values for these parameters are of the same order as those previously published for the oxidation of Br- in the same RTIL [Allen et al. J. Electroanal. Chem. 2005, 575, 311]. Next, the cyclic voltammetry of five different inorganic iodide salts was studied by dissolving small amounts of the solid in [C(4)mim][NTf2]. Similar oxidation peaks were observed, revealing diffusion coefficients of ca. 0.55, 1.14, 1.23, 1.44, and 1.33 x 10(-11) m(2) s(-1) and solubilities of 714, 246, 54, 83, and 36 mM for LiI, NaI, KI, RbI, and CsI, respectively. The slightly smaller diffusion coefficients for the XI salts (compared to [C(4)mim]I) may indicate that I- is ion-paired with Li+, Na+, K+, Rb+, and Cs+ in the RTIL medium.