13C NMR investigations of molecular order of rod-like,bent-core,and thiophene mesogens

In this review, methods to obtain the orientational order of topologically variant molecular mesogens using by one- and two-dimensional (2D) solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy are described. Besides ¹³C chemical shifts, the ¹³C─¹H dipolar couplings measured from 2D-separated local field (SLF) technique are used for computing the order parameters of a variety of mesogens. The investigated molecules are composed of a variable number of rings in the core, that is, core ranging from simply one ring to five rings. Among the mesogens investigated, a special focus has been placed on mesogens with thiophene rings, which are gaining popularity as liquid crystalline organic semiconductors. The replacement of a phenyl ring by thiophene in the core has a dramatic influence on molecular topology, as observed from the measured order parameters. The review highlights the advantages of the 2D SLF method for understanding the local dynamics and for mapping the topology of mesogens through the measured order parameters. SLF NMR studies of as many as 24 molecular mesogens that vary in terms of the molecular structure as well as topology are covered in the review. Order parameters of the rings have been estimated from the ¹³C─¹H dipolar couplings in the nematic, smectic A, smectic C, and tilted hexatic phases as well as in B₁ and B₂ mesophases of various mesogens. It is anticipated that, in the years to come, the 2D SLF method would provide advanced molecular information on structurally complex mesogens that are emerging in liquid crystal science through the incessant efforts of synthetic chemists. The mini review covers the orientational order of topologically variant molecular mesogens determined by 1D and 2D solid-state ¹³C NMR spectroscopy. Accordingly, rod-like, bent-core, and thiophene mesogens were subjected to 2D SLF measurements to get the order parameters from which the topology was established. The replacement of phenyl ring by thiophene and its influence on order parameters as well as on molecular topology is also discussed.     

Electrochemical and Spectroscopic Studies on the Interaction of Malachite Green with DNA and Its Application

The interaction of malachite green (MG) with double‐stranded DNA (dsDNA) in pH 7.0 Britton–Robinson (B–R) buffer solution was investigated by electrochemical and spectrophotometric methods. Within the potential scan range of ?1.0 to +1.5 V (vs. SCE), MG has two oxidative peaks at 0.547 V and 0.833 V and one reductive peak at 0.362 V on cyclic voltammogram at the scan rate of 0.20 V/s. After the addition of dsDNA into the MG solution, the oxidative peak current at 0.547 V decreases obviously. The electrochemical parameters, such as the charge transfer coefficient (α), the surface reaction rate constant (k_s) and the diffusion coefficient (D), were calculated and compared between in the absence and presence of dsDNA. The results show that these parameters of MG after adding dsDNA have greatly changed, which indicates that an electrochemical active complex was formed. The interaction mechanisms of MG with dsDNA are discussed in some details from the electrochemistry and UV‐vis spectrophotometry. The reduction of the peak current of MG after adding dsDNA was further used for the quantification of dsDNA by differential pulse voltammetry (DPV). The linear range for dsDNA is in the range of 10.0–100.0 μg/mL with the linear regression equation as Δi_p (μA)=0.065+0.0096 C (μg/mL) and the detection limit of 6.0 μg/mL (3σ). The influences of coexisting substances were investigated and artificial samples were determined with satisfactory results.     

Recent theories of gas sorption in polymers

Theories and models are presented for gas sorption in polymers above and below the glass transition temperature. With the exception of predictive theories that do not represent the data well, the models are fit to data for the carbon dioxide/silicone rubber and carbon dioxide/polycarbonate systems for the purposes of comparison. During the past decade, a number of new models and theories have been proposed specifically for gas sorption in glassy polymers. Each new model attempts to incorporate aspects of the gas sorption process that are unique to polymers below the glass transition temperature. This review discusses these recent advances, the assumptions used in their development and their advantages and disadvantages.     

高压下C60晶体玻璃化行为的理论研究

通过构造C_(60)分子间的相互作用，研究了在不同压力下C_(60)晶体中的取向有序结构．利用计算出来的两个取向之间的能量差和相隔势驿，研究了热平衡时取向占有几率和玻璃化转变温度的压力相关性．结果与实验符合．     

Voltammetric Detection of the DNA Interaction with Toluidine Blue

Binding reactions of toluidine blue (TB) with herring fish DNA in pH 6.0 Britton–Robinson (B–R) buffer solution have been investigated by cyclic voltammetry and linear‐sweep voltammetry at a glassy carbon electrode. TB has a couple of well‐defined redox peaks. The addition of DNA into the TB solution resulted in the decrease of the redox‐peak currents and the shift negatively of the anodic peak potential. The values of the electrochemical parameters such as the electron number of the electrochemical reaction, the electron transfer coefficient and the electrochemical reaction standard rate constant in the absence and presence of DNA, as well as the values of binding constant and binding ratio of DNA with TB were obtained. Almost unchanged values of the electrochemical parameters in the absence and presence of DNA show that nonelectroactive complexes were formed when TB interacted with DNA. DNA concentration can be determined by the decrease of the peak current of TB. The binding mode of TB with DNA was discussed.     

过氧化物模拟酶在介体型生物传感器方面应用初探

meso-四(4-磺基苯)卟啉锰(Ⅲ)作为过氧化物模拟酶可催化H_2O_2与K_4Fe(CN)_6反应。电流响应与H_2O_2浓度在3.0×10~(-4)～1.0×10~(-3)mol/L范围内呈线性关系。重现性和回收率良好。抗坏血酸和DL-半胱氨酸干扰严重。     

裸玻碳电极伏安测定甲氰咪胍

提出了裸ＧＣＥ不需任何处理测定甲氰咪胍的方法，浓度在３×１０＾－７－６×１０＾－５ｇ／ｍＬ，范围内与峰电流呈线性关系，ＲＳＤ为２．２％，回收率为９６％－１０２％。该方法操作简便快速，大多数金属离子和多种有机生化物质不干扰测定，方法用于片剂和加标尿样中甲氰咪胍的测定与药典方法对照，获得满意结果，并对电极反应进行了初步探讨。     

Anodic Stripping Voltammetry of Heavy Metals at Nanocrystalline Boron‐Doped Diamond Electrode

Boron‐doped Diamond (BDD) electrode has become one of the important tools for heavy metal detection. By studying some analytical parameters of DPASV method, like deposition time and potential in different electrolyte concentrations (acetate buffer), the conditions for detecting very low metal ion levels (Zn, Cd, Pb, and Cu) could be chosen. Diluted electrolyte (0.01 M buffer) was one of the factors favoring low detection and quantification limits, but its quantification range is short in comparison to more concentrated media. For ?1.7 V deposition potential, the detection of single metal at ppb levels was reached in 60 s deposition time. Understanding different metal‐metal interactions shows the limits to the simultaneous determination of heavy metals at BDD. Quantification was possible for the simultaneous determination of Zn, Cd and Pb despite the overlapping of Zn and Cd peaks. The performance of the BDD was compared with that of another C‐based solid electrode: the glassy carbon electrode (without mercury plating). A lower base line current, wider potential range, higher sensitivity (3 to 5 times higher than GC) and longevity of the material were noticed for the BDD.     

药物分子在玻碳电极上的电分析化学研究──Ⅴ．安乃近的伏安行为及测定

提出了一种测定安乃近新法。由于安乃近没有电活性，故将安乃近和盐酸在１００℃共热后生成电活性产物，用玻碳电极在０．１ｍｏｌ／ＬＮａＯＨ中得一良好的阳极氧化伏安峰，Ｅｐ＋０．３５Ｖ（ｖｓ·Ａｇ／ＡｇＣｌ）左右，峰电流与安乃近浓度在０．１～１００ｍｇ／Ｌ之间呈线性关系，分析了制剂安乃近的含量，实验证实电极反应属于扩散控制的不可逆过程。     

Study of Factors Affecting the Performance of Voltammetric Copper Sensors Based on Gly‐Gly‐His Modified Glassy Carbon and Gold Electrodes

This paper reports a study of the factors affecting the analytical performance of gold and glassy carbon electrodes modified with the tripeptide Gly‐Gly‐His for the detection of copper ions. Gly‐Gly‐His is attached to a glassy carbon (GC) surface modified with 4‐carboxyphenyl moieties or a gold surface modified with 3‐mercaptopropionic acid by the reaction of the N‐terminal amine group of the peptide with the carboxylic acid groups of the monolayer via carbodiimide activation. X‐ray photoelectron spectroscopy was used to characterize the steps in the biosensor fabrication. It was found that the analytical performance of a sensor prepared with Gly‐Gly‐His on a GC electrode was similar to that on a gold electrode under the same conditions. The performance was greatly enhanced at higher temperature, no added salt during copper accumulation and longer accumulation time within a pH range of 7–9. Interference studies and investigations of stability of the Gly‐Gly‐His sensor are reported. Analysis of natural water samples show that the sensors measure only copper ions that can complex at the sensor surface. Strongly complexed copper in natural water is not measured. Despite greater stability of diazonium salt derived monolayers on carbon surfaces compared with alkanethiols self‐assembled monolayers on gold, the stability of the sensors was essentially the same regardless of the modification procedure.