Aqueous solutions—A new perspective. Amorphous carbohydrates: Science and application technology

At a recent meeting of the International Symposium on Solution Chemistry I presented a paper dealing with aqueous solutions in which water was present not in excess but as one component of a supersaturated solution with polyhydroxy compounds. In response to a request from the Editor of this Journal I have submitted this article in which I outline my general interest in the subject and its importance as a new direction for solution chemists.     

Synthesis and properties of niobia films derived from niobium pentaethoxide

The hydrolysis of niobium pentaethoxide precursor in the presence of triethylamine (TEA) is discussed. Three precursors with TEA/Nb(OEt)₅ mole ratios of 0.25, 0.4 and 0.8 were prepared. Niobia colloids with different appearance were obtained after autoclaving the above precursors at 250°C during 12 h. The surface roughness and microstructure of niobia films prepared with the colloids by spread coating method are strongly dependent on the TEA/Nb(OEt)₅ mole ratio. At a value of 0.4 TEA/Nb(OEt)₅ mole ratio, a niobia film with large surface roughness can be achieved. It is opaque and mechanically stable and has differently ordered needle microstructure. The crystalline structure and photoelectrochemical property of niobia film with the largest surface roughness were examined. The effect of CO₂ gas bubbling, reflux and addition of 2-methoxyethanol on the hydrolysis of Nb(OEt)₅ and the nature of the Nb₂O₅ films is also discussed.     

Methyl cellulose-based edible films and coatings I. Effect of plasticizer content on water and 1-octen-3-ol sorption and transport

Edible films were prepared from methyl cellulose with various concentrations of poly(ethylene glycol) 400 (PEG400) used as a plasticizer. Water vapour and 1-octen-3-ol (an aroma compound) were selected as hydrophilic and hydrophobic volatile penetrants respectively. Their solubility and permeability through methyl cellulose-based edible films were studied using gas chromatography methods. Whatever penetrant was used, the flux increased with the PEG400 content. Transfer behaviour, i.e., the order of increased magnitude of the transfer rate, strongly depends on the nature of the volatile compound. However, water sorption only depends on the PEG400 content whereas the aroma compound sorption is affected by both the water and the PEG400 concentrations. Relationships between solubility and permeability can be partially explained by the plasticization phenomenon.     

Ruthenized screen-printed choline oxidase-based biosensors for measurement of anticholinesterase activity

Plastic disposable choline biosensors based on ruthenized-carbon screen-printed electrodes were prepared and their use for monitoring organophosphorus pesticides and carbamates is described. The presence of 0.5% ruthenium on activated carbon mixed to form a simple graphite-based ink for the working electrode surface increased the sensitivity towards hydrogen peroxide. The choline biosensor is based on such an electrode coupled with choline oxidase immobilized by adsorption and was used to detect the inhibition effect of carbamates and organophosphorus pesticides on acetylcholinesterase. With the optimized procedure described (pH, buffer composition, incubation time, substrate concentration), concentrations of pesticides (Carbofuran) as low as 1 nM could be detected.     

Ion interaction approach to calculations of volumetric properties of aqueous multiple-solute electrolyte solutions

The ion interaction approach developed by Pitzer was used for the prediction of volumetric properties of mixed electrolyte solutions at 25°C based on parameters calculated from experimental data for single-solute electrolyte solutions. Such an approach was shown to be especially effective for application to the calculation of volumetric properties of natural hypersaline brines and of industrial electrolyte solutions of large complexity. The use of the latest recommended sets of volumetric ion interaction parameters for single electrolyte solutions and symmetrical mixing parameters for Na–K–Cl ion combinations considerably improved the precision of the density calculations of highly concentrated mixed electrolyte solutions and of various natural waters.     

硅钼杂多阴离子薄膜修饰电极的研究和应用——线性扫描伏安法测定水中可溶性硅酸盐

本文研究了以玻碳电极为基体的1:12硅钼杂多酸根(SiMo_(12)O_(40)~(4-)简称12-MSA)修饰电极的制备及其电化学行为,将12-MSA电极应用于线性扫描伏安法测定天然水中可溶性硅酸盐,结果满意.硅浓度在8.0×10~(-7)～1.7×10~(-3)mol/L,相对标准偏差(n=7)为1.85％,加标回收率为98.2％～103.6％,SiMo_(12)电极具有优良的选择性和稳定性。     

催化褪色光度法测定微量锰（Ⅱ）的研究

本文研究在硫酸介质中，锰（Ⅱ）催化ＥＤＴＡ还原重铬酸银，而使之褪色的新指示反应。确定了催化褪色反应动力学条件，锰（Ⅱ）的浓度在０－０．４μｇ／ｍｌ范围内，工作曲线呈良好的线性关系，检测限为０．０１１μｇ／ｍＬ，该方法用于天然水及污水中锰的测定，获得满意结果。     

影响苯胺电化学计量聚合因素的探讨

本文对影响苯胺电化学计量聚合的因素进行了探讨，这些因素包括：电化学聚合方法、电极电位（Ｅ）、电流密度（Ｉ），以及苯胺单体和酸溶液的浓度等，实验结果表明，最合适的聚合方法为恒电流法，其条件为：电极电位不大于０．７０Ｖ（ｖｓ．ＳＣＥ）聚合电流密度（Ｉ）约为０．０５ｍＡ／ｃｍ＾２，苯胺单体浓度为１．１ｍｏｌ／Ｌ，酸（ＨＣｌ）的浓度则为２．２ｍｏｌ／Ｌ     

Metal island coated polymer sensor for direct determination of the volume effect of chaotropic agents

A new optical sensor is presented, based on the analyte reaction resulting in swelling and shrinking of a thin polymer layer. Changing the concentration of ions in a new bisazide photo-cross-linked poly(vinylpyrrolidone) polymer results in a concentration-dependent volume change of the hydrated gel. The volume response of the sensor induced by different ions is fully reversible over more than 250 cycles. The response of the device depends on the type, the charge and the concentration of the ions. The sensor material is part of an optical thin film system which transforms the variations in volume of the polymer into spectral information. The steady state of the sensor response is obtained within 60 s. The response time is mainly limited by the pump rate, the back pressure and the total volume of the system but not by the swelling of the sensor polymer. A comparative study of ion effects has demonstrated a fundamental correlation of the polymer swelling properties with the Hofmeister series of chaotropic agents. Thus it is concluded that the photopolymer, which is solubilized in aqueous solutions by the interaction of its amide structure with the solvent, behaves like the backbone amide structure of proteins.     

茶汤及河水中铬的形态分析

本文采用７１７型强碱性阴离子交换树脂、活性炭分离富集与偶氮胂Ⅲ光度法结合，研究了铬形态的分离及测定，提出了铬的形态分析方法，有此法测定了茶汤及河水中铬的总量，悬浮态．溶解态、无机态、有机态、Ｃｒ（Ⅲ）和Ｃｒ（Ⅵ）。茶汤中铬主要以有机态存在，而河水中铬则主要以悬浮态存在。