Solution Medium Control of the Ru(bpy)32+/Methyl Viologen/EDTA Photochemical System

The value of φ(MV⁺·) from the photolysis of the Ru(bpy)₃²⁺/MV²⁺/EDTA system depends on the pH of the solution and the concentrations of the three components. The pairing of cations with EDTA in alkaline solution, and the formation of large aggregates at high substrate concentrations, affects the yields of redox products from the excited-state electron-transfer reaction. The degree of linearity of Stern-Volmer luminescence quenching plots, and the values of the quenching rate constants, are functions of solution medium.     

负离子对紫精光还原和电氧化还原性能的影响

负离子对紫精光还原和电氧化还原性能的影响冯敏辉，刘伟区，梁兆熙（中山大学高分子研究所，广州，５１０２７５）关键词紫精化合物，负离子，电氧化还原，光还原，化学还原合成了不同负离子（Ｆ－、Ｃｌ－、Ｂｒ－、Ｉ－、ＳＣＮ－、ＣｌＯ４－）的芳基紫精聚合物，并研...     

聚N－（4，4＇－联吡啶盐）－p－乙烯基吡啶的电还原及光还原行为

合成了三种新型的主链为聚４－乙烯基吡啶的侧链型紫精聚合物和相应的小分子紫精，研究了它们的电还原及光还原行为。结果表明这类侧链型紫精聚合物的电还原和在异丙醇水溶液中的光还原都存在明显的聚合物效应，还原后生成的自由基正离子分子内缔合的倾向比相应的小分子紫精大得多．     

CMC系列高分子表面活性剂的胶束形态

高分子表面活性剂分子量高 ,分子中兼具亲水和疏水链段 ,在选择性溶剂水中同小分子表面活性剂一样 ,可形成疏水链段为核心、亲水链段为外壳的胶束结构 ,但高分子量又使其表现出许多不同于低分子表面活性剂的形态特征 ,如胶束的多种形态、尺寸分布多分散性等等 ,而这些形态特征对高分子表面活性剂的界面活性、增粘、乳化等性能有决定性的影响．结构规整的嵌段或接枝共聚物在选择性溶剂中的分子聚集形态已有研究 ［１,２］,亲水亲油性的高分子表面活性剂在水溶液中由于结构复杂、水溶液中氢键作用及静电作用力等因素造成的困难 ,因而研究较少…     

取代苯甲腈类有机污染物水解行为的研究

研究了10种二取代苯甲腈类有机污染物的水解行为,用反相高效液相色谱测定了不同pH值和不同溫度下的水解速度常数。结果表明,含羟基的化合物在酸,碱和中性水介质中均不易水解;其它化合物仅在碱性介质中水解,其碱性催化水解速度常数与Hammett取代基常数以及酸常数之间呈近似线性关系。相关方程为:lgk_B=1.45σ-0.859和lgk_B=-1.34pK_(?)-4.83。     

聚苯胺/凹凸棒石负载纳米铁降解水溶液中甲基橙

以聚苯胺/凹凸棒石(PANI/ATP)为载体,采用液相还原法合成了负载型纳米零价铁(nZVI),用扫描电子显微镜(SEM)、透射电子显微镜(TEM)及X射线光电子能谱分析仪(XPS)等技术手段对纳米复合材料进行表征,考察了反应时间和pH值对甲基橙降解性能的影响,对降解过程进行了动力学分析,探讨了nZVI/PANI/ATP复合材料对甲基橙的降解机理。 结果表明,nZVI/PANI/ATP复合材料在较大pH值范围内能有效降解水中甲基橙并具有降解长效性,当催化剂用量1.0 g/L,降解体积50 mL,甲基橙的浓度20 mg/L,降解时间30 min时,复合材料对甲基橙的降解率达到95.8%以上,对甲基橙的降解过程符合准二级动力学模型。     

Thermal Aggregation of Methyl Cellulose in Aqueous Solution: A Thermodynamic Study and Protein Partitioning Behaviour

The formation of a biphasic system from aqueous solutions of methyl cellulose induced by temperature was studied through heating curves of the polymer solution measured by absorbance spectroscopy, differential scanning calorimetry and solution viscosimetry. The treatment of the heating curve data according to a reversible two-state transition model allows us to calculate the middle point temperature (T_m) of the formation of the two phases and the thermodynamic functions associated to the polymer aggregation. The middle point temperature was found within the range 50–70 °C. It decreased significantly in a Na₂SO₄ 0.3 M medium when the polymer concentration increased. The heat associated to the two-phase formation was positive and it increased with increases in temperature. Cosolutes that affect the water structure induced changes in the T_m values, which suggests the presence of a hydrophobic effect in the two-phase formation from the polymer solution. Hydrophilic proteins were partitioned in favour of the methyl cellulose rich phase according to their surface hydrophobicity. The partition was also influenced by the presence of salts that modify the protein hydrophobicity such as sodium sulphate.     

电-Fenton及类电-Fenton技术处理水中有机污染物

传统Fenton技术是一种广泛用于水体里有机污染物降解的高级氧化技术(advanced oxidation technologies, AOTs)。它利用Fenton试剂Fe²⁺与H₂O₂反应生成具有强氧化性的羟基自由基(^·OH),从而降解有机污染物。基于相似的机理,过渡金属离子(Fe²⁺、Co²⁺和Ag⁺等)也可与过硫酸盐反应生成氧化能力较强的硫酸根自由基(SO₄^·-),而被称之为类Fenton技术。传统Fenton技术存在Fe²⁺投加量多,产生的铁污泥多等缺点,因此,有学者将Fenton技术与电化学技术结合,使Fe²⁺在阴极得以持续再生,这就是广为关注的电-Fenton技术。同样地,类Fenton技术也遇到与传统Fenton技术相似的问题。借鉴电-Fenton技术的成功应用,基于硫酸根自由基的类电-Fenton技术应运而生。本文在介绍电-Fenton和类电-Fenton技术原理的基础上,概括了电-Fenton和类电-Fenton技术的主要类型及其改进方法,并就值得深入研究的问题和热点趋势进行了展望。     

Aqueous Polymerization of Methyl Methacrylate

Aqueous polymerization of methyl methacrylate (MMA), initiated by the potassium bromate-thioglycollic acid (TGA) redox system, has been studied at 30 ± 0.2° C under positive pressure of nitrogen. The rate is given by K[MMA] [TGA] ⁰[KBrO₃]^x where × = 1 for lower KBrO₃ concentrations and 0.5 for higher KBrO₃ concentrations. The reaction has been studied over the 20–45°C range. The activation energy was found to be 65.72 kJ/mol (15.71 kcal/mol) in the investigated range of temperature. Inorganic electrolytes except MnSO₄·4H₂O and Na₂C₂O₄ depress both the rate of polymerization and the maximum conversion. All the alcohols (viz., MeOH, EtOH, iso-PrOH, tert-BuOH) and acetone depress the rate of polymerization as well as the maximum conversion.     

甲基化的β-环糊精与十六烷基三甲基溴化胺的相互作用

环糊精与表面活性剂的相互作用已有许多研究,但多局限于β－环糊精（β－CD）,而修饰的β－环糊精与表面活性剂的相互作用研究较少[1－3]．分子内扭转电荷转移（TICT）激发态对介质极性高度敏感性,已成功地用于探针环糊精与表面活性剂的相互作用[4]．研究表明,β－CD能够诱     

Determination of Phosphate in Aqueous Solutions Containing NTA and EDTA

Abstract

A simple and precise colorimetric method of determining phosphate in aqueous solutions containing nitrilotriacetic acid (NTA) or ethylendiaminetetraacetic acid (EDTA) is described. It involves precipitation of the NTA or EDTA by acidification to pH 1.5 and colorimetric determination of the phosphate in the filtrate by a heteropoly blue method. The method is sensitive and accurate, and it permits determination of microgram amounts of phosphate in samples of aqueous solutions containing up to 300 mM of NTA and (or) EDTA.     

Novel Method of Producing Polymer Gels in Aqueous Solution Using UV Irradiation

Summary: We developed a novel method of producing polymer gels in aqueous solution using UV irradiation. Persulfates were effective photosensitive initiators of polymerization and/or gelation of acryloyl‐type monomers/polymers. The gelation was confirmed by an abrupt increase in light scattering intensity, 〈I(q)〉_T, at the gelation point. The gelation method entails significant advantages: it does not need any cross‐linkers, temperature control (heating), and additives except the persulfate.

The UV irradiation time dependence of light scattering intensity, 〈I(q)〉_T, for pre‐gel solutions containing N‐isopropylacrylamide (NIPAm) and/or ammonium persulfate (APS).     

Pseudo-Topochemical Synthesis of α-Fe in Aqueous Solution Using an Aluminum Matrix

Processes occurring in synthesis of α-Fe from a Fe(III) solution using an aluminum matrix were studied. The reaction kinetics strongly depends on the state of the matrix.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005, pp. 177–183.Original Russian Text Copyright © 2005 by Dresvyannikov, Kolpakov.     

Molecular Recognition and Scavenging of Arsenate from Aqueous Solution Using Dimetallic Receptors

A series of copper(II), nickel(II) and zinc(II) dimetallic complexes were prepared and their affinities towards arsenate investigated. Indicator displacement assays (IDAs) were carried out to establish the complexes with best affinities towards arsenate. A di‐zinc complex ( 3 ) was selected and its arsenate‐binding abilities investigated by isothermal titration calorimetry (ITC). The X‐ray crystal structure of this metallo‐receptor bound to arsenate is also reported, which allowed us to establish the binding mode between 3 and this oxyanion. Immobilising 3 onto HypoGel resin yielded a novel adsorbent (Zn–HypoGel) with high affinity for arsenate. Adsorption of arsenate from competitive solutions and natural groundwater was greater than that of the commercially used iron oxide Bayoxide E33. Zn–HypoGel could be efficiently and simply regenerated by washing with sodium acetate solution.     

Competitive Sorption of Copper and Nickel Ions from Aqueous Solution Using Peat

Bicomponent aqueous solutions of copper and nickel ions have been used to investigate the sorption of metal ions onto peat. Peat, a low cost sorbent, has shown a high capacity for the sorption of single component metal ions attributed to extensive carboxylic acids within its structure. Copper and nickel ions were selected as typical metals in the effluents of electroplating industries. The effects of competitive sorption in batch systems were studied at various metal ion concentrations. In this study the Butler and Ockrent model was modified using a coefficient, . Two models were developed based on the interaction coefficient . The first model incorporates a constant fixed factor for each metal ion into the Butler-Ockrent equation. The second model incorporates a variable factor into the Butler-Ockrent equation; this interaction factor varies as a function of sorbent surface coverage. Predicted equilibrium data are found to be in excellent agreement with experimental values using both modified models for various mole ratios of copper and nickel ions in competitive sorption.     

The Oxidation of Thiocyanate to Polythiocyanic Acid Using Peroxydisulfate in Aqueous Solution

Abstract

The oxidation of thiocyanate to polythiocyanic acid by peroxydisulfate was carried out in an aqueous solution at room temperature. The primary step is the decomposition of peroxydisulfate into sulfate-free radicals. At room temperature in the presence of peroxydisulfate as a oxidizing agent, HSCN polymerizes to (HSCN)_n. The oxidation of thiocyanate in an aqueous solution is often complicated, but here we obtained the polythiocyanic acid as a major product. The products were characterized by elemental analysis, IR, UV- visible, H-NMR spectroscopy, and X-ray powder diffraction.     

Amplified Production of Singlet Oxygen in Aqueous Solution Using Metal Enhancement Effects

Studies involving metal enhancement effects have gained popularity, and enhancement of fluorescence due to the close proximity of a dye molecule to a metal nanoparticle is well documented. Although enhancement of singlet oxygen production by metal has been reported, studies are relatively scarce and so far only stationary silver island films have been proven to be adequate to do so. Herein, we describe the synthesis and characterization of core–shell nanoparticles on which a photosensitizer acting as source of singlet oxygen has been covalently attached to the nanoparticle surface. As a proof of concept, silver nanoparticles with a diameter around 68 nm were chosen as the metallic core, and were coated by a silica shell of about 22 nm in thickness. The silica shell plays a dual role as a spacer and a medium onto which the photosensitizer, rose bengal (RB), has been covalently attached. These novel core–shell nanoparticles allow for the amplification of singlet oxygen production by 3.8 times, which is similar to the amplification found for RB in proximity of silver island films.     

Structure of Aqueous Methyl and Propyl Methyl Cellulose Solutions in the Initial Stage of Gelation

Evolution of the supramolecular associate structure of moderately concentrated aqueous methyl and propyl methyl cellulose solutions, as dependent on the degree of substitution by propyl groups, is studied by the polarized light scattering using the Debye-Bueche-Stein theory.