Preparation of polysulfonebenzylthiourea-reactive ultrafiltration plate membranes and their rejection properties for heavy toxic metal cations

The asymmetric membranes were prepared via phase inversion method, by using chloromethyl polysulfone as membrane materials, polyethylene glycol (PEG) as pore forming agent to improve the morphology and function of resultant membranes, N,N-dimethylacetamide as solvent, and water as the extraction solvent. Then the highly qualified polysulfonebenzylthiourea-reactive ultrafiltration plate membrane was prepared successively through the reactions between the chloromethyl polysulfone matrix membrane and thiourea. The thiourea-functionalized polysulfone plate reactive ultrafiltration membrane was used for the rejection of heavy toxic metal cations such as Cd²⁺ and Zn²⁺ through the coordination of the thiourea group and heavy toxic metal cations, in which the effects of the morphological and the structure of the membrane on the rejection properties were investigated. The rejection conditions, including the concentration of heavy toxic metal cations, temperature and pH of the solution had significant effects on the rejection capacity of polysulfonebenzylthiourea-reactive ultrafiltration membrane. The reactive ultrafiltration membrane containing thiourea group can be conveniently recovered by dilute hydrochloric acid for coordination of heavy toxic metal cations, which would have wide application for the treatment of waste-water-containing heavy toxic metal cations. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Robust Silver(I) Catalyst for the Carboxylative Cyclization of Propargylic Alcohols with Carbon Dioxide under Ambient Conditions

Inspired by the bulkier bis(triphenylphosphine)–silver cation‐induced mechanism of propargylic alcohols and carbon dioxide through the alkyl carbonate intermediate, a robust dual‐component catalytic system consisting of silver acetate and tetraheptylammonium bromide was rationally developed for the synthesis of α‐methylene cyclic carbonates under ambient conditions without employing any additional organic base and ligand. This is one of the most effective catalysts reported to date for this conversion, with a very high turnover number of up to 6024, probably due to the synergistic effect of Lewis basic and Lewis acidic species for the activation of both propargylic alcohol and carbon dioxide by the formation of the alkyl carbonate with a bulkier counterion. Notably, this catalyst also worked well for the carboxylative cyclization of propargylic amines with carbon dioxide with the highest turnover number of 544.

     

Quaternary Ammonium Salts and Their Antimicrobial Potential: Targets or Nonspecific Interactions?

For more than 50 years dequalinium chloride has been used successfully as an antiseptic drug and disinfectant, particularly for clinical purposes. Given the success of dequalinium chloride, several series of mono- and bisquaternary ammonium compounds have been designed and reported to have improved antimicrobial activity. Furthermore, many of them exhibit high activity against mycobacteria and protozoa, especially against plasmodia. This review discusses the structure-activity relationships and the modes of action of the various series of (bis)quaternary ammonium compounds.     

高价金属离子对MBR中胞外聚合物影响的研究进展

膜生物反应器(membrane bioreactor,MBR)作为一种高效的污水处理及回用工艺,比传统的活性污泥法具有更多优势.然而,膜污染问题是限制其广泛应用的主要瓶颈,可导致出水通量下降、跨膜压差增加、洗膜及换膜频繁等.众多研究证实向MBR中投加高价金属离子可有效减缓膜污染,本文首先简述胞外聚合物(extracellularpolymeric substances,EPS)和高价金属离子与污泥混合液间的作用机理,其次,总结常用的三种高价金属离子(钙、铁、铝离子)在污泥混合液中分布规律及其影响.最后对高价金属离子在未来的应用进行展望.     

活性炭电极对不同阳离子电吸附行为的研究

自制活性炭电极,并用于不同含量的KCl、CdCl_2、CuCl_2和FeCl_3溶液电吸附行为研究.结果表明,多价离子吸附速率和吸附容量大,但脱附率低;单价离子吸附速率和吸附容量小,但脱附率高;同价态离子,离子半径越小的离子越容易被吸附.各离子在活性炭电极上的电吸附,均符合2级动力学方程,速率常数K与电压U关系符合指数函数,在相同电压下,吸附速率常数K(Fe~(3+))>K(Cu~(2+))>K(Cd~(2+))>K(K~+);吸附等温线均符合Langmuir等温式,活性炭电极的最大吸附量q_m与操作电压U线性相关,在相同电压下,活性炭电极的最大吸附容量q_m(Fe~(3+))>q_m(Cu~(2+))>q_m(Cd~(2+))>q_m(K~+).循环伏安和交流阻抗进一步验证了电吸附试验结果.     

Recovery of rare-earth metal neodymium from aqueous solutions by poly-γ-glutamic acid and its sodium salt as biosorbents:Effects of solution pH on neodymium recovery mechanisms

For recovery of metals from low-concentration sources, biosorption is one of promising technologies and poly-γ-glutamic acid(γ-PGA) has been known as a potential biosorbent for recovery of heavy metals from aqueous solutions. Effects of solution pH on recovery of rare-earth metal Nd are systematically examined to clarify mechanisms of Nd recovery by y-PGA and its sodium salt(y-PGANa). The recovery efficiency of Nd by y-PGA increases from 2.4 to 19.6% as pH increases from 2 to 4. Subsequently the Nd recovery efficiencies for y-PGA and y-PGANa remain almost constant in the range of pH from 4 to 7. For pH 7 the increase in Nd recovery is significant and 100% recovery of Nd is achieved at pH 9. The pH dependency on Nd recovery by y-PGANa is similar to that by y-PGA. Contributions of adsorption and precipitation/coagulation to Nd recovery process are quantified. Whereas the adsorption dominates Nd recovery at lower pH(～4), the precipitation/coagulation controls Nd recovery process for pH 7. At higher pH, purple gel precipitates are observed. The maximum adsorption capacities for γ-PGA and yPGANa are 215 mg-Nd/(g-γ-PGA) at pH 4 and 305 mg-Nd/(g-y-PGANa) at pH 3, respectively. From the spectra of FT-IR and XPS, the biosorption of Nd onto y-PGA and y-PGANa via electrostatic interaction with carboxylate anions at pH 3 is verified. The Nd complexation with amide and carboxylate anion groups on γ-PGA and γ-PGANa may also contribute to the Nd recovery. The biosorption isotherms for Nd recovery by γ-PGA and γ-PGANa can be satisfactorily fitted by the Langmuir model. The thermodynamic studies suggest that the biosorptions of Nd by γ-PGA and γ-PGANa are endothermic. The utilization of γ-PGA and γ-PGANa as potential and eco-friendly biosorbents for the highly effective recovery of Nd from aqueous solution is confirmed.     

喹啉季铵盐与金属阳离子作为盐酸酸化缓蚀剂的协同作用

季铵盐类缓蚀剂与金属阳离子的协同缓蚀作用广泛应用于高温酸化缓蚀剂领域,开展相关研究对于诠释高温酸化缓蚀剂多组分协同作用机理具有重要意义。合成了喹啉季铵盐缓蚀剂,研究了不同浓度的Sb2O3,CuI及NiSO4与喹啉季铵盐在20%盐酸,140℃环境中对N80钢的协同作用效果。结果表明,最优化的缓蚀剂配方为2%(质量分数)喹啉季铵盐+0.5%(质量分数)Sb2O3。针对这一最优化配方,通过表面SEM,EDS及XRD分析,研究了两种缓蚀剂组分之间的协同缓蚀作用机理。研究结果表明,喹啉季铵盐与锑化物协同作用形成复合膜是缓蚀的主要原因。增效剂Sb2O3在固液界面还原为单质Sb,沉积于金属表面,与酸化缓蚀剂主剂(成膜物质,喹啉季铵盐)共同形成复合膜,达到缓蚀作用。     

Micellar thin-layer chromatographic separation of heavy metal cations: Effect of organic and inorganic additives on migration behavior

The migration behavior of heavy metal cations on cellulose layers using aqueous micellar, hydro-organic, and water-organic-surfactant mobile phases was investigated. Anionic, cationic, and nonionic surfactant systems were examined over a 0.001–5% concentration range. Brij-35, a nonionic surfactant capable of forming charged complexes with some metal ions, was identified as the best surfactant. The effect of the presence of organic additives, such as dimethylsulfoxide, dimethylformamide, methanol and acetone, on the mobility of metal ions was also studied. Acetone was found to be the most effective additive at 10% concentration with 3% Brij. Quantitative determination of UO₂ ²⁺ by spectrophotometry after preliminary thin-layer chromatographic (TLC) separation from Fe³⁺ and Hg²⁺ was also performed. A maximal recovery of 93% was obtained. This TLC method is rapid, with development times averaging 2 min.     

Novel self-cross-linked multi-imidazolium cations long flexible side chains triblock copolymer anion exchange membrane based on ROMP-type polybenzonorbornadiene

A novel benzonorbornadiene derivative (BenzoNBD-Bis(Im⁺Br⁻-Im⁺I⁻)) grafted by multi-imidazolium cations side-chains combined the rigid alkyl spacer and flexible alkoxy spacer is designed and synthesized. Then, the BenzoNBD-Bis(Im⁺Br⁻-Im⁺I⁻) monomer is copolymerized with the epoxy functionalized norbornene monomer (NB-MGE) and norbornene (NB) via ring-opening metathesis polymerization (ROMP) using Grubbs 3rd catalyst. All as-designed triblock copolymer membranes (TBCMs) show a thermal decomposition temperature beyond 310 °C and can well be dissolved in common organic solvents. The self-cross-linked structure of anion exchange membrane (AEM) is confirmed by gel fraction and tensile measurement. The water uptake and swelling ratio of TBCMs and AEMs are also measured. Major properties required for AEMs such as ion exchange capacity (IEC), hydroxide conductivity and alkaline stability are investigated. AEM-9.09 shows a hydroxide conductivity of 100.74 mS cm⁻¹ at 80 °C. Besides, the micro-phase separated morphology of AEM is confirmed by TEM, AFM and SAXS analyses, AEMs formed distinct micro-phase separation. The as-prepared AEM exhibits a peak power density of 174.5 mW cm⁻² at 365.1 mA cm⁻² tested in a H₂/O₂ single-cell anion exchange membrane fuel cell (AEMFC) at 60 °C. The newly developed strategy of self-cross-linked multi-imidazolium cations long side-chains triblock benzonorbornadiene copolymer provides an effective method to develop high-performance AEMs.     

Competitive binding of divalent cations to poly(α-hydroxyacrylic acid)

The competitive binding of divalent cations (Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺) on poly(α-hydroxyacrylic acid) (PHA) and poly(acrylic acid) (PAA) was investigated by equilibrium dialysis. In the Mg/Ca mixed system, binding selectivity for Ca²⁺ over Mg²⁺ was significantly higher in PHA than in PAA; this was attributed to coordination of α-OH groups on PHA to Ca²⁺. The binding ability and selectivity for the transition metal cations were almost the same for PHA and PAA at neutral pH, while PHA maintained appreciably higher degrees of binding than PAA in acidic solutions (pH about 3). This cation binding ability of PHA was ascribed to the lower pK_a value in the relevant pH region. © 1998 SCI.