Synthesis of organically bridged trialkoxysilanes bearing acetoxymethyl groups and applications to reverse osmosis membranes

New bridged trialkoxysilanes bearing acetoxymethyl groups were synthesized by double hydrosilylation of 1,6‐diacetoxy‐2,4‐butadiyne, using two equivalents of triethoxysilane and a metal catalyst. With a Ru catalyst, the reaction proceeded via anti‐addition to provide BTES‐Ac‐a as a single isomer, while a similar reaction with a Pt or Rh catalyst provided an isomeric mixture of syn ‐adducts BTES‐Ac‐b. Reverse osmosis (RO) silica membranes were prepared by the sol–gel process with BTES‐Ac‐a and BTES‐Ac‐b and the membranes were examined with respect to water desalination using a 2000 ppm NaCl aqueous solution. NaCl rejection of the membranes increased to reach 96% at the early stage of the RO experiments. However, the rejection decreased gradually to 85% after 70 and 200 h for BTES‐Ac‐a and BTES‐Ac‐b, respectively, due to hydrolytic decomposition of the silica network during the experiments. In contrast, a membrane prepared from copolymerization of BTES‐Ac‐a with ethane‐bridged bistrialkoxysilane (BTES‐E1) showed improved stability towards hydrolysis with stable NaCl rejection of 96% with higher water permeance (3.5 × 10⁻¹³ m³ m⁻² s⁻¹ Pa⁻¹) than that of a membrane prepared by homopolymerization of BTES‐E1 (2.7 × 10⁻¹⁴ m³ m⁻² s⁻¹ Pa⁻¹) reported previously.     

含AQP仿生膜在水处理中的应用

水通道蛋白(aquaporin, AQP)是一种对水分子具有高选择性和渗透性的跨膜蛋白。近几年来,含AQP的仿生膜有望克服传统膜材料通量与截留率之间的上限平衡问题,因此,它在海水淡化和水处理领域的应用吸引了越来越多研究者的关注。本文对含AQP仿生渗透膜的制备方法及性能进行了综述,分别介绍了含AQP双层膜结构仿生膜和封装含AQP囊泡的仿生膜这两大类膜结构所对应的不同制备方法。同时,对含AQP仿生膜中膜结构的组成方式、装载AQP蛋白的囊泡材料、制膜过程中的操作条件等因素对膜结构和性能的影响进行了探究讨论。综合文中所述不同膜的膜性能,得出现阶段含AQP仿生膜还存在着膜面积小、膜机械强度不够高、AQP装载量较低及易受外界因素影响的缺陷,并提出在克服膜缺陷的同时寻找其他仿生水通道及离子通道的思路,使未来仿生膜获得更宽阔的发展道路。     

Ionic imprinted polymer for nickel recognition by using the bi-functionalized 5-vinyl-8-hydroxyquinoline as a monomer: Application as a new solid phase extraction support

A new ionic imprinted polymer (IIP) for Ni(II) recognition/pre-concentration was prepared via precipitation polymerization using 2-(diethylamino) ethyl methacrylate (DEM) and divinylbenzene (DVB) as a crosslinking agent in the presence of nickel(II) and 5-vynil-8-hydroxyquinoline (5-VHQ) as a bi-functionalized ligand. An important increase on the selectivity of the synthesised IIP for nickel(II) ions was obtained when comparing to the use of 8-hydroxyquinoline (8-HQ) as a ligand. The synthesised IIP was used as a new support for solid phase extraction (SPE) of nickel(II) from seawater before inductively coupled plasma optical emission spectrometry (ICP-OES) detection. Variables affecting the SPE process, such as pH, load and elution flow rates, and concentration and volume of the eluting solution, were fully evaluated. The optimised procedure consists of a sample loading (100 mL of seawater at a pH of 9.0 ± 0.1) through IIP-SPE cartridges containing 300 mg of the synthesised IIP at a flow rate of 3.0 mL min^{− 1}. Elution was performed by passing 2.5 mL of 2.0 M nitric acid at a flow rate of 1.5 mL min^{− 1}, which gave a pre-concentration factor of 40. The limit of detection (LOD) of the method was 0.26 µg L^{− 1}, while the relative standard deviation (RSD) for eleven replicated measurements was 3%. Accuracy of the method was assessed by analyzing SLEW-3 (estuarine water) and TM-23.3 (lake water) certified reference materials. In addition to the selectivity of the synthesised material for nickel(II) ions against other transition metal ions and major alkaline and alkaline-earth metals (Na⁺, K⁺, Mg²⁺ and Ca²⁺) in seawater, it can be stated that the salt matrix is efficiently removed by using the proposed IIP-SPE procedure.     

Reverse flow injection analysis of nanomolar soluble reactive phosphorus in seawater with a long path length liquid waveguide capillary cell and spectrophotometric detection

A novel reverse flow injection analysis method coupled with a liquid waveguide capillary cell (LWCC) and spectrophotometric detection for the determination of nanomolar soluble reactive phosphorus in seawater was established. Reagent was injected into the sample stream and detected in a 2-m path length LWCC with detection wavelength set at 710 nm. Experimental parameters, including the reagent concentration, the injection volume, the flow rate and the length of the mixing coil, were optimized based on univariate experimental design. The interference of silicate and arsenate were also investigated. Under optimized conditions, the linearity and the detection limit of the proposed method were found to be 0-165.0 nM and 0.5 nM, which was estimated to be three times the standard deviation of the measurement blanks (n = 9). The relative standard deviations for the determination of 24.7 and 82.5 nM samples were 1.54% and 1.86% (n = 9), respectively. Three seawater samples were analyzed with recoveries ranging from 87.8% to 101.8%. Using the Student's t-test at the 95% confidence level, the results of the proposed method and a segmented flow analyzer reference method for determination of the two samples showed no significant difference. The proposed method had the advantages of being less reagent consuming, more sensitive and with higher throughput (15 h⁻¹).     

Rapid and direct speciation of methyltins in seawater by an on-line coupled high performance liquid chromatography-hydride generation-ICP/MS system

A novel on-line coupled HPLC-hydride generation (HG)-ICP/MS system was developed for rapid, direct and sensitive speciation of methyltins in seawater without any pretreatment step. Methyltin compounds were separated by reversed phase HPLC, and then on-line reacted with potassium borohydride and acetic acid to generate volatile hydride products. The volatile derivatization products were separated in the spray chamber of ICP/MS and then introduced into ICP/MS by argon gas for detection. Monomethyltin (MMT), dimethyltin (DMT) and trimethyltin (TMT) were baseline separated in less than 15 min by reversed phase HPLC. The influence of KBH₄ concentration and type of acid on the system performance was investigated and optimized. Calibration curves, based on peak heights against concentration, were linear in the range of 0.5-50 ng (Sn) mL⁻¹ of methyltins with correlation coefficients of 0.9990, 0.9990 and 0.9996 for MMT, DMT and TMT, respectively. The relative standard deviations measured at 10 ng (Sn) mL⁻¹ for these three methyltins were in the range of 0.6-1.4% (n = 5), and the calculated detection limits (S/N = 3) for MMT, DMT and TMT were 0.266, 0.095 and 0.039 ng (Sn) mL⁻¹, respectively. This method was successfully applied to the speciation of methyltins in seawater with spiked recovery in the range of 95.4-106.9%. MMT and DMT were detected in all the seawater samples with concentrations in the range of 1.0-1.5 and 0.30-0.57 ng (Sn) mL⁻¹ for MMT and DMT, respectively.     

Fluorescence spectroscopy applied to the optimisation of a desalting step by electrodialysis for the characterisation of marine organic matter

The isolation and characterisation of marine dissolved organic matter (DOM) are still not readily achieved today. The study of this chemically complex material is particularly difficult, especially as it is hindered by the high salinity of seawater. It is therefore essential to develop a method in which a sufficient quantity of marine organic matter can be collected for structural analyses. Reverse osmosis (RO) is often used for the concentration of DOM from freshwaters, due to the fact that DOM is not modified during RO and that DOC recoveries are high (about 80%). Unfortunately, RO cannot be used directly to isolate marine DOM, since both salts and organic matter are concentrated during the process. Therefore, marine samples have to be desalted before their concentration by RO.     

基于分光光度法的海水原位硅酸盐微芯片分析传感器的研制

基于酸性条件下硅酸盐与钼酸铵反应生成硅钼黄后被还原成硅钼蓝的原理,借助微流控芯片平台,建立基于连续流动-分光光度法快速测定海水硅酸盐的分析传感器,传感器测定周期约为300 s,采用双光程方式拓展测量范围,线性测量范围可达0～400 μmol·L-1,双光程的检出限分别为45.1 nmol·L-1和1.6 μmol·L-1;当海水盐度大于15时,传感器测量准确度和稳定性基本不受盐度影响,且实际海水加标回收率在98.1%～104.0%之间。2015年11月在胶州湾开展了20个站点海试和同步比对试验,结果显示,该系统具有准确度高、简单、集成度高、水样消耗少、抗干扰能力强等优点,可用于海水原位硅酸盐的分析。     

Effluent treatment using electrochemically bleached seawater-oxidative degradation of pollutants

Use of seawater electrolytically enriched with hypochlorite and the in situ generation of hypochlorite on the high seas, stand a good chance for disinfection and decrease of bio and non-biodegradable organics in effluent before discharged into estuaries and deep oceans. Enriched seawater effectively decreased the biological oxygen demand measured over 5 days (BOD) and chemical oxygen demand (COD) levels of semi-treated wastewater. The oxidative degradation of Brilliant Blue, a triaryl industrial dye by hypochlorite and electrolytically enriched seawater are compared at pH 6.5. Both had similar magnitude second-order rate constants (21±1 M⁻¹ s⁻¹) and procedure is feasible. Increase in acid concentration enhanced the reaction rate. With 1:1 and 1:100 molar ratios of dye to hypochlorite, the COD=140 mg L⁻¹ of 1.0×10⁻³ M dye reduced to 100 and 30 mg L⁻¹ respectively.     

Trace ion analysis of seawater by capillary electrophoresis: determination of iodide using transient isotachophoretic preconcentration

An improved transient isotachophoresis (tITP) procedure for the preconcentration of iodide from highly saline matrices was developed with the objective to quantify iodide in seawater by capillary electrophoresis (CE). The procedure takes advantage of introducing cetyltrimethylammonium chloride into the high-sodium chloride background electrolyte, which due to a specific interaction with iodide amended placement of the analyte at a large distance from the matrix chloride (the latter performed the role of a leading anion). Computer simulation showed that 2-(N-morpholino)ethanesulfonate could be adopted as a suitable terminating ion to enable isotachophoretic focusing at the beginning of the CE run. Under optimized tITP conditions, the sensitivity response of iodide was improved by a factor of 140 over normal CE mode. This allowed for direct UV detection of as low as 0.6 microg/L iodide and made feasible CE analysis of undiluted surface seawater samples where iodide was found at a 30 microg/L level. The applicability of the proposed tITP-CE method could apparently be extended to the determination of other trace seawater anions (e.g., iodate).     

工业级碱性海水电解:近期进展和展望

由太阳能、风能和海洋等可再生能源驱动的工业级水分解产氢为能源和环境的可持续性发展开辟了一条极具潜力的道路。然而,在工业上最先进电解技术使用高纯水作为氢源,这将带来严重的淡水资源危机。海水分解为饮用水短缺提供了一条切实可行的解决途径,但仍面临规模工业化生产的巨大挑战。在这里,我们总结了海水分解的最新进展,包括反应机制、电极设计标准和直接海水分解的工业电解槽。深入讨论了应对海水电解中的关键挑战,如活性位点、反应选择性、耐腐蚀性和传质能力等的解决方案。此外,该文章重点总结了海水电解设备的最新发展,并提出了设计长寿命直接海水电解装置的有效策略。最后,我们对直接海水电解的未来机遇和挑战提出了自己的观点。