Fundamental studies on the intermediate layer of a bipolar membrane: Part III. Effect of starburst dendrimer PAMAM on water dissociation at the interface of a bipolar membrane

Starburst dendrimer polyamidoamine (PAMAM) with ellipsoidal or spheroidal shape is structure-regular and has much more amino groups than conventional polymers. This paper investigates the possibility of these amino groups on water dissociation in a bipolar membrane interface. To do this, a bipolar membrane is prepared by casting the solution of sulfonated poly(phenylene oxide) (SPPO) in dimethyl formamide (DMF) on a commercial anion exchange membrane that is immersed in PAMAM aqueous solution in advance. The existence of PAMAM adsorbed on the membrane is proved by X-ray photoelectron spectroscopy (XPS), and the adsorption amount is evaluated by weighting method. The junction thickness of the prepared bipolar membrane is determined by electrochemical impedance spectroscopy (EIS), and the performance is evaluated by current–voltage curves. The experiments show that both the generation and concentration of PAMAM would strongly affect the characteristics of the bipolar membranes. There exists a transitional concentration for various generations PAMAMs to catalyze effectively the water dissociation, and above or below the transitional concentration the performance of bipolar membranes is decreasing. The higher the generation, the lower the concentration. Moreover, at a fixed solution concentration, there is not the simple relation of monotone decreasing or increasing between the performance of bipolar membranes and the generations of PAMAMs. All these can be explained according to the characteristics of PAMAMs combined with available water dissociation theory.     

全自动QuEChERS样品制备系统结合高效液相色谱-串联质谱法检测植物源性食品中34种农药残留

建立了全自动QuEChERS样品制备系统结合高效液相色谱-串联质谱（HPLC-MS/MS）同时检测植物源性食品中34种农药残留的分析方法。方法利用全自动QuEChERS样品制备系统涡旋振动和离心功能，将手动QuEChERS方法中样品提取和分散固相萃取相结合；优化了操作参数及前处理步骤，在多反应监测（MRM）模式下检测，基质匹配外标法定量。从方法学验证角度对全自动QuEChERS法与手动QuEChERS法进行了比较。结果表明：该方法中大多数农药在一定范围内呈现良好的线性关系，相关系数（R²）均大于0.99，检出限为0.76~3.60 μg/kg，定量限为2.28~10.80 μg/kg，加标回收率为53.0%~125.2%，相对标准偏差（RSD）<15.9%（n=5）。该方法与手动QuEChERS法的方法验证比对结果显示差异不明显，用于植物源性食品中多农药残留检测可有效降低劳动强度和出错概率。     

Studies on the Complexes of N,N′-Bis[o-(diphenylphosphino)benzylidene]ethylenediamine with Transition Metal Ions

The thermodynamic parameters for the interaction of Cu²⁺, Ni²⁺, Co²⁺, Cd²⁺, andAg⁺ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag⁺ exhibited remarkably higher complexation selectivity.Ag⁺ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg⁺–M²⁺ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag⁺ was observed in both single and competitiveAg⁺–M²⁺ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P₂N₂) with silver,[Ag(P₂N₂)] (NO₃), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P2_1/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) ³ and Z = 4.     

Optimized Separation of Nine Xanthones by Microemulsion Electrokinetic Chromatography

A microemulsion electrokinetic chromatography method has been firstly used for the separation of the therapeutically important xanthones from Securidaca inappendiculata. The separation of the nine xanthones was systematically optimized with respect to pH, composition of microemulsion,addition of cyclodextrins, applied voltage and column temperature. Baseline separation was successfully achieved for the nine xanthones, which was also compared with that by micellar electrokinetic chromtography.     

Bis­(ethyl­enedi­amine)copper(II) bis(O,O′‐diethyl di­thio­phosphate)

In the structure of the title compound, [Cu^II­(en)₂][(EtO)₂P(S)S]₂ (en is ethyl­ene­di­amine) or [Cu(C₂H₈N₂)₂](C₄H₁₀O₂PS₂)₂, the Cu atom lies on a center of inversion and is coordinated in a slightly distorted square coordination geometry by four N atoms from two ethyl­enedi­amine mol­ecules. The diethyl di­thio­phosphate moieties, (EtO)₂P(S)S^?, act as counter‐anions.     

双核银络合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成与结构

二-(二苯基膦)甲烷(dppm)是一种易与金属形成多核络合物的有机膦配体。我们用dppm作为配体合成了一系列银的多核络合物,并对其结构进行了研究。本文报导了其中一个双核化合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成及晶体结构、分子结构的测定。     

尺寸排除色谱扩展因子的保留体积依赖性

尺寸排除色谱扩展函数的方差即尺寸排除色谱柱中单分散高分子峰的扩展因子,以窄分布聚苯乙烯标样用分子量分离和扩展效应同时标准的方法作了测量。简单的理论分析导出了一个方程以表示扩展因子的保留体积依赖性,其中包括四个具有明确物理意义并可实验测量的参数。该方程与实验数据符合得相当好,并解释了扩展因子极值出现的条件。     

石墨炉原子吸收光谱无标样分析法的研究：Ⅰ.消除基体干扰

实现石墨炉原子吸收光谱绝对分析必须消除基体干扰，本研究采用有机基体改进剂，管壁原子化、热解涂层石墨管，峰面积积分吸收信号，Ｄ２灯或Ｚｅｅｍａｎ效应扣除背景，有效地控制和消除了海水基体对Ａｓ，Ｃｄ，Ｃｏ，Ｃｒ，Ｃｕ，Ｍｎ，Ｎｉ，Ｐｂ和Ｖ等元素的干扰，实现了无干扰测定。     

应用扩展的重叠分辨率法优化液相色谱条件分离二茂铁类化合物

本文对优化液相色谱分离条件的重叠分辨率法进行了改进与扩展：首先利用全范围的二元线性梯度淋洗进行溶剂强度的优化，再通过重叠分辨率法进行了溶剂选择性的优化，并且建立了计算机系统，使此方法程序化。利用此方法建立了分离Ｎ－二茂铁甲酰基－Ｎ＇－芳基硫脲类衍生物的最佳流动相体系。     

Preparation,characterization of crystalline zirconium phosphates and study on their acid stability and ion exchange behavior with uranyl ions

Two kinds of crystalline zirconium phosphate, - and -ZrP were prepared by direct method, and characterized by means of X-ray powder diffractometry, thermogravimetric analysis and pH titration. The total exchange capacity of -ZrP and -ZrP for Na⁺ ions determined by pH titration was 8.80 mmol/(g Zr(HPO₄)₂·6H₂O) and 3.80 mmol/(g NH₄ZrH(PO₄)₂·H₂O), respectively. The thermodynamic equilibrium constant of exchange reactions on -ZrP and on -ZrP at 25.0°C is 2.5 and 1.1, respectively. Although UO ₂ ²⁺ in solution is more preferred by -ZrP than by -ZrP, the selectivity of -ZrP for UO ₂ ²⁺ decreases with decreasing pH value while less effect of pH on the amount of UO ₂ ²⁺ ions exchanged to -ZrP has been found. It is also interesting to find out that both H⁺ and NH ₄ ⁺ ions in -ZrP can be replaced by UO ₂ ²⁺ ions existed in concentrated solution.