Polypyrrole Bilayers: Charge Trapping and Application for Amperometric Ions Sensing

Bilayers composed of polypyrrole: doped by perchlorate ions (PPy(ClO₄) – anion exchanging inner layer) and by dodecyl sulfate ions (PPy(DS) – cation exchanging outer layer) are very effective charge trapping systems that are usually not observed for other bilayers comprised of polypyrrole. Chronopotentiometric experiments carried out for oxidation and reduction showed that the trapping effect in the inner layer resulted from different ion exchange properties of the component polymers, leading to a low permeability of the reduced outer layer towards anions. Estimated diffusion coefficients of Cl^? anions in the oxidized and reduced PPy(DS) are in the range of 10^?9 and lower than 10^?10 cm² s^?1, respectively. The presence of the outer layer limiting the ion transfer was found to be beneficial to improve the signal resolution in amperometric mode of ion sensing within wide KCl concentration range, from 10^?5 M up to 3 M. The influence of experimental conditions (film thickness, response time) on optimization of this novel kind of polymeric bilayer ion sensors was studied.     

全自动高温水解-离子色谱法测定氧化镧铈中氟、氯

为探究稀土氧化物中氟(F)和氯(Cl)元素含量的快速检测方法,通过全自动高温水解仪对氧化镧铈样品进行前处理,并利用氢氧根体系离子色谱仪检测吸收液中F-、Cl-离子的含量,建立了基于全自动高温水解-离子色谱法测定氧化镧铈中的F、Cl元素含量的快速检测方法,该方法有效避免了传统前处理方法过程复杂、分析时间慢、极易受人为干扰的问题。称取0.3g氧化镧铈样品,在氧气流量为300 mL/min,1100 ℃高温下水解燃烧20 min,吸收定容为体积20mL的吸收液,以NAOH(15mmol/L)作为淋洗液,经色谱柱分离,测得F-与Cl-在质量浓度为1.00 mg/L-15.00 mg/L范围内,质量浓度与离子色谱峰面积呈线性关系,相关系数均为0.9999。检出限分别为0.003mg/L和0.12mg/L。全自动高温水解仪联用离子色谱仪检测系统对氧化镧铈中F-的平均加标回收率测定结果为98.4%,标准偏差RSD为0.94%;对Cl-的加标回收率测定结果为97.8%,RSD为2.86%。说明该方法较高准确度及精密度,测试结果准确可靠满足企业和检测机构的测试需求,为稀土氧化中氟、氯元素含量的研究及相关产品的开发提供了理论基础。     

一例含阴离子水簇的钴配合物的合成、结构及理论研究

金属配合物中的水簇研究为研究宏观意义上的水以及与蛋白质分子有关的水分子提供了有效途径。本文合成了一个含有阴离子水簇的带状超分子配合物[Co(2,2-bipy)₂(N₃)₂](N₃)_0.5Cl_0.5·2H₂O(1,2, 2-bipy=2, 2-联吡啶)。单晶结构解析表明,配合物属于三斜晶系,P-1空间群,晶胞参数为:a=0.822 54(7) nm,b=1.175 58(9) nm,c=1.237 06(10) nm,α=91.379 0(10)°,β=92.151 0(10)°,γ=108.119 0(10)°,V=1.135 27(16) nm³,由一个单核[Co(2,2-bipy)₂(N₃)₂]⁺配合物阳离子、两个非配位水分子、0.5个游离的叠氮离子和0.5个氯离子组成,叠氮离子和氯离子位置无序,占有率各为50%。两个客体水分子通过强烈的分子间氢键作用形成了环状水四聚体,且与无序的N^-₃和Cl^-通过氢键作用形成了一个[(H₂O)₄(N₃)Cl]^2- 阴离子水簇。此外,本文基于密度泛函理论(DFT)对配合物[Co(2,2-bipy)₂(N₃)₂]⁺阳离子进行了量子化学计算,分析了其单点能和原子电荷,并计算了中心金属离子的氧化态,计算结果与实验相吻合。     

Evaluation of Water Ammonium Ion Test Kit and Its Feasibility for the Analysis of Protein in Food

The traditional method for the determination of protein in food needs the operations of digestion, distillation, absorption, and titration; therefore, it is complicated and time-consuming and requires professional personnel. Is there a more convenient and faster detection method that can directly determine the ammonium ions in protein digestion solution to obtain the protein content of food and avoid the distillation–absorption–titration process? The feasibility of water ammonium ion test kits for food protein rapid detection was discussed here. After digestion, the protein in food transforms into ammonium ions in the digestion solution. Because of the variety of food, there are many different inorganic ions left in the food digestion solution, and at the same time, digestion agents are added in the digestion process and become potential interference factors in ammonium determination. Therefore, the detection accuracy of ammonium test kits needs to be evaluated first, including their anti-interference ability. The standard curve of ammonium was established by the test kit. When the ammonium concentration was 0.00–2.50 mg/L, the absorbance at 620 nm was linearly related to the ammonium concentration, the determination coefficient R² was 0.9995, and the detection limit of this method was 0.01 mg/L. The influences of temperature, pH value, and reaction time on the test kit method were discussed. The precision was 0.90–3.33%; the repeatability was 1.71–4.86%; and the recovery rate of tap water, river water, and sea water was controlled within 90–103%. The anti-interference ability of the evaluated test kit was better than that of the national standard detection method. The test kit, combined with sample pretreatment and protein conversion formula, was used to detect protein in different types of food (milk powder, rice flour, wheat flour, soy, banana, milk, fish food, chicken food, and dog food). The results showed that there were no significant differences (ρ > 0.05) between the national method and the test kit method. The ammonium ion test kit method shortened the determination time and had higher sensitivity, showing its potential for the rapid determination of food protein.     

一种超高耐久混凝土——梯度结构混凝土

分析超高耐久混凝土的研究现状,提出了一种高耐久、低成本的超高耐久混凝土--梯度结构混凝土(Gradient Structural Concrete,简称GSC),采用电量法和氯离子扩散系数法来评价梯度结构混凝土的抗氯离子渗透性能,最后进行梯度结构混凝土的寿命预测与成本分析.结果表明,高性能混凝土(High Performance Concrete,简称HPC)、无细观界面过渡区水泥基复合材料(Meso-interfacial transition zone-free cement-based materials,简称 MIF)和梯度结构混凝土MIF-HPC的6 h导电量和氯离子扩散系数的排列顺序均为:HPC>MIF-HPC>MIF,其抗氯离子渗透性能排列顺序为:MIF>MIF-HPC>HPC.梯度结构混凝土的成本会有所增加,但由于其氯离子渗透性能大幅降低,其使用寿命得到大幅延长,使得其年损耗费用大幅下降.     

Nanostructured Polyelectrolyte-based System as a Toolbox for Metal Ions Detection

The capability of certain heavy metal ions to induce fluorescence decrease by a quenching mechanism suggested us to design and build a sensor potentially tunable for different ions at different concentrations. We propose a quenching-based sensor exploiting a nanostructured architecture in which fluorescent molecules (the sensing probe) are entrapped to recognize a specific analyte (heavy metal ions) through an optical transduction. The polyelectrolyte nanostructured system, named nanocapsule, improves the fluorophore-ion quenching sensitivity allowing a micromolar detection. Furthermore we couple our sensor with an electrical device in order to refine the sensing procedure: the electric field created allows a metal ions spatial gradient, necessary to detect a specific element on a single sample solution, avoiding a comparative analysis with an intensity reference value. Results obtained will show the advantages and the potentialities of our system as a smart toolbox for metal ions detection.     

Stationary states of crystal growth in three dimensions

A new Markov process describing crystal growth in three dimensions is introduced. States of the process are configurations of the crystal surface, which has a terrace-edge-kink structure. The states are continuous along edges but discrete across edges, in accordance with the very different rates for the two types of captures of particles. Stationary distributions, describing steady crystal growth, are found in general. To our knowledge, these are the first examples of stationary distributions for layered crystal growth in three dimensions. The steady growth rate and other quantities are obtained explicitly for two interacting edges. For many interacting edges, growth behavior is determined (a) in various asymptotic regimes including thermodynamic limits, (b) via simulations, and (c) using series (cluster) expansions in the slope of the surface, the first three coefficients being computed. The theoretical growth rates show a marked dependence on surface dimensions. This may contribute to the size dependence and dispersion in the observed growth rate of small crystals.     

脉冲高功率离子二极管的动力学模拟

基于等离子体的爆炸发射模型,利用自洽的2.5维的胞中粒子（PIC）模拟程序MAGIC模拟了平板型磁绝缘离子二极管中电子和质子的动力学特性。给出了电压为300kV,外加磁场为2倍临界磁场情况下的二极管特性,阴阳极间隙中带电粒子的空间和相空间分布,以及净电荷密度分布和电场分布,结果表明,引出束流密度比单离子Child-Langmuir公式计算的结果大5倍;外加磁场导致在阴极附近形成虚阴极。空间电荷使得阴阳极间隙中电场扰动和增强。     

离子通道电子束回旋脉塞的等离子体波效应

研究了离子通道回旋电子束脉塞（ICECM）中的等离子体波非线性效应。利用流体理论与自洽非线性理论方法对ICECM中等离子体波效应的微观机理进行了分析。研究发现,等离子体波加强了电子束的纵向群聚,束-波互作用的能量交换效率及系统增益得到明显提高。数值模拟计算表明,对于中等等离子体密度、1.5kA电流和1MV加速电压的电子束,系统能够获得的脉冲功率和频率分别为200MW和280GHz的毫米波束。