四硼酸锂水溶液体系的热容及离子相互作用

采用Setaram BT 2.15微量热仪测定了Li₂B₄O₇-H₂O体系(Li₂B₄O₇的浓度为0.00415~0.4208 mol/kg)在298.15, 308.15和323.15 K下的热容, 分别计算了不同温度和浓度下的表观摩尔热容, 并获得了不同温度下表观摩尔热容与浓度的关系式. 基于Li₂B₄O₇-H₂O体系的热容测定结果, 应用Pitzer电解质溶液离子相互作用表观摩尔热容模型, 拟合获得了四硼酸锂在不同温度下的Pitzer单盐参数.     

四硼酸钾水溶液结构

研究了298.15和323.15K广泛浓度范围内四硼酸钾溶液pH,并根据化学反应平衡常数和牛顿迭代法计算获得了溶液化学物种分布图.典型样品用拉曼光谱进行核实.研究表明,高浓溶液中存在主要化学物种是B4O5(OH)24-,次要化学物种是B3O3(OH)4-和B(OH)4-.用X射线散射法研究了298和323K高浓四硼酸钾溶液结构.用几何模型定量描述B4O5(OH)42-,B3O3(OH)-4和B(OH)-4离子内、离子间、分子间的相互作用,并用最小二乘法进行精修.模型计算和精修给出硼氧六元环内原子间距和配位数,并与晶体结构很好一致,表明高浓溶液中离子内有序程度较高.同时给出K+和硼酸根离子水合数和水合距离,以及接触离子对的结构信息,并进一步简单讨论温度和浓度变化对溶剂结构的影响.     

Pt/TiO2光催化分解四硼酸钾水溶液制氢

研究了以四硼酸钾溶液作反应体系，在1%Pt／TiO2光催化剂的作用下光催化分解水制氢的反应，发现该体系能使放氢速率明显提高．放氢速率还随B4O7^2-浓度的增大而增大．在此基础上，还对B4O7^2-的作用机理进行了探讨，BRO7^2-在该反应体系中主要是通过物理作用有效的阻止了逆反应的发生，从而使放氢速率得以提高．     

Heat Capacity of Micellization of Lithium Perfluoroalkanoates in Aqueous Solution

Specific heats of aqueous solutions of lithium perfluoroalkanoates, from C₆ to C₉, were determined at 298.15 K at concentrations below and above the critical micelle concentration. Infinite dilution apparent molar heat capacities are compared with literature data for corresponding salts with different counterions. Heat capacities of micellization of these surfactants in water were calculated from the specific heat data and also by measurements of the heat of micellization at two temperatures, 298.15 K and 308.15 K. The data were treated under the assumption of the pseudo-phase separation model. The two series of data agree in the case of perfluorononanoate but diverge for perfluorosurfactants with shorter hydrophobic chains. The results are interpreted in terms of the extent of the applicability of the adopted chemical model. Heat capacities of the micellization process obtained from experimental specific heats compare well with literature values relative to the sodium salts of the examined anions.     

过饱和五硼酸钠溶液结构

用快速X射线衍射法测量了298和323K时过饱和五硼酸钠溶液的时间空间平均结构,得到了溶液径向分布函数.通过模型设计及理论计算获得了B-B、B-O、O-O、Na-O、Na-B原子对相互作用的理论偏径向分布函数,并讨论了浓度和温度对五硼酸钠溶液结构的影响.在五硼酸钠过饱和溶液中六水合Na+形成八面体结构,其平均配位数随浓度和温度变化不大,作用距离随温度升高及浓度减小而减小;给出了溶液中主要硼酸盐离子B3O3(OH)4-、B5O6(OH)4-和B(OH)3的水合结构,较高温度及较高浓度有利于更高聚合的多聚硼酸根离子的形成;浓度对硼酸盐离子的第一水合层的水合数影响较大,在较浓的五硼酸钠过饱和溶液中,五硼酸根离子的一个端氧单齿配位到Na+上形成离子对,Na-B特征距离为0.328nm.     

X荧光玻璃熔片法分析铁矿石

使用无水四硼酸锂作为溶剂，在1050℃熔融制样，以X荧光光谱法测定铁矿石中铁、硅、铝、钙、镁、锰、钛、磷、硫等元素，其分析结果的精密度和准确度可与化学法相比。     

聚丙烯酰胺结构与水溶液粘度保持率

聚丙烯酰胺衍生物(PAM)是高温高矿化度油藏的关键性助剂之一,为适应油藏高温环境,PAM不仅需要具有优异的热稳定性,还应在温度升高时具有较高的粘度保持率。与耐温抗盐单体共聚显著改善了PAM的热稳定性,已有许多文章总结了这一领域的进展。相对而言,关于PAM水溶液在高温时粘度保持率的报道较少。本文从聚合物分子构造以及其在水溶液中的聚集态结构出发,总结了PAM水溶液粘度保持率与结构的关系。主要包括在线性主链上引入支化侧链来提高聚合物分子链刚性,以及利用超分子相互作用形成物理交联网络改变PAM在水溶液中的聚集态结构。此外,展望了耐温抗盐PAM的发展趋势。     

A Computer Simulation of the Electronic Structure of Leucine in Aqueous Solution

In order to obtain the electronic structure of leucine (Leu) in aqueous solution, we studied three systems: Leu+7H₂O, Leu+8H₂O and Leu+9H₂O. The results indicated that the system Leu+8H₂O was the only choice which was both acceptable and doable: its computational effort was affordable, and it could simulate a main part of the solvent effect on the electronic structure of Leu in solution. Based on the system Leu+8H₂O, all-electron, ab initio calculations were performed to construct an equivalent potential of water for the electronic structure of Leu with dipoles. The results showed that the main effect of water on the electronic structure of Leu was raising the occupied states about 0.0824 Ry on average, and broadening the energy gap by 11%. The water effect on the electronic structure of Leu could be well simulated by the dipole potential. The obtained equivalent potential can be applied directly to the electronic structure calculation of proteins in solution.     

Thermodynamic Properties of Aqueous Solutions of Lithium Chloride

Vapor pressure of aqueous solutions of lithium chloride were measured by differential static method, in a concentration range of 12.9-44.2% weight and in the temperature range of 30-100°C. The experimental data were fitted to the Antoine type equation: log P = A( m ) + B( m )/ T + C( m )/ T 2 , where A, B, and C are constants which are concentration dependent. Enthalpies of solution were calculated by the Haltenberger method using experimental vapor pressure data and heat capacity data. The Duhring and enthalpy-concentration charts have been constructed. These charts may be useful in the performance studies of absorption heat pumps.     

Conformational Modularity of an Abiotic Secondary‐Structure Motif in Aqueous Solution

We have investigated an abiotic secondary structure based on the stacking of alternating electron‐rich (1,5‐dialkoxynaphthalene (Dan)) and electron‐deficient (1,4,5,8‐naphthalene‐tetracarboxylic diimide (Ndi)=benzo[lmn][3,8]phenanthroline‐1,3,6,8(2H,7H)‐tetrone) aromatic units. Previously, the specifics of conformational behavior were uncovered in the minimal folding unit, namely the dimer, consisting of one Dan and one Ndi unit linked through various amino acid residues. Here is reported the investigation of a series of larger oligomers (trimers and tetramers) composed of selected dimer units. We determined that some of the larger oligomers displayed conformational modularity, that is, the persistence of subunit‐conformational propensities when those subunits were used as components of larger structures. Conformational modularity can be viewed as a desirable property of folding molecules because it simplifies not only the design of larger, more complex oligomers, but also the structural analyses of such species.     

Unstable Supramolecular Structure of [Bmim][BF4] in Aqueous Solution

To unravel the exact composition and structure of aggregates in an aqueous solution of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF₄]), we performed static and dynamic light-scattering measurements, as well as transmission electron microscopy (TEM). Results from this work show that the aggregates are vesicles and unstable; herein, we discuss the driving force behind the self-assembly. Apart from the van der Waals forces and repulsive electrostatic interactions between adjacent cation clusters, the hydrogen-bonding forces as well as counterion effects might also contribute to this driving force. The information obtained here is useful for a better understanding of the vital role that aggregation behavior plays in the field of ionic liquid recovery, and its potential use in controlled release, drug delivery, and petroleum recovery.     

Structure and Surface Properties of High-density Polyelectrolyte Brushes at the Interface of Aqueous Solution

Zwitterionic and cationic polyelectrolyte brushes were prepared by surface-initiated atom transfer radical polymerization of 2-methacryloyloxy- ethyl phosphorylcholine (MPC) and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA), respectively. The poly(DMAEMA) brush was treated with methyl iodide to form poly[2-(methacryloyloxy) ethyltrimethylammonium iodide] [poly(METAI)]. The effects of ionic strength on brush structure and surface properties of densely grafted polyelectrolyte brushes were analyzed by contact angle measurements, neutron reflectivity (NR) and macroscopic friction tests. Both polyelectrolyte brushes exhibited hydrophilic properties. The contact angle of the poly(MPC) brush surface against water was ca. 0° in air and the contact angle of the air bubble in water was ca. 170°. The air bubble in water hardly attached to the poly(MPC) brush surface, indicating super hydrophilic characteristics. NR measurements of poly(MPC) and poly(METAI) brushes showed that the grafted polymer chains were extended from the substrate surface in a good solvent such as water. Interestingly, NR study did not reveal the shrinkage of the brush chain in salt solution. The polyelectrolyte brushes immersed in both water and NaCl solution at various concentrations showed a low friction coefficient and low adhesion force.     

Acidity and Structure of Isosaccharinate in Aqueous Solution: A Nuclear Magnetic Resonance Study

Dilute aqueous solutions of the calcium and sodium salts of -d-isosaccharinate (ISA) have been analyzed by ¹³C and ¹H NMR spectroscopy. The positions of the six ¹³C ISA NMR lines show a pH dependence that can be used to infer that the most acidic proton is the one associated with the carboxylate group, with an aver- age log k⁰ of –3.27 for the reaction H(ISA) H⁺ + ISA^– in solutions made with the sodium salt. In acidic solutions (pH < 4),=" nmr=" signals=" were=" found=" that=" could=" be=" assigned=" to=">-d-isosaccharinate-1,4-lactone (ISL), formed from the dehydration of H(ISA). The pH dependence of the H(ISA) ¹³C line positions, furthermore, reveals that the deprotonated H(ISA) at neutral to high pH assumes a conformation with the carboxylate anion hydrogen-bonded to the secondary alcohol and the cation (Na⁺ or Ca²⁺) interacting with the tertiary alcohol.     

Structure and Properties of Electrochemically Synthesized Silver Nanoparticles in Aqueous Solution by High-Resolution Techniques

The aim of this work was to deeply investigate the structure and properties of electrochemically synthesized silver nanoparticles (AgNPs) through high-resolution techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), Zeta Potential measurements, and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS). Strong brightness, tendency to generate nanoclusters containing an odd number of atoms, and absence of the free silver ions in solution were observed. The research also highlighted that the chemical and physical properties of the AgNPs seemed to be related to their peculiar oxidative state as suggested by X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRPD) analyses. Finally, the MTT assay tested the low cytotoxicity of the investigated AgNPs.     

四硼酸锶SrB4O7的晶体结构及其非线性光学性质

采用Kyropoulos法生长出高质量大尺寸的SrB4O7晶体,以单晶X射线衍射法确定了其晶体结构,讨论了与文献报道的晶体结构测量结果存在差异的原因,指出了前人工作中存在的问题,并研究了该晶体的非线性光学性质.     

锂离子电池电解质溶液的研究

本文报道了 5磺基水杨酸苯氧基硼酸锂 (LiB(SO3 )C6H3 (O) (COO)OC6H5)的合成及其在乙烯碳酸酯 (ED) /二甲基碳酸酯 (DMC)及丙烯酸酯 (PC) /二甲基亚砜 (DMSO)混合溶剂中电化学性能的研究 .     

Effect of Surface Structure on Behavior of RuO2 Electrodes in Sulfuric Acid Aqueous Solution

The electrochemical properties of RuO₂ electrodes are studied by means of cyclic voltammetry, potential step, and impedance measurements in aqueous 0.5 mol/dm³ H₂SO₄ as a supporting electrolyte solution and applying the hanging electrolyte meniscus technique. Two types of the electrodes are used: bulk as-grown single-crystal having (101) exposed interface and 500 nm film produced by reactive RF magnetron sputtering at 450°C. The surface structure of the RuO₂ electrodes prepared by different techniques is defined from X-ray LAUE backscattering. Experimental data show that, for both RuO₂ electrodes, the charging components include a slow diffusion-controlled contribution, due to proton injection–ejection. The diffusion characteristics and the diffusion coefficients for the same electrodes are estimated and reported.