Mechanistic insights into intramolecular phosphate group transfer during collision induced dissociation of phosphopeptides

We report on the rearrangement chemistry of model phosphorylated peptides during collision‐induced dissociation (CID), where intramolecular phosphate group transfers are observed from donor to acceptor residues. Such “scrambling” could result in inaccurate modification localization, potentially leading to misidentifications. Systematic studies presented herein provide mechanistic insights for the unusually high phosphate group rearrangements presented some time ago by Reid and coworkers (Proteomics 2013, 13 [6], 964‐973). It is postulated here that a basic residue like histidine can play a key role in mediating the phosphate group transfer by deprotonating the serine acceptor site. The proposed mechanism is consistent with the observation that fast collisional activation by collision‐cell CID and higher‐energy collisional dissociation (HCD) can shut down rearrangement chemistry. Additionally, the rearrangement chemistry is highly dependent on the charge state of the peptide, mirroring previous studies that less rearrangement is observed under mobile proton conditions.     

Basic [Au25(SCH2CH2Py)18]−⋅Na+ Clusters: Synthesis,Layered Crystallographic Arrangement,and Unique Surface Protonation

The synthesis of high‐purity and high‐yield Au₂₅ clusters protected by the basic pyridyl ethanethiol (HSCH₂CH₂Py, 4‐PyET and 2‐PyET) is presented. Single‐crystal X‐ray diffraction of the [Au₂₅(4‐PyET)₁₈]^??Na⁺ clusters has revealed a structure similar to that known for the phenyl ethanethiolate analogue, but with pyridyl‐N coordination to Na⁺, a more relaxed ligand shell, and a profoundly layered arrangement in the solid state. Because of the pendant Py moiety, the [Au₂₅(PyET)₁₈]^? clusters are endowed with unique (de)protonation equilibria, which has been characterized in detail by UV/Vis absorption and ¹H NMR spectroscopy. [Au₂₅(PyET)₁₈]^? clusters showed an unexpectedly H⁺‐dependent solubility that is tunable in aqueous and organic solvents. The successful synthesis of the basic Py‐terminated thiolate‐protected Au₂₅ clusters paves the way to realize a new family of metalloid clusters possessing basic properties.     

Epoxide‐derived mixed‐mode chromatographic stationary phases for separation of active substances in fixed‐dose combination drugs

A method for the preparation of novel mixed‐mode reversed‐phase/strong cation exchange stationary phase for the separation of fixed‐dose combination drugs has been developed. An epoxysilane bonded silica prepared by vapor phase deposition was used as a starting material to produce diol, octadecyl, sulfonate, and mixed octadecyl/sulfonate groups bonded silica phases. The chemical structure and surface coverage of the functional groups on these synthesized phases were confirmed by fourier‐transform infrared and solid‐state ¹³C NMR spectroscopy and elemental analysis. Alkylbenzene homologs, basic drugs, nucleobases and alkylaniline homologs were used as probes to demonstrate the reversed‐phase, ion exchange, hydrophilic interaction and mixed‐mode retention behaviors of these stationary phases. The octadecyl/sulfonate bonded silica exhibits pronounced mixed‐mode retention behavior and superior retentivity and selectivity for alkylaniline homologs. The mixed‐mode retention is affected by either ionic or solvent strength in the mobile phase, permiting optimization of a separation by fine tuning these parameters. The mixed‐mode stationary phase was applied to separate two fixed‐dose combination drugs: compound reserpine tablets and compound methoxyphenamine capsules. The results show that simultaneous separation of multiple substances in the compound dosage can be achieved on the mixed‐mode phase, which makes multi‐cycles of analysis for multiple components obsolete.     

高职学生化学基础知识缺失成因及修补对策

介绍了高职学生化学基础知识缺失的成因、范围和对学习基础化学的影响;提出了利用微课、翻转课堂、学法指导等来修补化学基础知识缺失的方案。     

基于部分基变量的LP问题矩阵算法

基于部分基变量提出了LP问题的矩阵算法. 该算法以最优基矩阵的一个充分必要条件为基础,首先将一个初始矩阵转化为右端项和检验数均满足要求的矩阵,再转为检验数满足要求的基矩阵,最后转化为最优基矩阵.该算法具有使用范围广、计算规模小、计算过程简化、计算机易于实现的优势.矩阵算法的核心运算是求逆矩阵的运算,提出了矩阵算法的求逆问题,讨论并给出了求逆快速算法,该算法充分利用了矩阵算法迭代过程中提供的原来的逆矩阵的信息经过简单的变换得到新的逆矩阵,该算法比直接求逆法计算效率更高.     

电位滴定法研究离子液体的碱性

近年来碱性离子液体的设计、合成及应用获得广泛关注. 离子液体碱性表征对于碱性离子液体的应用具有重要意义. 然而, 关于碱性离子液体碱性表征深入研究的报道还比较少. 我们合成了系列碱性离子液体, 利用电位滴定法测定了碱性离子液体的pK_b值, 通过相应pK_b值来表征离子液体的碱性强度, 最后考察了离子液体碱性与其结构之间的关联关系. 结果表明, 羧酸根碱性离子液体的碱性主要由阴离子决定, 但不同的阳离子也会影响到其碱性强度, 从而对离子液体的碱性进行微调; 对于胺基功能化的咪唑型离子液体, 由于离子液体结构中咪唑阳离子具有较强的吸电子诱导效应, 相对于对应的三乙胺其碱性显著下降.     

光子晶体在分析化学中的应用

光子晶体是一新兴的光学材料,正越来越多地应用于分析化学领域,有可能成为新的研究热点。本文着重介绍与分析化学相关的光子晶体研究,特别关注其在色谱、毛细管与芯片电泳等分离分析方面的应用。     

Force criterion of different electrolytes in microchannel

The control and handling of fluids is central to many applications of the lab-on-chip. This paper analyzes the basic theory of manipulating different electrolytes and finds the two-dimensional model. Coulomb force and dielectric force belonging to the body force of different electrolytes in the microchannel were analyzed. The force criterion at the interface was concluded, and testified by the specific example. Three basic equations were analyzed and applied to simulate the phenomenon. The force criterion was proved to be correct based on the simulation results.     

数值摄动算法及其CFD格式

作者提出的数值摄动算法把流体动力学效应耦合进NS方程组和对流扩散（CD）方程离散的数学基本格式（MBS）,特别是耦合进最简单的MBS即一阶迎风和二阶中心格式之中,由此构建成一系列新格式,称呼方便和强调耦合流体动力学起见,称它们为流体力学基本格式（FMBS）。构建FMBS的主要步骤是把MBS中的通量摄动重构为步长的幂级数,利用空间分裂和导出的高阶流体动力学关系式,把结点变量展开成Taylor级数,通过消除重构格式修正微分方程的截断误差诸项求出幂级数的待定系数,由此获得非线性FMBS。FMBS的公式是MBS与 （及 ）之简单多项式的乘积, 和 分别是网格Reynolds数和网格CFL数。FMBS和MBS使用相同结点,简单性彼此相当,但FMBS精度高稳定范围大,例如FMBS包含了许多绝对稳定和绝对正型、高阶迎风和中心有限差分（FD）格式和有限体积（FV）格式,这些格式对网格Reynolds数的任意值均为不振荡格式。可见对不振荡CFD格式的构建,数值摄动算法提供了不同于调节数值耗散等常见的人为构建方法,而利用流体力学自身关系以及把迎风机制通过上、下游摄动重构引入中心MBS的解析构建方法,FMBS除了直接应用于流体计算外;对于通过调节数值耗散、色散和数值群速度特性重构高分辨率格式的研究,最简单FMBS提供了比最简单MBS更精确、但同样简单的基础和起步格式。FMBS用于计算不可压缩流,可压缩流,液滴萃取传质,微通道两相流等,均获得良好数值结果或与已有Benchmark解一致的数值结果。已有文献称数值摄动算法为新型高精度格式和高的算法和高的格式;本文FMBS比数值摄动格式的称呼可更好反映FMBS的物理内容。文中也讨论了值得进一步研究的一些课题,该法亦可用于其它一些数学物理方程（例如,简化Boltzmann方程、磁流体方程、KdV-Burgers方程等）MBS耦合物理动力学效应的重构。      

重建极性连续统理论的基本定律和原理(Ⅺ)——兼容性问题

对现有连续统场论中存在若干有关兼容性问题进行了简略的评论．根据重建的极性的连续统基本定律阐述三类兼容性问题．第一类是讨论各基本定律间的兼容性问题．第二类是讨论微极连续统基本定律兼容一般连续统基本定律的问题．第三类是讨论微极连续统基本定律兼容刚体动力学基本方程的问题．推导出的结果有助于深刻理解各种连续统理论的基本定律体系的结构和它们之间的联系．明确地指出,在传统的连续统场论的基本均衡定律的框架下,相容性问题是不可能自然地得到解决．