Combining selection valve and mixing chamber for nanoflow gradient generation: Toward developing a liquid chromatography cartridge coupled with mass spectrometer for protein and peptide analysis

Toward developing a micro HPLC cartridge, we have recently built a high-pressure electroosmotic pump (EOP). However, we do not recommend people to use this pump to deliver an organic solvent directly, because it often makes the pump rate unstable. We have experimented several approaches to address this issue, but none of them are satisfactory. Here, we develop an innovative approach to address this issue. We first create an abruption (a dead-volume) within a fluid conduit. We then utilize an EOP to withdraw, via a selection valve, a train of eluent solutions having decreasing eluting power into the fluid conduit. When these solutions are further aspirated through the dead-volume, these solutions are partially mixed, smoothening concentration transitions between two adjacent eluent solutions. As these solutions are pushed back, through the dead-volume again, a smooth gradient profile is formed. In this work, we characterize this scheme for gradient formation, and we incorporate this approach with a high-pressure EOP, a nanoliter injection valve, and a capillary column, yielding a micro HPLC system. We then couple this micro HPLC with an electrospray ionization – mass spectrometer for peptide and protein separations and identifications.     

The role of benzoic acid in proline‐catalyzed asymmetric michael addition: A density functional theory study

In asymmetric Michael addition between ketones and nitroolefins catalyzed by L ‐proline, we observed that it was benzoic acid or its derivatives rather than other proton acid that could accelerate the reaction greatly, and different benzoic acid derivatives brought different yields. To explain the experimental phenomena, a density functional theory study was performed to elucidate the mechanism of proline‐catalyzed asymmetric Michael addition with benzoic acid. The results of the theoretical calculation at the level of B3LYP/6‐311+G(2df,p)//B3LYP/6‐31G(d) demonstrated that benzoic acid played two major roles in the formation of nitroalkane: assisting proton transfer and activating the nitro group. In the stage of enamine formation from imine, the energy profiles of benzoic acid derivatives were also calculated to investigate the reasons why different benzoic acid derivatives caused different yields. The results demonstrated that the pK_a value was the major factor for p‐substituted benzoic acid derivatives to improve the yields, whereas for m/o‐substituted benzoic acid derivatives, both pK_a value and electronic and steric effects could significantly increase the yields. The calculated results would be very helpful for understanding the reaction mechanism of Michael addition and provide some insights into the selection of efficient additives for similar experiments. © 2012 Wiley Periodicals, Inc.     

Graphdiyne:A Versatile Material in Electrochemical Energy Conversion and Storage

Graphdiyne(GDY),which is composed of sp2-/sp-hybridized carbon atoms,has attracted increasing attention.In the structure of GDY,the existence of large triangular-like pores,well dispersed electron-rich cavities as well as a large π-conjugated structure endows GDY with a natural bandgap,fast electron/ion transport,and tunable electronic properties.These unique features make GDY competitive in areas of gas separation and capture,electronics,detectors,catalysts,biomedicine and therapy,and energy-related fields.Benefiting from the facile synthesis method,various GDY structures and GDY-based composites have been successfully prepared and show great potential in the practical application of energy storage and catalysis areas.Here,this review aims at providing a timely and comprehensive update on the preparation and application of GDY materials.The current development of GDY materials in various electrochemical fields especially in energy conversion,energy storage,and catalysis is mainly summarized.Moreover,the potential development prospects are also discussed.     

基于平面度的燃料电池电化学性能模拟

 固体氧化物燃料电池的翘曲会影响电极-盖板界面的接触情况,从而影响电化学性能,对相关制造工艺提出了很大的挑战．为了分析燃料电池平面度对放电过程的影响,揭示其潜在的风险,我们建立了两个基于有限元法的仿真模型,对考虑平面度缺陷的燃料电池封装和放电进行分析．在对固体氧化物燃料电池进行平面度测量的基础上,首先建立了具有真实燃料电池翘曲特性的几何模型,分析封装过程中接触压力的分布情况．然后将接触电阻的仿真结果导入到三维多物理场耦合模型中,模拟具有平面度缺陷的燃料电池电化学性能．计算结果展示了燃料电池两侧封装过程中接触压力的分布情况．通过对比有接触电阻和无接触电阻的燃料电池电流密度,分析了电池与盖板的接触对放电过程的影响．结果表明,燃料电池的凹陷面较难达到满意的接触状态,需要比凸起面更大的封装压力．燃料电池表面接触电阻的变化将引起电流传导路径的变化,产生局部高电流或低电流．这项工作强调了在燃料电池中保持均匀分布的接触电阻的重要性,为今后的优化工作奠定了基础．     

Double perovskite oxides Sr_2Mg_(1-x)Fe_xMoO(6-δ) for catalytic oxidation of methane

The double perovskite oxides Sr2Mg1-xF exMoO6-δ were investigated as catalysts for the methane oxidation.The structural properties of catalysts were characterized in detail by X-ray diffraction,X-ray photoelectron spectroscopy and X-ray absorption spectroscopy.The catalytic property was strongly influenced by the Fe substitution.The relation between catalytic performance and the degree of Fe substitution was examined with regard to the structure and surface characteristics of the mixed oxides.The Fe-containing catalysts exhibited higher activity attributable to the possible(Fe2+,Mo6+) and (Fe3+,Mo5+)valency pairs,and the highest activity was observed for Sr2Mg0.2Fe0.8MoO6-δ.The enhancement of the catalytic activity may be correlated with the Fe-relating surface lattice oxygen species and was discussed in view of the presence of oxygen vacancies.     

荧光法测定SD大白鼠不同脑区的单胺类神经递质

以荧光光谱法定量地研究了不同浓度的司考林作用下,鼠脑组织中去甲肾上腺素、多巴胺和5-羟色胺的定量变化,从而表达了中枢神经递质的变化规律.     

Incorporating high-pressure electroosmotic pump and a nano-flow gradient generator into a miniaturized liquid chromatographic system for peptide analysis

We integrate a high-pressure electroosmotic pump (EOP), a nanoflow gradient generator, and a capillary column into a miniaturized liquid chromatographic system that can be directly coupled with a mass spectrometer for proteomic analysis. We have recently developed a low-cost high-pressure EOP capable of generating pressure of tens of thousands psi, ideal for uses in miniaturized HPLC. The pump worked smoothly when it was used for isocratic elutions. When it was used for gradient elutions, generating reproducible gradient profiles was challenging; because the pump rate fluctuated when the pump was used to pump high-content organic solvents. This presents an issue for separating proteins/peptides since high-content organic solvents are often utilized. In this work, we solve this problem by incorporating our high-pressure EOP with a nano-flow gradient generator so that the EOP needs only to pump an aqueous solution. With this combination, we develop a capillary-based nano-HPLC system capable of performing nano-flow gradient elution; the pump rate is stable, and the gradient profiles are reproducible and can be conveniently tuned. To demonstrate its utility, we couple it with either a UV absorbance detector or a mass spectrometer for peptide separations.     

A new one‐step smoothing newton method for the second‐order cone complementarity problem

In this paper, we present a new one‐step smoothing Newton method for solving the second‐order cone complementarity problem (SOCCP). Based on a new smoothing function, the SOCCP is approximated by a family of parameterized smooth equations. At each iteration, the proposed algorithm only need to solve one system of linear equations and perform only one Armijo‐type line search. The algorithm is proved to be convergent globally and superlinearly without requiring strict complementarity at the SOCCP solution. Moreover, the algorithm has locally quadratic convergence under mild conditions. Numerical experiments demonstrate the feasibility and efficiency of the new algorithm. Copyright © 2010 John Wiley & Sons, Ltd.     

A global harmonic Arnoldi method for large non-Hermitian eigenproblems with an application to multiple eigenvalue problems

The global Arnoldi method can be used to compute exterior eigenpairs of a large non-Hermitian matrix A, but it does not work well for interior eigenvalue problems. Based on the global Arnoldi process that generates an F-orthonormal basis of a matrix Krylov subspace, we propose a global harmonic Arnoldi method for computing certain harmonic F-Ritz pairs that are used to approximate some interior eigenpairs. We propose computing the F-Rayleigh quotients of the large non-Hermitian matrix with respect to harmonic F-Ritz vectors and taking them as new approximate eigenvalues. They are better and more reliable than the harmonic F-Ritz values. The global harmonic Arnoldi method inherits convergence properties of the harmonic Arnoldi method applied to a larger matrix whose distinct eigenvalues are the same as those of the original given matrix. Some properties of the harmonic F-Ritz vectors are presented. As an application, assuming that A is diagonalizable, we show that the global harmonic Arnoldi method is able to solve multiple eigenvalue problems both in theory and in practice. To be practical, we develop an implicitly restarted global harmonic Arnoldi algorithm with certain harmonic F-shifts suggested. In particular, this algorithm can be adaptively used to solve multiple eigenvalue problems. Numerical experiments show that the algorithm is efficient for the eigenproblem and is reliable for quite ill-conditioned multiple eigenproblems.