Ultra-high capacity liquid chromatography chip/quadrupole time-of-flight mass spectrometry for pharmaceutical analysis

Nanoflow liquid chromatography/mass spectrometry (nano-LC/MS) has attracted increasing interest in virtue of high sensitivity, low sample consumption, and minimal matrix effect. In this work a HPLC-Chip/quadrupole time-of-flight (Q-TOF) MS device with a new ultra-high capacity small molecule chip (UHC-Chip) which features a 500 nL enrichment column and a 150 mm × 75 μm analytical column, was evaluated with a drug mixture covering a wide range of polarities. Excellent chromatographic precision with 0.1-0.5% RSD for retention time and 1.7-9.0% RSD for peak area, low limit of detection, good chip-to-chip reproducibility and linearity were obtained by using this UHC-Chip. Compared with the standard HPLC-Chip with 40 nL trapping column, the UHC-Chip showed higher enrichment capability and hence gave a higher response in signal detection. Additionally, 4-30 times increase in sensitivity was obtained compared with conventional LC/MS, which indicated that UHC-Chip/MS was a valuable tool for the quantitative analysis of low level impurities and degradation products in pharmaceuticals. Moreover, satisfactory results obtained from trace drug analysis of serum samples further proved its practicality and potential for use in drug testing and development.     

Biotinylated thermoresponsive core cross-linked nanoparticles via RAFT polymerization and "click" chemistry

A straightforward approach to the synthesis of "clickable" thermoresponsive core cross-linked (CCL) nanoparticles was developed. This approach was based on reversible addition-fragmentation chain transfer (RAFT) radical cross-linking polymerization of styrene and divinylbenzene with azide-functionalized poly(N-isopropylacrylamide) (PNIPAM-N(3)) as macro chain transfer agent in a selective solvent. Spherical nanoparticles with a diameter of 12nm were obtained after 24h polymerization. When the lyophilized CCL nanoparticles were dispersed in THF, spherical nanoparticles were observed, confirming the stability of CCL nanoparticles. The transmission electron microscopy (TEM) studies demonstrated that spherical nanoparticles and wormlike structure coexisted in the aqueous solution. The CCL nanoparticles have a lower critical solution temperature (LCST) at about 29.6°C, a little lower than that of PNIPAM homopolymer. Biotin molecules were conjugated to the surface of CCL nanoparticles via "click" chemistry in aqueous media. After bioconjugation, the LCST shifted to 28.3°C. The bioavailability of biotin to protein avidin was evaluated by a 4'-hydroxyazobenzene-2-carboxylic acid/avidin (HABA/avidin) binding assay and TEM.     

Facile electrochemical synthesis of hexagonal Cu2O nanotube arrays and their application

Large-scale and highly oriented single-crystalline hexagonal Cu(2)O nanotube arrays have been successfully synthesized using a two-step solution approach, which involves the electrodeposition of oriented Cu(2)O nanorods and a subsequent dissolution technique along the c axis to form a tubular structure. Herein, NH(4)Cl was found to be an effectual additive, and it can successfully realize the dissolution process of Cu(2)O from nanorods to nanotubes. The dissolution mechanism of Cu(2)O from nanorods to nanotubes was illustrated in detail. These prepared Cu(2)O nanotube arrays were characterized by SEM, EDS, XRD, XPS, and TEM. The photoluminescence (PL) spectrum of Cu(2)O nanotube arrays was also measured, and it shows there is a greater fraction of copper or oxygen vacancies in these prepared Cu(2)O nanotubes. Finally, the applications of Cu(2)O nanotube arrays for gas sensors were investigated in this paper.     

Unusual multi-step sequential Au(III)/Au(II) processes of gold(III) quinoxalinoporphyrins in acidic non-aqueous media

The electrochemistry of gold(III) mono- and bis-quinoxalinoporphyrins was examined in CH(2)Cl(2) or PhCN containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) before and after the addition of trifluoroacetic acid to solution. The investigated porphyrins are represented as Au(PQ)PF(6) and Au(QPQ)PF(6), where P is the dianion of the 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin and Q is a quinoxaline group fused to a β,β'-pyrrolic position of the porphyrin macrocycle; in Au(QPQ)PF(6) there is a linear arrangement where the quinoxalines are fused to pyrrolic positions that are opposite each other. The porphyrin without the fused quinoxaline groups, Au(P)PF(6), was also investigated under the same solution conditions. In the absence of acid, all three gold(III) porphyrins undergo a single reversible Au(III)/Au(II) process leading to the formation of a Au(II) porphyrin which can be further reduced at more negative potentials to give stepwise the Au(II) porphyrin π-anion radical and dianion, respectively. However, in the presence of acid, the initial Au(III)/Au(II) processes of Au(PQ)PF(6) and Au(QPQ)PF(6) are followed by an internal electron transfer and protonation to regenerate new Au(III) porphyrins assigned as Au(III)(PQH)(+) and Au(III)(QPQH)(+). Both protonated gold(III) quinoxalinoporphyrins then undergo a second Au(III)/Au(II) process at more negative potentials. The electrogenerated monoprotonated monoquinoxalinoporphyrin, Au(II)(PQH), is then further reduced to its π-anion radical and dianion forms, but this is not the case for the monoprotonated bis-quinoxalinoporphyrin, Au(II)(QPQH), which accepts a second proton and is rapidly converted to Au(III)(HQPQH)(+) before undergoing a third Au(III)/Au(II) process to produce Au(II)(HQPQH) as a final product. Thus, Au(P)PF(6) undergoes one metal-centered reduction while Au(PQ)PF(6) and Au(QPQ)PF(6) exhibit two and three Au(III)/Au(II) processes, respectively. These unusual multistep sequential Au(III)/Au(II) processes were monitored by thin-layer spectroelectrochemistry and a reduction/oxidation mechanism for Au(PQ)PF(6) and Au(QPQ)PF(6) in acidic media is proposed.     

On optimizing edge connectivity of product graphs

This work studies the super edge connectivity and super restricted edge connectivity of direct product graphs, Cartesian product graphs, strong product graphs and lexicographic product graphs. As a result, sufficient conditions for optimizing the edge connectivity and restricted edge connectivity of these graphs are presented.     

Minimal-speed selection of traveling waves to the Lotka–Volterra competition model

In this paper the minimal-speed determinacy of traveling wave fronts of a two-species competition model of diffusive Lotka–Volterra type is investigated. First, a cooperative system is obtained from the classical Lotka–Volterra competition model. Then, we apply the upper-lower solution technique on the cooperative system to study the traveling waves as well as its minimal-speed selection mechanisms: linear or nonlinear. New types of upper and lower solutions are established. Previous results for the linear speed selection are extended, and novel results on both linear and nonlinear selections are derived.     

Free axisymmetric vibration of transversely isotropic laminated circular plates

Based on the three dimensional elastic theory, the state equation of the axisymmetric free vibration of transversely isotropic circular plates is established. Taking the advantage of finite Hankel transform, two exact solutions are derived for two boundary conditions, i. e. the rigid-slipping boundary and elastic simply supported boundary. Finally, numerical results are presented and compared with those of FEM. The project is supported by the National Natural Science Foundation of China and the Zhejiang Provincial Natural Science Foundation.     

SiGe HBT大信号等效电路模型

基于SiGe HBT(异质结双极晶体管)的物理模型，建立了描述SiGe HBT的大信号等效电路模型.该等效电路模型考虑了准饱和效应和自热效应等，模型分为本征和非本征两部分，物理意义清晰，拓扑结构相对简单.该模型嵌入了PSPICE软件的DEVEO(器件方程开发包)中.在PSPICE软件资源的支持下，利用该模型对SiGe HBT器件进行了交直流特性模拟分析，模拟结果与理论分析结果相一致，并且与文献报道的结果符合较好. 关键词： SiGe HBT 等效电路模型 PSPICE     

On the integral representation formula for a two‐component elastic composite

The aim of this paper is to derive, in the Hilbert space setting, an integral representation formula for the effective elasticity tensor for a two‐component composite of elastic materials, not necessarily well‐ordered. This integral representation formula implies a relation which links the effective elastic moduli to the N‐point correlation functions of the microstructure. Such relation not only facilitates a powerful scheme for systematic incorporation of microstructural information into bounds on the effective elastic moduli but also provides a theoretical foundation for inverse‐homogenization. The analysis presented in this paper can be generalized to an n‐component composite of elastic materials. The relations developed here can be applied to the inverse‐homogenization for a special class of linear viscoelastic composites. The results will be presented in another paper. Copyright © 2005 John Wiley & Sons, Ltd.     

用自适应MG法,FMG法求解Helmholtz方程

本文针对Ｖ循环、Ｗ循环和多重网格法中最优光滑次数及循环体个数难以确定的缺点，以Ｈｅｌｍｈｏｌｔｚ方程为例给出自适应的多重网格算法和自适应的完全多重网格算法。