An experimental design based strategy to optimize a capillary electrophoresis method for the separation of 19 polycyclic aromatic hydrocarbons

Because of their high toxicity, international regulatory institutions recommend monitoring specific polycyclic aromatic hydrocarbons (PAHs) in environmental and food samples. A fast, selective and sensitive method is therefore required for their quantitation in such complex samples. This article deals with the optimization, based on an experimental design strategy, of a cyclodextrin (CD) modified capillary zone electrophoresis separation method for the simultaneous separation of 19 PAHs listed as priority pollutants. First, using a central composite design, the normalized peak-start and peak-end times were modelled as functions of the factors that most affect PAH electrophoretic behavior: the concentrations of the anionic sulfobutylether-β-CD and neutral methyl-β-CD, and the percentage of MeOH in the background electrolyte. Then, to circumvent computational difficulties resulting from the changes in migration order likely to occur while varying experimental conditions, an original approach based on the systematic evaluation of the time intervals between all the possible pairs of peaks was used. Finally, a desirability analysis based on the smallest time interval between two consecutive peaks and on the overall analysis time, allowed us to achieve, for the first time in CE, full resolution of all 19 PAHs in less than 18 min. Using this optimized capillary electrophoresis method, a vegetable oil was successfully analyzed, proving its suitability for real complex sample analysis.     

毛细管区带电泳测定D1蛋白酶的活性及其抑制剂先导化合物的筛选

建立了毛细管区带电泳技术快速测定D1蛋白酶活性及其抑制剂先导化合物的筛选方法。实验选用未涂层熔融石英毛细管(43 cm 5mm)和磷酸盐缓冲溶液(50 mmol/L, pH 3.0)作为分离介质,运行电压18 kV,测定了D1蛋白酶的活性并对部分抑制剂先导化合物进行了筛选。结果表明, ITP26和ITP21两种异噁唑噻唑哌啶类先导化合物对蛋白酶活性具有抑制作用,抑制率分别为26%和13%。     

A new method for quantitative determination of two uronic acids by CZE with direct UV detection

A new method using capillary zone electrophoresis was developed for the rapid quantification of two common uronic acids, galacturonic acid and glucuronic acid, based on utilization of an alkaline background electrolyte with reversed electroosmotic flow (EOF) within 16 min. The method relies on in‐capillary reaction and direct UV detection at the wavelength 270 nm. The optimum electrolyte solution was prepared of 130 mm sodium hydroxide, 36 mm disodium hydrogen phosphate dihydrate and 0.5 mm cetyltrimethylammonium bromide. EOF was reversed to detect uronic acids and to improve the separation of neutral sugars. The established method was validated and the results showed good linearity, high precision and satisfactory sensitivity. The newly developed method was successfully applied to analyze galacturonic acid and glucuronic acid content in Forsythia suspensa polysaccharides. The method is fast since only sample hydrolysis and dilution are required in the sample preparation. Copyright © 2010 John Wiley & Sons, Ltd.     

A local hermitian RBF meshless numerical method for the solution of multi‐zone problems

The local Hermitian interpolation (LHI) method is a strong‐form meshless numerical technique in which the solution domain is covered by a series of small and heavily overlapping radial basis function (RBF) interpolation systems. Aside from its meshless nature and the ability to work on very large scattered datasets, the main strength of the LHI method lies in the formation of local interpolations, which themselves satisfy both boundary and governing PDE operators, leading to an accurate and stable reconstruction of partial derivatives without the need for artificial upwinding or adaptive stencil selection. In this work, an extension is proposed to the LHI formulation which allows the accurate capture of solution profiles across discontinuities in governing equation parameters. Continuity of solution value and mass flux is enforced between otherwise disconnected interpolation systems, at the location of the discontinuity. In contrast to other local meshless methods, due to the robustness of the Hermite RBF formulation, it is possible to impose both matching conditions simultaneously at the interface nodes. The procedure is demonstrated for 1D and 3D convection–diffusion problems, both steady and unsteady, with discontinuities in various PDE properties. The analytical solution profiles for these problems, which experience discontinuities in their first derivatives, are replicated to a high degree of accuracy. The technique has been developed as a tool for solving flow and transport problems around geological layers, as experienced in groundwater flow problems. The accuracy of the captured solution profiles, in scenarios where the local convective velocities exceed those typically encountered in such Darcy flow problems, suggests that the technique is indeed suitable for modeling discontinuities in porous media properties. © 2010 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 27: 1201–1230, 2011     

Analysis of therapeutic peptides in human urine by combination of capillary zone electrophoresis-electrospray mass spectrometry with preparative capillary isotachophoresis sample pretreatment

The presented study deals with the off-line coupling of preparative isotachophoresis (pITP) with on-line combination of capillary zone electrophoresis with electrospray mass spectrometric detection (CZE-ESI-MS) used for the analysis of therapeutic peptides (anserine, carnosine, and buserelin) in complex matrix (urine). Preparative capillary isotachophoresis, operating in a discontinuous fractionation mode in column-coupling configuration, served as a sample pretreatment technique to separation, and fractionation of mixture of therapeutic peptides present in urine at low concentration level. The fractions isolated by pITP procedure were subsequently analyzed by capillary zone electrophoresis with electrospray mass spectrometric detection. Acetic acid at 200 mmol L(-1) concentration served as background electrolyte in CZE stage and it is compatible with MS detection in positive ionization mode. In pITP fractionation procedure, sodium cation (10 mmol L(-1) concentration) as leading ion and beta-alanine as terminating ion (20 mmol L(-1) concentration) were used. While using CZE-ESI-MS, the limits of detection were 0.18 μg mL(-1) for carnosine, 0.17 μg mL(-1) for anserine and 0.64 μg mL(-1) for buserelin in water and 0.19 μg mL(-1) for carnosine, 0.50 μg mL(-1) for anserine and 0.74 μg mL(-1) for buserelin in 10 times diluted urine, respectively. The cleaning power of pITP sample pretreatment was proved as the peptides provided the higher MS signals at lower concentration levels resulting from the minimized matrix effects. The quality of obtained MS/MS spectra was very good so that they can provide information about the structure of analytes, and they were used for verification of the analytes identities. The pITP pretreatment improved the detection limits of the analyzed therapeutic peptides at least 25 times compared to the CZE-ESI-MS itself.     

Hoek–Brown criterion applied to circular tunnel using elastoplasticity and in situ axial stress

Based on the nonlinear Hoek–Brown failure criterion, elastoplastic analytical solutions are developed for the elastoplastic stresses, strains and plastic zones around a circular tunnel subjected to different value of the axial in situ stress. Effects of the transverse in situ stress, the axial in situ stress and the strength parameters of rock masses on the elastoplastic stresses, strains and plastic zones in the surrounding rock masses are investigated. It is found from the numerical results that the stresses, strains, and plastic zones in the surrounding rock depend not only on the transverse in situ stress but also on the axial in situ stress as well as the mechanical parameters of rock masses.     

Separation work analysis of cohesive law and consistently coupled cohesive law

An appropriate coupled cohesive law for predicting the mixed mode failure is established by combining normal separation and tangential separation of surfaces in the cohesive zone model(CZM) and the cohesive element method.The Xu-Needleman exponential cohesive law with the fully shear failure mechanism is one of the most popular models.Based on the proposed consistently coupled rule/principle,the Xu-Needleman law with the fully shear failure mechanism is proved to be a non-consistently coupled cohesive la...     

基于DPM系统的风化岩软弱区定位以及性质描述

风化岩体中存在软弱区,这些软弱区导致岩体的力学性能大幅度降低。现阶段往往采用地质钻孔取样对岩体中的软弱区进行定位以及性质分析。但是,由于造价以及工期方面的原因,地质钻孔数量非常有限,这些软弱区很难被有效定位,这在分析风化岩体的力学性能中造成了很大的隐患,成为边坡、基坑设计施工过程中岩体失稳的重要原因。本文介绍了一个风化岩体软弱区定位和性质描述的新方法。该方法应用钻孔过程监测系统(DPM)对土钉、锚杆、抗滑桩以及其他加固体的钻孔过程进行监测,无需取样,通过对钻孔过程数据的分析,实现对软弱区的定位和性质描述。工程实例证明,基于DPM系统的钻孔过程分析方法能够快速有效的定位和描述风化岩体中的软弱区。该方法的出现为风化岩体的工程勘察提供了新的思路,为基于该方法的岩体质量评价系统的建立打下了坚实的基础。     

Band-pass filtered velocity statistics in decaying turbulent box

For homogeneous isotropic turbulence study, the acquisition of band-pass filtered velocity increments (FVI) in a non-forced turbulent box is still a challenge both experimentally and numerically. Turbulence and associated physical processes, at a given instant, are permanently contaminated by a forcing process which can seldom be universal. The situation tends to be the origin of intermittency and the non-Gaussian probability density distribution for acceleration and velocity gradients. To reveal implied mechanism, grid turbulence is adapted to observe non-perturbed homogeneous isotropic turbulence. The velocity increments (VI) can be obtained following Comte-Bellot and Corrsin (GCBC) by means of two point-two time shifted velocity measurements. It is difficult to obtain decaying turbulence (DT) at large turbulent Reynolds number without pollution coming from walls. Nevertheless it is also significant to investigate DT in low Reynolds number regimes to determine non-polluted tendencies. The similarity of DT between particle image velocimetry (PIV) and hot wire anemometry measurements by GCBC are presented. Here we focus our tendency on VI and FVI probability density function (PDF) shapes in this letter. In conclusion, the tendency to Gaussian shape in inertial zone wavenumbers, demonstrates that there will be no intermittency if turbulent cascade is not perturbed.     

A novel monochromator for experiments with ultrashort X‐ray pulses

Aiming at advancing storage‐ring‐based ultrafast X‐ray science, over the past few years many upgrades have been undertaken to continue improving beamline performance and photon flux at the Femtoslicing facility at BESSY II. In this article the particular design upgrade of one of the key optical components, the zone‐plate monochromator (ZPM) beamline, is reported. The beamline is devoted to optical pump/soft X‐ray probe applications with 100 fs (FWHM) X‐ray pulses in the soft X‐ray range at variable polarization. A novel approach consisting of an array of nine off‐axis reflection zone plates is used for a gapless coverage of the spectral range between 410 and 1333 eV at a designed resolution of E/ΔE = 500 and a pulse elongation of only 30 fs. With the upgrade of the ZPM the following was achieved: a smaller focus, an improved spectral resolution and bandwidth as well as excellent long‐term stability. The beamline will enable a new class of ultrafast applications with variable optical excitation wavelength and variable polarization.