Separation and determination of nitroaniline isomers by capillary zone electrophoresis with amperometric detection

In this paper, capillary zone electrophoresis with amperometric detection (CZE-AD) was firstly applied to the simultaneous separation and determination of nitroaniline positional isomers. The three analytes could be perfectly analyzed by using the buffer of extreme pH. The effects of several important factors were investigated to find optimum conditions. A carbon-disk electrode was used as working electrode. The optimal conditions were 40 mmol/L tartaric acid-sodium tartrate (pH 1.2) as running buffer, 17 kV as separation voltage and 1.10 V (versus saturated calomel reference electrode, SCE) as detection potential. Under the optimum conditions, o-, m- and p-nitroaniline were separated successfully and good linearity, reproducibility and recovery results were obtained. The detection limit for m-nitroaniline was as low as at 9.06 × 10⁻⁹ mol/L. This proposed method demonstrated long-term stability and reproducibility with relative standard deviations of less than 1.8% for migration time and 1.1% for peak areas. The utility of this method was demonstrated by monitoring dyestuff wastewater and the assay results were satisfactory.     

Analysis of enantiomers in biological matrices by charged cyclodextrin-mediated capillary zone electrophoresis in column-coupling arrangement with capillary isotachophoresis

The possibility to apply charged chiral selector as buffer additive in capillary zone electrophoresis (CZE) on-line coupled with capillary isotachophoresis (CITP) was studied. Enantioseparations and determinations of trace (ng/ml) antihistaminic drugs [pheniramine (PHM), dimethindene (DIM), dioxopromethazine (DIO)] present in samples of complex ionic matrices (urine) served as model examples. A negatively charged carboxyethyl-β-cyclodextrin (CE-β-CD) was used as a chiral selector in analytical CZE stage following upon a sample pretreatment by CITP (preconcentration of the analytes from 5 to 20-times diluted urine samples, partial sample clean up removing macroconstituents from the sample matrices). A high recognition capability of the oppositely charged CE-β-CD was demonstrated by enantioselective retardation of the drugs in presence of micro-and semi-macroconstituents migrating in CZE stage and detectable by UV detector. In this way, enantiomers of the drugs could be easily separated and determined. Due to lack of interferences between the drugs and sample-matrix constituents in presence of charged CE-β-CD, demands on both spacers in CITP step and multiple column-switching were minimized. CITP-CZE method with charged selector appeared to be a useful analytical approach for the trace enantiomers in complex ionic matrices as it combined enhanced separation selectivity and sample loadabitlity with high separation efficiency and provided favorable performance parameters including sensitivity, linearity, precision, accuracy/recovery and robustness with minimal demands on sample preparation. Analysis of urine sample taken from a patient treated by PHM, showing concentration profile of PHM enantiomers and their metabolites, illustrated potentialities of the method in clinical research.     

Field-amplified on-line sample stacking for determination of carnosine-related peptides by capillary electrophoresis

An on-line sample stacking method, namely field-amplified sample injection, has been developed for the separation and determination of carnosine, anserine, and homocarnosine by capillary electrophoresis. Using electrokinetic injection, about 130- to 160-fold improvement of sensitivity was achieved without loss of separation efficiency when compared to conventional sample injection. For conventional injection, the samples were dissolved in running buffer and then hydrodynamically injected for 10 s (3.45 kPa). Various parameters affecting separation and sample stacking were optimized. Under optimum conditions, linear responses were obtained over two orders of magnitude and the detection limits (defined as S/N = 3) of carnosine, anserine, and homocarnosine were 1.5 x 10(-8) to 1.6 x 10(-8) mol/L.     

Quantitative investigation of the interaction between granulocyte-macrophage colony-stimulating factor and heparin by capillary zone electrophoresis

The interactions between granulocyte-macrophage colony-stimulating factor (GM-CSF) and heparin or low-molecular weight heparin (LMWH) were studied by CZE. It was found that GM-CSF could bind to both heparin and LMWH. The binding constants were calculated from Scatchard regression to be (6.5 +/- 0.8) x 10(5)/M and (11.2 +/- 0.7) x 10(5)/M, respectively. The specificity of the interaction between GM-CSF and heparin was also studied by employing another sulfated K carrageenan oligosaccharide as a control. Results showed that K carrageenan oligosaccharide could not interact with GM-CSF, indicating that GM-CSF could specifically interact with heparin.     

Robust pursuit of a hybrid evader

A pursuit-evasion differential game with bounded controls and prescribed duration is considered. The evader has two possible dynamics, while the pursuer dynamics is fixed. The evader can change the dynamics once during the game. The pursuer knows the possible dynamics of the evader, but not the actual one. The optimal pursuer strategy in this game is obtained. It is robust with respect to the control of the evader, the order of its dynamics and the time of the mode change. The capture conditions of the game are established and the pursuer capture zone is constructed. An illustrative example of the game is also presented.     

隧道与前方大型溶洞应力集中叠加效应

在陆家寨岩溶隧道施工期间,曾预报并揭露大型溶洞,施工过程中接近溶腔段围岩变形较大且伴随围岩块体脱落,给隧道施工带来极大的安全隐患。基于深埋球形洞室的弹塑性二次应力分布,结合新奥法隧道施工理念,利用FLAC3D模拟隧道开挖接近并进入大型溶洞的过程。在自重应力场下分析不同大小的球形洞室周围应力场对隧道围岩变形的影响。结果表明:球形洞室会在周围形成中心半径为1. 5倍洞室半径的应力集中带;隧道开挖接近应力集中带时,将引起隧道前方应力集中区与溶洞应力集中带的叠加;随着隧道继续开挖,叠加效应在下一个进尺完成后失效;分布在隧道两侧围岩,该叠加再分散的过程会造成拱顶、拱肩的变形增大,影响隧道开挖的安全。研究为中国岩溶隧道的建设有重要的参考和借鉴价值。     

黄土塬斜坡带地震波激发数值模拟与波场特征

黄土塬斜坡带的地震资料品质最差,研究程度极低。采用先进的交错网格、谱元法和高阶有限差分波场模拟算法,对斜坡带地震波激发进行了数值模拟,准确地反映了地震波场特征,从理论上优选出地震波激发参数。经试验提出一套超多井组合地震波激发技术,取得了高精度的三维地震资料。     

龙门山重力滑脱作用形成挤压性构造的物理模拟实验

研究龙门山构造带在晚印支早期阶段的构造动力学作用机制,以及在此机制下的重力滑脱作用形成局部挤压环境的可能性。通过以重力为动力的构造物理模拟实验研究,表明在板内的差异隆升背景下可以导致重力滑脱作用发生,在重力滑脱作用下在滑脱体前缘形成挤压性构造变形可能性是存在的。结合龙门山构造带前人的研究资料和国内外近年相关研究成果,龙门山构造带的形成过程可能是在晚印支早期历经了拉张性构造环境后叠上冲推覆过程,从而形成现今的构造格局。     

储层性能层间差异的成岩因素——以塔里木盆地群苦恰克构造带泥盆系东河塘组砂岩为例

基于塔里木盆地群苦恰克构造带内泥盆系东河塘组的上、下两段砂岩储层物性表现出强烈的层间差异性特征(下段砂岩储集物性明显优于上段砂岩的储集物的物性),而这种差异性并非由前期沉积水动力因素所导致,而是由后期储层内成岩改造的差异所引发,对样品进行详细的显微观测和矿物成分研究.研究结果表明:发育于埋藏成岩期石英胶结效应的层间差异造就了上述储集物性的层间差异性;下段砂岩内由于伊利石矿物以包膜的形式包裹于石英颗粒表面,抑制了石英胶结,使得原生孔隙较好地保存;而上段砂岩内强烈的石英胶结使得原生孔隙消失;其岩石物理性质呈现出刚性特征,作为东河塘组上下两段砂岩成岩改造差异的连带效应,在同等外部构造应变环境下,上段砂岩内的裂隙产出现象更加频繁.     

外墙外保温施工质量控制与火灾预防

针对粘贴保温板外保温、保温浆料外保温、有网现浇外保温、无网现浇外保温等4大流行的外墙外保温系统,提出了其施工质量控制要点,并就外保温系统的防火构造、防火新规以及施工防火措施进行探讨．