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71.
王明明  沈菁  宋婷  李胜清  陈浩 《分析化学》2012,40(5):809-810
1 引 言 百草枯属有机杂环类季铵盐除草剂,由于它具有优良的除草效果,已广泛应用于多种作物的杂草防治.百草枯具有极强的水溶性,极易迁移至水体环境中,从而对饮用水的质量安全构成潜在威胁.目前,百草枯的残留检测方法主要有分光光度法[1]、液相色谱-质谱联用法[2]、气相色谱质谱联用法[3]和毛细管电泳法(CE) [4~6].采用分光光度法测定百草枯,不仅操作繁琐费时,而且灵敏度低.采用气相色谱法测定百草枯,通常需要衍生化,应用较少[3].采用液相色谱法测定百草枯,通常需要在流动相中添加离子对试剂[2].毛细管电泳具有分离效率高,分析速度快等优点,已被广泛用于水样中百草枯残留的测定.然而,毛细管电泳灵敏度不高,极大地限制了其在实际样品分析中的应用.场放大样品进样(FASI)是一种简单有效的在线富集方法,其富集倍数可达1000倍[7],可有效提高毛细管电泳技术的灵敏度,因此应用较为广泛.本实验建立了场放大样品进样-压力辅助毛细管区带电泳法(CZE),用于测定饮用水中百草枯的残留量.  相似文献   
72.
Summary Capillary zone electrophoresis using cyclodextrins and a chiral crown ether as buffer constituents was studied for the enantiomeric separation of drugs and amino acids. Based on results obtained from separation of racemic -amino acids both chiral selectors are compared with respect to resolution, efficiency and retention time. For (±)-Quinagolide effects of buffer composition and temperature are examined using -cyclodextrin as chiral agent. Optimum conditions were pH 2.5 at 30 mmol L–1 -cyclodextrin. A linear dependence of retention on -cyclodextrin concentration allowed calculation of formation constants of the host-guest complexes. Buffer concentration and temperature also influence resolution. The application of a chiral crown ether to the separation of optical isomers in capillary zone electrophoresis is described for the first time. Chiral recognition of solutes depends on the formation of protonated alkyl amines and separation is attributed to the formation of diastereomeric host-guest complexes with different interactions for each enantiomer. The effects of crown ether concentration on resolution are presented.  相似文献   
73.
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.  相似文献   
74.
Definitions of the limit of detection (LOD) based on the probability of false positive and/or false negative errors have been proposed over the past years. Although such definitions are straightforward and valid for any kind of analytical system, proposed methodologies to estimate the LOD are usually simplified to signals with Gaussian noise. Additionally, there is a general misconception that two systems with the same LOD provide the same amount of information on the source regardless of the prior probability of presenting a blank/analyte sample. Based upon an analogy between an analytical system and a binary communication channel, in this paper we show that the amount of information that can be extracted from an analytical system depends on the probability of presenting the two different possible states. We propose a new definition of LOD utilizing information theory tools that deals with noise of any kind and allows the introduction of prior knowledge easily. Unlike most traditional LOD estimation approaches, the proposed definition is based on the amount of information that the chemical instrumentation system provides on the chemical information source. Our findings indicate that the benchmark of analytical systems based on the ability to provide information about the presence/absence of the analyte (our proposed approach) is a more general and proper framework, while converging to the usual values when dealing with Gaussian noise.  相似文献   
75.
    
It is shown that expectation values of Poisson‐distributed random numbers exist not only for the well known positive integer powers but also for negative integer powers. A recursion formula for the calculation of expectation values of powers differing by one is given. This recursion formula helps to find an analytical representation for both positive and negative integer powers in terms of the hypergeometric function.  相似文献   
76.
    
The thermal variant of the classical nucleation‐growth‐separation principle is shown, both theoretically and experimentally, to be a reliable tool for studying protein crystal nucleation. The classical nucleation theory is used to elucidate the temperature dependence of crystal nucleus size. A one‐to‐one ratio of the number density of nuclei formed to crystals grown to visible size is achieved using the nucleation‐growth‐separation method. The experiments conducted in such a way show that new nuclei are prevented from appearing while avoiding any crystal loss due to dissolution. The same method is used to study experimentally the interval of growth temperatures where the number density of (nucleated) crystals is relatively insensitive to the growth temperature. It is argued that this temperature interval corresponds to the width of the so‐called metastable zone.  相似文献   
77.
    
Potassium Acetate (CH3COOK) and Potassium Citrate (K3C6H5O7) as new additives were added into the potassium dihydrogen phosphate (KDP) solutions in different molar ratios. The metastable zone width and induction period with and without these additives were determined and compared. Dielectric measurements on pure and doped KDP crystals at various temperatures ranging from 313 to 423 K were carried out by the conventional parallel plate capacitor method which results low dielectric constant value dielectrics in doped crystals. The high resolution XRD studies show that CH3COOK doped KDP crystal and K3C6H5O7 doped KDP crystal do not contain any internal structural grain boundaries and indicates that the crystalline perfection is very good. Moreover, the addition of these potassium additives improves the quality of the crystal and yields highly transparent crystals with well defined features. The effect of additives on the growth, nucleation kinetics, structural, NLO and optical properties has been investigated. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
78.
    
The flow above the free end of a surface-mounted finite-height cylinder was studied in a low-speed wind tunnel using particle image velocimetry (PIV). Velocity measurements were made in vertical and horizontal measurement planes above the free end of finite cylinders of aspect ratios AR = 9, 7, 5 and 3, at a Reynolds number of Re = 4.2 × 104. The relative thickness of the boundary layer on the ground plane was δ/D = 1.7. Flow separating from the leading edge formed a prominent recirculation zone on the free-end surface. The legs of the mean arch vortex contained within the recirculation zone terminate on the free-end surface on either side of the centreline. Separated flow from the leading edge attaches onto the upper surface of the cylinder along a prominent attachment line. Local separation downstream of the leading edge is also induced by the reverse flow and arch vortex circulation within the recirculation zone. As the cylinder aspect ratio is lowered from AR = 9 to AR = 3, the thickness of the recirculation zone increases, the arch vortex centre moves downstream and higher above the free-end surface, the attachment position moves downstream, and the termination points of the arch vortex move upstream. A lowering of the aspect ratio therefore results in accentuated curvature of the arch vortex line. Changes in aspect ratio also influence the vorticity generation in the near-wake region and the shape of the attachment line.  相似文献   
79.
    
Steady flow past a torus with an aspect ratio less than 5 and its axis aligned with the flow is studied numerically by solving the steady, axisymmetric Navier–Stokes equations. The wake structure behind tori exhibits diverse behaviours. The detached recirculating zone on the axis, the attached recirculating zone, and the detached recirculating zone behind the torus tube may appear individually or concurrently, depending on the aspect ratio and the Reynolds number. A wake structure map is summarized based on the observed flow behaviours. Six flow regimes with different wake behaviours are identified and the corresponding flow regime map is plotted, which include the no-recirculating-zone regime, the single-detached-recirculating-zone regime, the single-attached-recirculating-zone regime, the two-recirculating-zone regime I, the two-recirculating-zone regime II, and the three-recirculating-zone regime. Over the range of aspect ratio 1.9<AR<2.4, the detached wake initially increases but then decreases in size with Reynolds number, and eventually disappears at Reynolds numbers beyond a critical value (depending on the aspect ratio). The underlying mechanisms of the onset and disappearance of the recirculating zones are discussed in terms of vorticity accumulation and base bleed. The recirculating zone first occurs when the maximum vorticity on the surface of the torus exceeds about 5. The detached recirculating zone on the axis of the torus disappears once the flow rate through the hole of the torus is beyond a certain threshold. In addition, the present results suggest that different transition modes to non-axisymmetric flow for tori with different aspect ratios reported in the literature may result from the wake structures prior to the transition.  相似文献   
80.
    
In this paper, a robust projection method on a locally refined mesh is proposed for two‐ and three‐dimensional viscous incompressible flows. The proposed method is robust not only when the interface between two meshes is located in a smooth flow region but also when the interface is located in a flow region with large gradients and/or strong unsteadiness. In numerical simulations, a locally refined mesh saves many grid points in regions of relatively small gradients compared with a uniform mesh. For efficiency and ease of implementation, we consider a two‐level blocked structure, for which both of the coarse and fine meshes are uniform Cartesian ones individually. Unfortunately, the introduction of the two‐level blocked mesh results in an important but difficult issue: coupling of the coarse and fine meshes. In this paper, by properly addressing the issue of the coupling, we propose a stable and accurate projection method on a locally refined staggered mesh for both two‐ and three‐dimensional viscous incompressible flows. The proposed projection method is based on two principles: the linear interpolation technique and the consistent discretization of both sides of the pressure Poisson equation. The proposed algorithm is straightforward owing to the linear interpolation technique, is stable and accurate, is easy to extend from two‐ to three‐dimensional flows, and is valid even when flows with large gradients cross the interface between the two meshes. The resulting pressure Poisson equation is non‐symmetric on a locally refined mesh. The numerical results for a series of exact solutions for 2D and 3D viscous incompressible flows verify the stability and accuracy of the proposed projection method. The method is also applied to some challenging problems, including turbulent flows around particles, flows induced by impulsively started/stopped particles, and flows induced by particles near solid walls, to test the stability and accuracy. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
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