Overloaded elution band profiles of ionizable compounds in reversed‐phase liquid chromatography: Influence of the competition between the neutral and the ionic species

The parameters that affect the shape of the band profiles of acido‐basic compounds under moderately overloaded conditions (sample size less than 500 nmol for a conventional column) in RPLC are discussed. Only analytes that have a single pK_a are considered. In the buffer mobile phase used for their elution, their dissociation may, under certain conditions, cause a significant pH perturbation during the passage of the band. Two consecutive injections (3.3 and 10 μL) of each one of three sample solutions (0.5, 5, and 50 mM) of ten compounds were injected on five C₁₈‐bonded packing materials, including the 5 μm Xterra‐C₁₈ (121 Å), 5 μm Gemini‐C₁₈ (110 Å), 5 μm Luna‐C₁₈(2) (93 Å), 3.5 μm Extend‐C₁₈ (80 Å), and 2.7 μm Halo‐C₁₈ (90 Å). The mobile phase was an aqueous solution of methanol buffered at a constant _W^WpH of 6, with a phosphate buffer. The total concentration of the phosphate groups was constant at 50 mM. The methanol concentration was adjusted to keep all the retention factors between 1 and 10. The compounds injected were phenol, caffeine, 3‐phenyl 1‐propanol, 2‐phenyl butyric acid, amphetamine, aniline, benzylamine, p‐toluidine, procainamidium chloride, and propranololium chloride. Depending on the relative values of the analyte pK_a and the buffer solution pH, these analytes elute as the neutral, the cationic, or the anionic species. The influence of structural parameters such as the charge, the size, and the hydrophobicity of the analytes on the shape of its overloaded band profile is discussed. Simple but general rules predict these shapes. An original adsorption model is proposed that accounts for the unusual peak shapes observed when the analyte is partially dissociated in the buffer solution during its elution.     

Modification of Spatial Coherence by Means of Low-Order Zernike-Mode Adaptive Optics

Spatial coherence of the field modified by low-order adaptive optics is analyzed to establish a theoretical basis for the recent idea of using adaptive optics as a spatial coherence modifier. In this context low-order adaptive optics has the ability to correct some of the low-order aberrations specified by Zernike polynomials. The initial field to be modified is assumed to be a spatially partially coherent one resulting from phase disturbance. It is demonstrated, as in the previous study, that low-order adaptive optics serves to enhance the spatial coherence of the resultant field and that the effect of the enhancement becomes stronger as the spatial coherence of the initially partially coherent field increases. Potential applications of low-order adaptive optics as a spatial coherence modifier are briefly discussed.     

The spectrum of cyclic BSA(ν, 3, λ; α) with α = 2, 3

Balanced sampling plans excluding contiguous units (or BSEC) were first introduced by Hedayat, Rao, and Stufken in 1988. In this paper, we generalize the concept of a cyclic BSEC to a cyclic balanced sampling plan to avoid the selection of adjacent units (or CBSA for short) and use Langford and extended Langford sequences to construct a cyclic BSA(ν, 3, λ; α) with α = 2, 3. We finally establish the necessary and sufficient conditions for the existence of a cyclic BSA(ν, 3, λ; α) where α = 2, 3. © 2005 Wiley Periodicals, Inc. J Combin Designs.     

Computation of the eigenvalues of Sturm-Liouville problems with parameter dependent boundary conditions using the regularized sampling method

The purpose in this paper is to compute the eigenvalues of Sturm-Liouville problems with quite general separated boundary conditions nonlinear in the eigenvalue parameter using the regularized sampling method, an improvement on the method based on Shannon sampling theory, which does not involve any multiple integration and provides higher order estimates of the eigenvalues at a very low cost. A few examples shall be presented to illustrate the power of the method and a comparison made with the the exact eigenvalues obtained as squares of the zeros of the exact characteristic functions.

     

Discretization and resolution of the (<Emphasis Type="Italic">r</Emphasis>|<Emphasis Type="Italic">X</Emphasis><Subscript><Emphasis Type="Italic">p</Emphasis></Subscript>)-medianoid problem involving quality criteria

In this paper an extension of the (r|X _p )-medianoid on networks introduced by Hakimi (1983) is studied. In this extension the customer considers not only the distance but some characteristics of the facilities such as store size, quality of service and parking space. A new firm wants to establishr new facilities which have to compete with thep facilities that already exist in the market. The entry firm wants to find their locations and characteristics to maximize profits. Three different customer choice rules (binary, partially binary and proportional preferences) are considered. Some discretization results are obtained and a resolution procedure is proposed. The problem is solved combining a global search algorithm based on a branch and bound procedure with some combinatorial heuristics (greedy, interchange, and tabu search). Some computational experiences are presented. Partially supported by Ministerio de Ciencia y Tecnología (Spain) and FEDER, grant BFM2002-04525-C02-01.     

钢球质量监测最佳抽检方案的确定

本文介绍概率抽样法在钢球生产过程中的应用,通过此法确定钢球生产中各工序质量监测的最佳抽检方案,以确保产品被接受的概率最大。     

On the Solution of Discontinuous IVPs by Adaptive Runge–Kutta Codes

In this paper an automatic technique for handling discontinuous IVPs when they are solved by means of adaptive Runge–Kutta codes is proposed. This technique detects, accurately locates and passes the discontinuities in the solution of IVPs by using the information generated by the code along the numerical integration together with a continuous interpolant of the discrete solution. A remarkable feature is that it does not require additional information on the location of the discontinuities. Some numerical experiments are presented to illustrate the reliability and efficiency of the proposed algorithms.     

Determination of styrene in olive oil by an automatic purge-and-trap system coupled to gas chromatography-mass spectrometry

Summary A new gas chromatographic method using an automatic purge-and-trap system coupled to a GC with mass selective detection to analyze styrene at the parts-per-trillions (ng kg^–1) level is described. The method shows a good sensitivity and the detection limit is 10 ng kg^–1 with a relative standard deviation (RSD) of 4.7% for 164 ng kg^–1 styrene in olive oil. This analytical method has been successfully applied to the analysis of styrene in extra-virgin olive oil from the European market.     

t—BuNO二聚体在不同溶剂中裂解机理的研究

本文利用＾１ＨＮＭＲ，ＵＶ－Ｖｉｓ方法，研究了ｔ－ＢｕＮＯ二聚体在有机溶剂及水溶液中的裂解反应产物，分析了其反应的动力学，提出了在非极性的有机相中ｔ－ＢｕＮＯ二聚体为均裂反应，而在极性的水相中为均裂和异裂同时进行的竞争反应。     

GS-221高速摄影测量仪测角信息的采集与处理

在GS-221高速摄影测量仪中,测角信息采集与处理速度的快慢是重要性能指标之一。本文讨论了如何在尽可能短的时间内对测角信息进行采集和处理的软件实现方法。