High performance liquid chromatographic determination of N-nitrosoamines by pre-column fluorescence derivatization with acridone-N-acetyl chloride

A sensitive high performance liquid chromatographic method for the determination of N-nitrosoamines with pre-column fluorescence derivatization has been developed. N-nitrosoamines are first changed into secondary amines using denitrosation reagent, then react with acridone-N-acetyl chloride (ARC-Cl) to produce corresponding secondary amine derivatives, which exhibit a strong fluorescence. Maximum emission for ARC derivatives is 430 nm (lambda(ex) 404 nm). The labelled derivatives are very stable, less than 4% decomposition occurs after heating at 40 degrees C for 24 h. Fluorescence intensities of derivatives are higher in neutral and alkaline than in acidic solutions. This method, in conjunction with a multi-gradient program, offers a baseline resolution of the ARC derivatives from a linear acetonitrile gradient. Separation is carried out on a reverse phase C(18) column. Derivatization and chromatographic conditions are optimized. The relative standard deviation (n=6) at an analytical concentration of 10 pmol of each N-nitroamine is less than 4.5%. The detection limits at the fmol level. The method described is also suitable for analysis of other amino compounds in different biological samples.     

THREE-DIMENSIONAL VISCOUS FLOW THROUGH A ROTATING CHANNEL: A PSEUDOSPECTRAL MATRIX METHOD APPROACH

A Fourier–Chebyshev pseudospectral method is used for the numerical simulation of incompressible flows in a three-dimensio nal channel of square cross-section with rotation. Realistic, non-periodic boundary conditions that impose no-slip conditions in two directions (spanwis e and vertical directions) are used. The Navier–Stokes equations are integrated in time using a fractional step method. The Poisson equations for pressure and the Helmholtz equation for velocity are solved using a matrix diagonalization (eigenfunction decomposition) method, through which we are able to reduce a three-dimensional matrix problem to a simple algebraic vector equation. This results in signficant savings in computer storage requirement, particularly for large-scale computations. Verification of the numerical algorithm and code is carried out by comparing with a limiting case of an exact steady state solution for a one-dimensional channel flow and also with a two-dimensional rotating channel case. Two-cell and four-cell two-dimensional flow patterns are observed in the numerical experiment. It is found that the four-cell flow pattern is stable to symmetri cal disturbances but unstable to asymmetrical disturbances.     

旋量值函数的Plemelj公式

对比于多复变中的Bochner-Martinelli型积分的Plernelj公式,定义了艾米尔特Clifford分析中旋量值函数的Cauchy型积分及Cauchy主值积分,得到了旋量值函数的Plemelj公式,最后给出一些特殊情形的Bochner-Martinelli型积分的Plemelj公式.     

Study of the chromatographic behavior and inclusion constants of new fluorescence agents by use of cyclodextrin additives under conditions of steady- and dynamic-state equilibrium and with fluorescence detection

Summary We report four new derivatization agents, acridone-N-acetic acid (ARC), carbazole-9-ylacetic acid (CRA), carbazole-9-ylpropionic acid (CRP), and 2-methyl-2-carbazole-9-ylacetic acid (MCRA), with strong fluorescence emission which has low dependence on solvent polarity. The emission maxima for ARC, CRA, CRP, and MCRA were 430 nm (λ_ex 404 nm), 368 nm (λ_ex 335 nm), 356 nm (λ_ex 340 nm) and 360 nm (λ_ex 330 nm), respectively. The effects of mobile-phase composition, pH, and temperature on the liquid chromatographic retention behavior of the four fluorescence agents were investigated. An experimental model was established for calculating the inclusion constants of cyclodextrin (CD) complexes in the dynamic state, using β-cyclodextrin (β-CD) and hydroxypropyl-β-cyclodextrin (HP-β-CD) as examples, and different mobilephase compositions. On the basis of the model, the inclusion constants of the solutes in pure water (K _fw) were determined by extrapolation. The thermodynamic parameters (ΔH ^o and ΔS ^o) and dissociation constantsK _am for the solutes in this chromatographic system were obtained by means of capacity factor (k) values using a corresponding model formulation.     

A simple and mild derivatization method for hydroxyl compounds using condensation agent carbazole-9-N-(2-methyl)-acetyl-benzene-disulfonate and its application for the determination of volatile alcohols from plasma by HPLC with fluorescence detection

A simple and sensitive HPLC method for the determination of hydroxyl compounds including volatile alcohols from spiked plasma, using a fluorescent condensation agent, namely carbazole-9-N-(2-methyl)-acetyl-benzene-disulfonate (CMABS), has been developed. A mixture of alcohols and pyridine in dichloromethane was treated with CMABS to give a quantitative yield of esters. The maximum fluorescence emissions for the derivatized alcohols are at 365 nm (λ_ex 335 nm). Studies on derivatization conditions indicate that alcohols react very fast with CMABS in presence of pyridine in dichloromethane to give the corresponding fluorescent derivatives. The method, in conjunction with a multi-step gradient, offers a baseline resolution of the common alcohol derivatives on a reversed-phase C₁₈ column, which is more convenient and more efficient than previous methods which require the prior conversion of the carboxylic acids to the acyl chlorides. The application of this method to the analysis of volatile alcohols in plasma was also investigated. The LC separation shows good selectivity and reproducibility for alcohol derivatives. The relative standard deviations ?(n = 5) for 100 pmol of each alcohol are < 4%. The detection limits are at the fmol level for C₁–C₃ alcohols and pmol level for C₄–C₉ alcohols. Received: 9 November 1998 / Revised: 3 May 1999 / Accepted: 6 May 1999     

MgB2超导薄膜正常态电阻特性研究

研究了MgB2超导薄膜正常态电阻的影响因素,探讨了与之相应的超导电性机制。MgB2超导薄膜样品采用两步异位退火的Mg扩散方法制备,通过电阻~温度曲线测量、扫描电子显微镜形貌观测和光学金相显微镜观察等方法研究了所制备薄膜的基本特性。实验结果表明,先驱硼薄膜的纯度严重影响着所生成的MgB2超导薄膜的转变温度,退火温度越高,影响越大;退火温度高的样品,正常态电阻大;退火时间长的样品正常态电阻大。