CORRELATION-ANALYSIS IN STRUCTURE AND CHROMATOGRAPHIC DATA OF ORGANOPHOSPHORUS COMPOUNDS BY GAI

This approach is undertaken to examine the correlation ability of the general a(N)-index (GAI) to predict chromatographic behavior. The test is performed on various types of organophosphorus compounds. The results demonstrate that the GAI possesses a good correlation with chromatographic properties.

Quantitative relationship between chromatographic retentions and molecular structures of polychlorinated dibenzo-p-dioxins (PCDDs)

A new approach to study the quantitative relationships between chromatographic retentions and molecular structures of polychlorinated dibenzo-p-dioxins (PCDDs) is described. The retention equations of PCDDs log k' = A + B/T in gas chromatography (GC) are used to evaluate the properties of the regression coefficients A and B, which have been widely accepted as highly reliable chromatographic retentions. The quantitative relationships between the A, B values and the molecular structures are found. The molecular descriptors given for the first time in this article are very effective. As a result, the regression equations are derived with correlation coefficients greater than 0.9995. The A, B values of PCDDs with no standards available have been predicted according to these relationships. They are very useful in chromatographic identification. The retention times of all PCDDs can be conveniently predicted at any temperature program. Compared with the data obtained from the relevant experiments, the results of prediction are very accurate. (C) 2000 Elsevier Science Ltd. All rights reserved.

A new method of predicting of gas chromatographic retention indices for polychlorinated dibenzofurans (PCDFs)

A new method has been developed to describe the quantitative relationship between molecular structures of PCDFs and their gas chromatographic retention indices on a 30-m fused silica column coated with DB-5 stationary phase. The regression equation is derived with a multiple correlation coefficient greater than 0.9995. The highest residual is 20 index units. The standard deviation is less than 7 index units. Using this regression equation, the retention indices of PCDFs for which data is not available have also been predicted. (C) 2000 Elsevier Science Ltd. All rights reserved.

Determination of alcohols by high-performance liquid chromatography with fluorimetric detection after pre-column derivatisation with carbazole-9-N-acetic acid and chromatographic behaviour of alcoholic derivatives

Alcohols were derivatised to their carbazole-9-N-acetic acid (CRA) esters with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC . HCl) as the dehydrating agent. Studies on derivatisation conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives. The retention behaviour of alcohol derivatives was investigated by varying mobile phase compositions (ACN-water and MeOH-water). The parameters from the equation log k'=A-BX were evaluated by retention data of derivatives using an isocratic elution with different mobile phases. The results indicated that the parameters derived allowed computation of retention factors in good agreement with experiments. At the same time, a general equation was derived that makes possible predictions of partition coefficient in binary mobile phases with different proportions of organic solvent to water based on some simple regression analysis. The LC separation for the derivatised alcohols containing higher carbon alcohols showed good reproducibility on a reversed-phase C-18 column with gradient elution. The detection limits (excitation at 335 nm, emission at 360 nm) for derivatised alcohols (signal-to-noise ratio=3:1) were in the range of 0.1-0.4 pg per injection. (C) 2001 Elsevier Science B.V. All rights reserved.

Reversed-phase high-performance liquid chromatographic investigation of urinary normal and modified nucleosides of cancer patients

Post-transcriptional modifications in RNA give rise to free modified ribonucleosides circulating in the blood stream and excreted in urine. Due to their abnormal levels in conjunction with several tumor diseases, they have been suggested as possible tumor markers. The developed RP-HPLC method has been applied to analyze the urinary nucleosides in 34 urinary samples from 15 kinds of cancer patients. The statistical analyses showed the urinary nucleoside excretion, especially modified nucleoside levels, in cancer patients were significantly higher than those in normal healthy volunteers. Factor analysis was used to classify the patients with cancer and normal healthy humans. It was found that using 15 urinary nucleoside levels or only five modified nucleoside levels as data vectors the factor analysis plot displayed two almost separate clusters representing each group. (C) 1999 Elsevier Science B.V. All rights reserved.

Evaluation of nonlinear chromatographic performance by frontal analysis using a simple multi-plate mathematical model

A multi-plate (NIP) mathematical model was proposed by frontal analysis to evaluate nonlinear chromatographic performance. One of its advantages is that the parameters may be easily calculated from experimental data. Moreover, there is a good correlation between it and the equilibrium-dispersive (E-D) or Thomas models. This shows that it can well accommodate both types of band broadening that is comprised of either diffusion-dominated processes or kinetic sorption processes. The MP model can well describe experimental breakthrough curves that were obtained from membrane affinity chromatography and column reversed-phase liquid chromatography. Furthermore, the coefficients of mass transfer may be calculated according to the relationship between the MP model and the E-D or Thomas models. (C) 2004 Elsevier B.V. All rights reserved.