用紫外-可见光检测器进行色谱峰的光谱分析方法

采用紫外－可见光检测器和自编吸收光谱分析程序对色谱峰在１９５～７００ｎｍ波长范围内进行扫描,得到样品和标准品的吸收光谱图,通过对二者进行比较来鉴定色谱峰纯度,操作简便,具有一定的实用价值。     

The principle of optimization of binary mobile phase composition of multi-step linear gradient elution

The basic principle of optimal method called “moving overlapping resolution mapping method” to select the optimal binary mobile phase composition of multi-step linear gradient liquid chromatography is discussed with simultaneously considering effects of position of solute inside the column and mobile phase composition on peak resolution and retention value, then a BASIC program based on this principle is developed in IBM-PC computer. The validities of both principle of optimization and BASIC program are confirmed by separation of samples containing bile acids and PAHs in RP-HPLC.     

A quantitative densitometric method for the rapid separation and quantitation of the major lipids of tissues and lipoproteins by high-performance thin-layer chromatography. II. Reduction of the densitometric data

A BASIC program is described for acquisition of data and data reduction for an automated densitometric system for quantitation of lipids separated by high-performance thin-layer chromatography. The program allows calculation of mass of samples from log/log calibration curves computed from standards. The calculated masses are reported as nmol/volume or nmol/mg protein. The program contains a flexible dialog system which permits its use for a variety of applications in addition to the system described for quantitation of lipids.     

Calculation of retention indices at an assigned temperature from temperature-programmed data

Summary A method is presented for the calculation of retention indices at an assigned temperature from temperature-programmed data. If the retention times at two different program rates for the solutes and the n-alkanes are known, the retention indices at an assigned temperature can be calculated directly.     

Computer-assisted automatic peak recognition and result evaluation for analysis of chlorinated hydrocarbons in environmental samples

A data manipulation method has been developed for automatic peak recognition and result evaluation in the analysis of organic chlorinated hydrocarbons with dual-column gas chromatography. Based on the retention times of two internal standards, pentachlorotoluene and decachlorobiphenyl, the retention times of chlorinated hydrocarbons can be calibrated automatically and accurately. It is very convenient to identify the peaks by comparing the retention times of samples with the calibrated retention times calculated from the relative retention indices of standards. Meanwhile, with a suggested two-step evaluation method the evaluation coefficients and the suitable quantitative results of each component can be automatically achieved for practical samples in an analytical system using two columns with different polarities and two internal standards.     

Prediction of retention values in linear temperature programming of narrow and mega-bore capillary columns

Retention times in linear temperature programmed gas chromatography on narrow bore and megabore capillary columns have been calculated from experimental retention times measured at three isothermal temperatures: an iterative procedure performed by BASIC programs was used to obtain the values of the constants enabling the calculation of the programmed temperature retention times. Different methods of calculation have been compared.     

Determination of monoamines and indoles in amniotic fluid by high-performance liquid chromatography-electrochemical detection.

A technique is presented for the separation and detection in amniotic fluid of various substances associated with catecholamine metabolism. Monoamines and their metabolites were separated using reversed-phase ion-pair high-performance liquid chromatography. Detection and quantification were performed electrochemically. The retention times of 28 standards associated with the monoamines and their precursors and metabolites were evaluated with 14 different eluents. On the basis of the retention times of each standard and the modification of the retention times of the various peaks detected in amniotic fluid, the following substances were identified in this biological fluid: 4-hydroxy-3-methoxyphenylacetic acid, 5-hydroxyindoleacetic acid, 3,4-dihydroxyphenylacetic acid, 4-hydroxy-3-methoxyphenylglycol, epinephrine, 4-hydroxy-3-methoxymandelic acid, octopamine, tyrosine and tryptophan.     

Gas chromatographic peak identification for polybrominated diphenyl ethers under different temperature programs

A method has been developed for gas chromatographic peak recognition of polybrominated diphenyl ethers (PBDEs) under different temperature programs. On the basis of an identification database of retention parameters (A, B values) of gas chromatography and retention times of the selected internal standards, the retention times of BDEs can be accurately estimated. In comparison with the experimental retention values, the predicted retention times have been proved to be very accurate. In addition, owing to only a part of BDE analytical standards are available, using 40 BDEs as a training set, the quantitative relationship between retention parameters of BDEs and molecular connectivity indexes has been found. The correlation coefficients are greater than 0.997. The A, B values of all the remaining 169 BDE congeners have been predicted.     

Improved theory of cyclical electrical field flow fractionation

Previously reported theories for cyclical electrical field flow fractionation (CyElFFF) are severely limited in that they do not account for diffusion, steric, or electric double layer effects. Experiments have shown that these theories overpredict the retention of particles in CyElFFF. In this work, we present a model for prediction of steric, diffusion, and electrical effects. The electrical double layer effects are treated using a lumped electrical circuit model that accounts for the field shielding by the electrical double layer formed at the electrode-carrier interface. The electrical effects are shown to dominate retention times and outweigh the contributions of diffusion and particle size. Detailed results from the simulations are presented in this work, and a comparison between the theoretical and experimental results obtained from the retentions of polystyrene particle standards is presented in this paper. The models are shown to correctly predict the retention of the polystyrene standards in CyElFFF with a reasonable error, while existing models are shown to have significant failings.     

Computation of acidity constants of a polyprotic acid from nuclear magnetic resonance or u.v.-visible spectrophotometric data

A least-squares program in BASIC is presented for the rigorous calculation of the equilibrium parameters in the dissociation of a polyprotic acid H_qA and of the spectra of all the individual species at equilibrium. The behaviour of the program is discussed for a simulated case involving n.m.r, and for a spectrophotometric study of eriochrome black T.     

A Computer Program for the Evaluation of Non-isothermal Kinetic Parameters

A program for the evaluation of non-isothermal kinetic parameters is presented. The program allows evaluation of the kinetic parameters under constant heating rate or constant reaction rate conditions. The simulation of temperature vs. conversion curves is also possible. A regression method is included, which allows a discrimination between various conversion functions and also evaluation of the activation parameters. The program was tested with various simulated decomposition curves and the non-isothermal decomposition curves of calcium oxalate. The program is written in Visual BASIC 4.0 and can be run under Windows 95 ©.     

Biochemical data-processing with microcomputers : Part 3. On-line data acquisition from a continuous flow analyzer

A program, written in BASIC, is described which allows data acquisition from a continuous flow analyzer. The program was developed for a readily available microcomputer, but should be easily modified for use on similar machines. Once the peak height has been measured, the concentration of the analyte is calculated by reference to a previously defined calibration. The program is designed to handle data from more than one channel, although there is a practical limit of 3–4 simultaneously active channels. The results of the separate assays are collated and printed as a group for each specimen, even when the analytical methods require different times for completion.     

Standardization of test conditions for high performance liquid chromatography columns

Summary Comparisons of columns, column packings and column packing methods are made difficult and sometimes invalidated by differences and inadequacies in the test procedures used and the experimental data recorded. This paper reviews test procedures and recommends standards for a) the experimental and test parameters which must be recorded in order to enable comparisons to be made from laboratory to laboratory, b) the group of chromatographic parameters which best represent column performance for comparative purposes, with methods for their calculation, c) test solutes and eluents for some different types of packing materials. A computer program in BASIC is given which converts the experimental parameters into relevant chromatographic parameters.     

Application of optimization procedures for the separation of anabolic compounds by high-performance liquid chromatography

A simple systematic approach is presented for optimizing high-performance liquid chromatographic separations of anabolics with multi-component isocratic mobile phases. A computer program was obtained and adjusted for use with an IBM-compatible XT personal computer. The program requires experimental retention data with three quaternary solvent mixtures to calculate the optimum solvent composition using a geometric model of a prism. For each possible composition of the mobile phase the set of retention data can be calculated. Applications are shown for mixtures of anabolic compounds using a mobile phase composed of methanol, tetrahydrofuran and acetonitrile. The predicted retention data agreed very well with the experimental data.     

Identification of the electrophoretic peaks of the phenylthiohydantoin derivatives of amino acids

Two techniques for identifying the peaks of phenylthiohydantoin (PTH) amino acids separated under the conditions of micellar electrokinetic chromatography were compared. The first technique is linear regression analysis, in which the retention time of an amino acid is a function of the retention times of two retention-time standards. The second technique takes into account hydrophobicity constants logD′, which were calculated using the ACD/LC Simulator 8.0 program package from ACDLabs (Canada). These constants provide an opportunity to calculate the relative migration times of PTH amino acids taking into account the velocity of the electroosmotic flow. The first technique allows us to identify the electrophoretic peaks of all 16 amino acids separated; the second procedure allows us to predict the elution order of the electrophoretic peaks; the use of a correlation equation gives better results.     

Microcomputer simulation of the countercurrent liquid-liquid distribution

The simulation of the countercurrent liquid-liquid distribution by using a microcomputer is described. The computer program that is proposed for this simulation has been made in BASIC language and its characteristics are discussed. According to the wide possibility of calculation that this program presents, several simulations of different solute mixtures have been performed.     

Novel gas chromatography-mass spectrometry database for automatic identification and quantification of micropollutants

A novel gas chromatography-mass spectroscopy (GC-MS) database for identification and quantification of micropollutants in environmental and food samples is reported. GC retention times, calibration curves, and mass spectra of nearly 700 chemicals were registered in the database, and the GC retention times of registered chemicals in actual samples were predicted from the retention times of n-alkanes measured before sample analysis. Differences between predicted and actual retention times were less than 3 s, an accuracy that is nearly identical to that obtained by analysis of standard substances. After the retention times were predicted, a calibration file for the GC-MS instrument was created from the predicted retention times, calibration curves, and mass spectra of the registered chemicals. With the resulting calibration file, automated identification of all the chemicals in actual samples was possible without the use of standards, and the identification method was as reliable as conventional methods. When the GC inlet, column, and tuning conditions were adjusted using GC-MS performance check standards, relative standard deviations of 20% or less for determination values could be obtained. More than 90% of the chemicals in the database could be detected at a sensitivity sufficient for all practical purposes (100 pg or less). Because each chemical in the database, to which new substances can easily be added, can be determined in 1 h, micropollutants in samples can be analyzed efficiently and inexpensively.     

Dicholorbenzyl alkyl ether homologs as retention index markers and internal standards for the analysis of environmental samples using capillary gas chromatography

A homologous series of 2,4-dichlorobenzyl alkyl ethers (DCBEs) have been synthesized and purified for use as retention index calibrants and internal standards. They are stable, sensitive to ECD and FID and ideal for GC-MS, with base peaks at m/z 159/161. The retention index calibration against the n-alkanes for a linear temperature program (LTP) series is given and recommendations made for the most suitable members of the DCBE series for use as internal standards in organochlorine (OC) residue analysis.     

Automated fatty acid analysis.

An automated system for the analysis of fatty acids is described. Samples dissolved in CS2 are automatically injected and separated by temperature programmed gas chromatography. Peak areas and retention times were measured by an electronic integrator, and recorded on punched paper tape. Peaks are identified and amounts calculated by an off-line computer program based on one or more internal standards. The system is designed for use with samples of at least 10 mug. Some of the problems adn limitations are discussed.