A new gas chromatographic retention index for pesticides and related compounds

A new gas chromatographic (GC) retention index based on a homologous series of tri-n-alkylamines is proposed for use in the detection of pesticides and related compounds because the standard n-paraffin hydrocarbons used for the Kovats index do not show up well on the nitrogen-phosphorus detectors commonly used in pesticide analysis. Using fused silica bonded phase capillary columns (DB-1 or DB-5), the trialkylamine indices of 106 selected pesticides and related compounds were measured and their relationship to the Kovats index determined.     

HPLC Retention Index Scale for Nitrogen-Bridged Compounds

Abstract

Retention indices of some nitrogen-bridged compounds having pharmacological activity have been determined. A retention index scale based on the relative retention of a homologous series of C₃-C₂₃ 2-keto alkanes has been worked out. Linear relationships were found between RI and logP, allowing a prediction of retention indices.

The relationships between the structures and the retention indices of these compounds have been interpreted.     

GC behaviour of symmetrical n-dialkyl sulphides under isothermal and temperature programming conditions

Retention indices were determined for a homologous series of n-dialkyl sulphides on three stationary phases (SE-30, OV-17 and XE-60) under isothermal and linear temperature programming conditions. Under these two different GC conditions, equations were derived for each of the three stationary phases which showed the dependence of retention index on the number of carbon atoms and the boiling points for a homologous series of n-dialkyl sulphides. The equation for the correlation isothermal retention index was shown to be applicable to the identification of n-dialkyl sulphides using linear temperature programming. It was found that the GC behaviour of n-dialkyl sulphides makes these compounds suitable for use as a standard series instead of n-alkanes for the calculation of retention indices in GC analysis in which detectors insensitive to n-alkanes are employed. The use of the homologous series of n-dialkyl sulphides for the calculation of sulphide retention indices can be great practical importance in the microanalysis of natural compounds. We have used this method successfully in the analysis of pesticides containing S-atoms.     

Kovats and lee retention indices determined by gas chromatography/mass spectrometry for organic compounds of environmental interest

Retention indices of standard organic compounds of environmental interest were determined by gas chromatography/mass spectrometry, using a DB-5 fused-silica capillary column. Retention indices are useful references for tentative compound identification by gas chromatography, or confirmation by gas chromatography/mass spectrometry. They provide elution order for isomers that might be indistinguishable based on mass spectra. Modified Kovats and Lee retention indices are given for polycyclic aromatic hydrocarbons; sulfur heterocycles; nitrogen heterocycles; aromatic amines; oxygen heterocycles; phenols; alcohols; ketones; alkanes; nitriles; and methylesters of fatty, dicarboxylic, and aromatic acids for comparison and reference. Retention index values for heterocycles by gas chromatography/mass spectrometry are comparable with gas chromatography values previously reported.     

Prediction of gas chromatographic retention indices of polychlorinated dibenzothiophenes on non-polar columns

Polychlorodibenzothiophenes (PCDTs) have been found in several kinds of environmental samples. The lack of reference compounds has meant that very little is known about their gas chromatographic behavior. Here we discuss the retention of 19 authentic PCDTs and their sulfones on the widely used gas chromatographic stationary phases DB-5 and DB-5ms. The retention order is different from that of the polychlorodibenzofurans. The data generated allowed us to carry out a multiple linear regression to generate parameters for predicting the retention indices of unknown congeners based only on their structural features.     

Retention index calculation without n-alkanes--the virtual carbon number

For the fast gas chromatographic identification of separated components the retention index is still one of the most often used tools, although mass spectrometry is available in almost all analytical laboratories. For the calculation of the retention indices it is not necessary to use n-alkanes or any other homologous series. If the analyte contains some compounds, not necessarily belonging to a homologous series, with well-known retention indices those compounds can be used as index references and the index of the other compounds can be calculated as is done using n-alkanes. The only difference is that instead of the carbon number of the n-alkanes, virtual carbon numbers of the reference compounds should be used. The method of calculation, and the effect of this method of calculation on the reproducibility are discussed in this paper, and analyses of some halogenated compounds and marjoram oil are used as experimental examples.     

Retention index database for identification of general green leaf volatiles in plants by coupled capillary gas chromatography-mass spectrometry

A series of ubiquitously occurring saturated and monounsaturated six-carbon aldehydes, alcohols and esters thereof is summarised as ‘green leaf volatiles’ (GLVs). The present study gives a comprehensive data collection of retention indices of 35 GLVs on commonly used non-polar DB-5, mid-polar DB-1701, and polar DB-Wax stationary phases. Seventeen commercially not available compounds were synthesised. Thus, the present study allows reliable identification of most known GLV in natural plant volatile samples. Applications revealed the presence of several seldom reported GLVs in headspace samples of mechanically damaged plant leaves of Carpinus betulus and Fagus sylvatica.     

Copolymer of Di (methacryloyloxymethyl) naphthalene and divinylbenzene as a column packing for high-performance liquid chromatography

Summary A new porous polyaromatic ester packing was synthetized for high performance liquid chromatography. The relationship between retention and chain length of the members of homologous series of alkylbenzenes, N-alkylanilines, alkylarylethers, alkylbenzoates and alkylarylketones on this new stationary phase using different eluents was investigated. Using the alkylarylketone scale the retention indices of the homologues and test compounds were calculated. The results were compared with those obtained for poly (styrene-divinylbenzene) polymers. For both types of packing the first members of each homologous series gave non-linear behaviour. The methylene group index increments are different for the studied homologous series; thus there is no simple additivity of the retention indices. The efficiency of the porous polymeric columns is a function of the capacity factor of the solute and the organic component of the eluent.     

Forming taxonomic groups of organic compounds for calculating gas-chromatographic retention indices from physicochemical constants

The traditional approach to calculations of gas-chromatographic retention indices from physicochemical constants of organic compounds in homologous series does not encompass all possible objects. Forming different taxonomic groups of compounds by variations in the formal unsaturation, the number of atoms of different elements within molecules, or any complex fragments of structure/composition makes it possible to calculate unknown retention indices by several independent methods from different arrays of initial data. The application of simple three-parameter equations provides an accuracy comparable to the modern interlaboratory error of determination of retention indices for any compounds. St. Petersburg State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 6, pp. 176–182, November–December, 1994. Translated by L. Smolina     

Retention factor and retention index of homologous series compounds in microemulsion electrokinetic chromatography employing suppressed electroosmosis

The retention factor (k) and retention index (I) of homologous series compounds such as alkylbenzenes (BZ), alkylaryl ketones, alkylbenzoates, and alkylparabens in microemulsion electrokinetic chromatography (MEEKC) with suppressed electroosmosis were investigated in a wide range of SDS concentrations ([SDS]), temperatures, and concentrations of organic cosolvents (phi). Using BZ as standards, the retention indices of other homologous series compounds were determined and they were found to be independent of [SDS] and temperature, while are dependent on the types and concentrations of organic cosolvents. The retention factor linearly increases with increasing [SDS], while linearly decreases with increasing temperature. The value of log k linearly decreases with increasing phi for methanol, ethanol, or ACN, while decreases by a second-degree polynomial with increasing phi for 2-propanol. Excellent agreement was found between the observed and predicted values of log k of analytes in MEEKC at given [SDS] and phi, where the predicted values were obtained from modified equations of the linear relationship of log k as functions of [SDS], the number of carbons, and phi. Therefore, both k and I can be used for peak identification of homologous series compounds.     

Gas chromatographic separation of PF3 substituted group 6 metal carbonyl complexes using serially-coupled capillary columns

The retention of group 6 metal trifluorophosphine carbonyl compounds in serially-coupled gas capillary columns has been studied as a function of different column configurations. For the trifluorophosphine-substituted Mo, W, and Cr carbonyls, as well as the analogous Fe compounds, it was observed that the maximum resolution achievable by the coupled column technique was dependent on the order in which the nonpolar (DB-1) and moderately polar (DB-1701) columns were connected. The optimum configuration was different, however, for each series M(PF₃)_x(CO)_6?x(M = Cr, Mo, or W) or Fe(PF₃)_x(CO)_5?x. It was also observed that the use of coupled columns of dissimilar polarity can, in some cases, actually decrease resolution relative to that obtained by coupled identical columns (i. e. DB-1 + DB-1, or DB-1701 + DB-1701).     

直链单炔烃保留指数与分子结构关系研究

根据同系直链单炔烃保留指数与同碳数正构烷烃保留指数差值与分子碳数间关系曲线拟合，提出预测同系直链单炔烃保留指数的较准确公式。研究并发现同碳数直链单炔烃各异构体分子中三键位置与化合物保留指数具有指数关系，首次提出了据分子中三键位置预测其保留指数的较准确公式。解决了从低碳数直链单炔烃保留指数预测高碳数直链单炔烃保留指数问题。     

Analysis of chemical warfare agents. II. Use of thiols and statistical experimental design for the trace level determination of vesicant compounds in air samples

Thermal desorption with gas chromatography-mass spectrometry (TD-GC-MS) remains the technique of choice for analysis of trace concentrations of analytes in air samples. This paper describes the development and application of a method for analysing the vesicant compounds sulfur mustard and Lewisites I-III. 3,4-Dimercaptotoluene and butanethiol were used to spike sorbent tubes and vesicant vapours sampled; Lewisite I and II reacted with the thiols while sulfur mustard and Lewisite III did not. Statistical experimental design was used to optimise thermal desorption parameters and the optimum method used to determine vesicant compounds in headspace samples taken from a decontamination trial. 3,4-Dimercaptotoluene reacted with Lewisites I and II to give a common derivative with a limit of detection (LOD) of 260 microg m(-3), while the butanethiol gave distinct derivatives with limits of detection around 30 microg m(-3).     

Retention indices as identification tool in pyrolysis-capillary gas chromatography

Pyrolysis-capillary gas chromatography (Py-cGC) represents important method to identify the analytes in the mixture after thermal degradation. This combines high effective analyte separation on-line coupled with thermal degradation process that depends on analyte structure. System of retention indices has been used for identification of the analytes after on-line pyrolysis and chromatographic separation. The pyrolysate composition has been studied during thermal degradation of polymethylmethacrylate (PMMA) at different pyrolysis temperatures and chromatographic column conditions. Homologues series of n-alkanes have been used for calculation of pyrolysate Kováts retention indices (I) and compared with mass spectrometric (MS) data of pyrolysate model mixture. To identify PMMA thermal degradation products the high density polyethylene (HDPE) as additive standard producing triplets of the olefin homologous series during co-pyrolysis has been used. These homologous series enable to calculate programmed temperature retention indices (ITPGC) to identify the analytes present in the pyrolysate. Calculated I values were compared with published I values databases to identify analytes yielded at different pyrolysis temperatures.     

The advantage of dual-column approach and retention indices combined with refined reporting in gas chromatographic drug screening

A dual-column gas chromatographic retention index method was evaluated for the toxicological screening for basic drugs in autopsy blood samples. The dual-column approach with DB-5 and DB-1701 capillary columns doubles the Identification Power of the corresponding single column methods. The long-term intralaboratory variation of the dialkylfluoroaniline series based retention indices of drugs in blood ranged from 0.03% to 0.2% which was generally better than that obtained using the relative retention time. Novel software is described for the processing and reporting of the dual-column chromatographic data in analytically useful form. Besides retention data, the response factors served as an additional identification factor.     

Use of Retention Data as the First Step in the Identification of Cyclic Organic Peroxides in Temperature-Programmed Gas Chromatography

Temperature-programmed retention indices for eleven cyclic organic peroxides were determined by gas chromatography on slightly polar 5% biphenyl 95% dimethylpolysiloxane columns (DB-5 and Rtx-5MS) at three heating rates (5, 10, and 20° min⁻¹) from 60 to 300°C, using different chromatographs. Cyclic organic diperoxides and triperoxides had nearly constant retention indices when different heating rates and a short isothermal hold time (5 min) before the programmed increase in temperature were used. The usefulness of temperature-programmed retention indices was shown by using the data to predict the retention times and structures of unknown diperoxides or triperoxides derived from ketones. This is the first step in the identification of unknown cyclic organic peroxides, a process would otherwise require the availability of reference compounds. Revised: 7 and 17 November 2005     

Gas chromatographic separation of substituted pyridines

Capillary gas chromatographic methodology for separation of complex mixtures of substituted pyridines has been demonstrated on polar (CAM) and non-polar (DB-5) columns. Separations are characterized by high resolution, high sensitivity, a wide dynamic detector range, and good reproducibility. For the first time, Kováts retention indices have been calculated for pyridine and substituted pyridines. Correlations of retention indices with physico-chemical properties, such as hydrogen bonding, pyridine pKa and Hammett substituent constants are discussed.     

Structural regularities governing sorption and gas chromatographic retention of aromatic nitrogen-containing heterocyclic compounds

The regularities governing differences in the gas chromatographic retention indices of aromatic nitrogen-containing heterocyclic compounds were studied during gas chromatographic analysis on a nonpolar capillary column. The retention indices of pyrrole, pyrazole, imidazole, 1,2,4-triazole, oxazole, thiazole, isoxazole, pyridine, pyridazine, pyrimidine, pyrazine, ands-triazine and their alkyl derivatives depend on the number, nature, and arrangement of heteroatoms and alkyl groups in the cycles. The majority of homologous series ofn-alkyl-substituted azoles and azines andn-alkylbenzenes is characterized by anomalously high differences between the retnetion indices of ethyl and methyl homologs. A scheme of calculation of retention indices of aromatic heterocyclic compounds from increments of heteroatoms was proposed.     

Use of the hexane-2,2,2-trifluoroethanol system in partition chromatography

The use of the hexane-2,2,2-trifluoroethanol heterophase system of solvents in partition chromatography is characterized. Gas-chromatographic retention indices and partition coefficients are used for the identification of organic compounds in this technique. The partition coefficients of compounds from 12 homologous series were measured in this heterophase system, and parameters for their group identification were calculated. The examples of the use of this system for solving different analytical problems are considered.     

The analysis of C4–C11 hydrocarbons in naphtha and reformate with a new apolar fused silica column

This paper deals with the separation of alkanes, naphthenes, and aromatic compounds in naphtha and reformate, on a newly developed apolar high resolution GC column. The selectivity of this apolar phase has been compared with those of squalane, DB-1, and SE-30. A total of 95 hydrocarbons were reliably identified, mostly by GC-MS. Repeated measurements of Kováts retention indices are presented as evidence for the reproducible manufacture of fused silica columns coated with this phase.