Gas chromatography-mass spectrometry analysis of alkylphenols in produced water from offshore oil installations as pentafluorobenzoate derivatives

A simple, highly selective and sensitive method for the determination of 14 representative alkylphenols from phenol (C0) to nonylphenol (C9) in produced water is described. Solid-phase extraction (SPE) by anion-exchange sorbent is used to extract alkylphenols from produced water. The samples are then derivatised by pentafluorobenzoyl chloride and analysed on GC-MS (negative ion chemical ionisation, NCI). The derivatisation procedure has been validated by means of two-level factorial design (2(7-4)) experiments. Quantification is done with isotope dilution of five internal standards of different alkyl chain length. The detection limits were at low ng/l levels. A comparison with GC-MS analysis of non-derivatised alkylphenol samples revealed the advantage of derivatisation as described in the method.     

Gas chromatography-mass spectrometry analysis of alkylphenols in cod (Gadus morhua) tissues as pentafluorobenzoate derivatives

A highly selective and sensitive method for the determination of 30 meta- and para-substituted alkylphenols from phenol (C0) to nonylphenol (C9) in biota is described. Dichloromethane extracts of spiked cod liver and muscle samples are cleaned up by gel permeation chromatography, derivatised with pentafluorobenzoyl chloride and analysed by gas chromatography-mass spectrometry with negative-ion chemical ionisation. Quantification is done with isotope dilution of five internal standards of different chain length. The detection limits were in the low microg/kg levels. There were encountered problems with background levels of 4-nonylphenol. 4-Nonylphenol isomers were found in a number of plastic and rubber products used in the laboratory.     

烷基苯酚类化合物的气相色谱保留值与其结构参数的定量关系

计算了44个烷基苯酚类化合物的组成、拓扑、几何、静电和量子化学等结构参数,运用启发式方法对这些结构参数进行筛选,得到了含3个变量的化合物的定量结构与色谱保留值的线性关系模型,同时以这3个变量作为支持向量机模型的输入变量建立非线性回归模型。两种方法的相关系数(R2 )分别为0.98和0.92,相应的均方根误差分别是0.99和2.77。通过对两种模型的稳定性和预测能力的比较,发现线性模型能够更好地反映烷基苯酚的气相色谱保留值与其结构参数之间的定量关系。在已知烷基苯酚类化合物结构参数的情况下,线性回归模型更有助于它们的色谱分析。     

Gas chromatographic system for the identification of halogenated pesticides by retention indices using n-alkanes as standards

A gas chromatographic system for the evaluation of linear temperature-programmed retention indices allowing n-alkanes to be adopted as the reference retention markers for any type of analyte, irrespective of the atoms present in their molecules, is described. It is based on the simultaneous use of two different detectors (a flame ionization detector and a specific detector suitable for the sample components), both connected (in parallel) to the same column outlet. The performance of this system has been tested by measuring the retention indices of fifteen chlorinated pesticides under conditions of linear programming temperature, by adopting an electron-capture detector as the specific detector. The reliability of the retention indices thus determined has been proven by verifying that they can be reproduced under different chromatographic conditions.     

Temperature programmed retention indices: Calculation from isothermal data. Part 1: Theory

Direct conversion of isothermal to temperature programmed indices is not possible. In this work it is shown that linear temperature programmed retention indices can only be calculated from isothermal retention data if the temperature dependence of both the distribution coefficients and the column dead time are taken into account. Procedures are described which allow calculation of retention temperatures and from these, accurate programmed retention indices. Within certain limits the initial oven temperature and programming rate can be chosen freely. The prerequisite for this calculation is the availability of reliable isothermal retention data (retention times, retention factors, relative retention times, or retention indices) at two different temperatures for one column. The use of compiled isothermal retention indices at two different temperatures for the calculation of retention temperatures and thus temperature programmed indices is demonstrated. For the column for which programmed retention indices have to be determined, the isothermal retention times of the n-alkanes and the column dead time as a function of temperature have to be known in addition to the compiled data for a given stationary phase. Once the programmed retention indices have been calculated for a given column the concept allows the calculation of temperature programmed indices for columns with different specifications. The characteristics which can be varied are: column length, column inner diameter, phase-ratio, initial oven temperature, and programming rate.     

Characterization of stationary phases based on monosubstituted benzene retention indices using correspondence factor analysis and linear solvation energy relationships in RPLC

In reversed-phase liquid chromatography (RPLC), the comparison of experimental results obtained from different columns is a complex problem. A correspondence factor analysis (CFA) and a linear solvation energy relationship (LSER) were applied on retention data to characterize second-order intermolecular interactions responsible for retention on a set of RPLC columns. Seven octadecyl-C₁₈ columns with different packing materials are obtained from different manufacturers and one octyl-C₈ column. The retention data were determined under isocratic conditions using a methanol–water (65:35, v/v) mobile phase. The chromatographic retention indices based on alkan-2-ones and alkyl aryl ketones retention index scales are calculated using a multiparametric least-squares regressions iterative method. The CFA and LSER results permitted to highlight that the retention indices were appropriate for studying the second-order retention mechanisms on the eight chromatographic systems investigated and exhibited the best reproducibility. Although many earlier studies have reported the use of chemometric methods to characterize chemical factors affecting retention in RPLC using retention factors as retention parameters, this is the first study based on retention indices.     

Evaluation of automated sample preparation, retention time locked gas chromatography-mass spectrometry and data analysis methods for the metabolomic study of Arabidopsis species

In this paper, automated sample preparation, retention time locked gas chromatography-mass spectrometry (GC-MS) and data analysis methods for the metabolomics study were evaluated. A miniaturized and automated derivatisation method using sequential oximation and silylation was applied to a polar extract of 4 types (2 types×2 ages) of Arabidopsis thaliana, a popular model organism often used in plant sciences and genetics. Automation of the derivatisation process offers excellent repeatability, and the time between sample preparation and analysis was short and constant, reducing artifact formation. Retention time locked (RTL) gas chromatography-mass spectrometry was used, resulting in reproducible retention times and GC-MS profiles. Two approaches were used for data analysis. XCMS followed by principal component analysis (approach 1) and AMDIS deconvolution combined with a commercially available program (Mass Profiler Professional) followed by principal component analysis (approach 2) were compared. Several features that were up- or down-regulated in the different types were detected.     

Retention indices in micellar electrokinetic chromatography

The use of retention indices in micellar electrokinetic chromatography (MEKC) is evaluated both from a theoretical and a practical point of view. Fundamental equations for the determination of retention indices in MEKC are described, showing that retention indices are independent of the surfactant concentration. Possibilities as well as limitations of different homologous series as reference standards are described. In addition, the practical application of retention indices for identification, investigation of solute-micelle interactions, characterization and classification of pseudo-stationary phases and determination of solute lipophilicity are discussed.     

Gas chromatographic behaviour and pharmacological activity of neuroleptica

Biological activity in vitro, quantified as equilibrium inhibition constants to the dopamine receptor, of a series of neuroleptica are correlated with parameters describing polar and apolar interactions of these molecules with the receptor. Gas-chromatographic retention indices on stationary phases of different polarity are compared with parameters that are classically used in such quantitative structure/activity studies. To describe a polar interactions, a series of classical parameters such as several valence molecular indices and log k′ in a reversed-phase h.p.l.c. system are included; retention indices on the apolar stationary phase, OV101, are used as the gas-chromatographic (g.c.) parameter. To take the more specific polar interactions into account, quantum-chemical charge parameters such as the dipole moment and the charge on atoms directly involved in the interaction were calculated. Retention indices on the more polar phase OV17 are taken as the g.c. parameter for polar interactions. It is shown that the retention indices on OV101 can replace classical parameters describing aspecific or apolar interactions. The retention indices of OV17 do not correlate with biological activity and are worse than the charge parameters.     

Derivatisation of arginine residues with malondialdehyde for the analysis of peptides and protein digests by LC-ESI-MS/MS

In this study a selective tagging strategy for the derivatisation of arginine residues in peptides is presented. It is based on the reaction of the guanidine group of the arginine side-chain with malondialdehyde (MDA) under strongly acidic conditions, in which a stable pyrimidine ring is formed. The reaction conditions have been optimised so that quantitative modification can be achieved for a variety of peptides. The label has a strong influence on the polarity and basicity of the arginine side-chain and thus on the chromatographic and mass spectrometric properties of arginine-containing peptides. For example, retention, particularly of small and polar peptides as well as arginine-rich peptides, is significantly increased by derivatisation, and therefore sensitivity is also enhanced in liquid chromatography-mass spectrometry (LC-MS). The arginine side-chain also has a strong impact on the fragmentation behaviour of peptides in tandem mass spectrometry. This has been investigated for standard peptides for which, in some cases, significantly more fragment ions were formed after derivatisation. Finally, the method was tested for tryptic digests of standard proteins to demonstrate how the tagging strategy can give improved or complementary information for protein identification.     

Multiresidue analysis of acidic and polar organic contaminants in water samples by stir-bar sorptive extraction-liquid desorption-gas chromatography-mass spectrometry

The feasibility of stir-bar sorptive extraction (SBSE) followed by liquid desorption in combination with large volume injection (LVI)-in port silylation and gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of a broad range of 46 acidic and polar organic pollutants in water samples has been evaluated. The target analytes included phenols (nitrophenols, chlorophenols, bromophenols and alkylphenols), acidic herbicides (phenoxy acids and dicamba) and several pharmaceuticals. Experimental variables affecting derivatisation yield and peak shape as a function of different experimental PTV parameters [initial injection time, pressure and temperature and the ratio solvent volume/N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) volume] were first optimised by an experimental design approach. Subsequently, SBSE conditions, such as pH, ionic strength, agitation speed and extraction time were investigated. After optimisation, the method failed only for the extraction of most polar phenols and some pharmaceuticals, being suitable for the determination of 37 (out of 46) pollutants, with detection limits for these analytes ranging between 1 and 800 ng/L and being lower than 25 ng/L in most cases. Finally, the developed method was validated and applied to the determination of target analytes in various aqueous environmental matrices, including ground, river and wastewater. Acceptable accuracy (70-130%) and precision values (<20%) were obtained for most analytes independently of the matrix, with the exception of some alkylphenols, where an isotopically labelled internal standard would be required in order to correct for matrix effects. Among the drawbacks of the method, carryover was identified as the main problem even though the Twisters were cleaned repeatedly.     

Comparability of retention indices of polar substances at elevated temperatures

Summary The non-linear dependency of the retention indices of drugs on temperature is demonstrated hence an indication of the actual working temperature is essential. Fixed temperatures for the determination of retention indices of drugs are proposed. Interlaboratory comparisons of the retention indices of 14 drugs frequently encountered in analytical practice are made for the first time on two stationary phases in three laboratories and on four GC apparatus. The data show that, in comparison with literature values, the interlaboratory deviation is reduced by 1/3 to 1/2 if same temperatures are used. Standardization of the temperature of determination of the retention indices of drugs and unknown substances in biological specimens on OV-1 and OV-17 is proposed.     

模拟保留指数法分析汽油族组成

传统上用气相色谱正构烃类为基准的Kovats保留指数或线性保留指数对汽油的组份进行定性，分析汽油族组成．但此方法有一定的局限性，一是不适合多阶程序升温过程的分析，其次是对于烯烃含量较多的汽油用软件自动识别分析时，需人工干预，色谱峰总的识别率经常低于90.0％．提出了模拟指数的概念和计算规则．采用模拟保留指数定性，色谱峰识别准确，色谱峰总的识别率一般能达99．5％以上．     

Sorption characteristics ofN-alkylimidazoles under conditions of capillary chromatography

The retention indices forN-n-alkyl (C₁-C₅) substituted imidazoles with Me, Et, Pr, and Bu groups in different positions of the cycle were determined. Two capillary columns with OV-101/KF and PEG-40M/KF were used. The two nitrogen atoms of the imidazole molecule were shown to have different effects on the contributions of the alkyl groups to the retention indices. The maximum and minimum contributions are observed for the substituents at the 5 and 4 positions of the imidazole cycle, respectively. An increase in a size of the C _m H_2m+1 substituent attached to the N(1) atom has a notable effect only on the contributions of the alkyl groups at the 2 and 5 positions. The retention indices values for a homologous series with ann-alkyl group attached to the N or C(2) atom were described by a universal type equation. The obtained equations can be used for predicting the retention indices of new homologs and identification ofN-alkylimidazoles in complex mixtures.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 309–313, February, 1995.     

Comparison of Retention Indices of Some Monosubstituted Benzenes Calculated by Different Mathematical Methods in RP-LC

In reversed phase liquid chromatography, the retention indices of benzene and nine mono substituted benzenes with different functionality based on the alkan-2-ones and alkyl aryl ketones retention index standards have been determined by the application of two new mathematical adaptation methods, viz. a multiparametric least-squares regression iterative method based on the determination of the adjusted retention times and a local cubic interpolation method directly using the total retention times. The two methods were applied to two types of columns. The first group includes four octadecyl-C₁₈ columns with different packing materials obtained from different manufacturers, while the second comprises an octyl-C₈ column. The retention indices have been extensively studied using either methanol–water or acetonitrile–water mobile phase systems. The influences of the concentration of the organic modifier in the mobile phase (methanol or acetonitrile), the column temperature, and the column packing material on retention indices of the set of the ten monoaromatics studied were also investigated. The calculated multiparametric retention indices values, those obtained by the local cubic interpolation and Kováts’ methods are compared. Good agreement was observed between the retention indices calculated by the three methods.     

Determination of retention indices in constant inlet pressure mode and conversion among different column temperature conditions in comprehensive two-dimensional gas chromatography

A method to determine the second dimensional real retention time, dead times on both dimensions and retention indices in constant inlet pressure mode was developed in comprehensive two-dimensional gas chromatography. At the same time, the conversion of GC x GC retention indices among different column temperature conditions were also conducted based on some thermodynamics parameters. The calculation accuracies are better than 1.0 retention index unit. Furthermore, a retention index database was developed and used to identify the compounds in a cigarette essential oil sample. It showed that identification by the database was of close agreement with by time-of-flight mass spectrometry, and some isomers could also be distinguished based on the retention index database.     

Gas-chromatographic identification of fluorine-containing organic compounds

The gas-chromatographic retention of a series of fluoroalkylarenes on the standard nonpolar polydimethylsiloxane stationary phase OV-101 was characterized, and the retention indices of these compounds were determined. It was found that large negative values of the homological increments of these constants can serve as a sign of fluorine derivatives that contain no less than three fluorine atoms per molecule. The retention indices on polar inorganic sorbents, the silica gels Silipor 75 and Silipor 600, were chosen as the second chromatographic parameter. On these sorbents (unlike partition separation), the nonadditivity effect of the retention indices of polyfunctional organic compounds with respect to their simpler structural analogs was found for the first time. It was found that a mutual correlation between indices for this combination of a phase and a sorbent was lower than that for the combinations of phases with different polarities; this fact is responsible for the higher information content of this combination for the identification of compounds from this class.     

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.     

Chromatographic characteristics of α-alkynols

Chromatographic retention indices on a standard nonpolar poly(dimethylsiloxane) phase were determined for 33 α-alkynols and their 27 dehydration products (conjugated alkenynes). The resulting data are proposed to be verified using the retention indices of acetylenic alcohols estimated by the additive scheme from the retention indices of isostructural alkynes with the inclusion of increments for secondary and tertiary hydroxy groups. The analogous approach to data the verification of data for alkenynes is based on correlation of their retention indices with normal boiling points.