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1.
Igor G. Zenkevich Eugene V. Eliseenkov Alexander N. Kasatochkin 《Chromatographia》2009,70(5-6):839-849
Identification of the products of free-radical chlorination of cyclohexane seems to be a complex analytical problem due to the following principal reasons: (1) the available reference information (both standard mass spectra and gas chromatographic retention indices, RI) is strongly restricted to the data for only few simplest congeners, (2) mass spectra of isomeric chlorinated derivatives are practically indistinguishable, and (3) the number of isomers increases with the growing number of chlorine atoms in the molecule until six. To solve this problem, the modified additive scheme for precalculation of the RIs of chlorinated cyclohexanes on standard non-polar polydimethyl siloxane stationary phases was proposed and used. This approach is based on the data for congeners with fewer number of chlorine atoms in the molecule; the principal feature is its applicability to a diastereomers. The final set of both experimental and precalculated RI values permits us to identify unambiguously more than 20 products of cyclohexane chlorination in reaction mixtures. Different modes of the quality control of evaluated retention indices are discussed. 相似文献
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3.
Prediction of gas chromatographic retention indices of polychlorinated dibenzothiophenes on non-polar columns 总被引:1,自引:0,他引:1
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. 相似文献
4.
The chlorinated organic compounds are very important from the point of view of the chemical industry and environmental protection, and therefore the gas chromatographic analysis of these compounds is very interesting for analytical chemists. In this paper we studied the relationship between the molecular structure and gas chromatographic retention on several stationary phases having different polarity and at several temperatures of benzene and 12 chlorobenzene compounds as model compounds. A coding system involving primary (mosaic increments) and secondary (bond increments)calculation methods was developed. The retention indices of benzene and the chlorobenzenes calculated on HP-5 at 120 degrees C shows a better performance of the mosaic increments (average absolute deviation delta of 1.7 retention index units) compared with the bond increments (delta = 11.7 retention index units). Retention factors, k, calculated with mosaic increments for chlorobenzenes on SPB-1 and WAX-10, at 140 degrees C, yield average relative errors of epsilon = 0.9 and 3.5%, respectively. Therefore, the presented paper provides a new possibility for precalculation of the retention data. 相似文献
5.
This paper presents an extension of a previous investigation in which the behavior of nonpolar compounds in temperature-programmed
gas chromatographic runs was predicted using thermodynamic (entropy and enthalpy) parameters derived from isothermal runs.
In a similar manner, entropy and enthalpy parameters were determined for a Grob standard mixture of compounds with widely
varying chemical characteristics. These parameters were used to predict the retention times and chromatographic behaviors
of the compounds on four gas chromatography capillary columns: three that had phenyl-based stationary phases (with degrees
of substitution of 0%, 5% and 50%) and one with (50%) cyanopropyl substitution. The predictions matched data empirically obtained
from temperature-programmed chromatographic runs for all of the compounds extremely well, despite the wide variations in polarity
of both the compounds and stationary phases. Thus, the results indicate that such simulations could greatly reduce the time
and material costs of chromatographic optimizations. 相似文献
6.
Chlorobiphenyl congeners (CBs) are used as indicator compounds in analysis performed to determine whether or not PCB concentrations in food products, waste mineral oil, and environmental samples comply with the maximum levels permitted by legislation. Seven of these compounds have been checked for coelution with other CB congeners by means of a multidimensional gas chromatographic method utilizing a combination of two narrow bore columns, one coated with a conventional non-polar stationary phase and the other with a liquid crystalline (smectic) stationary phase. Peaks of the relevant CBs have been transferred, by heart cutting, from the non-polar column to the liquid crystal column, on which unambiguous separation from possible coeluting CB congeners was obtained. It has been shown that if the seven congeners are analyzed solely on a single, non-polar capillary column the results obtained for two of them may be affected by coelution of other compounds. 相似文献
7.
Ballschmiter K Klingler D Ellinger S Hackenberg R 《Analytical and bioanalytical chemistry》2005,382(8):1859-1870
The semi-experimental approach to approximating physicochemical data relevant to environmental distribution (vapor pressure and gas–octanol distribution) by correlation with gas chromatography (GC) retention data has been extended to the determination of Kow values. We estimated Kow values >104 for polychlorinated biphenyls (PCB), which are often derived by liquid chromatography, by correlation with gas chromatographic retention data. Selecting a set of reference compounds with known Kow values for relative retention time (RRT) correlation enables easy and accurate semi-empirical calculation of further Kow values for a given group of congeners. The RRT/log Kow correlation is validated in this paper with regard to the following gas chromatographic conditions: (1) isothermal versus temperature-programmed elution, (2) the possible effect of the polarity of the stationary phase, and (3) the effect of the format of the standardized GC retention data. The advantages of our Kow(GC) method can be summarized as follows: complex mixtures can be analyzed, only amounts in the nanogram-range or less are required, Kow values of isomers can be determined and the exact structure of compounds need not be known. Normalized GC retention data of persistent organic pollutants are readily available. The quality of the Kow values obtained by the GC method compares well with that for other Kow estimation methods. It depends mainly on the accuracy of the Kow data of the structurally correlated compounds used as standards for the correlation cohort. The Kow(GC) data for all 209 PCB congeners are given.Dedicated to the memory of Wilhelm Fresenius 相似文献
8.
This paper generalizes studies on the influence of carrier gas on relative and absolute retention values. This line of research is also of importance due to the fact that, in the opinion of many chromatographers, the role of the carrier gas is limited only to transporting analyzed compounds along the column. However, even under conditions of the conventional capillary gas-liquid chromatography (i.e. at column pressures under 5 atm) carrier gas (its nature and pressure) significantly influences retention and separation of the analyzed compounds. First, carrier gas (N2 and CO2, for example) dramatically affects relative retention values. For this reason, one should use limit values of alpha(ij) (0) = lim alpha(ij)(P(av)) and I(i)(0) = lim Ii(Pav) I(0) = limI(i) (Pav) with Pav-->0 as chromatographic constants, rather than traditional relative retention values alpha(ij)(P(av)) and I(i)(P(av)). Second, the average pressure Pav of the carrier gas in a column and the nature of the carrier gas influence the selectivity of the gas-stationary liquid phase chromatographic system. Third, wishing to maximize the role of the carrier gas as a factor that improves separation of analyzed compounds, we should design a special gas chromatograph that would allow work with pressures in the column up to 30-50 atm. 相似文献
9.
Summary The gas chromatographic behaviour of a series of compounds of different polarity on columns of Ethofat 60/25 on Chromosorb P HMDS (an inactive support) and Chromosorb 101 (an active support) was investigated. To observe how the support influences the chromatographic process, we separated the contribution to the retention volume of the interaction phenomena associated with the stationary phase, the solid support and the corresponding interfaces. In some cases the Chromosorb 101 exerts an influence on the process even with high percentages (>10%) of stationary phase. The values of the experimental partition constants of a series of compounds and the factors that contribute to adsorption on these columns are calculated. 相似文献
10.
I.G. Zenkevich V.I. Babushok P.J. LinstromE. White V S.E. Stein 《Journal of chromatography. A》2009,1216(38):6651-6661
The effective use of gas chromatographic retention data presented in the form of retention indices (RI) requires the development of a comprehensive structure-based digital archive of retention parameters. Development of such an archive includes the collection of all available RI values for a variety of compounds including replicates measured under slightly different conditions. Review of retention data often shows a relatively wide range of RI values for certain well studied compounds that is larger than expected on the basis of the simple reproducibility of experimental measurements. The finding of unusual RI data distributions and their examination presents a possible way to detect and correct errors during the development of comprehensive RI libraries. 相似文献
11.
烷烃同系物气相色谱保留指数的分子拓扑研究 总被引:13,自引:0,他引:13
定义了分子中原子的平衡电负性,并用原子的平衡电负性对分子图进行着色,在距离矩阵的基础上结合分子中各原子的支化度构建了一种新的拓扑指数N1,N2和N3。该拓扑指数对分子结构实现惟一性表征,具有优良的结构选择性。将拓扑指数N1,N2和N3与烷烃在固定相角鲨烷(柱温50 ℃)及SE-30(柱温80 ℃)上的气相色谱保留指数进行多元线性回归,结果表明烷烃的气相色谱保留指数可分别定量描述为I(Squalane)=23.97842N1-3.86562N2+0.787379N3+42.33061,I(SE-30)=23.83937N1-3.5687N2+0.939876N3+22.11952。用上述回归方程对烷烃的气相色谱保留指数进行预测,结果表明预测值与实验值的平均相对误差均为1.31%,预测结果误差在实验误差范围内。 相似文献
12.
Ichiro Takeda 《Journal of separation science》1991,14(12):824-828
Numerous reports have appeared on the determination of temperature programmed retention indexes in gas chromatography and although chromatographic variables should be completely consistent with published data if such indexes are to be of use, the reproduction of such rigorous parameters is quite difficult. This report presents an approximate method for using published values of temperature programmed retention indexes in isothermal chromatography. In general, the temperature dependence of the isothermal retention indexes of a number of compounds can be expressed as a series of oblique lines on a plot with retention index as the abscissa and temperature as the ordinate; the elution order of the compounds at a given, isothermal, temperature is then indicated by the points at which the compounds' oblique lines cut the horizontal line corresponding to the temperature of interest. In linear temperature programmed chromatography, the horizontal line representing isothermal operation becomes, to a first approximation, a sloping line with a gradient corresponding to the programming rate: this has been verified experimentally and may be valid over a wide range of temperatures. This line can be used to predict isothermal retention indexes for use in qualitative analysis. 相似文献
13.
Yuhui Wei Lili Xi Dongxia Chen Xin'an Wu Huanxiang Liu Xiaojun Yao 《Journal of separation science》2010,33(13):1980-1990
The essential oils extracted from three kinds of herbs were separated by a 5% phenylmethyl silicone (DB‐5MS) bonded phase fused‐silica capillary column and identified by MS. Seventy‐four of the compounds identified were selected as origin data, and their chemical structure and gas chromatographic retention times (RT) were performed to build a quantitative structure–retention relationship model by genetic algorithm and multiple linear regressions analysis. The predictive ability of the model was verified by internal validation (leave‐one‐out, fivefold, cross‐validation and Y‐scrambling). As for external validation, the model was also applied to predict the gas chromatographic RT of the 14 volatile compounds not used for model development from essential oil of Radix angelicae sinensis. The applicability domain was checked by the leverage approach to verify prediction reliability. The results obtained using several validations indicated that the best quantitative structure–retention relationship model was robust and satisfactory, could provide a feasible and effective tool for predicting the gas chromatographic RT of volatile compounds and could be also applied to help in identifying the compound with the same gas chromatographic RT. 相似文献
14.
This work presents linear temperature programmed retention indices on the columns with stationary phases of 5% phenylpolydimethyl silicone of 389 organic compounds, including extractive substances of plant tissues and environmentally important compounds. Certain factors which influence the values and reproducibility of retention indices during gas chromatographic analysis of multicomponent mixtures are discussed. 相似文献
15.
Igor G. Zenkevich 《Journal of separation science》1998,21(10):565-568
It was shown that reciprocally unambiguous conformity between GC retention indices (at least for the commonly used standard nonpolar polydimethylsiloxane liquid phases) and boiling points of organic compounds is typical not only within one-dimensional taxonomic groups (homologous series and/or groups of congeners), but also within two- and multidimensional taxonomic groups (with simultaneous variations of some structural fragments). In all cases, this conformity is described by three-parameter non-linear equations log RI = a log Tb + b (n1 + Σ ki ni) + c, where n1 is the serial number of homologue within corresponding series and ni is the number of other structural fragments in the molecules. The coefficients ki in this equation reflect the relative alterations of molecular polarizabilities and may be estimated as ratios of refractions ki = RD(X)/RD(CH2), where X are variable structural fragments within a group of congeners, RD(CH2) = 4.647 cm3mol−1. The approach under discussion permits precalculation of the retention indices of any organic compounds with known boiling points. The precision of proposed method of RI precalculation is comparable with the contemporary level of interlaboratory reproducibility of experimental RI determination with standard nonpolar liquid phases (5–10 i.u.). 相似文献
16.
Quantitative structure-retention relationship (QSRR) model for the estimation of retention indices (RIs)of 39 oxygen-containing compounds containing ketones and esters was established by our newly introduced distance-based atom-type indices DAI. The useful application of the novel DAI indices has been demonstrated by developing accurate predictive equations for gas chromatographic retention indices. The statistical results of the multiple linear regression for the final model are r=0.9973 and s=8.23. Furthermore, an external test set of 10 oxo-containing compounds can be accurately predicted with the final equation giving the following statistical results: r pred=0.9966 and s pred=8.56. 相似文献
17.
18.
Gerald Remberg Pat Sandra Wolfgang Nyiry Norbert Winker A. Nikiforov 《Analytical and bioanalytical chemistry》1998,362(4):404-408
The distribution of the 8557 theoretically possible structures of polychlorinated terphenyls (PCT) over the different degrees of chlorination and basic terphenyl backbones has been calculated and is presented in detail. As congeners missing chlorine atoms in an ortho position are suspected to be as noxious to organisms as dioxins, the number of these congeners is specified as well. The gas chromatographic retention behavior of 14 PCT single standards is studied on four stationary liquid phases for capillary columns (HP-Ultra 1, HP-5MS, RSL-300 and Polycarbonate) relative to 2,2′,3,4,4′,5,5′-heptachlorobiphenyl and shows no consequent separation of PCT in terms of the degree of chlorination. Individual congeners have been assessed for their suitability as internal standards in PCT analysis. 相似文献
19.
J. Lintschinger P. Schramel A. Hatalak-Rauscher I. Wendler B. Michalke 《Analytical and bioanalytical chemistry》1998,361(3):313-318
Gas chromatographic (GC) and liquid chromatographic methods for the investigation of phenylarsenic compounds are presented.
With gas chromatography using an electron capture detector (ECD), the chemical warfare agents PFIFFIKUS, CLARK I and CLARK
II can be detected. After derivatization with mercaptans and dimercaptans the sum of diphenylarsenic compounds resp. phenylarsenic
and phenylarsonic compounds can be detected as the mercapto resp. dimercapto derivatives. High performance liquid chromatography
(HPLC) analysis may be used for the detection of triphenylarsenic compounds and ADAMSITE.
Received: 17 July 1997 / Accepted: 9 October 1997 相似文献
20.
Stacy S. Vander Pol John R. Kucklick Stefan D. Leigh Barbara J. Porter Michele M. Schantz 《Analytical and bioanalytical chemistry》2010,397(2):483-492
Toxaphene is a complex technical mixture that has been found ubiquitously in the environment but has caused issues for analysis,
especially of individual congeners. This paper reports the elution order of 26 major toxaphene congeners on three gas chromatographic
columns. The three different stationary phases generally had similar elution orders for the toxaphene congeners, but fewer
co-elutions occurred on a low-bleed, low-polarity column. These congeners (except for two that co-eluted and were not added
to the calibration mixture) were examined in air particulate matter standard reference materials (SRMs), 1648a, 1649a, and
1649b as well as SRM 3067 toxaphene in methanol for assignment of reference values. SRM 3067 had mass fractions an order of
magnitude greater than the air particulate SRMs, which ranged from 0.568 ± 0.018 ng g−1 dry mass (B9-2006 in SRM 1648a) to 12.9 ± 0.20 ng g−1 dry mass (B9-715 (P 58) in SRM 1649a). The three air particulate SRMs all had different mass fractions and proportions of
congeners relative to the sum of the toxaphene congeners. SRM 3067 may be useful as a technical mixture toxaphene congener
calibrant. SRMs 1648a and 1649b will serve as reference materials for the analysis of 21 (three congeners were not included
due to values below the detection limit or a potential polychlorinated biphenyl co-elution) toxaphene congeners in atmospheric
particulate samples. 相似文献