Sorption properties of heterocyclic compounds differing by heteroatom in capillary gas chromatography

The dependence of sorption properties on the nature of heteroatoms in substituted five- and six-membered heterocyclic compounds with two heteroatoms (sulfur and oxygen), thiophenes and furans bearing alkyl, formyl, acetyl, and sulfide substituents have been investigated. Equations for calculating the retention indices of analogs have been proposed, and the indices of 35 previously non-investigated substances of these classes have been predicted.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1224–1227, July, 1993.     

Temperature changes of sorption parameters of di-n-alkylketones and methylcyclohexanones in capillary gas chromatography

The gas chromatographic behavior of di-n-alkylketones and isomeric methylcyclohexanones at variable temperatures in the isothermal runs has been studied using three capillary columns coated with SE-30, OV-225, and PEG-40M/KF stationary phases. The retention indices and their temperature increments were determined, and the partial molar free energies of the compounds under study were calculated. A linear dependence of the values of the partial molar free energy of sorption on the homologue number in di-n-alkylketones is not observed for the first member on the nonpolar SE-30 phase and for the third member on the polar OV-225 and PEG-40M/KF phases. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 328–332, February, 1997.     

Calculation of the thermondynamic values of alkylthiazoles from the Kovats retention indices on the basis of the non-linear additivity principle

Summary Retention indices and their energy equivalents were determined for ten alkylthiazoles analysed on the stationary phases Apiezon L, Triton X-305 and Carbowax 1000. It was found that the energy contributions of identical alkyl groups to the partial molar free energy of sorption of a molecule are not equivalent. Smaller energy contribututions are due to the α-position of alkyl groups with respect to the heteroatoms in the thiazole ring (α-effect). This effect was most pronounced for 2-alkylthiazoles. Higher sorption energies were found for dimethylthiazoles with two methylgroups in a vicinal position. The retention indices were predicted for ten other di- and tri-substituted methyl, ethyl and propyl thiazoles on the basis of the so-called α- and ortho-effects. The predicted values are in good agreement with the experimentally determined values. Dedicated to Prof. Dr. E. sz. Kováts (Ecole Polytechnique Fédérale de Lausanne) on the occasion of his sixtieth birthday.     

Investigation of the role of the carrier gas in capillary gas-solid chromatography

Nonideal interactions of the sorbate and the carrier gas and adsorption of the sorbate on the adsorbent surface in capillary gas-solid chromatography were studied. Chromatographic retention was found to be largely determined by adsorption processes. With respect to the retention coefficients (capacity factors) of a sorbate (k) with different carrier gases (P₁ and P₂), the correlation relationshipk(P₂) =A·k(P₁) +B (A, B are parameters of the equation) is closely obeyed. The advantages of carbon dioxide as the carrier gas were analyzed; the use of carbon dioxide allows the efficiency of the column to be enhanced.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 627–633, March, 1996.     

Thermodynamic characteristics of sorption of heterocyclic compounds m capillary gas chromatography

Dependences of sorption energies of sulfur-, oxygen-, and nitrogen-containing heterocyclic compounds on the nature of heteroatoms, structure of substituents and their position in the ring were studied. The contributions of heteroatoms, functional and alkyl groups to the energy of dispersive interaction of position isomers with nonpolar stationary phases were determined for imidazoles, piperidines, morpholines, thiomorpholines, dioxalanes, oxathiolanes, dithiolanes, thiophenes, and furans. The nonequivalence of contributions of the same substituents to the sorption energy of each of the heterocyclic compounds, depending on the nature of the heteroatom and position of the substituent, was shown. The obtained values of contributions of heteroatoms and substituents can be used for apriori calculation of retention indices of position isomers of five- and six-membered heterocycles containing one or two heteroatoms in the ring.Translated from lzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2033–2038, August, 1996.     

Prediction of the retention indices of methyl pyridines and pyrazines in capillary gas chromatography based on the non-linear additivity of the sorption energy

Summary Methylbenzenes, pyridines and pyrazines were investigated on fused-silica and glass capillary columns coated with SE-30 and PEG-40M/KF liquid phases, at two temperatures, 80° and 110°C. The contribution of the methylene groups to the partial molar free sorption energy was determined for methylpyridines and pyrazines. Equations are proposed for the calculation of the retention indices of methyl pyridines and pyrazines. These equations are based on the ortho- and α-effects of the methyl groups. The predicted indices have been experimentally tested for six dimethyl- and trimethylpyridines, and four methylpyrazines. Good accuracy of the calculation permits to use this method for the identification of methylpyridines and pyrazines in complex mixtures. Enlarged text of the paper presented at the Eighth International Symposium on Capillary Chromatography, Riva del Garda, Italy, May 19–21, 1987.     

Peculiar features of sorption of positional isomers of formyl-, acetyl-, and aminopyridines in capillary gas-liquid chromatography

The GLC retention parameters of α-, β-, and γ-isomers of formyl-, acetyl-, and aminopyridines were determined on two columns with stationary phases of different polarities. The contributions of formyl, acetyl, methyl, and amino groups located in the α-, β-, and γ-positions of the ring to the retention indices were calculated. The contributions of these groups to the retention were found to depend on their positions with respect to the N atom of the ring and are the smallest for α-substituents. The difference between pyridines containing electron-withdrawing substituents and those containing electron-donating substituents is manifested as different orders of elution of α-, β-, and γ-derivatives. The distinctions between the GLC behaviors of pyridines, benzenes, and furans with the same substituents were identified. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 91–94, January, 1997.     

气相色谱法鉴别缓慢生长分枝杆菌

采用毛细管气相色谱法对９种缓慢生长分枝杆菌的化学成分进行了分析。结果表明,不同菌种的色谱图存在明显的差异。对７５株临床菌株进行色谱法鉴别,并与传统生物学鉴定法作了对比。     

Reciprocally Unambiguous Conformity Between GC Retention Indices and Boiling Points within Two- and Multidimensional Taxonomic Groups of Organic Compounds

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 T_b + b (n₁ + Σ k_i n_i) + c, where n₁ is the serial number of homologue within corresponding series and n_i is the number of other structural fragments in the molecules. The coefficients k_i in this equation reflect the relative alterations of molecular polarizabilities and may be estimated as ratios of refractions k_i = R_D(X)/R_D(CH₂), where X are variable structural fragments within a group of congeners, R_D(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.).     

Determination of thermodynamic functions of sorption for cyclohexyl-, piperidyl-, morpholyl-, and thiomorpholyl-n-alkanes by capillary gas-liquid chromatography

The values of partial molar free energy (G), enthalpy (H), and entropy (S) of sorption in the homologous series ofN-alkylpiperidines,N-alkylmorpholines,N-alkyl thiomorpholines, and alkylcyclohexanes were determined. It was found that the free energy of sorption is determined to a greater extent by the enthalpy term than by the entropy one. The free energy of sorption of the first homolog decreases when then-alkyl chain is attached directly to the carbon atom of the cycle and increases in the case ofN-alkylsubstituted heterocycles. The influence of the heteroatom nature on intermolecular interactions of homologs with the nonpolar stationary phase was quantitatively estimated on the basis of thermodynamic data.Dead time necessary for calculation of the retention factor was determined by the retention of methane injected into the column simultaneously with the sample.Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2030–2032, August, 1996.     

The influence of alkyl substituents on the chromatographic indicator of self-association of<Emphasis Type="Italic">N</Emphasis>-containing heterocyclic compounds

The chromatographic indicator of the ability of substances to form associates in a pure liquid δT _b.p. proposed in our previous study was used to estimate the capacity for self-association of alkyl-substituted imidazoles, pyrazoles, pyrroles, oxazoles, isoxazoles, pyridazines, pyrimidines, pyrazines, and pyridines. Alkyl substituents introduced in heterocyclic compounds decrease the δT _b.p. values, which is consistent with the data on the heats of self-association of heterocyclic compounds in pure liquids. The reasons for the difference between the boiling point of a compound at standard pressure and its “gas-chromatographic boiling point” are discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp 319–322, February, 2000.     

An equation for the calculation of retention indices in temperature-programmed gas chromatography with allowance for the nonlinear variation of the retention parameters ofn-alkanes

In view of the nonlinear variation of the temperature increments ofn-alkanes found previously, the accuracy of the calculations of the retention indices (I _pr) of substances in temperature-programmed capillary gas chromatography carried out in terms of six known equations was verified. A new four-parameter equation was proposed, and a general method for the calculation of its coefficients, suitable for all stationary phases, based on the adjusted retention times ofn-alkanes was suggested. The coefficients of the equation for 12 temperature variation programs were determined. Using the homologous series of methyl esters of fatty acids as an example, it was shown that the proposed equation ensures the minimum error of determination ofI _pr under various conditions. The equation also makes it possible to carry out interpolation and extrapolation calculations. The coefficients of the equation are found using the least-squares method based on data for any 4–5 referencen-alkanes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 323–327, February, 1997.     

Dependence of the relative retention of organic compounds on the nature and pressure of the carrier gas and on the thickness of the PEG-20M film in the capillary column

The effects of the carrier gas nature and pressure on the relative retention values of organic compounds were studied using a series of capillary columns differing in the film thickness of the polar stationary phase (PEG-20M). Relative retention depends linearly on the carrier gas pressure. This dependence becomes more pronounced in the following order of carrier gases: helium < nitrogen < carbon dioxide. The limiting relative retention at a carrier gas pressure approaching zero rather than relative retention values measured experimentally (relative retention time, Kovats retention index,etc.) is an invariant characteristic of a compound subjected to chromatography. For the carrier gases studied, the limiting retention values almost does not depend on the nature of the carrier gas used. The limiting indicating the complex absorption-adsorption nature of these parameters. Dissolution of a carrier gas in the stationary liquid phase has an effect on the relative retention. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2177–2186, December, 1997.     

Chromatographic and IR characteristics of methyl-, formyl-, and acetyl-substituted furans and thiophenes

The GC and FTIR spectral characteristics of methyl-, formyl-, and acetyl-substituted furans and thiophenes were determined. The substituent contributions to the retention indices were calculated. It was found that contributions of identical substituents differ according to the nature of the heterocycle, their position relative to the heteroatom and other neighboring groups. The contributions of CH₃-, CHO-, and COCH₃-groups in the -position of the cycle for monosubstituted substances were equal to the contributions of these groups in monosubstituted benzenes. The contributions of carbonyl groups in the-position were greater than in the -position for the same groups. The contributions were found to be nonadditive for disubstituted methyl and carbonyl-containing thiophenes and furans. The presence of two carbonyl groups as substituents in furans and thiophenes results in reduction of the sorption energy of the latter, which is known as «negative» -effect. The scheme fora priori calculation of retention indices taking into account the non-uniformity of the contributions of methyl and carbonyl substituents in thiophenes and furans was suggested. The indices of 12 unknown substances of these classes were calculated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 70–75, January, 1994.This work was carried out with financial support from the Russian fundamental Research Fund (project No. 93-03-4969).     

Optimization strategies in micellar electrokinetic capillary chromatography. Optimization of the temperature of the separation capillary

Summary The influence of the temperature of the capillary on the separation of small molecules by micellar electrokinetic chromatography with buffers containing sodium dodecyl sulfate was examined. Investigated parameters were the electroosmotic velocity, the migration velocity of the micelles, the strength of the electric current, retention factors and plate numbers. Thermodynamic parameters associated with micelle solubilization were evaluated from the variation of the retention factor with temperature. An investigation was carried out as to whether the dependence of the electroosmotic velocity and the migration velocity of the micelles are mainly due to the decrease in viscosity and dielectric constant with increase in temperature. The temperature of the capillary strongly affects the plate numbers for various solutes obtained with the same chromatographic system. In order to exclude secondary effects by alteration of the instrumental band broadening and the electroosmotic velocity with temperature, a method is presented that permits the development of chromatograms in MEKC at various temperatures with constant injected plug length and constant electroosmotic velocity. The results are discussed from the point of view of minimizing the analysis time and optimizing the resolution.     

The influence of molecular conformation ofN-alkylsubstituted six-membered cyclic amines and alkylcyclohexanes on the thermodynamic characteristics of sorption in gas chromatography

The standard partial molar free energies, enthalpies, and entropies of sorption of the methylene units in the homologous series of alkylcyclohexanes andN-alkylsubstituted sixmembered heterocycles (piperidines, morpholines, and thiomorpholines) were determined on a capillary column with the methylsiloxane OV-101 stationary phase at 70–150°C. A characteristic feature of all series under study is an abnormally high increase in the values of thermodynamic parameters of sorption on going from the methyl to the ethyl homolog. This peculiarity is believed to be associated with the presence of thegauche butane orgauche methylethylamine fragments in the ethyl homolog. Thesegauche fragments have an increased sorption activity under conditions of gas chromatography in comparison with the correspondingtrans form. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 500–503, March, 1997.     

Equilibrium chromatographic characteristics of capillary column coated with polytrimethylpropyne for separating polar and non-polar organic compounds by gas capillary chromatography

The temperature dependence (50—180 °C) of the retention factor for 35 hydrocarbons and their oxygen-containing derivatives was studied using a capillary column coated with a new film-forming polymeric adsorbent polytrimethylsilylpropyne (PTMSP). The heats of adsorption for 24 organic polar and non-polar compounds on PTMSP were determined. They turned out to be lower than the heats of adsorption of the same compounds on Porapak Q widely used in gas chromatography. The new adsorbent PTMSP is characterized by high selectivity suitable for practical application.     

The influence of the carrier gas on retention in capillary gas-solid chromatography

In capillary gas-solid chromatography where interactions between solute and carrier gas and adsorption of the solute on the surface of the adsorbent are considered to be imperfect, it has been shown that chromatographic retention is determined largely by adsorption processes. It has been established that correlation relationships k(P₂)=A k(P₁) + B, where k is the retention factor, and A and B are equation constants, was valid for use of different carrier gases P₁ and P₂. Column efficiency could be improved by use of carbon dioxide. The advantages of using carbon dioxide as the carrier gas were investigated.     

Live retention database for identification of compounds in capillary gas chromatographic analysis --Principle and structure

A live retention database for compound identification in isothermal and any step temperature programmed capillary gas chromatography has been developed. The database utilizes the Kovats retention indices of compounds on a given stationary phase and the retention time of n-alkanes measured at isothermal conditions on the column to be used, together with the programming parameters. Identification is performed by search operation that compares the calculated results with the retention values of unknown peaks. Cross-reference of the search results of different operating conditions is performed automatically by the database in order to increase the reliability of the identification. The error of the database conversion is ≤± 0.5 index unit, or ≤± 1% on retention time. This paper describes the principle and the structure of the database in detail. The experimental results for different calsses of compounds tested at divers operating conditions will be presented in Part Ⅱ.     

Determination of the isomeric distribution and associated impurities in commercial diethylbenzenes by capillary gas chromatography

A capillary gas chromatographic method for the quantitative analysis of diethylbenzene fractions is described. Estimation of ortho-, meta- and para-isomers and other C₉ and C₁₀ aromatic impurities is covered. The conditions developed involve the use of a capillary column of Carbowax-1540 (300 feet × 0.01 inch) under isothermal operation. The retention index data for a number of aromatics are presented at four temperatures (90, 100, 110 and 120°C). The method offers a good choice for any level of concentration both for isomers and impurities commonly encountered within a reasonable analysis time.