Porous polymers coated with stationary phases. Contribution of the support to retention behaviour in gas chromatography

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.     

Prediction of HPLC retention times in gradient elution from isocratic data application to a set of non-homologous compounds and different stationary phases

Summary Polymethyloctylsiloxane-coated stationary phases have been prepared for liquid chromatography, by thermal reaction. The influence of the reaction conditions on retention and efficiency of test substances with different structures has been discussed. The materials have good stability in both acidic and basic eluents.     

Prediction of retention data from stationary phase constants in gas chromatography

Summary Specific retention volumes and retention indices for selected compounds can be predicted from different sets of stationary phase constants by multiple regression. Errors in the corresponding calculated retention times are between 5 and 15%. Intercept (A) and slope (B) values are given for 72 McReynolds stationary phases. The A value can be predicted from the retention index of benzene with a standard deviation of 9%.     

Porous polymers coated with stationary phases. Contribution of the support to retention behaviour in gas chromatography. Chromosorb 102 coated with ethofat 60/25, squalane and fractonitril VI. Calculation of the experimental partition constants

Summary Following previous work on the solute-stationary phase-adsorbent interaction phenomena associated with the use of Chromosorb 101 support in gas chromatography, the retention of different polarity compounds on columns of Ethofat, squalane and Fractonitril VI on Chromosorb 102 has been studied. The experimental partition coefficients in these three liquid phases have been compared with those ones obtained earlier on Chromosorb 101 and Chromosorb P. The values have been related to the geometry of the support surface and the different coating of the liquid phases by scanning electron microscopy.     

Gas chromatography in qualitative analyses. An investigation of the oxidation of some silicones used as gas chromatographic stationary phases

Summary The on-column oxidation of apolar and polar silicones used as gas chromatographic stationary phases is investigated. Even at 225° the effects of oxidation are found to be slight. Of the materials investigated the methylphenylsilicones are the most stable.     

阳离子取代基对离子液体气相色谱固定相保留性能的影响

以双-三氟甲烷磺酰亚胺离子（［NTf₂］^-）、三氟甲基磺酸根离子（［TFO］^-）和六氟磷酸根离子（［PF₆］^-）为阴离子,合成了含有丙基、丁基、壬基、乙苯基或氰甲基等阳离子取代基的聚合乙烯基咪唑基离子液体固定相,制备了13种离子液体石英毛细管色谱柱。考察了离子液体固定相结构与色谱柱McReynolds常数、热稳定性和测试化合物保留行为之间的构效关系,研究了阳离子取代基对固定相保留性能的影响规律;同时考察了测试化合物保留指数随温度变化的规律。结果表明,所合成的离子液体固定相具有较强的极性,其保留性能不仅与阳离子取代基的性质密切相关,而且受取代基结构和阴离子影响明显;在考察的温度范围内,测试化合物的保留指数变化规律与传统色谱固定相完全相同。     

Porous polymers coated with stationary phases Contribution of the support to retention behaviour in gas chromatography II. Chromosorb 101 and squalene; Chromosorb 101 and fractonitril VI

Summary Following previous work on the solue-stationary liquid phase-adsorben interaction phenomena associated with the use of active Chromosorb 101 support in gas chromatography, we have studied the retention of a series of different polarity compounds on columns of squalane and Fractonitril VI on Chromosorb P HMDS (an inactive support) and Chromosorb 101 (an active support). The experimental particion coefficients in these stationary phases and the adsorption constants on the Chromosorb 101 support have been calculated assuming that the partition and adsorption mechanisms are essentially independent.Principle author.     

Comparison of two liquid crystals as stationary phases in capillary gas chromatography

Summary The comparative gas chromatographic behavior has been investigated for two new liquid-crystal stationary phases, 2-(3-chlorobenzyloxy)-3-hexanoxy-4-(4-chlorobenzoyloxy)-4′-(4-methylbenzoyloxy)azobenzene (denoted 3-Cl) and 2-(3-methylbenzyloxy)-3-hexanoxy-4-(4-chlorobenzoyloxy)-4′-(4-methylbenzoyloxy)azobenzene (denoted 3-CH₃). The structures of the main core of the two liquid crystals are the same but they differ by lateral aromatic branch— 3-chlorobenzyloxy and 3-methylbenzoyloxy. Their thermal properties were established by use of differential scanning calorimetry (DSC) and their chromatographic separation properties by use of glass capillary columns. Interesting analytical performance was obtained in the separation of isomeric aromatic compounds, polyaromatic compounds, volatile aroma compounds, andcis andtrans isomers. Separation efficiency was higher for 3-Cl, especially for volatile aroma compounds, light aromatic compounds, and polyaromatic compounds, although the phases were similar in otherways.     

Correlation method for comparison of selectivity and retention on different chiral stationary phases

Summary The main chromatographic properties: selectivity and retention of two chiral stationary phases: (R)-3,5-dinitrobenzoylphenylglycine (CSP I) and (S)-3,5-dinitro-benzoylleucine (CSP II) have been compared on the basis of correlation of retention factors of derivatized esters of amino acids and derivatized aminoalcohols. The differences in retention and selectivity for the two CSPs can be easily estimated from the correlation equation. It is shown that in the case of the correlation for two sets of retention factors obtained on two different CSPs, it is mainly the intercept that decides which CSP has the better selectivity. It is demonstrated that the correlation method provides more informations on the selectivity and retention than comparison of the chromatographic data of single pairs of enantiomers. Additionally, the possible influence of the polar modifier mixed with n-hexane as diluent on the constants in the correlation equation is demonstrated.     

Nucleosides as stationary phases for the separation of xylenol isomers by gas-liquid chromatography

Summary Adenosine, guanosine and inosine used as liquid phases in gas chromatography permits the separation of all six xylenol isomers.     

The allyl bonded stationary phase. II. Conversions to new phases for gas chromatography

Summary The presence of the double bond on the allyl moiety has been utilized as a site for addition reactions which could produce new stationary phases. Bromination and hydrobromination reactions have been employed to prove the feasibility of making modifications to the allyl bonded phase. Both retention volumes and thermodynamic parameters for the solutes studied change upon conversion to one of the brominated phases. Sample size studies are consistent with a bonded phase adsorption mechanism. FTIR spectra also confirm the modifications which have occurred on the allyl bonded material.     

The system of universal retention indices and aspects of its application in gas chromatography

Summary The universal retention index has been developed on the basis of a critical analysis of the forms of chromatographic retention data presentation. Methods are presented for the determination of the universal retention index. The advantages of the universal retention index system in the evaluation of the selectivity and classification of stationary phases and in the determination of the composition of binary and polynary stationary phases are discussed. The thermodynamic aspect of the suggested system of chromatographic retention data presentation is also considered.     

Influence of Van der Waals' volume of ethers,esters, carbonyls and alcohols on retention in gas chromatography stationary phases of different polyrity

Summary Equations for Retention Index (I) versus Van der Waals, volume (V_w) on squalane are studied for alcohols, carbonyls, esters and ethers. Each equation includes linear and branching substances with different positions of the functional group in the carbon chain. The study is extended to stationary phases with polarities from 4.29 to 91.54 on the Tarjan et al. scale. Variations of the slope and origin ordinate values with the polarity of the stationary phase are discussed.     

Superselective aqueous inorganic phases in vapor-phase gas chromatography

Chromatographic characteristcs of aqueous solutions of inorganic electrolytes, a new class of stationary liquid phases (SLP) for vapor-phase chromatography, are considered. The SLP are characterized by an unusually high selectivity to organic compounds of the R-X type (R is a hydrocarbon radical, X is a polar group,e.g., hydroxyl, carboxyl, and amine; for instance, light C₁-C₆ alcohols are eluted from the column with a water-containing phase in the following order: hexanol<pentanol<butanol<propanol<ethanol<methanol). The nature of the electrolyte used and its concentration in the water-containing SLP have a crucial influence on the column selectivity and the degree of separation of the compounds subjected to chromatography. This feature provides the possibility of controlling the column selectivity by changing the content of water vapor in the mobile phase. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1831–1840, October, 1999.     

Preparation and retention characteristics of different phenyl phases for reversed-phase liquid chromatography

Summary Three different phenyl phases were prepared. The amount of organic moiety bound on silica support was determined from thermogravimetric curves of the modified silica gel. The specific surface areas of gels were obtained from nitrogen sorption measurement at –196°C. The effect on separation and selectivity of the different bonded-phenyl functional groups was studied. The selectivity of the phenyl-bonded silica gels was examined and compared with octadecyl (ODS) silica in liquid chromatography. Corresponding to the high surface concentration of functional groups, the capacity factors of solutes, normalized to unit surface area of the adsorbent, k/S_BET were found to decrease in the sequence phenylmethyl>diphenyl>triphenyl. Polar solutes are retained in greater extent on the phenyl phases than on the ODS phase.     

两种带有不同间隔臂的环糊精键合固定相保留行为的评价

选取14种模型化合物对两种带有不同间隔臂的环糊精键合固定相(Click Alkyl-CD、Click OEG-CD)进行了反相液相色谱模式下的保留行为评价。通过梯度洗脱条件下保留参数计算方法和CSASS软件,根据3次线性梯度的保留值数据,测出14种溶质分子在两种固定相上的保留参数,在此基础上考察流动相含乙腈浓度与保留因子的关系后发现,Click Alkyl-CD和Click OEG-CD在分离非极性和中等极性化合物时主要基于反相液相色谱模式,而某些化合物(如吲唑)在Click OEG-CD上的保留受多种作用力影响,并不基于反相液相色谱模式。疏水性评价结果表明,反相分离模式下Click Alkyl-CD的保留参数和正辛醇-水分配常数的相关性较好(R=0.7),说明其具有比较强的疏水性;而Click OEG-CD的相关性不高(R＜0.3),说明疏水作用力以外的其他作用力对化合物在反相模式下的保留影响较大。     

Gas chromatographic determination of adsorption terms on Chromosorb 102 coated with squalane and Fractonitril VI. Study of adsorption phenomena using porous polymers coated with liquid phases

Summary The behaviour of Chromosorb 101 and Chromosorb 102 supports coated with Ethofat 60/25, squalane and Fractonitril VI is compared. The adsorption constants of different solutes of varying polarity on these packings were calculated as well the surface areas for Chromosorb 102. The validity of the proposed equation used for correcting the specific surface areas of Chromosorb 102 for the molar volumes of each solute and the solubility parameters of the compounds, adsorbent and liquid phases is shown.