Retention characteristics of porous graphitic carbon in subcritical fluid chromatography with carbon dioxide-methanol mobile phases

Numerous relationships usually used in high-performance liquid chromatography (HPLC) for describing the retention on porous graphitic carbon (PGC) have been applied in subcritical fluid chromatography, with CO2-methanol mobile phases. As reported in HPLC, octanol-water partition coefficient failed to fit the retention, whereas satisfactory results were obtained with the sum of partial negative charges. A better fit was reached by using the solvation parameter model, allowing a better understanding of the interactions developed between the solute, the stationary and the mobile phases. Results show that the dominant contribution to retention was given by the polarizability (E) and the volume (V), while the hydrogen-bond basicity (B) was not selected in the retention model, whatever the methanol content. The increase in methanol percentage favours the retention decrease, mainly through the volume for hydrophobic compounds, and through the hydrogen-bond acidity for polar compounds.     

Sulfur hexafluoride as a mobile phase for supercritical fluid chromatography

Summary The capabilities of sulfur hexafluoride as a mobile phase for supercritical-fluid chromatography are investigated. An evaluation of its overall utility on the basis of separations of standard aromatic hydrocarbon odel mixtures performed on a variety of bonded-phase, packed columns with UV detection is presented. The dependence of separation performance upon operational parameters is also examined. A comparative evaluation of the chroamtographic properties of supercitrical sulfur hexafluoride and those of supercritical carbon dioxide is developed from these separations under corresponding supercritical state conditions.     

Computer-assisted retention prediction of polycyclic aromatic hydrocarbons in supercritical fluid chromatography using carbon dioxide as the mobile phase

Summary The dependence of the capacity factor of polycyclic aromatic hydrocarbons on column temperature and on the density of the mobile phase in supercritical-fluid chromatography was investigated using carbon dioxide as the mobile phase. Logarithmic capacity factors of polycyclic aromatic hydrocarbons were obtained as a linear function of the reciprocal column temperature at a constant molar volume of carbon dioxide.The application of the Retention Prediction System to supercritical-fluid chromatography is demonstrated: one can predict the retention of polycyclic aromatic hydrocarbons using equations including column temperature, density and the physico-chemical properties of the solutes as the parameters.     

Chromatographic study of terpene derivatives on porous graphitic carbon stationary phase with beta-cyclodextrin as mobile phase modifier

The stoichiometric coefficients and apparent formation constants (Kf) of alpha-terpineol, thymol, geraniol and linalool complexes with beta-cyclodextrin (beta-CD) were determined using HPLC with a porous graphitic carbon (PGC) chromatographic support. Measurements were performed with four different methanol-water mobile phases. All the terpene derivatives under study form 1:1 guest-CD complexes. Graphs of Kf as a function of the mobile phase composition appeared different from those classically described for RP-C18 and suggest that the PGC stationary phase could play an active role in the complexation process. Solute-CD inclusion and solute-stationary phase interactions may be involved in this specific behavior.     

手性流动相添加剂法拆分比索洛尔对映体

以羧甲基-β-环糊精作为手性流动相添加剂,建立了高效液相色谱拆分比索洛尔对映体的方法。系统考察了手性添加剂的种类及浓度、流动相中甲醇的含量、pH值和流速等因素对拆分的影响。色谱分离条件:流动相甲醇∶乙腈∶水为20∶67∶13(V/V/V),羧甲基-β-环糊精浓度为0.5g.L-1,pH值为4.07(以三乙胺-冰乙酸调节),流速为0.3mL.min-1,检测波长223nm,对映体得到基线分离,分离度为1.89。     

Polyacrylate liquid crystalline stationary phases in supercritical fluid chromatography with carbon dioxide mobile phase

Summary New polyacrylate liquid crystalline compounds were coated onto glass or fused-silica capillary columns as stationary phases and applied to supercritical fluid chromatography. These stationary phases, were very stable: no bleeding was observed at 200°C and up to 200kg/cm² pressures of carbon dioxide mobile phase. The wide working range of the capillary column was extended below the g-n transition temperature. Isomeric compounds such as - and -methoxynaphthalene, anthracene and phenanthrene and several phenolic compounds were separated.     

Retention behaviour in liquid and supercritical fluid chromatography using methanol or diethyl ether as mobile phase

Summary Effects of column temperature and pressure on the retention behaviour of aromatic hydrocarbons were investigated in liquid and supercritical fluid chromatography by using a packed column and methanol or diethyl ether as the mobile phase. Oligomers of styrene, polysiloxane and a non-ionic detergent were separated by temperature- and pressure-gradient elution.     

以L-酒石酸正己酯-硼酸配合物作为反相液相色谱手性流动相添加剂拆分5种β-受体阻滞剂

本文以L-酒石酸正己酯-硼酸配合物为手性流动相添加剂,建立了普萘洛尔、艾司洛尔、美托洛尔、比索洛尔、索他洛尔和阿替洛尔六种β-受体阻滞剂的反相高效液相色谱手性分离方法。对影响对映体分离的主要因素：L-酒石酸正己酯、硼酸浓度,缓冲溶液种类、浓度、pH值和有机改性剂-甲醇含量等进行了详细考察。最佳色谱条件为：Venusil MP-C18色谱柱（4.6 mm × 250 mm,5 μm）,流动相为15 mmol/L乙酸铵-甲醇（体积比为20: 80或30: 70,含60 mmol/L硼酸,70 mmol/L L-酒石酸正己酯,醋酸调节pH值6.00）,检测波长214 nm。在最佳分离条件下,五对对映体（普萘洛尔、艾司洛尔、美托洛尔、比索洛尔、索他洛尔）可以分别获得基线分离。     

Effects of modifiers in subcritical fluid chromatography on retention with porous graphitic carbon

The effect of different modifiers in subcritical fluid chromatography (SubFC) on interactions between solute and porous graphitic carbon (PGC) and between solute and carbon dioxide-modifier mobile phases was studied by the use of linear solvation energy relationships (LSERs). This study was performed to allow efficient optimization of the composition of the carbon dioxide-modifier mobile phase in regard of the chemical nature of the solutes to be separated. With all modifiers tested (methanol, ethanol, n-propanol, isopropanol, acetonitrile, tetrahydrofuran and hexane), the solute/stationary phase interactions are greater than the solute/mobile phase ones. Dispersion interactions and charge transfer between electron donor solute and electron acceptor PGC mainly explain the retention on this surface, whatever the modifier. These interactions are quite constant over the range of modifier percentage studied (5-40%). For acidic compounds, the retention variation is mainly related to the change in the basic character of mobile and stationary phase due to the variation of modifier percentage. Changes in eluting strength are mostly related to adsorption of mobile phase onto the PGC with methanol and acetonitrile, and to the increase of dispersion interactions between the solute and the mobile phase for other modifiers. Relationships between varied selectivities and solvation parameter values have been studied and are discussed in this paper.     

Chiral ligand-exchange chromatography of amino acids using porous graphitic carbon coated with a dinaphthyl derivative of neamine

In this paper, we describe the preparation and the evaluation of a porous graphitic carbon (PGC) column coated with a new dinaphthyl derivative of neamine for chiral ligand-exchange (LE) chromatography. It was shown that the graphitic surface/dinaphthyl anchor system efficiently (1.15 μmol/m²) and stably (three months of intensive use) adsorbs the neamine template onto the chromatographic support. The resulting coated PGC stationary phase showed appreciable LE-based enantioselective properties towards several native amino acids. Chromatographic separation of methionine enantiomers using a dinaphtyl neamine-based ligand-exchange chiral stationary phase     

Chiral ion-pair chromatography on porous graphitized carbon using N-blocked dipeptides as counter ions

Two newly synthesized chiral di-anionic counter ions were tested for enantiomeric resolution of a set of amino alcohols on porous graphitized carbon, Hypercarb. Z-L-Aspartyl-L-proline dissolved in methanol baseline resolved nine of 12 tested racemates. One of its diastereoisomers, Z-L-aspartyl-D-proline was also tested but resulted in low separation factors, <1.1. Sodium hydroxide was added to the mobile phase in order to titrate the counter ion to its mono- or di-anionic form. Results show that the di-anionic form was found to be superior to the mono-anionic form regarding enantioselectivity. Increased content of the counter ion in the mobile phase, with constant ratio between counter ion and sodium hydroxide concentration, decreased retention but only slightly affected enantioselectivity. Increased retention and enantioselectivity were observed with decreased column temperature. Resolution factors >3 were obtained between the enantiomers in atenolol and metoprolol with a total retention time of less than 15 min. Further, all four stereoisomers of an analogue to metoprolol were separated using Hypercarb and a mobile phase of 5 mM Z-L-aspartyl-L-proline and 9 mM sodium hydroxide in methanol.     

手性流动相添加剂法拆分盐酸氯丙那林对映体

盐酸氯丙那林(Clorprenaline hydrochloride)其化学名为α-[[(1-甲基乙基)氨基]甲基]-2-氯-苯甲醇盐酸盐,分子中含有一个手性碳原子,分子式见图1.临床上使用的是盐酸氯丙那林外消旋体,可用于支气管哮喘、哮喘型支气管炎、慢性支气管炎合并肺气肿,可止喘并改善肺功能.     

Retention characteristics of porous graphitic carbon in reversed-phase liquid chromatography with methanol-water mobile phases

The solvation parameter model is used to study the retention mechanism of neutral organic compounds on porous graphitic carbon with methanol-water mobile phases containing from 0-100% (v/v) methanol. The dominant contribution to retention is the cavity formation-dispersion interaction term, composed of favorable interactions in the mobile phase (hydrophobic effect) and additional contributions from adsorption on the graphite surface. Electron lone pair and dipole-type interactions in the adsorbed state result in increased retention. Hydrogen-bonding interactions are more favorable in the mobile phase resulting in lower retention. The changes in the system constants of the solvation parameter model for cavity formation-dispersion interactions and hydrogen-bond interactions are linearly related to the volume fraction of water in the mobile phase. The system constants for electron lone pair interactions and dipole-type interactions are non-linear and go through a maximum and minimum value, respectively, at a specific mobile phase composition. The solvation parameter model poorly predicts the retention properties of angular molecules. This is probably due to the failure of the characteristic volume to correctly model the contact surface area for the interaction of angular molecules with the planar graphite surface. General factors affecting the quality of model fits for adsorbents are discussed.     

Wheat digalactosyldiacylglycerol molecular species profiling using porous graphitic carbon stationary phase

The potential of porous graphitic carbon stationary phase (PGC) was assessed for the separation of molecular species of digalactosyldiacylglycerol (DGDG). Detection was by an evaporative light scattering detector (ELSD). A conventional optimization strategy allowed definition of a quaternary non-aqueous mobile phase and separation of 9 wheat DGDG molecular species with isocratic elution: methanol/toluene/tetrahydrofuran/chloroform 64.3/21.5/13.7/0.5 v/v with 0.1% of triethylamine and a stoichiometric amount of formic acid. The molecular species were identified by LC/MS. The chromatographic behavior of DGDG on PGC was then compared to previous studies. The addition of a carbon double bond on the alkyl chain decreased the retention. This contribution was less important when the number of unsaturations increased in the alkyl chain. The consequence of this retention behavior with PGC was an elution order of molecular species which did not agree with the partition number as observed with C18 grafted stationary phases.