Effects of solvent density on retention in gas-liquid chromatography. I. Alkanes solutes in polyethylene glycol stationary phases.

Gas-liquid chromatographic columns were prepared coating silica capillaries with poly(oxyethylene) polymers of different molecular mass distributions, in the range of low number-average molar masses, where the density still varies significantly. A novel, high-temperature, rapid evaporation method was developed and applied to the static coating of the low-molecular-mass stationary phases. The analysis of alkanes retention data from these columns reveals that the dependence of the partition coefficient with the solvent macroscopic density is mainly due to a variation of entropy. Enthalpies of solute transfer contribute poorly to the observed variations of retention. Since the alkanes solubility diminishes with the increasing solvent density, and this variation is weakly dependent with temperature, it is concluded that the decrease of free-volume in the liquid is responsible for this behavior.

Hold-up time in gas chromatography. V. Dependence of the retention of n-alkanes on the chromatographic variables in isothermal gas chromatography.

The chromatographic behaviour of n-alkanes and other homologous series in isothermal gas chromatography has been shown to depart from the "linear" representation of the logarithms of the adjusted retention times vs. carbon number. One of the expressions proposed to describe this behaviour is tR(z)=A+exp(B+CzD). In this paper, a regression analysis shows that three of the parameters of the equation depend on different chromatographic variables such as hold-up time, average linear gas velocity, volume and polarity of the stationary phase and temperature of the column. The fourth parameter (D), responsible for the departure from the "linearity", does not depend on any chromatographic variable, and represents a gradual decrease of the contribution of the methylene groups to the general properties of n-alkanes, with no relation to the chromatographic phenomenon.

A new look at the lipid composition of the plasma membrane of human blood platelets relative to the GPIIb/IIIa (integrin cxIIß3) content.

The total lipids of the human platelet plasma membrane (HPPM) from 50 ml of blood of healthy subjects were extracted, quantified and related to the mass content of the major intrinsic membrane protein, the glycoprotein IIb/IIIa (GPIIb/IIIa). The HPPM total lipid/GPIIb/IIIa weight ratio determined was 5.40 ± 0.20, independently of the membrane washing procedure used, with the cholesterol/GPIIb/IIIa and phospholipid/GPIIb/IIIa molar ratios of 800 ± 50 and 1200 ± 40, respectively. If the distribution of lipids around each intrinsic protein were proportional to its mass, the lipids around a molecule of GPIIb/IIIa will occupy about 120 nm(2) of the membrane plane, which is about one and a half times the cross-sectional area of the extracellular head of GPIIb/IIIa, as estimated by electron microscopy. The lipid extracts were further subjected to thin-layer chromatography to separate and quantify the different phospholipid fractions, the free fatty acids and the neutral lipid fraction and the distribution of fatty acids in each fraction was determined by gas chromatography after methanolysis. The phospholipid molar distribution was SPM(22.3 ± 0.9%), PC(36.2 ± 1.0%), PE(24.9 ± 0.9%), PS(12.1 ± 0.6%) and PI(4.5 ± 0.4%) and the free fatty acid fraction represented 2.9 ± 0.4% of the total fatty acids in HPPM. The fatty acid chain length ranged from 14 to 24 carbons, comprising unsaturated fatty acids (47.3% molar per cent of the total) of which 40.7 ± 2.0% were monosaturated and 40.7 ± 0.9% tetraunsaturated. Palmitic, stearic, oleic and arachidonic acids represent 66% of the total fatty acids of HPPM, being: 68.9 ± 5.3% of palmitic acid and 63.3 ± 6.9% of oleic acid in PC; 50.9 ± 3.8% of arachidonic acid in PE; and 30.5 ± 2.4% of stearic acid in PS. We discuss the methodological modifications and the new data in relation with the major differences in HPPM lipid composition found in the literature. The data obtained provides a comprehensive and accurate description of the lipid composition of HPPM on which to rely as a reference for basic and medical studies.

Ageing of columns of homogeneous mixed stationary phases in gas chromatography.

Chromatographic columns of homogeneous mixed phase prepared with squalane and polyethylene glycol 1540 have been subjected to an ageing process of about 1700 hours at 100 degrees C followed by a similar period of time at 120 degrees C. Little change is observed at the lower temperature, while at 120 degrees C, a selective loss of the most volatile component of the mixture seems to occur, producing changes in the values of the retention indices obtained.