Chain length dependent modification of lipid organization by low levels of 25-hydroxycholesterol and 25-hydroxycholecalciferol. A laser Raman study.
We have used Raman spectroscopy to investigate the thermal transitions of multibilayered liposomes composed of lecithins, i.e., dilauroyllecithin, dimyristoyllecithin, dipalmitoyllecithin, distearoyllecithin, or egg lecithin, plus 5-cholesten-3,25-diol (25-hydroxycholesterol), 25-hydroxycholecalciferol, and vitamin D3. We recorded the CH-stretching (2800-3000-cm-1) regions of the Raman spectra at various temperatures and employed plots of temperature vs. the intensity of the 2880- or 2930-cm-1 bands relative to that of the 2850-cm-1 feature, i.e., the ratios I2880/I2850 and I2930/I2850, to estimate thermal transitions. These plots show multiple discontinuities, each of which may be ascribed to a state change of a separate phase with distinctive proportions of lecithins and cholesterol derivatives. Low concentrations of 25-hydroxycholesterol and 25-OH-D3 (greater than or equal to 0.2 mol%) abolish the pretransition and split the main transitions of dilauroyllecithin (4 degrees C) and dimyristoyllecithin (23 degrees C) into two. The midpoint of the new small transition centers at about 3-4 degrees C lower than those of the respective main transitions of dilauroyllecithin and dimyristoyllecithin. A further increase in the molar ratio of 25-hydroxycholesterol and 25-hydroxycholecalciferol decreases the amplitudes of the new and the main transitions (dilauroyl- and dimyristoyllecithin). The transitions of dipalmitoyllecithin and distearoyllecithin at 2 mol % concentrations of either sterol remain unaffected. There was no splitting in the main transition of either dipalmitoyllecithin or distearoyllecithin in the presence of these sterols. The perturbing effect of the 25-hydroxysterols follows the order dilauroyllecithin greater than dimyristoyllecithin greater than dipalmitoyllecithin greater than distearoyllecithin.(ABSTRACT TRUNCATED AT 250 WORDS)
D002112:Calcifediol; D006888:Hydroxycholesterols; D007834:Lasers; D008051:Lipid Bilayers; D010713:Phosphatidylcholines; D013059:Spectrum Analysis, Raman; D013329:Structure-Activity Relationship; D013696:Temperature
D006888:Hydroxycholesterols; D008051:Lipid Bilayers; D010713:Phosphatidylcholines; C007997:25-hydroxycholesterol; D002112:Calcifediol