Fourier transform infrared spectroscopy has been used to study the infrared-active acyl chain vibrational modes of fully hydrated multibilayers of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (L-DPPC) over the temperature range 0-55 degrees C. Frequencies, bandwidths, and other spectral parameters were measured as a function of temperature for the methylene scissoring, rocking, and wagging modes, as well as for the C-H stretching modes, and they were used to monitor the packing of the acyl chains. Particular emphasis was placed on determining the nature of the pretransition event. It is shown that between 36 and 38 degrees C the spectral changes are indicative of a phase change in the acyl chain packing from an orthorhombid to a hexagonal subcell. It is also concluded that in the gel phase, at all temperatures below the main transition, the acyl chains are predominantly in all-trans conformations and that the temperature-dependent variations of spectral parameters result from changes in interchain interactions.
The conformational/configurational dependence of the frequencies of the deuterium-isolated C–H stretching modes of the gas-phase alkanes C1, C2, n-C3, n-C4(t and g), n-C5(tt and gt), cyclo-C6, iso-C4, and neo-C5 are reported. Most of the isolated C–H frequencies were obtained from Raman spectra of specifically and randomly protonated deuterohydrocarbons. An extraordinarily precise correlation is found between the observed isolated C–H frequencies and the corresponding ab initio calculated C–H bond lengths. In the case of the n-alkanes, the observed C–H frequencies tend to fall in clusters that are regularly spaced with an average separation of about 14.5±1 cm−1. The clustering occurs because the isolated C–H stretching frequencies are determined by the structure of the n-alkane in the immediate vicinity of the C–H bond. The relation between frequency and local structure can be expressed in a simple way and used to predict the effect of conformational change.
The thermotropic phase behavior of fully hydrated Na+ and/or NH4+ salts of 1,2-dimyristoyl-sn-glycero-3-phospho-L-serine (DMPS) was determined by temperature-dependent infrared spectra. The molecular level properties and thermal phase behavior of DMPS-Li+ complexes were also characterized by infrared spectroscopy. With increasing concentrations of Li+, the infrared spectra reveal the appearance of a second, more ordered, lipid phase which shows a gel to liquid-crystal transition at significantly higher temperatures (75-95 degrees C) than the Na+ or NH4+ salts of DMPS (39 degrees C). Li+ binds to the phosphate and carboxylate groups of DMPS, resulting in the following changes: (1) water of hydration is lost from both the carboxylate and phosphate groups; (2) there are changes in the conformation of the glycerol backbone but not in the P-O ester bonds of the phosphate group which remain in the gauche-gauche conformation; and (3) the packing of the fatty acyl chains becomes more ordered. In addition, the properties of the DMPS-Ca2+ complex were studied by infrared spectroscopy. While the DMPS-Ca2+ complex is also characterized by rigidly packed, well-ordered fatty acyl chains, the mode of Ca2+ binding to the DMPS head groups differs significantly from that of Li+ binding. By comparison, with dry DMPS-Ca2+ [Casal, H. L., Mantsch, H. H., Paltauf, F., & Hauser, H. (1987) Biochim. Biophys. Acta (in press)], the phosphate group undergoes a conformational change, probably to the antiplanar-antiplanar conformation, and loses its water of hydration.(ABSTRACT TRUNCATED AT 250 WORDS)
The infrared spectra of aqueous dispersions of a homologous series of symmetric-chain, disaturated phosphatidylcholines, with fatty acyl chain lengths ranging from 12 to 19 carbons, have been measured at comparable reduced temperatures in their liquid-crystalline phases. The infrared spectra of these compounds contain bands that are dependent on the conformation of the fatty acyl chains. In particular, in the 1400-1300-cm-1 spectral region, there are bands due to CH2 wagging which are specific for the different types of gauche conformers. Thus, gauche-trans-gauché sequences (or kinks) give a band at 1367 cm-1, end-gauche conformers a band at 1341 cm-1, and double-gauche conformers a band at 1355 cm-1. The intensities of these bands were determined and normalized to the intensity of the conformation-insensitive band due to symmetric methyl bending at 1378 cm-1. The intensities of the different "gauche" bands yield a "per chain" intensity, which is directly related to the concentration of the different types of conformational defects. We find that, within experimental error, the concentration of end-gauche and double-gauche conformers is relatively low and practically invariant with chain length when a series of homologous phosphatidylcholines are compared at the same reduced temperature. In contrast, the concentration of gauche-trans-gauché sequences (kink defects) is much higher and increases as the chain length increases. For dipalmitoylphosphatidylcholine we find that there are about 1.2 kink, 0.5-0.6 end-gauche, and 0.4 double-gauche conformers per hydrocarbon chain.(ABSTRACT TRUNCATED AT 250 WORDS)
Glycophorin from the human erythrocyte membrane has been isolated in pure form and reconstituted into large unilamellar vesicles comprised of binary mixtures of 1,2-dipalmitoyl-3-sn-phosphatidylcholine (DPPC) and chain perdeuterated 1,2-dimyristoyl-3-sn-phosphatidylcholine (DMPC-d54). The effect of temperature and protein on lipid structure and mixing was monitored by using Fourier transform infrared spectroscopy; deuteration of one of the components of the mixture permits observation of the protein interaction with each lipid species. The melting curves were analyzed by assuming that each lipid chain can exist in one of two physical states (i.e., gel or liquid crystalline), characterized by a temperature-dependent Lorentzian distribution for the line shape of the C-H or C-D stretching vibrations. The fraction of each lipid component melted at temperatures within the two-phase region of the phase diagram was calculated and approximate phase diagrams were constructed. Addition of protein lowers the liquidus line of the phase diagram while leaving the solidus line essentially unchanged. No lipid phase separation is observed. The effect of protein is more pronounced on the DPPC component than on the DMPC-d54. The former is significantly more disordered and/or fluidized at all lipid mole fractions in the ternary system than in the binary phospholipid mixture.
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