Biomedical subjects

J W Doane

Publications and source records attributed to J W Doane.

6 recordsLinked to original sources

PubMed1988

The interaction of n-alkanols with lipid bilayer membranes: a 2H-NMR study.

The interaction of eight n-alkanols with bilayers of dimyristoylphosphatidylcholine (DMPC) has been studied by deuterium nuclear magnetic resonance (2H-NMR). At comparable temperatures and concentrations of solute in the bilayer, order parameters measured at the 1-methylene segment of the n-alkanols show a maximum for n-dodecanol. For both n-dodecanol and n-tetradecanol, orientational ordering shows a maximum at the C-4 to C-7 methylene segments, with labels at both ends of the n-alkanol exhibiting reduced order. These observations are consistent with earlier findings for n-octanol and n-decanol. Unlike the longer chain n-alkanols, ordering in n-butanol decreases from the hydroxyl group end to the methyl group end of the molecule. Orientational ordering at nine inequivalent sites in DMPC, has also been measured as a function of temperature, for bilayers containing n-butanol, n-octanol, n-dodecanol and n-tetradecanol. At the 3R,S sites on the glycerol backbone, for comparable temperatures and solute concentrations, n-butanol produces a larger disordering than the other n-alkanols. This result probably reflects the greater fraction of time spent by the hydroxyl group of n-butanol in the vicinity of the lipid polar head group compared with the hydroxyl group in longer chain n-alkanols. It was found that n-octanol orders the acyl chains of DMPC, unlike n-butanol which disorders them, and the longer chain n-alkanols which have little effect. Within experimental error, the effect of n-dodecanol on order at all sites in DMPC is the same as n-tetradecanol. The influence of n-alkanols on DMPC ordering at twelve sites has been compared with that of cholesterol which is shown to interact with DMPC bilayers in a distinctly different manner from the n-alkanols.

Alcohols↗

PubMed1987

Pretranstional phenomena in phospholipid/water multilayers.

We have measured the water order in monodomain phospholipid samples using 2H nuclear magnetic resonance (NMR) and analyzed the splittings in terms of critical exponents. Our data and the model developed to interpret them in terms of fluctuations provide an explanation of the puzzling sharp reduction of water order near the chain-ordering phase transition. The temperature range of the fluctuations is approximately the same as that observed for increased 22Na+ efflux from phospholipid vesicles.

1,2-Dipalmitoylphosphatidylcholine↗

PubMed1985

Spatial modulation of water ordering in lecithin bilayers. Evidence for a ripple-ripple phase transition.

Intense motional averaging effects on the 2H nuclear magnetic resonance (NMR) spectrum of 2H2O that occur in aqueous dispersions of dimyristoyl-sn-glycero-3-phosphocholine (Myr2-PtdCho) are explained by a spatial modulation in the orientational order of the water induced by ripplelike structures. The ratio of the amplitude to the periodic length of the ripples, A/lambda, at a molar ratio of water/Myr2-PtdCho of 9.5:1, is measured by 2H NMR and found to be consistent with x-ray measurements of this ratio in the P beta phase of dipalmitoyl-sn-glycero-3-phosphocholine (Pam2-PtdCho) bilayers. The sensitivity of 2H NMR allows us to report the presence of two distinct ripple phases mediated with a discontinuous change in the value of A/lambda. This result suggests that the two ripple structures observed for several phospholipid systems in excess water by freeze-fracture electron microscopy may be associated with two different phases instead of the same phase as previously assumed.

Dimyristoylphosphatidylcholine↗

PubMed1985

A model of orientational ordering in phosphatidylcholine bilayers based on conformational analysis of the glycerol backbone region.

Molecular and conformational ordering in aqueous multilamellar suspensions of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) have been examined by deuterium nuclear magnetic resonance (2H NMR) in the liquid crystalline (L alpha) phase. Motionally averaged quadrupolar splittings vQ from six sites in the vicinity of the glycerol backbone have been analyzed by a molecular frame and order matrix approach in which the usual assumption of a freely-rotating molecule is not invoked. By assuming a relatively rigid glycerol backbone region, the six vQ values are found to be consistent with a conformation of the glycerol backbone that is almost identical to that of one of the two structures in crystalline DMPC dihydrate (Pearson, R. H., and I. Pascher, 1979, Nature (Lond.) 281: 499-501). The orientation of the most-ordered axis of the DMPC molecule is found to be tilted at an angle of 27 +/- 2 degrees with respect to the long axis of the sn-1 chain in its extended all trans conformation. The ordering of the most ordered molecular axis with respect to the bilayer normal is expressed by an order parameter of Szz approximately equal to 0.6 +/- 0.1, consistent with values in analogous thermotropic liquid crystals.

Dimyristoylphosphatidylcholine↗

PubMed1982

Phase transitions in phosphatidylcholine multibilayers.

The (2)H NMR spectrum of a multilamellar dispersion of 1-myristoyl-2-[14,14,14-(2)H(3)]myristoyl-sn-glycero-3-phosphocholine with 1 mol% cholesterol in excess water has been recorded at temperatures between -15 degrees C and 36 degrees C. Motionally averaged quadrupole coupling constants nu(Q) and motionally induced asymmetry parameters eta are obtained by spectral analysis. Values of these quantities indicate that, at temperatures below -4 degrees C, any rotational motion of the molecules about their molecular long axis is slow on the NMR time scale. At temperatures immediately above the pretransition these same parameters show that a fast-rotational motion is occurring about the molecular long axis. This rotational motion is hindered in that the molecules flip about a twofold symmetry axis. Between -4 degrees C and the pretransition, spectra appear as the superposition of two powder patterns, one corresponding to the pattern observed below -4 degrees C and the other to the pattern above the pretransition. The relative contribution of the latter increases with temperature until the pretransition is reached. These data have been interpreted in two ways: either the sample between -4 degrees C and the pretransition contains two populations of rapidly and slowly rotating molecules, or there is only a single population of molecules undergoing a 180 degrees flipping motion on the time scale of the NMR measurement. The latter interpretation is more consistent with other experimental findings. At the temperature of the main transition the hydrocarbon chains melt. In the absence of cholesterol, spectra are more complex in that the line shape is reproduced by the superposition of three spectral powder patterns between -4 degrees C and the pretransition and by the superposition of two spectral patterns above the pretransition. It is postulated that these two patterns observed above the pretransition are in direct correspondence to the two ripple structures observed by freeze-fracture electron microscopy in the absence of cholesterol.

Chemical Phenomena↗

PubMed1979

Orientational order and rotational diffusion of the head group in the bilayer membrane. A nuclear magnetic resonance study.

An order parameter-based interpretation is applied to the temperature dependence of the deuterium magnetic resonance splittings and the anisotropic contribution to the chemical shift for 31P from the head groups of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). It is shown that the rotational motion of the molecule about its long axis is not a free rotational motion as normally assumed, but instead a biased one. Changes in the degree of biasing appear to be primarily responsible for the variation of the NMR spectra with temperature. The degree of biasing is described by orientational order parameters. With the use of these order parameters, it is shown that the temperature dependence of the anisotropic contribution to the chemical shift for 31P can be predicted from that of the deuterium quadrupole splittings.

Deuterium↗