Structure and Thermotropic Behaviour of Mixed Choline Phospholipid Model Membranes

1997 ◽  
Vol 30 (5) ◽  
pp. 776-780 ◽  
Author(s):  
G. Degovics ◽  
A. Latal ◽  
E. Prenner ◽  
M. Kriechbaum ◽  
K. Lohner

Phosphatidylcholines and sphingomyelins are among the most abundant lipids in mammalian cell membranes, being major components of platelets or erythrocytes, and of the lipid monolayer of lipoproteins. General efforts have been devoted to the elucidation of the interaction of the ubiquitous membrane component cholesterol with these choline phospholipids, but fewer studies have been reported on the interaction between the phospholipids themselves. A gel to liquid-crystalline phase transition was observed for pure sphingomyelin liposomes at physiological temperature, while palmitoyloleoyl phosphatidylcholine adopts a liquid-crystalline phase in the temperature range 273–323 K. The two phospholipids are miscible at all molar ratios in the liquid-crystalline phase, characterized by very similar lamellar repeat distances for all binary lipid mixtures. The gel phase of pure sphingolipid liposomes exhibited a markedly smaller lamellar repeat distance as compared to mixed lipid vesicles, which increased slightly with temperature for the pure sphingomyelin (66.9–69.2 Å). Concomitantly, altered hydrocarbon chain packing was observed. Similar diffractograms were obtained in the presence of 10 mol% phosphatidylcholine. However, in the composition range between 20 and 60 mol% phosphatidylcholine in the phosphatidylcholine–sphingomyelin admixture, the lamellar repeat distance in the gel phase was markedly increased and remained almost constant (around 75 Å) below the phase transition.

Copper 11 complexes of the fatty acids exhibit a thermotropic liquid crystalline phase of the columnar type. X-ray diffraction studies of this mesophase indicate that the spine of a column is made of regularly stacked dicopper tetracarboxylate cores, which are surrounded by disordered, liquid-like alkyl chains. In turn, the column axes occupy the nodes of a two-dimensional hexagonal lattice. Examination of the local environment of the copper atoms by Cu Ka 2 EXAFS spectroscopy reveals insignificant changes in bond lengths within the binuclear core upon the transition from the lamellar crystalline phase to the columnar mesophase. However, a slight, but sharp, decrease of the magnetic moment of the dicopper unit is observed at the solid-mesophase transition temperature (A/4eff « —0.04 ■ The columnar mesophase, and the crystalline phase alike, obey a Bleaney-Bowers relation. The singlet-triplet gap is higher in the former ( -2J = 310-330 cm -1 against 290-300 cm -1 ). Dirhodium 11.11 complexes of selected fatty acids were prepared, and their thermal behaviour was investigated. They exhibit the same thermotropic columnar mesophase as their Cu 11 congeners, reflecting the presence of isostructural dimetallic cores in both series. The metal-metal single bond that is present in these dirhodium 11,11 mesogens is Raman active (iv Rh _ Rh - 350 cm -1 ) ; it is a potential probe of the change in molecular and supramolecular structures of this class of compounds at their phase transition. Diruthenium 11.11 complexes of fatty acids were obtained by Cr 11 reduction of the mixed-valence chlorodiruthenium 11.111 tetrabutyrate, followed by ligand exchange with the appropriate carboxylic acid. Magnetic susceptibility studies indicate that these diruthenium 11.11 carboxylates have an M 5 = 0 ground state and a thermally accessible M 8 = ± 1 excited state, suggesting a zero-field split ( D = 300 cm -1 } a 2 7i 4 5 2 (5*7t*) 4 configuration. The formation of a columnar liquid-crystalline phase is reflected by a sharp increase in the magnetic moment of these complexes at the phase transition (A ju,ef{% +0


2009 ◽  
Vol 131 (8) ◽  
pp. 2934-2941 ◽  
Author(s):  
Yves Bodenthin ◽  
Guntram Schwarz ◽  
Zbigniew Tomkowicz ◽  
Thomas Geue ◽  
Wolfgang Haase ◽  
...  

Author(s):  
Keiichi Moriya ◽  
Toshiya Suzuki ◽  
Yasuyuki Kawanishi ◽  
Tsuyoshi Masuda ◽  
Hiroshi Mizusaki ◽  
...  

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