Different properties of H2O- and D2O-containing phospholipid-based reverse micelles near a critical temperature.
Dipalmitoylphosphatidylcholine (DPPC)/water/pyridine reverse micelles have been found to transform from a clear liquid into a glass when the DPPC-to-water volume fraction is in the 0.78-0.89 range at 28 or 26 degrees C depending on whether water is H2O or D2O. Their study by SANS, FT-IR, and 1H NMR for this composition has shown remarkable effects of the isotopic nature of water on their structural and dynamic properties. By SANS, between 38 and 43.5 degrees C, micelles appear as either flexible polymer-like cylinders or short rods depending on whether water is H2O or D2O. On the basis of this dual aspect, micelles have been visualized as branched cylinders whose quasi-spherical branching points would be prone to assemble into short rods. In addition, when water contains more than 40% of D2O, a Bragg reflection emerges at 0.12 A(-1) on SANS spectra, evidencing an organization of micelles. In addition, FT-IR spectra show that DPPC phosphate groups are D bonded only when water is D2O. Consequently, we assumed that forces prone to organize the D2O-containing micelles are D-bonded water bridges between neighboring micelles at the level of their branching points. In fact, ab initio calculations have shown that water dimers are more stable when the bridging atom is D rather than H. These water bridges could be formed due to the fact that branching points, able to slide along micelles, keep close for a longer time when water is D2O than when it is H2O. Indeed, it has been shown experimentally that the lateral diffusion of phospholipid molecules in any layer is slower in the first case. Formation of such bridges triggers a deuteron migration between micelles evidenced by the 1/T1 relaxation rate of deuterons of water in D2O-containing micelles measured at 43 degrees C by 1H NMR.
Milhaud
Jeannine
J
Laboratoire de Biophysique Moléculaire, Cellulaire et Tissulaire (BIOMOCETI), Unité mixte 7033 CNRS-Université Paris VI, 4 Place Jussieu, 75252 Paris Cedex 05, France. milhaud@ccr.jussieu.fr
Hantz
Edith
E
Liquier
Jean
J