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重水对磷脂酰胆碱双层膜相变相关热力学量的影响。

Effect of deuterium oxide on the thermodynamic quantities associated with phase transitions of phosphatidylcholine bilayer membranes.

作者信息

Matsuki Hitoshi, Okuno Hiroko, Sakano Fumihiko, Kusube Masataka, Kaneshina Shoji

机构信息

Department of Biological Science and Technology, Faculty of Engineering, The University of Tokushima, Japan.

出版信息

Biochim Biophys Acta. 2005 Jun 15;1712(1):92-100. doi: 10.1016/j.bbamem.2005.03.005. Epub 2005 Apr 2.

Abstract

The bilayer phase transitions of three kinds of phospholipids, dipalmitoylphosphatidylcholine (DPPC), distearoylphosphatidylcholine (DSPC) and dihexadecylphosphatidylcholine (DHPC), in deuterium oxide (D(2)O) and hydrogen oxide (H(2)O) were observed by differential scanning calorimetry (DSC) under ambient pressure and light-transmittance measurements under high pressure. The DSC measurements showed that the substitution of H(2)O by D(2)O affected the pretransition temperatures and the main-transition enthalpies of all PC bilayers. The temperature-pressure phase diagrams for these PC bilayer membranes in both solvents were constructed by use of the data of light-transmittance measurements. Regarding the main transition of all PC bilayer membranes, there was no appreciable difference between the transition temperatures in D(2)O and H(2)O under high pressure. On the other hand, the phase transitions among the gel phases including the pretransition were significantly affected by the solvent substitution. The thermodynamic quantities of phase transitions for the PC bilayer membranes were evaluated and the differences in thermodynamic properties by the water substitution were considered from the difference of interfacial-free energy per molecule in the bilayer in both solvents. It was proved that the substitution of H(2)O by D(2)O causes shrinkage of the molecular area of phospholipid at bilayer interface due to the difference in bond strength between deuterium and hydrogen bonds and produces the great influence on the bilayer phase with the smaller area. Further, the induction of bilayer interdigitation in D(2)O turned out to need higher pressures than in H(2)O.

摘要

在常压下,通过差示扫描量热法(DSC)观察了三种磷脂,即二棕榈酰磷脂酰胆碱(DPPC)、二硬脂酰磷脂酰胆碱(DSPC)和二十六烷基磷脂酰胆碱(DHPC)在重水(D₂O)和水(H₂O)中的双层相变,并在高压下进行了透光率测量。DSC测量表明,用D₂O替代H₂O会影响所有PC双层膜的预转变温度和主转变焓。利用透光率测量数据构建了这两种溶剂中这些PC双层膜的温度-压力相图。对于所有PC双层膜的主转变,在高压下D₂O和H₂O中的转变温度没有明显差异。另一方面,包括预转变在内的凝胶相之间的相变受到溶剂替代的显著影响。评估了PC双层膜相变的热力学量,并从两种溶剂中双层膜中每分子界面自由能的差异考虑了水替代对热力学性质的影响。事实证明,用D₂O替代H₂O会由于氘键和氢键之间键强的差异导致双层界面处磷脂分子面积收缩,并对面积较小的双层相产生重大影响。此外,结果表明,在D₂O中诱导双层交叉排列比在H₂O中需要更高的压力。

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