Effects of cis and trans unsaturation on the structure of phospholipid bilayers: a high-pressure infrared spectroscopic study.

Effects of cis and trans unsaturation on the structure of phospholipid bilayers: a high-pressure infrared spectroscopic study.
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顺式和反式不饱和度对磷脂双层结构的影响:高压红外光谱研究。

DOI:
10.1021/bi00386a006
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发表时间:
1987
期刊:
影响因子:
2.9
通讯作者:
H. Mantsch
H. Mantsch
中科院分区:
生物学3区
文献类型:
--
作者:
D. Siminovitch;P. Wong;H. Mantsch

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为了比较顺式和反式不饱和对磷脂双层膜结构和堆积的影响,在28℃的钻石顶压室中测量了1,2-二油酰基-sn-甘油-3-磷胆碱(DOPC)和1,2-二油酰基-sn-甘油-3-磷胆碱(DEPC)水分散体的红外光谱。红外光谱表明,在0.7kbar和5.2kbar的临界压力下,DEPC和DOPC分别发生了压力诱导的液晶-凝胶相变。在它们各自的临界压力以下,DOPC和DEPC的红外光谱基本上是无法区分的,而在这些压力以上,这两种脂类的正压行为有非常显著的差异。具体地说,在DOPC的5.2-Kbar转变处,与界面C=O基团、烯烃CH=CH基团和末端CH3基团相关的谱带的频率、强度和宽度发生了显著变化,而DEPC的相应谱带对压力诱导的相变相对不敏感。DOPC中不寻常的谱带形状变化归因于油酰基链的独特堆积排列,以适应相邻顺式双键的弯曲几何形状。此外,在DEPC中,在5kbar以上,观测到了CH2剪切模和摇摆模的明确的关联场分裂,其幅度与饱和脂肪体系中在可比压力下观察到的非常相似。在36kbar以下DOPC的对应谱带没有关联场分裂,这表明弯曲的油酰基链紧密堆积在一起,所有的链相互平行。
In order to compare the effects of cis and trans unsaturation on the structure and packing of phospholipid bilayers, infrared spectra of aqueous dispersions of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 1,2-dielaidoyl-sn-glycero-3-phosphocholine (DEPC) were measured in a diamond anvil cell at 28 degrees C as a function of pressure up to 36 kbar. The infrared spectra indicate that DEPC and DOPC undergo pressure-induced liquid-crystalline to gel phase transitions at critical pressures of 0.7 and 5.2 kbar, respectively. Below their respective critical pressures, the infrared spectra of DOPC and DEPC are essentially indistinguishable, whereas above these pressures, there are very pronounced differences in the barotropic behavior of these two lipids. Specifically, at the 5.2-kbar transition in DOPC, there are significant changes in the frequencies, intensities, and widths of bands associated with the interfacial C = O groups, the olefinic CH = CH groups, and the terminal CH3 groups, whereas the corresponding bands of DEPC are, by contrast, relatively insensitive to the pressure-induced phase transition. The unusual band shape changes in DOPC are attributed to a unique packing arrangement of the oleoyl acyl chains required to accommodate the bent geometries of adjacent cis double bonds. Moreover, above 5 kbar in DEPC, well-defined correlation field splittings of the CH2 scissoring and rocking modes are observed, with magnitudes very similar to those observed at comparable pressures in saturated lipid systems. The absence of correlation field splittings of the corresponding bands of DOPC up to 36 kbar suggests that the bent oleoyl acyl chains are closely packed with all chains oriented parallel to each other.
傅里叶变换红外光谱鉴定含有 Ca2-ATP 酶的重构磷脂囊泡中的凝胶相域。
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发表时间: 1986
期刊: Biochimica et biophysica acta
影响因子: --
作者:
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1,3-二棕榈酰-甘油-2-磷酸胆碱的结构和热致性质。
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发表时间: 1983
影响因子: 5.6
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DOI: 10.1021/bi00516a040
发表时间: 1981
期刊: Biochemistry
影响因子: 2.9
作者:
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通讯作者: Fleischer,S