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组织磷脂的31P核磁共振:Mg2+、Ca2+、Na+和K+阳离子的竞争

31P NMR of tissue phospholipids: competition for Mg2+, Ca2+, Na+ and K+ cations.

作者信息

Merchant T E, Glonek T

机构信息

Department of Radiation Oncology, Memorial Sloan-Kettering Cancer Center, New York, New York 10021.

出版信息

Lipids. 1992 Jul;27(7):551-9. doi: 10.1007/BF02536139.

DOI:10.1007/BF02536139
PMID:1453886
Abstract

Phosphatidylcholine (PC), phosphatidylethanolamine (PE), ethanolamine plasmalogen (EPLAS), sphingomyelin (SPH), phosphatidylinositol (PI), phosphatidylserine (PS), cardiolipin (CL), phosphatidylglycerol (PG) and phosphatidic acid (PA) were dispersed together in Cs(ethylenedinitrilo)tetraacetic acid-scrubbed chloroform/methanol solution, and high resolution 31P nuclear magnetic resonance spectra were recorded. In separate titration experiments, Mg2+ and Ca2+ were added to the dispersed phospholipid mixture to determine the relative interaction potentials of each of the phospholipids for each of the added cations. The association of cations with individual phospholipids was indicated by 31P chemical-shift changes, signal broadening, signal quenching or a combination of these. The titrations revealed that CL had the highest, and PA the next highest, interaction potential for Mg2+ cations. In contrast, PS and PA had the highest, and CL the next highest, interaction potential for Ca2+. Considering only interactions with Ca2+ ions, the phospholipids can be divided into three distinct groups: PS and PA (high interaction potential); CL, PI and PG (intermediate interaction potential); and EPLAS, PE, SPH and PC (essentially no interaction potential). The two phospholipids with the least interaction potential for either of the alkaline-earth cations were PC and SPH. Na+ and K+ ion interactions with PA, CL, PI and PG were unique and resulted in positive chemical-shift changes relative to the chemical shifts in the presence of Cs+ ions. Relative to both Cs+ and K+ ions, chemical shifts in the presence of Na+ ions were deshielded delta greater than 0.1 ppm in the order PA greater than CL greater than PI greater than PG.

摘要

将磷脂酰胆碱(PC)、磷脂酰乙醇胺(PE)、乙醇胺缩醛磷脂(EPLAS)、鞘磷脂(SPH)、磷脂酰肌醇(PI)、磷脂酰丝氨酸(PS)、心磷脂(CL)、磷脂酰甘油(PG)和磷脂酸(PA)一起分散于经乙二胺四乙酸洗涤的氯仿/甲醇溶液中,并记录高分辨率的³¹P核磁共振谱。在单独的滴定实验中,向分散的磷脂混合物中加入Mg²⁺和Ca²⁺,以确定每种磷脂与每种添加阳离子的相对相互作用势。阳离子与单个磷脂的缔合通过³¹P化学位移变化、信号展宽、信号猝灭或这些情况的组合来表明。滴定结果显示,CL对Mg²⁺阳离子的相互作用势最高,PA次之。相比之下,PS和PA对Ca²⁺的相互作用势最高,CL次之。仅考虑与Ca²⁺离子的相互作用时,磷脂可分为三个不同的组:PS和PA(高相互作用势);CL、PI和PG(中等相互作用势);以及EPLAS、PE、SPH和PC(基本无相互作用势)。对两种碱土金属阳离子相互作用势最低的两种磷脂是PC和SPH。Na⁺和K⁺离子与PA、CL、PI和PG的相互作用独特,相对于存在Cs⁺离子时的化学位移,会导致化学位移正向变化。相对于Cs⁺和K⁺离子,存在Na⁺离子时的化学位移去屏蔽δ大于0.1 ppm,顺序为PA>CL>PI>PG。

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