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使用新型结构探针通过傅里叶变换红外光谱和拉曼光谱对糖类 - 磷脂酰胆碱相互作用的研究。

FT infrared and Raman investigation of saccharide-phosphatidylcholine interactions using novel structure probes.

作者信息

Grdadolnik J, Hadzi D

机构信息

National Institute of Chemistry, Ljubljana, Slovenia.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 1998 Oct;54A(12):1989-2000. doi: 10.1016/s1386-1425(98)00111-5.

Abstract

Conformational consequences of adduct formation between saccharides (trehalose, glucose, raffinose) and sorbitol with dipalmitoylphosphatidylcholine (DPPC) in multibilayers are revealed by relative intensity changes of the band components corresponding to the nu asN(CH3)3 and nu sC-N(CH3)3 stretching modes of the choline chain terminal and those of the nu C = O band. The conformational sensitivity of those modes was demonstrated previously (J. Grdadolnik et al., Chem. Phys. Lipids 65 (1993) 121) and used to demonstrate the effects of stepwise hydration of phosphatidylcholines. The latter are compared with the effects of saccharide binding and found to be qualitatively similar, but not identical. The same is true of the low frequency shifts of the nu asPO2- vibration: the shifts due to saccharide binding correspond to the binding of six to seven water molecules per phosphate which is about 20 cm-1 less than the shift caused by full hydration. A particularly interesting finding concerns the appearance of two bands in the nu asPO2- region of the DPPC-saccharide adducts. The relative intensities of the two bands (1243 and 1223 cm-1) change on additional hydration; it is the one at 1223 cm-1 that prevails at high hydration levels. Major changes in saccharide conformation are not detectable but minor differences between the DPPC bound and crystal spectra are observed.

摘要

多层膜中糖类(海藻糖、葡萄糖、棉子糖)和山梨醇与二棕榈酰磷脂酰胆碱(DPPC)形成加合物的构象后果,通过与胆碱链末端的νasN(CH3)3和νsC-N(CH3)3伸缩模式以及νC = O带相对应的谱带成分的相对强度变化得以揭示。这些模式的构象敏感性先前已得到证明(J. Grdadolnik等人,《化学与物理脂质》65 (1993) 121),并用于证明磷脂酰胆碱逐步水合的影响。将后者与糖类结合的影响进行比较,发现它们在定性上相似,但并不完全相同。νasPO2-振动的低频位移情况也是如此:糖类结合引起的位移对应于每个磷酸基团结合六到七个水分子,这比完全水合引起的位移小约20 cm-1。一个特别有趣的发现涉及DPPC-糖类加合物的νasPO2-区域出现的两个谱带。这两个谱带(1243和1223 cm-1)的相对强度在进一步水合时会发生变化;在高水合水平下占主导的是1223 cm-1处的谱带。未检测到糖类构象的重大变化,但观察到了DPPC结合光谱与晶体光谱之间的细微差异。

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