STUDY OF IONIC STRUCTURES IN PHOSPHOLIPIDS BY INFRARED SPECTRA.
STUDY OF IONIC STRUCTURES IN PHOSPHOLIPIDS BY INFRARED SPECTRA.
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通过红外光谱研究磷脂中的离子结构。
DOI：
10.1016/s0021-9258(18)97335-7
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发表时间：
1965
期刊：
影响因子：
--
通讯作者：
R. Katzman
中科院分区：
文献类型：
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作者：
M. B. Abramson;W. T. Norton;R. Katzman
许多研究人员已经对脂类的红外吸收光谱进行了研究，他们主要感兴趣的是利用这些光谱来鉴定所研究的各种物质或进行定量评估。然而，光谱可以进一步用于了解分子中存在的离子基团，并识别当脂质与离子介质反应时离子结构的变化。Kimura和Nagai(2)在对磷脂酰丝氨酸光谱的研究中指出，当这种脂质用酸或碱处理时，明显的变化，并将其中一些归因于羧酸基的电离变化。Abramson，Katzman和Gregor(3)，与这项工作一致，表明盐型磷脂酰丝氨酸产生在6.1P处有强吸收的光谱，而在酸性形态下不存在。这归因于-COO-共振。这种对羧基光谱变化的认识对阐明分子结构是有价值的。在这篇通讯中，描述了几种磷脂的磷酸基团电离过程中发生的变化。结果表明，红外光电子能谱可用于研究这些化合物及其相关的正磷酸酯类化合物的电离变化。此外，虽然不同的作者已经将吸收频率范围指定为电离和非电离的磷酸基团(4-7)，但这些范围是宽的和重叠的。这些作者在将特定的吸收带分配给特定的化学基团方面也存在分歧。本文试图更紧密地鉴定磷脂的这些谱带，并利用它们来识别这些化合物的结构特征。为了帮助理解更复杂的磷脂分子，我们对十八烷基磷酸二氢、双十八烷基磷酸氢以及这两种酯的钠盐进行了研究。磷脂酸及其盐类似于十八烷基磷酸二氢；而磷脂酰丝氨酸、卵磷脂、鞘磷脂和磷脂酰乙醇胺，正磷酸的二酯，在有限的方式上类似于十八烷基磷酸二氢。
The infrared absorption spectra of lipids have been studied by numerous investigators chiefly interested in using the spectra to identify the various substances studied or for quantitative estimations. However, the spectra can be further used to obtain an understanding of the ionic groups that are present in the molecule and to identify changes in ionic structures arising as the lipid reacts with an ionic medium. Kimura and Nagai (2) in a study of the spectra of phosphatidylserine pointed out changes that were evident as this lipid was treated with acid or base, and attributed some of these to changes in the ionization of the carboxylic acid group. Abramson, Katzman, and Gregor (3), in agreement with this work, showed that the salt forms of phosphatidylserine produce spectra with strong absorbance at 6.1 p which does not exist in the acid form. This is attributed to the-COO- resonance. This recognition of the changes in the spectra of the carboxyl group was valuable in elucidating the structure of the molecule. In this communication the changes occurring in the ionization of the phosphate group of several phospholipids are described. It is shown that the infrared spect, ra can be used to study the changes in the ionization of these compounds and related esters of orthophosphoric acid. Adlthough various authors have assigned absorption frequency ranges to the ionized and unionized phosphate groups (4-7), these ranges are broad and overlap. These authors also disagree in their assignment of specific absorption bands to definite chemical groups. An attempt is made in this paper to identify these bands more closely for phospholipids and to use them for the recognition of structural characteristics of these compounds.To aid in the understanding of the more complex phospholipid molecules a study was made of octadecyl dihydrogen phosphate, dioctadecyl hydrogen phosphate, and the sodium salts of both these esters. Phosphatidic acid and its salt resemble octadecyl dihydrogen phosphate; while phosphatidylserine, lecithin, sphingomyelin, and phosphatidylethanolamine, diesters of orthophosphoric acid, are similar in a limited way to dioctadecyl hydrogen phosphate.