It is well-known that aqueous dispersions of phospholipids spontaneously assemble into bilayer structures. These structures have numerous applications across chemistry and materials science and form the fundamental structural unit of the biological membrane. The particular environment of the lipid bilayer, with a water-poor low dielectric core surrounded by a more polar and better hydrated interfacial region, gives the membrane particular biophysical and physicochemical properties and presents a unique environment for chemical reactions to occur. Many different types of molecule spanning a range of sizes, from dissolved gases through small organics to proteins, are able to interact with membranes and promote chemical changes to lipids that subsequently affect the physicochemical properties of the bilayer. This Review describes the chemical reactivity exhibited by lipids in their membrane form, with an emphasis on conditions where the lipids are well hydrated in the form of bilayers. Key topics include the following: lytic reactions of glyceryl esters, including hydrolysis, aminolysis, and transesterification; oxidation reactions of alkenes in unsaturated fatty acids and sterols, including autoxidation and oxidation by singlet oxygen; reactivity of headgroups, particularly with reactive carbonyl species; and E/Z isomerization of alkenes. The consequences of reactivity for biological activity and biophysical properties are also discussed.

中文翻译：

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膜脂的化学反应性

众所周知，磷脂的水分散体会自发组装成双层结构。这些结构在化学和材料科学领域有广泛的应用，并形成生物膜的基本结构单元。脂质双层的特殊环境，具有被极性更强且水合性更好的界面区域包围的贫水低介电核心，赋予膜特殊的生物物理和物理化学性质，并为化学反应的发生提供了独特的环境。许多不同类型的分子（从溶解的气体到小有机物再到蛋白质）的大小范围广泛，能够与膜相互作用并促进脂质发生化学变化，从而影响双层的物理化学性质。本综述描述了膜形式的脂质所表现出的化学反应性，重点是脂质以双层形式充分水合的条件。关键主题包括：甘油酯的裂解反应，包括水解、氨解和酯交换；不饱和脂肪酸和甾醇中烯烃的氧化反应，包括自氧化和单线态氧氧化；头基的反应性，特别是与反应性羰基物质的反应性；和烯烃的E / Z异构化。还讨论了反应性对生物活性和生物物理特性的影响。