Department of Biological Sciences and Institute of Structural and Molecular Biology, Birkbeck College, University of London, Malet Street, London WC1E 7HX, UK.
Langmuir. 2013 Apr 9;29(14):4594-602. doi: 10.1021/la304312y. Epub 2013 Mar 26.
The presence of unsaturated lipids in lung surfactant is important for proper respiratory function. In this work, we have used neutron reflection and surface pressure measurements to study the reaction of the ubiquitous pollutant gas-phase ozone, O3, with pure and mixed phospholipid monolayers at the air-water interface. The results reveal that the reaction of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, with ozone leads to the rapid loss of the terminal C9 portion of the oleoyl strand of POPC from the air-water interface. The loss of the C9 portion from the interface is accompanied by an increase in the surface pressure (decrease in surface tension) of the film at the air-water interface. The results suggest that the portion of the oxidized oleoyl strand that is still attached to the lipid headgroup rapidly reverses its orientation and penetrates the air-water interface alongside the original headgroup, thus increasing the surface pressure. The reaction of POPC with ozone also leads to a loss of material from the palmitoyl strand, but the loss of palmitoyl material occurs after the loss of the terminal C9 portion from the oleoyl strand of the molecule, suggesting that the palmitoyl material is lost in a secondary reaction step. Further experiments studying the reaction of mixed monolayers composed of unsaturated lipid POPC and saturated lipid dipalmitoyl-sn-glycero-3-phosphocholine, DPPC, revealed that no loss of DPPC from the air-water interface occurs, eliminating the possibility that a reactive species such as an OH radical is formed and is able to attack nearby lipid chains. The reaction of ozone with the mixed films does cause a significant change in the surface pressure of the air-water interface. Thus, the reaction of unsaturated lipids in lung surfactant changes and impairs the physical properties of the film at the air-water interface.
肺表面活性物质中不饱和脂质的存在对正常呼吸功能很重要。在这项工作中,我们使用中子反射和表面压力测量来研究普遍存在的污染物气相臭氧,O3,与纯和混合磷脂单层在气液界面的反应。结果表明,不饱和脂质 1-棕榈酰-2-油酰-sn-甘油-3-磷酸胆碱(POPC)与臭氧的反应导致 POPC 的油酰链末端 C9 部分从气液界面迅速损失。界面处 C9 部分的损失伴随着气液界面处膜的表面压力(表面张力降低)增加。结果表明,与脂质头部基团仍附着的氧化油酰链的部分迅速反转其取向并与原始头部基团一起穿透气液界面,从而增加表面压力。POPC 与臭氧的反应也会导致棕榈酰链的物质损失,但棕榈酰物质的损失发生在分子的油酰链的末端 C9 部分损失之后,这表明棕榈酰物质是在次级反应步骤中损失的。进一步研究由不饱和脂质 POPC 和饱和脂质二棕榈酰-sn-甘油-3-磷酸胆碱(DPPC)组成的混合单层的反应的实验表明,没有 DPPC 从气液界面损失,消除了形成反应性物质(如 OH 自由基)的可能性,并且能够攻击附近的脂质链。臭氧与混合膜的反应确实会导致气液界面表面压力的显著变化。因此,肺表面活性剂中不饱和脂质的反应改变并损害了气液界面处膜的物理性质。