Adams Ellen M, Verreault Dominique, Jayarathne Thilina, Cochran Richard E, Stone Elizabeth A, Allen Heather C
Department of Chemistry & Biochemistry, The Ohio State University, Columbus, Ohio 43210, USA.
Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA.
Phys Chem Chem Phys. 2016 Nov 30;18(47):32345-32357. doi: 10.1039/c6cp06887a.
Transition metals are known to be enriched in organic-coated marine aerosols, but the impact these cations have on their surface properties is not well understood. Here the effect of Zn enrichment on the surface properties of a dipalmitoylphosphatidylcholine (DPPC) monolayer was investigated and compared to that of the alkaline earth metal Sr, an ion not enriched in aerosols. Phase behavior of the DPPC film on concentrated aqueous solutions was probed with surface pressure-area isotherms while domain morphology was monitored with Brewster angle microscopy (BAM). Infrared reflection-absorption spectroscopy (IRRAS) and vibrational sum frequency generation (VSFG) spectroscopy were used to assess the impact of cations on the conformation and orientation of alkyl chains as well as the hydration state of the carbonyl and phosphatidylcholine (PC) moieties. Results of compression isotherms and BAM show that Zn strongly interacts with DPPC molecules, and induces condensation of the monolayer while Sr only weakly interacts with the monolayer in expanded phases. Conformational order and orientation of alkyl chains in the condensed phase are not significantly altered by either cation. IRRAS indicates that Sr has weak interactions with the PC headgroup. Zn ions cause dehydration of carbonyl groups and binds to the phosphate group in a 2 : 1 bridging complex. Findings here suggest that Sr is not enriched in aerosols because it behaves similar to a monovalent ion and only weakly interacts with the monolayer, while enrichment of Zn is due to strong binding to the lipid film.
已知过渡金属在有机包覆的海洋气溶胶中含量丰富,但这些阳离子对其表面性质的影响尚不清楚。在此,研究了锌富集对二棕榈酰磷脂酰胆碱(DPPC)单分子层表面性质的影响,并与碱土金属锶(一种在气溶胶中不富集的离子)进行了比较。用表面压力-面积等温线探测DPPC膜在浓水溶液上的相行为,同时用布鲁斯特角显微镜(BAM)监测畴形态。利用红外反射吸收光谱(IRRAS)和振动和频产生(VSFG)光谱来评估阳离子对烷基链的构象和取向以及羰基和磷脂酰胆碱(PC)部分的水合状态的影响。压缩等温线和BAM的结果表明,锌与DPPC分子强烈相互作用,并诱导单分子层凝聚,而锶在膨胀相中仅与单分子层弱相互作用。两种阳离子均未显著改变凝聚相中烷基链的构象有序性和取向。IRRAS表明,锶与PC头基的相互作用较弱。锌离子导致羰基脱水,并以2∶1的桥连络合物形式与磷酸基团结合。此处的研究结果表明,锶在气溶胶中不富集是因为它的行为类似于单价离子,仅与单分子层弱相互作用,而锌的富集是由于其与脂质膜的强烈结合。