Ellen M. Adams

Surface Potential of DPPC Monolayers on Concentrated Aqueous Salt Solutions.

The presence and exchange of electrical charges on the surfaces of marine aerosols influence their ability to act as cloud condensation nuclei and play a role in thundercloud electrification. Although interactions exist between surface-active inorganic ions and organic compounds, their role in surface charging of marine aerosols is not well understood. In this study, the surface potential of dipalmitoylphosphatidylcholine (DPPC) monolayers, a zwitterionic phospholipid found in the sea surface microlayer, is measured on concentrated (0.3-2.0 M) chloride salt solutions containing marine-relevant cations (Na(+), K(+), Mg(2+), Ca(2+)) to model and elucidate the electrical properties of organic-covered marine aerosols. Monovalent cations show only a weak effect on the surface potential of DPPC monolayers in the condensed phase compared to water. In contrast, Mg(2+) and Ca(2+) increase the surface potential, indicating different cation binding modes and affinities for the PC headgroup. Moreover, it is found that for divalent chloride salt solutions, the PC headgroup and interfacial water molecules make the largest dipolar contribution to the surface potential. This study shows that for equal charge concentrations, divalent cations impact surface potential of DPPC monolayers more strongly than monovalents likely through changes in the PC headgroup orientation induced by their complexation along with the lesser ordering of interfacial water molecules caused by phosphate group charge screening.

Effect of cation enrichment on dipalmitoylphosphatidylcholine (DPPC) monolayers at the air-water interface

The effect of highly concentrated salt solutions of marine-relevant cations (Na(+), K(+), Mg(2+), and Ca(2+)) on Langmuir monolayers of dipalmitoylphosphatidylcholine (DPPC) was investigated by means of surface pressure-area isotherms, Brewster angle microscopy (BAM), and infrared reflection-absorption spectroscopy (IRRAS). It was found that monovalent cations and Mg(2+) have similar phase behavior, causing DPPC monolayers to expand, while Ca(2+) induces condensation. All cations disrupted the surface morphology at high cation concentration, resulting in decreased reflectivity from the monolayer. Monolayer refractive index was calculated from BAM image intensity in the liquid condensed phase and decreased with increasing cation concentration, which suggests that orientation of the alkyl chains change. Monovalent ions increase ordering of the alkyl chains, more than divalents, yet have little interaction with the DPPC headgroup. Mg(2+) induces gauche defects in the alkyl chain and increases headgroup hydration at low lipid coverage but increases chain ordering and dehydrates the headgroup at high lipid coverage. Ca(2+) orders alkyl chains and dehydrates the phosphate moiety, independent of lipid phase. At the highest salt concentration investigated, significant narrowing of the asymmetric PO2(-) vibrational mode occurs and is attributed to considerable dehydration of the DPPC headgroup.

Cation effects on interfacial water organization of aqueous chloride solutions. I. Monovalent cations: Li+, Na+, K+, and NH4(+).

The influence of monovalent cations on the interfacial water organization of alkali (LiCl, NaCl, and KCl) and ammonium chloride (NH4Cl) salt solutions was investigated using surface-sensitive conventional vibrational sum frequency generation (VSFG) and heterodyne-detected (HD-)VSFG spectroscopy. It was found in the conventional VSFG spectra that LiCl and NH4Cl significantly perturb water’s hydrogen-bonding network. In contrast, NaCl and KCl had little effect on the interfacial water structure and exhibited weak concentration dependency. The Im χs(2)(ωIR) spectra from HD-VSFG further revealed that, for all chloride solutions, the net transition dipole moments of hydrogen-bonded water molecules (O → H) are oriented more toward the vapor phase relative to neat water. This suggests the presence of an interfacial electric field generated from the formation of an ionic double layer in the interfacial region with a distribution of Cl(-) ions located above the countercations, in agreement with predictions from MD simulations. The magnitude of this electric field shows a small but definite cation specificity and follows the order Li(+) ≈ Na(+) > NH4(+) > K(+). The observed trend was found to be in good agreement with previously published surface potential data.

Surface organization of a DPPC monolayer on concentrated SrCl2 and ZnCl2 solutions

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 Zn2+ enrichment on the surface properties of a dipalmitoylphosphatidylcholine (DPPC) monolayer was investigated and compared to that of the alkaline earth metal Sr2+, 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 Zn2+ strongly interacts with DPPC molecules, and induces condensation of the monolayer while Sr2+ 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 Sr2+ has weak interactions with the PC headgroup. Zn2+ ions cause dehydration of carbonyl groups and binds to the phosphate group in a 2 : 1 bridging complex. Findings here suggest that Sr2+ is not enriched in aerosols because it behaves similar to a monovalent ion and only weakly interacts with the monolayer, while enrichment of Zn2+ is due to strong binding to the lipid film.

Interaction of L-Phenylalanine with a Phospholipid Monolayer at the Water-Air Interface.

The interaction of L-phenylalanine with a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayer at the air-water interface was explored using a combination of experimental techniques and molecular dynamics (MD) simulations. By means of Langmuir trough methods and Brewster angle microscopy, L-phenylalanine was shown to significantly alter the interfacial tension and the surface domain morphology of the DPPC film. In addition, confocal microscopy was used to explore the aggregation state of L-phenylalanine in the bulk aqueous phase. Finally, MD simulations were performed to gain molecular-level information on the interactions of L-phenylalanine and DPPC at the interface. Taken together, these results show that L-phenylalanine intercalates into a DPPC film at the air-water interface, thereby affecting the surface tension, phase morphology, and ordering of the DPPC film. The results are discussed in the context of biological systems and the mechanism of diseases such as phenylketonuria.