Interactions of Dimethylsulfoxide with a Dipalmitoylphosphatidylcholine Monolayer Studied by Vibrational Sum Frequency Generation

The interactions between phospholipid monolayers and dimethylsulfoxide (DMSO) molecules were investigated by vibrational sum frequency generation (VSFG) spectroscopy in a Langmuir trough system. Both the head and the tail groups of dipalmitoylphosphatidylcholine (DPPC) as well as DMSO were probed to provide a comprehensive understanding of the interactions between DPPC and DMSO molecules. A condensing effect is observed for the DPPC monolayer on a concentrated DMSO subphase (>20 mol %). This effect results in a well-ordered conformation for the DPPC alkyl chains at very large mean molecular areas. Interactions between DMSO and DPPC headgroups were also studied. DMSO-induced dehydration of the DPPC phosphate group is revealed at DMSO concentration above 10 mol %. The average orientation of DMSO with DPPC versus dipalmitoylphosphate sodium salt (DPPA) monolayers was compared. The comparison revealed that DMSO molecules are perturbed and reorient because of the interfacial electric field created by the charged lipid headgroups. The orientation of the DPPC alkyl chains remains nearly unchanged in the liquid condensed phase with the addition of DMSO. This suggests that DMSO molecules are expelled from the condensed monolayer. In addition, implications for the DMSO-induced permeability enhancement of biological membranes from this work are discussed.