Ordering effects of cholesterol on sphingomyelin monolayers investigated by high-resolution broadband sum-frequency generation vibrational spectroscopy

This report investigated the ordering of the alky chain of sphingomyelin （SMs） monolayers induced by cholesterol at the air/water interface using high-resolution broadband sum frequency generation vibrational spectroscopy （HR-BB-SFG-VS）. The SFG spectra of the three nature sphingomyelin/cholesterol mixture monolayers with two concentrations of the cholesterol at the air/water interface are performed under different polarization combination. A new resolved CH2 symmetric stretching （d＋, ~2834 cm-1） and the CH3 symmetric stretching （r＋, ~2874 cm-1） mode are applied to characterize the conformational order in the sphingomyelin/cholesterol mixture monolayers. It was found that the cholesterol make the sphingosine backbones more conformational order. During this process, the conformational order of the N-linked acyl chain remains unaltered. Moreover, the sphingosine backbones of SMs have much larger contributions to gauche defects of SMs than one in the N-linked acyl chain. These results presented here not only shed lights on understanding of the interactions of sphingomyelin molecules with cholesterol molecules at interface but also demonstrates the ability of HR-BB-SFG to probe such complicated molecular systems.

Interfacial Water Structure in Langmuir Monolayer and Gibbs Layer Probed by Sum Frequency Generation Vibrational Spectroscopy

Langmuir monolayer and Gibbs layer exhibit surface-active properties and it can be used as simple model systems to investigate the physicochemical properties of biological membranes. In this report, we presented the OH stretching vibration of H2O in the 4＂-n-pentyl-4-cyano-p-terphenyl （5CT）, nonadecanenitrile （C18CN） Langmuir monolayer and compared them with CH3CN Gibbs layer at the air/water interface with polarization SFG-VS. This study demonstrated that the hydrogen bond network is different in the Langmuir monolayer of 5CT, C18CN from CH3CN Gibbs layer at the air/water interface which showed two different water structures on the different surface layer. The results provided a deeper insight into understanding the hydrogen bond on the interfaces.