Browsing by Author "Ye, S"
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- ItemCharacterizing the photoinduced switching process of a nitrospiropyran self-assembled monolayer using in situ sum frequency generation spectroscopy(American Chemical Society, 2012-10-02) Darwish, TA; Tong, YJ; James, M; Hanley, TL; Peng, QL; Ye, SSum frequency generation (SFG) vibrational spectroscopy is employed to investigate the reversible, photoinduced spiro -> merocyanine isomerization of a self-assembled monolayer, the result of attachment of nitrospiropyran to a gold surface using a dithiolane anchoring group. The attachment of these molecular "alligator clips" to spiropyran molecules provide an easily accessible method to self-assemble a robust monolayer of spiropyran on a gold surface, which allows photoswitching of the spiropyran units. Probing the symmetric and antisymmetric stretching modes of the nitro group allows the determination of the structural orientation of the charged moiety with respect to the surface normal as well as the isomerization rates under photoinduced switching conditions. The photoisomerization of the spiropyran SAM on the gold surface is much faster than the rates of switching spiropyrans in a solid crystalline form, and the rate of thermal relaxation of the opened to closed form in this study is found to be on the same time scale as the relaxation of spiropyran when present in solutions with polar solvents. © 2012, American Chemical Society.
- ItemStructure and lateral Iiteraction in mixed monolayers of dioctadecyldimethylammonium chloride (DOAC) and stearyl alcohol(American Chemical Society, 2013-05-07) Ge, A; Wu, H; Darwish, TA; James, M; Osawa, M; Ye, Sπ-A isotherms, atomic force microscopy (AFM), and sum frequency generation (SFG) vibrational spectroscopy are employed to investigate the molecular structure and lateral interactions in mixed monolayers of dioctadecyldimethylammonium chloride (DOAC) and stearyl alcohol (SA) at air/water and air/solid interfaces. To avoid possible interference between the two molecules in the SFG spectroscopic measurements, perprotonated DOAC and perdeuterated SA (dSA) were used. The thermodynamic analyses for the π-A isotherms show that DOAC is miscible with dSA. SFG observations reveal that DOAC molecules become conformationally ordered as dSA molecules are introduced into the monolayer. AFM observations demonstrate coexistence of DOAC-rich and dSA-rich domains in the mixed monolayer with ratios different from their initial composition in the subphase. The present study suggests that DOAC molecules in the mixed monolayer are condensed by mixing with dSA in which the repulsive interactions between positively charged head groups of the DOAC molecules are largely reduced along with an increase of van der Waals interactions with dSA.© 2013, American Chemical Society.