title: Interaction of self-assembled monolayers of oligo(ethylene glycol)-terminated alkanethiols with water studied by vibrational sum-frequency generation.
abstract: Vibrational sum-frequency generation (VSFG) was used to investigate the conformational changes in self-assembled monolayers (SAMs) of (1-mercaptoundec-11-yl) hexa(ethylene glycol) monomethylether (EG6-OMe) on gold when exposed to liquid water. VSFG spectra of the EG6-OMe SAMs were recorded before, during, and after exposure of the films to water and after a subsequent evacuation step. While in contact with water the entire ethylene glycol chains are found in a random, solvated state, after removal from the fluid water molecules remain absorbed only at the terminal groups of the film giving rise to distinct conformational changes. After evacuation, the structure of the EG6-OMe SAM reverts to its original state, indicating that water has been removed from the monolayer. Our findings support recent ab initio calculations and Monte Carlo simulations on the interaction of ethylene glycol-terminated monolayers with water.
authors.affiliation: Angewandte Physikalische Chemie, Universität Heidelberg, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany.
authors.forename: R Y
authors.initials: RY
authors.lastname: Wang
authors.forename: M
authors.initials: M
authors.lastname: Himmelhaus
authors.forename: J
authors.initials: J
authors.lastname: Fick
authors.forename: S
authors.initials: S
authors.lastname: Herrwerth
authors.forename: W
authors.initials: W
authors.lastname: Eck
authors.forename: M
authors.initials: M
authors.lastname: Grunze
mesh_terms: D000042:Absorption; D000473:Alkanes / Q000737:chemistry*; D006046:Gold / Q000737:chemistry; D057927:Hydrophobic and Hydrophilic Interactions; D008968:Molecular Conformation; D011092:Polyethylene Glycols / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013059:Spectrum Analysis, Raman / Q000379:methods; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D000473:Alkanes; D013438:Sulfhydryl Compounds; D014867:Water; D011092:Polyethylene Glycols; D006046:Gold