title: Can cyclopropyl-terminated self-assembled monolayers on gold be used to mimic the surface of polyethylene?
abstract: This paper describes the formation of a new series of monolayer films generated by the self-assembly of omega-cyclopropylalkanethiols, CyPr(CH(2))(n)SH (n = 9-13), onto the surface of gold. Procedures used to prepare the omega-cyclopropylalkanethiol adsorbates are also reported. Methyl-, vinyl-, and isopropyl-terminated self-assembled monolayers (SAMs) were also prepared and used as reference films to evaluate the structure and properties of the new cyclopropyl-terminated films. Ellipsometry and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) were used to examine the structure of the SAMs. A small but systematically lower thickness of the new films compared to that of analogous methyl-terminated SAMs was observed. Also, the orientation of the ring with respect to the surface normal was observed to vary systematically with the number of methylene groups in the adsorbate backbone (i.e., odd vs even chain lengths). Measurements of wettability by contact angle goniometry also revealed a small but reproducible "odd-even" effect for all contacting liquids used, except hexadecane, which almost completely wet the surfaces (theta(a) = 10-13 degrees ). When compared to the wettability data obtained from methyl- and isopropyl-terminated SAMs, the wettability data obtained from the cyclopropyl-terminated SAMs suggest that these films offer an increased density of atomic contacts per unit area across the surface, and thus enhanced attractive interactions with contacting liquids. Comparison of the wettabilities of vinyl-terminated and cyclopropyl-terminated films is complicated by dipole-induced dipole interactions and/or pi-pi interactions between the surfaces and the probe liquids. Furthermore, the significantly similar wettabilities of the cyclopropyl-terminated SAMs and the surface of polyethylene suggests that these SAMs (and perhaps other SAMs with judiciously designed tailgroups) can be used to mimic the interfacial properties of polymeric materials without complications arising from surface reconstruction.
authors.affiliation: Department of Chemistry, University of Houston, Houston, TX 77204-5003, USA.
authors.forename: David
authors.initials: D
authors.lastname: Barriet
authors.forename: Pawilai
authors.initials: P
authors.lastname: Chinwangso
authors.forename: T Randall
authors.initials: TR
authors.lastname: Lee
mesh_terms: D000327:Adsorption; D006046:Gold / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008422:Materials Testing; D008956:Models, Chemical; D020959:Polyethylene / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry; D013499:Surface Properties; D017155:Wettability
chemical_list: D011108:Polymers; D006046:Gold; D020959:Polyethylene