title: Poly(L-lysine) Interfaces via Dual Click Reactions on Surface-Bound Custom-Designed Dithiol Adsorbates.
abstract: Surfaces modified with poly(L-lysine) can be used to immobilize selected biomolecules electrostatically. This report describes the preparation of a set of self-assembled monolayers (SAMs) from three different azide-terminated adsorbates as platforms for performing controlled surface attachments and as a means of determining the parameters that afford stable poly(L-lysine)-modified SAM surfaces having controlled packing densities. A maleimide-terminated alkyne linker was "clicked" to the azide-terminated surfaces via a copper-catalyzed cycloaddition reaction to produce the attachment sites for the polypeptides. A thiol-Michael addition was then used to immobilize cysteine-terminated poly(L-lysine) moieties on the gold surface, avoiding adsorbate self-reactions with this two-step procedure. Each step in this process was analyzed by ellipsometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, and contact angle goniometry to determine which adsorbate structure most effectively produced the targeted polypeptide interface. Additionally, a series of mixed SAMs using an azidoalkanethiol in combination with a normal alkanethiol having an equivalent alkyl chain were prepared to provide data to determine how dilution of the azide reactive site on the SAM surface influences the initial click reaction. Overall, the collected data demonstrate the advantages of an appropriately designed bidentate absorbate and its potential to form effective platforms for biomolecule surface attachment via click reactions.
authors.affiliation: Departments of Chemistry and Chemical Engineering and the Texas Center for Superconductivity, University of Houston, Houston, Texas 77204-5003, United States.
authors.forename: Amin
authors.initials: A
authors.lastname: Shakiba
authors.affiliation: Departments of Chemistry and Chemical Engineering and the Texas Center for Superconductivity, University of Houston, Houston, Texas 77204-5003, United States.
authors.forename: Andrew C
authors.initials: AC
authors.lastname: Jamison
authors.affiliation: Departments of Chemistry and Chemical Engineering and the Texas Center for Superconductivity, University of Houston, Houston, Texas 77204-5003, United States.
authors.forename: T Randall
authors.initials: TR
authors.lastname: Lee
mesh_terms: D000327:Adsorption; D057930:Click Chemistry; D015394:Molecular Structure; D011107:Polylysine / Q000737:chemistry*; D013499:Surface Properties; D014050:Toluene / Q000031:analogs & derivatives* / Q000737:chemistry
chemical_list: D011107:Polylysine; D014050:Toluene; C004848:dithiol