title: Control of the orientational order and nonlinear optical response of the "push-pull" chromophore RuPZn via specific incorporation into densely packed monolayer ensembles of an amphiphilic four-helix bundle peptide: characterization of the peptide-chromophore complexes.
abstract: "Push-pull" chromophores based on extended pi-electron systems have been designed to exhibit exceptionally large molecular hyperpolarizabilities. We have engineered an amphiphilic four-helix bundle peptide to vectorially incorporate such hyperpolarizable chromophores having a metalloporphyrin moiety, with high specificity into the interior core of the bundle. The amphiphilic exterior of the bundle facilitates the formation of densely packed monolayer ensembles of the vectorially oriented peptide-chromophore complexes at the liquid-gas interface. Chemical specificity designed into the ends of the bundle facilitates the subsequent covalent attachment of these monolayer ensembles onto the surface of an inorganic substrate. In this article, we describe the structural characterization of these monolayer ensembles at each stage of their fabrication for one such peptide-chromophore complex designated as AP0-RuPZn. In the accompanying article, we describe the characterization of their macroscopic nonlinear optical properties.
authors.affiliation: Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
authors.forename: Venkata
authors.initials: V
authors.lastname: Krishnan
authors.forename: Andrey
authors.initials: A
authors.lastname: Tronin
authors.forename: Joseph
authors.initials: J
authors.lastname: Strzalka
authors.forename: H Christopher
authors.initials: HC
authors.lastname: Fry
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Therien
authors.forename: J Kent
authors.initials: JK
authors.lastname: Blasie
mesh_terms: D000595:Amino Acid Sequence; D005740:Gases / Q000737:chemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D008969:Molecular Sequence Data; D017711:Nonlinear Dynamics; D055620:Optical Phenomena; D009942:Organometallic Compounds / Q000737:chemistry*; D010455:Peptides / Q000737:chemistry*; D017433:Protein Structure, Secondary; D013056:Spectrophotometry, Ultraviolet; D014867:Water / Q000737:chemistry; D014961:X-Ray Diffraction
chemical_list: D005740:Gases; D008665:Metalloporphyrins; D009942:Organometallic Compounds; D010455:Peptides; C553738:ruthenium(II) (5-(4'-ethynyl-(2,2'-6',2''-terpyridinyl))-10,20-bis(phenyl)porphinato)zinc(II)-(2,2'-6',2''-terpyridine); D014867:Water