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.

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10.1021/ja1010702

Publication Info

Krishnan, Venkata, Andrey Tronin, Joseph Strzalka, H Christopher Fry, Michael J Therien and J Kent Blasie (2010). 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. J Am Chem Soc, 132(32). pp. 11083–11092. 10.1021/ja1010702 Retrieved from https://hdl.handle.net/10161/4040.

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Therien

Michael J. Therien

William R. Kenan, Jr. Distinguished Professor of Chemistry

Our research involves the synthesis of compounds, supramolecular assemblies, nano-scale objects, and electronic materials with unusual ground-and excited-state characteristics, and interrogating these structures using state-of-the-art transient optical, spectroscopic, photophysical, and electrochemical methods. Over chemical dimensions that span molecules to materials, we probe experimental and theoretical aspects of charge migration reactions and ultrafast electron transfer processes. Insights into the structure-property relationships of molecular, nanoscale, and macroscopic materials allow us to fabricate polarizable and hyperpolarizable chromophores, structures for molecular electronics applications, optical limiters, and a wide range of other electrooptic and photonic materials that include novel conducting polymers, structures for solar energy conversion, and new platforms for in vivo optical imaging. Other efforts in our laboratory involve the elaborating de novo electron- and energy-transfer proteins, interrogating catalytic redox reactions, designing catalysts for small molecule activation, and developing new tools to manipulate nanoscale structures.


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