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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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja1010702· OSTI ID:1036152
 [1];  [2];  [2];  [2];  [2];  [2]
  1. Departments of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, and Duke University, Durham, North Carolina 27708; University of Pensylvania
  2. Departments of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, and Duke University, Durham, North Carolina 27708

Push-pull chromophores based on extended-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.

Research Organization:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Organization:
USDOE SC Office of Basic Energy Sciences (SC-22)
DOE Contract Number:
FG02-04ER46156
OSTI ID:
1036152
Report Number(s):
DOE-ER46156-15
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 32 Vol. 132; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

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