title: Fluorinated aminoanthranilamides: non-native amino acids for bringing proteomic approaches to charge-transfer systems.
abstract: The ability to control charge transfer at molecular and nanometer scales represents the ultimate level of electronic mastery, and its impacts cannot be overstated. As electrostatic analogues of magnets, electrets possess ordered electric dipoles that present key paradigms for directing transduction of electrons and holes. Herein we describe the design and development of fluorinated aminoanthranilamides, derivatives of non-native aromatic beta-amino acids, as building blocks for hole-transfer molecular electrets. A highly regio-selective nucleophilic aromatic substitution of difluorinated nitrobenzoic acid provides the underpinnings for an array of unprecedented anthranilamide structures. Spin density distribution and electrochemical analyses reveal that fluorine induces about 200 mV positive shifts in reduction potentials without compromising the stability of the oxidized residues, making them invaluable building blocks for hole-transfer systems. These findings open unexplored routes to novel amino-acid structures, setting a foundation for bringing principles of proteomics to designs of charge-transfer systems.
authors.affiliation: Department of Bioengineering, University of California, Riverside, CA 92521, USA. vullev@ucr.edu.
authors.forename: Jillian M
authors.initials: JM
authors.lastname: Larsen-Clinton
authors.affiliation: Department of Chemistry, University of California, Riverside, CA 92521, USA.
authors.forename: Eli M
authors.initials: EM
authors.lastname: Espinoza
authors.affiliation: Department of Chemistry, University of California, Riverside, CA 92521, USA.
authors.forename: Maximillian
authors.initials: M
authors.lastname: F Mayther
authors.affiliation: Department of Bioengineering, University of California, Riverside, CA 92521, USA. vullev@ucr.edu.
authors.forename: John
authors.initials: J
authors.lastname: Clark
authors.affiliation: Department of Bioengineering, University of California, Riverside, CA 92521, USA. vullev@ucr.edu.
authors.forename: Christina
authors.initials: C
authors.lastname: Tao
authors.affiliation: Department of Bioengineering, University of California, Riverside, CA 92521, USA. vullev@ucr.edu.
authors.forename: Duoduo
authors.initials: D
authors.lastname: Bao
authors.affiliation: Department of Bioengineering, University of California, Riverside, CA 92521, USA. vullev@ucr.edu.
authors.forename: Christa M
authors.initials: CM
authors.lastname: Larino
authors.affiliation: Department of Bioengineering, University of California, Riverside, CA 92521, USA. vullev@ucr.edu and Materials Science and Engineering Program, University of California, Riverside, CA 92521, USA.
authors.forename: Michelle
authors.initials: M
authors.lastname: Wurch
authors.affiliation: Department of Bioengineering, University of California, Riverside, CA 92521, USA. vullev@ucr.edu.
authors.forename: Stephanie
authors.initials: S
authors.lastname: Lara
authors.affiliation: Department of Bioengineering, University of California, Riverside, CA 92521, USA. vullev@ucr.edu and Department of Chemistry, University of California, Riverside, CA 92521, USA and Materials Science and Engineering Program, University of California, Riverside, CA 92521, USA and Department of Biochemistry, University of California, Riverside, CA 92521, USA.
authors.forename: Valentine I
authors.identifier: http://orcid.org/0000-0002-3416-9686
authors.initials: VI
authors.lastname: Vullev
mesh_terms: D000596:Amino Acids / Q000737:chemistry*; D054879:Halogenation; D009682:Magnetic Resonance Spectroscopy; D040901:Proteomics; D011789:Quantum Theory; D013237:Stereoisomerism; D062367:ortho-Aminobenzoates / Q000737:chemistry*
chemical_list: D000596:Amino Acids; D062367:ortho-Aminobenzoates; C000219:anthranilamide