title: Photoinduced Electron Transfer Elicits a Change in the Static Dielectric Constant of a de Novo Designed Protein.
abstract: We provide a direct measure of the change in effective dielectric constant (ε(S)) within a protein matrix after a photoinduced electron transfer (ET) reaction. A linked donor-bridge-acceptor molecule, PZn-Ph-NDI, consisting of a (porphinato)Zn donor (PZn), a phenyl bridge (Ph), and a naphthalene diimide acceptor (NDI), is shown to be a "meter" to indicate protein dielectric environment. We calibrated PZn-Ph-NDI ET dynamics as a function of solvent dielectric, and computationally de novo designed a protein SCPZnI3 to bind PZn-Ph-NDI in its interior. Mapping the protein ET dynamics onto the calibrated ET catalogue shows that SCPZnI3 undergoes a switch in the effective dielectric constant following photoinduced ET, from ε(S) ≈ 8 to ε(S) ≈ 3.
authors: Nicholas F
authors: NF
authors: Polizzi
authors: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Matthew J
authors: MJ
authors: Eibling
authors: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Jose Manuel
authors: JM
authors: Perez-Aguilar
authors: Jeff
authors: J
authors: Rawson
authors: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Christopher J
authors: CJ
authors: Lanci
authors: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: H Christopher
authors: HC
authors: Fry
authors: David N
authors: DN
authors: Beratan
authors: Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors: Jeffery G
authors: JG
authors: Saven
authors: Michael J
authors: MJ
authors: Therien
mesh_terms: D004579:Electron Transport; D007094:Imides / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D055668:Photochemical Processes; D011506:Proteins / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry
chemical_list: D007094:Imides; D009281:Naphthalenes; D009942:Organometallic Compounds; D011506:Proteins; C542131:naphthalenediimide; D015032:Zinc