Solvent Dynamical Control of Ultrafast Ground State Electron Transfer:  Implications for Class II−III Mixed Valency

2007 ◽  
Vol 129 (42) ◽  
pp. 12772-12779 ◽  
Author(s):  
Benjamin J. Lear ◽  
Starla D. Glover ◽  
J. Catherine Salsman ◽  
Casey H. Londergan ◽  
Clifford P. Kubiak
Keyword(s):  
Electron Transfer ◽  
Ground State ◽  
Class Ii ◽  
Mixed Valency ◽  
State Electron ◽  
Dynamical Control ◽  
Ground State Electron

Ground-state electron transfer in all-polymer donor–acceptor heterojunctions

2020 ◽  
Vol 19 (7) ◽  
pp. 738-744 ◽  
Author(s):  
Kai Xu ◽  
Hengda Sun ◽  
Tero-Petri Ruoko ◽  
Gang Wang ◽  
Renee Kroon ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Ground State ◽  
State Electron ◽  
Donor Acceptor ◽  
Ground State Electron

Ground state electron transfer between TCNE and one or more 16-electron species containing vanadium, osmium, ruthenium or cobalt

1996 ◽  
Vol 251 (1-2) ◽  
pp. 239-248 ◽  
Author(s):  
Frank Baumann ◽  
Martina Heilmann ◽  
Walther Matheis ◽  
Andreas Schulz ◽  
Wolfgang Kaim ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Ground State ◽  
State Electron ◽  
Ground State Electron

scholarly journals Ground-State Electron Transfer as an Initiation Mechanism for Asymmetric Hydroalkylations in Radical Biocatalysis

2021 ◽  
Author(s):  
Haigen Fu ◽  
Heather Lam ◽  
Megan Emmanuel ◽  
Ji Hye Kim ◽  
Braddock Sandoval ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Ground State ◽  
Saturation Mutagenesis ◽  
Wild Type ◽  
Initiation Mechanism ◽  
Radical Initiation ◽  
Enzyme Active Site ◽  
Bond Forming ◽  
State Electron ◽  
Ground State Electron

<p>Stereoselective bond-forming reactions are essential tools in modern organic synthesis. However, catalytic strategies for controlling the stereochemical outcome of radical-mediated C–C bond formation remain underdeveloped.<b> </b>Here, we report an ‘ene’-reductase catalyzed asymmetric hydroalkylation of olefins using α-bromoketones as radical precursors. In these reactions, radical initiation occurs <i>via</i> ground-state electron transfer from the flavin cofactor located within the enzyme active site, representing a mechanistic departure from previous photoenzymatic hydroalkylations. Four rounds of site saturation mutagenesis based on wild-type nicotinamide-dependent cyclohexanone reductase (NCR) were deployed to access a variant capable of catalyzing a cyclization to furnish β-chiral cyclopentanones with high levels of enantioselectivity. Additionally, the wild-type NCR was identified that could catalyze the intermolecular coupling with precise stereochemical control over the radical termination step. This report demonstrates this enzyme family’s catalytic versatility and highlights the opportunity for protein engineering to address reactivity and selectivity challenges in radical biocatalysis. </p>

scholarly journals Ground-State Electron Transfer as an Initiation Mechanism for Asymmetric Hydroalkylations in Radical Biocatalysis

2021 ◽  
Author(s):  
Haigen Fu ◽  
Heather Lam ◽  
Megan Emmanuel ◽  
Ji Hye Kim ◽  
Braddock Sandoval ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Ground State ◽  
Saturation Mutagenesis ◽  
Wild Type ◽  
Initiation Mechanism ◽  
Radical Initiation ◽  
Enzyme Active Site ◽  
Bond Forming ◽  
State Electron ◽  
Ground State Electron

<p>Stereoselective bond-forming reactions are essential tools in modern organic synthesis. However, catalytic strategies for controlling the stereochemical outcome of radical-mediated C–C bond formation remain underdeveloped.<b> </b>Here, we report an ‘ene’-reductase catalyzed asymmetric hydroalkylation of olefins using α-bromoketones as radical precursors. In these reactions, radical initiation occurs <i>via</i> ground-state electron transfer from the flavin cofactor located within the enzyme active site, representing a mechanistic departure from previous photoenzymatic hydroalkylations. Four rounds of site saturation mutagenesis based on wild-type nicotinamide-dependent cyclohexanone reductase (NCR) were deployed to access a variant capable of catalyzing a cyclization to furnish β-chiral cyclopentanones with high levels of enantioselectivity. Additionally, the wild-type NCR was identified that could catalyze the intermolecular coupling with precise stereochemical control over the radical termination step. This report demonstrates this enzyme family’s catalytic versatility and highlights the opportunity for protein engineering to address reactivity and selectivity challenges in radical biocatalysis. </p>

Erratum: Why is the ground state electron configuration for Lithium 1s(2)2s ?

2021 ◽  
Author(s):  
Will Stacey ◽  
Frank Marsiglio
Keyword(s):  
Ground State ◽  
Virial Theorem ◽  
Variational Calculation ◽  
Electron Configuration ◽  
State Electron ◽  
Ground State Electron

Abstract For the variational calculation involving the 1s22s state, we inadvertently filed energy contributions into the wrong categories, with the result that the Virial Theorem appeared to be violated. The overall calculation of the energy was done correctly, and appropriate assignment of the different energy contributions now confirms that the Virial Theorem is obeyed. Obviously, our conclusions are unchanged.

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