Structural consequences of the one-electron reduction of d4[Mo(CO)2(η-PhCCPh)Tp′]+and the electronic structure of the d5radicals [M(CO)L(η-MeCCMe)Tp′] {L = CO and P(OCH2)3CEt}

2006 ◽  
pp. 3466-3477 ◽  
Author(s):  
Christopher J. Adams ◽  
Ian M. Bartlett ◽  
Supakorn Boonyuen ◽  
Neil G. Connelly ◽  
David J. Harding ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Electron Reduction ◽  
The One

scholarly journals Redox and Antioxidant Modulation of Circadian Rhythms: Effects of Nitroxyl, N-Acetylcysteine and Glutathione

Molecules ◽  
2021 ◽  
Vol 26 (9) ◽  
pp. 2514
Author(s):  
Santiago Andrés Plano ◽  
Fernando Martín Baidanoff ◽  
Laura Lucía Trebucq ◽  
Sebastián Ángel Suarez ◽  
Fabio Doctorovich ◽  
...  
Keyword(s):  
Soluble Guanylate Cyclase ◽  
Phase Locking ◽  
Cyclic Guanosine Monophosphate ◽  
Guanosine Monophosphate ◽  
Circadian Phase ◽  
Subjective Night ◽  
Circadian Time ◽  
Electron Reduction ◽  
Locomotor Rhythms ◽  
The One

The circadian clock at the hypothalamic suprachiasmatic nucleus (SCN) entrains output rhythms to 24-h light cycles. To entrain by phase-advances, light signaling at the end of subjective night (circadian time 18, CT18) requires free radical nitric oxide (NO•) binding to soluble guanylate cyclase (sGC) heme group, activating the cyclic guanosine monophosphate (cGMP)-dependent protein kinase (PKG). Phase-delays at CT14 seem to be independent of NO•, whose redox-related species were yet to be investigated. Here, the one-electron reduction of NO• nitroxyl was pharmacologically delivered by Angeli’s salt (AS) donor to assess its modulation on phase-resetting of locomotor rhythms in hamsters. Intracerebroventricular AS generated nitroxyl at the SCN, promoting phase-delays at CT14, but potentiated light-induced phase-advances at CT18. Glutathione/glutathione disulfide (GSH/GSSG) couple measured in SCN homogenates showed higher values at CT14 (i.e., more reduced) than at CT18 (oxidized). In addition, administration of antioxidants N-acetylcysteine (NAC) and GSH induced delays per se at CT14 but did not affect light-induced advances at CT18. Thus, the relative of NO• nitroxyl generates phase-delays in a reductive SCN environment, while an oxidative favors photic-advances. These data suggest that circadian phase-locking mechanisms should include redox SCN environment, generating relatives of NO•, as well as coupling with the molecular oscillator.

scholarly journals Synthesis and electronic structure determination of uranium(vi) ligand radical complexes

2016 ◽  
Vol 45 (31) ◽  
pp. 12576-12586 ◽  
Author(s):  
Khrystyna Herasymchuk ◽  
Linus Chiang ◽  
Cassandra E. Hayes ◽  
Matthew L. Brown ◽  
Jeffrey S. Ovens ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Structure Determination ◽  
Salen Ligands ◽  
The One

Pentagonal bipyramidal uranyl (UO22+) complexes of salen ligands were prepared and the electronic structure of the one-electron oxidized species[1a–c]+were investigated in solution.

One electron reduction transforms high-valent low-spin cobalt alkylidene into high-spin cobalt(ii) carbene radical

2020 ◽  
Vol 56 (60) ◽  
pp. 8416-8419
Author(s):  
Amanda Grass ◽  
James A. Bellow ◽  
Gregory Morrison ◽  
Hans-Conrad zur Loye ◽  
Richard L. Lord ◽  
...  
Keyword(s):  
Electronic Structure ◽  
High Spin ◽  
Ligand Environment ◽  
Electron Reduction ◽  
High Valent

Synthesis, electronic structure, and reactivity of a novel Co(ii) carbene radical in the bis(alkoxide) ligand environment are reported.

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