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Lewis Acid Coordination Redirects S-Nitrosothiol Signaling Output.


ABSTRACT: S-Nitrosothiols (RSNOs) serve as air-stable reservoirs for nitric oxide in biology. While copper enzymes promote NO release from RSNOs by serving as Lewis acids for intramolecular electron-transfer, redox-innocent Lewis acids separate these two functions to reveal the effect of coordination on structure and reactivity. The synthetic Lewis acid B(C6 F5 )3 coordinates to the RSNO oxygen atom, leading to profound changes in the RSNO electronic structure and reactivity. Although RSNOs possess relatively negative reduction potentials, B(C6 F5 )3 coordination increases their reduction potential by over 1 V into the physiologically accessible +0.1 V vs. NHE. Outer-sphere chemical reduction gives the Lewis acid stabilized hyponitrite dianion trans-[LA-O-N=N-O-LA]2- [LA=B(C6 F5 )3 ], which releases N2 O upon acidification. Mechanistic and computational studies support initial reduction to the [RSNO-B(C6 F5 )3 ] radical anion, which is susceptible to N-N coupling prior to loss of RSSR.

SUBMITTER: Hosseininasab V 

PROVIDER: S-EPMC7385465 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Lewis Acid Coordination Redirects S-Nitrosothiol Signaling Output.

Hosseininasab Valiallah V   McQuilken Alison C AC   Bakhoda Abolghasem Gus AG   Bertke Jeffery A JA   Timerghazin Qadir K QK   Warren Timothy H TH  

Angewandte Chemie (International ed. in English) 20200417 27


S-Nitrosothiols (RSNOs) serve as air-stable reservoirs for nitric oxide in biology. While copper enzymes promote NO release from RSNOs by serving as Lewis acids for intramolecular electron-transfer, redox-innocent Lewis acids separate these two functions to reveal the effect of coordination on structure and reactivity. The synthetic Lewis acid B(C<sub>6</sub> F<sub>5</sub> )<sub>3</sub> coordinates to the RSNO oxygen atom, leading to profound changes in the RSNO electronic structure and reactivi  ...[more]

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