Reaction of hydrogen peroxide with coordinated superoxide in [(NH3)5CoIII(μ-O2)CoIII(NH3)5]5+: a mechanistic study

2009 ◽  
pp. 5469 ◽  
Author(s):  
Ritu Mishra ◽  
Subrata Mukhopadhyay ◽  
Rupendranath Banerjee
Keyword(s):  
Hydrogen Peroxide ◽  
Mechanistic Study

scholarly journals Mechanistic Study of the Conversion of Superoxide to Oxygen and Hydrogen Peroxide in Carbon Nanoparticles

2016 ◽  
Vol 8 (24) ◽  
pp. 15086-15092 ◽  
Author(s):  
Almaz S. Jalilov ◽  
Chenhao Zhang ◽  
Errol L. G. Samuel ◽  
William K. A. Sikkema ◽  
Gang Wu ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Carbon Nanoparticles ◽  
Mechanistic Study

Photochemical Hydroxylation of Salicylic Acid with Hydrogen Peroxide; Mechanistic Study of Substrate Sensitized Reaction

1996 ◽  
Vol 61 (12) ◽  
pp. 1729-1737 ◽  
Author(s):  
Kamil Lang ◽  
Jiřina Brodilová ◽  
Stanislav Luňák
Keyword(s):  
Hydrogen Peroxide ◽  
Salicylic Acid ◽  
Quantum Yields ◽  
Mechanistic Study ◽  
Isomer Ratio ◽  
Dihydroxybenzoic Acid ◽  
Effect Of Ph ◽  
Product Ratio

The photochemical hydroxylation of salicylic acid (SA) by hydrogen peroxide proceeds via the same intermediate independently of the excited reactant (i.e. SA or H2O2). This conclusion is supported by the similar effect of pH on the quantum yields and on the isomer ratio of formed products: 2,3-dihydroxybenzoic acid (2,3-DHB) and 2,5-dihydroxybenzoic acid (2,5-DHB). The product ratio ([2,3-DHB]/[2,5-DHB]) is not affected by H2O2 concentration.

scholarly journals From Hydrogen Peroxide-Responsive Boronated Nucleosides Towards Antisense Therapeutics – A Computational Mechanistic Study

2019 ◽  
Vol 92 (2) ◽  
pp. 287-295
Author(s):  
Tana Tandarić ◽  
Lucija Hok ◽  
Robert Vianello
Keyword(s):  
Hydrogen Peroxide ◽  
Genetic Disorders ◽  
Md Simulations ◽  
Chemical Mechanism ◽  
Nucleophilic Attack ◽  
Mechanistic Study ◽  
Stimuli Responsive ◽  
Nucleic Acid Therapeutics ◽  
Promising Tool ◽  
Synthetic Approaches

We used a combination of MD simulations and DFT calculations to reveal the precise chemical mechanism underlying the conversion of boronated nucleosides to natural nucleosides in the presence of hydrogen peroxide, which was recently experimentally demonstrated by Morihiro and Obika et al. (Chem. Sci. 2018, 9, 1112). Our results show that this process is initiated by the H2O2 deprotonation to a base concerted with the nucleophilic attack of the resulting OOH– anion onto the boron atom as the rate-limiting step of the overall transformation. This liberates a free base, followed by the 1,2-rearrangement to the C–OOH– adduct. Lastly, breaking of the O–O bond within the peroxide moiety cleaves the boron–carbon bond, giving boronic acid ester and the matching ketone as the final products. The obtained reaction profiles successfully interpret a much higher conversion rate of the thymine derivative over its guanine analogue, and rationalize why t-Bu-hydroperoxide is hindering the conversion, thus placing both aspects in firm agreement with experiments. The offered insight represents a promising tool for the future synthetic approaches of stimuli-responsive biomolecules, especially chemically caged prodrug-type nucleic acid therapeutics, bearing significant importance due to their application potential in diagnostics and therapy of various genetic disorders.

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