Mechanistic Studies on the Reaction between R<sub>2</sub>N‐NONOates and Aquacobalamin: Evidence for Direct Transfer of a Nitroxyl Group from R<sub>2</sub>N‐NONOates to Cobalt(III) Centers

“…The second model we consider in this article involves an adduct formation and parallel decay of one of the reactants. The earlier experimental example is the ligand substitution reaction between the vitamin B 12 derivative aquacobalamin/hydroxycobalamin (H 2 OCbl + /HOCbl) and secondary amine NONOates, R 2 N‐NONOates . The latter reagents (the “ligand”) was confirmed to undergo a decomposition, a process that was termed “silent killer” later because it does not change the observed absorbance values.…”

Section: Resultsmentioning

confidence: 99%

“…In the experimental example , C was the ligand whereas D was the metal‐containing species H 2 OCbl + /HOCbl. This scheme seems to be often encountered in the literature of the kinetics of diverse chemical reactions .…”

Section: Resultsmentioning

confidence: 99%

“…In the recent literature, two cases have been identified when the procedure described in the preceding paragraph was successful, yet the possibility of a reversible second–order reaction was ruled out based on independent experimental observations or plausible chemical considerations . In both cases, numerical integration of alternative kinetic schemes was used to show that other interpretations of the experimental data are also in agreement with the kinetic observations.…”

Section: Introductionmentioning

confidence: 99%

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Reaction Schemes That Are Easily Confused with a Reversible First-Order Reaction

Balogh

Lente

Kalmár³

et al. 2015

Int. J. Chem. Kinet.

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A detailed kinetic analysis of two schemes, one involving coupled consecutive processes and another featuring parallel reactions and decay of ???, is presented here using Taylor series expansion. It is shown that both of these schemes are easily confused with the reversible second order reaction in a routine kinetic study. The kinetic traces predicted by both schemes are sufficiently close to pseudo-first order curves so that it is practically impossible to identify the deviations based on data with the usual experimental errors, which was also demonstrated by fitting simulated theoretical curves to exponential functions. The dependence of the pseudo-first order rate constants on the concentration of the excess reagent features the same trend as in the case of a reversible reaction: a straight line with an intercept is observed. This analysis emphasizes that the reversible nature of reactions should be demonstrated by direct equilibrium studies, kinetic observations alone might be misleading.

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“…They react with copper(II) to produce coordination complexes in which the metal binds the ligand’s two oxygens without oxidizing it,(10) although reductive nitrosylation has been implicated in the reactions of diazeniumdiolate ions with other metal centers. 11,12 …”

Section: Probing the Chemistry Of 1 And Analogous Ions As A Starting mentioning

confidence: 99%

Fifty Years of Diazeniumdiolate Research. From Laboratory Curiosity to Broad-Spectrum Biomedical Advances

2011

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Here I show that a “pure” research project, seemingly totally lacking in practical application when it was first published, can years later spark a whole new scientific field with the potential to revolutionize clinical practice. A 1961 publication describing adducts of nitric oxide (NO) with certain nucleophiles attracted little notice at the time, but later work showing that the adducts could be hydrolyzed to regenerate the NO in bioactive form has provided the foundation for a host of biomedical applications. Crucial to the discovery of widely used tools for studying NO’s chemical biology as well as for the design of a variety of promising therapeutic advances has been the increasingly detailed understanding of the physicochemical properties of these “diazeniumdiolates” (also known as NONOates).

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Mechanistic Studies on the Reaction between R₂N‐NONOates and Aquacobalamin: Evidence for Direct Transfer of a Nitroxyl Group from R₂N‐NONOates to Cobalt(III) Centers

Cited by 39 publications

References 39 publications

Reactions of Cobinamide with Glucose and Fructose

Reactions of Cobinamide with Glucose and Fructose

Reaction Schemes That Are Easily Confused with a Reversible First-Order Reaction

Fifty Years of Diazeniumdiolate Research. From Laboratory Curiosity to Broad-Spectrum Biomedical Advances

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Mechanistic Studies on the Reaction between R2N‐NONOates and Aquacobalamin: Evidence for Direct Transfer of a Nitroxyl Group from R2N‐NONOates to Cobalt(III) Centers

Cited by 39 publications

References 39 publications

Reactions of Cobinamide with Glucose and Fructose

Reactions of Cobinamide with Glucose and Fructose

Reaction Schemes That Are Easily Confused with a Reversible First-Order Reaction

Fifty Years of Diazeniumdiolate Research. From Laboratory Curiosity to Broad-Spectrum Biomedical Advances

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Mechanistic Studies on the Reaction between R₂N‐NONOates and Aquacobalamin: Evidence for Direct Transfer of a Nitroxyl Group from R₂N‐NONOates to Cobalt(III) Centers