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Kinetics and mechanism of the reaction of hydrogen sulfide with diaquacobinamide in aqueous solution.

ABSTRACT: We conducted a detailed kinetic study of the reaction of the vitamin B12 analog diaquacobinamide ((H2O)2Cbi(III)) with hydrogen sulfide in water from pH 3 to 11. The reaction proceeds in three steps: (i) formation of three different complexes between cobinamide and hydrogen sulfide, viz. (HO-)(HS-)Cbi(III), (H2O)(HS-)Cbi(III), and (HS-)2Cbi(III); (ii) inner-sphere electron transfer (ISET) in the two complexes with one coordinated HS- to form the reduced cobinamide complex [(H)S]Cbi(II); and (iii) addition of a second molecule of hydrogen sulfide to the reduced cobinamide. ISET does not proceed in the (HS-)2Cbi(III) complex. The final products of the reaction between cobinamide and hydrogen sulfide were found to be independent of pH, with the main product being a complex of cobinamide(II) with the anion-radical SSH2-.

SUBMITTER: Salnikov DS

PROVIDER: S-EPMC4286256 | biostudies-literature | 2014 Sep

REPOSITORIES: biostudies-literature

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Kinetics and mechanism of the reaction of hydrogen sulfide with diaquacobinamide in aqueous solution.

Salnikov Denis S DS Makarov Sergei V SV van Eldik Rudi R Kucherenko Polina N PN Boss Gerry R GR

European journal of inorganic chemistry 20140901 25

We conducted a detailed kinetic study of the reaction of the vitamin B12 analog diaquacobinamide ((H2O)2Cbi(III)) with hydrogen sulfide in water from pH 3 to 11. The reaction proceeds in three steps: (i) formation of three different complexes between cobinamide and hydrogen sulfide, viz. (HO-)(HS-)Cbi(III), (H2O)(HS-)Cbi(III), and (HS-)2Cbi(III); (ii) inner-sphere electron transfer (ISET) in the tw ...[more]

PMID: 25580081

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Project description:Hypertension is a major risk factor for chronic kidney disease (CKD), and renal inflammation is an integral part in this pathology. Hydrogen sulfide (H2S) has been shown to mitigate renal damage through reduction in blood pressure and ROS; however, the exact mechanisms are not clear. While several studies have underlined the role of epigenetics in renal inflammation and dysfunction, the mechanisms through which epigenetic regulators play a role in hypertension are not well defined. In this study, we sought to identify whether microRNAs are dysregulated in response to angiotensin II (ANG II)-induced hypertension in the kidney and whether a H2S donor, GYY4137, could reverse the microRNA alteration and kidney function. Wild-type (C57BL/6J) mice were treated without or with ANG II and GYY4137 for 4 wk. Blood pressure, renal blood flow, and resistive index (RI) were measured. MicroRNA microarrays were conducted and subsequent target prediction revealed genes associated with a proinflammatory response. ANG II treatment significantly increased blood pressure, decreased blood flow in the renal cortex, increased RI, and reduced renal function. These effects were ameliorated in mice treated with GYY4137. Microarray analysis revealed downregulation of miR-129 in ANG II-treated mice and upregulation after GYY4137 treatment. Quantitation of proteins involved in the inflammatory response and DNA methylation revealed upregulation of IL-17A and DNA methyltransferase 3a, whereas H2S production enzymes and anti-inflammatory IL-10 were reduced. Taken together, our data suggest that downregulation of miR-129 plays a significant role in ANG II-induced renal inflammation and functional outcomes and that GYY4137 improves renal function by reversing miR-129 expression.NEW & NOTEWORTHY We investigated epigenetic changes that occur in the hypertensive kidney and how H2S supplementation reverses adverse effects. Inflammation, aberrant methylation, and dysfunction were observed in the hypertensive kidney, and these effects were alleviated with H2S supplementation. We identify miR-129 as a potential regulator of blood pressure and H2S regulation.

Dataset Information

Kinetics and mechanism of the reaction of hydrogen sulfide with diaquacobinamide in aqueous solution.

Publications

Kinetics and mechanism of the reaction of hydrogen sulfide with diaquacobinamide in aqueous solution.

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