Anorganische Stickstoffverbindungen V. Reaktionen des Nitrohydroxylaminats mit zweiwertigen Kationen

Vepřek-Šiška, J.; Pliška, V.; Šmirous, F.

doi:10.1135/cccc19593548

Cited by 6 publications

(6 citation statements)

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“…Upon measurement at 37°C (data not shown), a similar curve shape was obtained, but the rate constants only varied from 0.0069 s −1 at pH 3 to 0.0015 s −1 at pH 10. At pH 3, Angeli’s salt sharply transitions from an HNO donor to an NO donor, 28–30 which is consistent with the sharp rise in decomposition rate below pH 4. In contrast, the rate profile for IPA/NO shows a single broad transition, a slight acceleration at high pH, and a 250-fold variance in rate constant.…”

Section: Resultssupporting

confidence: 70%

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HNO and NO Release from a Primary Amine-Based Diazeniumdiolate As a Function of pH

et al. 2011

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The growing evidence that nitroxyl (HNO) has a rich pharmacological potential that differs from that of nitric oxide (NO) has intensified interest in HNO donors. Recently, the diazeniumdiolate (NONOate) based on isopropylamine (IPA/NO; Na[(CH3)2CHNH(N(O)NO)]) was demonstrated to function under physiological conditions as an organic analogue to the commonly used HNO donor Angeli’s salt (Na2N2O3). The decomposition mechanism of Angeli’s salt is dependent on pH, with transition from an HNO to an NO donor occurring abruptly near pH 3. Here, pH is shown to also affect product formation from IPA/NO. Chemical analysis of HNO and NO production led to refinement of an earlier, quantum mechanically based prediction of the pH-dependent decomposition mechanisms of primary amine NONOates such as IPA/NO. Under basic conditions, the amine proton of IPA/NO is able to initiate decomposition to HNO by tautomerization to the nitroso nitrogen (N2). At lower pH, protonation activates a competing pathway to NO production. At pH 8, the donor properties of IPA/NO and Angeli’s salt are demonstrated to be comparable, suggesting that at or above this pH, IPA/NO is primarily an HNO donor. Below pH 5, NO is the major product, while IPA/NO functions as a dual donor of HNO and NO at intermediate pH. This pH-dependent variability in product formation may prove useful in examination of the chemistry of NO and HNO. Furthermore, primary amine NONOates may serve as a tunable class of nitrogen oxide donor.

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Section: Resultssupporting

confidence: 70%

“…These results support prior reports that Angeli’s salt converts from an HNO donor to an NO donor at pH 3. 28–30 At pH 2, enhancement of the signal over that in the absence of ferricyanide may suggest minor production of HNO. Reaction of HNO with NO (Eqs.…”

Section: Resultsmentioning

confidence: 99%

HNO and NO Release from a Primary Amine-Based Diazeniumdiolate As a Function of pH

et al. 2011

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“…Seminal papers on cobalt-catalyzed water oxidation appeared in the 70s and 80s that showed that Co II salts are Reviews 7258 www.angewandte.org able to catalyze the oxidation of water by permanganate, [173,174] hypochlorite, [175] persulfate, [175] perruthenate, and ferrate, [174] and also [IrCl 6 ] 2À and (Ru(bipy) 3 ] 3+ complexes. [176] In 1967, Anbar and Pecht proposed a mechanism for water oxidation in acidic to neutral solution that involved a bis(mhydroxo)dicobalt(III) species.…”

Section: Co III /Co Ii : a Redox Couple For Water Oxidationmentioning

confidence: 99%

Splitting Water with Cobalt

2011

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The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable, and efficient systems for the conversion and storage of renewable energy sources, such as solar energy. The production of hydrogen, a fuel with remarkable properties, through sunlight-driven water splitting appears to be a promising and appealing solution. While the active sites of enzymes involved in the overall water-splitting process in natural systems, namely hydrogenases and photosystem II, use iron, nickel, and manganese ions, cobalt has emerged in the past five years as the most versatile non-noble metal for the development of synthetic H(2)- and O(2)-evolving catalysts. Such catalysts can be further coupled with photosensitizers to generate photocatalytic systems for light-induced hydrogen evolution from water.

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“…Scheme 7 Reactions involved in the kinetic simulations which describe appropriately the reaction of metalloporphyrins with AS (HN 2 O 3 − ) in the absence and presence of dioxygen, at pH 7 [54,[56][57][58][59]66,67,129]. Under anaerobic conditions, AS in solution decomposes to produce only nitrite and HNO, which dimerizes yielding nitrous oxide.…”

Section: Tablementioning

confidence: 99%