THE RADIATION CHEMISTRY OF ALKALINE HYPOBROMITE SOLUTIONS<sup>1</sup>

Cheek, C. H.; Linnenbom, V. J.

doi:10.1021/j100803a028

Cited by 22 publications

(11 citation statements)

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“…(16) These are identical with the equations derived by Cheek & Linnenbom (1963), although the mechanism proposed by these authors is certainly incorrect, and from them the values of £ e~ + GK, Gon, GHz and CHao2 could be obtained. However, it is obvious from the data presented here th a t the above mechanism is inadequate in detail on two counts.…”

Section: Discussionsupporting

confidence: 78%

“…The data in table 1 (a) clearly demonstrate that the value of -BrO-) depends upon pH, in contrast to Cheek & Linnenbom's (1963) findings. These authors also found that relatively high concentrations of bromide ion lower G( -BrO-).…”

Section: R E S U L T Smentioning

confidence: 65%

“…The first system to be investigated in the second group comprised alkaline solu tions of sodium hypobromite (Cheek & Linnenbom 1963); however, the recent detailed information obtained on the reactions of oxybromine species (Buxton & Dainton 1968, preceding paper) shows that the mechanism proposed for this system and used to derive values of Ge-, G(m and is incorrect. In this paper we report results of a reinvestigation of this system in the absence and presence of nitrous oxide.…”

mentioning

confidence: 99%

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Radical and molecular yields in the γ -radiolysis of water - V. The sodium hypobromite system

Buxton

Dainton

1968

Proc. R. Soc. Lond. A

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The radiolysis of alkaline aqueous solutions of sodium hypobromite has been investigated to determine the effect of high pH on the primary radical yields. The reaction mechanism is fully established only when sodium bromite is present to capture BrO radicals, and the results show G e - aq. + G H = 2.9, G OH = 2·3, G H 2 O 2 = 0·7 and G H 2 = 0·4 up to pH 13. In the presence of N 2 O G (N 2 ) increases by 0.3 between pH 12 and 14, which is thought to be due to some process other than the conversion of H to e - aq. .

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Section: Discussionsupporting

confidence: 78%

Section: R E S U L T Smentioning

confidence: 65%

mentioning

confidence: 99%

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Radical and molecular yields in the γ -radiolysis of water - V. The sodium hypobromite system

Buxton

Dainton

1968

Proc. R. Soc. Lond. A

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“…Draganic (54) conclude that the hydroxyl radical yield is about 3 in strongly basic solu tions. Haissinsky, Jove & Szymanski (55) find a small effect of pH on the hydrogen peroxide yield in contrast to other reports (52,41).…”

mentioning

confidence: 59%

Radiation Chemistry

Schwarz¹

1965

Annu. Rev. Phys. Chem.

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“…67 Aqueous bromine solutions were prepared daily by dissolving Br2(l) in NaOH(aq) and spectrophotometrically titrated (λmax(H2O) ) 331 nm, ) 326 M -1 ‚cm -1 when pH > 12). 68 All other chemicals were of the best quality available and used without further purification. All solutions were made up with twice-distilled water.…”

Section: Methodsmentioning

confidence: 99%

Intracellular Oxidation of Dipeptides. Base-Promoted Elimination from N-Halodipeptides to 2-[N-Alkyl-N-(2-N-alkylimino-2-alkylethanoyl)amino]-2,2-dialkylethanoic Acids

et al. 2001

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One of the possible ways of intracellular oxidation of peptides is via the formation of the corresponding (N-X)-dipeptides, that then undergo base-promoted elimination to yield intermediate 2-[N-alkyl-N-(2-N-alkylimino-2-alkylethanoyl)amino]-2,2-dialkylethanoic acids, which subsequently hydrolyze. Such an elimination process is general-base catalyzed, with Brønsted beta values ranging from 0.26 to 0.31, which suggests an essentially constant degree of proton transfer at the TS. For (N-X)-dipeptides, the ratio k(N-Br)/k(N-Cl) ranges from 2.5 to 15, suggesting a structural dependence of the degree of N-X bond breaking at the TS. The values of beta and k(N-Br)/k(N-Cl) support a concerted asynchronous A(xh)D(H)D(N) mechanism, its TS changing from reactant-like to slightly nitrenium-like depending on the structure of the starting dipeptide. As a consequence of the antiperiplanarity requirements of the reaction, the steric interaction between the leaving group and the substituent on the C bearing the H to be eliminated controls the reaction rate. Such steric interaction is rather important, as indicated by the steric crossed-interaction coefficient (p(ssy') = 0.33). Semiempirical calculations show that bulky substituents in the vicinity of the reaction center imply additional energy requirements for the system to achieve the antiperiplanarity needed at the TS for the reaction to proceed. From the observations reported it follows that (N-X)-dipeptides lose their oxidizing power more readily than analogous (N-X)-amino acids or (N-X)-amines, opening a possible pathway to lessen intracellular halogen-based oxidative stress.

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THE RADIATION CHEMISTRY OF ALKALINE HYPOBROMITE SOLUTIONS¹

Cited by 22 publications

References 1 publication

Radical and molecular yields in the γ -radiolysis of water - V. The sodium hypobromite system

Radical and molecular yields in the γ -radiolysis of water - V. The sodium hypobromite system

Radiation Chemistry

Intracellular Oxidation of Dipeptides. Base-Promoted Elimination from N-Halodipeptides to 2-[N-Alkyl-N-(2-N-alkylimino-2-alkylethanoyl)amino]-2,2-dialkylethanoic Acids

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THE RADIATION CHEMISTRY OF ALKALINE HYPOBROMITE SOLUTIONS1

Cited by 22 publications

References 1 publication

Radical and molecular yields in the γ -radiolysis of water - V. The sodium hypobromite system

Radical and molecular yields in the γ -radiolysis of water - V. The sodium hypobromite system

Radiation Chemistry

Intracellular Oxidation of Dipeptides. Base-Promoted Elimination from N-Halodipeptides to 2-[N-Alkyl-N-(2-N-alkylimino-2-alkylethanoyl)amino]-2,2-dialkylethanoic Acids

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THE RADIATION CHEMISTRY OF ALKALINE HYPOBROMITE SOLUTIONS¹