Kinetics of the ClO + NO2 + M reaction

Molina, Mario J.; Molina, Luisa T.; Ishiwata, Takashi

doi:10.1021/j100460a026

Cited by 60 publications

(74 citation statements)

References 7 publications

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“…There is excellent agreement between the various studies of this reaction in the falloff region close to the low pressure limit Cox and Lewis, 1979;Molina et al, 1980;Dasch et al, 1981;Handwerk and Zellner, 1984;Wallington and Cox, 1986;Percival et al, 1997 Reliability log k ∞ = ± 0.5 over the temperature range 250-350 K.…”

Section: Comments On Preferred Valuesmentioning

confidence: 52%

“…Alternatively, one may follow our policy of choosing a more reasonable F c such as recommended by Cobos and Troe (2003) and then fit k ∞ . Using F c =0.4 such as recommended also for HO+NO 2 (+M) → HONO 2 (+M), the rate data in the falloff range below 1 bar from Percival et al (1997) are well reproduced with a temperature independent k ∞ =(7±2)×10 −11 cm 3 molecule −1 s −1 .…”

Section: Comments On Preferred Valuesmentioning

confidence: 68%

“…There are two alternatives for a representation of the rate data at pressures up to 1 bar. One may use the values chosen by Percival et al (1997) with F c =0.6 and a temperature dependent k ∞ such as given in the table. Alternatively, one may follow our policy of choosing a more reasonable F c such as recommended by Cobos and Troe (2003) and then fit k ∞ .…”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

“…The preferred quantum yield values are based on the results of Molina et al (1980), Butler and Phillips (1983), Vogt and Schindler (1992), and Schindler et al (1987). An upper limit of 2 <0.02 was determined by Butler and Phillips (1983) at 308 nm.…”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III – gas phase reactions of inorganic halogens

et al. 2007

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Abstract. This article, the third in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of inorganic halogen species, which were last published in J. Phys. Chem. Ref. Data, in 2000 (Atkinson et al., 2000, were updated on the IUPAC website in 2003 and are updated again in the present evaluation. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations were made.

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Section: Comments On Preferred Valuesmentioning

confidence: 52%

Section: Comments On Preferred Valuesmentioning

confidence: 68%

Section: Comments On Preferred Valuesmentioning

confidence: 99%

Section: Comments On Preferred Valuesmentioning

confidence: 99%

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III – gas phase reactions of inorganic halogens

et al. 2007

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“…An FAD-O-Cl intermediate could react via a one-electron mechanism to form • Cl as the chlorinating species. Photolysis of ROCl to • Cl and • RO has been observed (47,48). However, in vanadium-dependent haloperoxides, a radical-generating reaction has been ruled out in favor of a mechanism generating cationic bromine (30).…”

Section: Discussionmentioning

confidence: 99%

Robust in vitro activity of RebF and RebH, a two-component reductase/halogenase, generating 7-chlorotryptophan during rebeccamycin biosynthesis

Yeh

Garneau²,

Walsh³

2005

Proc. Natl. Acad. Sci. U.S.A.

253

278

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The indolocarbazole antitumor agent rebeccamycin is modified by chlorine atoms on each of two indole moieties of the aglycone scaffold. These halogens are incorporated during the initial step of its biosynthesis from conversion of L-Trp to 7-chlorotryptophan. Two genes in the biosynthetic cluster, rebF and rebH, are predicted to encode the flavin reductase and halogenase components of an FADH 2-dependent halogenase, a class of enzymes involved in the biosynthesis of numerous halogenated natural products. Here, we report that, in the presence of O 2, chloride ion, and L-Trp as cosubstrates, purified RebH displays robust regiospecific halogenating activity to generate 7-chlorotryptophan over at least 50 catalytic cycles. Halogenation by RebH required the addition of RebF, which catalyzes the NADH-dependent reduction of FAD to provide FADH 2 for the halogenase. Maximal rates were achieved at a RebF͞RebH ratio of 3:1. In air-saturated solutions, a k cat of 1.4 min ؊1 was observed for the RebF͞RebH system but increased at least 10-fold in low-pO 2 conditions. RebH was also able to use bromide ions to generate monobrominated Trp. The demonstration of robust chlorinating activity by RebF͞RebH sets up this system for the probing of mechanistic questions regarding this intriguing class of enzymes.enzymology ͉ natural product biosynthesis ͉ flavoenzyme

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Pressure and Temperature Dependence of the Reaction ClO + NO₂ (+ N₂) → ClONO₂ (+ N₂)

Handwerk

Zellner

1984

Ber Bunsenges Phys Chem

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Rate constants for the recombination reaction (1) ClO + NO2 (+ N2) → ClONO2 (+ N2) have been measured in the pressure range 23 – 1040 mbar and at temperatures of 264, 298 and 343 K using flash photolysis to generate ClO radicals and time dependent UV absorption in the A‐X system as their monitor. k1, is found to show a strong pressure dependence with an onset to “fall‐off” at pressures above ∼ 50 mbar. The “fall‐off” behaviour is interpreted in terms of complete and symmetrical Kassel integrals and is found to be in agreement with the accepted low pressure limit as well as with a theoretical estimate of the high pressure limiting rate constant, k1∞ = 1.2 · 10−11 cm3/s.

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Kinetics of the ClO + NO2 + M reaction

Cited by 60 publications

References 7 publications

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III – gas phase reactions of inorganic halogens

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III – gas phase reactions of inorganic halogens

Robust in vitro activity of RebF and RebH, a two-component reductase/halogenase, generating 7-chlorotryptophan during rebeccamycin biosynthesis

Pressure and Temperature Dependence of the Reaction ClO + NO₂ (+ N₂) → ClONO₂ (+ N₂)

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Kinetics of the ClO + NO2 + M reaction

Cited by 60 publications

References 7 publications

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III – gas phase reactions of inorganic halogens

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III – gas phase reactions of inorganic halogens

Robust in vitro activity of RebF and RebH, a two-component reductase/halogenase, generating 7-chlorotryptophan during rebeccamycin biosynthesis

Pressure and Temperature Dependence of the Reaction ClO + NO2 (+ N2) → ClONO2 (+ N2)

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Pressure and Temperature Dependence of the Reaction ClO + NO₂ (+ N₂) → ClONO₂ (+ N₂)