Large primary kinetic isotope effects in the abstraction of hydrogen from organic compounds by a fluorinated radical in waterElectronic supplementary information (ESI) available: Tables of kinetic data and plots of kinetic data. See http://www.rsc.org/suppdata/ob/b4/b405075d/

2004 ◽  
Vol 2 (14) ◽  
pp. 2087 ◽  
Author(s):  
Joseph A. Cradlebaugh ◽  
Li Zhang ◽  
A. B. Shtarev ◽  
Bruce E. Smart ◽  
William R. Dolbier, Jr.
Keyword(s):  
Organic Compounds ◽  
Kinetic Data ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Supplementary Information ◽  
Kinetic Isotope ◽  
Fluorinated Radical ◽  
Large Primary

scholarly journals Dependence between the photochemical age of light aromatic hydrocarbons and the carbon isotope ratios of atmospheric nitrophenols

2019 ◽  
Vol 19 (8) ◽  
pp. 5495-5509
Author(s):  
Marina Saccon ◽  
Anna Kornilova ◽  
Lin Huang ◽  
Jochen Rudolph
Keyword(s):  
Carbon Isotope ◽  
Organic Compounds ◽  
Mechanistic Model ◽  
Isotope Effects ◽  
Isotope Ratios ◽  
Kinetic Isotope Effects ◽  
Laboratory Studies ◽  
Carbon Isotope Ratios ◽  
Kinetic Isotope ◽  
Volatile Organic

Abstract. Concepts were developed to establish relationships between the stable carbon isotope ratios of nitrophenols in the atmosphere and the photochemical processing of their precursors, light aromatic volatile organic compounds. These concepts were based on the assumption that nitrophenols are formed dominantly from the photo-oxidation of aromatic volatile organic compounds (VOCs). A mass balance model as well as various scenarios based on the proposed mechanism of nitrophenol formation were formulated and applied to derive the time-integrated exposure of the precursors to processing by OH radicals (∫[OH]dt) from ambient observations made between 2009 and 2012 in Toronto, Canada. The mechanistic model included the possibility of isotopic fractionation during intermediate steps, rather than only during the initial reaction step. This model takes kinetic isotope effects for the reaction of the precursor VOC with the hydroxyl radical and their respective rate constants into account, as well as carbon isotope ratio source signatures. While many of these values are known, there are some, such as the kinetic isotope effects of reactions of first- and second-generation products, which are unknown. These values were predicted in this study based on basic principles and published laboratory measurements of kinetic carbon isotope effects and were applied to the mechanistic model. Due to the uncertainty of the estimates based on general principles, three scenarios were used with different values for isotope effects that were not known from laboratory studies. Comparison of the dependence between nitrophenol carbon isotope ratios and ∫[OH]dt with published results of laboratory studies and ambient observations was used to narrow the range of plausible scenarios for the mechanistic model. The results also suggests that mass-balance-based models do not adequately describe the dependence between nitrophenol carbon isotope ratios and ∫[OH]dt.

Reactions of Muonium with simple biochemical solutes in water and micelles

1991 ◽  
Vol 69 (8) ◽  
pp. 1252-1258 ◽  
Author(s):  
Mary V. Barnabas ◽  
David C. Walker
Keyword(s):  
Reaction Mechanism ◽  
Organic Compounds ◽  
Rate Constants ◽  
Enhancement Factor ◽  
Isotope Effects ◽  
Ph Dependence ◽  
Kinetic Isotope Effects ◽  
Natural State ◽  
Sugar Phosphate ◽  
Kinetic Isotope

Rate constants are reported for the reaction of muonium atoms in water with some 36 organic compounds, many of interest in biology. These kM values range from < l05 to 7 × 1010 M−1 s−1, according to the type of reaction involved, with the sugar–phosphate backbones of nucleic acids being at the low end and their bases at the high end. They are compared with corresponding published H-atom data (kH), where possible, and show kinetic-isotope-effects ranging over five orders of magnitude. Since all kH data were obtained at pH = 1, while kM values refer to pH ~ 7 of the natural state, the pH-dependence of kM was examined in representative cases. The changes found result from protonation of the solute rather than a changed reactivity of Mu on being converted to MuH+. On localizing the solutes in the hydrophobic phase of dilute micelles, the reactivity of Mu was again measured (kM(mic)). The resulting "enhancement" factor was considered in terms of: the reaction mechanism, its dependence on microenvironment (solvation), and the concentrating effect of mutual confinement to small sections of a biphasal system. Key words: kinetic isotope effects, muonium, biochemicals, micelles.

Kinetics and Stereochemistry of Elimination of Nitrous-Acid From 1-Para-Nitrophenyl-2-Nitroethyl Derivatives

1986 ◽  
Vol 39 (2) ◽  
pp. 281 ◽  
Author(s):  
RK Norris ◽  
TA Wright
Keyword(s):  
Isotope Effect ◽  
Nitrous Acid ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Positive Entropy ◽  
Kinetic Isotope ◽  
Entropy Of Activation ◽  
Large Primary

The eliminations of nitrous acid from the compounds (1) and (6) are E2 processes, which proceed with a large primary kinetic isotope effect and with antiperiplanar stereochemistry. The rate of elimination of HNO2 from (1) is intermediate between the rate of elimination of HCl from (4) and HBr from (5). This order of nucleofugality , namely Br- > NO2- > Cl -, results from a more positive entropy of activation for the elimination of nitrous acid. The presence of an α-chlorine, as in compounds (8), (28) and (29), leads to elimination processes which are E1cB-like, with low primary kinetic isotope effects and with lack of stereospecificity.

Model calculations of isotope effects. IX. Origin of large hydrogen and carbon isotope effects in the deprotonation of 2-nitropropane by pyridine bases

1983 ◽  
Vol 36 (8) ◽  
pp. 1521
Author(s):  
DJ McLennan
Keyword(s):  
Transition State ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Bond Orders ◽  
Model Calculations ◽  
Kinetic Isotope ◽  
Pyridine Bases ◽  
State Models ◽  
Experimental Findings ◽  
Large Primary

The abnormally large primary hydrogen and carbon kinetic isotope effects found in the deprotonation of 2-nitropropane by hindered pyridine bases are investigated by means of model calculations. Transition-state models have been varied between tight and loose extremes, and between carbanion-like and nitronate-like structures. The only models that reproduce the experimental findings are those in which the sum of the bond orders to the transferring proton is less than unity (loose transition states) and which are subject to tunnelling corrections.

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