Permeable membrane/mass spectrometric measurement of solvent proton/deuterium, carbon-12/carbon-13, and oxygen-16/oxygen-18 kinetic isotope effects associated with .alpha.-chymotrypsin deacylation: evidence for reaction mechanism plasticity

Biochemistry ◽  
1986 ◽  
Vol 25 (23) ◽  
pp. 7328-7336 ◽  
Author(s):  
Awadhesh K. Mishra ◽  
Michael H. Klapper
Keyword(s):  
Reaction Mechanism ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Mass Spectrometric ◽  
Permeable Membrane ◽  
Mass Spectrometric Measurement ◽  
Spectrometric Measurement ◽  
Kinetic Isotope ◽  
Solvent Proton

Measurement of heavy atom kinetic isotope effects by direct mass spectrometric analysis

1979 ◽  
Vol 51 (9) ◽  
pp. 1375-1379 ◽  
Author(s):  
Steven. Rosenberg ◽  
Jack F. Kirsch
Keyword(s):  
Isotope Effects ◽  
Heavy Atom ◽  
Kinetic Isotope Effects ◽  
Mass Spectrometric ◽  
Mass Spectrometric Analysis ◽  
Spectrometric Analysis ◽  
Kinetic Isotope

Permeable membrane-mass spectrometric measurement of reaction kinetics

1981 ◽  
Vol 53 (7) ◽  
pp. 981-985 ◽  
Author(s):  
K. C. Calvo ◽  
C. R. Weisenberger ◽  
L. B. Anderson ◽  
M. H. Klapper
Keyword(s):  
Reaction Kinetics ◽  
Mass Spectrometric ◽  
Permeable Membrane ◽  
Mass Spectrometric Measurement ◽  
Spectrometric Measurement

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.

scholarly journals Enzymatic Δ1-Dehydrogenation of 3-Ketosteroids—Reconciliation of Kinetic Isotope Effects with the Reaction Mechanism

ACS Catalysis ◽  
2021 ◽  
pp. 8211-8225
Author(s):  
Michał Glanowski ◽  
Patrycja Wójcik ◽  
Magdalena Procner ◽  
Tomasz Borowski ◽  
Dawid Lupa ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope
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