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1 and is consistent with a significant primary deuterium isotope effect.
2 dehydrogenation reaction exhibited the same deuterium isotope effect.
3 dependence, and a larger than usual upfield deuterium isotope effect.
4 inding specificity was assessed by using the deuterium isotope effect.
5 alysis and inhibition, we determined solvent deuterium isotope effects.
6 postulated on the basis of spectroscopy and deuterium isotope effects.
7 sidered unlikely given the lack of a solvent deuterium isotope effect above the breakpoint in the pH
8 Ru and zero order in phosphine, and kinetic deuterium isotope effects all point to a mechanism invol
11 r, the observation in N694C of a significant deuterium isotope effect, anaerobic reduction of iron by
12 .0064 (assuming 5.7 as the intrinsic primary deuterium isotope effect and 1.054 as the product of the
14 ental steps were associated with an hydrogen/deuterium isotope effect and that glycolate alpha-deprot
18 values of the theoretically relevant kinetic deuterium-isotope effect and its dependence on temperatu
19 decreases in activity, the measured solvent deuterium isotope effects, and changes in the pH depende
20 ith the NADPH-supported P450 reactions, high deuterium isotope effects ( approximately 7) were seen i
21 while a small pH-independent primary kinetic deuterium isotope effect (approximately 1.3) is observed
23 For Mg(2+)-assisted reactions, the solvent deuterium isotope effects are 1.23 and 0.25 for general
25 Furthermore, we demonstrate that solvent deuterium isotope effects are involved in the thermal de
29 cal shifts, a Steiner-Limbach correlation, a deuterium isotope effect as well as quantitative values
31 onsistent with a stepwise mechanism with the deuterium isotope effect at C3 being only on the decarbo
36 ean lipoxygenase 1 have indicated very large deuterium isotope effects, but have not been able to dis
42 kylation of DMN had a high intrinsic kinetic deuterium isotope effect ((D)k(app) approximately 10), w
44 tions of the intrinsic primary and secondary deuterium isotope effects ((D)k = 2.7, (alpha)(-D)k = 1.
53 to solvent accessibility by detection of the deuterium isotope effect for Y(Z) oxidation and by 2H ES
54 ly fast in the catalytic cycle; high kinetic deuterium isotope effects for all four lauric acid hydro
55 In contrast, significant suppression of the deuterium isotope effects for CYP2B1 occurred only with
59 )/k(D) = 9.7 and 6.8, respectively), whereas deuterium isotope effects for the naphthyl and biphenyl
61 r oxidation of malate, while the equilibrium deuterium isotope effect from deuteration at C-2 of the
62 Noncompetitive measurements of the primary deuterium isotope effect give a value of ca. 40 which is
63 , high noncompetitive intermolecular kinetic deuterium isotope effects (>/= 5.5) were observed for al
67 er conditions of catalytic turnover, kinetic deuterium isotope effects have been measured as a functi
69 ms and in the P-O(R) ester bond, and solvent deuterium isotope effects, have been measured for the hy
72 liable temperature dependence of the kinetic deuterium isotope effect in a 1,5-hydrogen shift, the ti
77 lack of significant kinetic and partitioning deuterium isotope effects indicates that the isomerizati
78 ind that the magnitude of the conformational deuterium isotope effect is 252.1, 28.3, and 7.1 J/mol (
80 e results it is estimated that the aldehydic deuterium isotope effect is approximately 1.9 after form
85 traction mechanism, in line with the kinetic deuterium isotope effects, k(H)/k(D), of 2.0 and 3.1 mea
91 microM, respectively, and a primary kinetic deuterium isotope effect of 1.3 and 1.8 on V/ K AcCoA an
93 )]farnesylcysteine as a substrate, a primary deuterium isotope effect of 2 was observed on the steady
96 respectively, giving a calculated intrinsic deuterium isotope effect of 3.3 +/- 0.9, consistent with
97 eavage of the oxo linkage exhibits a solvent deuterium isotope effect of 3.6, but a similar effect is
99 icroM, respectively, while a primary kinetic deuterium isotope effect of about 1.4 was obtained on V,
101 ocus on determining if the unusual aldehydic deuterium isotope effect of approximately 1.5 observed i
102 is asynchronous, however, with an intrinsic deuterium isotope effect of approximately 5 and a 13C is
110 omparison of the pH profiles and the solvent deuterium isotope effects of A. thaliana GS and the Arg-
111 50) 2E1 substrates are known to show kinetic deuterium isotope effects of approximately 5 on Km (DK =
112 SB hydrolysis in the dark state and a strong deuterium isotope effect on dark state SB hydrolysis.
115 n is the finding that [3-(2)H]-10 exhibits a deuterium isotope effect on inactivation of 3.3, suggest
125 oxidation and reduction rates for Y(Z), the deuterium isotope effect on these rates, and the Y(Z)* -
127 , lungs, kidneys, and spleen showed a robust deuterium isotope effect on uptake, IQ, k3, and lambdak3
132 High intermolecular non-competitive kinetic deuterium isotope effects on both kcat and kcat/Km, from
137 imental and theoretical investigation of the deuterium isotope effects on the bacterial luciferase re
139 hy, (1)H NMR, site-directed mutagenesis, and deuterium isotope effects on the geometry and chemical s
140 Primary deuterium [NADPH(D)] and solvent deuterium isotope effects on the kinetic parameters were
142 (R)-NADPD but not (S)-NADPD showed kinetic deuterium isotope effects on V and V/K of about 1.9 and
146 th substrate and coenzyme, together with the deuterium isotope effects on Vmax and Vmax/Km, have been
150 d by solvation changes that generate solvent deuterium isotope effects originating from hydrogen ion
154 The combination of solvent and substrate deuterium isotope effects rules out solvent deuterium ex
156 uted tetrahydropyridines, we have undertaken deuterium isotope effect studies on the substrate and in
159 howed a pH 6 activity maximum but no kinetic deuterium isotope effect, suggesting protons are not tra
160 o acetaldehyde is characterized by a kinetic deuterium isotope effect that increases K(m) with no eff
162 00Lys mutant does not exhibit the very large deuterium isotope effects that are observed for homolysi
163 er, pressure increases the primary intrinsic deuterium isotope effect, the opposite of what was obser
164 C-clorgyline ((11)C-clorgyline-D2) using the deuterium isotope effect to assess binding specificity.
165 IE results and the lack of a kinetic solvent deuterium isotope effect together provide strong evidenc
168 , (iv) the lack of a non-competitive kinetic deuterium isotope effect, (v) the lack of a kinetic burs
169 atter compound, a substantial intermolecular deuterium isotope effect was observed for N-demethylatio
171 A prominent secondary four-bond hydrogen/deuterium isotope effect was observed from proton NMR at
174 homoisocitrate as the substrate, no primary deuterium isotope effect was observed, and a small (13)C
175 % of that for the wild-type complex, and the deuterium isotope effect was significantly decreased.
176 he solvent, primary, secondary, and multiple deuterium isotope effects were most consistent with a ch
177 p is not rate-limiting, while larger primary deuterium isotope effects were observed for poor ketoaci
178 rs at 107.5 +/- 3 s-1 and exhibits a 10-fold deuterium isotope effect when (4R)-[2H]NADH is substitut
179 k of a kinetic burst, and (vi) the lack of a deuterium isotope effect when the reaction was initiated
181 mutations increase the value of the primary deuterium isotope effect with tryptophan as a substrate,
182 re observed in the magnitudes of the primary deuterium isotope effects with NADPD, consistent with de
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