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1 d us to measure the apparent large intrinsic kinetic isotope effect.
2 re limit of the reaction rate and by the H/D kinetic isotope effect.
3 th temperature and exhibit a large, primary, kinetic isotope effect.
4 e or temperature dependence of the intrinsic kinetic isotope effect.
5 f 19 kJ mol(-1) and a approximately 2.5-fold kinetic isotope effect.
6 ence of suppression of the intrinsic maximum kinetic isotope effect.
7 incorporation into biomolecules and minimal kinetic isotope effect.
8 ics, revealing a large temperature-dependent kinetic isotope effect.
9 and buffer concentration and have weaker H/D kinetic isotope effects.
10 n of both the thermal rate constants and the kinetic isotope effects.
11 ical calculations and by examining secondary kinetic isotope effects.
12 c solvent effects, Arrhenius parameters, and kinetic isotope effects.
14 we found a marked increase of apparent (13)C-kinetic isotope effects ((13)C-AKIE) and decrease of 4-C
16 lement the analysis of competitive oxygen-18 kinetic isotope effects ((18)O KIEs) upon consumption of
17 l) and aqueous O2 consumption, derived (18)O-kinetic isotope effects ((18)O-KIE) for the reactions of
18 cently reported abnormal secondary deuterium kinetic isotope effects (2 degrees KIEs) for hydride tra
19 h pH-rate profiles, pKa and DeltaS() values, kinetic isotope effects ((2)H, (10)B, (13)C), linear fre
20 nalysis based on the measurement of multiple kinetic isotope effects.(36)S-labeled l-methionine and S
21 Cleavage at U exhibits a large 5' deuterium kinetic isotope effect, a potential signature of a base
22 l(-) concentrations induces a large apparent kinetic isotope effect (AKIE = 1.010-1.018) likely assoc
27 the corresponding (13)C- and (15)N-apparent kinetic isotope effects (AKIEs) of four nitrophenol-biod
29 ), derived apparent (13)C-, (2)H-, and (15)N-kinetic isotope effects (AKIEs), and characterized react
37 s of the anomalous temperature dependence of kinetic isotope effects and computational simulations.
38 to -20 degrees C, as inferred from measured kinetic isotope effects and corresponding electronic-str
39 and second order in [catalyst], while large kinetic isotope effects and group 2 element-dependent De
40 ch and that mechanistic experiments, such as kinetic isotope effects and kinetic solvent effects, are
41 at residues Thr169, His548, and Asn593, and kinetic isotope effects and pH-dependence studies of the
43 consistent with the experimentally measured kinetic isotope effects and reconciles the discrepancies
44 studied using a combination of experimental kinetic isotope effects and theoretical calculations.
47 asurements, kinetic competition experiments, kinetic isotope effects, and hydrogen atom transfer reag
48 experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catal
49 nsertion, as supported by reaction kinetics, kinetic isotope effects, and isotopic labeling studies.
51 ation with linear free-energy relationships, kinetic isotope effects, and stoichiometric experiments,
52 d study of linear free energy relationships, kinetic isotope effects, and the first quantitative expe
55 imately 100 micros; E(a) = 0.34 +/- 0.08 eV; kinetic isotope effect, approximately 3); however, the p
57 Herein we show that unusually large chlorine kinetic isotope effects are associated with reactions in
58 isolated complexes, deuterium labeling, and kinetic isotope effects are consistent with a catalytic
60 diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with publi
61 Both solvent O-H and substrate C-H deuterium kinetic isotope effects are observed for these reactions
66 ric intermediate decays with a large solvent kinetic isotope effect, as expected when proton delivery
67 to the mechanism by examining the deuterium kinetic isotope effect associated with the hydrogen tran
69 t generally tended to be negative due to the kinetic isotope effect associated with thermal NOx produ
71 general method for the measurement of (13)C kinetic isotope effects at natural abundance for reactio
72 on ((12)C/(14)C) and secondary ((1)H3/(3)H3) kinetic isotope effects at the transferred methyl group,
73 dramatic, order-of-magnitude-strong, quantum kinetic isotope effect by measuring the absolute Penning
74 Measurements of reaction rates and carbon kinetic isotope effects (CKIE) for decarboxylation of is
75 hat the phenolic proton exhibits a secondary kinetic isotope effect, consistent with the calculations
76 ylide was studied by a combination of (13)C kinetic isotope effects, conventional calculations, and
77 nated by NH(4)(+), in combination with known kinetic isotope effects, could lead to eukaryotic biomas
85 ensive mechanistic studies showed an inverse kinetic isotope effect, fast H2/D2 scrambling and slow a
86 (3) H at their benzylic C atoms, owing to a kinetic isotope effect favoring hydrogen abstraction fro
87 effect for CFC-11 apparently similar to the kinetic isotope effect for (abiotic) ZVI degradation.
92 tution did not change the solvent or primary kinetic isotope effect for proton abstraction, consisten
99 psilonbulk values were converted to apparent kinetic isotope effects for carbon (AKIE) in order to ch
101 rmining step, and substantial differences in kinetic isotope effects for different substrates; both t
104 This result was further confirmed by primary kinetic isotope effects for which saturating with alphaK
113 rrent study presents the first-ever observed kinetic isotope effect in a metal combustion reaction an
114 constrain ab initio calculations, making the kinetic isotope effect in the cold regime necessary to r
117 esults suggest a large difference in the H/D kinetic isotope effects in nitrogen and argon matrices (
118 ived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide
119 dolase reaction, and the analysis of solvent kinetic isotope effects in steady-state and pre-steady-s
120 The comparison of experimental and predicted kinetic isotope effects in the alpha-cleavage of alkoxy
122 Escherichia coli (EcDHFR), where the enzyme kinetic isotope effect increased slightly with increasin
124 e negative entropy of activation and inverse kinetic isotope effect indicate that H-H bond formation
126 ition of Bronsted acids reveal a primary H/D kinetic isotope effect, indicating that transfer of prot
127 tion in substrate U is deuterated, a primary kinetic isotope effect is observed, which indisputably i
128 the methylene group, a significant apparent kinetic isotope effect is only found in the reductive pe
129 echanisms of these processes using kinetics, kinetic isotope effects, isotopic labeling experiments,
131 ts, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 +/- 1.7), agree
133 ata for the reaction of ClSiH with Me(3)SiH, kinetic isotope effects, k(D)/k(H), in the range from 7.
137 state of phosphoroimidazolide hydrolysis by kinetic isotope effect (KIE) and linear free energy rela
139 hensive labeling studies, rate measurements, kinetic isotope effect (KIE) experiments, synthetic stud
141 abstraction is overall-rate-determining [the kinetic isotope effect (KIE) for 1-d(1) conversion to 2
143 pecies with nine hydrocarbons shows that the kinetic isotope effect (KIE) involves strong tunneling a
145 endent below approximately 10 K, and a large kinetic isotope effect (KIE) is observed upon substituti
147 Hammett analysis, radical clock experiments, kinetic isotope effect (KIE) measurements (kH/kD = 3.0 +
149 edia has been studied by the use of multiple kinetic isotope effect (KIE) measurements in conjunction
150 in order to characterize, by use of multiple kinetic isotope effect (KIE) measurements, the glycosyla
154 SO(2)(-) and TpT exhibits a V(max) deuterium kinetic isotope effect (KIE) of 1.7 +/- 0.2, which is sm
155 he acetonitrile/water solvent mixture; a H/D kinetic isotope effect (KIE) of 2.0 +/- 0.4 is associate
160 oacylation did not exhibit a significant H/D kinetic isotope effect (KIE) with respect to the aldehyd
162 test these two possibilities using secondary kinetic isotope effect (KIE), mutagenesis study, and pri
165 that precludes calculation of apparent (2)H-kinetic isotope effects (KIE) as well as the process ide
166 r hydrogen has been shown to lead to massive kinetic isotope effects (KIE) for soybean lipoxygenase (
168 through analysis of kinetic competition and kinetic isotope effects (KIE): (i) a mechanism dominatin
171 tate, and ligand binding kinetics, intrinsic kinetic isotope effects (KIEint) on the chemical step, a
172 the temperature-dependence of the intrinsic kinetic isotope effects (KIEs) and other kinetic paramet
173 neling reactions, as a result of its unusual kinetic isotope effects (KIEs) and their temperature dep
175 studied using a combination of experimental kinetic isotope effects (KIEs) and theoretical calculati
179 ng the TS using a suite of five experimental kinetic isotope effects (KIEs) as constraints for the ca
180 t of [Formula: see text]-secondary deuterium kinetic isotope effects (KIEs) at all sites of [Formula:
181 and iPr(2)N horizontal lineBH(2) allowed the kinetic isotope effects (KIEs) attending the hydrogen tr
182 A new method is presented for measuring kinetic isotope effects (KIEs) by (1)H-detected 2D [(13)
183 (EIEs), binding isotope effects (BIEs), and kinetic isotope effects (KIEs) for a range of phosphate
186 or distance (DAD) distribution and intrinsic kinetic isotope effects (KIEs) for the dihydrofolate red
187 tunneling, and the temperature dependence of kinetic isotope effects (KIEs) has emerged as the "gold
189 investigated with pH, solvent viscosity, and kinetic isotope effects (KIEs) in steady-state kinetics
191 ide insight into reaction mechanisms because kinetic isotope effects (KIEs) of both elements are refl
192 ay be generally applicable for examining the kinetic isotope effects (KIEs) of posttranslational modi
193 ter than that of the protiated form, causing kinetic isotope effects (KIEs) of ~1.3 on k(cat) and k(c
194 We performed transition state analysis using kinetic isotope effects (KIEs) on AroA-catalyzed EPSP hy
197 C, H, and N isotope enrichment factors and kinetic isotope effects (KIEs) were derived from the com
198 The carbonyl-C, carbonyl-O, and leaving-S kinetic isotope effects (KIEs) were determined for the h
201 can be established by matching experimental kinetic isotope effects (KIEs) with theoretical predicti
202 ilarity extended to the associated secondary kinetic isotope effects (KIEs), indicating very similar
203 this step with experimental data, as well as kinetic isotope effects (KIEs), supports this prediction
209 n can be addressed by measuring steady-state kinetic isotope effects (KIEs); however, their interpret
210 nvestigations with the aid of Hammett plots, kinetic isotope effects, labeled stereochemical probes,
215 H(CD3)(SiMe3)](+) is used, suggesting an H/D kinetic isotope effect much larger (apparently >16,000)
216 c analysis coupled with the normal (13)(V/K) kinetic isotope effect observed on C-4 of oxaloacetate [
217 This conclusion was supported by the inverse kinetic isotope effect observed with deuterated 1S, the
223 e covalent thioimide reduction and a smaller kinetic isotope effect of 1.8 on the imine reduction to
225 simulation reveal a large primary deuterium kinetic isotope effect of 3.3 on the covalent thioimide
226 es from experiments which identify a primary kinetic isotope effect of 5.4 for the deformylation reac
230 The latter proceed with a relatively small kinetic isotope effect of kH/kD = 7 for the iron(IV)-tos
235 precursors; (b) obtain information about the kinetic isotope effects of as yet undescribed enzymes, t
236 d to their known precursors and to the known kinetic isotope effects of enzymes involved in their bio
239 These findings can (i) be related to known kinetic isotope effects of some of the enzymes concerned
240 Here the temperature-dependence of intrinsic kinetic isotope effects of the enzyme formate dehydrogen
241 or hydrogen at a ribose 5'-carbon produces a kinetic isotope effect on cleavage; the major cleavage p
244 studies at short times show that there is no kinetic isotope effect on the initial step in the reacti
245 al for substantial benefits of the deuterium kinetic isotope effect on the safety and disposition of
246 is C-C "lyase" activity, we investigated the kinetic isotope effect on the steady-state turnover of N
248 Temperature-dependent measurements of the kinetic isotope effects over a 60 degrees C temperature
249 netic studies, H/D exchange experiments, and kinetic isotope effects provide clear support for a bime
250 transfer complex absorbance and experimental kinetic isotope effect reaction data, we show that this
254 h are subject to kinetic solvent effects and kinetic isotope effects similar to RSOH and other good H
255 -independent (pH 6.5), we determined solvent kinetic isotope effects (SKIEs) for three substrates who
263 temporal course of the reaction by (1)H NMR, kinetic isotope effect studies, and control experiments.
264 s that support these calculations, including kinetic isotope effect studies, H/D exchange studies, an
265 h other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-s
267 ans-Polayni graph and the finding of a large kinetic isotope effect suggest that hydrogen abstraction
269 ol pKa, and the absence of deuterium solvent kinetic isotope effects suggested stepwise mechanisms wi
270 urements) rule out a stepwise mechanism, and kinetic isotope effects support concerted proton-electro
271 ports an O-atom insertion mechanism, and H/D kinetic isotope effects support net hydride-transfer oxi
273 eactivity constitutes the first example of a kinetic isotope effect that discriminates between the fo
274 d TEAH(+) displays a potential-dependent H/D kinetic isotope effect that is not observed for DIPEAH(+
275 ent bimolecular rate constants and deuterium kinetic isotope effects that increase in proportion to c
277 n the basis of the small values of deuterium kinetic isotope effects, the relatively high and negativ
279 cts feature the strategic use of a deuterium kinetic isotope effect to improve the efficiency of a la
280 ns, isotopic incorporation from solvent, and kinetic isotope effects, to define the mechanism and an
282 The two variants provide nearly identical kinetic isotope effect values (2.8-3.0), suggesting that
283 ulations of commitment factors from observed kinetic isotope effect values support a hydride transfer
284 gating, we determined vibrational as well as kinetic isotope effects (VIEs and KIEs) of carboxylic gr
286 a bromopyrone, but a highly unusual, inverse kinetic isotope effect was evident using a chlorocoumari
288 investigating the temperature dependence of kinetic isotope effects, we present evidence that the re
289 experiments, substrate analogs, and primary kinetic isotope effects, we show that the interaction be
291 y Me-(3)H3, Me-(2)H3, 5'-(14)C, and 5'-(3)H2 kinetic isotope effects were measured for the methylatio
295 including determination of the rate law and kinetic isotope effects, were utilized to identify a cha
296 he reaction is presented showing a lack of a kinetic isotope effect when generating deuterothiophenol
298 f the intermediate ketols and on the solvent kinetic isotope effects, whereby the condensations are f
299 alyzed proton transfer shows a prominent H/D kinetic isotope effect, which is determined to be 8.3 x
300 tum tunnelling can give rise to experimental kinetic isotope effects with complex temperature depende
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