ライフサイエンスコーパス: kinetic isotope effect

1 ics, revealing a large temperature-dependent kinetic isotope effect.

2 step, in agreement with an observed primary kinetic isotope effect.

3 d us to measure the apparent large intrinsic kinetic isotope effect.

4 nable to account for this pronounced inverse kinetic isotope effect.

5 incorporation into biomolecules and minimal kinetic isotope effect.

6 -first-order kinetics and exhibits a sizable kinetic isotope effect.

7 re limit of the reaction rate and by the H/D kinetic isotope effect.

8 th temperature and exhibit a large, primary, kinetic isotope effect.

9 f 19 kJ mol(-1) and a approximately 2.5-fold kinetic isotope effect.

10 and buffer concentration and have weaker H/D kinetic isotope effects.

11 in after the latter values were adjusted for kinetic isotope effects.

12 Primary deuterium kinetic isotope effects (1 degrees DKIE) on (kcat/KGA, M

13 we found a marked increase of apparent (13)C-kinetic isotope effects ((13)C-AKIE) and decrease of 4-C

14 Calculated carbon apparent kinetic isotope effects ((13)C-AKIE) fell with 1.005 to

15 l) and aqueous O2 consumption, derived (18)O-kinetic isotope effects ((18)O-KIE) for the reactions of

16 cently reported abnormal secondary deuterium kinetic isotope effects (2 degrees KIEs) for hydride tra

17 h pH-rate profiles, pKa and DeltaS() values, kinetic isotope effects ((2)H, (10)B, (13)C), linear fre

18 nalysis based on the measurement of multiple kinetic isotope effects.(36)S-labeled l-methionine and S

19 Cleavage at U exhibits a large 5' deuterium kinetic isotope effect, a potential signature of a base

20 l(-) concentrations induces a large apparent kinetic isotope effect (AKIE = 1.010-1.018) likely assoc

21 The corresponding apparent kinetic isotope effects (AKIE) for ipso-hydroxylation we

22 f the Rayleigh approach to evaluate apparent kinetic isotope effects (AKIE) was confirmed.

23 The apparent 15N kinetic isotope effects (AKIE) were almost identical for

24 zyme specificity of apparent (13)C- and (2)H-kinetic isotope effects (AKIEs) associated with the dehy

25 Derivation of apparent kinetic isotope effects (AKIEs) for the reaction with oz

26 Apparent kinetic isotope effects (AKIEs) of 1.0070 +/- 0.0002 (13

27 the corresponding (13)C- and (15)N-apparent kinetic isotope effects (AKIEs) of four nitrophenol-biod

28 otope fraction with apparent (13)C- and (2)H-kinetic isotope effects (AKIEs) of up to 1.029 +/- 0.001

29 Carbon and chlorine apparent kinetic isotope effects (AKIEs) were in general agreemen

30 ent position on the apparent (13)C and (15)N kinetic isotope effects (AKIEs).

31 A kinetic simulation including kinetic isotope effects allowed determination of the pri

32 eled PFAS molecules to take advantage of the kinetic isotope effect and demonstrate that indeed PFAS

33 structure of the apoenzyme together with the kinetic isotope effect and mutagenesis experiments furth

34 In this study, we use a combination of kinetic isotope effect and proton inventory studies to e

35 The results of kinetic isotope effect and structural studies indicate r

36 Both the [4-(2)H]NADH (NADD) kinetic isotope effect and the D2O solvent isotope effec

37 Significant deuterium kinetic isotope effects and a positive correlation of se

38 Taken together, the reported kinetic isotope effects and computational modeling are c

39 to -20 degrees C, as inferred from measured kinetic isotope effects and corresponding electronic-str

40 Kinetic isotope effects and DFT calculations completed a

41 ch and that mechanistic experiments, such as kinetic isotope effects and kinetic solvent effects, are

42 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.

45 Mossbauer spectroscopy, kinetic isotope effect, and gas adsorption measurements

46 asurements for initiation, monomer-dependent kinetic isotope effects, and activation parameters were

47 Isotopic-labeling experiments, kinetic isotope effects, and computational studies clear

48 rted by stoichiometric Cr(V) kinetics, (13)C kinetic isotope effects, and density functional theory (

49 asurements, kinetic competition experiments, kinetic isotope effects, and hydrogen atom transfer reag

50 experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catal

51 Catalytic rate laws, kinetic isotope effects, and spectroscopic data show tha

52 ation with linear free-energy relationships, kinetic isotope effects, and stoichiometric experiments,

53 d study of linear free energy relationships, kinetic isotope effects, and the first quantitative expe

54 Evaluation of reaction kinetics, isotope effects, and commitment-to-catalysis b

55 Thus, the H/D kinetic isotope effect appears as the major limiting fac

56 Different reaction rates resulting from the kinetic isotope effect are observed.

57 isolated complexes, deuterium labeling, and kinetic isotope effects are consistent with a catalytic

58 s to determine activation parameters and the kinetic isotope effects are consistent with a mechanism

59 The experimental and calculated kinetic isotope effects are consistent with an SN2 chemi

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

62 ized, and expressions for rate constants and kinetic isotope effects are provided.

63 Gas-phase rate constants and kinetic isotope effects are reported for a variety of su

64 nthene-(d(2)), large, nonclassical deuterium kinetic isotope effects are roughly estimated for both F

65 Kinetic isotope effects arising from deuterium-for-hydro

66 p53, their TSs were solved with experimental kinetic isotope effects as computational constraints.

67 to the mechanism by examining the deuterium kinetic isotope effect associated with the hydrogen tran

68 Here, we report a large kinetic isotope effect associated with the rate-limiting

69 t generally tended to be negative due to the kinetic isotope effect associated with thermal NOx produ

70 We report a large kinetic isotope effect at 298 K, kH/kD approximately 150

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 RMCF analysis predicts that the H/D primary kinetic isotope effect can serve as a probe for these me

75 Measurements of reaction rates and carbon kinetic isotope effects (CKIE) for decarboxylation of is

76 hat the phenolic proton exhibits a secondary kinetic isotope effect, consistent with the calculations

77 ylide was studied by a combination of (13)C kinetic isotope effects, conventional calculations, and

78 A combination of kinetic isotope effects, crossover experiments, and comp

79 These results along with kinetic isotope effect determinations revealed that the

80 ulations and preliminary measurements of the kinetic isotope effects establish a concerted but asynch

81 (DFT) computational studies and results of a kinetic isotope effect experiment.

82 he mechanism of C-H amination was probed via kinetic isotope effect experiments [ k(H)/ k(D) = 10.2(9

83 probed via initial rate kinetic analysis and kinetic isotope effect experiments [k(H)/k(D) = 38.4(1)]

84 nt work, quantum mechanical computations and kinetic isotope effect experiments demonstrate that the

85 Deuterium labeling and kinetic isotope effect experiments indicate that C-H act

86 Moreover, solvent kinetic isotope effect experiments using deuterium oxide

87 l of mechanistic techniques, including (13)C kinetic isotope effect experiments, deuterated labeling

88 ensive mechanistic studies showed an inverse kinetic isotope effect, fast H2/D2 scrambling and slow a

89 (3) H at their benzylic C atoms, owing to a kinetic isotope effect favoring hydrogen abstraction fro

90 Deuteration at C-3 produced a strong kinetic isotope effect for 3-hydroxylation but not 4-hyd

91 A kinetic isotope effect for Compound I decay suggests tha

92 The enzyme kinetic isotope effect for hydride transfer was close to

93 tution did not change the solvent or primary kinetic isotope effect for proton abstraction, consisten

94 Kinetics studies determine a large kinetic isotope effect for the replacement of the transf

95 Computed values of the kinetic isotope effect for this step are inverse, consis

96 We report the kinetic isotope effects for (18)O within selenate during

97 el and excellent agreement with experimental kinetic isotope effects for all models used.

98 Other studies included kinetic isotope effects for both dissociation and H exch

99 Here, we measured intrinsic kinetic isotope effects for both N23PP and N23PP/G51PEKN

100 psilonbulk values were converted to apparent kinetic isotope effects for carbon (AKIE) in order to ch

101 For the first time, kinetic isotope effects for carbon-to-metal hydrogen ato

102 rmining step, and substantial differences in kinetic isotope effects for different substrates; both t

103 on between nitrite (NO(2)(-)) and water, and kinetic isotope effects for oxygen atom incorporation, w

104 The calculated kinetic isotope effects for p-nitrophenyl phosphate prov

105 In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and

106 Second, the primary kinetic isotope effects from deuterated nicotinamide nuc

107 Kinetic isotope effects from the use of deuterated buffe

108 A large substrate kinetic isotope effect (>/=8) for OleT compound I decay

109 Kinetic isotope effects have been used successfully to p

110 Experimental (13)C kinetic isotope effects have been used to interrogate th

111 For Pd/NZVI, the solvent kinetic isotope effect [i.e., kobs(H2O)/kobs(D2O) or SKI

112 The lack of electronic and kinetic isotope effects implies a rate-determining phosp

113 mical measurements indicate the absence of a kinetic isotope effect, implying that the precatalytic p

114 rrent study presents the first-ever observed kinetic isotope effect in a metal combustion reaction an

115 constrain ab initio calculations, making the kinetic isotope effect in the cold regime necessary to r

116 The secondary deuterium kinetic isotope effect in the reaction leading to comple

117 Kinetic isotope effects in AdoMet-dependent methyltransf

118 Experimentally determined kinetic isotope effects in conjunction with DFT-based an

119 esults suggest a large difference in the H/D kinetic isotope effects in nitrogen and argon matrices (

120 ived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide

121 The comparison of experimental and predicted kinetic isotope effects in the alpha-cleavage of alkoxy

122 Computed activation parameters and kinetic isotope effects, in combination with proton-inve

123 Escherichia coli (EcDHFR), where the enzyme kinetic isotope effect increased slightly with increasin

124 The deuterium kinetic isotope effect increases to 3.2, consistent with

125 e negative entropy of activation and inverse kinetic isotope effect indicate that H-H bond formation

126 Kinetic isotope effects indicated that the C-H bond clea

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,

130 The kinetic isotope effect k(CH3)/k(CT3) for methyl transfer

131 -H bond strength of the H atom donor, with a kinetic isotope effect ( k(H)/ k(D) = 4.8) comparable to

132 The corresponding kinetic isotope effect ( k(H)/ k(D) ~ 20) indicates that

133 Observations of a significant kinetic isotope effect (k(H) /k(D) =5.7) for the reactio

134 ts, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 +/- 1.7), agree

135 A large kinetic isotope effect (kH/kD = 20) suggests proton coup

136 A large, primary intermolecular kinetic isotope effect (KIE = 31.9 +/- 1.0) suggests H-a

137 The observed kinetic isotope effect (KIE = kH/kD) ranged from 1.2 to

138 -80 degrees C); thus, the hydrogen/deuterium kinetic isotope effect (KIE) = 6, consistent with H-atom

139 Here, we describe coordinated kinetic isotope effect (KIE) analyses, molecular dynamic

140 Here we demonstrate kinetic isotope effect (KIE) analysis enables direct eva

141 state of phosphoroimidazolide hydrolysis by kinetic isotope effect (KIE) and linear free energy rela

142 hensive labeling studies, rate measurements, kinetic isotope effect (KIE) experiments, synthetic stud

143 In concert with kinetic isotope effect (KIE) experiments, these computat

144 As a result, the kinetic isotope effect (KIE) for the hydrogen evolution

145 pecies with nine hydrocarbons shows that the kinetic isotope effect (KIE) involves strong tunneling a

146 An unusual H/D kinetic isotope effect (KIE) is described, in which isot

147 endent below approximately 10 K, and a large kinetic isotope effect (KIE) is observed upon substituti

148 The kinetic isotope effect (KIE) is used to experimentally e

149 Hammett analysis, radical clock experiments, kinetic isotope effect (KIE) measurements (kH/kD = 3.0 +

150 Kinetic isotope effect (KIE) measurements are a powerful

151 edia has been studied by the use of multiple kinetic isotope effect (KIE) measurements in conjunction

152 nistic proposal is supported by NMR studies, kinetic isotope effect (KIE) measurements, and DFT calcu

153 The kinetic isotope effect (KIE) observed for doubly labeled

154 Here, we identify and explain the kinetic isotope effect (KIE) observed for the oxidation

155 mechanism with kET = 2.7 x 10(7) s(-1) and a kinetic isotope effect (KIE) of 0.99 +/- 0.03.

156 the presence of alpha-FAD displayed a normal kinetic isotope effect (KIE) of 2.1, whereas the KIE was

157 An H/D kinetic isotope effect (KIE) of 80 is found at -20 degre

158 Heavy-atom kinetic isotope effect (KIE) studies are consistent with

159 Furthermore, multiple kinetic isotope effect (KIE) studies revealed a stepwise

160 Mechanistic investigations, including kinetic isotope effect (KIE) studies, reveal that cataly

161 oacylation did not exhibit a significant H/D kinetic isotope effect (KIE) with respect to the aldehyd

162 We used kinetic isotope effect (KIE), commitment factor (Cf), an

163 test these two possibilities using secondary kinetic isotope effect (KIE), mutagenesis study, and pri

164 xidation by humic acid and attributed to the kinetic isotope effect (KIE).

165 behavior and large but temperature-dependent kinetic isotope effects (KIE 32 at -40 degrees C).

166 upled electron-transfer mechanism; large H/D kinetic isotope effects (KIE) are observed.

167 that precludes calculation of apparent (2)H-kinetic isotope effects (KIE) as well as the process ide

168 r hydrogen has been shown to lead to massive kinetic isotope effects (KIE) for soybean lipoxygenase (

169 Significant kinetic isotope effects (KIE) were observed with a facto

170 Tunneling-corrected kinetic-isotope effect (KIE) calculations matched the ex

171 helium temperatures and shows a rather large kinetic isotope effect, KIE = 10.

172 tate, and ligand binding kinetics, intrinsic kinetic isotope effects (KIEint) on the chemical step, a

173 Differences in the kinetic isotope effects (KIEs) accompanying NADP(+) redu

174 the temperature-dependence of the intrinsic kinetic isotope effects (KIEs) and other kinetic paramet

175 neling reactions, as a result of its unusual kinetic isotope effects (KIEs) and their temperature dep

176 studied using a combination of experimental kinetic isotope effects (KIEs) and theoretical calculati

177 Kinetic isotope effects (KIEs) are nearly temperature-in

178 ng the TS using a suite of five experimental kinetic isotope effects (KIEs) as constraints for the ca

179 t of [Formula: see text]-secondary deuterium kinetic isotope effects (KIEs) at all sites of [Formula:

180 (EIEs), binding isotope effects (BIEs), and kinetic isotope effects (KIEs) for a range of phosphate

181 In contrast, the primary kinetic isotope effects (KIEs) for C-H activation and th

182 Here the temperature dependence of kinetic isotope effects (KIEs) for hydride transfer betw

183 Large intramolecular (13)C kinetic isotope effects (KIEs) for the di-pai-methane re

184 tunneling, and the temperature dependence of kinetic isotope effects (KIEs) has emerged as the "gold

185 Ensemble-based measurements of kinetic isotope effects (KIEs) have advanced physical un

186 this goal by measuring H/D and (12) C/(13) C kinetic isotope effects (KIEs) in plasmonic photosynthes

187 investigated with pH, solvent viscosity, and kinetic isotope effects (KIEs) in steady-state kinetics

188 The kinetic isotope effects (KIEs) in this enzyme have previ

189 to 87 kcal/mol to afford rate constants and kinetic isotope effects (KIEs) of 2-6 that are comparabl

190 ide insight into reaction mechanisms because kinetic isotope effects (KIEs) of both elements are refl

191 ay be generally applicable for examining the kinetic isotope effects (KIEs) of posttranslational modi

192 and remote beta-type N-CH(3)/CD(3) 2 degrees kinetic isotope effects (KIEs) on 10-methylacridine (MAH

193 ergy dependence of the rate constant and the kinetic isotope effects (KIEs) showed that the PCET mech

194 What do experimentally measured kinetic isotope effects (KIEs) tell us about H-abstracti

195 This method allows kinetic isotope effects (KIEs) to be determined with sub

196 C, H, and N isotope enrichment factors and kinetic isotope effects (KIEs) were derived from the com

197 The carbonyl-C, carbonyl-O, and leaving-S kinetic isotope effects (KIEs) were determined for the h

198 Solvent (D2O) and secondary formyl-H kinetic isotope effects (KIEs) were measured by an NMR s

199 ilarity extended to the associated secondary kinetic isotope effects (KIEs), indicating very similar

200 this step with experimental data, as well as kinetic isotope effects (KIEs), supports this prediction

201 ntrast with previously reported inverse (<1) kinetic isotope effects (KIEs).

202 16Ala, together with deuterium oxide solvent kinetic isotope effects (KIEs).

203 s in N2O), enrichment factors (epsilon), and kinetic isotope effects (KIEs).

204 is of nicotinamide mononucleotide (NMN) from kinetic isotope effects (KIEs).

205 n can be addressed by measuring steady-state kinetic isotope effects (KIEs); however, their interpret

206 nvestigations with the aid of Hammett plots, kinetic isotope effects, labeled stereochemical probes,

207 near temperature-independence of its primary kinetic isotope effect, low catalytic efficiency, and el

208 Kinetic investigations as well as the kinetic isotope effect measured confirmed that the hydri

209 Finally, the deuterium kinetic isotope effects measured suggest that the initia

210 Here, a combination of kinetic isotope effect measurements and quantum chemical

211 VTNA) of reaction time courses and deuterium kinetic isotope effect measurements established a kineti

212 kinetics, and natural abundance (12)C/(13)C kinetic isotope effect measurements.

213 The growing tool kit of kinetics, kinetic isotope effects, molecular biology, biophysics,

214 H(CD3)(SiMe3)](+) is used, suggesting an H/D kinetic isotope effect much larger (apparently >16,000)

215 Heavy atom (13)C/(12)C kinetic isotope effects near unity also support post rat

216 proceeds in ~800 ps, without any significant kinetic isotope effect, nor a pH effect between pH 6.5 a

217 c analysis coupled with the normal (13)(V/K) kinetic isotope effect observed on C-4 of oxaloacetate [

218 This conclusion was supported by the inverse kinetic isotope effect observed with deuterated 1S, the

219 nsistent with the observed inverse secondary kinetic isotope effect of 0.85.

220 A primary (13)C/(12)C kinetic isotope effect of 1.022(4) was measured at 23 de

221 A minimal kinetic isotope effect of 1.10(5) was observed, suggesti

222 dependence of the kinetics, and from a D2/H2 kinetic isotope effect of 1.2(+/-0.3).

223 a concerted PCET (tau = 4.7 mus) with an H/D kinetic isotope effect of 1.4 +/- 0.2.

224 This step shows a solvent kinetic isotope effect of 1.7.

225 e covalent thioimide reduction and a smaller kinetic isotope effect of 1.8 on the imine reduction to

226 An observed kinetic isotope effect of 10.1 was measured in human liv

227 mining attack at the THF C-H(D) bonds with a kinetic isotope effect of 10.2.

228 simulation reveal a large primary deuterium kinetic isotope effect of 3.3 on the covalent thioimide

229 es from experiments which identify a primary kinetic isotope effect of 5.4 for the deformylation reac

230 Reactions with deuterated acid display a kinetic isotope effect of 9 +/- 1.

231 The corresponding kinetic isotope effect of approximately 10 is attributed

232 erated species, giving rise to a significant kinetic isotope effect of approximately 50.

233 The latter proceed with a relatively small kinetic isotope effect of kH/kD = 7 for the iron(IV)-tos

234 A hydrogen/deuterium kinetic isotope effect of nearly 2 implicates O-H(D) bon

235 erivative that exhibits steady-state solvent kinetic isotope effects of 1.4 on both V and V/K.

236 Kinetic isotope effects of 1.5-2.3 (on kcat/Km ) were ob

237 Large primary deuterium kinetic isotope effects of 13.4 +/- 1.0 and 16.8 +/- 1.4

238 Kinetic isotope effects of 26.7 and 0.12 were determined

239 precursors; (b) obtain information about the kinetic isotope effects of as yet undescribed enzymes, t

240 d to their known precursors and to the known kinetic isotope effects of enzymes involved in their bio

241 While the apparent (13)C- and (2)H-kinetic isotope effects of nitrobenzene, nitrotoluene is

242 These findings can (i) be related to known kinetic isotope effects of some of the enzymes concerned

243 Here the temperature-dependence of intrinsic kinetic isotope effects of the enzyme formate dehydrogen

244 or hydrogen at a ribose 5'-carbon produces a kinetic isotope effect on cleavage; the major cleavage p

245 The observed kinetic isotope effect on H atom versus D atom abstracti

246 al for substantial benefits of the deuterium kinetic isotope effect on the safety and disposition of

247 is C-C "lyase" activity, we investigated the kinetic isotope effect on the steady-state turnover of N

248 We have measured delta-secondary kinetic isotope effects operating through four bonds for

249 Temperature-dependent measurements of the kinetic isotope effects over a 60 degrees C temperature

250 netic studies, H/D exchange experiments, and kinetic isotope effects provide clear support for a bime

251 transfer complex absorbance and experimental kinetic isotope effect reaction data, we show that this

252 Third, the apparent kinetic isotope effects related to the methyl group are

253 The unanticipated large kinetic isotope effects reported here for the tocopherol

254 Mechanistic studies especially using kinetic isotope effects show that cleavage by oxidative

255 h are subject to kinetic solvent effects and kinetic isotope effects similar to RSOH and other good H

256 -independent (pH 6.5), we determined solvent kinetic isotope effects (SKIEs) for three substrates who

257 Product analysis, kinetic isotope effects, stereochemical labeling, radica

258 Mechanistic details are established from kinetic isotope effect studies and density functional th

259 Kinetic isotope effect studies determine that the rate c

260 Kinetic isotope effect studies indicate that C-H pallada

261 Mass spectrometry and (1)H NMR based kinetic isotope effect studies revealed C-H bond activat

262 Furthermore, kinetic isotope effect studies support that the cis-amin

263 A series of secondary kinetic isotope effect studies using a range of ligands

264 temporal course of the reaction by (1)H NMR, kinetic isotope effect studies, and control experiments.

265 s that support these calculations, including kinetic isotope effect studies, H/D exchange studies, an

266 Hammett and kinetic isotope effect studies, in combination with comp

267 h other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-s

268 hrough a series of (12)C/(13)C and (1)H/(2)H kinetic isotope effect studies, the rate-determining ste

269 As elucidated by DFT calculations and (13)C kinetic isotope effect studies, the rate-limiting and en

270 sulfur isotope-labeled substrates for sulfur kinetic isotope effect studies.

271 of cross-coupling was obtained by deuterium kinetic isotope effect studies.

272 ans-Polayni graph and the finding of a large kinetic isotope effect suggest that hydrogen abstraction

273 Reaction progress kinetic analysis and kinetic isotope effects suggest that the stereodefining

274 ol pKa, and the absence of deuterium solvent kinetic isotope effects suggested stepwise mechanisms wi

275 urements) rule out a stepwise mechanism, and kinetic isotope effects support concerted proton-electro

276 Carbon kinetic isotope effects supported a rate-determining AdE

277 eactivity constitutes the first example of a kinetic isotope effect that discriminates between the fo

278 d TEAH(+) displays a potential-dependent H/D kinetic isotope effect that is not observed for DIPEAH(+

279 ent bimolecular rate constants and deuterium kinetic isotope effects that increase in proportion to c

280 From the Arrhenius plot of the kinetic isotope effect, the ratio of the preexponential

281 n the basis of the small values of deuterium kinetic isotope effects, the relatively high and negativ

282 ns, isotopic incorporation from solvent, and kinetic isotope effects, to define the mechanism and an

283 ts biphasic decay kinetics with no deuterium kinetic isotope effect upon PhSD substitution.

284 The two variants provide nearly identical kinetic isotope effect values (2.8-3.0), suggesting that

285 ulations of commitment factors from observed kinetic isotope effect values support a hydride transfer

286 gating, we determined vibrational as well as kinetic isotope effects (VIEs and KIEs) of carboxylic gr

287 The kinetic isotope effect was determined to be 0.67 using 1

288 a bromopyrone, but a highly unusual, inverse kinetic isotope effect was evident using a chlorocoumari

289 The kinetic isotope effect was found to vary linearly with t

290 experiments, substrate analogs, and primary kinetic isotope effects, we show that the interaction be

291 Kinetic isotope effects were measured for the methylatio

292 y Me-(3)H3, Me-(2)H3, 5'-(14)C, and 5'-(3)H2 kinetic isotope effects were measured for the methylatio

293 Intramolecular (12)C/(13)C kinetic isotope effects were predicted to be substantial

294 The intrinsic kinetic isotope effects were used as boundary constraint

295 Experimental kinetic isotope effects were used to guide quantum mecha

296 he reaction is presented showing a lack of a kinetic isotope effect when generating deuterothiophenol

297 Calculations of kinetic isotope effects, when including the solute inter

298 f the intermediate ketols and on the solvent kinetic isotope effects, whereby the condensations are f

299 The deuterium kinetic isotope effect, which compares the rate of a che

300 alyzed proton transfer shows a prominent H/D kinetic isotope effect, which is determined to be 8.3 x