ライフサイエンスコーパス: rate-determining

1 , we conclude that the rearrangement step is rate determining.

2 on transfer to water and was suggested to be rate determining.

3 s indicate the nucleophilic addition step is rate determining.

4 nism with the cleavage of Cbeta-H bond being rate determining.

5 ; formation of this knock-on intermediate is rate determining.

6 gesting that this step is at least partially rate determining.

7 , which was previously believed to be solely rate-determining.

8 onding transition state is both enantio- and rate-determining.

9 fusion through the aqueous boundary layer is rate-determining.

10 rates, with the splitting step likely being rate-determining.

11 er between the ester and sodium formamide is rate-determining.

12 e substrates in which C-H bond activation is rate-determining.

13 ct, even though hydrogen transfer may not be rate-determining.

14 that substrate-inhibited alkene insertion is rate-determining.

15 rising multiple carboxylates was found to be rate-determining.

16 of the iodonium ylide at the iminium ion is rate-determining.

17 enamine, to form the carbon-carbon bond, as rate-determining.

18 way and the single-step acylation process is rate-determining.

19 Subsequent rate-determining 1,3-hydrogen migration followed by retr

20 Carbon kinetic isotope effects supported a rate-determining AdE3 mechanism wherein alkyne activatio

21 para-substituted styrenes are indicative of rate-determining alkene insertion in the catalytic cycle

22 mplicated the formation of an amine-assisted rate-determining alkene insertion transition state in wh

23 r than a reflection of a reduced barrier for rate-determining alkene insertion.

24 to elucidate the catalytic mechanism of the rate-determining amine oxidation step in the lysine-spec

25 strate that ubiquinol-10 dissociation is not rate determining and deduce that ubiquinone-10 has both

26 ) the subsequent migratory insertion step is rate determining and occurs in a concerted manner.

27 resent in excess, so complex I is completely rate determining and the Q10 pool is kept oxidized under

28 rom experiment that reductive elimination is rate-determining and forms the anti-Markovnikov product.

29 formation of the product iminium species is rate-determining and is promoted by both the reaction pr

30 te metal carbenes, C-H cleavage is partially rate-determining and must be promoted to effect reactivi

31 mutations show that the switch in P5c is not rate-determining and suggest that non-native interaction

32 netics studies indicate that O(2) binding is rate-determining and that O-O bond cleavage and electron

33 n of the neutral tetrahedral intermediate is rate-determining and which is mainly amine-assisted at l

34 etic simulations show that the first step is rate-determining and yields Arrhenius barriers that are

35 W PT path is a new element, this step is not rate determining, and the catalytic effect is actually d

36 protonation at the indole-2 position was not rate determining as demonstrated by kinetic isotope effe

37 F solvent showed that 1 reacted with THF via rate-determining attack at the THF C-H(D) bonds with a k

38 All reactions proceed with rate-determining attack of the electrophile at the nucle

39 2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4

40 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV.

41 These studies point to rate-determining binding of H(2) followed by proton-coup

42 cated that the C-H bond cleavage step is not rate-determining, but the C-H bond cleavage and C-Si bon

43 bon monoxide and support a pathway involving rate-determining C-C coupling of the isocyanate ligands.

44 Together, these data imply that the rate-determining C-H bond cleavage occurs between PyO an

45 n into an iridium-alkoxide bond, followed by rate-determining C-H reductive elimination to yield the

46 and+/-0.0 per thousand, pH 1.75), indicating rate-determining C-S bond cleavage in TrzN.

47 trimethylenemethane complex, which undergoes rate-determining carbometalation through a transition st

48 pecies that is capable of releasing PCA upon rate-determining carbon-carbon bond cleavage.

49 uildup during the cyclization and supporting rate-determining concerted cyclization.

50 ion of azidohydrin intermediates followed by rate-determining concerted N(2)-loss/shift of the alkyl

51 es are controlled by a nucleotide-dependent, rate-determining conformational change in EF-Tu.

52 ough an enehydrazine intermediate before the rate-determining cyclization of the hydrazone onto the a

53 This low-barrier step is followed by the rate-determining dearomatization and formation of H(2).

54 ed acid sites is crucial in accelerating the rate-determining (dehydration) reaction, that is, the fi

55 eagents and then providing chloride for post-rate-determining demethylation/neutralization of the res

56 The energy difference between the rate-determining diastereomeric transition structures in

57 , the variant Tyr216Trp, for which ET is not rate determining, displays a solvent KIE of unity.

58 sic forms of the tryptophan derivative, in a rate-determining electron-transfer step followed by depr

59 The rate-determining elementary step (tau, approximately 30

60 a large primary alpha-deuterium KIE support rate-determining enamine formation.

61 Constitutive expression of the rate-determining enzyme hindered activation of CS utiliz

62 We determine that the rate-determining enzyme in CS breakdown is responsible f

63 entional view that alpha-amylase is the only rate-determining enzyme involved in starch digestion and

64 FB3), which activates phosphofructokinase, a rate-determining enzyme of glycolysis.

65 PHYTOENE SYNTHASE (PSY), the first and main rate-determining enzyme of the carotenoid pathway.

66 We propose that these early and late rate-determining events are intramolecular conformationa

67 d phenol-to-rhenium electron transfer in the rate-determining excited-state deactivation step, and th

68 idate gene underlying ENDO-2, operating as a rate-determining factor of endoreduplication.

69 'CH)2} (18) generated transient imide 25 via rate-determining, first-order methane elimination (KIE a

70 n of an aggregation competent state as being rate determining followed by rapid polymerization with t

71 Product dissociation is therefore rate determining for isomerization of IPP with a rate co

72 r to a Cu(II)-superoxo intermediate is fully rate-determining for k(cat)/K(m)(O(2)).

73 Interestingly, the reductive elimination is rate-determining for the major diastereomeric product, w

74 c product, while the Cu(I) migration step is rate-determining for the minor.

75 The behavior is consistent with rate-determining formation of a 2-substituted carbocatio

76 sis of a mechanism that proceeds through the rate-determining formation of a hydrogen bonded pre-reac

77 A catalytic cycle involving rate-determining formation of a reactive imido species i

78 The rate-determining formation of this intermediate involves

79 support the origin of the inversion as being rate-determining formylation of cis-enolate 27 from a mi

80 only two adjustable parameters-the number of rate-determining genes and the energy barrier for metabo

81 ior in C-H substrate and are consistent with rate-determining hydrogen atom transfer.

82 tic data show that these reactions occur via rate-determining hydrogen-atom transfer (HAT), with a li

83 ubsequent transmembrane movements and may be rate determining in the transport cycle.

84 ysulfonium intermediate has been shown to be rate-determining in the Swern oxidation of benzyl alcoho

85 n arrangement that facilitated self-decay by rate-determining intramolecular hydrogen atom abstractio

86 ty, indicating that decarboxylation is fully rate-determining; k(cat)/K(M) displays a fractional depe

87 -classical Phi(M)-values (Phi(M) > 1) in the rate-determining loop 1 substructure, and conclusively i

88 the zinc-bound water molecule in the initial rate-determining nucleophilic attack step, and then shut

89 rder H < Me < OMe < NMe(2), which supports a rate-determining oxygen atom transfer reaction involving

90 tronic and kinetic isotope effects implies a rate-determining phosphine dissociation for the decarbon

91 ng barrier is apparently a proxy for related rate-determining physical properties.

92 establishes that C-C cleavage is part of the rate-determining process, intrinsic CKIEs for decarboxyl

93 ever, a kinetic study reveals a one-electron rate-determining process, ket = 1.6 M(-1) s(-1) (-90 deg

94 In the rate-determining process, the diferrous-dinitrosyl conve

95 To understand the rate determining processes during the equilibration of p

96 , increasing the H(2) pressure increases the rate-determining product desorption under the conditions

97 le formation of the new C-C-bond followed by rate-determining proton shift.

98 Mechanistic studies implicated a rate-determining protonation step in the generation of t

99 re is likely to involve proton motion in the rate-determining reaction step.

100 g to an Osborn type hydrogenation cycle with rate determining reductive elimination of the alkane.

101 tion of an alkylnickel-aryl intermediate and rate-determining reductive elimination to form the carbo

102 rease in turnover via an acceleration of the rate-determining release of K(+) to the cytoplasm, E2(K(

103 neutral process, in which the first step is rate determining, requiring protonation of adenine (N(7)

104 dicating their rapid single addition and the rate-determining ring opening of the low-strain olefin.

105 The proposed aggregation mechanism of p53 of rate-determining sequential unfolding and combination of

106 ylperoxy radical is the major oxidant in the rate-determining SET step that is followed by competing

107 sed reaction mechanism is characterized by a rate-determining sigma-bond metathesis of an alkoxide co

108 Dehydrogenation of the alkane is not rate-determining since pentane and pentane-d12 can be de

109 The mechanism consists of a rate-determining single electron transfer (SET) that is

110 well with the calculated rate constants for rate-determining single electron transfer (SET).

111 fate anion [EtSO(4)](-) demonstrate that the rate determining step (RDS) is second order in aldehyde,

112 arrier of DeltaG(double dagger)=0.43 eV, the rate determining step (RDS).

113 analysis suggests reductive CO coupling as a rate determining step for C2 products, while n-propanol

114 w samples significantly, indicating that the rate determining step in extraction for these compounds

115 Moreover, the rate determining step of nitrate reduction (reduction to

116 he Ru-O2 complex plays a crucial role in the rate determining step of the catalytic cycle, but the ex

117 xidative addition to the Cu(I) center as the rate determining step.

118 hat O-O bond heterolysis is likely to be the rate-determining step (RDS) at the mass transfer limited

119 y-Rideal (ER) mechanism using H2O + e(-) The rate-determining step (RDS) is C-C coupling of two CO, w

120 udies of six alkyne subtypes reveal that the rate-determining step (RDS) of an aromatic ynamine class

121 ng the involvement of N-H bond-breaking in a rate-determining step (RDS) which is not ring-closure.

122 the experimentally observed barrier for the rate-determining step and its pH dependence.

123 Product release is the rate-determining step and largely determines k(cat).

124 tein reorganization at the interface was the rate-determining step and not diffusion to the interface

125 iodine provide mechanistic insight into the rate-determining step and the oxidation state of Pd in t

126 ithin the eight-membered metallacycle in the rate-determining step as a function of the steric demand

127 0-nm-sized particles of LiMn2 O4 reveals the rate-determining step at high overpotentials to be the t

128 more thermostable enzyme and a change in the rate-determining step at low temperature.

129 anism for fragmentation with a change in the rate-determining step between the two series.

130 echanistic studies have established that the rate-determining step can vary with the structure of the

131 ninase from Pseudomonas fluorescens, and the rate-determining step changes from release of the second

132 approximately 130 mV per decade points to a rate-determining step comprised of water dissociation an

133 This suggests that there is a change in rate-determining step for benzoate formation with differ

134 data implicate reductive elimination as the rate-determining step for both monomers.

135 dependence that results from a change in the rate-determining step for charge recombination from radi

136 analysis) experiments demonstrates that the rate-determining step for CO formation is the conversion

137 The QM formation is the rate-determining step for DNA cross-linking.

138 ction at a C2'-endo nucleotide comprises the rate-determining step for folding an entire 154 nucleoti

139 n degradation from the native 3' end, is the rate-determining step for mRNA decay.

140 cating the absence of proton transfer in the rate-determining step for the association of thrombin wi

141 The rate-determining step for these cascades is typically th

142 udies suggest that oxidative addition is the rate-determining step for this process.

143 ed study of the physical half-process in the rate-determining step from its chemical counterpart.

144 ds by a stepwise mechanism, with a change in rate-determining step from proton transfer to the loss o

145 is indicates that the C-H bond formed in the rate-determining step has a bond dissociation free energ

146 us-dinitrosyl by the proximal FMNH(2) in the rate-determining step have been proposed.

147 ard the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel

148 ss I aminoacyl-tRNA synthetases (aaRSs), the rate-determining step in aminoacylation is the dissociat

149 Our calculations suggest that the rate-determining step in both cases consists of a C-C co

150 olving both the reductase and oxygenase, the rate-determining step in catalysis is the dissociation o

151 Acetyl-CoA carboxylase (ACC) catalyzes the rate-determining step in de novo lipogenesis and plays a

152 monotonously with acyl chain length, is the rate-determining step in iPLAbeta-mediated hydrolysis of

153 , and limits its potential to accelerate the rate-determining step in oxidative regeneration.

154 the impact of PDI and its subdomains on the rate-determining step in ribonuclease A folding and on t

155 ical rearrangement and that this step is the rate-determining step in substrate radical decay.

156 Product release is the rate-determining step in the arene syn-dihydroxylation r

157 n of a doubly protonated intermediate as the rate-determining step in the carbocation-mediated cis to

158 The rate-determining step in the catalytic cycle of E. coli

159 e we show that negative cooperativity in the rate-determining step in the E1 component of the Escheri

160 ns for such profound effects as shifting the rate-determining step in the electrocatalytic reduction

161 the acyl-enzyme intermediate appears to be a rate-determining step in the hydrolysis of JH by MsJHE.

162 yribonucleoside kinases (dNKs) carry out the rate-determining step in the nucleoside salvage pathway

163 lubilized by apoA-I; apparently, this is the rate-determining step in the overall ABCA1-mediated cell

164 through the polymer shell is found to be the rate-determining step in the overall process.

165 iates, where the initial chlorination is the rate-determining step in the overall sequence of reactio

166 The rate-determining step in the overall turnover of the bc(

167 The rate-determining step in the oxidative regeneration path

168 This is the rate-determining step in the reaction cycle and is follo

169 substrates were identified according to the rate-determining step in the reaction.

170 ctroscopy leading to the conclusion that the rate-determining step in the stereomutation of such pipe

171 This H atom transfer reaction is the rate-determining step in the tocopherol-mediated peroxid

172 suggest lysosomal integrity as a significant rate-determining step in the transmission of alpha-syn p

173 ne beta-synthase (dCBS), which catalyzes the rate-determining step in the TSP, is a positive regulato

174 rpsT P1, yfcZ, and ydfG--to characterize the rate-determining step in their degradation.

175 The rate-determining step in these reactions is the uptake o

176 dative addition of an O-H bond in H2O is the rate-determining step in this reaction.

177 Kinetic studies reveal that the rate-determining step in this S(N)1 pathway is the catal

178 the hydride delivery to the substrate is the rate-determining step inside the capsule.

179 r) = +14.1 cm(3) mol(-1)), consistent with a rate-determining step involving movement of the Leu 16 r

180 his enthalpy difference, suggesting that the rate-determining step is associated either with the mobi

181 The rate-determining step is bond formation at the alkyne te

182 In the absence of ligand, the rate-determining step is dominated by the formation of l

183 minary mechanistic studies indicate that the rate-determining step is not C-H bond cleavage but are i

184 tic species involved in the polymerization's rate-determining step is not coordinated to pyridine.

185 s the reduction, even though the strain-free rate-determining step is orthogonal to the pulling direc

186 y barrier (18.8 kcal/mol) calculated for the rate-determining step is reasonably close to the experim

187 are consistent with a mechanism in which the rate-determining step is the addition of electrochemical

188 Through calculating energy barriers, the rate-determining step is the displacive transition.

189 ugh a birth and spread process, in which the rate-determining step is the formation on the surface of

190 The rate-determining step is the hydrophosphination with an

191 Directly following this rate-determining step is the intramolecular syn-beta-eli

192 the formation of alpha-chloroglycine is the rate-determining step likely proceeding through the form

193 The rate-determining step of ethanol photocatalytic oxidatio

194 e-turnover kinetic analysis reveals that the rate-determining step of FEN1 switches as a function of

195 ning enzyme, which catalyzes the initial and rate-determining step of l-tryptophan (l-Trp) metabolism

196 ning enzyme, which catalyzes the initial and rate-determining step of L-tryptophan (L-Trp) metabolism

197 Ir.POM(8-) yield the transition state of the rate-determining step of nucleation.

198 a2 suggested that as the pH is elevated, the rate-determining step of RNR can be altered from a confo

199 The rate-determining step of the activated complex is the tr

200 ral acid-catalyzed elimination as the likely rate-determining step of the addition-elimination hydrol

201 The rate-determining step of the asymmetric cycle is the rel

202 A bimetallic Co species is invoked in the rate-determining step of the catalysis according to kine

203 mediates, which appear to be involved in the rate-determining step of the catalytic cycle.

204 plex on the reaction pathway just before the rate-determining step of the concerted pathway and a SET

205 l results show that C-H bond cleavage is the rate-determining step of the current borylation reaction

206 Studies also show that the rate-determining step of the fluoronium forming SN1 reac

207 rrupts the sigmatropic shift and changes the rate-determining step of the interrupted cascade from th

208 f the two allenes, which was found to be the rate-determining step of the overall reaction.

209 The rate-determining step of the oxidative half-reaction was

210 and UV spectroscopy and determined that the rate-determining step of the process is formation of a S

211 ific experiments allowed us to establish the rate-determining step of the reaction and to advance a r

212 topped-flow kinetic studies suggest that the rate-determining step of the reaction is likely to be th

213 an intermediate with C-Cl bond, acts as the rate-determining step of the reaction.

214 on of the arylpalladium intermediate, is the rate-determining step of the reaction.

215 this carbon-hydrogen bond is involved in the rate-determining step of the reaction.

216 he Pd(II) center in this intermediate is the rate-determining step of the reaction.

217 ize the molecular mechanism of the first and rate-determining step of the splicing process (i.e., the

218 rnover nuclease assays, we have assigned the rate-determining step of the steady state nuclease react

219 release precedes the release of Pi, and the rate-determining step of the symmetric cycle becomes the

220 rization and hydrolysis, suggesting that the rate-determining step of these processes involves breaki

221 ep of the ring opening of the epoxide is the rate-determining step of these reactions.

222 lly, LiCl was found to have no effect on the rate-determining step or molecular weight distribution i

223 These isotope effects are consistent with a rate-determining step that occurs prior to breaking eith

224 o lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional

225 The rate-determining step to methane and ethylene formation

226 lf the oxidant but decays via a unimolecular rate-determining step to unmask a powerful oxidant.

227 This indicated that the rate-determining step was reductive elimination from the

228 law as well as activation parameters for the rate-determining step were derived and complemented by a

229 n of the resulting fatty acids to aldehydes (rate-determining step) is uniquely catalyzed via two par

230 sfer from the catalyst to the alcohol as the rate-determining step, and carbonate anion serving as th

231 inear free energy relationships for a single rate-determining step, and substantial differences in ki

232 The methyl transfer is the rate-determining step, and the obtained free energy barr

233 ate along a reaction coordinate, a switch of rate-determining step, and the possible turning of a tra

234 Modulations of the rate-determining step, by variation of the concentration

235 The post-rate-determining step, C-H bond activation of pyridine,

236 calculated E(a) value (23.3 kcal/mol) in the rate-determining step, i.e., the homolysis of I2k, agree

237 g hydrogen atom abstraction is the principle rate-determining step, involving a tunneling mechanism f

238 Although PPi release is the rate-determining step, it is not the specificity-determi

239 hows that all reactions proceed via a common rate-determining step, the nucleophilic attack of 3-5 at

240 lacycle-forming oxidative cyclization as the rate-determining step, this study illustrates that the c

241 4-O-5 ether bonds, C-O bond cleavage is the rate-determining step, with the reactants competing with

242 triple bond, which is generally considered a rate-determining step.

243 cal disproportionation reaction (RRD) as the rate-determining step.

244 ween cerium cations and hydroxyl ions is the rate-determining step.

245 rly 2 implicates O-H(D) bond breaking in the rate-determining step.

246 tion, our data show that it is not a primary rate-determining step.

247 at undergoes a charge rearrangement in KSI's rate-determining step.

248 found to reduce the reaction barrier of the rate-determining step.

249 to the carbonyl of the lactone moiety is the rate-determining step.

250 est that hydrogen abstraction is engaged the rate-determining step.

251 H bonds are simultaneously broken during the rate-determining step.

252 olymer phosphonate ester by a monomer as the rate-determining step.

253 cleavage of the C-H bond takes place in the rate-determining step.

254 nd scission and that C2 deprotonation is the rate-determining step.

255 nation from this position is involved in the rate-determining step.

256 via a single electron transfer (SET) as the rate-determining step.

257 ))(2) --> E1 + 2K(+) transition is the major rate-determining step.

258 alkyne into the rhodium-thiolate bond is the rate-determining step.

259 The ene reaction of two alkynes is the rate-determining step.

260 The alkene insertion is the rate-determining step.

261 e N-N bond of 1 by the Cu(I) catalyst is the rate-determining step.

262 higher free energy reaction barrier for the rate-determining step.

263 than the overall cycle rate, and thus not a rate-determining step.

264 pared with GES-1, and no longer has a single rate-determining step.

265 tic studies suggest that C-H cleavage is the rate-determining step.

266 ere it requires lower energy to initiate the rate-determining step.

267 hat the cleavage of the leaving group is the rate-determining step.

268 H bond cleavage is irreversible, but not the rate-determining step.

269 studies revealed C-H bond activation as the rate-determining step.

270 hydroxide and a full negative charge in the rate-determining step.

271 ng the N-N bond of N2O during a bimolecular, rate-determining step.

272 bimetallic Ni(III) to generate ethane as the rate-determining step.

273 ron transfer in the initial oxidation as the rate-determining step.

274 are thought to involve C-H activation as the rate-determining step.

275 to the apo-[4Fe-4S] enzyme, well before the rate-determining step.

276 ond cleavage, which has been found to be the rate-determining step.

277 uired to reorient the peroxyl radical at the rate-determining step.

278 om an ammonium nitronate intermediate as the rate-determining step.

279 For AA, there are multiple rate determining steps (RDS) at both high and low temper

280 tly reduces the activation enthalpies of the rate determining steps in reference to the oxygenated sy

281 The results indicate new rate-determining steps for both phases.

282 In the transition states in the rate-determining steps for the two pathways, carbon-oxyg

283 ensitive trends, we disentangle the separate rate-determining steps in each particle across the very

284 ying TL conformational changes as one of two rate-determining steps in elongation.

285 sic CKIE of 1.051 and suggests two partially rate-determining steps in the decarboxylation of 1: tran

286 for separate first-irreversible and overall rate-determining steps in the hydration reaction, with t

287 The Gibbs activation energies of the rate-determining steps of each mechanism were defined.

288 g unimolecular silyl loss or C-O cleavage as rate-determining steps toward carbide formation.

289 e, and alpha-hydrogen abstraction is overall-rate-determining [the kinetic isotope effect (KIE) for 1

290 the participation of a water molecule in the rate determining transition state, in such a way that th

291 H(double dagger) = 17 to 21 kcal/mol) in the rate-determining transition state.

292 ion along the pulling axis in the respective rate-determining transition states.

293 h of the two (salen)Co(III) complexes in the rate-determining transition structure is important for p

294 form a 2:1 catalyst-substrate complex in the rate-determining transition structure.

295 ne) are essential to locate the product- and rate-determining transition structures (C-N bond formati

296 barriers is determined by the least stable (rate-determining) transition state.

297 ial region and its key role in promoting the rate-determining Volmer step.

298 he process of N-O bond rotation only becomes rate determining when in the presence of pervasive steri

299 mutations are uncovered at an unprecedented rate, determining which combinations of genetic alterati

300 ions reveal that C-C cleavage to form PCA is rate-determining with significant variation in the magni