ライフサイエンスコーパス: rate-determining

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

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

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

4 s indicate the nucleophilic addition step is rate determining.

5 dict the reaction of Fe(II) with N(2)O to be rate determining.

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

7 int to the second protonation event as being rate-determining.

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

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

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

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

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

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

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

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

16 with initial homolysis of an Ir-H bond being rate-determining.

17 hat the C-H activation step may be partially rate-determining.

18 wise mechanism in which electron transfer is rate-determining.

19 reductive elimination barriers, which become rate-determining.

20 catalyst, computations are consistent with a rate-determining (2 + 1)-cheletropic reaction, in which

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

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

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

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

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

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

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

33 The first step of the cycloaddition is rate-determining, and reaction occurs by attack on the c

34 Rate-determining association of 1-octene to ((tric)PDI)F

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

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

37 ons reveals a stepwise mechanism featuring a rate determining barrier of only DeltaE( ) = 0.6 eV, con

38 2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4

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

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

41 isotope effects near unity also support post rate-determining C-C bond formation.

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

43 rimary isotope effects are consistent with a rate-determining C-H cleavage.

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

45 chanistically, CH(4) activation proceeds via rate-determining C-H scission to form a surface-bound C(

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

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

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

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

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

51 ts corresponding neutral alpha-radical via a rate-determining CPET.

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

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

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

55 the amines at the electrophiles followed by rate-determining deprotonation of the intermediate ammon

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 identify critical reaction intermediates and rate-determining elementary reactions, thereby providing

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

61 tion of the amine alpha-C-H bond followed by rate-determining elimination of the beta-C-H bond.

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

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

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

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

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

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

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

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

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

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

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

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

76 The rate-determining formation of this intermediate involves

77 Rate-determining fragmentation then delivers methyl sulf

78 reduction of the barrier of the initial (and rate-determining) H-atom abstraction from the stearoyl s

79 roposed mechanism of rapid iminyl formation, rate-determining HAA, and subsequent radical recombinati

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

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

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

83 alation and the subsequent deprotonation are rate-determining in the catalytic cycle.

84 matic searches of the genome are potentially rate-determining in vivo.

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

86 mical properties are often indicative of the rate-determining mechanism, with lipophilic molecules te

87 Rate-determining opening of the chelate by an ancillary

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

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

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

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

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

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

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

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

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

97 ysis of microkinetic models to determine the rate-determining reactions using the degree of rate cont

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

114 , with dehydration of the MGO-dihydrate as a rate determining step.

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

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

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

118 initiate the reaction with 1,5-H shift as a rate-determining step (RDS), and the fastest 1,5-H shift

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

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

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

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

123 0-nm-sized particles of LiMn2 O4 reveals the rate-determining step at high overpotentials to be the t

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

125 a revealed that the diffusion of ions is the rate-determining step at the three different time stages

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

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

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

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

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

131 The rate-determining step for cracking is C-C bond attack of

132 The rate-determining step for dehydrogenation is the beta-hy

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

134 electron transfer reaction was the probable rate-determining step for HAA reduction.

135 1)H/(2)H kinetic isotope effect studies, the rate-determining step for the polymerization was determi

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

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

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

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

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

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

142 ric DHA has previously been suggested as the rate-determining step in formation of methylglyoxal, the

143 The rate-determining step in free radical lipid peroxidation

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

145 The rate-determining step in oxygen reduction is the protona

146 ality control by showing that priming is the rate-determining step in protein degradation as directed

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

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

149 he cobalt phthalocyanine complex changes the rate-determining step in the CO(2) reduction mechanism a

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

151 tope effect determinations revealed that the rate-determining step in the Friedel-Crafts transformati

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

169 ride shift/electrocyclization process as the rate-determining step is proposed and discussed vs possi

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

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

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

173 The rate-determining step is the hydrophosphination with an

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

175 y to flavonol through hydrolysis reaction is rate-determining step of considered process.

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

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

178 Kinetic studies provide evidence that the rate-determining step of pol beta catalysis is phosphodi

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

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

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

182 demonstrate that the C-H bond rupture is the rate-determining step of the catalysis.

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

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

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

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

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

188 pic and electrokinetic data, we identify the rate-determining step of the OER as the release of dioxy

189 reform the phosphine oxide catalyst, is the rate-determining step of the overall process and is sign

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

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

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

193 ectron-donating core substituents affect the rate-determining step of the reaction.

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

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

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

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

198 hat the oxidation of Cr(III) to Cr(V) is the rate-determining step of the reaction.

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

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

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

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

203 suggest that the final hydroarylation is the rate-determining step of this cascade process.

204 dized U(VI) from the UO(2)(s) surface as the rate-determining step rather than electron transfer or i

205 The initial deoxygenation involves a rate-determining step that consists of a (3+1) cheletrop

206 composed by two adjacent Co(IV) atoms and a rate-determining step that involves oxygen-oxygen bond f

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

208 The rate-determining step to methane and ethylene formation

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

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

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

212 dependence on the substrate and water and a rate-determining step which involves the first electron

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

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

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

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

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

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

219 at the substrate and PdL are involved in the rate-determining step, indicating that the C-H activatio

220 .0) suggests H-atom abstraction (HAA) is the rate-determining step, indicative of H-atom tunneling be

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

222 ctive sites during MDA, reaction mechanisms, rate-determining step, kinetics and catalyst activity of

223 ch protons do not seem to be involved in the rate-determining step, leading to a transiently negative

224 cycle is proposed with Si-H insertion as the rate-determining step, supported by kinetic isotope expe

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

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

227 4-O-5 ether bonds, C-O bond cleavage is the rate-determining step, with the reactants competing with

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

251 bond activation is irreversible and not 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 Ar pathway, and phosphine elimination is the rate-determining step.

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

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

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

259 stent with H-atom abstraction by S being the rate-determining step.

260 e cleavage of the C-H bond of alcohol is the rate-determining step.

261 -determining step(s) usually occur after the rate-determining step.

262 ups in lowering the activation energy at the rate-determining step.

263 metalation step might not be involved in the rate-determining step.

264 e involvement of Sn-H bond activation in the rate-determining step.

265 rption of formic acid on the catalyst as the rate-determining step.

266 that it (CO(2)) is directly involved in the rate-determining step.

267 ectron transfer is involved in the catalytic rate-determining step.

268 nerates the acrylonitrile is found to be the rate-determining step.

269 onded amine aggregates is proposed to be the rate-determining step.

270 ermediate dibenzyl ether and to identify the rate-determining step.

271 molysis of the resulting intermediate is the rate-determining step.

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

273 halogen bond cleavage is not involved in the rate-determining step.

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

275 pathways of ORR are firstly reviewed and the rate-determining steps based on the reaction intermediat

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

277 arance steps, which are considered to be the rate-determining steps for many promoters.

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

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

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

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

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

283 tion, binding, and product release are often rate-determining steps in which enthalpy-entropy compens

284 k(D) = 3.6(5) and 10.8(6)], showing that the rate-determining steps involve C-H activation.

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

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

287 support a stereospecific mechanism in which rate-determining substitution occurs from a catalyst-don

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

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

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

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

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

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

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

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

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

297 cess nucleophile identify transmetalation as rate-determining, whereas C-H activation is shown to be

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

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

300 ation of the dioxonium cation 9, followed by rate determining yet reversible ring opening by acetonit