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1 rate deuteration, but displays a substantial solvent isotope effect.
2 pe effect of 1,002 +/- 0.012 and the inverse solvent isotope effect.
3 ted by the measurements of large solvent and solvent isotope effects.
4 y-state kinetics and deuterium substrate and solvent isotope effects.
5 and thus contribute to the observed kinetic solvent isotope effects.
6 eters k (cat), K(m) , and k (cat)/K(m) ; and solvent isotope effects.
7 in a RNase are coupled and display identical solvent isotope effects.
8 ofiles of wild-type and mutant ribozymes and solvent isotope effects.
11 fects in the L --> D direction and increased solvent isotope effects (1.5-2-fold) but unchanged prima
14 e reaction was subject to an inverse kinetic solvent isotope effect analogous to that observed in the
15 s process shows an inverse k(H)/k(D) kinetic solvent isotope effect and involves protonation of a nea
18 In addition, the mutants display increased solvent isotope effects and increased levels of steady-s
19 followed the Hofmeister series, analysis of solvent isotope effects and of the changes in LCST with
20 rate of YZ(*) decay exhibited a significant solvent isotope effect, and the rate of recombination an
21 use of dead-end and product inhibition, the solvent isotope effect, and the solvent viscosity effect
22 th measurements of rate/pH profiles, kinetic solvent isotope effects, and ion dependence of GTP hydro
23 pH-dependent NMR chemical exchange, kinetic solvent isotope effects, and mutation, we show that a lo
24 is of protein stability, kinetic parameters, solvent isotope effects, and pH-rate profiles for key Sr
25 a) measurements of the active site cysteine, solvent isotope effects, and solvent viscosity effects,
26 eriments, we use pH-rate profiles, deuterium solvent isotope effects, and solvent viscosity measureme
29 ted lactate establishes that the primary and solvent isotope effects arise from the same chemical ste
30 nalysis suggests that future measurements of solvent isotope effects as a function of pressure, in th
31 transfer is suggested by multiple substrate/solvent isotope effects, as well as a proton transfer in
32 ly pH-independent (pH 5-9.5), shows no D(2)O solvent isotope effect at pH 7.7, and decreases with inc
36 t substrate pro-alpha-factor exhibits a weak solvent isotope effect, but neither this isotope effect
39 hese experiments include pH profiles and H/D solvent isotope effects consistent with proton transfer,
43 is significantly different from the reported solvent isotope effect for the hydrolysis of sialyglycos
46 , we determined temperature dependencies and solvent isotope effects for the alpha-chymotrypsin-catal
50 state, a result consistent with experimental solvent isotope effects for this enzyme and with establi
52 through a process involving a rate-limiting solvent isotope effect, generating conformational change
53 ts protonated form and shows a large kinetic solvent isotope effect (H(2)O/D(2)O) of 5.2 +/- 0.5, ind
56 alize lyase activity with an unusual inverse solvent isotope effect in an engineered microbial system
57 y isotope effects (1.5-2-fold) but unchanged solvent isotope effects in the L --> D direction and inc
58 anistic studies of FIH have revealed inverse solvent isotope effects in the steady-state rate constan
61 roposed mechanisms for both high and low pH, solvent isotope effects indicate that proton transfer st
63 ependent of pH and did not involve a kinetic solvent isotope effect, indicating that no proton is inv
64 neral base catalysis: a) the k(H2 O)/k(D2 O) solvent isotope effect is 1.4; b) the rate law (hydrolys
69 similarities to mammalian POPs, however the solvent isotope effect (k(0)/k(1)) was 2.2 at both high
70 is observed using PhCDO, and a large inverse solvent isotope effect (k(D)/k(H) approximately 5.9) is
72 lso was found to be subject to a substantial solvent isotope effect (kH/kD = 2.7), which is significa
73 solvent effects for 3, including the kinetic solvent isotope effect (KSIE) of 2.18 for methanol, are
76 ated sugar, together with the absence of any solvent isotope effect, lead to the conclusion that hydr
79 tments to catalysis accompanying the kinetic solvent isotope effect means that this portion of the pr
80 is of the effects of pH, metal substitution, solvent isotope effects, mutant proteins, and alternativ
81 s proposed as an explanation for the inverse solvent isotope effect observed on V/K(DD-CoA) when eith
84 e extraction of an inverse intrinsic kinetic solvent isotope effect of 1.1 (i.e., (D(2(O)))V/K = 0.9)
88 hydride transfer and an inverse equilibrium solvent isotope effect of 2.6 (i.e., (D(2(O)))K(s) = 0.4
89 orming G(734)., and the decay exhibits a H/D solvent isotope effect of 3.4, consistent with H-atom tr
91 ed to zero buffer concentration show a small solvent isotope effect of k(H(2)O)/k(D(2)O) = 1.1, consi
92 sis with a single proton in flight, a normal solvent isotope effect of k(H)/k(D) = 1.5, and when extr
93 d mechanism is implicated through an inverse solvent isotope effect of k(HO(-))/k(DO(-)) = 0.5 and a
101 e presence of D(2)O revealed a large inverse solvent isotope effect on both inactivation and acetylat
103 oyl-L-alanine does not exhibit a significant solvent isotope effect on k(cat) ((H)k/(D)k = 0.96 +/- 0
104 t) decreases for this mutant and the kinetic solvent isotope effect on k(cat), which was 2.0 in WT, i
108 e and 3.5 for the flavin domain, whereas the solvent isotope effect on this kinetic parameter is 1.0
109 rium oxide as the solvent, consistent with a solvent isotope effect on V(max) of 2.6 observed in stea
110 e measured for these substrates that reflect solvent isotope effects on hydrogen atom transfers that
118 viscosity effects, 18O isotope effects, and solvent isotope effects on the kinetic parameter Vmax/Km
119 system, including unprecedented H(2)O/D(2)O solvent isotope effects on the O(2)(a(1)Delta(g)) format
124 salt, and does not exhibit a primary kinetic solvent isotope effect over the range of pH and cation c
125 lytic rate, coupling efficiency, and kinetic solvent isotope effect parameters, highlighting an impor
130 e use of dead-end and product inhibition and solvent-isotope effect reveals that both domains catalyz
131 ger solution made up from heavy water, whose solvent isotope effect should reduce the probability, th
133 re was a significant (k(cat))(H)/(k(cat))(D) solvent isotope effect (SIE) for unphosphorylated Tie2 (
134 strate concentrations, a substantial inverse solvent isotope effect (SIE) is observed on V(max)/K(M)
137 rnover over a wide pH-range, with an inverse solvent isotope effect (SIE) of k(cat) observed ((D(2)O)
139 rmed by a temperature-dependent, k(cat)/K(M) solvent isotope effect (SIE), which indicated a hydrogen
140 emperature kinetic isotope effects (KIE) and solvent isotope effects (SIE), we demonstrate that both
144 as investigated using steady-state kinetics, solvent isotope effects (SIEs), and competitive oxygen k
145 f a beta-silyl carbocation intermediate, and solvent isotope effect studies indicate that this cation
148 n-metal-based reactivity, we present kinetic solvent isotope effect studies, variable time normalizat
151 otope effect at pH < 8 can be explained by a solvent isotope effect that affects the free energy chan
152 is, may yield precise estimates of intrinsic solvent isotope effects that are not fully expressed on
154 ng steps in the oxidative half-reaction, the solvent isotope effect, viscosity effect, and O-18 isoto
156 presence of both divalent metal ions, and no solvent isotope effect was measured on either "burst" ph
157 rs k cat, K m, and k cat/ K m along with the solvent isotope effect were examined for the Fe-type NHa
158 DH (NADD) kinetic isotope effect and the D2O solvent isotope effect were increased in dual-label expe
159 ffect, and the rate of recombination and the solvent isotope effect were pH independent from pH 5.0 t
166 peroxide intermediate and an inverse kinetic solvent isotope effect, which indicates that this proton
168 ined and show a significantly larger kinetic solvent isotope effect, with an overall magnitude of 10