“…The naturally occurring nitrogen (N) isotopes, (15)N and (14)N, exhibit different reaction rates during many microbial N transformation processes, which results in N isotope fractionation. …”
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“…To fill this gap, we proposed a new concept of biogeochemical modeling—termed substrate-explicit modeling—that enables parameterizing OM-specific oxidative degradation pathways and reaction rates based on the thermodynamic properties of OM pools. …”
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“…At higher water pressures (10–75 kPa H(2)O), water–ethanol clusters reach their maximum stable size ((C(2)H(5)OH)(H(+))(H(2)O)(4–5)), and water begins to form extended hydrogen-bonded networks; concomitantly, rate inhibition by water (up to –3 reaction order) becomes stronger than expected from the molecularity of the reaction, reflecting the more extensive disruption of hydrogen bonds at DEE-formation transition states that contain an additional solvated non-polar ethyl group compared to the relevant reactant cluster, as described by non-ideal thermodynamic formalisms of reaction rates. Microporous voids of different hydrophilic binding site density (Beta; varying H(+) and Si–OH density) and different size and shape (Beta, MFI, TON, CHA, AEI, FAU), influence the relative extents to which intermediates and transition states disrupt their confined water networks, which manifest as different kinetic orders of inhibition at high water pressures. …”
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“…The apparent Michaelis–Menten kinetics of CH(4) oxidation in mounds were estimated from in situ reaction rates. Methane affinities of the communities were in the low micromolar range, which is one to two orders of magnitude higher than those of upland soils, but significantly lower than those measured in soils with a large CH(4) source such as landfill cover soils. …”
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“…Changing from cysteine to either serine (more basic) or aspartate (more acidic) modifies the sidechain pKa and thus the barrier for the proton exchange step. The reaction rates for H(2) oxidation or H(2) evolution were surveyed and measured for model [FeFe]-hydrogenases, and the results show that the initial proton-transfer step in [FeFe]-hydrogenase is tightly coupled to the control of reactivity; a change from cysteine to more basic serine favored H(2) oxidation in all enzymes, whereas a change to more acidic aspartate caused a shift in preference toward H(2) evolution. …”
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“…Also, for the water-assisted pathways, the ratio of the partition function of the transition state to the partition functions of the reactants is similar to the respective bare reaction. Therefore, the reaction rates of the bare pathways are more than the water-assisted paths that include the 1WHA complex and are less than the paths that involve the 1WTA and 1WTB complexes.…”
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“…Reactions are governed by kinetic laws that describe reaction rates. Selecting the appropriate kinetic laws is difficult for many modelers. …”
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“…The activation parameters, which have been obtained from fitting the reaction rates at different temperatures to the Eyring equation for ruthenium [ΔH(cis-trans)(‡)= 122.8 ± 1.3; ΔH(trans-cis)(‡)= 138.8 ± 1.0 kJ/mol; ΔS(cis-trans)(‡)= −18.7 ± 3.6; ΔS(trans-cis)(‡)= 31.8 ± 2.7 J/(mol·K)] and osmium [ΔH(cis-trans)(‡)= 200.7 ± 0.7; ΔH(trans-cis)(‡)= 168.2 ± 0.6 kJ/mol; ΔS(cis-trans)(‡)= 142.7 ± 8.9; ΔS(trans-cis)(‡)= 85.9 ± 3.9 J/(mol·K)] reflect the inertness of these systems. …”
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“…Notably, the O(2) reaction rates vary by a factor of 10(5) across the series, following the order [3](+) > [2](+) > [4](2+), even though the complexes have similar structures and Fe(3+/2+) redox potentials. …”
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“…[Image: see text] The active site of an enzyme is surrounded by a fluctuating environment of protein and solvent conformational states, and a realistic calculation of chemical reaction rates and kinetic isotope effects of enzyme-catalyzed reactions must take account of this environmental diversity. …”
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“…Skin reaction and Mazzotti reaction rates were compared with Fisher’s exact and a paired t-test, respectively. …”
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“…Thus, CYPs enhance reaction rates and selectivity/specificity via a hitherto unrecognized modality. …”
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“…Metabolomic data suggest that even though these mycoplasmas are extremely similar in terms of genome and metabolism, distinct products and reaction rates may be the result of differential expression throughout the species. …”
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“…BACKGROUND: Despite claims as key enzymes in enzymatic delignification, very scarce information on the reaction rates between the ligninolytic versatile peroxidase (VP) and lignin peroxidase (LiP) and the lignin polymer is available, due to methodological difficulties related to lignin heterogeneity and low solubility. …”
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“…Initiator paste inhibition times and maximum reaction rates were described well by Arrhenius plots. …”
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“…One role of the promoter(s) in the commercial catalyst is the inhibition of the methanol decomposition reaction, thus allowing higher MeOH synthesis reaction rates in those regimes not controlled by thermodynamics.…”
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“…RESULTS: After excluding studies that did not meet our inclusion criteria, four studies were analyzed for adverse reaction rates and three for mortality rates. Overall, there was no significant difference in mortality between low-dose and conventional-dose SMX-TMP groups (relative risk [RR]: 0.55, 95% confidence interval [CI], 0.18 -1.70). …”
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“…The cycle length was 1 month, adverse reaction rates were from CHRONOS-3, mean body surface area was referenced from published literature, cost values are referenced from published literature and Drugbank, utility values were referenced from the published literature, and the primary endpoint was the incremental cost-effectiveness ratio (ICER). …”
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“…The ICC of the blood flow values derived from the retinal–choroidal complex and the intraorbital segments of the optic nerve between the two observers showed satisfactory concordance (all ICC > 0.932, p < 0.001). The adverse reaction rates of ASL and FFA were 2.20 and 3.30%, respectively. …”
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“…Multivariate analyses showed that in DLBCL patients with genetic abnormality detected by FISH, the treatment and disease types were independent prognostic factors. The adverse reaction rates were similar in R-DA-EPOCH and R-CHOP (P>0.05). …”
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