Steady state, and kinetics

Paulsen, H., and Wintermeyer, W. (1986). tRNA topography during translocation Steady-state and kinetic fluorescence energy-transfer studies. Biochemistry 25, 2749-2756. 

Atkinson AJ Jr. The cerebrospinal fluid glucose concentration. Steady state and kinetic studies in patients with cryptococcal meningitis. Am Rev Resp Dis 1969 99 59-66. 

Steady-state and kinetic methods of hydride and cold vapour generation... 

Weissbach F., Kreibich G., Bartels K. and Schiilke W. (1988) Rapid determination of L-lysine with an enzyme electrode by steady-state and kinetic measurement. Acta Biotechnol., 8,269-274. 

Time Dependence—The Transient Approach to Steady-State and Saturation Kinetics... 

A reader familiar with the first edition will be able to see that the second derives from it. The objective of this edition remains the same to present those aspects of chemical kinetics that will aid scientists who are interested in characterizing the mechanisms of chemical reactions. The additions and changes have been quite substantial. The differences lie in the extent and thoroughness of the treatments given, the expansion to include new reaction schemes, the more detailed treatment of complex kinetic schemes, the analysis of steady-state and other approximations, the study of reaction intermediates, and the introduction of numerical solutions for complex patterns. 

Toward these ends, the kinetics of a wider set of reaction schemes is presented in the text, to make the solutions available for convenient reference. The steady-state approach is covered more extensively, and the mathematics of other approximations ( improved steady-state and prior-equilibrium) is given and compared. Coverage of data analysis and curve fitting has been greatly expanded, with an emphasis on nonlinear least-squares regression. 

A typical electrochemical promotion experiment includes kinetic measurements under open and closed circuit conditions as well as study of the effect of catalyst potential or work function on catalytic rate and selectivity under steady state and transient conditions. In kinetic measurements one should change the partial pressure of each reactant while... 

Fig. 8. A model of bases on steady-state and pre-steady-state kinetic data. Ps indicate the two phosphorylation sites. Cl, CII and NIII refer to domains A, B, and C, respectively.

Steady state and non steady state kinetic measurements suggest that methane carbon dioxide reforming proceeds in sequential steps combining dissociation and surface reaction of methane and CO2 During admission of pulses of methane on the supported Pt catalysts and on the oxide supports, methane decomposes into hydrogen and surface carbon The amount of CH, converted per pulse decreases drastically after the third pulse (this corresponds to about 2-3 molecules of CH< converted per Pt atom) indicating that the reaction stops when Pt is covered with (reactive) carbon CO2 is also concluded to dissociate under reaction conditions generating CO and adsorbed... 

The current is recorded as a function of time. Since the potential also varies with time, the results are usually reported as the potential dependence of current, or plots of i vs. E (Fig.12.7), hence the name voltammetry. Curve 1 in Fig. 12.7 shows schematically the polarization curve recorded for an electrochemical reaction under steady-state conditions, and curve 2 shows the corresponding kinetic current 4 (the current in the absence of concentration changes). Unless the potential scan rate v is very low, there is no time for attainment of the steady state, and the reactant surface concentration will be higher than it would be in the steady state. For this reason the... 

Enzymes that catalyze redox reactions are usually large molecules (molecular mass typically in the range 30-300 kDa), and the effects of the protein environment distant from the active site are not always well understood. However, the structures and reactions occurring at their active sites can be characterized by a combination of spectroscopic methods. X-ray crystallography, transient and steady-state solution kinetics, and electrochemistry. Catalytic states of enzyme active sites are usually better defined than active sites on metal surfaces. 

Under conditions of nonlimiting interfacial kinetics the normalized steady-state current is governed primarily by the value of K y, which is the relative permeability of the solute in phase 2 compared to phase 1, rather than the actual value of or y. In contrast, the current time characteristics are found to be highly dependent on the individual K. and y values. Figure 16 illustrates the chronoamperometric behavior for K = 10, log(L) = —0.8 and for a fixed value of Kf.y = 2. It can be seen clearly from this plot that whereas the current-time behavior is sensitive to the value of Kg and y, in all cases the curves tend to be the same steady-state current in the long-time limit. This difference between the steady-state and chronoamperometric characteristics could, in principle, be exploited in determining the concentration and diffusion coefficient of a solute in a phase that is not in direct contact with the UME probe. 

The determination of bisubstrate reaction mechanism is based on a combination of steady state and, possibly, pre-steady state kinetic studies. This can include determination of apparent substrate cooperativity, as described in Chapter 2, study of product and dead-end inhibiton patterns (Chapter 2), and attempts to identify... 

This is the basic relationship of electrode kinetics including the concentration overpotential. Equations (5.4.40) and (5.4.41) are valid for both steady-state and time-dependent currents. 

Rittmann, B.E. and McCarty, P.L., Model of steady-state biofilm kinetics, Biotech. Bioeng., 22, 2343-2357, 1980. 

Unlike the previous kinetics imposed by the sink condition, steady-state transport kinetics under non-sink conditions will lead to equilibrium partitioning between the aqueous phase of the donor and receiver compartments and the cell mono-layer. In contrast to the sink condition wherein CR 0 at any time, under nonsink conditions CR increases throughout time until equilibrium is attained. As previously stated in Eqs. (1) and (3), the rate of mass disappearing from the donor solution is... 

In the above section, we have shown that the whole apparatus of a cell is organised by thermodynamic and kinetic constraints on concentrations of all its chemical components. We know, in fact, that individually and cooperatively the organic and inorganic molecules and ions are controlled in a cell in a given state provided that external conditions of material and energy availability are fixed. This is known as a homeostatic steady state and not an equilibrium condition. Now there are two kinds of constraints, which we mentioned in Chapter 3. The first is equilibrium, which applies when combinations of components are in balanced concentration with their free entities... 

Livingston, A. G., Biodegradation of 3,4-Dichloroaniline in a Fluidized Bed Bioreactor and a Steady-State Biofilm Kinetic Model Biotechnol. Bioeng., 38 260 (1991)... 

Recently, the steady-state reaction kinetics of CO oxidation at high pressure over Ru , Rh " , Pt, Pd, and Ir single crystals have been studied in our laboratory. These studies have convincingly demonstrated the applicability and advantages of model single crystal studies, which combine UHV surface analysis techniques with high pressure kinetic measurements, in the elucidation of reaction mechanisms over supported catalysts. 

The kinetics data on the reactions of silyl radicals with carbon-centred radicals are also available. The rate constant for the cross-combination of CHs with MesSi was measured to be 6.6 x 10 M s in the gas phase [19]. Studies on the steady-state and the pulse radiolysis of EtsSiH in methanol showed that the cross-combination of Et3Si with CH30 andHOCH2 occurs with rate constants of 1.1 x 10 and 0.7 x 10 M s , respectively [20]. 

Consider two simple cases of extraction processes in which kinetics are controlled by interfacial film diffusion (the solutions are always considered stirred). The two cases are treated with the simplifying assumptions introduced in section 2 (i.e., steady-state and linear concentration gradients throughout the diffusional films). 

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