Activation kinetics

Stimulation of acetylcholine release results in small but significant increases in cytosolic Ca + concentrations within 100 ms (Fig. 2). The cytosolic Ca2+ concentration continues to increase for 3 s of continuous stimulation, reaching values of 225 nM relative to the resting value of 115 nM (Word et al., 1994). The 

Not until 500 ms following neurostimulation is there a significant increase in RLC phosphorylation, coincident with the latency in force development (Fig. 

However, after this latency, myosin RLC phosphorylation and stiffness both increase more rapidly than either force or cytosolic concentrations (Fig. 2). Interestingly, the kinetics of myosin RLC phosphorylation are described as a pseudo-first-order rate of 1 s i, showing no evidence of an ordered or cooperative phosphorylation of myosin RLC (Kamm and Stull, 

FIG U R E 2 Kinetic properties of cellular processes leading to MLCK activation in neurally stimulated tracheal smooth muscle. 

The rate of phosphorylation is greater than the estimated rate of dephosphorylation, 0.25 s (Kamm and Stull, 1985b). Measurements of nonphosphory-lated, monophosphorylated, and diphosphorylated forms of myosin in tracheal smooth muscle tissue provide direct evidence that myosin RLC phosphorylation occurs as a random rather than an ordered or cooperative phosphorylation process (Persechini etal., 1986). These results are consistent with biochemical measurements (Sellers et al., 1983 Trybus and Lowey, 

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A particularly interesting example of Kv-channel inactivation is represented by HERG-channels. HERG-channels have faster inactivation than activation kinetics, and they very rapidly recover from inactivation at negative membrane potentials. This behavior may result in a situation where most of the current carried by HERG-channels occurs during their recovery from inactivation at negative potentials, that is, it represents an inward rather than outward current. 

Activation volumes for aquation of Schiff base complexes [Fe(C5H4NCH=NHR)3]2+ (R = Me, Et, nPr, nBu) are between +11 and +14 cm3 mol-1 (107), and thus within the range established earlier (108) for (substituted) tris-l,10-phenanthroline-iron(II) complexes, viz. +11 to +22 cm3 mol-1. These positive values are consistent with dissociative activation. Kinetic studies of the reaction of a CH2S(CH2)3SCH2 -linked bis(terpy) ligand (L6) with [Fe(terpy)2]2+ showed a very slow two-step process. The suggested mechanism consisted of slow loss of one terpy, rapid formation of [Fe(terpy)(L6)], and finally slow displacement of the second terpy as the partially-bonded L6 becomes hexadentate (109). 

However, it is possible that the heterocatalyst becomes the dominant one, either if it is more stable and thus formed in large excess, or if it is a more active, kinetically dominant catalyst. Recently, both Reetz et al. and Feringa/Min-naard/de Vries et al. have shown that this approach can be beneficial. Earlier attempts by Chen and Xiao using mixtures of monodentate phosphites based on bisphenol and a chiral alcohol were not successful [39]. In our experience, the majority of catalysts based on mixtures of monodentate ligands show a poorer performance than the individual homo-catalysts. However, in a few instances there is a positive effect. 

Chetty SC, Aldous CN, Rashatwar SS, et al. 1983b. Effect of chlordecone on pH- and temperature-dependent substrate activation kinetics of rat brain synaptosomal ATPases. Biochem Pharmacol 32(21 ) 3205-3211. 

Solution to the activity kinetic problem requires integration of the selectivity transformation Eq. (11) ... 

The activity kinetics were estimated in seven additional steps. 

R16H selectivity and activity kinetics were fit over a wide range of temperature and pressure. Reforming selectivity is shown in Figs. 16 and 17, where benzene and hexane are plotted against C5-, the extent of reaction parameter. The effect of pressure on reforming a 50/50 mixture of benzene and cyclohexane at 756 K is shown in Fig. 16. Selectivity to benzene improves significantly when pressure is decreased from 2620 to 1220 kPa. In fact, at 2620 kPa, hexane is favored over benzene when the C5 yield exceeds 10%. This selectivity behavior can be seen in the selectivity rate constants ... 

KINPTR s real-time activity kinetics determine the adiabatic reactor inlet temperature required to make a target octane. The accuracy of KINPTR s reactor inlet temperature predictions is shown in Fig. 30 for a wide range of process conditions. The average deviation is + 3.8 K with no significant bias. This degree of accuracy is very reasonable considering the sensitivity of catalyst activity to start-up conditions and initial catalyst state (e.g., chloride added). 

D = the metal dispersion at sintering time t D0 = the initial metal dispersion k = the activated kinetic rate constant of sintering n = the sintering order... 

Supported metal catalysts are much easier to employ and have obvious attractions for industrial use from their ease of handling and economic considerations of obtaining maximum utilisation of the catalytically active metal, by using very small particles with a high surface-to-volume ratio, which are stable on the support and not susceptible to sintering. In spite of the inherent difficulties of variable activity, kinetics and activation energies [11] associated with their use, supported metals have been extensively used as hydrogenation catalysts. 

The treatment given in this section is analogous to the Lindemann theory of unimolecu-lar reactions. It provides a general explanation of pressure effects in bimolecular chemical activation reactions. A more sound theoretical treatment of chemical activation kinetics is given in Section 10.5. 

Before an immobilized enzyme can be used for an industrial process, it is essential to characterize it in terms of its catalytic and kinetic properties. A quantitative assay must be developed to measure the activity, kinetic parameters, and stability of the enzyme. In a coupling reaction, H202 rapidly reacts with phenol and 4-aminoantipyrine (electron donor) in the presence of peroxidase to produce a quinoneimine chromogen (Equation E12.2, Figure El 1.2), which is intensely colored with a maximum absorbance at 510 nm. (This is the same as the product formed in the analysis of cholesterol in Experiment 11.)... 

A Critical Amount of Energy Is Needed for the Reactants to Reach the Transition State Catalysts Speed up Reactions by Lowering the Free Energy of Activation Kinetics of Enzyme-Catalyzed Reactions... 

Bulteau-Pignoux L, Derand R, Metaye T, Joffre M, Becq F. 2002. Genistein modifies the activation kinetics and magnitude of phosphorylated wild-type and G551D-CFTR chloride currents. J Membr Biol 188 175-182. 

Benfenati F, Valtorta F, Rubenstein JL et al (1992b) Synaptic vesicle-associated Ca2+/calmodulin-dependent protein kinase II is a binding protein for synapsin I. Nature 359 417-20 Benians A, Nobles M, Hosny S et al (2005) Regulators of G-protein signaling form a quaternary complex with the agonist, receptor, and G-protein. A novel explanation for the acceleration of signaling activation kinetics. J Biol Chem 280 13383-94... 

Particle clouds are active kinetic systems. If condensable vapors are present, new particles will be formed or existing particles will grow or shrink, depending on the... 

Table 18.1 Substrate (autocamtide-2) and calmodulin activation kinetics in recombinant CaMKII holoenzymes purified from Baculovirus-infected insect cells...

The activation properties of CaMKII have been well documented in vitro and are understood in considerable molecular detail. In contrast, much less is known about CaMKII activation kinetics in intact cells that display complex and localized Ca2+ transients as well as phosphatase activities that reverse autophosphorylation events. Using autonomous activity as a quantitative index of CaMKII activation, we have... 

A differential equation describing the material balance around a section of the system was first derived, and the equation was made dimensionless by appropriate substitutions. Scale-up criteria were then established by evaluating the dimensionless groups. A mathematical model was further developed based on the kinetics of the reaction, describing the effect of the process variables on the conversion, yield, and catalyst activity. Kinetic parameters were determined by means of both analogue and digital computers. 

Competition between reactant, solvent and product molecules for adsorption within the zeolite micropores is demonstrated directly (adsorption experiments) and indirectly (effect of the framework Si/Al ratio on the activity, kinetic studies) to occur during Fine Chemical synthesis over molecular sieve catalysts. This competition, which is specific for molecular sieves (because of confinement effects within their micropores), adds up to the competition which exists over any catalyst for the chemisorption of reactant, solvent and product molecules on the active sites. Both types of competition could affect significantly the activity, stability and selectivity of the zeolite catalysts. Although the relative contributions of these two types of competition cannot be estimated, the large change in the activity of the acidic sites (TOF) with the zeolite polarity seems to indicate that the competition for adsorption within the zeolite micropores often plays the major role. 

Plateau Pressure/Temperature Plateau Slope Hysteresis Heat of Reaction Hydrogen Capacity Volume Change Rate of Decrepitation Ease of Activation Kinetics of Reaction Tolerance to Gaseous Impurities Chemical Stability (Disproportionation)... 

Gardiol, A., and Preiss, J. 1990. Escherichia coli E-39 ADPglucose synthetase has different activation kinetics from the wild type allosteric enzyme. Arch. Biochem. Biophys. 280, 175-180. 

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