Comparison of k with

The current problems in determining intracellular concentrations mean that comparisons of K with F yield only qualitative information on displacement from equilibrium. More precise determinations are required for calculating the reversibility function, R (Table I) and hence intrinsic sensitivities (Section III, B). 

This approach has not been used as extensively as the comparison of K with r but is likely to provide more accurate determinations of reversibility since it does not require a separate determination of K, and does not involve the problem of free and bound concentrations. However, the specific activity of the labeled intermediate is required and, for a radioactive isotope, this will require extraction, separation, and measurement of the concentration of the intermediate. This specific activity and, hence, the calculated rate will therefore be subject to the errors associated with the determination of concentrations by cell disruption. 

Bimolecular rate constants (k p = k bs/[R]x where [R]x represents the total concentration of one of the two reactants and whose concentration is larger than that of the second reactant, S, by a factor of more than 5) for 1,3-dipolar cycloaddition reactions of benzonitrile oxide (18) with a series of Af-substituted maleim-ides (19a-19c) in micelles of nonionic surfactants, C,2Eg, C,2E23, Cj Ejo, and CigE2o, fit reasonably well to a kinetic equation similar to Equation 3.61 (Chapter 3)." The calculated values of vary from 0.30 to 0.39 for all four nonionic micelles. Nearly 3-fold micellar deceleration effects have been shown to be similar to the effect of mixed water/1-propanol solvent with [H2O] about 15 M on k pp. However, a comparison of k with k pp in such water-organic solvents does not provide detailed information about the exact nature of the reaction environment in the micellar pseudophase. Instead, it provides information about the question insofar as the micellar reaction environment is satisfactorily mimicked by such mixed water-organic solvents. 

Figure 9,16 Comparison of theory with experiment for rg/a versus K. The solid line is drawn according to the theory for flexible chains in a cylindrical pore. Experimental points show some data, with pore dimensions determined by mercury penetration (circles, a = 21 nm) and gas adsorption (squares, a= 41 nm). [From W. W. Yau and C. P. yidXont, Polym. Prepr. 12 797 (1971), used with permission.]...

Mannhold, R., Dross, K., Rekker, R. F. Drug lipophilidty in QSAR practice. I. A comparison of experimental with calculative approaches. Quant. Struct.-Act. Relat. 1990, 9, 21-28. 

Hoerauf, A., Volkmann, L., Nissen-Paehle, K., Schmetz, C., Autenrieth, I., Buttner, D.W. and Fleischer, B. (2000b) Targeting of Wolbachia endobacteria in Litomosoides sigmodontis comparison of tetracyclines with chloramphenicol, macrolides and ciprofloxacin. Tropical Medicine and International Health 5, 275-279. 

Let us now turn to a comparison of theory with experiment. Comparing (95), (84), and (68), we find that the dependence of the photocatalytic effect K on the position of the Fermi level at the surface s and in the bulk cv of an unexcited sample for the oxidation of water is the same as for the oxidation of CO or for the hydrogen-deuterium exchange reaction. For this reason, such factors as the introduction of impurities into a specimen, the adsorption of gases on the surface of the specimen, and the preliminary treatment of the specimen will exert the same influence on the photocatalytic effect in all the three reactions indicated above. The dependence of K on the intensity I of the exciting light must also be the same in all the three cases. 

Jacob, S., Garcia, S., Hayreh, D. and McClintock, M. K. (2002) Psychological effects of musky compounds Comparison of androstadienone with androstenol and muscone. Horm. Behav. 42, 274-283. 

DNA catalyzes the racemization of [Fe(phen)3] " "—the rate is approximately doubled in the presence of 1,000 pM DNA. DNA also shifts the A A equilibrium towards a slight enantiomeric excess of the A form. The electrostatic and intercalative interactions of [Fe(phen)3] + and [Fe(phen)3] " " with DNA have been probed voltammetrically, and binding constants estimated. The [Fe(phen)3f+-DNA interaction appears to be primarily electrostatic, [Fe(4,7-Ph2phen)2(phen)] -DNA interaction to be intercalative. The discussions in these recent publications suggest that early work on the kinetics and mechanism of racemization of [M(bipy)3]" and [M(phen)3] " ", M = Ni, Cr as well as Fe, is in danger of being overlooked or forgotten. Comparison of k and AH values for racemization and dissociation shows that racemization of... 

Dipole moments and Kerr constants of dibenzoates of several diols are measured at 298 K. Theoretical analysis is performed with standard methods of the RIS model. Comparison of theory with experiment indicates that is almost insensitive to the conformational energies, particularly for m > 3. Kerr constants are much more sensitive to the conformational energies. Good agreement between theoretical and experimental values of both dipole moments and Kerr constants of all these compounds is achieved by adjustement of the optical parameters and the... 

Comparison of kh with the calculated k,ot = 0.15 d 1 shows that abiotic hydrolysis is the most important removal mechanism for BzC in the pond ( 75%>) thus, you have to worry about the transformation product benzyl alcohol (Fig. 12.1). About 7% is removed by flushing (kw = VIQ = 0.01 d"1), and the rest by other processes. Considering the properties of benzyl chloride (e.g., Kj0Vi, Ajaw, see Appendix C), the most likely additional elimination processes are gas exchange and biotransformation (see later chapters). 

Let us also notice that slow variations of K with Z imply that the gauge condition K may be treated as a semi-empirical parameter in practical calculations to reproduce, with a chosen K, the accurate oscillator strength values for the whole isoelectronic sequence. Thus, dependence of transition quantities on K may serve as the criterion of the accuracy of wave functions used instead of the comparison of two forms of 1-transition operators. In particular, the relative quantities of the coefficients of the equation fEi = aK2 + bK +c (the smaller the a value, the more exact the result), the position of the minimum of the parabola Kf = 0 (the larger the K value for which / = 0, the more exact is the approximation used, in the ideal case / = 0 for K = +oo) may also help to estimate the accuracy of the method utilized. 

The ternary complex model allows for cooperative interactions among ligand, receptor, and G protein as defined by the cooperativity factor a. With a lower limit of Kg established from the levels of RG precoupling, the comparisons of K,.A with K l indicate for both / 2AR and FPR that precoupled receptors (RG) would exhibit higher affinity for an agonist... 

Figure 9.3 Comparison of K, values for phosphonate inhibitors of thermolysin with Kulkcat values for the corresponding substrates (Bartlett, 1983 Morgan, 1991). Diagonal lines correspond to slopes of unity.

Three complexes of K+ with monoanionic C[4] and tBuC[4] in the cone conformation have been described with either O- and 7t-bonding or O-bonding alone,26 whereas strong Tt-bonding of K+ has been evidenced in the tetrametallic complex of four-fold deprotonated tBuC[4].27 The comparison of K+, Rb+, and Cs+ complexes of monoanionic C[4] and tBuC[4] is particularly interesting, as Cs+ is always complexed in an endo fashion, whereas Rb+ and K+ can be either exo- or endo-coordinated.28... 

Wolkoff, P. and Wilkins, C.K. (1994) Indoor VOCs from household floor dust comparison of headspace with desorbed VOCs method for VOC release determination. Indoor Air, 4, 248-54. 

Fig. 8. Comparison of k a, a and l data measured by pure oxygen and air absorption in pure sulphite solution and with addition of ocenol. Air absorption, filled symbols oxygen absorption, hollow symbols see Table 1.

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