Complexation constants measurement

Figure 5.7 Family-dependent relationships between diiodine complexation constants measured in alkanes, pKg 2, and in CCI4, logKc (in CCI4) nitriles (n), phosphoryls (o), it bases (x), thioethers (<)), pyridines fBj and selenoethers ( ). The dashed line of slope unity is drawn for comparison.

Table 5.5 Family-dependent relationships (Equation 5.11) between diiodine complexation constants measured in alkanes and in CCI4.

In the first step the hydrated ion and ligand form a solvent-separated complex this step is believed to be relatively fast. The second, slow, step involves the readjustment of the hydration sphere about the complex. The measured rate constants can be approximately related to the constants in Scheme IX by applying the fast preequilibrium assumption the result is k = Koko and k = k Q. However, the situation can be more complicated than this. - °... 

Measurement of complexing constants by radiochemical methods. S. Hubert, M. Hussonnois and R. Guillaumont, Struct. Bonding (Berlin), 1978, 34, 1-18 (29). 

Hubert S, Hussonois M, Guillaumont R (1978) Measurement of Complexing Constants by Radiochemical Methods. 34 1-18... 

The Kmax (and K, see below) constants determined from steady-state kinetic measurements are thus seen to be complex constants containing two or more of the individual rate constants illustrated in Fig. 2. 

This is a reasonable inference, because site binding is significant only with multivalent cations and strong electrostatic interactions. Under these conditions ion polarization occurs and bonds have some covalent character (Cotton Wilkinson, 1966). This is illustrated by the data of Gregor, Luttinger Loebl (1955a,b). They measured the complexation constants of poly(acrylic acid), 0 06 n in aqueous solution, with various divalent metals, which, as it so happens, are of interest to AB cements (Table 4.1). The order of stability was found to be... 

The measurement of potential Hg methylation and MeHg demethylation is significantly more complex than the measurement of HgT and MeHg concentrations in ambient samples. Methodological considerations include the maintenance of redox and temperature condition of samples during measurement, an understanding of the time course of both processes, and an understanding of the impact of spike level on the methylation and demethylation rate constants. Measurement of methylation and demethylation also requires the use of a tracer, and the abiUty to measure that trace analytically. 

The very slow dissociation rates for tight binding inhibitors offer some potential clinical advantages for such compounds, as described in detail in Chapter 6. Experimental determination of the value of k, can be quite challenging for these inhibitors. We have detailed in Chapters 5 and 6 several kinetic methods for estimating the value of the dissociation rate constant. When the value of kofS is extremely low, however, alternative methods may be required to estimate this kinetic constant. For example, equilibrium dialysis over the course of hours, or even days, may be required to achieve sufficient inhibitor release from the El complex for measurement. A significant issue with approaches like this is that the enzyme may not remain stable over the extended time course of such experiments. In some cases of extremely slow inhibitor dissociation, the limits of enzyme stability will preclude accurate determination of koff the best that one can do in these cases is to provide an upper limit on the value of this rate constant. 

The reactions of the bare sodium ion with all neutrals were determined to proceed via a three-body association mechanism and the rate constants measured cover a large range from a slow association reaction with NH3 to a near-collision rate with CH3OC2H4OCH3 (DMOE). The lifetimes of the intermediate complexes obtained using parameterized trajectory results and the experimental rates compare fairly well with predictions based on RRKM theory. The calculations also accounted for the large isotope effect observed for the more rapid clustering of ND3 than NH3 to Na+. 

Stability constants, measured in methanol solution, for alkaline earth complexes of a number of ionophores are given in Table XVI (280,289,571-577).8 The values for the complexes of valinomycin and enniatin B lie between the values for the crown ethers 15C5 and 18C6 (cf. Section II.C.5 above), for the middle four entries the values are slightly higher. Stabilities of enniatin B complexes show a modest maximum for Ca2+, and of valinomycin complexes show stabilities increasing up to Ba2+ (281). LogAi values for the Ca2+ complexes of acetate, benzoate, and salicylate are between 4.5 and 4.7 in methanol (578) - the... 

The second and third method allow the measurement of surface complexation constants at various transition metal loadings and consequently yield apparent composition dependent constants. In the first method on the contrary a truly thermodynamic constant is obtained under standard state conditions. 

When concentration of the complex is constant, the rate of formation of the complex is balanced by the rate of disappearance of the complex. If measurements of the reaction rate for any substrate concentration are made before the product is present in appreciable amounts the rate of the reverse reaction will be negligible and the rate constant k4 can be ignored. Under these conditions ky I k3... 

In order to study the shape of a polymer-Cu complex, viscometric measurements of a homogeneous solution of QPVP were carried out (Fig. 1). At constant QPVP concentration, an increase in the added amount of Cu ions causes a decrease in viscosity, which reveals that the polymer-ligand chain is markedly contracted due to intra-polymer chelation. An intra-polymer chelate takes a very compact form and Cu ions are crowded within the contracted polymer chain (Scheme 2). The adsorption of Cu ions on the polymer ligand is sigmoidal, as can be seen in Fig. 1. At a low... 

The purpose of the present article is to show how a radioactive tracer and radiochemical methods can be used to yield accurate measurements of complexing constants. 

The most common technique for the radiochemical determination of complexing constants utilizes partition methods which are based on reactions between two phases under static or dynamic conditions (chromatography). Partition methods offer the advantages of simplicity and rapidity and are amenable to a broad selection of phase compositions and arrangements. One of the most reliable partition methods, especially useful for measuring 0 , is solvent extraction. It is best applied to systems which exhibit compound formation (11). 

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