Interaction charged groups

In an ideal SEC separation, the mechanism is purely sieving, with no chemical interaction between the column matrix and the sample molecules. In practice, however, a small number of weakly charged groups on the surface of all TSK-GEL PW type packings can cause changes in elution order from that of an ideal system. Fortunately, the eluent composition can be varied greatly with TSK-GEL PW columns to be compatible with a wide range of neutral, polar, anionic, and cationic samples. Table 4.8 lists appropriate eluents for GFC of all polymer types on TSK-GEL PW type columns (11). 

For some nonionic, nonpolar polymers, such as polyethylene glycols, normal chromatograms can be obtained by using distilled water. Some more polar nonionic polymers exhibit abnormal peak shapes or minor peaks near the void volume when eluted with distilled water due to ionic interactions between the sample and the charged groups on the resin surface. To eliminate ionic interactions, a neutral salt, such as sodium nitrate or sodium sulfate, is added to the aqueous eluent. Generally, a salt concentration of 0.1-0.5 M is sufficient to overcome undesired ionic interactions. 

When a substrate enters the active site, charged groups may be forced to interact (unfavorably) with charges of like sign, resulting in electrostatic destabilization (Figure 16.6). The reaction pathway acts in part to remove this stress. If the charge on the substrate is diminished or lost in the course of reaction, electrostatic destabilization can result in rate acceleration. 

Furthermore it can be shown that besides the direct influence of hydrophilic and hydrophobic hydration on the conformation, the interaction of charged groups with ions is also strongly influenced by the hydration of the groups involved. Such studies were made largely by using relatively simple poly-a-aminoacids with ionogenic side chains as model substances. 

The diazonio group is a somewhat more complex substituent for such evaluations because it is charged, in contrast to the majority of substituents on which the Hammett treatment is based. The electrostatic interaction of the diazonio and other charged groups was calculated by Hoefnagel et al. (1978) and by Exner (1978). The substituent constants they obtained, including the effects of coulomb interactions, are only slightly different from those of Lewis and Johnson (1959). 

Figure6-10. Mode of binding of 2,3-bisphosphoglycerate to human deoxyhemoglobin. BPG interacts with three positively charged groups on each p chain.

Figure 6.3. Schematic potential energy curve describing the interactions between colloidal particles. The overall potential is a sum of an electrostatic repulsive term which arises due to any charged groups on the surface of the particle and the attractive van der Waals term.

Extensive forces arise from the electrical interaction between coimterions and polyions. There are two repulsive forces which act to extend a polyion. One results from coulombic repulsion between the charged groups on the polyion and the other from osmotic pressure of the counterions within, which seek to increase the space in which they can move. 

Molecules with polar atoms or charged groups can form intramolecular interactions such as internal H-bonds or cation-rr interactions. As a consequence energy minimization in vacuo often results in electrostatically collapsed conformations due to the dominance of these intramolecular interactions. Several compounds in... 

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