Immobilization of cations

A further complication is that the lowering of the rhizosphere pH and consequent depression of HCOs means that any Fe + entering the root will be accompanied by a proportion of Cr or S04 rather than HCO3 . When Fe + enters with HCO3, the acidity generated in Fe oxidation in the plant is neutralized by conversion of HCO3 to CO2, which is assimilated or lost. However when Fe + enters with a non-volatile anion, Fe + oxidation will produce the equivalent amount of free H+ in the plant, with damaging effects on plant tissues (van Mensvoort et al., 1985). 

This chapter has shown the complexity of the chemical and biological processes around wetland plant roots and the effects of the extreme electrochemical gradient between the root surface and surrounding soil. Models of nutrient uptake by plants in aerobic soil, which treat the root as a simple sink to which nutrients are delivered by mass flow and diffusion but the root not otherwise influencing the surrounding soil, work reasonably well for the more soluble nutrient ions. However, the complexity of the wetland root environment is such that such models are inadequate and more elaborate treatments are necessary. Many of the mechanisms involved are still poorly defined and speculative, but their potential significance is clear. 

---

The assumption of the association of Hb in the pores of carboxylic cation exchangers has been advanced in Ref. [47] on the basis of electron microscopy at the maximum filling, almost all the pore surface is filled with Hb associates which are ordered star-shaped structures. Interprotein interaction in the adsorption immobilization of enzymes have been reported in Refs. [74, 75]. 

Immobilization of neutral xenobiotics in soils by qnatemary ammoninm cations has been established, and its significance on the bioavailability of naphthalene to bacteria has been examined. Bioavailability was determined by the rates of desorption, and these differed between a strain of Pseudomonas putida and one of Alcaligenes sp. (Crocker et al. 1995). 

Cation exchange can be quite sensitive to other ions present in the environment. The calculation of pollutant mass immobilized by cation exchange is given by ... 

Clay minerals or phyllosilicates are lamellar natural and synthetic materials with high surface area, cation exchange and swelling properties, exfoliation ability, variable surface charge density and hydrophobic/hydrophilic character [85], They are good host structures for intercalation or adsorption of organic molecules and macromolecules, particularly proteins. On the basis of the natural adsorption of proteins by clay minerals and various clay complexes that occurs in soils, many authors have investigated the use of clay and clay-derived materials as matrices for the immobilization of enzymes, either for environmental chemistry purpose or in the chemical and material industries. 

Fontes tt al. [224,225 addressed the acid—base effects of the zeolites on enzymes in nonaqueous media by looking at how these materials affected the catalytic activity of cross-linked subtilisin microcrystals in supercritical fluids (C02, ethane) and in polar and nonpolar organic solvents (acetonitrile, hexane) at controlled water activity (aw). They were interested in how immobilization of subtilisin on zeolite could affected its ionization state and hence their catalytic performances. Transesterification activity of substilisin supported on NaA zeolite is improved up to 10-fold and 100-fold when performed under low aw values in supercritical-C02 and supercritical-ethane respectively. The increase is also observed when increasing the amount of zeolite due not only to a dehydrating effect but also to a cation exchange process between the surface proton of the enzyme and the sodium ions of the zeolite. The resulting basic form of the enzyme enhances the catalytic activity. In organic solvent the activity was even more enhanced than in sc-hexane, 10-fold and 20-fold for acetonitrile and hexane, respectively, probably due to a difference in the solubility of the acid byproduct. 

A variation of the SHB technology to immobilize cationic molecular catalysts on silica is shown in Figure 16.5 b. This involves SHB immobilization of the counter-... 

Lee et al. [103] synthesized a chiral Rh-complex with a bisphosphine-contain-ing cation as ligand (Fig. 41.8, 2) to improve the immobilization of the transition-metal complex within the ionic liquid. 

The immobilization of flavin in the cationic polysoaps [57] also facilitates flavin-mediated oxidation reactions (Shinkai et al., 1978b,c, 1980b). Interestingly, [57] oxidizes NADH according to Michaelis-Menten-type kinetics... 

---