Enzyme clays

Naidja A, Huang PM, Bollag J-M (2000) Enzyme-clay interactions and their impact on transformations of natural and anthropogenic organic compounds in soils. J Environ Qual 29 677-691... 

Finally, mention must be made of possible conjugation reactions in which a covalent bond is formed between a contaminant molecule and a second contami nant molecule or soil organic matter. Oxidative coupling reactions of phenolics and aromatic amines are catalyzed by extracellular enzymes, clays, and oxides (Wang et al., 1986 Liu et al., 1987 Fluang, 1990). The bioavailability of the synthetic organic within the product is reduced or possibly eliminated (Dec et al., 1990 Allard et al., 1994). 

In the past the mineral matrix was considered as inert, only providing stabilization support for enzymes and humic substances however, due to the overwhelming amount of evidence at the molecular level, there is no doubt that minerals participate in abiotic catalysis of humification reactions in soils. Naidja et al. (2000) referred to mineral particles as the Hidden Half of enzyme-clay complexes, which not only prolong the activity of immobilized enzymes but also are readily able to participate in electron transfer reactions. Many environmental factors can negatively affect the... 

Tietjen,T., and Wetzel, R. G. (2003). Extracellular enzyme-clay mineral complexes Enzyme adsorption, alteration of enzyme activity, and protection from photodegradation. Aq. Ecology 37, 331-339. 

A combination of techniques, such as powder X-ray diffraction (XRD) [56, 58], thermogravimetric analysis (TGA) [57], differential thermal analysis (DTA) [57], X-ray photoelectron spectroscopy (XPS) [56, 58], scanning electron microscopy (SEM) [26, 57], Fourier transform infrared (FT-IR) spectroscopy [57, 58] and BET N2 adsorption measurements [67], was used for structural characterization of the enzyme-clay conjugates. 

In this context, the adsorption of an aqueous enzyme-clay mixture onto an electrode surface was widely used for biosensor fabrication [32]. Owing to the presence of microchanels within the clay matrices, a chemical crosslinking step of the protein by glutaraldehyde was often carried out in order to prevent the release of the entrapped enzymes. 

Recommended model particle systems are enzymes immobilised on carriers ([27,44,45,47,49]), oil/water/surfactant or solvent/water/surfactant emulsions ([27, 44, 45] or [71, 72]) and a certain clay/polymer floccular system ([27, 42-52]), which have proved suitable in numerous tests. The enzyme resin described in [27,44,47] (acylase immobilised on an ion-exchanger) is used on an industrial scale for the cleavage of Penicillin G and is therefore also a biological material system. In Table 3 are given some data to model particle systems. 

In contrast to this, the enzyme resin is stressed less by gas sparging than by stirring (see Fig. 18 and 20). The same activity losses were observed first with 1 to 8 times greater specific adiabatic compression power Pj/ V than the maximum power density necessary for stirring. As in the case of the smooth disc, the effects of power input are only weak. The type of gas sparger and therefore the gas exit velocity are of no recognisable importance. The behaviour of the enzyme resin particles is thus completely different from that of the clay min-eral/polymer floes and the oil/water/surfactant droplet system, which are particularly intensively stressed by gas sparging. 

Interactions Between Fracturing Fluid Additives and Enzyme Breakers. Despite their advantages over conventional oxidative breakers, enzyme breakers have limitations because of interferences and incompatibilities with other additives. Interactions between enzyme breakers and fracturing fluid additives including biocides, clay stabilizers, and certain types of resin-coated proppants have been reported [1455]. 

A. S. Boyd and M. M. Mortland, Enzyme interactions with clays and clay-organic matter complexes. Soil Biochemistry, Vol. 6 (J.-M. Bollag and G. Stotzky, eds.), Marcel Dekker, New York, 1990, p. I. 

When supported complexes are the catalysts, two types of ionic solid were used zeolites and clays. The structures of these solids (microporous and lamellar respectively) help to improve the stability of the complex catalyst under the reaction conditions by preventing the catalytic species from undergoing dimerization or aggregation, both phenomena which are known to be deactivating. In some cases, the pore walls can tune the selectivity of the reaction by steric effects. The strong similarities of zeolites with the protein portion of natural enzymes was emphasized by Herron.20 The protein protects the active site from side reactions, sieves the substrate molecules, and provides a stereochemically demanding void. Metal complexes have been encapsulated in zeolites, successfully mimicking metalloenzymes for oxidation reactions. Two methods of synthesis of such encapsulated/intercalated complexes have been tested, as follows. 

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. 

The entrapment of various enzymes and proteins by clay minerals proceeds by weak interactions including electrostatic interactions, hydrogen and van der Waals bonding. Additivity of these various attractive forces renders the adsorption irreversible in some cases, but usually a leaching of enzyme is observed under working conditions. In order to fix the enzyme irreversibly at the surface of the clay layers different processes have been tried. In order to fix invertase on bentonite, Monsan and Durand [90] previously treated the clay mineral with a coupling agent,... 

The second source of biochemicals is molecules excreted from cells such as extracellular enzymes and other organic matter. A typical example is cellulase, which is excreted by fungi such as Penicillium in order to break down wood and woody material into sugars that can be used by the organisms. Other common extracellular enzymes found in soil are ureases and amylases. Often enzymes are associated with clay particles, and in such associations, their activity may be increased, decreased, unchanged, or completely destroyed [15],... 

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