Enzymes heterogeneity

Clark and Lyons [1] have primarily suggested a model of electrochemical sensor, based on the concept of an enzyme heterogenized on the electrode surface. 

Roberts MS, Donaldson JD, Rowland M. Models of hepatic elimination a comparison of stochastic models to describe residence time distributions and to predict the influence of drug distribution, enzyme heterogeneity, and systemic recycling on hepatic elimination. J Pharmacokinet Biopharm 1988 16 41-83. 

Even though the linear mass transfer coefficient (h ) is more frequently used in heterogeneous chemical kinetics, in enzyme heterogeneous kineties it is customary to... 

There is a need for correlation of structure, dynamical rearrangements, transition states and reaction intermediates of enzyme, heterogeneous and homogeneous catalytic systems through investigations of the same reactions imder similar experimental conditions. 

Process timescale is another parameter that affects enzyme heterogeneity. Quasi-isothermal processing and thus improved uniformity could be achieved in principle in... 

Most immunoassay kits and many commercial immunoassay analyzers are based on heterogenous EIA or FIA. These include an immunoassay system that uses FIA linked to radial partition chromatography of the antibody—antigen complex (39) a system that uses antibody-coated tubes for enzyme immunoassay of a variety of hormones and dmgs (40) and a system that uses either a sandwich or competitive FIA format to measure a variety of analytes (41). 

An immobilized enzyme-carrier complex is a special case that can employ the methodology developed for evaluation of a heterogeneous cat ytic system. The enzyme complex also has external diffusional effects, pore diffusional effects, and an effectiveness factor. When carried out in aqueous solutions, heat transfer is usually good, and it is safe to assume that isothermal conditions prevail for an immobihzed enzyme complex. 

As with organic solvents, proteins are not soluble in most of the ionic liquids when they are used as pure solvent. As a result, the enzyme is either applied in immobilized form, coupled to a support, or as a suspension in its native form. For production processes, the majority of enzymes are used as immobilized catalysts in order to facilitate handling and to improve their operational stability [24—26]. As support, either inorganic materials such as porous glass or different organic polymers are used [27]. These heterogeneous catalyst particles are subject to internal and external... 

It is not unusual for the full chemical potential of a reaction to be diminished by slower transport processes (i.e., to be transport limited). In fast liquid phase enzyme reactions, mechanical stirring rates can have a strong influence on the observed kinetics that may be limited by the rate of contacting of the reactants and enzymes. Most heterogeneous catalytic reactions take... 

P-Lactamases are enzymes that hydrolyze the P-lactam ring of P-lactamantibiotics (penicillins, cephalosporins, monobactams and carbapenems). They are the most common cause of P-lactam resistance. Most enzymes use a serine residue in the active site that attacks the P-lactam-amid carbonyl group. The covalently formed acylester is then hydrolyzed to reactivate the P-lacta-mase and liberates the inactivated antibiotic. Metallo P-lactamases use Zn(II) bound water for hydrolysis of the P-lactam bond. P-Lactamases constitute a heterogeneous group of enzymes with differences in molecular structures, in substrate preferences and in the genetic localizations of the encoding gene (Table 1). 

The enzyme poised at well-defined redox potentials appears to be in rather homogenous IR states 65, 84). Curiously, in corresponding EPR-monitored experiments, the Ni signal generally corresponds to significantly less than one spin/mole, indicating that the sample is heterogeneous with respect to it (77). 

For most applications, enzymes are purified after isolation from various types of organisms and microorganisms. Unfortunately, for process application, they are then usually quite unstable and highly sensitive to reaction conditions, which results in their short operational hfetimes. Moreover, while used in chemical transformations performed in water, most enzymes operate under homogeneous catalysis conditions and, as a rule, cannot be recovered in the active form from reaction mixtures for reuse. A common approach to overcome these limitations is based on immobilization of enzymes on solid supports. As a result of such an operation, heterogeneous biocatalysts, both for the aqueous and nonaqueous procedures, are obtained. 

An intriguing influence of a cosolvent immiscible with water on the enantioselec-tivity of the enzyme-catalyzed hydrolysis was observed. It was proven that enzyme enantioselectivity is directly correlated with the cosolvent hydrophobicity. In the best example, for ethyl ether as cosolvent, the reaction proceeded with E = 55, and the target compound was obtained in 33% yield with 92.7% ee. This finding may be of great practical importance, particularly in industrial processes [24], since it will enable better optimization of enzyme-catalyzed processes. It is clear that, in future, immobilized enzymes, as heterogeneous catalysts, wiU be widely used in most industrial transformations, especially in the preparation of pharmaceuticals [25]. 

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