Metal ions biological activity

Figure 1 Metal ions at active sites in biological catalysis.

Metal Ion Effects. The metal ion effects on the acid-catalyzed hydrolysis of PPS also were examined by Benkovic and Hevey (5). However, they observed that in water near pH 3, the rate enhancement in the presence of an excess of metal ion was at most only threefold (Mg2+, Ca2+, Al3+) and in some cases (Zn2+, Co2+, Cu2+) the rate was actually retarded. We thought that the substrate PPS and Mg2+ ion should be hydrated heavily in water so that their complexa-tion for rate enhancement is weak. If, however, the hydrolysis is carried out in a solvent of low water content, such complexation would not occur, and therefore, the rate enhancement might be more pronounced. This possibility appears to be supported by the fact that the active sites of many enzymes are hydrophobic. Of course, there is a possibility that the S—O fission may not require metal ion activation. In this connection, it is interesting to note that in biological phosphoryl-transfer reactions the enzymes generally require divalent metal ions for activity (7, 8, 9), but such metal ion dependency appears to be less important for sulfate-transfer enzymes. For example, many phosphatases require metal ions, but no sulfatase is known to be metal... 

Concanavalin A, a protein (isolated from jack-beans) which binds carbohydrates and has the general properties of a lectin , agglutinates and inhibits growth of malignant cells (Sharon and Lis, 1972), but it also agglutinates erythrocytes. Each monomeric unit of concanavalin A has one site that binds calcium ions and another that binds Zn ", Co ", or Mn-" ", and both sites must be occupied by the appropriate metal for biological activity to occur. 

Recent publications indicate the cloud-point extraction by phases of nonionic surfactant as an effective procedure for preconcentrating and separation of metal ions, organic pollutants and biologically active compounds. The effectiveness of the cloud-point extraction is due to its high selectivity and the possibility to obtain high coefficients of absolute preconcentrating while analyzing small volumes of the sample. Besides, the cloud-point extraction with non-ionic surfactants insures the low-cost, simple and accurate analytic procedures. 

Figure 8-15. The biological activity of some transition-metal ions illustrating the Irving-Williams series.

Consequently, the antioxidant activity of GA in biological systems is still an unresolved issue, and therefore it requires a more direct knowledge of the antioxidant capacity of GA that can be obtained by in vitro experiments against different types of oxidant species. The total antioxidant activity of a compound or substance is associated with several processes that include the scavenging of free radical species (eg. HO, ROO ), ability to quench reactive excited states (triplet excited states and/ or oxygen singlet molecular 1O2), and/or sequester of metal ions (Fe2+, Cu2+) to avoid the formation of HO by Fenton type reactions. In the following sections, we will discuss the in vitro antioxidant capacity of GA for some of these processes. 

The hypothesis that our biological world built on the DNA-RNA-protein central dogma was preceded by an RNA world in which RNA molecules carried both the genetic information and executed the gene functions (through ribozyme activity) is now widely accepted [130]. However, it is also well recognized that RNA due to its vulnerability to hydrolysis - especially as a result of catalysis by divalent metal ions - would not have been able to evolve in a harsh pre-biotic environment Also the formation of RNA under presumed pre-biotic conditions is extremely inefficient It is not so far-fetched to propose that a peptide nucleic acid-like molecule may have been able to function as a form of pre-biotic genetic material since it... 

Biological activity can be used in two ways for the bioremediation of metal-contaminated soils to immobilize the contaminants in situ or to remove them permanently from the soil matrix, depending on the properties of the reduced elements. Chromium and uranium are typical candidates for in situ immobilization processes. The bioreduction of Cr(VI) and Ur(VI) transforms highly soluble ions such as CrO and UO + to insoluble solid compounds, such as Cr(OH)3 and U02. The selenate anions SeO are also reduced to insoluble elemental selenium Se°. Bioprecipitation of heavy metals, such as Pb, Cd, and Zn, in the form of sulfides, is another in situ immobilization option that exploits the metabolic activity of sulfate-reducing bacteria without altering the valence state of metals. The removal of contaminants from the soil matrix is the most appropriate remediation strategy when bioreduction results in species that are more soluble compared to the initial oxidized element. This is the case for As(V) and Pu(IV), which are transformed to the more soluble As(III) and Pu(III) forms. This treatment option presupposes an installation for the efficient recovery and treatment of the aqueous phase containing the solubilized contaminants. 

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