Copper inactivation

The action of AA on -SH groups has been mentioned above Avigliano et al. (1978) have shown that in the absence of air, AAO is fully reduced by four mol of AA as recorded by optical and EFR spectra. The inhibition of some enzymes is caused by reducing the valency of the metal ion i.e , in xantbine oxidase, inactivation is achieved by changing cupric to cuprous state However, the copper inactivation was reversible ... 

Polyunsaturated fatty acids in vegetable oils, particularly finolenic esters in soybean oil, are especially sensitive to oxidation. Even a slight degree of oxidation, commonly referred to as flavor reversion, results in undesirable flavors, eg, beany, grassy, painty, or fishy. Oxidation is controlled by the exclusion of metal contaminants, eg, iron and copper addition of metal inactivators such as citric acid minimum exposure to air, protection from light, and selective hydrogenation to decrease the finolenate content to ca 3% (74). Careful quality control is essential for the production of acceptable edible soybean oil products (75). 

Kojic acid (5-hydroxy-4 pyran 4-1-2 methyl) is a fungal derivative which inactivates tyrosinase via chelation of copper. Concentrations range from 2 to 4%. It can be used for monotherapy or in combination with retinoids or other cosme-ceutical products such as glycolic acid. Compared with hydroquinone, these kojic acid formulations usually show less efficacy. However, they may be effective in patients who do not... 

In contrast to the effects obtained with viruses mentioned earlier, rous sarcoma virus (RSV) is inactivated by direct contact with 2 [81]. Evidence for the drug action by a chelate compound was obtained by using concentrations of 3a and copper(II) sulfate, neither of which individually affected enzyme activity or transforming abilities [82]. In a later study these workers showed that several metal complexes inhibit the RNA dependent DNA polymerases and the transforming ability of RSV, the most active compound being a 1 1 copper(II)... 

A substance which results in the chemical inactivation of a metal. The catalytic effect of heavy metals, mainly copper and manganese, on the oxidation of unsaturated compounds such as rubber, results in very rapid deterioration. Chelating agents convert the metal into a chelate co-ordination compound and thus render the metal inactive. The term sequestering agents has been applied to chelating agents but this infers that the metal has been removed and not merely inactivated. 

There is an irreversible enzymatic inactivation reaction, which occurs during the oxidation of the cyclizable and noncyclizable diphenols to oquinones. This inactivation process has been interpreted as being the result of a direct attack of an o-quinone on a nucleophilic residue (His) near the active enzyme center or of an attack of a copper-bound hydroxyl radical generated by the Cu(I)-peroxide complex. However, the latter hypothesis seems to be more probable, because inactivation also occurs in the presence of reducing agents that remove the o-quinones generated. 

The laccase molecule is a dimeric or tetrameric glycoprotein, which contains four copper atoms per monomer, distributed in three redox sites. More than 100 types of laccase have been characterized. These enzymes are glycoproteins with molecular weights of 50-130 kDa. Approximately 45% of the molecular weight of this enzyme in plants are carbohydrate portions, whereas fungal laccases contain less of a carbohydrate portion (10-30%). Some studies have suggested that the carbohydrate portion of the molecule ensures the conformational stability of the globule and protects it from proteolysis and inactivation by radicals (Morozova and others 2007). 

Amines such as diethylamine, morpholine, pyridine, and /V, /V, /V, /V -tetramethylethylene-diamine are used to solubilize the metal salt and increase the pH of the reaction system so as to lower the oxidation potential of the phenol reactant. The polymerization does not proceed if one uses an amine that forms an insoluble metal complex. Some copper-amine catalysts are inactivated by hydrolysis via the water formed as a by-product of polymerization. The presence of a desiccant such as anhydrous magnesium sulfate or 4-A molecular sieve in the reaction mixture prevents this inactivation. Polymerization is terminated by sweeping the reaction system with nitrogen and the catalyst is inactivated and removed by using an aqueous chelating agent. 

The bivalent ions of cadmium, cobalt, and copper, in concentrations of the order of 10-100 fiM, accelerate inactivation in experiments of the type shown in Figs. 4 and 5. An excess of Zn2+ prevents, or reverses, inactivation by these ions. 

Flavonoids have the ability to act as antioxidants by a free radical scavenging mechanism with the formation of less reactive flavonoid phenoxyl radicals [Eq. (1) and (2)]. On the other hand, through then-known chelating ability these compounds may inactivate transition metals ions (iron, copper), thereby suppressing the superoxide-driven Fenton Reaction, Eqs. (3) and (4), which is currently believed to be the most important route to activate oxygen species [51]. 

Ingestion of copper sulfate by humans causes vomiting, cramps, convulsions, and as little as 27 grams of the compound may cause deulh. An important part of the toxicity of copper to both plants and animals is probably due to its combination with thiol groups of certain enzymes, thereby inactivating them. The effects ol chronic exposure to copper in animals are cirrhosis of the liver, failure of growth, and jaundice. 

In chelated Versene, the copper ion has become a member of an inner ring structure in the molecule and is inactivated. It will remain so unless it is desired to reverse the process, such as in polymerization of synthetic rubber Chelates find numerous applications in chemical industries and in some analytical procedures, including those used in explosives labs(see CA s under Chelatometry)... 

The diazomethyl ketone functional group was first observed to be an affinity label by Buchanan and co-workers who showed that the antibiotic azaserine, an O-diazoacetyl derivative, 9 inhibited an enzyme in the biosynthesis of purine by alkylation of a cysteine residue. 10 The acid protease pepsin was then observed to be inhibited by peptidyl diazomethyl ketones in the presence of copper ions with the resulting esterification of an aspartate residue. 11 Two peptidyl diazomethyl ketones, Z-Phe-CHN2 and Z-Phe-Phe-CHN2, were found to irreversibly inactivate papain, a cysteine protease. 12 Since these reports, many peptidyl diazomethyl ketones have been prepared primarily as inhibitors of various cysteine proteases. 7 Peptidyl diazomethyl ketones are also synthetic intermediates and have been used to prepare chloromethyl ketones (Section 15.1.3), 13 bromomethyl ketones (Section 15.1.3), acyloxymethyl ketones, 14 and (i-peptides. 15 A few peptidyl diazoalkyl ketones have been reported. 16,17 ... 

---