Studies in the hydrolysis of metal ions -Part I.Copper

The hydrolysis of cupric ion has been studied at various ionic strengths (0·01, 0·05, 0·1 and 0·5 M). The results are analyzed employing 'core + links' theory, log-log plot, normalization plot, and extrapolation method for obtaining the pure mononuclear curve. The stability constants of Cu2(OH)2++, Cu3(OH)4++, Cu(OH)+ and Cu(OH)2 have been reported.

Hydrolysis of riboflavin in plants

The enzymic hydrolysis of riboflavin to lumichrome and ribitol by extracts of Crinum longifolium bulbs has been demonstrated. The enzyme was purified 48-fold by ZnSO4 treatment and ethanol fractionation, and concentrated by using Sephadex G-25. After establishing the stoichiometry of the reaction, the general properties of the purified enzyme were studied. The enzyme showed maximal activity at pH 7·5, and it had a requirement for reduced glutathione which could be replaced by cysteine or ascorbic acid. Mg2+ and Li+ activated the enzyme. The reaction was highly specific to riboflavin and was competitively inhibited by riboflavin 5′-phosphate.

Role of the leaving group in the base-catalysed hydrolysis of pseudo-esters

The relative insensitivity of the rate of hydrolysis of γ-pseudo-esters to the leaving group compared to that of the normal esters emphasises that the conjugative ability is an important factor in determining the rate of hydrolysis of esters

Hydrolysis of elemental sulphur in a homogeneous medium

Elemental sulphur dissolved in organic solvents (such as chloroform, carbon tetrachloride and benzene) reacts rapidly and quantitatively, with aqueous alkali at room temperature, when this immiscible liquid mixture is homogenized by the addition of ethyl alcohol. The products of reaction under these experimental conditions are sulphide, thiosulphate and a small quantity of sulphite. A mechanism involving the intermediate formation and decomposition of dihydrogen sulphoxide, HSOH, is suggested for the reaction.

Studies on the hydrolysis of metal ions - Part II-Nickel

A detailed investigation of the hydrolysis of nickel in the lower concentration range has been made. The results have been analysed on the basis of 'Core + links' theory and on the assumption of the formation of one predominant complex. Evidence is obtained for the formation of Ni2 (OH)62- and its stability constant is calculated to be 1038.78

Studies on nucleotide pyrophosphatase I. Partial purification and properties of a sheep liver enzyme that catalyzes the hydrolysis of dinucleotides

A partially purified sheep liver enzyme that hydrolyzed dinucleotides at the pyrophosphate bond was obtained by solubilizing the 18,000g sediment with n-butanol and fractionating the solubilized enzyme with acetone. The enzyme activity when measured using FAD as substrate, (FAD → FMN + AMP), was optimal at pH 9.7 and temperatures between 30 °–36 ° and at 60 °. The rate of release of FMN with time occurred with an initial lag of 30 sec, a linear increase for 1 min, and a subsequent irregular rate. In the presence of orthophosphate (Pi; 10 μImage ), FMN was released at an uniformly continuous and enhanced rate. 32Pi was not incorporated into the substrate or products. Sodium arsenate counteracted the effects of Pi. The apparent Km and Vmax were 0.133 mImage and 100 units; and 0.133 mImage and 200 units, in the absence and presence of Pi, respectively. The temperature optimum was 42 ° in the presence of Pi.Negative cooperative interactions observed at low concentrations of FAD were abolished by the addition of Pi. The inhibition by AMP was sigmoid and Pi abolished this sigmoidal response. The enzyme hydrolyzed in addition to FAD, NAD+ and NADP+. Nucleoside triphosphates were potent inhibitors of the enzyme activity. The partial inhibition of the enzyme by o-phenanthroline and by p-hydroxymercuribenzoate could be reversed by Fe2+ ions and by reduced glutathione, respectively.

Hydrolysis of Organophosphate Esters: Phosphotriesterase Activity of Metallo-beta-lactamase and Its Functional Mimics

The phosphotriesterase (PTE) activity of a series of binuclear and mononuclear zinc(II) complexes and metallo-beta-lactamase (m beta 1) from Bacillus cereus was studied. The binuclear complex 1, which exhibits good m beta 1 activity, shows poor PTE activity. In contrast,complex 2, a poor mimic of m beta 1, exhibits much higher activity than 1 The replacement of Cl- ligands by OH- is important for the high PTE activity of complex 2 because this complex does not show any catalytic activity in methanol. The natural enzyme m beta 1 from B. cereus is also found to be an inefficient catalyst in the hydrolysis of phosphotriesters. These observations indicate that the binding of beta-lactam substrates at the binuclear zinc(II) center is different from that of phosphotriesters. Furthermore, phosphodiesters, the products from the hydrolysis of triesters, significantly inhibit the PTE activity of m beta 1 and its functional mimics. Although the mononuclear complexes 3 and 4 exhibited significant m beta 1 activity, these complexes are found to be almost inactive in the hydrolysis of phosphotriesters. These observations indicate that the elimination of phosphodiesters from the reaction site is important for the PTE activity of zinc(II) complexes.

Bioremediation of diesel oil contaminated soil and water

Diesel spills contaminate aquatic and terrestrial environments. To prevent the environmental and health risks, the remediation needs to be advanced. Bioremediation, i.e., degradation by microbes, is one of the suitable methods for cleaning diesel contamination. In monitored natural attenuation technique are natural processes in situ combined, including bioremediation, volatilization, sorption, dilution and dispersion. Soil bacteria are capable of adapting to degrade environmental pollutants, but in addition, some soil types may have indigenous bacteria that are naturally suitable for degradation. The objectives for this work were (1) to find a feasible and economical technique to remediate oil spilled into Baltic Sea water and (2) to bioremediate soil contaminated by diesel oil. Moreover, the aim was (3) to study the potential for natural attenuation and the indigenous bacteria in soil, and possible adaptation to degrade diesel hydrocarbons. In the aquatic environment, the study concentrated on diesel oil sorption to cotton grass fiber, a natural by-product of peat harvesting. The impact of diesel pollution was followed in bacteria, phytoplankton and mussels. In a terrestrial environment, the focus was to compare the methods of enhanced biodegradation (biostimulation and bioaugmentation), and to study natural attenuation of oil hydrocarbons in different soil types and the effect that a history of previous contamination may have on the bioremediation potential. (1) In the aquatic environment, rapid removal of diesel oil was significant for survival of tested species and thereby diversity maintained. Cotton grass not only absorbed the diesel but also benefited the bacterial growth by providing a large colonizable surface area and hence oil-microbe contact area. Therefore use of this method would enhance bioremediation of diesel spills. (2) Biostimulation enhances bioremediation, and (3) indigenous diesel-degrading bacteria are present in boreal environments, so microbial inocula are not always needed. In the terrestrial environment experiments, the combination of aeration and addition of slowly released nitrogen advanced the oil hydrocarbon degradation. Previous contamination of soil gives the bacterial community the potential for rapid adaptation and efficient degradation of the same type of contaminant. When the freshly contaminated site needs addition of diesel degraders, previously contaminated and remediated soil could be used as a bacterial inoculum. Another choice of inoculum could be conifer forest soil, which provides a plentiful population of degraders, and based on the present results, could be considered as a safe non-polluted inoculum. According to the findings in this thesis, bioremediation (microbial degradation) and monitored natural attenuation (microbial, physical and chemical degradation) are both suitable techniques for remediation of diesel-contaminated sites in Finland.

On the High Frequency Dielectric Behavior of Castor Oil

The low frequency dielectric behavior of castor oil (a vegetable oil) has been analyzed quite exhaustively in the context of its application as impregnant in capacitors. For the sake of completeness and in order to understand the relaxation phenomena in this liquid dielectric, this high frequency dielectric study was undertaken. In order to compare its properties with a liquid dielectric used in similar application and whose high frequency behavior has been quite well analyzed, Arochlor 1476 was studied. It is observed that both liquids have distributed relaxation times. The distribution parameters together with the two distinct relaxation times have been calculated by measuring the average relaxation time. It has been found that the distinct relaxation times thus calculated represent the dielectric behavior quite satisfactorily. The average dipole moments, dipole radii and thermal activation energies for dipole relaxation have also been evaluated.

Aspects of tautomerism. 7. Study of keto participation in alkaline hydrolysis of normal esters of .gamma.-keto acids

Study of the alkaline hydrolysis of a number of variously substituted normal o-benzoylbenzoic esters has been reported. Although carbonyl-assisted hydrolysis is the general rule, in compounds containing strongly electron-donating groups, the ester function is directly attacked. The cause of rate enhancement in carbonyl-assisted hydrolysis and in greater detail the case of 6-substituted derivatives are discussed. It is shown that the carbonyl-assisted hydrolyses are characterized by decreased sensitivity to leaving-group structure. The implications of this result are pointed out.

Metallo-beta-lactamase-Catalyzed Hydrolysis of Cephalosporins: Some Mechanistic Insights into the Effect of Heterocyclic Thiones on Enzyme Activity

The hydrolysis of beta-lactam antibiotics using zinc-containing metallo-beta-lactamases (m beta l) is one of the major bacterial defense systems. These enzymes can catalyze the hydrolysis of a variety of antibiotics including the latest generation of cephalosporins, cephamycins, and imipenem. It is shown in this paper that the cephalosporins having heterocyclic - SR side chains are less prone to m beta l-mediated hydrolysis than the antibiotics that do not have such side chains. This is partly due to the inhibition of enzyme activity by the thione moieties eliminated during hydrolysis. When the enzymatic hydrolysis of oxacillin was carried out in the presence of heterocyclic thiones such as MU, MDT, DMETT, and MMA, the catalytic activity of the enzyme was inhibited significantly by these compounds. Although the heterocyclic - SR moieties eliminated from the beta-lactams upon hydrolysis undergo a rapid tautomerism between thione and thiol forms, these compounds act as thiolate ligands toward zinc(II) ions. The structural characterization of two model tetranuclear zinc(II) thiolate complexes indicates that the -SR side chains eliminated from the antibiotics may interact with the zinc(II) metal center of m beta l through their sulfur atoms.

Reactions of palladium chloride with amino spirocyclic cyclotriphosphazenes: Isolation and Crystal Structures of Novel Mono- and Bimetallic Complexes Formed by the Hydrolysis of a .lambda.5-Diazaphospholane Ring

The reaction of the amino spirocyclic cyclotriphosphazene N3P3(NMe2)4(NHCH2CH2CH2NH) (2) with palladium chloride gives the stable chelate complex [PdCl2.2] (4). An X-ray crystallographic study reveals that one of the nitrogen atoms of the diaminoalkane moiety and an adjacent phosphazene ring nitrogen atom are bonded to the metal. An analogous reaction with the phosphazene N3P3(NMe2)4(NHCH2CH2NH) (1) gives initially a similar complex which undergoes facile hydrolysis to give the novel monometallic and bimetallic complexes [PdCl2.HN3P3(O)(NMe2)4(NHCH2CH2NH2)] (5) and [PdCl{N3P3(NMe2)4(NCH2CH2NH2)}]2(O) (6), which have been structurally characterized; in the former, an (oxophosphazadienyl)ethylenediamine is chelated to the metal whereas, in the latter, an oxobridged bis(cyclotriphosphazene) acts as a hexadentate nitrogen donor ligand in its dianionic form. Crystal data for 4 : a = 14.137(1) angstrom, b = 8.3332(5) angstrom, c = 19.205(2) angstrom, beta = 96.108(7)degrees, P2(1)/c, Z = 4, R = 0.027 with 3090 reflections (F > 5sigma(F)). Crystal data for 5 : a = 8.368(2) angstrom, b = 16.841(4) A, c = 16.092(5) angstrom, beta = 98.31(2)degrees, P2(1)/n, Z = 4, R = 0.049 with 3519 reflections (F > 5sigma(F)). Crystal data for 6 : a = 22.455(6) angstrom, b = 14.882(3) angstrom, c = 13.026(5) angstrom, 6 = 98.55(2)degrees, C2/c, Z = 4, R = 0.038 with 3023 reflections (F > 5sigma(F)).

Effect of beta-lactamase-catalyzed hydrolysis of cephalosporins on peroxynitrite-mediated nitration of serum albumin and cytochrome c

The hydrolysis of beta-lactam antibiotics by beta-lactamases is one of the major bacterial defense systems. These enzymes generally hydrolyze a variety of antibiotics including the latest generation of cephalosporins, cephamycins and imipenem. In this paper, the effect of cephalosporins-based antibiotics on the peroxynitrite-mediated nitration of protein tyrosine is described. Although some of the antibiotics have weak inhibitory effect on the nitration reactions in the absence of beta-lactamase, they exhibit very strong inhibition in the presence of beta-lactamase. This is due to the elimination of heterocyclic thiol/thione moieties from cephalosporins by beta-lactamase-mediated hydrolysis. After the elimination, the thiols/thiones effectively scavenge peroxynitrite, leading to the inhibition of the nitration reactions.

Intramolecular Reactivity - Keto Participation in the Hydrolysis of N-Methyl-N-(9-Oxobicyclo[3.3.1]Nonan-2-Alpha-YL) Morpholinium Iodide, and A Cannizzaro-Type Reaction of 3-(2-Oxocyclohexyl)Propanal

Mechanistic studies of two intramolecular processes, nucleophilic displacement of N-methylmorpholinium in N-methyl-N-{9-oxobicyclo[3,3,1]nonan-2 alpha-yl}morpholinium iodide, anchimerically assisted by keto carbonyl, and a Cannizzaro-type reaction of 3-(2-oxocyclohexyl)propanal, occurring via axial hydride transfer onto the cyclohexanone, are reported.