Kinetic studies of cobalt alginate gels

Summary Sodium alginate sol can be converted into ionotropic gels by diffusion of di/or trivalent metal ions. The kinetics of this phase transition is studied by two different methods. It is found that the rate of gel membrane formation at the earlier stages is greater than that of the further gel growth. The kinetic studies of gel formation in the presence of a mixture of Cu²⁺ ions with either Co²⁺ or Ni²⁺ ions show that the exhaust of Co²⁺ and Ni^2- ions is remarkable only at the first stage of gel formation. Meanwhile the Cu²⁺ ions continue exchanging all the time with Na²⁺ ions in the alginate sol. The activation energy of gel formation is found to range between 17–23 kJ mol^–, indicating the diffusion control of the process.With 6 figures and 3 tables     

Stereochemical control of reductions. 9. Haptophilicity studies with 1,1-disubstituted 2-methyleneacenaphthenes

A series of 1-methyl-2-methyleneacenaphthenes has been synthesized, bearing an additional variable substituent (R) at the 1-position. These compounds have been hydrogenated in ethanol over a 5% Pd/C catalyst under standardized conditions in order to assess the haptophilicity of R, its ability to enforce addition of hydrogen from its own face of the molecule by coordination to the catalyst surface. The order of decreasing haptophilicity, assessed as the product epimer ratio, for the groups studied was R = CH(2)NH(2), CH(2)NMe(2), CH(2)OH, CHNOH, CH(2)OMe, CHO, CONH(2), CH(2)NHCOMe, COOK, COMe, CN, CONHOH, COOH, COOMe, COONa, COOLi. Because knowledge of group haptophilicities offers potential for stereochemical control in such reductions, comparisons are provided with haptophilic orders found in other molecular systems. It is shown that absolute haptophilicities can be manipulated by varying the dielectric constant of the solvent employed.     

A Facile Route to the Synthesis of New 2,3-Disubstituted Benzocoumarins

Triphenylphosphine catalyzes the reaction between 2-hydroxy-1-naphthaldehyde and π-deficient acetylenes to give the newly prepared benzo[f]chromenes. The mechanism for the formation of products is discussed.     

Catalytic activity of nickel(II), copper(II) and oxovanadium(II)‐dihydroindolone complexes towards homogeneous oxidation reactions

Three novel paramagnetic metal complexes (MH₂ID) of Ni²⁺, Cu²⁺ and VO²⁺ ions with 3‐hydroxy‐3,3’‐biindoline‐2,2’‐dione (dihydroindolone, H₄ID) were synthesized and characterized by different spectroscopic methods. The ligand (H₄ID) was synthesized via homocoupling reaction of isatin in presence of phenylalanine in methanol. Complexation of low valent Ni²⁺, Cu²⁺ ions and high valent VO²⁺ ions with H₄ID carried out in 1: 2 molar ratios. A comparison in the catalytic potential of paramagnetic complexes of low and high valent metal ion was explored in the oxidation processes of cis‐cyclooctene, benzyl alcohol and thiophene by an aqueous H₂O₂, as a green terminal oxidant, in the presence and absence of acetonitrile, as an organic solvent, at 85 °C. NiH₂ID, CuH₂ID and VOH₂ID show good catalytic activity, i.e. good chemo‐ and regioselectivity. VOH₂ID has the highest catalytic potential compared to both Ni²⁺‐ and Cu²⁺‐species in the same homogenous aerobic atmosphere. Catalytic oxidation of other alkenes and alcohols was also studied using NiH₂ID, CuH₂ID or VOH₂ID as a pre‐catalyst by an aqueous H₂O₂. A mechanistic pathway for those oxidation processes was proposed.     

Biochemical Properties of Tyrosinase from Aspergillus terreus and Penicillium copticola; Undecanoic Acid from Aspergillus flavus,an Endophyte of Moringa oleifera,Is a Novel Potent Tyrosinase Inhibitor

Tyrosinase is a copper-containing monooxygenase catalyzing the O-hydroxylation of tyrosine to 3,4-dihydroxyphenylalanine then to dopaquinone that is profoundly involved in melanin synthesis in eukaryotes. Overactivation of tyrosinase is correlated with hyperpigmentation that is metabolically correlated with severe pathological disorders, so, inhibition of this enzyme is the most effective approach in controlling the overproduction of melanin and its hazardous effects. Thus, searching for a powerful, selective inhibitor of human tyrosinase to limit the hyper-synthesis of melanin is a challenge. Unlike the difficulty of overexpression of human tyrosinase, using fungal tyrosinase as a model enzyme to the human one to evaluate the mechanistics of enzyme inhibition in response to various compounds is the most feasible strategy. Thus, the purification of highly catalytic-efficient fungal tyrosinase, exploring a novel inhibitor, and evaluating the mechanistics of enzyme inhibition are the main objectives of this work. Aspergillus terreus and Penicillium copticola were reported as the most potential tyrosinase producers. The biochemical properties suggest that this enzyme displays a higher structural and catalytic proximity to human tyrosinase. Upon nutritional bioprocessing by Plackett–Burman design, the yield of tyrosinase was increased by about 7.5-folds, compared to the control. The purified tyrosinase was strongly inhibited by kojic acid and A. flavus DCM extracts with IC₅₀ values of 15.1 and 12.6 µg/mL, respectively. From the spectroscopic analysis, the main anti-tyrosinase compounds of A. flavus extract was resolved, and verified as undecanoic acid. Further studies are ongoing to unravel the in vivo effect and cytotoxicity of this compound in fungi and human, that could be a novel drug to various diseases associated with hyperpigmentation by melanin.     

Similarities and Differences of Low Salinity Polymer and Low Salinity LPS (Linked Polymer Solutions) for Enhanced Oil Recovery

Linked polymer solution (LPS) is nano-size particles made of hydrolyzed polyacrylamide (HPAM) cross-linked with aluminum citrate. The propagation of LPS has been compared to non-cross-linked polymers at low brine salinity condition. The possible differences in properties and potentials for oil recovery have been investigated using water-wet and intermediate-wet cores. The target oil for polymer flooding (PF) is assumed to be the portion of the reservoir that has been bypassed by water during waterflooding and not the residual oil saturation in flooded zones. Our recent studies have shown that a positive synergy can be obtained by combining low salinity and PF. It has been claimed in the literature that cross-linking polymer such as colloidal dispersion gels (colloidal dispersion gels (CDG), micron-size aggregates) or LPS (nano-size particles) would extend the application of polymers to also include change in residual oil saturation. The results of this study indicated higher pressure buildup when low salinity LPS was propagated through brine saturated cores compared to low salinity polymer solution. The pressure buildup was even stronger for high salinity LPS injection. In two phase flow experiments, both polymer and LPS under low salinity condition, showed approximately similar propagation and oil recovery potential when injected into water-wet and intermediate-wet cores.     

Base-Catalyzed Oxidation of Carboxymethyl-cellulose Polymer by Permanganate

The kinetics and mechanism of the disproportionation of MnO(4)(-) via [CMC-MnVIO(4)(2-)] intermediate complex formation during the oxidation of carboxymethyl-cellulose (CMC) polysaccharide have been investigated spectrophotometrically at pH>/=12 and various temperatures (15-35 degrees C). The rate law was suggested as rate=k(obs)[MnO(4)(-)]. Kinetic and spectrophotometric measurements revealed the base-catalyzed formation of manganate(VI) transient species. A mechanism was postulated consistent with the experimental data. Copyright 2001 Academic Press.     

Kinetics of hydrolysis of some new heterocyclic azomethines

Kinetics of base hydrolysis of new heterocyclic azomethines derived from active methyl quaternary salts and aromatic nitroso compounds were investigated in the presence of 70% (wt/wt) water-methanol. The base hydrolysis of these compounds is strictly first-order with respect to OH^– and azomethine. The rate determining step is suggested to be the attack of the hydroxide ion on the free base. Effects of water content and nature of organic hydroxylic solvent have been studied. It is concluded that specific solute-solvent interactions through dispersion forces play a major role in the base hydrolysis rate of the azomethines investigated. The effect of pH (2.98 – 12.24) on hydrolysis rates of compounds having a diethylamino substituent in the presence of 30% methanol has been studied. In acidic media, the rate determining step is probably the water attack on the protonated substrate.