Kinetics and Mechanism of the Oxidation of Coomassie Brilliant Blue-R Dye by Hypochlorite and Role of Acid Therein

The kinetics of the oxidation of a triphenylmethane dye, Brilliant Blue-R (BB–Na+), in aqueous solution by hypochlorite as a function of pH was investigated. While the degradation of dye obeyed pseudo-first-order kinetics, the oxidation of the dye occurred through two competitive reactions facilitated by [OCl–] and [HOCl]. Both reactions exhibited first-order dependence on [OCl–] and [HOCl], respectively, but the hypochlorous acid initiated reaction was about ten times faster. The relative importance of the two paths rested on the pH-dependent concentrations of hypochlorite and hypochlorous acid. The overall second-order rate constants for the OCl– and HOCl initiated reactions are 1.2±0.2M–1 s–1 and 22.2±1.2M–1 s–1, respectively. The reaction energy parameters were determined as Ea=35.5 kJ mol–1,ΔHt=33.1 kJ mol–1 and ΔSt=–191.9 JK–1 mol–1 for the OCl– driven oxidation; and Ea= 26.8 kJ mol–1, ΔHt=29.3 kJ mol–1 and ΔSt=–204.6 JK–1 mol–1 for the HOCl facilitated reaction. The governing rate law and probable reaction mechanism were elucidated and validated by simulation. The three main oxidation products were 4-(4-ethoxyphenylamino)benzoic acid, 3-[(ethyl-hydroxyamino)methyl]benzene sulfonic acid and 6’-chloro-5’-hydroxybicyclohexylidene-2,5,2’-triene-4,4’-dione.KEYWORDS Brilliant Blue-R, oxidative degradation, hypochlorite, hypochlorous acid, kinetics, simulations.PDF and Supp files attache

Isoflavones from Calpurnia aurea subsp. Aurea and their Anticancer Activity

Background: Calpurnia aurea is an African medicinal plant used in many countries in Africa to treat a range of medical conditions or disorders.Extracts of the plant were shown to be active in antibacterial and  antioxidant assays as well as against lice, ticks and maggots. The aim of the study was to isolate the phytochemical constituents from the plant and to test them in appropriate bioassays dependent on the compounds isolated in order to provide a rationale for the use of the plant in ethno-medicine or to provide some information on its constituents.Materials and methods: The stem and bark of the plant was extracted with organic solvents of varying polarity and the extracts separated and purified using column chromatography. The isolated compounds were identified by NMR spectroscopy and the compounds were tested for their in vitro anticancer activity against breast (MCF7), renal (TK10) and melanoma  (UACC62) human cell lines using an in house method developed at the CSIR, South Africa.Results: The isoflavones, 4Œ,5,7-trihydroxyisoflavone (1), 7,3Œ-dihydroxy-5Œ-methoxyisoflavone (2), 7-hydroxy-4Œ,8- dimethoxyisoflavone (3), 7- acetoxy-4Œ,8-dimethoxyisoflavone (4) and 3',7-dihydroxy-4Œ,8-dimethoxyisoflavone (5), a pterocarpan (3-acetoxy-9-methoxypterocarpan) and a quinolizidine alkaloid (calpurnine) were isolated from the stem and bark of Calpurnia aurea. The tetrasubstituted isoflavone 5 was found to be the most active in the three cell lines amongst all the compounds tested. This was followed by trisubstituted isoflavone 2.Conclusion: The isoflavones showed moderate activity against the renal, melanoma and breast cancer cell lines tested against, with the isoflavones 2 and 5 showing the best activity of the compounds tested. These  isoflavones may have a synergistic effect with other anticancer drugs.Key words: Calpurnia aurea, Fabaceae, 5,6Œ-dihydroxy-2Œ,6-dimethoxyisoflavone, anti cancer

Antibacterial and Anti-Biofilm Activity of Flavonoids and Triterpenes Isolated from The Extracts of Ficus Sansibarica Warb. Subsp. Sansibarica (Moraceae) Extracts

Background: Ficus species are used in African traditional medicine in the treatment of a wide variety of ailments and diseases such as convulsive disorder, wound healing, gonorrhea, tuberculosis, diabetes, diarrhoeal infections, dysentery, malaria and HIV. The aim of this study was to isolate the phytochemical constituents in the plant and test them for their antibacterial activity.Materials and methods: The fruits, leaves and stem bark were extracted with organic solvents and the compounds in the extracts separated and purified by column chromatography before being identified by NMR spectroscopy and by comparison of the NMR data against values reported in the literature. The antibacterial activity of the pure compounds and extracts were tested using the disk diffusion method.Results: Three triterpenes and three flavonoids: lupeol acetate (1); cycloart-23-ene-3,25-diol (2); β-sitosterol (3); 5,7,4'-trihydroxyflavan-3-ol (4); epicatechin (5); and isovitexin (6) were isolated in this study. Antimicrobial activity was observed at 8 mg mL-1 for Staphylococcus aureus ATCC 29213 with four of the six isolated compounds, with no activity being observed at 1 – 4 mg mL-1 against Escherichia coli ATCC 25922, E. coli ATCC 35218 and S. aureus ATCC 43300. Epicatechin (5) was found to decrease adhesion of E. coli ATCC 25922 and S. aureus ATCC 29213. Decreased adhesion of S. aureus ATCC 29213 was also observed with 5,7,4'-trihydroxyflavan-3-ol (4) and isovitexin (6).Conclusions: The results of this study provide baseline information on F. sansibarica’s potential validity in the treatment of infections associated with Gram-positive microorganisms.Key words: Moraceae, Ficus sansibarica, antimicrobial, anti-adhesion properties, flavonoids, triterpenoids

Coincident isolation of a novel homoisoflavonoid from Resnova humifusa and Eucomis montana (Hyacinthoideae: Hyacinthaceae)

We report on the first phytochemical investigation of a member of the African genus Resnova (Hyacinthoideae: Hyacinthaceae). From the dichloromethane extract of the bulbs of both Resnova humifusa and Eucomis montana (Hyacinthoideae: Hyacinthaceae) a novel 3-benzyl-4-chromanone homoisoflavonoid, 5,6-dimethoxy-7-hydroxy-3-(4′-hydroxybenzyl)-4-chromanone, was isolated. A further 11 known homoisoflavonoids were also identified, the 12 in total presenting a clear biosynthetic sequence. Eight of the 12 compounds found were common to both species. © 2005 Elsevier Ltd. All rights reserved