Measurements of distribution coefficients and lipophilicity values for oleanolic acid and betulinic acid extracted from indigenous plants by hollow fibre supported liquid membrane

Hollow fibre supported liquid membrane (HFSLM) has been applied in the measurements of distribution constants, KD and lipophilicity (log P) values for the isomeric triterpenic acids, betulinic acid (BA) and oleanolic acid (OA) isolated from indigenous plants. The results have shown that BA had an optimum pH of 3.5 while the optimum sample pH for OA was ranging from 0.5 to 2.5. The log P values obtained for BA and OA were 6.61 and 6.12, respectively. The KD value obtained for BA was 0.29 while that for OA 0.16. The method has advantages of simplicity, use of minimal organic solvents and the ability to selectively extract only one isomer (OA) in the mixture with BA by optimizing pH conditions.KEY WORDS: Betulinic acid, Oleanolic acid, Hollow fibre supported liquid membrane, Distribution coefficient, Lipophilicity Bull. Chem. Soc. Ethiop. 2011, 25(3), 321-332

Natural organic matter in aquatic systems – a South African perspective

Natural organic matter (NOM) is a complex heterogeneous mixture of humic (HS) and non-humic substances which are widespread in the aquatic environment. Other constituents are amino acids, aliphatic and aromatic hydrocarbons containing oxygen, nitrogen and hydroxyl groups. It is the combination and proportions of these motifs which give NOM its overall polarity and reactivity. Its main origins include soils, residues of fauna and flora, microbial excrements and anthropogenic faecal loads, agriculture activities and urban landscapes. Due to the different origins of the precursor material and the extent of transformation it undergoes, the composition of NOM in different water bodies varies. Characterization methods for NOM can be divided into three broad categories namely: (i) direct measuring methods, which measure the amount of organic matter in the sample; (ii) spectrometric methods, which measure the amount of radiation absorbed and or released by chromophores; and (iii) fractionation methods, which separate NOM according to size and polarity. South Africa has 6 distinct water quality regions, and each region has a unique NOM character and quantity. Existing water treatment plants do not remove NOM to levels low enough to inhibit the formation of disinfection by-products (DBPs). Currently, research is focusing more on the use of alternative techniques for NOM removal; these include advanced oxidation processes (AOPs), nanomaterials, and ceramic membranes. While NOM is well studied in other parts of the world, to the best of our knowledge, there is no state-of-the-art investigation of the occurrence and removal of NOM in South African source waters. This review aims at (i) synthesizing literature on the nature, occurrence and ecological impact of NOM, (ii) evaluating the removal of NOM in the six different water quality regions of South Africa, and (iii) suggesting novel approaches that can be used to remove NOM in South Africa.Keywords: advanced oxidation, ceramic membranes, disinfection byproducts, treatability, water treatmen

Investigating the fate of natural organic matter at a drinking water treatment plant in South Africa using optical spectroscopy and chemometric analysis

The removal dynamics of biodegradable dissolved organic carbon (BDOC) and natural organic matter (NOM) polarity fractions at a water treatment plant (WTP) in South Africa was studied using UV-Vis absorbance, fluorescence excitation-emission matrix, and two-dimensional synchronous fluorescence spectroscopy (SFS). This study gave insights into the transformation of NOM due to treatment processes. The objectives of the study were: (i) to use chemometric analysis and two-dimensional SFS correlations to investigate the evolution of NOM arising from treatment processes, and (ii) to access the chemical profile dynamics of polarity and BDOC fractions throughout the treatment train. The UV254 absorbance, which indicates aromaticity, reduced by 45% along the WTP. Gaussian fitting of UV-Vis data showed a decreasing trend in intensity and number of bands along the treatment process. The removal efficiency of NOM components followed the order: humiclike (HL) > tyrosine-like (TYL) > fulvic-like (FL) > tryptophan-like (TPL) > microbial-like (MBL). At the source, the relative distribution of the hydrophobic (HPO), hydrophilic (HPI), and transphilic (TPI) fractions was 45%, 31%, and 24%, respectively. The HPI was recalcitrant to treatment, and the TYL component of the HPI fraction was conjectured to be a disinfection byproduct limiting reagent. The HL and FL components of the BDOC fraction were the major substrates for bacterial growth. According to two-dimensional-SFS correlation, TYL, TPL, and MBL varied concurrently across the treatment stages. Used for the first time in South Africa, the robustness of a multi-dimensional approach of optical methods coupled with chemometric tools for the assessment of the fate of NOM along the treatment processes was revealed by this study.Keywords: biodegradable dissolved organic, carbon, natural organic matter, optical spectroscopy, two-dimensional correlations, water treatmen

UHPLC/GC-TOF-MS metabolomics, MTT assay, and molecular docking studies reveal physostigmine as a new anticancer agent from the ethyl acetate and butanol fractions of Kigelia africana (Lam.) Benth. fruit extracts

Staff PublicationKigelia africana plant is widely used as a herbal remedy in preventing the onset and the treatment of cancer-related infections. With the increase in the research interest of the plant, the specific chemical compound or metabolite that confers its anticancer properties has not been adequately investigated. The ethyl acetate and butanol fractions of the fruit extracts were evaluated by 2-(4,5-dimethylthiazol-2-yl)- 3,5-diphenyl-2H-tetrazolium bromide assay against four different cell lines, with the ethyl acetate fraction having inhibition concentration values of 0.53 and 0.42 μM against Hep G2 and HeLa cells, respectively. More than 235 phytoconstituents were profiled using UHPLC-TOF-MS, while more than 15 chemical compounds were identified using GC–MS from the fractions. Molecular docking studies revealed that physostigmine, fluazifop, dexamethasone, sulfisomidine, and desmethylmirtazapine could favorably bind at higher binding energies of –8.3, –8.6, –8.2, and –8.1 kcal/mol, respectively, better than camptothecin with a binding energy of –7.9 kcal/mol. The results of this study showed that physostigmine interacted well with topoisomerase IIα and had a high score of pharmacokinetic prediction using absorption, distribution, metabolism, excretion, and toxicity profiles, thereby suggesting that drug design using physostigmine as a base structure could serve as an alternative against the toxic side effects of doxorubicin and camptothecin

<b>Hollow fibre supported liquid membrane extraction of diphenylhydramine, chlorpheniramine and ketoprofen in pharmaceutical products</b>

A simple sample pre-treatment method utilizing hollow fibre supported liquid membrane (HFSLM) was carried out on pharmaceuticals samples comprising of cough syrups (CS1 and CS2) and an anti-inflammatory product (AI). The active ingredients targeted in the extraction process were diphenylhydramine (DPH), chlorpheniramine (CPA) [(S)-γ-(4-chlorophenyl)-N,N-dimethyl-2-pyridinepropanamine maleate salt] and ketoprofen (KP) [(RS)2-(3-benzoylphenyl)-propionic acid] which were detected by a high performance liquid chromatograph (HPLC-UV/DAD) after HFSLM process. Factors controlling the efficiency of HFSLM extraction such as sample pH, stripping phase pH, enrichment time, stirring speed as well as the organic solvent used for the entrapment of these analytes were optimized to achieve the best selectivity and high enrichment factors. KP extracted from AI product had optimal pH of 10 for the stripping solution and 4 for sample with enrichment factors of 339. DPH had optimal pH of 12 (sample) and 3 for the stripping solution and had enrichment factors of 519. The optimal sample pH for CPA was 0.5 while the stripping phase pH was 13. The HFSLM technique showed 81% recovery of DPH from CS1, while for CPA from CS2 was 78 % and that of KP from AI was 80 %. The LODs obtained were 0.06 mu;g/L for all the compounds

Performance of Mn2+-modified bentonite clay for the removal of fluoride from aqueous solution

Alow-cost adsorbent produced from Mn2+-modified bentonite clay was evaluated for groundwater defluoridation. Batch experiments were used to evaluate the effect of contact time at various adsorbent dosages, adsorption isotherms and the effect of pH on fluoride removal. The results showed that the optimum F– uptake occurred within the first 30 min contact time and the percentage removal increased with increasing adsorbent dosage. The data fitted better to pseudo-second-order reaction indicating that F– adsorption occurred via chemisorption. The Weber-Morris model of intra-particle diffusion revealed that both surface and intra-particle diffusion processes were involved during the F– adsorption process. Furthermore, the batch results showed that pH of the solution governed the percentage of fluoride removal with the optimum of 75.2 % fluoride removal achieved at pH 4. The adsorbent chemical stability assessment showed that chemical species were leached at trace concentrations which are within the South African National Standards (SANS) limits. Electrostatic attraction and ion-exchange were established as the major mechanisms responsible for fluoride adsorption at acidic pH and at moderate to alkaline pH levels, respectively. The study demonstrated that Mn2+ intercalated bentonite clay has potential for application in defluoridation of groundwater.Keywords: Adsorption, defluoridation, ion exchange, ligand exchange, intra-particle diffusio

Characterisation of smectite-rich clay soil: Implication for groundwater defluoridation

Groundwater is a widely used and affordable source of drinking water in most of the rural areas of South Africa. Several studies have indicated that groundwater in some boreholes in South Africa has a fluoride concentration above the level recommended by the World Health Organization (1.5 mg/L). Fluoride concentrations above the permissible limit (&gt;1.5 mg/L) lead to dental fluorosis, with even higher concentrations leading to skeletal fluorosis. In the present work, we evaluate the application of smectite-rich clay soil from Mukondeni (Limpopo Province, South Africa) in defluoridation of groundwater. The clay soil was characterised by mineralogy using X-ray diffraction, by elemental composition using X-ray fluorescence and by morphology using scanning electron microscopy. Surface area and pore volume was determined by the Brunauer–Emmett–Teller surface analysis method. Cation exchange capacity and pHpzc of the soil were also evaluated using standard laboratory methods. Batch experiments were conducted to evaluate and optimise various operational parameters such as contact time, adsorbent dose, pH and initial adsorbate concentration. It was observed that 0.8 g/100 mL of smectite-rich clay soil removed up to 92% of fluoride from the initial concentration of 3 mg/L at a pH of 2 with a contact time of 30 min. The experimental data fitted well to a Langmuir adsorption isotherm and followed pseudo second order reaction kinetics. Smectite-rich clay soil showed 52% fluoride removal from field groundwater with an initial fluoride concentration of 5.4 mg/L at an initial pH of 2 and 44% removal at a natural pH of 7.8. Therefore smectite-rich clay soil from Mukondeni has potential for application in defluoridation of groundwater. Chemical modification is recommended to improve the defluoridation capacity. Significance:&nbsp; Physicochemical and mineralogical characterisation of smectite-rich clay soil Defluoridation of groundwater using smectite-rich clay soil Adsorption modelling using adsorption isotherms and kinetic model

Quantitative Variations of Intracellular Microcystin-LR, -RR and -YR in Samples Collected from Four Locations in Hartbeespoort Dam in North West Province (South Africa) During the 2010/2011 Summer Season

The Hartbeespoort (HBP) Dam is a reservoir used for agricultural, domestic supply of raw potable water and recreational activities in South Africa’s North-West Province. Eutrophication and cyanobacterial blooms have long been a cause of water-quality problems in this reservoir. The most prevalent bloom-forming species is Microcystis aeruginosa, often producing the toxin microcystin, a hepatotoxin which can negatively impact aquatic animal and human health, and poses a problem for potable water supply. Algal samples were collected monthly from four pre-determined sites in the dam during the summer months (December 2010–March 2011). Intracellular microcystins (MCs) were extracted using SPE C18 cartridges, followed by separation, identification and quantification using LC-ESI-MS techniques. Quantitative variation studies of MCs were conducted with respect to MC congener isolated, sampling site and month. Three main MC congeners (MC-RR, -LR and-YR) were isolated, identified and quantified. In addition, three minor MCs (MC-WR, MC-(H4)YR and (D-Asp3, Dha7)MC-RR were also identified, but were not quantified. The MC dominance followed the order MC-RR>MC-LR>MC-YR across all sites and time. The maximum and minimum concentrations were 268 µg/g and 0.14 µg/g DW for MC-RR and MC-YR, respectively, of the total MCs quantified from this study. One-way ANOVA showed that there were no significant differences between average MC concentrations recorded across months (P = 0.62), there was, however, a marginally-significant difference in concentrations among MC congeners (P = 0.06). ANCOVA revealed a highly significant interaction between sites and MC congeners on MC concentration (P < 0.001)

Synthesis and characterization of ion imprinted polymeric adsorbents for the selective recognition and removal of arsenic and selenium in wastewater samples

Arsenic (As) and selenium (Se) ion imprinted polymers, As-IIPs and Se-IIPs, were synthesized via bulk polymerization. The prepared materials were then characterized using Fourier Transform Infrared (FT-IR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). These characterization methods confirmed the difference between IIPs and non-imprinted polymers (NIP). From the adsorption studies done IIPs did not only show better adsorption than NIPs but also better selectivities as well. As adsorption using As-IIPs (AsAsIIPs) reached a maximum of 482 μg g−1 whilst Se adsorption using Se-IIPs (SeSeIIPs) reached a maximum of 447 μg g−1 after optimization of the sample pH, adsorption time and sample temperature. However these adsorption capacities were increased to 568 μg g−1 and 530 μg g−1 for As and Se respectively when column experiments were done at the same sample temperature and pH. Against Pb, Cd and Hg, As-IIPs and Se-IIPs showed selectivity towards As and Se, respectively