Scielo RSS <![CDATA[South African Journal of Chemistry]]> http://www.scielo.org.za/rss.php?pid=0379-435020210001&lang=en vol. 75 num. lang. en <![CDATA[SciELO Logo]]> http://www.scielo.org.za/img/en/fbpelogp.gif http://www.scielo.org.za <![CDATA[<b>Vortex-assisted Solid-Liquid Extraction for Rapid Screening of Oil Content in Jatropha Seed: an Alternative to the Modified Soxhlet Method</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100001&lng=en&nrm=iso&tlng=en In this study, an optimized vortex-assisted method for rapid screening of oil content in Jatropha curcas L. (Jatropha) seeds is described. A 2(4-1)IV fractional factorial design was employed to study the influence of vortex stirring rate, sample:solvent ratio, extraction time, and the number of extraction cycles in the Jatropha oil extraction efficiency. Gas chromatography-mass spectrometry (GC-MS) was used for the identification of the fatty acids. The number of extraction cycles was the most important factor, and the optimum conditions were two extractions with hexane at a sample:solvent ratio of 1:5 mg:μL, under vortex-stirring at 2500 rpm for 1 min. Linoleic acid, oleic acid and palmitic acid were the major fatty acids of Jatropha oil. The method showed inherent advantages of simplicity, accuracy, short time of analysis, and low consumption of both organic solvent and sample, and may serve as a cost-effective alternative to the modified Soxhlet method in estimation of oil content and composition in Jatropha breeding programmes. <![CDATA[<b>Evaluation of Bitter Kola Leaf Extract as an Anticorrosion Additive for Mild Steel in 1.2 M H<sub>2</sub>SO<sub>4</sub> Electrolyte</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100002&lng=en&nrm=iso&tlng=en Plant-based material, namely bitter kola leaf, as an additive for surface modification of mild steel in H2SO4 solution was thoroughly scrutinized using electrochemical, theoretical and optimization techniques. The functional groups, of the biomolecules of the bitter kola leaf extract, were examined using Fourier transform infrared spectrometry (FTIR) and gas chroma-tography-mass spectrophotometry (GC-MS). For clarification purpose, scanning electron microscopy (SEM) was used to inspect the texture of the degraded and inhibited steel after 21 h of immersion. For the response surface methodology (RSM), central composite design of Design-Expert Software was used to optimize the inhibition efficiency as a function of acid concentration, inhibitor concentration, temperature and time. The optimum inhibition efficiency of 93 % was obtained at 0.9 g L-1 bitter kola leaf. The mutual correlation between the considered variables and expected response was adequately interpreted by a quadratic model. The fitness of the model was justified by the following standards which include P-value (<0.0001), adjusted R² (0.9843), R² (0.991), adequate precision (43.14) and coefficient of variation (2.59). Bitter kola leaf extract behaved as a mixed-type inhibitor and adequately satisfied Langmuir adsorption isotherm. Furthermore, the theoretical modelling revealed the most active molecule of bitter kola leaf responsible for the overall inhibition. The experimental and theoretical results are in agreement that bitter kola leaf extract is a viable corrosion inhibitor of mild steel in H2SO4 solution. <![CDATA[<b>Quantum Chemistry of Cocaine and its Isomers I: Energetics, Reactivity and Solvation</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100003&lng=en&nrm=iso&tlng=en We investigate the rich stereochemistry of cocaine and its diastereoisomers from a theoretical perspective using density functional theory. The relative stability of the eight considered isomers is discussed, and a comparison of the corresponding internal coordinates is given. Our results reveal that the S-pseudococaine isomer is the most stable conformation, whereas the natural occurring isomer (R-cocaine) lies higher in energy. The different isomers' chemical reactivity is discussed based on the calculation of the hardness, softness, electrophilicity and dipole moment. It was found that the dipole moment varies over a broad range from 0.65 to 4.60 D, whereas the other properties are slightly modified. The solvent effect on the energy stability of the cocaine isomers was studied by considering chloroform, dimethyl-sulfoxide (DMSO) and water as implicit solvents. Our calculations show that the different isomers' energy order and their energy gaps are slightly modified due to solvent effects. However, in all cases, the S-pseudococaine remains the most stable isomer. However, the dipole moment and the chemical reactivity of the cocaine isomers increase with the solvent polarity. <![CDATA[<b>Study of 'Fingerprints' for Green Tea from Different Planting Areas in Eastern China</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100004&lng=en&nrm=iso&tlng=en Green tea is one of the main teas in China, which is unfermented and retains more natural substances of fresh tea leaves. This is the preliminary study of application of'fingerprints' based on differences in component composition of green tea. Five green teas from different areas in eastern China are analyzed, which are processed by microwave-assisted solvent (ethanol) extraction method to obtain tea polyphenols, flavonoids, polysaccharides, pigments (thearubigins, theaflavins, theabrownins). The results show that the component composition of five green teas are varied from each other; based on these contents varieties, we have constructed a 'fingerprint' and applied linear discriminant analysis (LDA) and hierarchical cluster analysis (HCA) to assist in the identification of these five green teas. This method does not require large, expensive instruments (such as high performance liquid chromatograph, gas chromatograph, mass spectrometer, etc.), and is easy to use, which provides a new avenue for the identification of tea. <![CDATA[<b>Ethylene Trimerization over Supported SNS and PNP</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100005&lng=en&nrm=iso&tlng=en Chromium(III) complexes with sulphur, nitrogen and phosphorus tridentate ligands were synthesized and characterized. These complexes were supported on SiO2 and characterized by BET surface area measurements, XRF, SEM-EDX and FTIR. The complexes were tested for activity and selectivity in the trimerization of ethylene. The substituent's effect and influence on the sulphur on the supported catalysts were studied using the ethyl and the decyl substituted catalysts. The influence of temperature on catalytic performance was evaluated using the PPP supported system. The most active supported catalyst, the decyl substituted SNS catalyst, showed good activity of up to 19 500 g/g Cr h-1 and selectivity of 97.3 % to C6 products (98.2 % 1-hexene). This activity and selectivity were comparable to the homogeneous counterpart's performance that achieved 22 000 g/g Cr h-1 and 98.2 % C6 products (96.7 % 1-hexene), which surpassed the ethyl substituted catalyst, which was not supported, under the same reaction conditions. The supported PPP catalyst activities showed it was sensitive to higher temperatures, but this depends on the supporting technique. <![CDATA[<b>Carbon Nanodots Derived from Natural Products</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100006&lng=en&nrm=iso&tlng=en This review highlights recent improvements, and present situations concerning the practical application of, natural products-based carbon nanodots (CNDs) in nanomedicine, sensors, drug delivery, bio-imaging, solar cells, photocatalysis and nano-encapsulation. CNDs are zero-dimensional carbonaceous nanomaterials that have recently drawn much attention because of their unique physicochemical properties, such as excellent biocompatibility and tunable photoluminescence, easy functionali-zation, solubility in water, dispersibility, and low toxicity. Additionally, they are environmentally friendly, abundant, easily accessible, and rich in multiple elements. Since CNDs derived from organic products have unique properties, we explored and found that the properties of CNDs may depend on the preparation method and the used precursors. This study also informs on the positioning of natural products in nanotechnology. <![CDATA[<b>Optimization and Kinetic Modelling of Total Phenols and Flavonoids Extraction from <i>Tilia cordata </i>M. Flowers</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100007&lng=en&nrm=iso&tlng=en The main goal was to optimize and establish the kinetics and the thermodynamics of the extraction process. An investigation into the effects of ethanol concentration (0-100 %), liquid to solid ratio (30-60 mL g-1), extraction temperature (25-65 °C), and extraction time (40-200 min) on the extraction of total phenols (TP) and total flavonoids (TF) from linden (Tilia cordata M.) flowers was performed using single-factor experiments. Experimental results showed that extraction conditions had a significant effect on the extraction of phenolic compounds. The optimized conditions were 50 % ethanol, liquid to solid ratio 60 mL g-1 for 120 min at 55 °C, with values of 17.05 mg GAE g-1 dry weight (d.w.) for TP and 13.32 mg CE g-1 d.w. for TF. Extracted phenolic compounds were analyzed by HPLC. The antioxidant activity of the extracts was evaluated by DPPH and ABTS assays. The applicability of different mathematical models (model based for the unsteady diffusion through the plant material, model based on the film theory and model of Ponomaryov) to describe the kinetics of the extraction process of TP and TF from linden flowers was studied as well. The mathematical models applied showed a good agreement with the experimental results, which allows their application in modelling and optimizing the solid/liquid extraction process to extract TP and TF from linden flowers. <![CDATA[<b>Micellar and Polymer Catalysis in the Kinetics of Oxidation of L-lysine by Permanganate Ion in Perchloric Acid Medium</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100008&lng=en&nrm=iso&tlng=en Kinetics of oxidation of L-lysine by permanganate ion in a perchloric acid medium was investigated to explore the order of the reaction with respect to oxidant and substrate and to study the catalytic behaviour of sodium lauryl sulphate (SLS) and polyethylene glycol (PEG). The reaction was found to be first-order with respect to the oxidant and the substrate and zero-order with respect to hydrogen ion. Changes in the sodium sulphate concentration produce a non-significant variation in the rate of the reaction. SLS and PEG were found to catalyze the reaction. Surfactant catalysis was modelled by Piszkiewicz's cooperativity model, while polymer catalysis was explained with the help of the Benesi-Hildebrand equation. The temperature dependence of the rate of the reaction was elucidated, and activation parameters were obtained. Interestingly, the reaction was found to possess positive activation entropy indicating the dissociative nature of the transition state and outer-sphere electron transfer mechanism. A mechanism of the reaction that is supported by the experimental findings was suggested. <![CDATA[<b>Optimization of Silica Extraction from Diatomaceous Earth using the Central Composite Design of Response Surface Methodology</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100009&lng=en&nrm=iso&tlng=en This work evaluated the extraction efficiency of silica from diatomaceous earth (DE) by conventional solvent extraction (CSE) and ultrasound-assisted extraction (UAE) under basic and acidic (HCl) conditions utilizing response surface methodology (RSM). A common statistical model was used to get the best percentage yield and percentage purity using RSM. Experimental parameters such as stirring time, NaOH concentration (for CSE), sonication time, NaOH/HCl concentration, cycle and amplitude (for UAE methods) were optimized using central composite design (CCD). The analytical responses, that is, percentage yield and percentage purity, were analyzed using ANOVA and regression analysis. The linear coefficient of determination, R², was high and precise. The overall yield and purity were highest for the UAE method under acid condition (pH 1-2, approximately), making it the most effective silica extraction method from DE. For this method, the optimal conditions for extracting Si from DE were 2 h of sonication, 220 mL of 2.82 M HCl as a leaching/extracting medium, 0.524 cycles and 72.6 % of amplitude. Under these conditions, 82 % of silica was yielded with a purity of about 95 %. The experimental results indicate that high-quality silica can be produced from DE in high yield so that DE can be an alternative silica source. <![CDATA[<b>Trends in NMR Structural Elucidation Of Polycyclic Cages, Namely: Adamantane, Pentacycloundecane and Trishomocubane</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100010&lng=en&nrm=iso&tlng=en Advances in Nuclear Magnetic Resonance (NMR) spectroscopy is a cornerstone in structure elucidation of polycyclic 'cage' scaffolds. Due to the compactness of these compounds, much overlap, as well as unique through-space and bond NMR interactions are frequently observed. This review serves as a guide for the NMR elucidation of future derivatives by providing some of the typical and relevant aspects of the characteristic trends, substituent patterns and chemical shift behaviour for the identification of the polycyclic structures, namely adamantane, pentacycloundecane and trishomocubane derivatives. <![CDATA[<b>Truncated Edge Cuprous Oxide Cube Architecture for Reduction of Nitrophenols</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100011&lng=en&nrm=iso&tlng=en Truncated cubic Cu-oxide nanocrystals with edge lengths of ca. 600 nm were prepared employing the low-cost copper (II) chloride as the precursor. XRD revealed that the truncated cubic Cu-oxide nanocrystals are present in both the CuI and Cu0 state. XPS characterisation gives insight into the amount of each state present in the as-prepared, oxidised, reduced and recovered catalyst species. The catalytic activity of the truncated cubic Cu-oxide nanocrystals was tested for the reduction of nitrophenols using NaBH4. After one catalytic cycle of the reduction of 4-nitrophenol, the activity almost halved. The SEM images revealed that the recovered catalyst showed some disfigurement of the structure, and XPS confirmed the reduction of the CuI to metallic Cu0. <![CDATA[<b>Degradation of o-Chloranil Using Nanocrystalline-Cellulose/TiO<sub>2</sub> Composites <i>via </i>a Solar Photocatalytic Route</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100012&lng=en&nrm=iso&tlng=en Water pollution by organic pollutants is a continuous and increasing problem of global concern. In this paper, we developed a nanocrystalline cellulose (NCC) and titania (TiO2) based nanocomposite for the photocatalytic degradation of o-chloranil via aqueous wet impregnation. Different NCC loadings (10, 20, 40, and 80%) were used, and several analytical and microscopy techniques characterised the NCC/TiO2 catalyst. The efficiency of TiO2 as a photo-catalyst was enhanced through the chiral nematic nature and potential charge carrier capacity of NCC, which lowered the rate of electron recombination. The NCC/TiO2 material was used in the solar-driven photo-degradation of o-chloranil (3,4,5,6-tetrachloro-1,2-benzoquinone), a by-product of a commonly used pesticide. The successful decomposition of o-chloranil led to the successful identification of three breakdown products, namely 2,3-dichloro-4,5-dioxohex-2-enedoic acid (DCA), 2,3-dioxosuccinic acid (DSA) and oxalic acid (OA). The 20% NCC/TiO2 catalyst was found to be optimum and showed excellent degradation and mineralisation of o-chloranil within 2 hours (~90% degradation after 2 hours or 0.00920 mols of the total 0.0102 mols). The degradation products were analysed and identified using GC-MS. The photo-catalyst offers many benefits, including ease of preparation, a low cost-factor, and high stability with no loss of activity. <![CDATA[<b>Occurrence and Fate of Amoxicillin and Penicillin G Antibiotics in Hospital Wastewater Treatment Plants: A Case Study - Gonbad Kavous, Iran</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100013&lng=en&nrm=iso&tlng=en Release of antibiotics to the environment as a result of wastewater effluent discharge is a cause for concern worldwide, as they pose a potential threat to human health and the earth ecosystem. Penicillin and amoxicillin are widely used antibiotics. Despite their rapid hydrolysis in aqueous matrices, their presence in the environment is widely investigated. The current study reported and analysed the current state of four hospital wastewater treatment plants (WWTPs) in Gonbad Kavous, Iran, during 2019, from the perspective of amoxicillin and penicillin G removals. WWTPs were sampled at various stages of the treatment process to determine at which stage the antibiotics are being removed. Concentrations of amoxicillin and penicillin G in raw wastewater, analysed by HPLC, varied from 0.35 to 1.02 and 0.02-0.31 /AgL-1, respectively. These values reduced in the final effluent, corresponding to overall efficiency in removing the studied antibiotics of 20-60.5%. Anaerobic processes (i.e. septic tank) slightly outperformed aerobic biological processes for both antibiotics' removal, and penicillin G was removed more efficiently than amoxicillin. Effects of wastewater physicochemical properties, including chemical oxygen demand (COD), biochemical oxygen demand (BOD), and total suspended solids (TSS) on antibiotics removal, were also studied. Whereas statistically significant correlations were noticed between COD, amoxicillin and penicillin G removals, their decline showed no correlation with TSS removal. Our study shows that despite the deployment of treatment plants, a considerable amount of antibiotics is released into receiving water bodies, resulting in significant amounts of these pharmaceuticals entering the environment. There is abundant room for further progress in the detection and quantification of pharmaceuticals and other emerging contaminants in hospital wastewaters and their metabolites and biodegradation products. <![CDATA[<b>Bioaccumulation and Human Risk Assessment of Heavy Metals in <i>Oreochromis niloticus </i>and <i>Clarias gariepinus </i>Fish Species from the Golinga Reservoir, Ghana</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100014&lng=en&nrm=iso&tlng=en The Nile tilapia (Oreochromis niloticus) and African catfish (Clarias gariepinus) from the Golinga reservoir in Northern Ghana are consumed as an alternative source of protein. In the current study, levels of selected metals (As, Cd, Fe, Co, Cr, Cu, Mn, Mo, Ni and Pb) in the two fish species and the fish condition were determined, and potential human health effects assessed. The metal concentrations in the edible fish muscles ranged from 0.16 mg kg-1 (Mn) to 101 mg kg-1 (Pb). The weight-length relationships showed that both fish were growing isometrically, and bioaccumulation of metals from the reservoir was considered insignificant with bioconcentration factors below 100 except for Mn, whose value was 161 in the gills of Oreochromis niloticus. The health risk assessment showed that Pb, Cd and As had Target Hazard Quotient values above 1 for both fish species, with that of As being as high as 19.6 for Oreochromis niloticus. The target cancer risk values for As, Cd, Cr and Pb were above the non-risk threshold of <10-6, indicating the risk of cancer developing over the years due to fish consumption. The metal concentration in the fish in the reservoir should therefore be constantly monitored and potential health risks associated with frequent consumption of the fish assessed. <![CDATA[<b>Synthesis and Biological Evaluation of New Chromenes and Chromeno[2,3-d] pyrimidines</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100015&lng=en&nrm=iso&tlng=en A simple and efficient approach has been developed to synthesise novel and functionalised 5H-chromeno[2,3-d] pyrimidines derivatives (4a-h). This approach entails treating 2-amino-3-cyano-4H-chromenes (3a-h) with formamidine acetate under microwave irradiations and solvent-free conditions. All structures of new compounds obtained in this study were characterised by IR, MS, 1H and 13C NMR analysis. Additionally, the synthesised compounds were investigated for their antibacterial and antioxidant potential. Compounds 3b, 3c, 3e, 4c and 4e showed significant activities. <![CDATA[<b>Selective Solid-Phase Extraction Using Molecularly Imprinted Polymers for the Analysis of Target Pesticides in Cannabis Bud</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100016&lng=en&nrm=iso&tlng=en A molecularly imprinted solid-phase extraction (MISPE) procedure was developed for the GC-MS analysis of four high priority pesticides (atrazine, terbuthylazine, acetochlor and alachlor) in a cannabis bud sample matrix. The study demonstrated that the synthesised polymer had a high affinity and good selectivity for either chloroacetamide or triazine classes of pesticide used as a template molecule during the molecularly imprinted polymerisation reaction. The MISPE procedure was optimised in terms of loading, washing and elution fractions utilising a range of aqueous methanol solutions for optimal recovery and minimal matrix interferences. The optimal wash fraction was 20% (v/v) methanol in an aqueous solution, whilst 70% (v/v) was used for the elution fraction. The selectivity, accuracy and recovery of the MISPEs were verified using a synthesised non-imprinted polymer and a commercial C18 cartridge as reference sorbents in comparative experiments. Approximately 3 g of the cannabis bud sample was spiked at a 0.05 mg/kg maximum residue limit (MRL) concentration. The recovery of the four selected pesticides extracted from the spiked samples ranged between 76.4-85.0% when utilising the optimised MISPE methods, compared to 91.6-96.9% for the C18 SPE. However, the use of the MISPE resulted in enhanced selectivity, as evidenced by GC-MS analysis, due to the extraction of less matrix interferences. Therefore, it can be concluded that the MISPE is a viable pre-treatment method for selective pesticide analysis in cannabis flowers using GC-MS when selectivity is valued for the extraction of target pesticides from a complex sample matrix. <![CDATA[<b>Preparation and Characterisation of the Cyano-Bridged Transition Metal Complexes Using N,N-Diethyl Thiourea as a Ligand</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100017&lng=en&nrm=iso&tlng=en New cyano bridged transition metal complexes, [Cu(detu)4Ni(CN)4]-2H2O (1) and [Zn(H2O)(detu)Ni(CN)4]-2H2O (2) (detu = N, N' diethyl thiourea) have been synthesised in powder form. Their structures were illuminated by using spectroscopic, thermal and elemental analysis techniques. The nickel atom exhibits square planar geometry in these complexes by coordinating with the cyano group's nitrogen atoms. The copper atom of 1 is six coordinated with two bridging cyano groups and four detu ligands. In contrast, the zinc atom of 2 is six coordinated with four bridging cyano groups, one detu ligand and one aqua ligand. In addition, the structure of 2 is formed from polymeric layers of |Zn-Ni(CN)(4)1 „ with the detu and aqua ligands bonded to the zinc atom. Thermal stabilities and decomposition products of 1 and 2 were examined in the static air atmosphere between 30 and 900 °C. <![CDATA[<b>Adsorption-Kinetic Studies of Mordant Exhaust Dyeing of Cotton and Silk Fabrics with Dye Extract of <i>M. lucida </i>Plant Species</b>]]> http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502021000100018&lng=en&nrm=iso&tlng=en The kinetics and adsorption isotherms of the extremely slow traditional natural exhaust dyeing that takes many hours or days have been studied purposely to find means of improving the process. The dyeing of cotton and silk fabrics using dye extract of M. lucida at 50 °C were elucidated with graphs to predict the reaction orders and identify the appropriate adsorption isotherm model(s). Since the dye is UV active, changes in UV absorbance were used in place of changes in concentrations. The simultaneous and post mordanting methods followed pseudo-second-order reactions, hence chemisorption. However, mordant application to the dyed fabrics during post mordant followed a pseudo-first-order model, largely physisorption. Dyeing has followed Langmuir and Freundlich isotherm models with linear correlation r² ranging between 1 and 0.998. From the Freundlich model and values of Langmuir constant R L (0.9307 to 1.0), the process is homogeneous, forming a favourable and linear monolayer. Accordingly, the dyeing speed can be improved by increasing the concentration of dye liquor. Additionally, according to the Freundlich model, higher dye intensity on fabrics is recorded in post mordanting.