South African Journal of Chemistry - latest Issue

The use of RNA macromolecules as therapeutic agents for HIV and other infectious diseases is promising but limited by suboptimal delivery to the target site. With HIV infection, this is particularly challenging since lymphocytes are particularly difficult to transfect. This paper describes an innovative strategy for the intracellular delivery of a novel single-stranded RNA (oligoribonucleotide) with putative anti-HIV activity. This strategy is based on a PEGylated gold nanoparticle scaffold covalently linked to the thiol-modified oligoribonucleotide via a cleavable N-succinimidyl 3-(2-pyridyldithio) propionate (SPDP) linker molecule. The nanoparticle was then coated with a cationic polymer (polyethyleneimine) to facilitate cell entry and endosomal escape. A synthetic anti-CD4 cyclic targeting peptide was attached to the polyethyleneimine-coated nanoparticle via an SPDP linker molecule, in an attempt to enhance uptake and selectivity. Synthesis, characterization, SPDP and RNA loading, cytotoxicity and antiviral activity of the nanoparticle are described. Approximately 45 000 strands of RNA were taken up per lymphocyte. Uptake was limited by relatively inefficient loading ofRNAonto the gold nanoparticle surface (1 strand per 4.8 nm2 of nanoparticle surface area) and significant aggregation of the nanoparticle in physiological solutions. No antiviral activity was demonstrated, possibly due to insufficient intracytoplasmic delivery of the RNA.

A low-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.

A LC-HRMS (liquid chromatography coupled with high resolution mass spectrometry) method for the detection and quantitation of several synthetic cannabinoids (JWH-018, JWH-019, JWH-073, JWH-081, JWH-122 JWH-200, JWH-250, AM-2201, (±)-CP 47,497, (C8)-CP 47,497, HU-211) and selected metabolites (JWH-018 N-(4-hydroxypentyl) and JWH-073 N-(3-hydroxybutyl)) in whole blood and urine was developed and validated. These methods were applied to postmortem cases from the Johannesburg Forensic Pathology Services Medicolegal Laboratory (FPS-MLL) to assess the prevalence of these synthetic cannabinoids amongst the local postmortem population. Urine samples were extracted utilizing a solid phase extraction (SPE) method, while blood samples were extracted utilizing liquid-liquid extraction (LLE) method. The accuracy of the analytes ranged from 88–107 % in whole blood (relative standard deviation (RSD) = 7.5–15.0 %), and from 95–109 % in urine (RSD = 4.9–11.9 %). The limits of detection (LOD) and the limits of quantitation (LOQ) for the analytes ranged between 0.675 ng mL^–1 and 3.375 ng mL^–1 in whole blood, and between 0.225 ng mL^–1 to 3.375 ng mL^–1 in urine. None of the postmortem cases tested positive for any of the targeted analytes. The sample population could be extended to living subjects such as those in drug rehabilitation centres or in hospitals to obtain a more accurate representation of the overall usage in South Africa.

The aluminium corrosion inhibition behaviour in the presence of Areca palm leaves (AL) extract in hydrochloric acid (0.5 M) medium was examined by chemical (mass loss), AC impedance spectroscopy, potentiodynamic polarization and surface (scanning electron microscopy) methods. Aluminium protection rates increased with an increase in the amount of AL extract to the 0.5 M HCl system and decreased with increasing in the contact time of aluminium metal and temperature of 0.5 M HCl solution. Arrhenius equation was applied in the determination of activation energy values. The other activation parameters such as activation entropy and enthalpy values were obtained from the transition state plot. The adsorption of AL extract species on the Al surface in 0.5 M HCl solution follows the Langmuir adsorption mechanism. Tafel curves reflect the mixed (both anodic and cathodic) inhibition behaviour of green inhibitor (AL extract species) on electrode surface (Al) in 0.5 M system. Impedance method indicates that the Al dissolution in hydrochloric acid environment was fully hindered by charge transfer process. The Al surface morphology was examined by applying scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques.

A fast and sensitive method was developed for determination of glyphosate, using flow injection analysis. The analyte was converted to a photoactive product that shows maximum absorbance at 405 nm. Beer’s law was obeyed over a range of 0.7–20 μg mL^–1. The limit of detection and quantification were found to be 0.20±0.01 and 0.70±0.02 μg mL^–1 with a high sample throughput of 60 samples h^–1. The investigation of interference effect shows that among the compounds studied, only aminomethyl phosphonic acid exhibits a signal enhancing effect when present in higher concentration ratio with the analyte and this can be assumed to be a limitation of the present method. The percentage recoveries and residue of glyphosate in wheat grains samples, were found in the range of 90.0 ± 0.6 % to 93.0 ± 0.6 % and 1.13 ± 0.009 μg g^–1, respectively.

This paper gives an overview of the application of hydrazide derivatives in acid media as corrosion inhibitors of mild steel. In chemical and petrochemical industries, mild steel is the major constructional material widely used. Acid solutions have been commonly used in these industries as pickling agents to remove rust or any scale from the mild steel surface. The excessive dissolution of mild steel in such aggressive medium can be best controlled by addition of suitable organic inhibitors. Hydrazide derivatives are widely used in such applications as mild steel corrosion inhibitors. The various factors which influence the corrosion inhibition efficiency of different hydrazide derivatives have been discussed. The information provided is useful for various industries where corrosion inhibitors are needed to protect mild steel structures which are being exposed to hydrochloric or sulphuric acid solutions.