Synthesized carbon nanodots for simultaneous extraction of personal care products and organophosphorus pesticides in wastewater samples prior to LC-MS/MS determination.

A simple, rapid and efficient solid-phase extraction method based on synthesized carbon nanodots was developed for the preconcentration and extraction of personal care products and organophosphorus pesticides in environmental matrices. Factorial (screening) and central composite designs were employed for the optimization of experimental conditions that could potentially influence the percentage recoveries of the target analytes. The experimental variables, including sample pH, mass of adsorbent, eluent volume and sample volume, were examined. Under the optimized conditions, the developed method was validated, and acceptable analytical results obtained showed good performance. The method accuracy carried out at two spiking levels (10 and 100 µg L-1) in different sample matrices ranged between 63 and 120%. The method precision based on relative standard deviation (% RSD) was < 10%. The linear range studied had a determination coefficient of (R2 > 0.995). The limits of detection (LOD) and limit of quantification (LOQ) established varied between 0.015-0.125 and 0.05-0.415 µg L-1 ,respectively. The ensuing method was applied successfully in the determination of the five multi-class organic compounds under study, in influent and effluent wastewater matrices, sampled from a municipal wastewater treatment plant located in Pretoria, South Africa.

Chemical Vapour Deposition of MWCNT on Silica Coated Fe3O4 and Use of Response Surface Methodology for Optimizing the Extraction of Organophosphorus Pesticides from Water.

Multiwalled carbon nanotube (MWCNT) was fixed onto the surface of a magnetic silica (Fe3O4@SiO2) substrate via chemical vapour deposition (CVD). Acetylene gas was used as the carbon source and cobalt oxide as the catalyst. The chemical and physical characteristics of the materials were investigated by transmission electron microscopy (TEM), Raman spectroscopy (RS), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), and nitrogen adsorption/desorption isotherm. The synthesized Fe3O4@SiO2-MWCNT nanocomposite was used as a magnetic solid phase extraction (MSPE) adsorbent for the preconcentration of organophosphorus pesticides (OPPs), specifically, azinphos methyl, chlorpyrifos, parathion, and malathion. The factors influencing the extraction efficiency such as pH, contact time, and adsorbent dosage were investigated and optimized by response surface methodology (RSM) and desirability function. Linear response was obtained in the concentration range of 10-200 µg/L for the analytes with determination coefficients ranging between 0.9955 and 0.9977. The limits of detection (LODs) and quantification (LOQs) were in the range of 0.004-0.150 µg/L and 0.013-0.499 µg/L, respectively. Fe3O4@SiO2-MWCNT was applied in the extraction and subsequent determination of OPPs in water samples from Vaal River and Vaal Dam with recoveries ranging from 84.0 to 101.4% (RSDs = 3.8-9.6%, n = 3) in Vaal River and 86.2 to 93.8% (RSDs = 2.9-10.4%, n = 3) in Vaal Dam. The obtained results showed that the newly synthesized Fe3O4@SiO2-MWCNT nanocomposite can be an efficient adsorbent with good potential for the preconcentration and extraction of selected OPPs from aqueous media.

Impact of Pyridyl Moieties on the Inhibitory Properties of Prominent Acyclic Metal Chelators Against Metallo-ß-Lactamase-Producing Enterobacteriaceae: Investigating the Molecular Basis of Acyclic Metal Chelators' Activity.

Carbapenem-resistant Enterobacteriaceae (CREs)-mediated infections remain a huge public health concern. CREs produce enzymes such as metallo-ß-lactamases (MBLs), which inactivate ß-lactam antibiotics. Hence, developing efficient molecules capable of inhibiting these enzymes remains a way forward to overcoming this phenomenon. In this study, we demonstrate that pyridyl moieties favor the inhibitory activity of cyclic metal-chelating agents through in vitro screening, molecular modeling, and docking assays. Di-(2-picolyl) amine and tris-(2-picolyl) amine exhibited great efficacy against different types of MBLs and strong binding affinity for NDM-1, whereas 2-picolyl amine did not show activity at a concentration of 64 mg/L in combination with meropenem; it further showed the lowest binding affinity from computational molecular analysis, commensurating with the in vitro screening assays. The findings revealed that the pyridyl group plays a vital role in the inhibitory activity of the tested molecules against CREs and should be exploited as potential MBL inhibitors.

Photoelectrocatalytic application of palladium decorated zinc oxide-expanded graphite electrode for the removal of 4-nitrophenol: experimental and computational studies.

A novel Pd-ZnO-expanded graphite (EG) photoelectrode was constructed from a Pd-ZnO-EG nanocomposite synthesised by a hydrothermal method and characterised using various techniques such as X-ray diffractometry (XRD), Raman spectroscopy, UV-Vis diffuse reflectance spectroscopy, nitrogen adsorption-desorption analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS). Cyclic voltammetry and photocurrent response measurements were also carried out on the electrode. The Pd-ZnO-EG electrode was employed in the photoelectrocatalytic removal of 4-nitrophenol as a target water pollutant at a neutral pH and with a current density of 7 mA cm-2. Optical studies revealed that the Pd-ZnO-EG absorbed strongly in the visible light region. The Pd-ZnO-EG electrode showed improved photoelectrocatalytic activity in relation to ZnO-EG and EG electrodes for the removal of the 4-nitrophenol. The photocurrent responses showed that the Pd-ZnO-EG nanocomposite electrode could be employed as a good photoelectrode for photoelectrocatalytic processes and environmental remediation such as treatment of industrial waste waters. Density functional theory method was used to model the oxidative degradation of 4-nitrophenol by the hydroxyl radical which generates hydroquinone, benzoquinone, 4-nitrocatechol, 4-nitroresorcinol and the opening of the 4-nitrophenol ring. Furthermore, the hydroxyl radical is regenerated and can further oxidise the ring structure and initiate a new degradation process.

Monitoring the fate and behavior of TiO2 nanoparticles: Simulated in a WWTP with industrial dye-stuff effluent according to OECD 303A.

The use of nanoparticles (NPs) in several consumer products has led to them finding their way into wastewater treatment plants (WWTPs). Some of these NPs have photocatalytic properties, thus providing a possible solution to textile industries to photodegrade dyes from their wastewater. Thus, the interaction of NPs with industrial dye effluents is inevitable. The Organization for Economic Co-operation and development (OECD) guideline for testing of chemical 303A was employed to study the fate and behaviour of TiO2 NPs in industrial dye-stuff effluent. This was due to the unavailability of NPs' fate and behaviour test protocols. The effect of TiO2 NPs on the treatment process was ascertained by measuring chemical oxygen demand (COD) and 5-day biological oxygen demand (BOD5). Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used to study the fate and behavior of TiO2 NPs. Acclimatization of bacteria to target pollutants was a crucial factor for the treatment efficiency of activated sludge in a simulated wastewater treatment plant (SWTP). The acclimatization of the activated sludge to the synthetic industrial dye-stuff effluent was successfully achieved. Effect of TiO2 NPs on the treatment process efficiency was then investigated. Addition of TiO2 NPs had no effect on the treatment process as chemical oxygen demand (COD) removal remained >80%. Measured total plate count (TPC) affirmed that the addition of TiO2 NPs had no effect on the treatment process. The removal of total nitrogen (TN) was not efficient as the treatment system was required to have an oxic and anoxic stage for efficient TN removal. Results from X-ray powder diffraction (XRD) confirmed that the anatase phase of the added TiO2 NPs remained unchanged even after exposure to the treatment plant. Removal of the NPs from the influent was facilitated by biosorption of the NPs on the activated sludge. Nanoparticles received by wastewater treatment plants will therefore reach the environment through sludge waste dumped in landfill. About 90% of TiO2 was retained in the activated sludge, and 10-11% escaped with the treated effluents. Scanning electron microscope (SEM) mapping micrographs together with an energy dispersive X-ray spectroscopy (EDS) confirmed the presence of Ti in the sludge.

Electrospun and functionalized PVDF/PAN nanocatalyst-loaded composite for dechlorination and photodegradation of pesticides in contaminated water.

A novel approach for the electrospinning and functionalization of nanocatalyst-loaded polyvinylidene fluoride/polyacrylonitrile (PVDF/PAN) composite grafted with acrylic acid (AA; which form polyacrylic acid (PAA) brush) and decorated with silver (Ag/PAN/PVDF-g-PAA-TiO2/Fe-Pd) designed for the dechlorination and photodegradation of pesticides was carried out. PAN was used both as a nitrogen dopant as well as a co-polymer. Smooth nanofibers were obtained by electrospinning a solution of 12:2 wt.% PVDF/PAN blend using dimethylformamide (DMF) as solvent. The nanofibers were grafted with AA by free-radical polymerization using 2,2'azobis(2-methylpropionitrile) (AIBN) as initiator. Both bimetallic iron-palladium (Fe-Pd) and titania (TiO2) nanoparticles (NP) were anchored on the grafted nanofibers via the carboxylate groups by in situ and ex situ synthesis. The Fe-Pd and nitrogen-doped TiO2 nanoparticles were subsequently used for dechlorination and oxidation of target pollutants (dieldrin, chlorpyrifos, diuron, and fipronil) to benign products. Structural and chemical characterizations of the composites were done using various techniques. These include surface area and porosity analyzer (ASAP) using the technique by Brunner Emmett Teller (BET), Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM) analyses were done. After dechlorination, the transformation products (TPs) for dieldrin, chlorpyrifos, diuron, and fipronil were obtained and identified using two-dimensional gas chromatography (time-of-flight) with a mass spectrometer detector (GCxGC-TOFMS). Analysis of total organic carbon (TOC) was carried out and used to extrapolate percentage mineralization. Experimental results showed that dechlorination efficiencies of 96, 93, 96, and 90 % for 1, 2, 2, and 3 h treatment period were respectively achieved for 5 ppm solutions of dieldrin, chlorpyrifos, diuron, and fipronil. The dechlorination of dieldrin, diuron, and fipronil follows first-order kinetics while that of chlorpyrifos followed pseudo-first order. Mineralization performance of 34 to 45 % were recorded when Fe-Pd was used, however upon electrospinning, doping, and grafting (Ag/PAN/PVDF-g-PAA-TiO2/Fe-Pd composite); it significantly increased to 99.9999 %. This composite reveals great potential for dechlorination and mineralization of pesticides in contaminated water.