A review on reactive oxygen species-induced mechanism pathways of pharmaceutical waste degradation: Acetaminophen as a drug waste model.

Innately designed to induce physiological changes, pharmaceuticals are foreknowingly hazardous to the ecosystem. Advanced oxidation processes (AOPs) are recognized as a set of contemporary and highly efficient methods being used as a contrivance for the removal of pharmaceutical residues. Since reactive oxygen species (ROS) are formed in these processes to interact and contribute directly toward the oxidation of target contaminant(s), a profound insight regarding the mechanisms of ROS leading to the degradation of pharmaceuticals is fundamentally significant. The conceptualization of some specific reaction mechanisms allows the design of an effective and safe degradation process that can empirically reduce the environmental impact of the micropollutants. This review mainly deliberates the mechanistic reaction pathways for ROS-mediated degradation of pharmaceuticals often leading to complete mineralization, with a focus on acetaminophen as a drug waste model.

Poly-(ionic liquid) coated with magnetic nanoparticles for micro solid phase extraction of polycyclic aromatic hydrocarbons in food samples.

Poly(methyl methacrylate-vinyl imidazole bromide) (poly-MMA-IL)-grafted magnetic nanoparticles were successfully developed and applied in the micro-magnetic solid phase extraction (µ-MSPE) for 16 types of polycyclic aromatic hydrocarbons (PAHs) from tea, fried food, and grilled food samples via gas chromatography flame ionization detector (GC-FID). One variable at a time (OVAT) and response surface methodology (RSM) were used for efficient optimization. The validation method showed a good coefficient of determination (R2) ranging from 0.9901 to 0.9982 (n = 3) with linearity of 0.2 µg L-1-500 µg L-1. Detection and quantification limits were 0.06 µg L-1-0.32 µg L-1 and 0.18 µg L-1-0.97 µg L-1. Additionally, satisfactory reproducibility was attained with intra-day and inter-day precisions having RSD ranges of 3.6%-11.1%. The spiked recovery value of 16 PAHs in fried food, grilled food and tea samples obtained from the night market in Malaysia ranged from 80%-12%, respectively.

The New Materials for Battery Electrode Prototypes.

In this article, we present the performance of Copper (Cu)/Graphene Nano Sheets (GNS) and C-π (Graphite, GNS, and Nitrogen-doped Graphene Nano Sheets (N-GNS)) as a new battery electrode prototype. The objectives of this research are to develop a number of prototypes of the battery electrode, namely Cu/GNS//Electrolyte//C-π, and to evaluate their respective performances. The GNS, N-GNS, and primary battery electrode prototypes (Cu/GNS/Electrolyte/C-π) were synthesized by using a modified Hummers method; the N-doped sheet was obtained by doping nitrogen at room temperature and the impregnation or the composite techniques, respectively. Commercial primary battery electrodes were also used as a reference in this research. The Graphite, GNS, N-GNS, commercial primary batteries electrode, and battery electrode prototypes were analyzed using an XRD, SEM-EDX, and electrical multimeter, respectively. The research data show that the Cu particles are well deposited on the GNS and N-GNS (XRD and SEM-EDX data). The presence of the Cu metal and electrolytes (NH4Cl and MnO2) materials can increase the electrical conductivities (335.6 S cm-1) and power density versus the energy density (4640.47 W kg-1 and 2557.55 Wh kg-1) of the Cu/GNS//Electrolyte//N-GNS compared to the commercial battery (electrical conductivity (902.2 S cm-1) and power density versus the energy density (76 W kg-1 and 43.95 W kg-1). Based on all of the research data, it may be concluded that Cu/GNS//Electrolyte//N-GNS can be used as a new battery electrode prototype with better performances and electrical activities.

Progress in Electrochemical Sensing of Heavy Metals Based on Amino Acids and Its Composites.

A detailed overview toward the advancement of amino acid-based electrochemical sensors on the detection of heavy metals is presented. Discussion is focused on the unique properties of various amino acids (AAs) and its composites which allow them being employed in a diverse range of sensing platforms. Formation of metal-ligand complexes in between metal ions and different AAs has been discussed. The essential insights on the interaction between amino acid-based sensors and target heavy metal ions (HMIs) are provided, along with the discussion on their pros and cons. Voltammetry analysis of metal ions based on various interfaces of electrochemical sensors has been highlighted, together with the incorporation of AAs with organic, inorganic and bio-materials. In all these cases, the amino acid modified electrodes have demonstrated large active surface area with abundant adsorption sites for HMIs. The developed sensors are promising for environmental applications, as evidenced by the high selectivity, high sensitivity, high catalytic activity, and low detection limits. The materials involved, fabrication techniques and its sensing mechanism were comprehensively discussed, and the future outlooks of electrochemical sensing platforms are emphasized in this review.

Hierarchical Activated Carbon-MnO2 Composite for Wide Potential Window Asymmetric Supercapacitor Devices in Organic Electrolyte.

The consumption of electrical energy grows alongside the development of global industry. Generating energy storage has become the primary focus of current research, examining supercapacitors with high power density. The primary raw material used in supercapacitor electrodes is activated carbon (AC). To improve the performance of activated carbon, we used manganese dioxide (MnO2), which has a theoretical capacitance of up to 1370 Fg-1. The composite-based activated carbon with a different mass of 0-20% MnO2 was successfully introduced as the positive electrode. The asymmetric cell supercapacitors based on activated carbon as the anode delivered an excellent gravimetric capacitance, energy density, and power density of 84.28 Fg-1, 14.88 Wh.kg-1, and 96.68 W.kg-1, respectively, at 1 M Et4NBF4, maintaining 88.88% after 1000 test cycles.

Rational Design of a Fluorescent Chromophore as a Calcium Receptor via DFT and Multivariate Approaches.

Computational and experimental approaches were adopted to utilize a chromophore diglycolic functionalized fluorescein derivative as a Ca2+ receptor. Fluorescein diglycolic acid (Fl-DGA, 1) was synthesized and used in multivariate determination of Ca2+ and K+. Full-structure computation shows that the complexes of 1 and Ca2+ have comparable energies regardless of additional interaction with lactone moiety. The initial formation of diglycolic-Ca2+ complex followed by macrocyclization is thermodynamically disfavored. A U-shaped pre-organized 1 allows Ca2+ to interact simultaneously with diglycolic and lactone motifs. Both motifs actively participate in Ca2+ recognition and the eleven methylene units in the undecyl arm provides excellent flexibility for reorganization and optimum interaction. Principal component analysis (PCA) of computational molecular properties reveals a simple method in evaluating motifs for cation recognition. Fragment models support full-structure results that negative charge causes significant structural changes, but do not reproduce the full extent of C-O bond breaking observed in the latter. Experimental optical responses show that 1 is selective towards Ca2+ and discriminates against K+ and Mg2+. PCA of emission intensities affords distinct clusters of 0.01, 0.1 and 1 mM Ca2+ and K+, and suggests applicability of this technique for simultaneous determination of cationic plant macronutrients in precision agriculture and a wide variety of other applications.

Dispersive Membrane Microextraction of Substituted Phenols from Honey Samples and a Brief Outlook on Its Sustainability Using Analytical Eco-Scale and Analytical GREEnness Metric Approach.

Honey is part and parcel of our daily nutrition, but in recent times it has been reported to be tainted by the presence of polar substituted phenols purported from the use of pesticides, herbicides, antimicrobial agents, etc. Honey's viscous nature and matrix complexity often result in analytical chemists resorting to derivatization for the detection of polar analytes such as substituted phenols. This study aims to overcome the matrix effect without derivatization and offer a more sustainable solution with notable sensitivity and selectivity using dispersive membrane microextraction alongside high-performance liquid chromatography (DMME-HPLC) with sporopollenin-methylimidazolium-based mixed matrix membrane (Sp-MIM-MMM). The DMME-HPLC approach successfully determined the presence of mono- and disubstituted phenols from unspiked honey samples with concentrations ranging from 7.8 to 154.7 ng/mL. The sustainability of the proposed method was also validated using the Analytical Eco-Scale (AES) and the Analytical GREEnness Metric (AGREE) where an excellent score of 94 and the encouraging score of 0.72 were recorded, respectively.

Three-dimensional porous calcium alginate fluorescence bead-based immunoassay for highly sensitive early diagnosis of breast cancer.

A sensitive biosensor capable of detecting trace concentrations of several cancer biomarkers in clinical samples is critical for early detection of cancer because different cancer biomarkers may be expressed at different stages of cancer. Previous multiplex studies using microarrays or color-coded beads had limited multiplex detection in a single well, and difficulty in optimizing and unifying the incubation parameters for all tests made in different wells had posed challenges to small sample size and lengthened assay time. Herein, we proposed a novel approach to achieve multiplex analysis on a single three-dimensional porous calcium alginate bead. Because of the high surface area to volume ratio of the calcium alginate immuno-bead, the sensitivity and linear dynamic range of the as-proposed multiplex analysis method are significantly improved. Based on the direct sandwich immunoassay principle, dual-capturing antibodies were encapsulated into a single 3D porous calcium alginate bead as a proof-of-concept for multiplexity detection of serum-HER2 and serum-CA125 breast cancer biomarkers. High sensitivity was attained, with LODs of 0.004 ng mL-1 for serum HER2, and 0.005 U mL-1 for serum CA125, both of which are below the clinical cutoff values, enabling for early breast cancer diagnosis. Stability tests revealed that the 3D immuno-beads were stable at 4 °C and room temperature (25 °C) for at least 14 days. Most importantly, the results obtained using the developed system were in good agreement with those obtained using standard methods while analyzing real clinical samples. In addition, the analysis required only approximately 30 min, which was much less time than typical ELISA techniques. When endogenous interferences were introduced, no cross-reactivity was observed. We anticipate this approach to be potentially used in the multiplex assays and biosensors.

Polymer-modified mesoporous silica microcubes (P@MSMCs) for the synergistic oxidative entrapment of Ag(i), Ti(iv), and Zn(ii) from natural river water.

Herein, we demonstrate a hydrothermal route to the one-pot synthesis of polymeric mesoporous silica microcubes (P@MSMCs) for the adsorption of heavy metal ions. During the synthesis of P@MSMCs from column silica gel, the roles and combination of the polymer and an etchant were characterized. Moreover, the porosity of P@MSMCs was tailored by adjusting the reaction temperature between 75 °C and 200 °C. The characterization through UV, FTIR, FESEM, XRD, BET, and EDX techniques exhibited that P@MSMCs have a well-ordered mesoporous structure with cubic morphology. The P@MSMCs had a diameter of 2 µm, with an average pore volume and pore size of 0.69 cm3 g-1 and 10.08 nm, respectively. The results indicated that the P@MSMCs have excellent adsorption capacity for Ag(i), Ti(iv), and Zn(ii) due to the formation of an aggregated complex. These aggregations led to affordable density difference-based separation of these metal ions through centrifugation, filtration or simple decantation. The removal efficiencies for Ag(i), Ti(iv), and Zn(ii) were observed to be 520, 720, and 850 mg g-1, respectively. The kinetic studies demonstrated that the adsorption performance fitted well to the pseudo-second-order kinetic model. The as-synthesized P@MSMCs were stable in the wide pH range of 4-8. Significantly, the recycling or reuse results displayed effective adsorption performance of these P@MSMCs for up to 5 cycles. The adsorption results obtained herein will promote the development of similar strategies for the removal of heavy metal ions from natural water.

Voltammetric sensing of formaldehyde by using a nanocomposite prepared by reductive deposition of palladium and platinum on polypyrrole-coated nitrogen-doped reduced graphene oxide.

The study presents the synthesis of polypyrrole-coated palladium platinum/nitrogen-doped reduced graphene oxide nanocomposites (PdPt-PPy/N-rGO NC) via direct the reduction of Pd(II) and Pt(II) in the presence of pyrrole monomer, N-rGO and L-cysteine as the reducing agent. X-ray diffraction confirmed the presence of metallic Pd and Pt from the reduction of Pd and Pt cations. Transmission electron microscopy images revealed the presence of Pd, Pt and PPy deposition on N-rGO. Impedance spectroscopy results gave a decreased charge transfer resistance due to the presence of N-rGO. The nanocomposites were synthesized with different Pd/Pt ratios (2:1, 1:1 and 1:2). A glassy carbon electrode (GCE) modified with the nanocomposite showed enhanced electrochemical sensing capability for formaldehyde in 0.1 M sulfuric acid solution. Cyclic voltammetry showed an increase in the formaldehyde oxidation peak current at the GCE modified with Pd2Pt1 PPy N-rGO. At a typical potential of 0.45 V (vs. SCE), the sensitivity in the linear segment was 345.8 µA.mM -1. cm-2. The voltammetric response was linear between 0.01 and 0.9 mM formaldehyde concentration range, with a 27 µM detection limit (at S/N = 3). Graphical abstract Schematic presentation of formaldehyde detection by Pd2Pt1-PPy/nitrogen-doped reduced Graphene Oxide Nanocomposite (Pd2Pt1-PPy /N-Gr NC). The decrease of charge transfer resistance and the agglomeration of deposited metals in the presence of N-rGO enhance the current response of the electrochemical sensor.

L-Glutamine-assisted synthesis of ZnO oatmeal-like/silver composites as an electrochemical sensor for Pb2+ detection.

We report a green synthesis of oatmeal ZnO/silver composites in the presence of L-glutamine as an electrochemical sensor for Pb2+ detection. The synthesis was performed via the direct reduction of Ag+ in the presence of L-glutamine in NaOH. X-ray diffraction indicated that the Ag+ was completely reduced to metallic Ag. The field emission scanning electron microscopy (FESEM) and energy dispersive X-ray results confirmed an oatmeal-like morphology of the ZnO with the presence of Ag. The FESEM images showed the effect of L-glutamine on the ZnO morphology. The EIS results confirmed a significant decrease in the charge transfer resistance of the modified glassy carbon electrode due to the presence of Ag. From the differential pulse voltammetry results, a linear working range for the concentration of Pb2+ between 5 and 6 nM with LOD of 0.078 nM (S/N = 3) was obtained. The sensitivity of the linear segment is 1.42 µA nM-1 cm-2. The presence of L-glutamine as the capping agent and stabilizer decreases the size of Ag nanoparticles and prevents the agglomeration of ZnO, respectively. Graphical abstract ᅟ.

Transport and retention behavior of carbonaceous colloids in natural aqueous medium: Impact of water chemistry.

Carbon based materials are emerging as a sustainable alternative to their metal-oxide counterparts. However, their transport behavior under natural aqueous environment is poorly understood. This study investigated the transport and retention profiles of carbon nanoparticles (CNPs) and graphene oxide quantum dots (GOQDs) through column experiments in saturated porous media. CNPs and GOQDs (30 mg/L) were dispersed in natural river water (RW) and passed through the column at a flow rate of 1 mL/min, which mimicking the natural water flow rate. After every 10 min, the column effluents were collected and the mass recovery and retention profiles were monitored. Results indicated that the transport of both carbonaceous colloids was predominantly controlled by surface potential and ionic composition of natural water. The CNPs with its high surface potential (-40 mV) exhibited more column transport and was less susceptible to solution pH (5.6-6.8) variation as compared to GOQDs (-24 mV). The results showed that, monovalent salt (NaCl) was one of the dominating factors for the retention and transport of carbonaceous colloids compared to divalent salt (CaCl2). Furthermore, the presence of natural organic matter (NOM) increased the transport of both carbonaceous colloids and thereby decreases the tendency for column retention.

Toxicity evaluation of ZnO and TiO2 nanomaterials in hydroponic red bean (Vigna angularis) plant: Physiology, biochemistry and kinetic transport.

The toxicity and kinetic uptake potential of zinc oxide (ZnO) and titanium dioxide (TiO2) nanomaterials into the red bean (Vigna angularis) plant were investigated. The results obtained revealed that ZnO, due to its high dissolution and strong binding capacity, readily accumulated in the root tissues and significantly inhibited the physiological activity of the plant. However, TiO2 had a positive effect on plant physiology, resulting in promoted growth. The results of biochemical experiments implied that ZnO, through the generation of oxidative stress, significantly reduced the chlorophyll content, carotenoids and activity of stress-controlling enzymes. On the contrary, no negative biochemical impact was observed in plants treated with TiO2. For the kinetic uptake and transport study, we designed two exposure systems in which ZnO and TiO2 were exposed to red bean seedlings individually or in a mixture approach. The results showed that in single metal oxide treatments, the uptake and transport increased with increasing exposure period from one week to three weeks. However, in the metal oxide co-exposure treatment, due to complexation and competition among the particles, the uptake and transport were remarkably decreased. This suggested that the kinetic transport pattern of the metal oxide mixtures varied compared to those of its individual constituents.

Enhanced amperometric detection of paracetamol by immobilized cobalt ion on functionalized MWCNTs - Chitosan thin film.

In the present study, a nanocomposite of f-MWCNTs-chitosan-Co was prepared by the immobilization of Co(II) on f-MWCNTs-chitosan by a self-assembly method and used for the quantitative determination of paracetamol (PR). The composite was characterized by field emission scanning electron microscopy (FESEM) and energy dispersive x-ray analysis (EDX). The electroactivity of cobalt immobilized on f-MWCNTs-chitosan was assessed during the electro-oxidation of paracetamol. The prepared GCE modified f-MWCNTs/CTS-Co showed strong electrocatalytic activity towards the oxidation of PR. The electrochemical performances were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). Under favorable experimental conditions, differential pulse voltammetry showed a linear dynamic range between 0.1 and 400 µmol L-1 with a detection limit of 0.01 µmol L-1 for the PR solution. The fabricated sensor exhibited significant selectivity towards PR detection. The fabricated sensor was successfully applied for the determination of PR in commercial tablets and human serum sample.

Assessment of groundwater salinity and quality in Gaza coastal aquifer, Gaza Strip, Palestine: An integrated statistical, geostatistical and hydrogeochemical approaches study.

A comprehensive study was conducted to identify the salinization origins and the major hydrogeochemical processes controlling the salinization and deterioration of the Gaza coastal aquifer system through a combination approaches of statistical and geostatistical techniques, and detailed hydrogeochemical assessments. These analyses were applied on ten physicochemical variables for 219 wells using STATA/SE12 and Surfer softwares. Geostatistical analysis of the groundwater salinity showed that seawater intrusion along the coastline, and saltwater up-coning inland highly influenced the groundwater salinity of the study area. The hierarchical cluster analysis (HCA) technique yielded seven distinct hydrogeochemical signature clusters; (C1&C2: Eocene brackish water invasion, C3 saltwater up-coning, C4 human inputs, C5 seawater intrusion, C6 & C7 rainfall and mixing inputs). Box plot shows a wide variation of most of the ions while Chadha's plot elucidates the predominance of Na-Cl (71.6%) and Ca/Mg-Cl (25%) water types. It is found that, the highest and the lowest levels of salinization and the highest level of nitrate pollution were recorded in the northern area. This result reflects the sensitivity of this area to the human activities and/or natural actions. Around 90.4% of the wells are nitrate polluted. The main source of nitrate pollution is the sewage inputs while the farming inputs are very limited and restricted mostly in the sensitive northern area. Among the hydrogeochemical processes, ion exchange process was the most effective process all over the study area. Carbonate dissolution was common in the study area with the highest level in clusters 6, 7, 4 and 2 in the north while Gypsum dissolution was significant only in cluster 1 in the south and limited in the other clusters. This integrated multi-techniques research should be of benefit for effective utilization and management of the Gaza coastal aquifer system as well as for future work in other similar aquifers systems.

Immunofluorescence-based biosensor for the determination of dengue virus NS1 in clinical samples.

The sharp increase in incidence of dengue infection has necessitated the development of methods for the rapid diagnosis of this deadly disease. Here we report the design and development of a reliable, sensitive, and specific optical immunosensor for the detection of the dengue nonstructural protein 1 (NS1) biomarker in clinical samples obtained during early stages of infection. The present optical NS1 immunosensor comprises a biosensing surface consisting of specific monoclonal NS1 antibody for immunofluorescence-based NS1 antigen determination using fluorescein isothiocyanate (FITC) conjugated to IgG antibody. The linear range of the optical immunosensor was from 15-500ngmL-1, with coefficient of determination (R2) of 0.92, high reproducibility (the relative standard deviation obtained was 2%), good stability for 21days at 4°C, and low detection limit (LOD) at 15ngmL-1. Furthermore, the optical immunosensor was capable of detecting NS1 analytes in plasma specimens from patients infected with the dengue virus, with low cross-reaction with plasma specimens containing the Japanese encephalitis virus (JEV) and Zika virus. No studies have been performed on the reproducibility and cross-reactivity regarding NS1 specificity, which is thus a limitation for optical NS1 immunosensors. In contrast, the present study addressed these limitations carefully where these two important experiments were conducted to showcase the robustness of our newly developed optical-based fluorescence immunosensor, which can be practically used for direct NS1 determination in any untreated clinical sample.

Reviews of the toxicity behavior of five potential engineered nanomaterials (ENMs) into the aquatic ecosystem.

Presently, engineered nanomaterials (ENMs) are used in a wide variety of commercial applications, resulting in an uncontrolled introduction into the aquatic environment. The purpose of this review is to summarize the pathways and factors that controlling the transport and toxicity of five extensively used ENMs. These toxicological pathways are of great importance and need to be addressed for sustainable implications of ENMs without environmental liabilities. Here we discuss five potentially utilized ENMs with their possible toxicological risk factors to aquatic plants, vertebrates model and microbes. Moreover, the key effect of ENMs surface transformations by significant reaction with environmental objects such as dissolved natural organic matter (DOM) and the effect of ENMs surface coating and surface charge will also be debated. The transformations of ENMs are subsequently facing a major ecological transition that is expected to create a substantial toxicological effect towards the ecosystem. These transformations largely involve chemical and physical processes, which depend on the properties of both ENMs and the receiving medium. In this review article, the critical issues that controlling the transport and toxicity of ENMs are reviewed by exploiting the latest reports and future directions and targets are keenly discussed to minimize the pessimistic effects of ENMs.

Geochemical characteristics of rare earth elements in different types of soil: A chemometric approach.

Rare earth elements (REEs) are becoming significant due to their huge applications in many industries, large-scale mining and refining activities. Increasing usage of such metals pose negative environmental impacts. In this research ICP-MS has been used to analyze soil samples collected from former ex-mining areas in the depths of 0-20 cm, 21-40 cm, and 41-60 cm of residential, mining, natural, and industrial areas of Perak. Principal component analysis (PCA) revealed that soil samples taken from different mining, industrial, residential, and natural areas are separated into four clusters. It was observed that REEs were abundant in most of the samples from mining areas. Concentration of the rare elements decrease in general as we move from surface soil to deeper soils.

Assessing anthropogenic levels, speciation, and potential mobility of rare earth elements (REEs) in ex-tin mining area.

A study was carried out to determine the level of rare earth elements (REEs) in water and sediment samples from ex-mining lakes and River in Kinta Valley, Perak, Malaysia. Surface water and sediments from an ex-mining lake and Kinta River water samples were analyzed for REEs by inductively coupled plasma mass spectrometry. The total concentration of REEs in the ex-mining lake water samples and sediments were found to be 3685 mg/l and 14159 mg/kg, respectively, while the total concentration of REEs in Kinta River water sample was found to be 1224 mg/l. REEs in mining lake water were found to be within 2.42 mg/l (Tb) to 46.50 mg/l (Ce), while for the Kinta River, it was 1.33 mg/l (Ho) to 29.95 mg/l (Ce). Sediment samples were also found with REEs from 9.81 mg/kg (Ho) to 765.84 mg/kg (Ce). Ce showed the highest average concentrations for mining lake (3.88 to 49.08 mg/l) and Kinta River (4.44 to 33.15 mg/l) water samples, while the concentration of La was the highest (11.59 to 771.61 mg/kg) in the mining lake sediment. Lu was shown to have the highest enrichment of REEs in ex-mining lake sediments (107.3). Multivariate statistical analyses such as factor analysis and principal component analysis indicated that REEs were associated and controlled by mixed origin, with similar contributions from anthropogenic and geogenic sources. The speciation study of REEs in ex-tin mining sediments using a modified five-stage sequential extraction procedure indicated that yttrium (Y), gadolinium (Gd), and lanthanum (La) were obtained at higher percentages from the adsorbed/exchanged/carbonate fraction. The average potential mobility of the REEs was arranged in a descending order: Yb > Gd > Y = Dy > Pr > Er > Tm > Eu > Nd > Tb > Sc > Lu > Ce > La, implying that under favorable conditions, these REEs could be released and subsequently pollute the environment.