A bifunctional MoS2/SGCN nanocatalyst for the electrochemical detection and degradation of hazardous 4-nitrophenol.

Herein, we reported the dual functions of molybdenum disulfide/sulfur-doped graphitic carbon nitride (MoS2/SGCN) composite as a sensing material for electrochemical detection of 4-NP and a catalyst for 4-NP degradation. The MoS2 nanosheet, sulfur-doped graphitic carbon nitride (SGCN) and MoS2/SGCN were characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) spectroscopy and X-ray photoelectron spectroscopy (XPS). Electrochemical characterization of these materials with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) in 1 mM K4[Fe(CN)6]3-/4- show that the composite has the lowest charge transfer resistance and the best electrocatalytic activity. The limit of detection (LOD) and the linear range of 4-nitrophenol at MoS2/SGCN modified glassy carbon electrode (MoS2/SGCN/GCE) were computed as 12.8 nM and 0.1 - 2.6 µM, respectively. Also, the percentage recoveries of 4-NP in spiked tap water samples ranged from 97.8 - 99.1 %. The electroanalysis of 4-NP in the presence of notable interferons shows that the proposed electrochemical sensor features outstanding selectivity toward 4-NP. Additionally, the results of the catalytic degradation of 4-NP at MoS2/SGCN show that the nanocatalyst catalyzed the transformation of 4-NP to 4-aminophenol (4-AP) with a first-order rate constant (k) estimated to be 4.2 ×10-2 s-1. The results of this study confirm that the MoS2/SGCN nanocatalyst is a useful implement for electroanalytical monitoring and catalytic degradation of the hazardous 4-NP in water samples.

Coco Monoethanolamide Surfactant as a Sustainable Corrosion Inhibitor for Mild Steel: Theoretical and Experimental Investigations.

Recent studies indicate that surfactants are a relatively new and effective class of corrosion inhibitors that almost entirely meet the criteria for a chemical to be used as an aqueous phase corrosion inhibitor. They possess the ideal hydrophilicity to hydrophobicity ratio, which is crucial for effective interfacial interactions. In this study, a coconut-based non-ionic surfactant, namely, coco monoethanolamide (CMEA), was investigated for corrosion inhibition behaviour against mild steel (MS) in 1 M HCl employing the experimental and computational techniques. The surface morphology was studied employing the scanning electron microscope (SEM), atomic force microscope (AFM), and contact measurements. The critical micelle concentration (CMC) was evaluated to be 0.556 mM and the surface tension corresponding to the CMC was 65.28 mN/m. CMEA manifests the best inhibition efficiency (η%) of 99.01% at 0.6163 mM (at 60 °C). CMEA performs as a mixed-type inhibitor and its adsorption at the MS/1 M HCl interface followed the Langmuir isotherm. The theoretical findings from density functional theory (DFT), Monte Carlo (MC), and molecular dynamics (MD) simulations accorded with the experimental findings. The MC simulation's assessment of CMEA's high adsorption energy (-185 Kcal/mol) proved that the CMEA efficiently and spontaneously adsorbs at the interface.

Molecular modelling of compounds used for corrosion inhibition studies: a review.

Molecular modelling of organic compounds using computational software has emerged as a powerful approach for theoretical determination of the corrosion inhibition potential of organic compounds. Some of the common techniques involved in the theoretical studies of corrosion inhibition potential and mechanisms include density functional theory (DFT), molecular dynamics (MD) and Monte Carlo (MC) simulations, and artificial neural network (ANN) and quantitative structure-activity relationship (QSAR) modeling. Using computational modelling, the chemical reactivity and corrosion inhibition activities of organic compounds can be explained. The modelling can be regarded as a time-saving and eco-friendly approach for screening organic compounds for corrosion inhibition potential before their wet laboratory synthesis would be carried out. Another advantage of computational modelling is that molecular sites responsible for interactions with metallic surfaces (active sites or adsorption sites) and the orientation of organic compounds can be easily predicted. Using different theoretical descriptors/parameters, the inhibition effectiveness and nature of the metal-inhibitor interactions can also be predicted. The present review article is a collection of major advancements in the field of computational modelling for the design and testing of the corrosion inhibition effectiveness of organic corrosion inhibitors.

Silver Nanoparticles Mediated by Costus afer Leaf Extract: Synthesis, Antibacterial, Antioxidant and Electrochemical Properties.

Synthesis of metallic and semiconductor nanoparticles through physical and chemical routes has been extensively reported. However, green synthesized metal nanoparticles are currently in the limelight due to the simplicity, cost-effectiveness and eco-friendliness of their synthesis. This study explored the use of aqueous leaf extract of Costus afer in the synthesis of silver nanoparticles (CA-AgNPs). The optical and structural properties of the resulting silver nanoparticles were studied using UV-visible spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infra-red spectrophotometer (FTIR). TEM images of the silver nanoparticles confirmed the existence of monodispersed spherical nanoparticles with a mean size of 20 nm. The FTIR spectra affirmed the presence of phytochemicals from the Costus afer leaf extract on the surface of the silver nanoparticles. The electrochemical characterization of a CA-AgNPs/multiwalled carbon nanotubes (MWCNT)-modified electrode was carried out to confirm the charge transfer properties of the nanocomposites. The comparative study showed that the CA-AgNPs/MWCNT-modified electrode demonstrated faster charge transport behaviour. The anodic current density of the electrodes in Fe(CN)6]4-/[Fe(CN)6]3- redox probe follows the order: GCE/CA-Ag/MWCNT (550 mA/cm²) > GCE/MWCNT (270 mA/cm²) > GCE (80 mA/cm²) > GCE/CA-Ag (7.93 mA/cm²). The silver nanoparticles were evaluated for their antibacterial properties against Gram negative (Escherichia coli, Klebsiella pneumonia, Pseudomonas aeruginosa) and Gram positive (Bacillus subtilis and Staphylococcus aureus) pathogens. The nanoparticles exhibited better inhibition of the bacterial strains compared to the precursors (leaf extract of Costus afer and silver nitrate). Furthermore, the ability of the nanoparticles to scavenge DPPH radicals at different concentrations was studied using the DPPH radical scavenging assay and compared to that of the leaf extract and ascorbic acid. The nanoparticles were better DPPH scavengers compared to the leaf extract and their antioxidant properties compared favorably the antioxidant results of ascorbic acid. The green approach to nanoparticles synthesis carried out in this research work is simple, non-polluting, inexpensive and non-hazardous.

Adsorption and Corrosion Inhibition Studies of Some Selected Dyes as Corrosion Inhibitors for Mild Steel in Acidic Medium: Gravimetric, Electrochemical, Quantum Chemical Studies and Synergistic Effect with Iodide Ions.

The corrosion inhibition properties of some organic dyes, namely Sunset Yellow (SS), Amaranth (AM), Allura Red (AR), Tartrazine (TZ) and Fast Green (FG), for mild steel corrosion in 0.5 M HCl solution, were investigated using gravimetric, potentiodynamic polarization techniques and quantum chemical calculations. The results showed that the studied dyes are good corrosion inhibitors with enhanced inhibition efficiencies. The inhibition efficiency of all the studied dyes increases with increase in concentration, and decreases with increase in temperature. The results showed that the inhibition efficiency of the dyes increases in the presence of KI due to synergistic interactions of the dye molecules with iodide (I(-)) ions. Potentiodynamic polarization results revealed that the studied dyes are mixed-type inhibitors both in the absence and presence of KI. The adsorption of the studied dyes on mild steel surface, with and without KI, obeys the Langmuir adsorption isotherm and involves physical adsorption mechanism. Quantum chemical calculations revealed that the most likely sites in the dye molecules for interactions with mild steel are the S, O, and N heteroatoms.

Some Phthalocyanine and Naphthalocyanine Derivatives as Corrosion Inhibitors for Aluminium in Acidic Medium: Experimental, Quantum Chemical Calculations, QSAR Studies and Synergistic Effect of Iodide Ions.

The effects of seven macrocyclic compounds comprising four phthalocyanines (Pcs) namely 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (Pc1), 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine (Pc2), 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (Pc3) and 29H,31H-phthalocyanine (Pc4), and three naphthalocyanines namely 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine (nPc1), 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (nPc2) and 2,3-naphthalocyanine (nP3) were investigated on the corrosion of aluminium (Al) in 1 M HCl using a gravimetric method, potentiodynamic polarization technique, quantum chemical calculations and quantitative structure activity relationship (QSAR). Synergistic effects of KI on the corrosion inhibition properties of the compounds were also investigated. All the studied compounds showed appreciable inhibition efficiencies, which decrease with increasing temperature from 30 °C to 70 °C. At each concentration of the inhibitor, addition of 0.1% KI increased the inhibition efficiency compared to the absence of KI indicating the occurrence of synergistic interactions between the studied molecules and I(-) ions. From the potentiodynamic polarization studies, the studied Pcs and nPcs are mixed type corrosion inhibitors both without and with addition of KI. The adsorption of the studied molecules on Al surface obeys the Langmuir adsorption isotherm, while the thermodynamic and kinetic parameters revealed that the adsorption of the studied compounds on Al surface is spontaneous and involves competitive physisorption and chemisorption mechanisms. The experimental results revealed the aggregated interactions between the inhibitor molecules and the results further indicated that the peripheral groups on the compounds affect these interactions. The calculated quantum chemical parameters and the QSAR results revealed the possibility of strong interactions between the studied inhibitors and metal surface. QSAR analysis on the quantum chemical parameters obtained with B3LYP/6-31G (d,p) method show that a combination of two quantum chemical parameters to form a composite index provides the best correlation with the experimental data.

Porphyrins as Corrosion Inhibitors for N80 Steel in 3.5% NaCl Solution: Electrochemical, Quantum Chemical, QSAR and Monte Carlo Simulations Studies.

The inhibition of the corrosion of N80 steel in 3.5 wt. % NaCl solution saturated with CO2 by four porphyrins, namely 5,10,15,20-tetrakis(4-hydroxyphenyl)-21H,23H-porphyrin (HPTB), 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphyrin (T4PP), 4,4',4″,4‴-(porphyrin-5,10,15,20-tetrayl)tetrakis(benzoic acid) (THP) and 5,10,15,20-tetraphenyl-21H,23H-porphyrin (TPP) was studied using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, scanning electrochemical microscopy (SECM) and scanning electron microscopy (SEM) techniques. The results showed that the inhibition efficiency, η% increases with increasing concentration of the inhibitors. The EIS results revealed that the N80 steel surface with adsorbed porphyrins exhibited non-ideal capacitive behaviour with reduced charge transfer activity. Potentiodynamic polarization measurements indicated that the studied porphyrins acted as mixed type inhibitors. The SECM results confirmed the adsorption of the porphyrins on N80 steel thereby forming a relatively insulated surface. The SEM also confirmed the formation of protective films of the porphyrins on N80 steel surface thereby protecting the surface from direct acid attack. Quantum chemical calculations, quantitative structure activity relationship (QSAR) were also carried out on the studied porphyrins and the results showed that the corrosion inhibition performances of the porphyrins could be related to their EHOMO, ELUMO, ω, and µ values. Monte Carlo simulation studies showed that THP has the highest adsorption energy, while T4PP has the least adsorption energy in agreement with the values of σ from quantum chemical calculations.

Zwitterions and betaines as highly soluble materials for sustainable corrosion protection: Interfacial chemistry and bonding with metal surfaces.

The primary requirements for interfacial adsorption and corrosion inhibition are solubility and the existence of polar functional groups, particularly charges. Traditional organic inhibitors have a solubility issue due to the hydrophobic moieties they incorporate. Most documented organic inhibitors have aromatic rings, hydrocarbon chains, and a few functional groups. The excellent solubility and high efficacy of zwitterions and betaines make them the perfect replacements for insoluble corrosion inhibitors. Zwitterions and betaines are more easily soluble because of interactions between their positive and negative charges (-COO-, -PO3-, -NH3, -NHR2, -NH2R, -SO3- etc.) and the polar solvents. The positive and negative charges also aid these molecules' physical and chemical adsorption at the metal-electrolyte interfaces. They develop a corrosion-inhibiting layer through their adsorption. After becoming adsorbed at the metal-electrolyte interface, they act as mixed-type inhibitors, slowing both cathodic and anodic processes. They usually adsorb according to the Langmuir adsorption isotherm. In this article, the corrosion inhibition potential of zwitterions and betaines in the aqueous phase, as well as their mode of action, are reviewed. This article details the advantages and disadvantages of utilizing zwitterions and betaines for sustainable corrosion protection.

Smart and emerging point of care electrochemical sensors based on nanomaterials for SARS-CoV-2 virus detection: Towards designing a future rapid diagnostic tool.

In the recent years, researchers from all over the world have become interested in the fabrication of advanced and innovative electrochemical and/or biosensors for respiratory virus detection with the use of nanotechnology. These fabricated sensors demonstrated a number of benefits, including precision, affordability, accessibility, and miniaturization which makes them a promising test method for point-of-care (PoC) screening for SARS-CoV-2 viral infection. In order to comprehend the principles of electrochemical sensing and the role of various types of sensing interfaces, we comprehensively explored the underlying principles of electroanalytical methods and terminologies related to it in this review. In addition, it is addressed how to fabricate electrochemical sensing devices incorporating nanomaterials as graphene, metal/metal oxides, metal organic frameworks (MOFs), MXenes, quantum dots, and polymers. We took an effort to carefully compile current developments, advantages, drawbacks, possible solutions in nanomaterials based electrochemical sensors.

Electrocatalytic oxidation of pyrrole on a quasi-reversible silver nanodumbbell particle surface for supramolecular porphyrin production.

Photoactive supramolecular porphyrin assemblies are attractive molecules for light-harvesting applications. This is due to their relatively non-toxicity, biological activities and charge and energy exchange characteristics. However, the extreme cost associated with their synthesis and requirements for toxic organic solvents during purification pose a challenge to the sustainability characteristics of their applications. This work presents the first report on the sustainable synthesis, spectroscopic and photophysical characterizations of a near-infrared (NIR) absorbing Ca(II)-meso-tetrakis (4-hydroxyphenyl)porphyrin using an electrolyzed pyrrole solution. The latter was obtained by cycling the pyrrole solution across the silver nanodumbbell particle surface at room temperature. The electrolyzed solution condensed readily with acidified p-hydroxybenzaldehyde, producing the targeted purple porphyrin. The non-electrolyzed pyrrole solution formed a green substance with significantly different optical properties. Remarkable differences were observed in the voltammograms of the silver nanodumbbell particles and those of the conventional gold electrode during the pyrrole cycling, suggesting different routes of porphyrin formation. The rationale behind these formations and the associated mechanisms were extensively discussed. Metalation with aqueous Ca2+ ion caused a Stokes shift of 38.75 eV. The current study shows the advantage of the electrochemical method towards obtaining sustainable light-harvesting porphyrin at room temperature without the need for high-energy-dependent conventional processes.

Structures, stabilization energies, and binding energies of quinoxaline···(H2O)(n), quinoxaline dimer, and quinoxaline···Cu complexes: a theoretical study.

Quinoxaline is a parent structure for a broad class of N-heteroaromatic compounds, many of which exhibit various biological activities. The interaction of quinoxaline with explicit water molecules or metal ions and the formation of quinoxaline dimer play an important role in many of the biological activities of quinoxaline. This study investigates the structures, stabilization, and binding energies of quinoxaline complexes with water, transition metal ions, and quinoxaline dimer to provide information on the preferred geometries, interaction energies, and type of noncovalent interactions accounting for the stability of the complexes. The investigations are performed in vacuo and in water solution using MP2 and DFT methods. The results of the study on the quinoxaline···(H(2)O)(n) show that the preferred adducts in vacuo involve one, two, or three water molecules hydrogen bonded to the N atom and the neighboring H atom of the C(sp2)-H group. The results in water solution show a preference for water-water clustering. The dimers of quinoxaline are stabilized by either π-π stacking or weak C-H···N intermolecular hydrogen bonds. The relative stability of the quinoxaline···Cu complexes depends on the site on which the Cu ion binds and the binding strength depends on both the nature of the cation and the binding site.

Electrochemical, surface morphological and computational evaluation on carbohydrazide Schiff bases as corrosion inhibitor for mild steel in acidic medium.

Anticorrosion and adsorption behaviour of synthesized carbohydrazide Schiff bases, namely (Z)-N'-(4-hydroxy-3-methoxybenzylidene)-6-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carbohydrazide(MBTC) and (Z)-N'-(3,4-dichlorobenzylidene)-6-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carbohydrazide (CBTC) was examined for mild steel (MS) in 15% HCl medium. The corrosion inhibition study was performed by using gravimetric, thermodynamic, electrochemical and theoretical studies including density functional theory (DFT), molecular dynamic simulation (MDS) and Monte Carlo simulations (MCS). The outcomes in terms of corrosion inhibition efficiency using electrochemical impedance spectroscopy (EIS) method at 303 K and 150 ppm concentration were 96.75% for MBTC and 95.14% for CBTC. Both inhibitors adsorbed on the MS surface through physical as well as chemical adsorption and followed the Langmuir isotherm. The mixed-type nature of both inhibitors was identified by polarization results. Surface analysis was done using FESEM, EDX, AFM and XPS studies and results showed that a protective layer of inhibitor molecules was developed over the surface of MS. The results of DFT, MCS and MDS are in accordance with experimental results obtained by weight loss and electrochemical methods.

Electrochemical sensor for the detection of adrenaline at poly(crystal violet) modified electrode: optimization and voltammetric studies.

Herein, we report the electropolymerization of crystal violet (CRV) on a bare glassy carbon electrode (GCE) for the detection of adrenaline (AD). Electropolymerization parameters such as electrolyte pH, scan rate and monomer concentrations were optimized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The characterization of CRV and poly(crystal violet) (PCV) was done using FT-IR, UV-visible spectroscopy and EIS. More importantly, the charge transfer resistance (Rct) and other EIS data recorded from the EIS of various forms of the poly(crystal violet) (PCV) modified glassy carbon electrode (GCE) in AD were used for identifying the best PCV modified electrode. Subsequent application of the electrode prepared at optimum conditions (PGCE) for AD detection using the square wave voltammetry (SWV) gave a limit of detection (LOD) of 2.86 µM over a linear range of 10.3-102.7 µM. This sensor also showed considerable stability, good AD recovery from the real sample (98.9%), and excellent reproducibility, making it a suitable analytical tool for AD detection at the micromolar level.

Electrochemical detection of selected heavy metals in water: a case study of African experiences.

The safety of water resources throughout the globe has been compromised by various human activities and climate change over the last decades. Consequently, the world is currently confronted with a severe shortage of water supply and a water safety crisis, amidst a growing population. With poor environmental regulations, indiscriminate budding of urban slums, poverty, and a lack of basic knowledge of hygiene and sanitation, the African water supply has been critically threatened by different organic and inorganic contaminants, which results in several health issues. Inorganic pollutants such as heavy metals are particularly of interest because they are mostly stable and non-biodegradable. Therefore, they are not easily removed from water. In different parts of the continent, the concentration of heavy metals in drinking water far exceeds the permissible level recommended by the World Health Organization (WHO). Worse still, this problem is expected to increase with growing population, industrialization, urbanization, and, of course, corruption of government and local officials. Most of the African population is ignorant of the standards of safe water. In addition, the populace lack access to affordable and reliable technologies and tools that could be used in the quantification of these pollutants. This problem is not only applicable to domestic, but also to commercial, communal, and industrial water sources. Hence, a global campaign has been launched to ensure constant assessment of the presence of these metals in the environment and to promote awareness of dangers associated with unsafe exposure to them. Various conventional spectroscopic heavy metal detection techniques have been used with great success across the world. However, such techniques suffer from some obvious setbacks, such as the cost of procurement and professionalism required to operate them, which have limited their applications. This paper, therefore, reviews the condition of African water sources, health implications of exposure to heavy metals, and the approaches explored by various indigenous electrochemists, to provide a fast, affordable, sensitive, selective, and stable electrochemical sensors for the quantification of the most significant heavy metals in our water bodies.

Formamidine-Based Thiuram Disulfides as Efficient Inhibitors of Acid Corrosion of Mild Steel: Electrochemical, Surface, and Density Functional Theory/Monte Carlo Simulation Studies.

Electrochemical, surface, and density functional theory (DFT)/Monte Carlo (MC) simulation studies were used in investigating the characteristics of N,N'-(disulfanne-1,2-dicarbonothioyl)bis(N,N'-bis(2,6-dimethylphenyl)formimidamide) (DS1), N,N'-(disulfanne-1,2-dicarbonothioyl)bis(N,N'-bis(2,6-diisopropylphenyl)formimidamide) (DS2), N,N'-(disulfanne-1,2-dicarbonothioyl)bis(N,N'-dimesitylformimidamide) (DS3), and N,N'-(disulfanne-1,2-dicarbonothioyl)bis(N,N'-bis(2,6-dichlorophenyl)formimidamide) (DS4) as inhibitors of acid corrosion of mild steel. The inhibitors were found to effectively reduce the rates of steel dissolution at the anode as well as cathodic hydrogen evolution. The order of inhibition efficiencies of studied compounds is DS1 (PDP/LPR/EIS: 98.60/97.98/96.94%) > DS2 (PDP/LPR/EIS: 98.36/96.86/96.90%) > DS3 (PDP/LPR/EIS: 94.66/87.44/94.30%) > DS4 (PDP/LPR/EIS: 83.57/77.02/75.17%) at 1.00 mM, and the overall efficiencies appeared to depend on the molecular and electronic structures of the compounds. The compounds offered high resistance to charge transfer across the electrode/electrolyte system by forming adsorbed film whose resistance increased with an increase in concentration. Findings suggested that the adsorption process involved combined chemisorption and physisorption. DFT calculations and MC simulations provided theoretical justifications for the experimental results.

Predicting protection capacities of pyrimidine-based corrosion inhibitors for mild steel/HCl interface using linear and nonlinear QSPR models.

Pyrimidine compounds have proven to be effective and efficient additives capable of protecting mild steel in acidic media. This class of organic compounds often functions as adsorption-type inhibitors of corrosion by forming a protective layer on the metallic substrate. The present study reports a computational study of forty pyrimidine compounds that have been investigated as sustainable inhibitors of mild steel corrosion in molar HCl solution. Quantitative structure property relationship was conducted using linear (multiple linear regression) and nonlinear (artificial neural network) models. Standardization method was employed in variable selection yielding five top chemical descriptors utilized for model development along with the inhibitor concentration. Multiple linear regression model yielded a fair predictive model. Artificial neural network model developed using k-fold cross-validation method provided a comprehensive insight into the corrosion protection mechanism of studied pyrimidine-based corrosion inhibitors. Using a multilayer perceptron with Levenberg-Marquardt algorithm, the study obtained the optimal model having a MSE of 8.479, RMSE of 2.912, MAD of 1.791, and MAPE of 2.648. The optimal neural network model was further utilized to forecast the protection capacities of nine non-synthesized pyrimidine derivatives. The predicted inhibition efficiencies ranged from 89 to 98%, revealing the significance of the considered chemical descriptors, the predictive capacity of the developed model, and the potency of the theoretical inhibitors.

Metathesis of fatty acid ester derivatives in 1,1-dialkyl and 1,2,3-trialkyl imidazolium type ionic liquids.

The self-metathesis of methyl oleate and methyl ricinoleate was carried out in the presence of ruthenium alkylidene catalysts 1-4 in [bmim] and [bdmim][X] type ionic liquids (RTILs) (X = PF(6) (-), BF(4) (-) and NTf(2) (-)) using the gas chromatographic technique. Best catalytic performance was obtained in [bdmim][X] type ionic liquids when compared with [bmim][X] type ionic liquids. Catalyst recycling studies were also carried out in the room temperature ionic liquids (RTILs) with catalysts 1-4 in order to explore their possible industrial application.

Electrochemical Characterization and Detection of Lead in Water Using SPCE Modified with BiONPs/PANI.

The need for constant assessment of river water qualities for both aquatic and other biological survival has emerged a top priority, due to increasing exposure to industrial pollutants. A disposable screen print carbon electrode was modified with a conductive polymer (PANI) and Zn and/or Cu oxides NPs, obtained through bioreduction in citrus peel extracts (lemon and orange), for ultra-sensitive detection of PB2+, in the Crocodile River water sample. The synthesized materials were characterized with Fourier-transform infra-red spectroscopy (FTIR), ultra-violet visible spectroscopy (UV-Vis), and scanning electron microscopy (SEM). The SPC-modified electrodes designated as SPCE/LPE/BiONPs/PANI and SPCE/OPE/BiONPs/PANI were characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) and eventually deployed in the electrochemical detection of PB2+ in water using square wave voltammetry (SWV) technique. The electrochemical responses of the modified electrodes for both CV and EIS in 0.1 M HCl demonstrated enhanced performance relative to the bare SPCE. A detection and quantification limit of 0.494 ppb and 1.647 were obtained at SPCE/LPE/BiONPs/PANI, respectively, while a detection and quantification limit of 2.79 ppb and 8.91 ppb, respectively, were derived from SPCE/OPE/BiONPs/PANI. The relative standard deviations (RSD) for SPC electrode at a 6.04 µM PB2+ analyte concentration was 4.76% and 0.98% at SPCE/LPE/BiONPs/PANI and SPCE/LPE/BiONPs/PANI, respectively. The effect of copper, zinc, iron, cobalt, nickel, and magnesium on the stripping peaks of PB2+ at SPCE/OPE/BiONPs/PANI, showed no significant change except for cobalt, with about 17.67% peak current drop. The sensors were assessed for possible determination of PB2+ in spiked river water samples. The average percentage recovery and RSD calculated were 94.25% and 3.74% (n = 3) at SPCE/LPE/BiONPs/PANI and, 96.70% and 3.71% (n = 3) at SPCE/OPE/BiONPs/PANI, respectively. Therefore, the fabricated sensor material could be used for environmental assessment of this highly toxic heavy metal in the aquatic system.

Conductive Nanodiamond-Based Detection of Neurotransmitters: One Decade, Few Sensors.

Nanodiamond (ND) is a class of carbon nanomaterial with covalently connected sp3 carbon atoms in its core and an sp2 carbon adorned surface via edge defects or doping. Endogenous chemicals that provoke physiological responses in the human system called neurotransmitters (NTs) have been detected with several sensors with carbon-based nanomaterials. Nanodiamonds (NDs), another class of carbon nanomaterial, have shown the requisite surface area and electrocatalytic activity toward NTs in the past decade. Surprisingly, only a few electrochemical ND based NT sensors are available. This work briefly looked into the performance of the available sensors, NT and ND interactions, and the possible reason for data paucity on the subject matter.

Electrochemical Detection of Endosulfan Using an AONP-PANI-SWCNT Modified Glassy Carbon Electrode.

This report narrates the successful application of a fabricated novel sensor for the trace detection of endosulfan (EDS). The sensor was made by modifying a glassy-carbon electrode (GCE) with polyaniline (PANI), chemically synthesized antimony oxide nanoparticles (AONPs), acid-functionalized, single-walled carbon nanotubes (fSWCNTs), and finally, the AONP-PANI-SWCNT nanocomposite. The electrochemical properties of the modified electrodes regarding endosulfan detection were investigated via cyclic voltammetry (CV) and square-wave voltammetry. The current response of the electrodes to EDS followed the trend GCE-AONP-PANI-SWCNT (-510 µA) > GCE-PANI (-59 µA) > GCE-AONPs (-11.4 µA) > GCE (-5.52 µA) > GCE-fSWCNTs (-0.168 µA). The obtained results indicated that the current response obtained at the AONP-PANI-SWCNT/GCE was higher with relatively low overpotential compared to those from the other electrodes investigated. This demonstrated the superiority of the AONP-PANI-SWCNT-modified GCE. The AONP-PANI-SWCNT/GCE demonstrated good electrocatalytic activities for the electrochemical reduction of EDS. The results obtained in this study are comparable with those in other reports. The sensitivity, limit of detection (LoD), and limit of quantification (LoQ) of AONP-PANI-SWCNT/GCE towards EDS was estimated to be 0.0623 µA/µM, 6.8 µM, and 20.6 µM, respectively. Selectivity, as well as the practical application of the fabricated sensor, were explored, and the results indicated that the EDS-reduction current was reduced by only 2.0% when interfering species were present, whilst average recoveries of EDS in real samples were above 97%.