Design of a Highly Selective Benzimidazole-Based Derivative for Optical and Solid-State Detection of Zinc Ion.

A novel series of benzimidazole-based molecules mimicking biological receptors, which exhibit selective coordination with zinc ions, were designed and synthesized. The photochromic behavior of these derivatives with various metal ions suggests a selective interaction of one of the receptors 2-(pyridin-2-yl)-4,7-di(thiophen-2-yl)-3H-benzo[d]imidazole (2c) with zinc ion. The lower limit of detection by photoluminescence quenching was determined to be 16 nM. The mechanism of selective complexation was elucidated by 1H nuclear magnetic resonance titrations and dynamic light scattering analysis. The stoichiometry of the formation of the Zn(2c)2 complex was evaluated by single-crystal X-ray diffraction and mass spectral techniques and calculated to be 2:1 (L:M). A change in the electronic energy levels on the sensor analyte interaction was observed by both ultraviolet photoelectron spectroscopy analysis and by density functional theory calculations, suggesting an electroactive semiconductor behavior. A symmetric Schottky structured sensor device was fabricated using the receptor 2c as the active sensing layer. A distinct change in current-voltage characteristics between the receptor and the complex suggests that the fabricated device could be used as a solid-state sensor for detecting zinc ion.

Sustainable removal of Cr(VI) using graphene oxide-zinc oxide nanohybrid: Adsorption kinetics, isotherms and thermodynamics.

Metal-based adsorbents are limited for hexavalent chromium [Cr(VI)] adsorption from aqueous solutions because of their low adsorption capacities and slow adsorption kinetics. In the present study, decorated zinc oxide (ZnO) nanoparticles (NPs) on graphene oxide (GO) nanoparticles were synthesized via the solvothermal process. The deposition of ZnO NPs on graphene oxide for the nanohybrid (ZnO-GO) improves Cr(VI) mobility in the nanocomposite or nanohybrid, thereby improving the Cr(VI) adsorption kinetics and removal capacity. Surface deposition of ZnO on graphene oxide was characterized through Fourie Transform Infra-red (FTIR), UV-Visible, X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive Spectroscopy (EDS), and Brunauer-Emmett-Teller (BET) techniques. These characterizations suggest the formation of ZnO-GO nanocomposite with a specific area of 32.95 m2/g and pore volume of 0.058 cm2/g. Batch adsorption analysis was carried to evaluate the influence of operational parameters, equilibrium isotherm, adsorption kinetics and thermodynamics. The removal efficiency of Cr(VI) increases with increasing time and adsorbent dosage. FTIR, FESEM and BET analysis before and after the adsorption studies suggest the obvious changes in the surface functionalization and morphology of the ZnO-GO nanocomposites. The removal efficiency increases from high-acidic to neutral pH and continues to decrease under alkaline conditions as well. Mathematical modeling validates that the adsorption follows Langmuir isotherm and fits well with the pseudo 2nd order kinetics (Type 5) model, indicating a homogeneous adsorption process. The thermodynamics study reveals that Cr(VI) adsorption on ZnO-GO is spontaneous, endothermic, and entropy-driven. A negative value of Gibb's Free Energy represents the thermodynamic spontaneity and feasibility of the sorption process. To the best of our knowledge, this is the first study of Cr(VI) removal from aqueous solution using this hybrid nanocomposite at near-neutral pH. The synthesized nanocomposites prove to be excellent candidates for Cr(VI) removal from water bodies and natural wastewater systems.

Chromium (VI) detection by microbial carbon dots: Microwave synthesis and mechanistic study.

Functionalized carbon dots (CDs) derived from Citrobacter freundii bacterial cells were used for selective detection of Cr(VI). A microwave-heating-based green synthesis approach is adopted to produce functionalized CDs from C. freundii bacterial cells (CF-CDs). The reaction was carried out in a 500 W microwave digester at 200°C for 20 min. The supernatant was filtered with a 0.2 µm filter and highly monodisperse CDs were obtained. Inherent functionalization of CF-CDs with nitrogen and oxygen-containing functional groups made them extremely selective toward Cr(VI) with a lower limit of detection of ~1.7 ppm. More importantly, CF-CDs could distinguish between Cr(VI) and Cr(III), which is highly desirable for practical applications. The fabricated sensor had a dual linear response range between 0 and 50 µM and 50-250 µM. The synthesized CDs were inherently functionalized which made them highly selective for Cr(VI) detection. CF-CDs also possess high stability over long storage period. This study reports the facile synthesis and characterization of a highly selective sensor for Cr(VI). As opposed to similar CDs sensors reported for Cr(VI), based on inner-filter effect, CF-CDs exhibit a strong, specific interaction toward Cr(VI), indicated by the large binding constant.

Biodegradation of phorate by bacterial strains in the presence of humic acid and metal ions.

Phorate is a systemic insecticide used to eradicate mites, insects, and nematodes. Extensive use of this organophosphate has engendered severe environmental concerns. The current research aimed to explore the kinetic pathways of phorate biodegradation in aqueous solutions. Two novel bacterial strains Pseudomonas aeruginosa strain PR1 (KP268772.1) and Pseudomonas sp. PR_02 (KP268773.1) were isolated, screened, and developed given their potential to degrade phorate. Mineralization of phorate was assayed with and without the addition of metal ions [Fe (II) and Cu (II)] and humic acid (HA). In 14 days, experiment both strains have consumed about 69%-94.5% (half-life from 3.58 to 6.02 days) of phorate. The observed biodegradation rate of phorate with Cu (II) in the system was 73% and 87%, with a half-life of 4.86 and 4.07 days for PR1 and PR2, respectively. The biodegradation of phorate using Fe(II) was 69% and 82%, with half-life periods 5.68 and 4.49 days. Meanwhile, incorporating HA, the phorate biodegradation was inhibited significantly, showing 71% and 85% degradation, with half-life periods of 6.02 and 5.02 days. The results indicated that both bacterial strains were able to mineralize phorate with PR2 > PR1. Summarizing, the inhibition in phorate biodegradation order under different conditions was as HA > Fe (II) > Cu (II). UV-visible measurements and gas chromatography-mass spectrometric assays indicated that the possible degradation pathway of phorate included ethoxy-phosphonothio-methanethiol S-mercaptomethyl-O,O-dihydrogen phosphorodithioate, diethyl-methylphosphonate, methane dithiol, ethanethiol, and phosphate, as the main metabolites identified. Therefore, it was concluded that the newly isolated Pseudomonas strains could be a potential candidates for biodegradation of phorate in a cost-effective, safe, and environmentally friendly alternative.

Occurrence, toxicity and remediation of polyethylene terephthalate plastics. A review.

Polyethylene terephthalate is a common plastic in many products such as viscose rayon for clothing, and packaging material in the food and beverage industries. Polyethylene terephthalate has beneficial properties such as light weight, high tensile strength, transparency and gas barrier. Nonetheless, there is actually increasing concern about plastic pollution and toxicity. Here we review the properties, occurrence, toxicity, remediation and analysis of polyethylene terephthalate as macroplastic, mesoplastic, microplastic and nanoplastic. Polyethylene terephthalate occurs in groundwater, drinking water, soils and sediments. Plastic uptake by humans induces diseases such as reducing migration and proliferation of human mesenchymal stem cells of bone marrow and endothelial progenitor cells. Polyethylene terephthalate can be degraded by physical, chemical and biological methods.

Chemically Room Temperature Crosslinked Polyvinyl Alcohol (PVA) with Anomalous Microwave Absorption Characteristics.

Polyvinyl alcohol (PVA) is a great interest polymer due to its excellent film-forming, emulsifying, microwave dielectrics and adhesive properties. However, PVA is a water-soluble synthetic polymer making it susceptible to environmental factors. In this work, PVA is crosslinked at room temperature using divinyl sulfone (DVS) as a crosslinker, and the obtained crosslinked PVA (XPVA) is water-insoluble. Crosslinking mechanism is proposed, thermal and microwave dielectric properties of X-PVA are studied. The studies revealed that X-PVA has better thermal stability and microwave absorption properties. The obtained minimum reflection loss (RL) of X-PVA is -23 dB (filler-free) with entire X-band (8.2-12.4 GHz) absorption bandwidth (RL ≤ -10 dB), indicating excellent microwave absorption properties. Artificial neural network (ANN) predicted RL of X-PVA also matched well with the experimental data. Electromagnetic power simulation suggests that the microwave power absorption density due to the dielectric loss is intrinsically predominant in X-PVA compared to the pristine PVA. Further, the ratio of electromagnetic energy to heat energy conversion power (absorption) of X-PVA is much higher than pristine PVA, indicating the suitability for self-powered devices. X-PVA also fulfils many commercial requirements such as bulk level facile synthesis, large area fabrications, ultralight, and inexpensive.

Adsorption and detoxification of pharmaceutical compounds from wastewater using nanomaterials: A review on mechanism, kinetics, valorization and circular economy.

Antibiotics overuse, inappropriate conduct, and discharge have led to adverse effects on various ecosystems. The occurrence of antibiotics in surface and drinking water is a matter of global concern. It is responsible for multiple disorders, including disruption of endocrine hormones and high chronic toxicity. The hospitals, pharmaceutical industries, households, cattle farms, and aquaculture are the primary discharging sources of antibiotics into the environment. This review provides complete detail on applying different nanomaterials or nanoparticles for the efficient removal of antibiotics from the diverse ecosystem with a broader perspective. Efforts have been made to focus on the degradation pathways and mechanism of antibiotic degradation using nanomaterials. More light has been shed on applying nanostructures in photocatalysis, which would be an economical and efficient solution. The nanoscale material or nanoparticles have incredible potential for mineralizing pharmaceutical compounds in aqueous solutions at low cost, easy handling characteristics, and high efficacy. Furthermore, nanoparticles can absorb the pharmaceutical by-products and wastes at a minimum cost as they can be easily recycled. With the increasing number of research in this direction, the valorization of pharmaceutical wastes and by-products will continue to expand as we progress from old conventional approaches towards nanotechnology. The utilization of nanomaterials in pharmaceutical wastewater remediation is discussed with a major focus on valorization, energy generation, and minimization and its role in the circular economy creating sustainable development.

Nitrates in the environment: A critical review of their distribution, sensing techniques, ecological effects and remediation.

Nitrate pollution is eminent in almost all the developing nations as a result of increased natural activities apart from anthropogenic pollution. The release of nitrates in more than critical quantities into the water bodies causes accretion impacts on living creatures, environmental receptors, and human vigour by accumulation through the food chain. Nitrates have recently acquired researchers' huge attention and extend their roots in environmental contamination of surface and groundwater systems. The presence of nitrate in high concentrations in surface and groundwater triggers several health problems, for instance, methemoglobinemia, diabetes, eruption of infectious disorders, harmfully influence aquatic organisms. Sensing nitrate is an alternate option for monitoring the distribution of nitrate in different water bodies. Here we review electrochemical, spectroscopic, and electrical modes of nitrate sensing. It is concluded that, among the various sensors discussed in this review, FET sensors are the most desirable choice. Their sensitivity, ease of use and scope for miniaturisation are exceptional. Advanced functional materials need to be designed to satiate the growing need for environmental monitoring. Different sources of nitrate contamination in ground and surface water can be estimated using different techniques such as nitrate isotopic composition, co contaminants, water tracers, and other specialized techniques. This review intends to explore the research work on remediation of nitrate from wastewater and soil using different processes such as reverse osmosis, chemical denitrification, biological denitrification, ion exchange, electrodialysis, and adsorption. Denitrification proves as a promising alternative over previously reported techniques in terms of their nitrate removal because of its high cost-effectiveness.

Multifunctional nanohybrid for simultaneous detection and removal of Arsenic(III) from aqueous solutions.

Herein, for the adsorption and detection of As (III), multifunctional nanohybrid have been synthesized using a solvothermal approach. Structural and functional characterizations confirmed the impregnation of the ZnO over graphene oxide. Nanohybrid exhibits a remarkable qmax (maximum adsorption capacity) of 8.17 mg/g, at an adsorbent dose of 3 g/L and pH of 8.23. Higher adsorption with nanohybrid was attributed to a large BET surface area of 32.950 m2/g. The chemical nature and adsorption behaviour of As(III) on ZnO-GO were studied by fitting the data with various adsorption isotherms (Langmuir & Freundlich) and kinetics models (six models). It is observed from the findings that removal of As(III) with ZnO-GO nanocomposite appears to be technically feasible with high removal efficiency. The feasibility of the nanocomposite to function as a sensor for the detection of As(III) was also evaluated. The fabricated sensor could detect As(III) with a lower limit of detection of 0.24 µM and linear range up to 80 µM. Overall, this study is significant in nanohybrid as a multifunctional composite for the adsorption and detection of As (III) from wastewater.

A novel CaO nanocomposite cross linked graphene oxide for Cr(VI) removal and sensing from wastewater.

A novel green nanocomposite has been prepared by immobilizing CaO nanoparticles (CaO NPs) on the surface of graphene oxide. Biogenic CaO-NPs were synthesized from Lala clamshells. Morphological and structural characterizations of the nanocomposite were studied extensively. The adsorption capacity (qmax) of the nanocomposite for removing Cr(VI) was 38.04 mg g-1. In addition to this, the adsorption data were adequately simulated with Langmuir, Freundlich, Temkin, and pseudo-second-order models, suggesting that the adsorption process was the combination of external mass transfer and chemisorption. Electrostatic interaction was the dominant mechanism for Cr(VI) removal. In addition, the synthesized nanocomposites also serve as an excellent sensor for Cr(VI) sensing, with a limit of detection (LOD) of 0.02 µM utilizing electrochemical methods. Therefore, this green nanocomposite can simultaneously serve as an adsorbent and sensor for Cr(VI)removal from aqueous solutions.

Micro (nano) plastics in wastewater: A critical review on toxicity risk assessment, behaviour, environmental impact and challenges.

With millions of tonnes of plastic pollution generated every year, small-sized plastic particles, including micro- and nanoplastics, end up in freshwater systems. Due to the very small size and very large specific surface area of nanoplastics, they are known to be persistent and toxic in our environment. These particles are also known to react with other water-borne contaminants and cause acute toxicity in organisms. Nanoplastics are prone to biomagnification and can be transported to humans through various pathways. This study aims to contribute towards understanding the behaviour of nanoplastics in our environment, specifically through identification of various sources, detection techniques, toxicity estimation, health risk in humans, environmental fate, recovery and reuse, and future challenges and limitations. Detailed review on the toxic effects of nanoplastics on various organisms and their degradation rates in soil and water matrices are provided. The suitability of small- and large-scale separation techniques for the removal of nanoplastics in wastewater treatment plants is also discussed. Current challenges and future perspectives in understanding the fate and transport of nanoplastics in the environment are also discussed. Research gaps, including the development of quantification techniques, estimation of degradation mechanisms, transport in marine ecosystems, and development of sensors to examine nanoplastics in the environment, are explored. Finally, we can limit the release of nanoplastics to the environment through reduction, reuse and recycling (3 Rs) of bulk plastic products.

Multifunctional Porous Organic Polymers: Tuning of Porosity, CO2, and H2 Storage and Visible-Light-Driven Photocatalysis.

A series of porous organic polymers (POPs) were fabricated based on a boron dipyrromethene (BODIPY) core. The variation of the substituents in the BODIPY core and the fine-tuning of the Sonogashira polycondenzation reaction with 1,3,5-triethynylbenzene led to the formation of POPs with a wide range of surface area and porosity. A 10-fold increase in surface area from 73 m2 g-1 in BDT1a polymer to 1010 m2 g-1 in BDT3 was obtained. Simultaneously, the porosity was changed from mesoporous to ultramicroporous. The surface area of BDT3 turned out to be the highest reported so far for BODIPY-based POPs. Molecular dynamics simulation coupled with Grand Canonical Monte Carlo simulations revealed the effect of substituents alkyl groups and rigidity of the core structures on the surface properties of the POPs. Detailed gas adsorption studies of the polymers revealed a high uptake of CO2 and H2. The highest uptake capacity of 16.5 wt % for CO2 at 273 K and 2.2 wt % for H2 at 77 K was observed for BDT3 at 1 bar pressure. The isosteric heat of adsorption (Qst) of BDT3 for CO2 was found to be as high as 30.6 kJ mol-1. Electron paramagnetic resonance studies revealed the generation of singlet oxygen upon photoexcitation of these polymers. The BODIPY-based POPs turned out to be excellent catalysts for visible-light-driven photo-oxidation of thioanisole. The present study establishes BODIPY-based POPs as a new class of multifunctional materials.