Visible-light induced effective and sustainable remediation of nitro organics pollutants using Pd-doped ZnO nanocatalyst.

Nitroaromatic compounds represent a class of highly toxic pollutants discharged into aquatic environments by various industrial activities, posing significant threats to ecological integrity and human health due to their persistent and hazardous nature. In this study, Pd-doped ZnO nanoparticles were investigated as a potential solution for the degradation of nitro organics, offering heightened photocatalytic efficacy and prolonged stability. The synthesis of Pd-doped ZnO NPs was achieved via the hydrothermal method, with subsequent analysis through XRD spectra and XPS confirming successful Pd doping within the ZnO matrix. Characterization through FESEM and HRTEM unveiled the heterogeneous morphologies of both undoped and Pd-doped ZnO nanoparticles. Additionally, UV-vis and PL spectroscopy provided insights into the optical properties, chemical bonding, and defect structures of the synthesized Pd-doped ZnO NPs. Pd doping induces a redshift in ZnO's absorption spectra, reducing the bandgap from 3.12 to 2.94 eV as Pd concentration rises from 0 to 0.2 wt.%. The photocatalytic degradation, following pseudo-first-order kinetics, achieved 90% nitrobenzene abatement (200 µg/L, pH 7) under visible light within 320 min with a catalyst loading of 16 µg/mL. The photocatalytic efficacy of 0.08 wt% Pd-doped ZnO (k = 0.058 min⁻1) exhibited a 25-fold enhancement compared to bare ZnO (k = 3.1 × 10-4 min-1). Subsequent quenching and ESR experiments identified hydroxyl radicals (OH•) as the predominant active species in the degradation mechanism. Mass spectrometry analysis unveiled potential breakdown intermediates, illuminating a plausible degradation pathway. The investigated Pd-doped ZnO nanoparticles demonstrated reusability for up to five successive treatment cycles, offering a sustainable solution to nitro organics contamination challenges.

Enhanced Visible-Light Photodetection with Undoped and Doped ZnO Thin-Film Self-Powered Photodetectors.

Photodetection plays an essential role in the visible-light zone and is important in modern science and technology owing to its potential applications in various fields. Fabrication of a stable photodetector remains a challenge for researchers. We demonstrated a high-response/recovery and self-powered undoped ZnO (UZO) and Cu-doped ZnO (CZO) thin film-based visible-light photodetector fabricated on a cost-effective Si substrate using reactive cosputtering. The structural, morphological, and optical properties of CZO and UZO thin films have been examined using X-ray diffraction, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and photoluminescence spectroscopy. The results of the CZO/n-Si photodetector compared with those of the undoped ZnO (UZO)/n-Si photodetector show that the CZO/n-Si exhibits a higher on/off ratio, responsivity, and detectivity than UZO/n-Si. Also, the CZO/n-Si photodetector shows high stability and reproducibility over 20 cycles after 180 days. A relative study of CZO/n-Si- and UZO/n-Si-based photodetectors reveals the enhanced performance of the CZO/n-Si photodetector, which has a high on/off ratio of ∼300 with a high specific detectivity of 2.8 × 1010 Jones for 75 mW visible light. The prepared self-powered CZO/n-Si/Ag thin film-based visible-light photodetector paves the way for the development of high-performance photodetector designs.

Ocimum sanctum Leaf Extract-Assisted Green Synthesis of Pd-Doped CuO Nanoparticles for Highly Sensitive and Selective NO2 Gas Sensors.

In view of facile, cost-effective, and environmentally friendly synthetic methods, palladium-doped copper oxide (Pd-CuO) nanoparticles have been synthesized from Ocimum sanctum (commonly known as "Tulsi") phytoextract for gas-sensing applications. The structural, morphological, and compositional properties of Pd-doped CuO nanoparticles were studied using various techniques such as XRD, FESEM, XPS, and EDX. The characterization results confirmed the doping of Pd on CuO nanoparticles, and Pd-CuO nanostructures appear as nanoflakes in FESEM analysis. The gas-sensing response of Pd (1.12 wt %)-CuO nanoflake-based sensor was measured at 5-100 ppm concentration of different gases, NO2, H2S, NH3, and H2, at 125 °C. Gas-sensing tests reveal that the sensitivity of the sensor were 81.7 and 38.9% for 100 and 5 ppm concentrations of NO2, respectively, which was significantly greater than that of pure CuO. The response and recovery times of the sensor were 72 and 98 s for 100 ppm of NO2 gas, while they were 90 and 50 s for 5 ppm NO2. The calculated limit of detection (LOD) value of the sensor is 0.8235. This appealing LOD is suitable for real-time gas detection. The gas sensor was found to exhibit excellent selectivity toward NO2 gas and repeatability and stability in humid (80%) conditions. The Pd doping in CuO nanostructures plays a significant role in escalating the sensitivity and selectivity of CuO-based NO2 gas sensor suitable to work at low operating temperatures.

Bioinspired palladium-doped manganese oxide nanocorns: a remarkable antimicrobial agent targeting phyto/animal pathogens.

Microbial pathogens are known for causing great environmental stress, owing to which emerging challenges like lack of eco-friendly remediation measures, development of drug-resistant and mutational microbial strains, etc., warrants novel and green routes as a stepping stone to serve such concerns sustainably. In the present study, palladium (Pd) doped manganese (II, III) oxide (Mn3O4) nanoparticles (NPs) were synthesized using an aqueous Syzygium aromaticum bud (ASAB) extract. Preliminary phytochemical analysis of ASAB extract indicates the presence of polyphenolics such as phenols, alkaloids, and flavonoids that can act as potential capping agents in NPs synthesis, which was later confirmed in FTIR analysis of pure and Pd-doped Mn3O4 NPs. XRD, Raman, and XPS analyses confirmed the Pd doping in Mn3O4 NPs. FESEM and HRTEM study reveals the mixed morphologies dominated by nanocorns appearance. Zeta potential investigation reveals high stability of the synthesized NPs in colloidal solutions. The developed Pd-doped Mn3O4 NPs were tested against two fungal phytopathogens, i.e., Sclerotinia sclerotiorum and Colletotrichum gloeosporioides, known for causing great economic losses in yield and quality of different plant species. The antifungal activity of synthesized Pd-doped Mn3O4 NPs displayed a dose-dependent response with a maximum of ~92%, and ~72% inhibition was recorded against S. sclerotiorum and C. gloeosporioides, respectively, at 1000 ppm concentration. However, C. gloeosporioides demonstrated higher sensitivity to Pd-doped Mn3O4 NPs upto 500 ppm) treatment than S. sclerotiorum. The prepared NPs also showed significant antibacterial activity against Enterococcus faecalis. The Pd-doped Mn3O4 NPs were effective even at low treatment doses, i.e., 50-100 ppm, with the highest Zone of inhibition obtained at 1000 ppm concentration. Our findings provide a novel, eco-benign, and cost-effective approach for formulating a nanomaterial composition offering multifaceted utilities as an effective antimicrobial agent.

Surface functionalized silver-doped ZnO nanocatalyst: a sustainable cooperative catalytic, photocatalytic and antibacterial platform for waste treatment.

The different dyes used and discharged in industrial settings and microbial pathogenic issues have raised serious concerns about the content of bodies of water and the impact that dyes and microbes have on the environment and human health. Efficient treatment of contaminated water is thus a major challenge that is of great interest to researchers around the world. In the present work, we have fabricated functionalized silver-doped ZnO nanoparticles (Ag-doped ZnO NPs) via a hydrothermal method for wastewater treatment. X-ray photoelectron spectroscopy analysis confirmed the doping of Ag with ZnO NPs, and X-ray diffractometry analysis showed a decreasing trend in the crystallite size of the synthesized ZnO NPs with increased Ag concentration. Field emission scanning electron microscopy study of pure ZnO NPs and Ag-doped ZnO NPs revealed nanocrystal aggregates with mixed morphologies, such as hexagonal and rod-shaped structures. Distribution of Ag on the ZnO lattice is confirmed by high-resolution transmission electron microscopy analysis. ZnO NPs with 4 wt% Ag doping showed a maximum degradation of ∼95% in 1.5 h of malachite green dye (80 mg L-1) under visible light and ∼85% in 4 h under dark conditions. Up to five successive treatment cycles using the 4 wt% Ag-doped ZnO NP nanocatalyst confirmed its reusability, as it was still capable of degrading ∼86% and 82% of the dye under visible light and dark conditions, respectively. This limits the risk of nanotoxicity and aids the cost-effectiveness of the overall treatment process. The synthesized NPs showed antibacterial activity in a dose-dependent manner. The zone of inhibition of the Ag-doped ZnO NPs was higher than that of the pure ZnO NPs for all doping content. The studied Ag-doped ZnO NPs thus offer a significant eco-friendly route for the effective treatment of water contaminated with synthetic dyes and fecal bacterial load.

Nanostructured metal oxide semiconductor-based sensors for greenhouse gas detection: progress and challenges.

Climate change and global warming have been two massive concerns for the scientific community during the last few decades. Anthropogenic emissions of greenhouse gases (GHGs) have greatly amplified the level of greenhouse gases in the Earth's atmosphere which results in the gradual heating of the atmosphere. The precise measurement and reliable quantification of GHGs emission in the environment are of the utmost priority for the study of climate change. The detection of GHGs such as carbon dioxide, methane, nitrous oxide and ozone is the first and foremost step in finding the solution to manage and reduce the concentration of these gases in the Earth's atmosphere. The nanostructured metal oxide semiconductor (NMOS) based technologies for sensing GHGs emission have been found most reliable and accurate. Owing to their fascinating structural and morphological properties metal oxide semiconductors become an important class of materials for GHGs emission sensing technology. In this review article, the current concentration of GHGs in the Earth's environment, dominant sources of anthropogenic emissions of these gases and consequently their possible impacts on human life have been described briefly. Further, the different available technologies for GHG sensors along with their principle of operation have been largely discussed. The advantages and disadvantages of each sensor technology have also been highlighted. In particular, this article presents a comprehensive study on the development of various NMOS-based GHGs sensors and their performance analysis in order to establish a strong detection technology for the anthropogenic GHGs. In the last, the scope for improved sensitivity, selectivity and response time for these sensors, their future trends and outlook for researchers are suggested in the conclusion of this article.

Bacterial Compatibility/Toxicity of Biogenic Silica (b-SiO2) Nanoparticles Synthesized from Biomass Rice Husk Ash.

Biogenic silica (b-SiO2) nanopowders from rice husk ash (RHA) were prepared by chemical method and their bacterial compatibility/toxicity was analyzed. The X-ray diffractometry (XRD) patterns of the b-SiO2 nanopowders indicated an amorphous feature due to the absence of any sharp peaks. Micrographs of the b-SiO2 revealed that sticky RHA synthesized SiO2 nanopowder (S1) had clustered spherical nanoparticles (70 nm diameter), while b-SiO2 nanopowder synthesized from red RHA (S2) and b-SiO2 nanopowder synthesized from brown RHA (S3) were purely spherical (20 nm and 10 nm diameter, respectively). Compared to the S1 (11.36 m2g-1) and S2 (234.93 m2g-1) nanopowders, the S3 nanopowders showed the highest surface area (280.16 m2g-1) due to the small particle size and high porosity. The core level of the X-ray photoelectron spectroscopy (XPS) spectra showed that Si was constituted by two components, Si 2p (102.2 eV) and Si 2s (153.8 eV), while Oxygen 1s was observed at 531.8 eV, confirming the formation of SiO2. The anti-bacterial activity of the b-SiO2 nanopowders was investigated using both gram-positive (Escherichia coli) and gram-negative (Staphylococcus aureus) microorganisms. Compared to S2 and S3 silica nanopowders, S1 demonstrated enhanced antibacterial activity. This study signifies the medical, biomedical, clinical, and biological importance and application of RHA-mediated synthesized b-SiO2.

DNA-probe-target interaction based detection of Brucella melitensis by using surface plasmon resonance.

Surface plasmon resonance (SPR) immunosensor using 4-mercaptobenzoic acid (4-MBA) modified gold (4-MBA/Au) SPR chip was developed first time for the detection of Brucella melitensis (B. melitensis) based on the screening of its complementary DNA target by using two different newly designed DNA probes of IS711 gene. Herein, interaction between DNA probes and target molecule are also investigated and result revealed that the interaction is spontaneous. The kinetics and thermodynamic results derived from the experimental data showed that the interaction between complementary DNA targets and probe 1 is more effective than that of probe 2. Equilibrium dissociation constant (KD) and maximum binding capacity of analyte (Bmax) values for the interaction of complementary DNA target with the immobilized DNA probes were calculated by using kinetic evaluation software, and found to be 15.3 pM (KD) and 81.02m° (Bmax) with probe 1 and 54.9pM and 55.29m° (Bmax), respectively. Moreover, real serum samples analysis were also carried out using immobilized probe 1 and probe 2 with SPR which showed the applicability of this methodology and provides an alternative way for the detection of B. melitensis in less than 10min. This remarkable sensing response of present methodology offer a real time and label free detection of biological warfare agent and provide an opportunity to make miniaturized sensor, indicating considerable promise for diverse environmental, bio-defence, clinical diagnostics, food safety, water and security applications.

Catalytic activity of Fe/ZrO2 nanoparticles for dimethyl sulfide oxidation.

A low-temperature vapor phase catalytic oxidation of dimethyl sulfide (DMS) with ozone over nano-sized Fe2O3-ZrO2 catalyst is carried out at temperatures of 50-200°C. Nanostructured Fe2O3-ZrO2 catalyst (FZN) is prepared by modified sol-gel method using citric acid as a chelating agent and conventional FZ catalyst is prepared with co-precipitation method. The catalysts are characterized using N2-BET surface area and pore size distributions, X-ray diffraction, TPR, TPD of DMS and NH3, SEM and TEM. The effects of operating temperature, ozone/DMS concentration and gas hourly space velocity (GHSV) on DMS removal efficiencies via catalytic ozonation are investigated. Relatively higher amount of ozone decomposition is observed on nanocatalyst compared to the co-precipitate catalyst from 50°C to 150°C. In contrast, at 200°C irrespective of the particle size, both catalysts performed similar activity. It clearly demonstrates that under ozone assisted catalytic oxidation over nanocatalyst offers the 100% of DMS conversion at lower temperature. The synthesized nanocatalyst and ozone are observed highly efficient for low temperature catalytic oxidation of DMS. The stability test shows that the nanocatalyst have relatively high activity and stability under the reaction conditions. A plausible reaction mechanism has been proposed for the oxidation of DMS based on the possible reaction products.

Antimicrobial properties of CuO nanorods and multi-armed nanoparticles against B. anthracis vegetative cells and endospores.

Two different kinds of CuO nanoparticles (NPs) namely CuO nanorods (PS2) and multi-armed nanoparticles (P5) were synthesized by wet and electrochemical routes, respectively. Their structure, morphology, size and compositions were characterized by SEM, EDX and XRD. The NPs demonstrated strong bactericidal potential against Bacillus anthracis cells and endospores. PS2 killed 92.17% of 4.5 × 10(4) CFU/mL B. anthracis cells within 1 h at a dose of 1 mg/mL. Whereas P5 showed a higher efficacy by killing 99.92% of 7 × 10(5) CFU/mL B. anthracis cells within 30 min at a dose of 0.5 mg/mL and 99.6% of 1.25 × 10(4) CFU/mL B. anthracis cells within 5 min at a dose of 2 mg/mL. More than 99% of spores were killed within 8 h with 2 mg/mL PS2 in LB media.

Surface plasmon resonance characterization of monoclonal and polyclonal antibodies of malaria for biosensor applications.

Surface plasmon resonance (SPR) screening of monoclonal and polyclonal antibodies of Plasmodium falciparum (MoabPf and PoabPf) for recombinant Histidine rich protein-II antigen (Ag) of Pf (rHRP-II Ag) was conducted in a real-time and label-free manner to select an appropriate antibody (Ab) for biosensor applications. In this study 4-mercaptobenzoic acid (4-MBA) modified gold SPR chip was used for immobilizing the Ag and then Ab was interacted. SEM image showed modification of SPR chip with 4-MBA and EDAX confirmed the presence of 4-MBA on the SPR chip. Equilibrium constant (KD) and maximum binding capacity of analyte (Bmax) values for the interaction of MoabPf or PoabPf with the immobilized rHRP-II Ag were calculated and found to be 0.517 nM and 48.61 m° for MoabPf and 2.288 nM and 46.80 m° for PoabPf, respectively. In addition, thermodynamic parameters such as ΔG, ΔH and ΔS were determined for the interaction between rHRP-II Ag and MoabPf or PoabPf and the values revealed that the interaction is spontaneous, exothermic and driven by entropy. The kinetics and thermodymanic results of this study revealed that the interaction between MoabPf and rHRP-II Ag is more effective than that of PoabPf due to the fact that MoabPf was derived from a single epitope (single clone) whereas the PoabPf was from the mixture of a number of epitopes (polyclones). Finally, SPR methodology was developed for the sensing of malarial antibodies. The limit of detection was found to be 5.6 pg with MoabPf which was found to be the best in our study.

Alumina-supported oxime for the degradation of sarin and diethylchlorophosphate.

1-(4-Chlorophenyl))-N-hydroxymethanimine and cyclohexyl-N-hydroxymethanimine were synthesized and a well-established oxime, i.e., 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride was purchased. Thereafter; all were loaded over Al(2)O(3) using incipient wetness technique. The prepared systems were characterized using surface area analyzer, scanning electron microscope, energy dispersive X-ray spectrophotometer, Fourier transform infrared spectrophotometer and thermogravimetric analyzer. Kinetics of the degradation of sarin (GB) and simulant, i.e. diethylchlorophosphate (DEClP) was studied over synthesized oxime impregnated Al(2)O(3) and results were compared with well reported oxime impregnated Al(2)O(3). Kinetics of reaction was found to be following the pseudo first order reaction kinetics. The order of reactivity of the prepared systems was found to be cyclohexyl-N-hydroxymethanimine/Al(2)O(3)>1-(4-chlorophenyl)-N-hydroxymethanimine/Al(2)O(3)>2-[(hydroxyimino)methyl]-1-methylpyridinium chloride/Al(2)O(3)>Al(2)O(3). From the reaction kinetics it was observed that the reaction with DEClP was faster than with GB. Cyclohexyl-N-hydroxymethanimine/Al(2)O(3) was found to be the most reactive system with half-life of 0.94 and 15 h for DEClP and GB respectively.

A convenient first aid kit for chemical and biological agents and for radiation exposure.

The chemical and biological warfare agents are extremely toxic in nature. They act rapidly even in very small quantities and death may occur in minutes. Hence, physical and medical protection must be provided immediately to save life or avoid serious injury. A first aid kit has thus been developed for providing immediate relief from chemical and biological warfare agents (FAKCBW) with the objective of easy detection, personal decontamination, antidote for chemical warfare agents (like nerve agents, sulphur mustard, phosgene, cyanide, radiation exposure and bacterial agents), along with basic medication aid for pain, fever and inflammation. The kit box also includes a user friendly handbook with a simple standard operating procedure. In addition, the kit is rugged to withstand normal jerks, vibration and is water-proof.

Catalytic removal of carbon monoxide over carbon supported palladium catalyst.

Carbon supported palladium (Pd/C) catalyst was prepared by impregnation of palladium chloride using incipient wetness technique, which was followed by liquid phase reduction with formaldehyde. Thereafter, Pd/C catalyst was characterized using X-ray diffractometery, scanning electron microscopy, atomic absorption spectroscopy, thermo gravimetry, differential scanning calorimetry and surface characterization techniques. Catalytic removal of carbon monoxide (CO) over Pd/C catalyst was studied under dynamic conditions. Pd/C catalyst was found to be continuously converting CO to CO(2) through the catalyzed reaction, i.e., CO+1/2O(2)→CO(2). Pd/C catalyst provided excellent protection against CO. Effects of palladium wt%, CO concentration, humidity, space velocity and reaction environment were also studied on the breakthrough behavior of CO.

Kinetics of degradation of sulfur mustard and sarin simulants on HKUST-1 metal organic framework.

The applicability of HKUST-1 for the degradation of sulfur mustard and sarin simulants was studied with and without coadsorbed water. Degradation was found to be via hydrolysis and dependent on the nucleophilic substitution reaction, vapour pressure and molecular diameter of the toxicants.

Surface plasmon resonance immunosensor for the detection of Salmonella typhi antibodies in buffer and patient serum.

Surface plasmon resonance (SPR) immunosensor using 4-mercaptobenzoic acid (4-MBA) modified gold SPR chip was developed first time for the detection of flagellin specific antibodies of Salmonella typhi (S. typhi). Flagellin protein of S. typhi was prepared by recombinant DNA technology. The modification of gold chip with 4-MBA was in-situ characterized by SPR and electrochemical impedance spectroscopy. By using kinetic evaluation software, K(D) and B(max) values were calculated and found to be 26.3 fM and 62.04 m°, respectively, for the immobilized monoclonal antibody (Moab) of recombinant flagellin (r-fla) protein of S. typhi (r-fla S. typhi). In addition, thermodynamic parameters such as ΔG, ΔH and ΔS were determined first time for r-fla S. typhi and Moab of r-fla S. typhi interactions and the values revealed the interaction between r-fla S. typhi and Moab of r-fla S. typhi as spontaneous, endothermic and entropy driven one. Moreover, healthy human serum samples and patient sera (Widal positive and Widal negative) were subjected to SPR analysis. The present SPR based approach provides an alternative way for S. typhi detection in less than 10 min.

Removal of sulphur mustard, sarin and simulants on impregnated silica nanoparticles.

Silica nanoparticles of diameter, 24-75 nm and surface area, 875 m(2)/g were synthesized using aero-gel route. Thereafter, nanoparticles were impregnated with reactive chemicals, and used as reactive adsorbent to study the removal of toxic nerve and blister chemical warfare agents and their simulants from solutions. Trichloroisocyanuric acid impregnated silica nanoparticles showed the best performance and indicated physisorption followed by chemisorption/degradation of toxicants. This indicated their suitability as universal decontaminant for nerve and blister agents. This system showed a decrease in t(1/2) from 1210 to 2.8 min for the removal of king of chemical warfare agents, i.e., sulphur mustard. Hydrolysis, dehydrohalogenation and oxidation reactions were found to be the route of degradation of toxicants over impregnated silica nanoparticles.

Effect of calcinations temperature of CuO nanoparticle on the kinetics of decontamination and decontamination products of sulphur mustard.

Present study investigates the potential of CuO nanoparticles calcined at different temperature for the decontamination of persistent chemical warfare agent sulphur mustard (HD) at room temperature (30 ± 2 °C). Nanoparticles were synthesized by precipitation method and characterized by using SEM, EDAX, XRD, and Raman Spectroscopy. Synthesized nanoparticles were tested as destructive adsorbents for the degradation of HD. Reactions were monitored by GC-FID technique and the reaction products characterized by GC-MS. It was observed that the rate of degradation of HD decreases with the increase in calcination temperature and there is a change in the percentage of product of HD degradation. GC-MS data indicated that the elimination product increases with increase in calcination temperature whereas the hydrolysis product decreases.

Significance of porous structure on degradatin of 2,2' dichloro diethyl sulphide and 2 chloroethyl ethyl sulphide on the surface of vanadium oxide nanostructure.

Degradation of the king of chemical warfare agent, 2,2' dichloro diethyl sulphide (HD), and its simulant 2 chloroethyl ethyl sulphide (CEES) were investigated on the surface of porous vanadium oxide nanotubes at room temperature (30 ± 2°C). Reaction kinetics was monitored by GC-FID technique and the reaction products were characterized by GC-MS. Data indicates that HD degraded faster relative to CEES inside the solid decontaminant compared to the reported liquid phase degradation of CEES and HD. Data explores the role of hydrolysis, elimination and oxidation reactions in the detoxification of HD and CEES and the first order rate constant and t(1/2) were calculated to be 0.026 h(-1), 26.6h for CEES and 0.052 h(-1), 13.24h for HD. In this report faster degradation of HD compared to CEES was explained on the basis of porous structure.

Photocatalytic inactivation of spores of Bacillus anthracis using titania nanomaterials.

Studies on photocatalytic inactivation of spores of Bacillus anthracis have been carried out using nanosized titania materials and UVA light or sun light. Results demonstrated pseudo first order behaviour of spore inactivation kinetics. The value of kinetic rate constant increased from 0.4h(-1) to 1.4h(-1) indicating photocatalysis facilitated by addition of nanosized titania. Nanosized titania exhibited superior inactivation kinetics on par with large sized titania. The value of kinetic rate constant increased from 0.02 h(-1) to 0.26 h(-1) on reduction of size from 1000 nm to 16 nm depicting the enhanced rate of inactivation of Bacillus anthracis Sterne spores on the decrease of particle size.