Studies on the removal of acid violet 7 dye from aqueous solutions by green ZnO@Fe3O4 chitosan-alginate nanocomposite synthesized using Camellia sinensis extract.

In the present study, ZnO-Fe3O4 nanoparticles were synthesized using the leaves of Camellia sinensis and immobilized in crosslinked alginate-chitosan polymer beads and tested for their photocatalytic applications. The prepared nanocomposite was used for the simultaneous adsorption and photocatalytic degradation of acid violet 7 (AV7) dye. The optimization of reaction conditions ensured higher dye removal efficacy up to 94.21 ± 1.02% using the nanocomposite under UV-C irradiation of 365 nm. The kinetics of the adsorption study fitted well with the pseudo-first-order reaction. The Langmuir model fitted better to the adsorption isotherms compared to the Freundlich and Temkin models. The mechanism of degradation was studied by analyzing the treated AV7 solution. The removal efficiency in tap water, groundwater, and lake water was 83.23 ± 0.4%, 69.13 ± 1.6%, and 67.89 ± 0.3%, respectively. The residual toxicity of the degraded AV7 solution was tested on model organisms like freshwater algae, Scenedesmus sp., and plant model, Allium cepa, demonstrating the lower toxicity of the degraded AV7 product. Finally, a cost-benefit analysis of the experiments was also carried out.

Toxicity evaluation of nano-TiO2 in the presence of functionalized microplastics at two trophic levels: Algae and crustaceans.

The rising use of contaminants such as nanoparticles and microplastics has taken a heavy toll on the marine environment. However, their combined toxic effects on the species across various trophic levels remain quite unexplored. The aim of this study was to explore the effects of three surface-functionalized (carboxylated, plain, and aminated) polystyrene microplastics on nano-TiO2 toxicity across two trophic levels containing Chlorella sp. as the prey and Artemia salina as the predator. The experiments carried out on Chlorella sp. include the toxicity assessment, oxidative stress determination, and uptake of nano-TiO2 (both in the presence and absence of microplastics). Results revealed that the aminated and plain polystyrene microplastics enhanced nano-TiO2 toxicity, while carboxylated microplastics decreased the toxic effects in Chlorella sp. On the other hand, toxicity assessment in Artemia salina was carried out using two different modes of exposure: aqueous and dietary routes. The aqueous route involving the direct exposure of nano-TiO2 and microplastics indicated greater toxicity, uptake, and accumulation in Artemia salina than the dietary route of exposure. Since dietary exposure decreased the toxicity, uptake, and accumulation of nano-TiO2, no change (p > 0.05) in the biomagnification factors of nano-TiO2 was noted for all the test concentrations of nano-TiO2 combined with and without microplastics. The computed values were less than 1, indicating negligible transfer of nano-TiO2 from Chlorella sp. to Artemia salina. Overall, the study highlights the two-level trophic toxicity and the transfer potential of nano-TiO2 under the influence of different microplastics.

Development of biogenic bimetallic Pd/Fe nanoparticle-impregnated aerobic microbial granules with potential for dye removal.

The objective of this study was to develop bimetallic core-shell Pd/Fe nanoparticles on the surface of aerobic microbial granules (Bio-Pd/Fe) and to evaluate their dye removal potential using a representative dye, methyl orange (MO). The aerobic microbial granules (1.5 ± 0.32 mm) were grown for 70 days in a 3-L glass sequencing batch reactor (SBR) with a 12-h cycle time. The Bio-Pd/Fe formation was catalyzed by the Bio-H2 gas produced by the granules. The developed Bio-Pd/Fe was further used for MO removal from aqueous solutions, and the reaction parameters were optimized by response surface methodology (RSM). The XRD, SEM, EDAX, elemental mapping, and XPS studies confirmed the formation of Bio-Pd/Fe. Under the optimized removal conditions, 99.33% MO could be removed by Bio-Pd/Fe, whereas removal by Bio-Pd, Bio-Fe, aerobic microbial granules, and heat-killed granules were found to be quite low (68.91 ± 0.2%, 76.8 ± 0.3%, 19.8 ± 0.6%, and 6.59 ± 0.2%, respectively). The mechanism of removal was investigated by UV-visible spectroscopy, redox potential analysis, HR-LCMS analyses of the solution phase, and XRD and XPS analyses of the solid sorbent. The degradation products of MO exhibited m/z values corresponding to 292, 212, and 160 m/z. The remnant toxicity of the intermediate degradation products was analysed using freshwater algae, Scenedesmus sp. And Allium cepa, as indicator organisms. These assays suggested that after the treatment with Bio-Pd/Fe, MO was transformed to a lesser toxic form.

Interactive effects of micro/nanoplastics and nanomaterials/pharmaceuticals: Their ecotoxicological consequences in the aquatic systems.

Micro/nanoplastics are ubiquitous in the environment and cause pollution of the aquatic ecosystem, in particular, which is a serious concern worldwide. Micro/nanoplastics can act as a vector for multiple co-contaminants that co-exist in the aquatic environment. Apart from micro/nanoplastics, nanomaterials and pharmaceuticals are other emerging contaminants that can also raise severe problems. Thus, in this review, the physicochemical interactions occurring between micro/nanoplastics and nanomaterials and pharmaceuticals and the factors (chemical and environmental) affecting the sorption efficiency of nanomaterials and pharmaceuticals have been addressed. Furthermore, the influence of micro/nanoplastics on the bioavailability and toxic effects of nanomaterials and pharmaceuticals on both freshwater and marine species has been highlighted. Additional focus has also been given to study the mechanism of toxicity of the micro/nanoplastics-nanomaterials and pharmaceuticals complex on the different species of different trophic levels. Finally, this review addresses the knowledge gaps and provides insights into the future research strategies to better understand the interactive mechanisms between the binary contaminants and also the toxicity mechanisms of micro/nanoplastics and nanomaterials and pharmaceuticals.

A review on tetracycline removal from aqueous systems by advanced treatment techniques.

Tetracycline (TC), a frequently used drug for human and veterinary therapeutics, is among the most common antibiotic residues found in nature. Lack of advanced treatment techniques in the wastewater treatment plants (WWTPs) to remove residual TC from domestic and hospital wastewater poses a serious environmental risk. It is important to have an insight into the different advanced treatment techniques for efficient removal of TC from the surface water and in the WWTPs. The aim of this review is to discuss the nature and occurrence of TC in surface water and to present an overview of the various advanced treatment techniques for TC removal. The advanced treatment techniques include advanced oxidation processes (photolysis, ozonation, and catalytic/UV light-based degradation), membrane filtration, reverse osmosis, and adsorption techniques. Adsorption and integrated oxidation treatment techniques are the most widely studied methods, and they are widely accepted because of less cost, reusability, and toxic-free nature. Further, the uses of various types of catalysts for photodegradation and various sorbents for adsorption of TC are also presented. Finally, the importance of green nanocomposite for environmental sustainability in TC removal is emphasized.

Bimetallic gold nanorods with enhanced biocorona formation for doxorubicin loading and sustained release.

The biomedical applicability of gold nanorods (AuNRs) arises due to their interesting optical and photothermal properties, which can result in the formation of a protein corona layer when exposed to the physiological system. The current study focuses on the effect of bimetallic coatings of AuNRs (AuNRs@Pd and AuNRs@Cu) on protein corona formation, and the potential application of protein-coronated bimetallic AuNRs was investigated for doxorubicin (dox) loading, release, and in vitro cytotoxicity analysis. Two significant proteins in blood serum, namely, human serum albumin (HSA) and transferrin, were chosen for the protein coronation. The variations in the protein adsorption patterns of monometallic and bimetallic AuNRs were studied based on the protein adsorption, zeta potential, and particle size measurements. A higher adsorption of hard and soft corona was observed for HSA due to their higher abundance and reactivity. The enhanced electropositive nature of these bimetals promoted higher corona formation (AuNR@Pd > AuNR@Cu > AuNRs) when compared with bare AuNRs, which in turn correlated with higher dox loading. The higher corona on bimetallic AuNRs helped to overcome the burst release of dox over a period of 48 h (AuNRs@Pd > AuNR@Cu > AuNRs) when compared to the respective monometallic AuNRs, and the dox release was slightly increased when tested in human plasma. Furthermore, a significant decrease in the cytotoxicity of protein-coronated bimetallic AuNRs as compared to monometallic AuNRs was also observed. Thus, it can be suggested that the use of engineered protein corona on bimetallic nanostructures can open new areas of research for cancer therapeutics.

A facile gold nanoparticle-based ELISA system for detection of osteopontin in saliva: Towards oral cancer diagnostics.

In the current study, we emphasize that osteopontin is overexpressed in oral squamous cell carcinoma. Overexpression of osteopontin levels was confirmed by mRNA quantification studies and immunohistochemistry analysis. Based on this, a gold nanoparticle-based ELISA system was developed for non-invasive osteopontin detection. The incorporation of AuNRs (Gold nanorods) or AuNSs (Gold nanospheres) in the conventional ELISA improved the sensitivity of analyses. A considerably lowered detection limit in case of AuNR (detection limit: 0.02ngmL-1) and AuNS (detection limit: 0.03ngmL-1) modified assay was obtained as compared to commercially available OPN ELISA kit (detection limit: 0.14ngmL-1). The modified ELISA had a wide linear detection range (0.31-20ngmL-1), good reproducibility, and specificity against the tested interferents in the saliva. Finally, the nanoELISA was validated with osteopontin spiked in artificial and normal saliva samples and observed to show good recovery (95.4-97.85%), which indicates the application potential of the developed kit for real sample analysis.

Significance of surface functionalization of Gold Nanorods for reduced effect on IgG stability and minimization of cytotoxicity.

Gold nanorods (AuNRs) used for biomedical applications could be encountered by biomolecules in the bloodstream, of which IgG is the most abundant antibody. With a view to mitigate their side effect on encountered proteins, the effect of Au concentration (5-40µM) and functionalization (CTAB-positive;PSS-negative; PEG-neutral) of AuNRs was investigated on the stability of a model protein, IgG (1µM). Electron microscopic images and particle size analyses indicated least aggregation behavior for PEG-AuNRs, which can be correlated to their neutral charge (from zeta potential analyses) or stearic hindrance of PEG chains. Variations in tryptophan domain were probed by UV-visible absorption and fluorescence quenching studies. Synchronous fluorescence study helped to provide information regarding variations in the hydrophobic region of IgG. The denaturation studies also indicated the stability of AuNR-IgG complex formation. These studies showed that positively charged IgG (pI: 7.8±1.0) was mostly affected by negatively charged PSS-AuNRs and least affected by PEG-AuNRs. This was verified by secondary structural investigations performed using CD and FTIR spectroscopy. For cytotoxicity studies on human lymphocytes, CTAB-AuNRs are known to show higher toxicity compared to PSS-AuNRs and PEG-AuNRs (least). Though PSS-functionalized AuNRs were shown to affect cells to a lesser degree based on the negative charge of cell membrane, they could hamper with positively charged biomolecules in the bloodstream before they reach the target, which must also be considered for choosing the right AuNR functionalization. Thus, this work indicates the effect of different AuNR functionalization on protein and cellular toxicity and stresses the necessity to use neutral particles to mitigate their side effect for theranostic applications.

Cytotoxicity of aluminum oxide nanoparticles on Allium cepa root tip--effects of oxidative stress generation and biouptake.

The commercial usage of Al2O3 nanoparticles (Al2O3 NPs) has gone up significantly in the recent times, enhancing the risk of environmental contamination with these agents and their consequent adverse effects on living systems. The current study has been designed to evaluate the cytogenetic potential of Al2O3 NPs in Allium cepa (root tip cells) at a range of exposure concentrations (0.01, 0.1, 1, 10, and 100 µg/mL), their uptake/internalization profile, and the oxidative stress generated. We noted a dose-dependent decrease in the mitotic index (42 to 28 %) and an increase in the number of chromosomal aberrations. Various chromosomal aberrations, e.g. sticky, multipolar and laggard chromosomes, chromosomal breaks, and the formation of binucleate cells, were observed by optical, fluorescence, and confocal laser scanning microscopy. FT-IR analysis demonstrated the surface chemical interaction between the nanoparticles and root tip cells. The biouptake of Al2O3 in particulate form led to reactive oxygen species generation, which in turn probably contributed to the induction of chromosomal aberrations.

Combined toxicity of two crystalline phases (anatase and rutile) of Titania nanoparticles towards freshwater microalgae: Chlorella sp.

In view of the increasing usage of anatase and rutile crystalline phases of titania NPs in the consumer products, their entry into the aquatic environment may pose a serious risk to the ecosystem. In the present study, the possible toxic impact of anatase and rutile nanoparticles (individually and in binary mixture) was investigated using freshwater microalgae, Chlorella sp. at low exposure concentrations (0.25, 0.5 and 1mg/L) in freshwater medium under UV irradiation. Reduction of cell viability as well as a reduction in chlorophyll content were observed due to the presence of NPs. An antagonistic effect was noted at certain concentrations of binary mixture such as (0.25, 0.25), (0.25, 0.5), and (0.5, 0.5) mg/L, and an additive effect for the other combinations, (0.25, 1), (0.5, 0.25), (0.5, 1), (1, 0.25), (1, 0.5), and (1, 1) mg/L. The hydrodynamic size analyses in the test medium revealed that rutile NPs were more stable in lake water than the anatase and binary mixtures [at 6h, the sizes of anatase (1mg/L), rutile NPs (1mg/L), and binary mixture (1, 1mg/L) were 948.83±35.01nm, 555.74±19.93nm, and 1620.24±237.87nm, respectively]. The generation of oxidative stress was found to be strongly dependent on the crystallinity of the nanoparticles. The transmission electron microscopic images revealed damages in the nucleus and cell membrane of algal cells due to the interaction of anatase NPs, whereas rutile NPs were found to cause chloroplast and internal organelle damages. Mis-shaped chloroplasts, lack of nucleus, and starch-pyrenoid complex were noted in binary-treated cells. The findings from the current study may facilitate the environmental risk assessment of titania NPs in an aquatic ecosystem.