Real-time sensitive detection of Cr (VI) in industrial wastewater and living cells using carbon dot decorated natural kyanite nanoparticles.

This article reports a facile strategy to detect hexavalent chromium (Cr (VI)) using a naturally formed mineral (kyanite) based fluorometric sensor. Nitrogenous carbon dots have been incorporated into natural kyanite (KYCD) nanoparticles causing a stable bright blue fluorescence compared to its pristine counterpart. This sensing probe structurally stabilizes and resists the agglomeration of carbon dots, thus retaining fluorescence quality for a longer period. The promising bright blue fluorescence has been utilized further to detect Cr (VI) in wastewater and living cells. Ease of synthesis, low cost, and stability of the system offers the benefit for large-scale production, which is convenient for industrial production the sensing probe. The sensor shows high selectivity and sensitivity (LOD and LOQ of 0.11 µM and 0.36 µM respectively in case of linear fitting, whereas 0.26 µM and 0.88 µM respectively for full range plot) towards hexavalent chromium in presence of other interfering elements. A detailed study of photoinduced electron transfer (PET) mediated rapid 'turn off' sensing mechanism was carried out using Time-Dependent Density functional (TDDFT) calculations. The sensing efficacy of the probe remains unaltered under a wide range of pH and can be effective in various water types. Onsite sampling and probing of Cr (VI) in tannery wastewater has been performed to validate its real-life efficiency that yields excellent results. The sensor can effectively detect chromium at a cellular level (HeLa cells) in a similar way as the bright blue fluorescence diminishes in presence of the quenching ion. Experimental in vitro studies along with theoretical docking analysis has been conducted to substantiate such issues and a higher possibility of fluorophore binding was found for Isoleucine (2.9 Å), Serine (2.96 Å), and Glycine (3.16 Å). This biocompatible sensor rapidly senses hexavalent chromium in living cells, which makes this efficient probe a true heavy metal-induced carcinogen sensor.

Flexible and reusable carbon dot decorated natural microcline membrane: a futuristic probe for multiple heavy metal induced carcinogen detection.

A flexible nano-engineered natural mineral (carbon dot doped natural microcline) based membrane (MCPV) has been developed, which can efficiently detect the presence of hexavalent chromium (Cr6+) and trivalent iron (Fe3+) ions in water by altering its fluorescence emission. Detailed characterization of the membrane was carried out using XRD, FT-IR spectroscopy, FESEM, TEM, and UV-Vis spectroscopy. Mechanical and temperature stabilities were also investigated. This new-generation sensor membrane is designed in such a way that it does not dissolve in water, keeping the water quality unaffected. The fluorescence studies were conducted at 414 nm and "turn-off" response was observed specifically for Fe3+ at 489 nm. A prominent red shift (530 nm) of the fluorescence maxima takes place when it comes to Cr6+. Figures of merit, such as LOD (8.7 µM for Cr6+ and 18.4 µM for Fe3+) and LOQ (29.1 µM for Cr6+ and 61.6 µM for Fe3+), were evaluated from the linear range (0-60 µM for Cr6+ and 0-30 µM for Fe3+) of the calibration curve (Stern-Volmer plots) showing high sensitivity of this sensing probe toward Cr6+ and Fe3+. Recovery and RSD calculations were done in various real-life water samples on intraday-interday basis to determine the accuracy of the sensor. This work validates the fact that the synthesized sensor membrane is capable of detecting these heavy metals in glutathione environment as well, which could be beneficial for early-stage carcinogen detection in living cells.

Microstructure Analysis and Chemical and Mechanical Characterization of the Shells of Three Freshwater Snails.

The shells of freshwater snails are discarded as waste, which qualify as biological materials with prospective multiple uses. To substantiate this proposition, an attempt was made to elucidate the physical and chemical properties of the shells of three freshwater snails, namely, Bellamya bengalensis, Pila globosa, and Brotia costula. The shells were prepared for electron microscopy and assessment of the calcium carbonate content, apart from the Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), and nanoindentation studies. The results indicated that the calcium carbonate content (y) of the shells ranged between 87 and 96% of the total weight (x) and complied with a power regression equation: y = 0.801x 1.016; R 2 = 0.994; r = +0.998; P < 0.001. Observations through SEM depicted different snail species-specific arrangement patterns of calcium carbonate crystals in the diverse layers of shells. The XRD, FTIR, and EDS observations revealed the dominance of the aragonite form of the calcium carbonate crystal in the microstructures of each snail shell with the occurrence of different shell surface functional groups. The Brunauer-Emmett-Teller analysis elucidated the surface textures of shell dust taken from each snail species; in addition, the nanohardness properties indicate the shells as a tough biocomposite exoskeleton. Species-specific variations in the shell morphology, microstructure, and calcium carbonate content were prominent for the three freshwater snails considered for the study. Nonetheless, the physical and chemical properties substantiate that the shells of B. bengalensis, P. globosa, and B. costula qualify as biological materials for sustainable use in various fields including bioremediation, biocatalyst, biomedical applications, and a source of lime. Since the shells of the freshwater snails are discarded as aquaculture waste, subsequent use as a biological material will support the "waste made useful" paradigm in sustainability, both from ecological and economic perspectives.

In Situ-Grown Cdot-Wrapped Boehmite Nanoparticles for Cr(VI) Sensing in Wastewater and a Theoretical Probe for Chromium-Induced Carcinogen Detection.

In modern society, massive industrialization escalates environmental degradation by liberating various contaminants into the environment. Hexavalent chromium is a heavy metal that is being discharged from tannery and other industries, resulting in various carcinogenic diseases. This study reports a carbon dot (cdot)-based fluorometric probe for detecting hexavalent chromium in water. This is the very first time that cdots are tailored over the boehmite nanoparticle's surface using an in situ approach. Validation of formation of the nanocomposite has been discussed in detail employing the Rietveld refinement-based X-ray crystallography method. Vibrational spectroscopy and electron microscopy of the sample authenticate the nucleation process and the growth mechanism. The Stern-Volmer approach and time-resolved fluorescence measurements justify the sensitivity of the sensor (∼58 nM), and selectivity is analyzed by exposing the material to different ionic environments. Density functional theory (DFT) is applied herein to analyze the origin of fluorescence and the sensing mechanism of the probe, which shows that photoinduced electron transfer is responsible for the turn-off-based sensing of Cr(VI). The molecular docking simulation is carried out to ensure the binding of cdots to the binding pocket of the glutathione enzyme, which is responsible for treating reactive oxygen species-mediated DNA damage due to elements such as hexavalent chromium. Time-dependent density functional calculations show that the fluorometric probe is capable of detecting Cr(VI) in living cells making it an early stage chromium-mediated carcinogen detector.

Nitrogenous carbon dot decorated natural microcline: an ameliorative dual fluorometric probe for Fe3+ and Cr6+ detection.

In the modern era, the escalation of heavy metal discharges, especially from the industrial sector, is causing an enormous threat to nature. This article explores the dual sensing of heavy metals (Cr6+ and Fe3+) using a naturally formed microcline based sensor. A nano-sized microcline (M) was obtained via a facile top-down synthesis. In order to enhance the fluorescence property of the material, nitrogenous carbon-dots were loaded into the porous structure of the microcline (MCD) causing a bright blue fluorescence with remarkable stability. Detailed analysis of the composition and structure of the natural nano-sensor was carried out using X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and BET analysis. This sensor material is highly selective towards Cr6+ and Fe3+, demonstrating a "turn-off" response in aqueous Fe3+ and a radical red shift of the fluorescence maxima for aqueous Cr6+. Density functional studies suggest that photoinduced electron transfer (PET) based quenching of fluorescence is responsible for these types of fluorescence alteration mechanisms. Efficient sensing of both Cr6+ and Fe3+ in various real-life water samples along with a real wastewater sample is also reported herein. A few studies have previously reported on efficient, natural material-based sensors, but they lack real-life applications due to their complicated synthesis and restricted functionalities. This work manages to overcome those drawbacks in its own fashion, providing a tremendously selective and sensitive (4 µM for Cr6+ and 19 µM for Fe3+) dual fluorescent probe.

Development of a Cu(ii) doped boehmite based multifunctional sensor for detection and removal of Cr(vi) from wastewater and conversion of Cr(vi) into an energy harvesting source.

This article reports a copper doped boehmite (CBH) based nano-material which is capable of detecting and removing hexavalent chromium simultaneously. Basic characterization has been performed to determine its phase purity, particle size (∼20 nm), morphology and surface properties (surface area 15.29 m2 g-1 and pore diameter 3.9 nm) by using some basic characterization tools. The Rietveld refinement method has been adopted to analyze the microstructural details of the synthesized nanostructure. Photoinduced electron transfer (PET) based quenching of fluorescence is mainly responsible for chromium sensing in this case. This nanosensor is exceptionally sensitive (limit of detection ∼ 6.24 µM) and merely selective towards hexavalent chromium ions. Industrial wastewater samples have also been used here to demonstrate the real life applicability of this material, which shows the same trend. This fluoro-sensor gains its multi-functionality when it comes to the adsorption based removal of Cr(vi) from wastewater. The synthesized material shows a remarkably high adsorption rate (∼85% in just 5 minutes) due to its sponge-like porous structure. Adsorption of hexavalent chromium from wastewater enhances the dielectric constant of this material significantly (∼7.93 times). Ionic polarization-dependent enhancement of the dielectric constant resulting from industrial wastewater treatment is a quite unmarked approach. Very low tangent loss with augmented dielectric permittivity makes this nano-material desirable for energy harvesting applications. Previously many articles have reported the sensing and removal of various industrial effluents. Keeping this in mind, this work has been designed and, apart from sensing and removal, it provides a new insight into energy harvesting from wastewater.

An insight into the structure, composition and hardness of a biological material: the shell of freshwater mussels.

The shell of the freshwater mussel (Mollusca: Bivalvia) is a composite biological material linked with multifunctional roles in sustaining ecosystem services. Apart from providing mechanical strength and support, the shell is an important site for adherence and growth of multiple types of algae and periphyton. Variations in the shell architecture are observed in the mussels both within a species and among different species. Considering the prospective utility of the shell of the freshwater mussels as a biological material, an assessment of the shell characteristics was accomplished using Corbicula bensoni and Lamellidens marginalis as model species. The calcium carbonate (CaCO3) content of the shells, physical features and mechanical strength were assessed along with the morphometric analysis. The CaCO3 content of the shell (upto 95% to 96% of the shell weight) of both the mussels was positively correlated with the shell length, suggesting increased deposition of CaCO3 in shells with the growth of the species. The cross sectioned views of FE-SEM images of the shells exhibited distinct layered structure with external periostracum and inner nacreous layer varying distinctly. In the growing region, the growth line was prominent in the mussel shells revealed through the FESEM images. In addition XRD, FTIR and EDS studies on the mussel shells confirmed the existence of both aragonite and calcite forms of the calcium carbonate crystals with the incidence of various functional groups. The mechanical strength of the mussel shells was explored through nanoindentation experiments, revealed significant strength at the nanoparticle level of the shells. It was apparent from the results that the shell of the freshwater mussel L. marginalis and C. bensoni qualify as a biological material with prospective multiple applications for human well-being and sustaining environmental quality.

Gd(III)-Doped Boehmite Nanoparticle: An Emergent Material for the Fluorescent Sensing of Cr(VI) in Wastewater and Live Cells.

This article reports the effect of Gd(III) doping on the structure, microstructure, and optical properties of boehmite nanoparticles. The bright-blue fluorescence along with a long lifetime makes our material an efficient candidate for optical applications. Our material particularly targets and eliminates hexavalent chromium ions (Cr(VI)) from aqueous media, which turns it into a multifunctional fluorescent nanosensor (MFNS). The development of an efficient hexavalent chromium ion (Cr(VI)) sensor to detect and quantify Cr(VI) ions is still a serious issue worldwide. Thus, this work will be very beneficial for various environmental applications. No such work has been reported so far which includes cost-effective and biocompatible boehmite nanoparticles in this field. Detailed synthesis and characterization procedures for the MFNS have been incorporated here. The biocompatibility of the MFNS has also been studied rigorously by performing cell survivability assay (MTT) and cellular morphology assessments. Our extensive research confirmed that the "turn-off" sensing mechanism of this sensor material is based on a collisional quenching model which initiates the photoinduced electron transfer (PET) process. High selectivity and sensitivity (∼1.05 × 10-5 M) of the MFNS toward hexavalent chromium ions even in real life wastewater samples have been confirmed, which makes this fluorescent probe a potential candidate for new age imaging and sensing technologies.

Effect of Morphology and Concentration on Crossover between Antioxidant and Pro-oxidant Activity of MgO Nanostructures.

The toxicity of nanomaterials can sometimes be attributed to photogenerated reactive oxygen species (ROS), but these ROS can also be scavenged by nanomaterials, yielding opportunities for crossover between the properties. The morphology of nanomaterials also influences such features due to defect-induced properties. Here we report morphology-induced crossover between pro-oxidant activity (ROS generation) and antioxidant activity (ROS scavenging) of MgO. To study this process in detail, we prepared three different nanostructures of MgO (nanoparticles, nanoplates, and nanorods) and characterized them by HRTEM. These three nanostructures effectively generate superoxide anions (O2•-) and hydroxyl radicals (•OH) at higher concentrations (>500 µg/mL) but scavenge O2•- at lower concentrations (40 µg/mL) with successful crossover at 200 µg/mL. Nanorods of MgO generate the highest levels of O2•-, whereas nanoparticles scavenge O2•- to the highest extent (60%). Photoluminescence studies reveal that such crossover is based on the suppression of F2+ and the evolution of F+, F2+, and F23+ defect centers. The evolution of these defect centers reflects the antibacterial activity of MgO nanostructures which is initiated at 200 µg/mL against Gram-positive S. aureus ATCC 29737 and among different bacterial strains including Gram-positive B. subtilis ATCC 6633 and M. luteus ATCC 10240 and Gram-negative E. coli ATCC K88 and K. pneumoniae ATCC 10031. Nanoparticles exhibited the highest antibacterial (92%) and antibiofilm activity (17%) against B. subtilis ATCC 6633 in the dark. Interestingly, the nitrogen-centered free radical DPPH is scavenged (100%) by nanoplates due to its large surface area (342.2 m2/g) and the presence of the F2+ defect state. The concentration-dependent interaction with an antioxidant defense system (ascorbic acid (AA)) highlights nanoparticles as potent scavengers of O2•- in the dark. Thus, our findings establish guidelines for the selection of MgO nanostructures for diverse therapeutic applications.

Nanomechanical responses of human hair.

Here we report the first ever studies on nanomechanical properties e.g., nanohardness and Young׳s modulus for human hair of Indian origin. Three types of hair samples e.g., virgin hair samples (VH), bleached hair samples (BH) and Fe-tannin complex colour treated hair samples (FT) with the treatment by a proprietary hair care product are used in the present work. The proprietary hair care product involves a Fe-salt based formulation. The hair samples are characterized by optical microscopy, atomic force microscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy (EDAX) genesis line map, EDAX spot mapping, nanoindentation, tensile fracture, and X-ray diffraction techniques. The nanoindentation studies are conducted on the cross-sections of the VH, BH and FT hair samples. The results prove that the nanomechanical properties e.g., nanohardness and Young׳s modulus are sensitive to measurement location e.g., cortex or medulla and presence or absence of the chemical treatment. Additional results obtained from the tensile fracture experiments establish that the trends reflected from the evaluations of the nanomechanical properties are general enough to hold good. Based on these observations a schematic model is developed. The model explains the present results in a qualitative yet satisfactory manner.