Geostatistical appraisal of water quality, contamination, source distribution of potentially toxic elements (PTEs) in the lower stretches of Subarnarekha River (Odisha), India, and health risk assessment by Monte Carlo simulation approach.

In the present study, the status of water quality, environmental contamination in the lower stretch of Subarnarekha River with respect to potentially toxic elements (PTEs), its seasonal distribution, and ecotoxicological health impacts were investigated. For this purpose, a combination of indexing approaches and geospatial methods was used. The estimated water quality index (WQI) has shown that the river water falls under "moderate to very poor" category during the pre-monsoon and "moderate to poor" category in the post-monsoon season. The abundance of PTEs (Pb, Cu, Ni, Cd, Fe, and Cr) was on the higher side during the pre-monsoon in comparison with the post-monsoon season. The results of contamination index (Cd) and heavy metal evaluation index (HEI) explain that Subarnarekha River has low-to-moderate levels of contamination with PTEs in the majority of sampling sites. However, HPI indicated that the river water is moderate-to-highly contaminated with PTEs in both seasons. Principal component analysis (PCA) and cluster analysis (CA) reveal that anthropogenic sources are prime contributors to PTEs contamination in Subarnarekha River. The potential non-cancerous health concerns for child and adults due to Cr and Pb in some sampling stations along the river stretch have been observed. The carcinogenic risk (CR) has been established for Cr, Pb, and Cd in Subarnarekha River with Cr (> 10-4) as the most unsafe element. Monte Carlo simulation (MCS) indicates a high risk of cancer hazards due to Cr (values > 1E-04) in present as well as future for both child and adults.

Co-containing metal-organic framework for high-performance asymmetric supercapacitors with functionalized reduced graphene oxide.

Nowadays, supercapacitors are the most coveted eco-friendly and sustainable next-generation energy storage devices. In this regard, developing supercapacitors with high energy density and power density has always been a challenge for researchers. Herein, we have exploited an electroactive Co-containing metal-organic framework (Co-MOF) using cheap and commercially available starting materials under refluxing conditions and explored its energy storage properties in three- and two-electrode methods. The Co-MOF exhibited a specific capacitance of 425 F g-1 at 2 A g-1, maintaining a capacitance of ∼78% over 2200 successive charge-discharge cycles in a three-electrode system. The two-electrode asymmetric supercapacitor (ASC) using Co-MOF as the working electrode and as-synthesized p-phenylenediamine (PPD)-functionalized reduced graphene oxide (PPD-rGO) as the counter electrode divulged a specific capacitance of 72.5 F g-1 at 2 A g-1 current density with ∼70% capacitive retention after 2200 successive charge-discharge cycles over a broad potential window of 0-1.6 V. Moreover, the ASC demonstrated a maximum power density of 11.9 kW kg-1 at 10 A g-1 and a maximum energy density of 25.8 W h kg-1 at 2 A g-1 current density. Owing to the stable electrochemical redox (Co2+/Co3+)-mediated pseudocapacitive behavior of the Co-MOF and the high surface area and electrical conductivity of in situ generated PPD-intercalated rGO, the fabricated ASC unveiled high-performance supercapacitive behaviors. To investigate the practical applicability of this material, solid-state (ASC) devices were fabricated by employing the Co-MOF as the positive electrode and PPD-rGO as the negative electrode in a KOH-based gel electrolyte, which could power a commercially available light-emitting diode bulb (∼1.8 V) for several seconds. Therefore, the elucidated high electrochemical energy storage performance of the prepared Co-MOF makes it a very promising electrode material for supercapacitors.

Proton transfer reactions of 4'-chloro substituted 3-hydroxyflavone in solvents and aqueous micelle solutions.

Flavonol 4'-chloro,3-hydroxyflavone (Cl-3HF) has been investigated in solvents of varying polarity and hydrogen-bonding capacity as well as in aqueous micelle solutions. Quantum chemical calculations indicate that although the Cl-atom at the 4'-position of the 2-phenyl ring weakly perturbs the electron distribution of the parent 3-hydroxyflavone, the nuclear framework remains largely intact, and excited state intra-molecular proton-transfer (ESIPT) is feasible. The ESIPT process in both polar solvents and micelles was found to be fast and irreversible, with remarkably long time-constants of several tens of picoseconds. This dramatic inhibition of the ESIPT rate (which is intrinsically a sub-picosecond event) could be rationalized in terms of the emergence of complexes between the solvent and the enol form of Cl-3HF, whose dynamics is coupled to the relatively slow dynamics of inter-molecular hydrogen bonds. In the micelle solutions, spectroscopic data establish that the guest Cl-3HF molecules localized almost exclusively at the polar exterior shell, where they experienced a nearly uniform local environment similar to that in moderately polar solvents. Thus, the Cl-3HF molecules tend to avoid the non-polar core of the micelles, in spite of being strongly hydrophobic themselves. This apparently unusual observation is explained by the formation of inter-molecularly hydrogen-bonded complexes between the guest Cl-3HF and the water molecules tethered to the polar shells of the micelles.