Biosynthesis of silver nanospheres, kinetic profiling and their application in the optical sensing of mercury and chlorite ions in aqueous solutions.

Pollution of water linked to microbial decontamination and extensive use of sodium chlorite (NaClO2) as a disinfectant, especially in the face of the current COVID-19 situation, is a serious water pollution issue that needs to be addressed. In this context, an environmentally friendly and cost-effective method has been developed for the biomimetic synthesis of Ag nanospheres (Ag NSs) using aqueous extract of Piper nigrum for the detection of chlorite (ClO2-) and mercury (Hg2+) ions. The strong antioxidant properties of the biomolecules present in the Piper nigrum extract reduce silver ions (Ag+) to Ag0. After optimization of the formulation parameters, it was observed that 1 mL of piper nigrum extract was sufficient to reduce and stabilize 100 mL of 1.5 mM of Ag+ in 2.5 h at 30 °C. X-ray diffraction (XRD) pattern of Ag NSs revealed their crystalline nature and the characteristic Bragg's diffraction peaks confirmed their face cubic crystal (FCC) lattice. The characteristic reddish-brown color and absorption surface plasmon resonance (SPR) band at 435 nm confirmed the successful fabrication of Ag NSs. Kinetic analysis revealed a three-phase growth pattern involving nucleation, growth and stabilization. Transmission electron microscopy (TEM) and High-resolution transmission electron microscopy (HRTEM) micrograms, showed spherical NSs with narrow polydispersity with particle size ranging from 10 to 30 nm. The synthesized NSs were exposed to various metal ions and anions. The absorption intensity of Ag NSs quenched in the presence of mercury ions (Hg2+) among the cations and Chlorite ions (ClO2-) among the anions. The limit of detection (LOD) of 7.47 µM and 1.11 µM was evaluated from the calibration curve for Hg2+ and ClO2-, respectively. Based on these promising results, it is suggested that the method reported is a low-cost and one step biogenic protocol for the synthesis of Ag NSs and their employment for the detection of Hg2+ and ClO2-ions.

Fabrication of novel carbon quantum dots modified bismuth oxide (α-Bi2O3/C-dots): Material properties and catalytic applications.

The present work reports the facile and the template free sonochemical synthesis of a novel catalyst, α-Bi2O3/C-dots, for the degradation of indigo carmine (IC) dye, its simulated dyebath effluent and levofloxacin under visible light catalysis. The compositional, structural, optical and morphological analysis of α-Bi2O3/C-dots was studied using analytical, spectroscopic and microscopic techniques. X-ray diffraction (XRD) results confirmed the presence of a monoclinic phase of α-Bi2O3 in the nanocomposite and crystallite size of 28.75 nm. Photoluminescence (PL) and UV-vis diffuse reflectance spectra (UV-DRS) studies showed good optical properties and a band gap of 2.49 eV. The synthesized photocatalyst showed superior visible-light driven photocatalytic activity for the degradation of indigo carmine dye (86% dye degradation in 120 min) compared to pure α-Bi2O3 (57%). α-Bi2O3/C-dots also exhibited 79% degradation of antibiotic drug levofloxacin within 120 min, under optimized conditions of pH, catalyst dose and initial dye concentration. Scavenger studies revealed that hydroxyl radicals and electrons played predominant roles in the photocatalytic degradation of IC dye. With respect to total organic carbon (TOC) analysis, 68.8% total organic carbon reduction of the IC dye (10 mg/L) was observed under the same experimental conditions. The catalytic efficiency of C-dots in the photocatalytic process is explained by proposing a degradation mechanism.

Mixed surfactant (altering chain length and head group) aggregates as an effective carrier for tuberculosis drug.

Surface properties and aggregation behavior of cationic-cationic and cationic-non-ionic mixed surfactant systems viz. Dodecylethyldimethylammonium bromide (DDAB) with a series of double chain cationic surfactants (DiDDAB, DMDTAB, and DODAB) and non-ionic surfactants (Brij 96, Tyloxapol and Tween 80) were analysed using surface tension and transmission electron microscopy (TEM). The effect of chain length of cationic surfactant and hydrophilic-lypophilic balance (HLB) prominently observed in critical aggregation (cac) value. The aqueous solubility of anti-tuberculosis drug: rifampicin (RIF) was comparatively studied by UV-vis spectroscopy in presence of formulated micelles and vesicles. RIF was significantly solubilised in aqueous medium using all the formulated aggregates. RIF is very unstable in basic medium (above pH-7) and in oxidizing media. Therefore, stability at pH-13 as well as in strong oxidising environment was monitored using UV-vis spectroscopy. To trace the locus of the drug encapsulation in the micelles/vesicles, fluorescence spectroscopy and TEM studies were carried out. Both the techniques stemmed in complimentary results and confirmed that, RIF is majorly populated at polar medium in cationic-cationic vesicles and favour to reside at hydrophobic medium of the nonionic-cationic micelles.

Ultrasound-assisted selective hydrogenation of C-5 acetylene alcohols with Lindlar catalysts.

The selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) was performed in the presence of Lindlar catalyst, comparing conventional stirring with sonication at different frequencies of 40, 380 and 850 kHz. Under conventional stirring, the reaction rates were limited by intrinsic kinetics, while in the case of sonication, the reaction rates were 50-90% slower. However, the apparent reaction rates were found to be significantly frequency dependent with the highest rate observed at 40 kHz. The original and the recovered catalysts after the hydrogenation reaction were compared using bulk elemental analysis, powder X-ray diffraction and scanning and transmission electron microscopy coupled with energy-dispersive X-ray analysis. The studies showed that sonication led to the frequency-dependent fracturing of polycrystalline support particles with the highest impact caused by 40 kHz sonication, while monocrystals were undamaged. In contrast, the leaching of Pd/Pb particles did not depend on the frequency, which suggests that sonication removed only loosely-bound catalyst particles.

Origin and analysis of aliphatic and cyclic hydrocarbons in northeast United Kingdom coastal marine sediments.

Sediment samples from multiple sites in the North Sea Coast of England were solvent extracted and analysed by a quadruple gas chromatograph equipped with a mass spectrometer detector in order to determine the concentration and distribution of aliphatic and alicyclic n-alkanes. Results indicate that most of the organic species present in the sediment samples consisted of anthropogenically derived long chain aliphatic and alicyclic n-alkanes ((n)C(10-15, 17, 19-21, 24, 26, 27, 29, 30, 33, 35, 36, 43)), n-alkanols, n-alkanals, n-alkanones, esters as well as many volatile organic compounds (VOCs). Chemical composition of samples and relative concentration were found to vary both spatially and temporally on all scales. These variations are mainly attributable to spatial and temporal variations in source but also parameters such as rainfall, turbulence and micro-organism activity also account for the observed trends.

Trace metal speciation and contamination in an intertidal estuary.

An analysis of the geochemical distribution of selected trace metals among various geochemical phases of the sediments in the Tees estuary was carried out using a sequential extraction technique and Differential Stripping Voltammetry. The sediments of the estuary are mainly organic rich clay silts and metal concentrations exceed those in the water column. Speciation results show that contamination of the estuary is mainly from anthropogenic sources. Pb and Zn are associated with the reducible, residual and oxidisable fractions. The speciation pattern of Cd was similar to those of lead and zinc. However there were also some exchangeable and bound to carbonate fractions although these were less significant. Cu is largely associated with the oxidisable and residual fractions, with insignificant bound to carbonate, exchangeable and reducible fractions. The most bioavailable forms of the metals are the free inorganic ions. Total metal concentrations in the estuary display a downward trend since the 1970s.

Ecological interpretation of metal contents and contaminant source characterisation of sediments from a megatidal estuary.

Sediments and the associated biota constitute an important compartment in the biogeochemical cycle of trace metals in soft substrate megatidal estuaries. The relationship between physicochemical, ecological properties, metal concentrations determined in megatidal estuary sediments from the French coast of the English Channel, the Baie des Veys and the macrobenthic organisms, are analysed, interpreted and reported. Total concentrations of zinc, cadmium, lead and copper were measured in mudflats and saltmarsh sediments using Differential Pulse Voltammetry. Sediment characteristics were obtained by measurement of particle size, water content, total organic carbon and carbonate content, using AFNOR standards. A semi-quantitative scale was used for assessing the density of the macrobenthic flora and fauna at each sampling site. Analysis of data obtained from this study showed a correlation between the concentrations of monitored trace metals and species of the macrobenthic fauna. The results of this study show that the physico-chemical characteristics of the sediments affect the retention of metals in the sediment and this in turn affects the biota.