Understanding electrocatalytic mechanisms and ultra-trace uranyl detection with Pd nanoparticles electrodeposited in deep eutectic solvents.

This research paper investigates the electrocatalytic mechanisms and ultra-trace detection abilities of uranyl ions (UO22+) using palladium nanoparticles (PdNPs) electrodeposited in deep eutectic solvents (DESs). The unique properties of DESs, such as their adjustable viscosity and ionic conductivity, offer an advantageous and environmentally friendly medium for Pd nanoparticle electrodeposition, resulting in highly active and stable electrocatalysts. Various characterization techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD), were used to examine the morphology, size distribution, and crystallographic structure of the Pd nanoparticles. Electrochemical tests revealed that the Pd-modified electrodes show exceptional electrocatalytic activity and current sensitivity towards uranyl ions, with detection limits as low as 3.4 nM. Density functional theory (DFT) calculations were conducted to elucidate the mechanism of the electrocatalytic reduction of UO22+ by the PdNPs, providing a plausible explanation for the high sensitivity of PdNPs in detecting uranyl ions based on the calculated structural parameters and reaction energetics. This study underscores the potential of Pd nanoparticles electrodeposited in DESs as a promising method for sensitive uranyl ion detection, contributing to advancements in environmental monitoring and nuclear safety.

Mechanistic Approach to Reveal Interaction of Uranyl Ions in Alkyltriphenylphosphonium Bromide-Based Deep Eutectic Solvent.

Speciation is known to control fundamental aspects of metal processing and electrochemical behavior such as solubility and redox potentials. Deep eutectic solvents (DESs) are an emerging class of green, low-cost and designer solvents and are being explored as alternatives for recycling nuclear fuel and critical materials. However, there is a lack of knowledge about the behavior of metals in them. Here, for the first time, we synthesized three new DESs based on alkyltriphenylphosphonium bromide (CnPPh3Br), with varied alkyl chain lengths (n), as the hydrogen-bond acceptor along with decanoic acid (DA) as the hydrogen-bond donor and explored the redox speciation of uranyl nitrate. The changes in the Fourier transform infrared and NMR spectra helped elucidate the formation of hydrogen bonds in DES. The absorption maxima of uranyl in DES was red-shifted by 10 nm compared to the free uranyl, with concomitant increase in intensity and luminescence lifetime, which suggested a strong interaction of uranyl nitrate with DES. Cyclic voltammetry was probed to understand the redox thermodynamics, transport properties, and heterogeneous electron transfer kinetics of the irreversible electron transfer of uranyl ions in the three DESs. Electrochemical and spectroscopic techniques together with density functional theory calculations unlocked microscopic insights into the solvation and speciation of UO22+ ions in three DESs and also the associated unusual trends observed in the physical properties of the DESs. The hydrogen-bonded structure of DES plays a crucial role in the redox behavior of the UO22+ ion due to its strong potent complexation with its components. The basic findings of the present work can have far-reaching consequences for the extraction, electrochemical separation, and future development of redox-based separation processes in the nuclear fuel cycle.

Deciphering the Role of Charge Compensator in Optical Properties of SrWO4:Eu3+:A (A = Li+, Na+, K+): Spectroscopic Insight Using Photoluminescence, Positron Annihilation, and X-ray Absorption.

Studies have been carried out to understand the specific role of the alkali charge compensator on the luminescence properties of an alkali ion (Li+, Na+, and K+) codoped SrWO4:Eu phosphor. The oxidation state of the europium ion was found to be +3 on the basis of X-ray absorption near edge structure (XANES) measurements. This is the first report of its kind where opposite effects of Li+ ion and Na+/K+ ions on photoluminescence intensity have been observed. Li+ ion codoping enhanced the photoluminescence intensity from SrWO4:Eu3+ phosphor while Na+/K+ ion codoping did not. On the other hand, the luminescence lifetime is maximum for the Na+ ion codoped sample and minimum for the Li+ ion codoped sample. The results could be explained successfully using time-resolved luminescence, positron annihilation lifetime spectroscopy (PALS), and extended X-ray absorption fine structure (EXAFS) spectroscopy measurements. Changes in the Eu-O bond length and Debye-Waller Factor (σ2) upon Li+/Na+/K+ codoping were monitored through EXAFS measurements. PALS also highlighted the fact that Li+ codoping is not contributing to reduction in the cation vacancies and might be occupying interstitial sites rather than lattice positions due to its very small size. On europium doping there is lowering in symmetry of SrO8 polyhedra from S4 to C6, which is reflected in an intense electric dipole transition in comparison to the magnetic dipole transition. This is also corroborated using trends in Judd-Ofelt parameters. The results have shown that the luminescence lifetime is better when the vacancy concentration is lower as induced by Na+ and K+ codoping, while the emission intensity is higher in the samples when distortion around Eu3+ is reduced as induced by Li+ codoping.

Ruthenium Nanoparticles Mediated Electrocatalytic Reduction of UO22+ Ions for Its Rapid and Sensitive Detection in Natural Waters.

Reduction of UO22+ ions to U4+ ions is difficult due to involvement of two axially bonded oxygen atoms, and often requires a catalyst to lower the activation barrier. The noble metal nanoparticles (NPs) exhibit high electrocatalytic activity, and could be employed for the sensitive and rapid quantifications of U022+ ions in the aqueous matrix. Therefore, the Pd, Ru, and Rh NPs decorated glassy carbon electrode were examined for their efficacy toward electrocatalytic reduction of UO22+ ions and observed that Ru NPs mediate efficiently the electro-reduction of UO22+ ions. The mechanism of the electroreduction of UO22+ by the RuNPs/GC was studied using density functional theory calculations which pointed different approach of 5f metal ions electroreduction unlike 4p metal ions such as As(III). RuNP decorated on the glassy carbon would be hydrated, which in turn assist to adsorb the uranyl sulfates through hydrogen bonding thus facilitated electro-reduction. Differential pulse voltammetric (DPV) technique, was used for rapid and sensitive quantification of UO22+ ions. The RuNPs/GC based DPV technique could be used to determine the concentration of uranyl in a few minutes with a detection limit of 1.95 ppb. The RuNPs/GC based DPV was evaluated for its analytical performance using seawater as well lake water and groundwater spiked with known amounts of UO22+.

Highly Sensitive Detection of Arsenite Based on Its Affinity toward Ruthenium Nanoparticles Decorated on Glassy Carbon Electrode.

Metallic ruthenium nanoparticles (Ru NPs) are formed on the glassy carbon electrode (GC) at electrodeposition potential of -0.75 V, as observed from X-ray photoelectron spectroscopy. Thus formed Ru NPs have the arsenite selective surface and conducting core that is ideally suited for designing a highly sensitive and reproducible response generating matrix for the arsenite detection at an ultratrace concentration in aqueous matrices. Contrary to this, arsenate ions sorb via chemical interactions on the ruthenium oxide (RuO2 and RuO3) NPs formed at -0.25 V, but not on the Ru NPs. For exploring a possibility of the quantification of arsenite in the ultratrace concentration range, the Ru NPs have been deposited on the GC by a potentiostatic pulse method of electrodeposition at optimized -0.75 V for 1000 s. Arsenite preconcentrates onto the Ru surface just by dipping the RuNPs/GC into the arsenite solution as it interacts chemically with Ru NPs. Electrochemical impedance spectroscopy of As(III) loaded RuNPs/GC shows a linear increase in the charge transfer resistance with an increase in As(III) conc. Using a differential pulse voltammetric technique, arsenite is oxidized to arsenate leading to its quantitative determination without any interference of Cu(2+) ions that are normally encountered in the water systems. Thus, the use of RuNPs/GC eliminates the need for a preconcentration step in stripping voltammetry, which requires optimization of the parameters like preconcentration potential, time, stirring, inferences, and so on. The RuNPs/GC based differential pulse voltammetric (DPV) technique can determine the concentration of arsenite in a few min with a detection limit of 0.1 ppb and 5.4% reproducibility. The sensitivity of 2.38 nA ppb(-1) obtained in the present work for As(III) quantification is considerably better than that reported in the literature, with a similar detection limit and mild conditions (pH = 2). The RuNPs/GC based DPV has been evaluated for its analytical performance using the lake water, ground water, and seawater samples spiked with known amounts of As(III).

Understanding the burden of food allergy among urban and rural school children from north India.

Background: There is paucity of reliable epidemiological data regarding the burden of food allergy in most developing countries, including India. Objective: To provide current estimates of the prevalence and distribution of food allergy among urban and rural school children aged 6-14 years in Delhi and the National Capital Region (NCR) of Khekra in India. Methods: A cross-sectional study was conducted from January 2022 to February 2023 to enroll school children, 6-14 years, from select urban and rural schools in Delhi and NCR. A questionnaire consisting of questions focused on household environment, early life factors, and pediatric food allergy characteristics was administered by a trained medical researcher to collect parent-proxy data. Univariate statistics were used to describe frequencies, percentages, and 95% confidence intervals for survey items. Results: The estimated prevalence of parent-reported food allergy was 0.8% (95% CI: 0.4-1.5; urban: 0.4%, 95% CI: 0.1-1.1; rural: 1.7%, 95% CI: 0.7-3.5). Fruits such as mango (0.3%, 95% CI: 0.1-0.9), strawberry (0.1%, 95% CI: 0.0-0.7), orange (0.1%, 95% CI: 0.0-0.7), and custard apple (0.1%, 95% CI: 0.0-0.7) were reported only by urban children, while rural children reported yogurt (0.6%, 95% CI: 0.1-1.8) and wheat (0.3%, 95% CI: 0.0-1.3). Both groups reported brinjal (also known as eggplant) and banana, 0.1% (95% CI: 0.0-0.7) of urban and 0.3% (95% CI: 0.0-1.3) of rural, respectively. Overall, commonly reported clinical symptoms were diarrhea and/or vomiting (100%, 95% CI: 76.2-100), abdominal pain (88.9%, 95% CI: 58.6-98.8), and rash/itchy skin (66.7%, 95% CI: 34.8-89.6). Among children with parent reported food allergy, 66.7% (95% CI: 34.8-89.6) of food allergies were physician diagnosed, of which 33.3% were diagnosed via history alone (95% CI:7.7-71.4) while 66.7% (95% CI: 28.6-92.3) were confirmed via skin prick test and/or blood test. Conclusion: The overall prevalence of food allergy is very low in Delhi and Khekra, India. Future work should focus on elucidating the complex interplay of early-life, environmental, genetic, and lifestyle factors to understand the reasons for India's low food allergy burden and improve epidemiological clues to prevention for the nations with higher disease burden.

Deep Eutectic Solvent-Based Highly Sensitive Turn-On Fluorescent Probe for D2O.

Owing to the importance of heavy water in spectroscopy, nuclear energy generation, chemical characterization, and biological industry, a design of a robust, cheap, nontoxic, and sensitive D2O sensor is very important. In this work, taking advantage of the singular emission fluorescence of the deep eutectic solvent prepared in our laboratory, we propose a first of its kind highly sensitive turn-on fluorescent sensor to effectively sense D2O at an ultratrace level based on rapid exchange of the labile DES proton with deuterium. This method can be used as a full-range heavy water detection strategy with a limit of detection of 0.079% (v/v) or 870 ppm. The isotopic purity (IP) obtained from DES fluorescence measurements is also in close agreement with that of the conventional FT-IR method. The current DES-based sensor thus allows both sensing and isotopic purity of D2O and can serve as one of the most sensitive monitoring strategies for heavy water analysis.

Understanding the excited state dynamics and redox behavior of highly luminescent and electrochemically active Eu(III)-DES complex.

Deep eutectic solvents (DES) are considered a novel class of environmentally benign molecular solvents that are considered as potential solvents for nuclear fuel reprocessing, material recycling, and many other technological applications in both research and industry. However, there is a complete dearth of understanding pertaining to the behavior of metal ions in DES. Herein, we have investigated the speciation, complexation behavior, photochemistry, and redox properties and tried to obtain insight into the chemical aspects of the europium ion in DES (synthesized from heptyltriphenylphosphonium bromide and decanoic acid). The same has been probed using time-resolved photoluminescence (TRPL), cyclic voltammetry (CV), synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) calculations. TRPL indicated the stabilization of europium in the +3 oxidation state, favoring the potential of the Eu(III)-DES complex to emit red light under near UV excitation and the existence of inefficient energy transfer between DES and Eu3+. EXAFS analysis revealed the presence of Eu-O and Eu-Br, which represent the local surroundings of Eu3+ in the Eu(III)-DES complex. TRPL measurement has also suggested two distinct local environments of europium ions in the complex. DFT calculations supported the EXAFS findings, confirming that the Eu(III)-DES structure involves not only the oxygen atom of decanoic acid but also the oxygen atoms from the nitrate ions, contributing to the local coordination of Eu(III). Electrochemical studies demonstrated that the redox reaction of Eu(III)/Eu(II) in DES displays quasi-reversible behavior. The reaction rate was observed to increase with higher temperatures. The findings of this study can contribute to the understanding of the fundamental properties and potential applications of this luminescent and electrochemically active complex and pave the way for further studies and the development of novel materials with enhanced luminescent and electrochemical properties.

Insight into Speciation and Electrochemistry of Uranyl Ions in Deep Eutectic Solvents.

Understanding the speciation of metal ions in heterogeneous hydrogen-bonded deep eutectic solvents (DES) has immense importance for their wide range of applications in green technology, environmental remediation, and nuclear industry. Unfortunately, the fundamental nature of the interaction between DES and actinide ions is almost completely unknown. In the present work, we outline the speciation, solvation mechanism, and redox chemistry of uranyl ion (UO22+) in DES consisting of choline chloride (ChCl) and urea as the hydrogen-bond donor. Electrochemical and spectroscopic techniques along with molecular dynamics (MD) simulations have provided a microscopic insight into the solvation and speciation of the UO22+ ion in DES and also on associated changes in physical composition of the DES. The hydrogen-bonded structure of DES plays an important role in the redox behavior of the UO22+ ion because of its strong complexation with DES components. X-ray absorption spectroscopy and MD simulations showed strong covalent interactions of uranyl ions with the constituents of DES, which led to rearrangement of the hydrogen-bonding network in it without formation of any clusters or aggregations. This, in turn, stabilizes the most unstable pentavalent uranium (UO2+) in the DES. MD analysis also highlights the fact that the number of H-bonds is reduced in the presence of uranyl nitrate irrespective of the presence of water with respect to pristine reline, which suggests high stability of the formed complexed species. The effect of added water up to 20 v/v % on speciation is insignificant for DES, but the presence of water influences the redox chemistry of UO22+ ions considerably. The fundamental findings of the present work would have far reaching consequences on understanding DES, particularly for application in the field of nuclear fuel reprocessing.

Remarkably enhanced direct dissolution of plutonium oxide in task-specific ionic liquid: insights from electrochemical and theoretical investigations.

The present work envisages an approach for direct dissolution of PuO2 in a task-specific ionic liquid (TSIL). An attractive possibility to electrodeposit plutonium from the mixture of TSIL and PuO2 has been explored further. The carboxyl functional group attached to the TSIL plays a key role in facilitating the dissolution of plutonium ions.

Rare earth indates (RE: La-Yb): influence of the synthesis route and heat treatment on the crystal structure.

Rare earth indates are an interesting class of compounds with rich crystallography. The present study explores the crystallographic phases observed in REInO3 (RE: La-Yb) systems and their dependence on synthesis routes and annealing temperature. All REInO3 compositions were synthesized by a solid state route as well as gel-combustion synthesis (GC) followed by annealing at different temperatures. The systems were well characterized by powder XRD studies and were analysed by Rietveld refinement for the structural parameters. The cell parameters were observed to decrease in accordance with the trend in ionic radii on proceeding from lighter to heavier rare earth ions. Interestingly, the synthesis route and the annealing temperature had a profound bearing on the phase relationships observed in the REInO3 series. The solid state synthesized samples depicted an orthorhombic phase (Pbnm) field for LaInO3 to SmInO3, followed by a hexagonal-type phase (P63cm) for GdInO3 to DyInO3. However, the phase field distribution was greatly influenced upon employing gel-combustion (GC) wherein both single-phasic hexagonal and orthorhombic phase fields were found to shrink. Annealing the GC-synthesized compositions to still higher temperatures (1250 °C) further evolved the phase boundaries. An important outcome of the study is observance of polymorphism in SmInO3 which crystallized in the hexagonal phase when synthesized by GC and orthorhombic phase by solid state synthesis. This reveals the all-important role played by synthesis conditions. The existence and energetics of the two polymorphs have been elucidated and discussed with the aid of theoretical studies.

Multifunctional pure and Eu(3+) doped ß-Ag2MoO4: photoluminescence, energy transfer dynamics and defect induced properties.

Pure and Eu(3+) doped ß-Ag2MoO4 were synthesized using a co-precipitation method at room temperature. The as prepared compounds were characterized systematically using X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, cyclic voltammetry (CV) and positron annihilation lifetime spectroscopy (PALS). It is observed that pure ß-Ag2MoO4 gives blue (445 nm) and green (550 nm) emission when irradiated with UV light. The origin of the green band was qualitatively explained from density functional theory (DFT) calculations using a suitable distortion model. It was observed that on doping europium ions, efficient energy transfer from molybdate to europium takes place. The excitation spectrum depicting f-f transitions (particularly 395 nm and 465 nm peaks) is much more intense than the CTB showing that Eu(3+) ions can be effectively excited by near UV-light. Based on DFT calculations it is proposed that due to the occurrence of Eu(3+) d-states in the conduction band (CB) as well as the strong contribution of Eu(3+) d-states to the impurity level present in the vicinity of the Fermi level, the host (ß-Ag2MoO4) to dopant (Eu(3+)) energy transfer is preferable. ß-Ag2MoO4 is also explored as a potential candidate for electrocatalysis of the oxygen reduction reaction (ORR). It was observed that the doping of europium ions in ß-Ag2MoO4 enhances the electrocatalytic activity toward the ORR. The presence of a large concentration of cation vacancies and large surface defects as suggested by positron annihilation lifetime spectroscopy (PALS) seem to be aiding the ORR.

Brugia malayi: establishment in inbred and outbred strains of mice.

Immunocompetent mouse model for human filarial parasite Brugia malayi is urgently required in view of the paucity of commercial reagents for other susceptible rodent viz. mastomys and gerbil. Genes within the major histocompatibility complex have been reported to influence the susceptibility of mouse to helminth parasites. Attempts have therefore been made in the present investigation to experimentally infect various inbred strains of mice viz. NZB/BINJ, BALB/c, AKR, C(3)H, and SJL/J with H-2 haplotype (H-2: d, d, k, k, s, respectively) and outbred strains of mice viz. Parks and Swiss. Findings indicate that susceptibility of mice to B. malayi is strain associated. This is the first report on the successful completion of full developmental cycle of subperiodic B. malayi in NZB/BINJ, an immunocompetent mouse strain. In some of the other strains, partial development or low degree of establishment of worms was observed.