Electrochemical water oxidation reaction by dinuclear Re(V) oxo complexes with a 1,4-benzoquinone core via the redox induced electron transfer (RIET) process.

We report two dinuclear rhenium(V) oxo complexes 1 and 2 types, [ReV(O)(Cl)3(L2-)ReV(O)(Cl)3][NBu4]2 (1, L2- = dianionic 2,5-dihydroxy 1,4-benzoquinone (DBQ2-)) and (2, L2- = dianionic chloranilic acid (CA2-) ligands), as a homogeneous electrocatalyst for water oxidation reactions in the acetonitrile-water mixture. The evolution of dioxygen gas at the anode was confirmed by a GC-TCD study. In controlled potential electrolysis (CPE), oxidation at 1.30 V (vs. Ag/AgCl) at neutral pH, 1 and 2 afforded 1+ [ReVI(O)(Cl)3(DBQ˙3-)ReVI(O)(Cl)3]- and 2+ [ReVI(O)(Cl)3(CA˙3-)ReVI(O)(Cl)3]- ions, respectively, via the redox induced electron transfer (RIET) process. Electrochemically generated species of 1+ and 2+ could be isolated in dry acetonitrile. 1+ and 2+ ions give strong EPR signals in fluid solution as well as under frozen glass conditions due to the [ReVI(O)(Cl)3(L˙3-)ReVI(O)(Cl)3]- ↔ [ReVI(O)(Cl)3(L2-)ReV(O)(Cl)3]- (where L2- = DBQ2- and CA2-) equilibrium. However, the continuation of the CPE study (1.30 V vs. Ag/AgCl) in the presence of acetonitrile-water mixture oxidised the in situ generated species of 1+ and 2+ to higher valent ReVIO species. These species (1+ and 2+) bound water through the water nucleophilic attack (WNA) to produce peroxide intermediate species of [ReV(OOH)(Cl)3(DBQ2-)ReV(OOH)(Cl)3] (A1) and [ReV(OOH)(Cl)3(CA2-)ReV(OOH)(Cl)3] (A2) for catalysts 1 and 2, respectively. Interestingly, A1 and A2 were authenticated and analysed by ESI mass spectrometry and infrared spectroscopy and were the active precursors of this water oxidation process. The extent of current generation under similar conditions suggested that complex 1 is superior to complex 2 for the water oxidation reaction. Notably, the maximum turnover frequency (TOFmax) of catalysts 1 and 2 were 2.1 and 1.6 s-1 at 0.27 V and 0.24 V over potential, respectively, which is very significant in WOR.

Anthocyanins: Potential phytochemical candidates for the amelioration of non-alcoholic fatty liver disease.

Nonalcoholic fatty liver disease (NAFLD) is described by too much hepatic fat deposition causing steatosis, which further develops into nonalcoholic steatohepatitis (NASH), defined by necroinflammation and fibrosis, progressing further to hepatic cirrhosis, hepatocellular carcinoma, and liver failure. NAFLD is linked to different aspects of the metabolic syndrome like obesity, insulin resistance, hypertension, and dyslipidemia, and its pathogenesis involves several elements including diet, obesity, disruption of lipid homeostasis, and a high buildup of triglycerides and other lipids in liver cells. It is therefore linked to an increase in the susceptibility to developing diabetes mellitus and cardiovascular diseases. Several interventions exist regarding its management, but the availability of natural sources through diet will be a benefit in dealing with the disorder due to the immensely growing dependence of the population worldwide on natural sources owing to their ability to treat the root cause of the disease. Anthocyanins (ACNs) are naturally occurring polyphenolic pigments that exist in the form of glycosides, which are the glucosides of anthocyanidins and are produced from flavonoids via the phenyl propanoid pathway. To understand their mode of action in NAFLD and their therapeutic potential, the literature on in vitro, in vivo, and clinical trials on naturally occurring ACN-rich sources was exhaustively reviewed. It was concluded that ACNs show their potential in the treatment of NAFLD through their antioxidant properties and their efficacy to control lipid metabolism, glucose homeostasis, transcription factors, and inflammation. This led to the conclusion that ACNs possess efficacy in the amelioration of NAFLD and the various features associated with it. However, additional clinical trials are required to justify the potential of ACNs in NAFLD.

Spin-flip excitation and negative energy dispersion in rotating Bose atoms.

We investigated the excitation spectra for the rotating Bose system in the fractional quantum Hall effect regime considering short-ranged Po¨schl-Teller and long-ranged Coulomb type interaction. We found the anomalous negative dispersion in the excited spectra for Jain's second and third series, whereas conventional spin-wave positive dispersion is observed in the case of Jain's first series. The higher order Jain series display negative curvature with roton minima at lower momenta and exhibit spin-wave excitation similar to conventional ferromagnets at higher momenta. This anomalous spin-flip excitonic state of particle-hole pairs arises due to the merging of two types of spin-reversed modes i.e. spin-wave with no change in Landau level (LL) index and spin-flip with decreasing LL index.

From fuzzy-TOPSIS to machine learning: A holistic approach to understanding groundwater fluoride contamination.

Fluoride (F-) contamination of groundwater is a prevalent environmental issue threatening public health worldwide and in India. This study targets an investigation into spatial distribution and contamination sources of fluoride in Dhanbad, India, to help develop tailored mitigation strategies. A triad of Multi Criteria Decision Making (MCDM) models (Fuzzy-TOPSIS), machine learning algorithms {logistic regression (LR), classification and regression tree (CART), Random Forest (RF)}, and classical methods has been undertaken here. Groundwater samples (n = 283) were collected for the purpose. Based on permissible limit (1.5 ppm) of fluoride in drinking water as set by the World Health Organization, samples were categorized as Unsafe (n = 67) and Safe (n = 216) groups. Mean fluoride concentration in Safe (0.63 ± 0.02 ppm) and Unsafe (3.69 ± 0.3 ppm) groups differed significantly (t-value = -10.04, p < 0.05). Physicochemical parameters (pH, electrical conductivity, total dissolved solids, total hardness, NO3-, HCO3-, SO42-, Cl-, Ca2+, Mg2+, K+, Na+ and F-) were recorded from samples of each group. The samples from 'Unsafe group' showed alkaline pH, the abundance of Na+ and HCO3- ions, prolonged rock water interaction in the aquifer, silicate weathering, carbonate dissolution, lack of Ca2+ and calcite precipitation which together facilitated the F- abundance. Aspatial distribution map of F- contamination was created, pinpointing the "contaminated pockets." Fuzzy- TOPSIS identified that samples from group Safe were closer to the ideal solution. Among these models, the LR proved superior, achieving the highest AUC score of 95.6 % compared to RF (91.3 %) followed by CART (69.4 %). This study successfully identified the primary contributors to F- contamination in groundwater and the developed models can help predicting fluoride contamination in other areas. The combination of different methodologies (Fuzzy-TOPSIS, machine learning algorithms, and classical methods) results in a synergistic effect where the strengths of each approach compensate for the limitations of the other.

O2 Activation by a Coordinated -NH- Function: Hydrogen Atom Transfer and Aromatic Ring Oxidation.

Herein, we disclose a unique method of oxidation of a 1,4-naphthoquinone ring in air. We report that (1,4-naphthoquinone)-NH-N=C(OH)Ph (H3L) coordinated to octahedral ruthenium(II) and osmium(II) ions activates an 3O2 molecule spontaneously. Hydrogen atom transfer (HAT) from the -NH- function of H3L to 3O2 and subsequent (2e + 2H+) oxidation forming (1,3,4-trioxonaphthalen)=N-N=C(OH)Ph (HLOX) have been established. The H3L → HLOX transformation occurs via (3-hydroperoxy-1,4-naphthoquinone)=N-N=C(O-)Ph (HLOOH-) as an intermediate. The primary step is HAT generating H2L•- and hydroperoxide (OOH•) radicals. H2L•- is delocalized over the aromatic ring and incites coupling reactions via ortho carbon and produces coordinated HLOOH-. In solution, the homolytic cleavage of the peroxo bond leads to aromatic ring oxidation, affording LOX-. Ruthenium(II) and osmium(II) complexes of the types [MII(H2L-)(PPh3)2X], [MII(HLOOH-)(PPh3)2X], and trans-[MII(LOX-)(PPh3)2X] were successfully isolated in good yields. Notably, the cyclic voltammograms of all of the complexes exhibit reversible anodic waves due to MIII/MII redox couples. The rate constants of the [MII(H2L-)(PPh3)2X] → [MII(HLOOH-)(PPh3)2X] conversions determined by time-driven UV-vis spectroscopy in dry CH2Cl2, wet CH2Cl2, and D2O wet CH2Cl2 in air at 298 K follow the order kCH2Cl2-H2O> kCH2Cl2-D2O> kCH2Cl2. It is established that the rate constants are dependent on the 3O2 content of the solution but not on the concentration of the complex.

Unprecedented C-C Bond Formation via Ipso Nucleophilic Substitution of 2,4-Dinitrobenzene Sulfonic Acid with Active Methylene Compounds.

The sulfonic acid functionalization of sufficiently electron-deficient benzene sulfonic acids undergoes ipso nucleophilic substitution with various active methylene compounds, leading to new C-C bond formation. Good to excellent yields are obtained under mild conditions without transition-metal (Pd or Cu) catalyst, PTC, and ligand. No solid waste is generated. It is a highly effective strategy for incorporating various active methylene compounds into the o-nitro-substituted benzene ring. This method has been applied not only for synthesizing APIs but also in materials chemistry. It shows a novel route for creating heavily crowded all-carbon quaternary centers. Carbon-carbon bond formation by substituting a sulfonic acid group was unknown.

Influence of ortho group in rhodamine B hydrazide based Schiff base for selective recognition of Cu2+ and Fe3+ ions: A mechanistic approach by DFT and colorimetric studies.

Herein we have implemented a computational approach in designing sensor molecules for the selective recognition of Cu2+ and Fe3+ ions. Seven rhodamine B hydrazide-based Schiff base derivatives were designed and analysed their chemosensing properties against Cu2+ and Fe3+ ions in ethanol solution theoretically. The theoretical calculations revealed that the selective recognition of Cu2+ and Fe3+ ions takes place via spirolactam ring-opening and there is a pivotal role of ortho substituents and N-heteroatoms. The two best chemosensors were synthesised and used for the detection of Cu2+ and Fe3+ ions by colorimetric methods.

Exploring the Dynamic Heterogeneity at the Interface of a Protein in Aqueous Ionic Liquid Solutions.

Room temperature molecular dynamics (MD) simulations of the globular protein α-lactalbumin in aqueous solutions containing BMIM (1-butyl-3-methylimidazolium) based ionic liquids (ILs) with a series of Hofmeister anions have been carried out. In particular, effects of anions of different shapes/sizes and hydrophobic/hydrophilic characters, namely, thiocyanate (SCN-), dicyanamide (DCA-), methyl sulfate (MS-), triflate (TFO-), and bis(trifluoromethane) sulfonimide (TF2N-) on the heterogeneous dynamic environment at the interface around the protein have been explored. The calculations revealed exchange of population between water and IL cation-anion components beyond the first layer of bound water molecules at the protein surface. Further, increasingly restricted diffusivity of the IL components and water around the protein has been found to be associated with a longer time scale for the onset of dynamic heterogeneity at the interface. Restricted diffusivity of water molecules at the interface in the presence of the ILs has been found to be correlated with the longer time scale of structural relaxations of protein-water hydrogen bonds at the interface. More importantly, the time scale associated with the reorientations of the anions has been found to be anticorrelated with their translational diffusivity, with the effect being more at the interface as compared to the bulk IL solutions. It is demonstrated that the nonuniform ability of the anions to form hydrogen bonds with water due to their differential shapes and hydrophilic characters is the origin of such anticorrelation.

Review of Electrostatic Force Calculation Methods and Their Acceleration in Molecular Dynamics Packages Using Graphics Processors.

Molecular dynamics (MD) simulations probe the conformational repertoire of macromolecular systems using Newtonian dynamic equations. The time scales of MD simulations allow the exploration of biologically relevant phenomena and can elucidate spatial and temporal properties of the building blocks of life, such as deoxyribonucleic acid (DNA) and protein, across microsecond (µs) time scales using femtosecond (fs) time steps. A principal bottleneck toward extending MD calculations to larger time scales is the long-range electrostatic force measuring component of the naive nonbonded force computation algorithm, which scales with a complexity of (N, number of atoms). In this review, we present various methods to determine electrostatic interactions in often-used open-source MD packages as well as the implementation details that facilitate acceleration of the electrostatic interaction calculation.

Technical advances on current research trends and explore the future scope on nutrient recovery from waste-streams: a review and bibliometric analysis from 2000 to 2020.

An exponentially growing global population has led to an increase in nutrient pollution in different aqueous bodies. Although different processes have successfully removed nutrients from wastewater on a large scale, a limited number of studies have been reported on efficiency, cost-effectiveness, and future potential of physical, chemical, and biological nutrient recovery methods to overcome the depletion of natural resources. Therefore, researchers need to understand current research trends by applying different approaches to investigate higher efficient nutrient recovery technologies. In this article, the research patterns and in-depth review of various nutrient recovery processes have been circumscribed with the application of bibliometric and attractive index (AAI) vs. activity index (AI) analysis. The performance, advantages, limitations, and future prospects of different nutrient recovery methods have also been addressed. More than 70% of study publications were published in the last decade in chemical and biological processes, which might be related to more rigorous effluent quality rules and increasing water pollution. The future prediction in the field of nutrient recovery has been predicted using S-curve analysis, and it was found that the number of publications in the saturated state in chemical methods was highest. However, the growth rate of the biological-based nutrient recovery methods is greater, which may be because of their huge research scope, cost-effectiveness, and easy operation methods. This study can assist researchers in understanding the current research scenario in nutrient recovery techniques and provide the research scope in nutrient recovery from wastewater in the future.

Mono Versus Dinuclear Vanadium(V) Complexes: Solvent Dependent Structural Versatility and Electro Syntheses of Mixed-Valence Oxovanadium(IV/V) Entities in Solution.

Two mononuclear oxidovanadium(V) complexes type of [VVO(L1)(OMe)(MeOH)] (1), [VVO(L2)(OMe)(MeOH)] (2) and two [V2O3]4+ core of µ-oxidodioxidodivanadium(V) complexes (L1)(O)VV-O-VV(O)(L1) (3) and (L2)(O)VV-O-VV(O)(L2) (4) and two complexes [VVO(L1)(8-Hq)] (5) and [VVO(L2)(8-Hq)] (6) incorporating 8-hydroxyquinoline (8-hq) as co-ligand have been reported where L1 [(E)-N'-(2-hydroxybenzylidene)cinnamohydrazide] and L2 [(2E,N'E)-N'-(2-hydroxybenzylidene)-3-(naphthalen-1-yl)acrylohydrazide] are the dianionic forms of the conjugated keto-imine functionalized substituted hydrazone ligands. The µ-oxidodioxidodivanadium complexes are generated upon switching the solvent from methanol to acetonitrile. The X-ray analysis showed octahedral geometry for the mononuclear complexes 1, 2 and 5 but oxido-bridged dinuclear complexes 3 and 4 formed penta-coordinated square-pyramidal geometry about metal atoms. Two mixed-valence species of type II, 3a and 4a, of general formulae (L)(O)VIV-O-VV(O)(L), are being generated upon constant potential electrolysis (CPE) of 3 and 4 respectively. Frozen solution EPR spectra have 13 hyperfine lines, revealing the unpaired electron is majorly localized on one of the two vanadium centres. All these complexes have been well characterized by physio-chemical techniques and the density functional theory (DFT) calculations were applied to obtain further insight into the electronic structure of this type of molecule. The oxidomethoxido complexes 1 and 2 were taken to investigate the catechol oxidase mimicking activity following the oxidation of 3,5-di-tert-butyl catechol (3,5-DTBC) to 3,5-di-tert-butyl benzoquinone (3,5-DTBQ).

Reconfigurable perovskite nickelate electronics for artificial intelligence.

Reconfigurable devices offer the ability to program electronic circuits on demand. In this work, we demonstrated on-demand creation of artificial neurons, synapses, and memory capacitors in post-fabricated perovskite NdNiO3 devices that can be simply reconfigured for a specific purpose by single-shot electric pulses. The sensitivity of electronic properties of perovskite nickelates to the local distribution of hydrogen ions enabled these results. With experimental data from our memory capacitors, simulation results of a reservoir computing framework showed excellent performance for tasks such as digit recognition and classification of electrocardiogram heartbeat activity. Using our reconfigurable artificial neurons and synapses, simulated dynamic networks outperformed static networks for incremental learning scenarios. The ability to fashion the building blocks of brain-inspired computers on demand opens up new directions in adaptive networks.

Effect of magnetic field on the removal of copper from aqueous solution using activated carbon derived from rice husk.

Adsorptive removal of copper by activated carbon derived from modified rice husk (ACRH) was studied in the presence and absence of magnetic field (MF). The ACRH was prepared from the normal rice husk treated by NaOH solution and subsequent pyrolysis at 450 °C in the absence of oxygen. The physicochemical properties of ACRH's were determined before and after the adsorption process to delineate the adsorption mechanism. The BET analysis confirmed that the fabricated ACRH has a specific surface area of 8.244 m2/g with a mesopore to micropore ratio of 0.974. It was observed that the micropore structure gradually replaced the mesopores, and the surface area of the micropore increased (from 0.9219 to 4.1764 m2/g), and the pore diameter was also decreased from 180.381 to 46.249 Å after pyrolysis. The CHNO/S test result reveals that the carbon content was increased from 42 to 67.8% in the ACRH after pyrolysis. The batch sorption studies were performed by varying the initial adsorbate concentration, temperature, agitation speed, pH, adsorbent dose and contact time for magnetic and non-magnetic conditions to analyze the effect of the magnetic field. The univariate studies show that the maximum experimental adsorption capacity was 4.522 mg/g and 3.855 mg/g, respectively, for these two conditions (representing the magnetic impact) at 25 °C with an adsorbent dose of 2 g/L and an agitation speed of 150 rpm. It was also observed that the removal efficiency was 94.55% and 77.96% (magnetic and non-magnetic condition) at pH 7 with a concentration of 10 mg/L in 2 h. The test result on the impact of exposure time on the magnetic field suggested that the magnetic memory influenced the removal efficiency; after 40 to 60 min, the maximum removal efficiency was achieved, around 80 to 90%. The pseudo-second-order kinetic model was best fitted with the experimental data with a rate constant as 0.1749 and 0.1006 g/mg/min for these two conditions. The Temkin model delineates the adsorption isotherm suggesting the heat generated during the adsorption process is linearly abate with the coverage of the surface area of the adsorbent. The thermodynamic model confirms that the copper adsorption is spontaneous (ΔG = - 3.91 kJ/mol and - 6.02 kJ/mol), wherein the negative enthalpy value (ΔH = - 36.74 kJ/mol and - 25.74 kJ/mol) suggested that the process is exothermic irrespective of magnetic interference. The significant enhancement of copper removal was observed by incorporating the magnetic field, showing an increase in sorption capacity by 17.48% and a reduction of reaction time by 88.12%.

Importance of Solvent in Guiding the Conformational Properties of an Intrinsically Disordered Peptide.

Aggregated form of α-synuclein in the brain has been found to be the major component of Lewy bodies that are hallmarks of Parkinson's disease (PD), the second most devastating neurodegenerative disorder. We have carried out room-temperature all-atom molecular dynamics (MD) simulations of an ensemble of widely different α-synuclein1-95 peptide monomer conformations in aqueous solution. Attempts have been made to obtain a generic understanding of the local conformational motions of different repeat unit segments, namely R1-R7, of the peptide and the correlated properties of the solvent at the interface. The analyses revealed relatively greater rigidity of the hydrophobic R6 unit as compared to the other repeat units of the peptide. Besides, water molecules around R6 have been found to be less structured and weakly interacting with the peptide. These are important observations as the R6 unit with reduced conformational motions can act as the nucleation site for the aggregation process, while less structured weakly interacting water around it can become displaced easily, thereby facilitating the hydrophobic collapse of the peptide monomers and their association during the nucleation phase at higher concentrations. In addition, we demonstrated presence of doubly coordinated highly ordered as well as triply coordinated relatively disordered water molecules at the interface. We believe that while the ordered water molecules can favor water-mediated interactions between different peptide monomers, the randomly ordered ones on the other hand are likely to be expelled easily from the interface, thereby facilitating direct peptide-peptide interactions during the aggregation process.

Neuromorphic learning with Mott insulator NiO.

Habituation and sensitization (nonassociative learning) are among the most fundamental forms of learning and memory behavior present in organisms that enable adaptation and learning in dynamic environments. Emulating such features of intelligence found in nature in the solid state can serve as inspiration for algorithmic simulations in artificial neural networks and potential use in neuromorphic computing. Here, we demonstrate nonassociative learning with a prototypical Mott insulator, nickel oxide (NiO), under a variety of external stimuli at and above room temperature. Similar to biological species such as Aplysia, habituation and sensitization of NiO possess time-dependent plasticity relying on both strength and time interval between stimuli. A combination of experimental approaches and first-principles calculations reveals that such learning behavior of NiO results from dynamic modulation of its defect and electronic structure. An artificial neural network model inspired by such nonassociative learning is simulated to show advantages for an unsupervised clustering task in accuracy and reducing catastrophic interference, which could help mitigate the stability-plasticity dilemma. Mott insulators can therefore serve as building blocks to examine learning behavior noted in biology and inspire new learning algorithms for artificial intelligence.

Contrasting Effects of Ionic Liquids of Varying Degree of Hydrophilicity on the Conformational and Interfacial Properties of a Globular Protein.

Ionic liquids (ILs), depending on their cation-anion combinations, are known to influence the conformational properties and activities of proteins in a nonuniform manner. To obtain microscopic understanding of such influence, it is important to characterize protein-IL interactions and explore the modified solvation environment around the protein. In this work, molecular dynamics (MD) simulations of the globular protein α-lactalbumin have been carried out in aqueous IL solutions containing 1-butyl-3-methylimidazolium cations (BMIM+) in combination with a series of anions with varying degree of hydrophilicity, namely, hexafluorophosphate (PF6-), ethyl sulfate (ETS-), acetate (OAc-), chloride (Cl-), dicyanamide (DCA-), and nitrate (NO3-) . The calculations revealed that ILs with hydrophobic and hydrophilic anions have contrasting influence on conformational flexibility of the protein. It is further observed that the BMIM+ cations exhibit site-specific orientations at the interface depending on the hydrophilicity of the anion component. Most importantly, the results demonstrated enhanced propensity of hydrophilic ILs to replace relatively weaker protein-water hydrogen bonds by stronger protein-IL hydrogen bonds at the protein surface as compared to the hydrophobic ILs. Such breaking of protein-water hydrogen bonds at a greater extent leads to greater loss of water hydrating the protein in the presence of hydrophilic ILs, thereby reducing the protein's stability.

Geomorphic controls on shallow groundwater arsenic contamination in Bengal basin, India.

The study was conducted to explore the influence of geomorphic features scattered throughout the area on the occurrence and distribution of arsenic in shallow groundwater. GIS techniques were frequently used to identify the geomorphic features and to correlate with arsenic distribution patterns. The study shows that the occurrence of geomorphic features and their distribution have a vital role in the heterogeneous distribution pattern of arsenic in shallow groundwater. The frequency distribution of geomorphic features is found similar to the arsenic distribution pattern. The moderate to highly contaminated zones are mostly consolidated to the central and southeastern part of the study area. Arsenic contamination levels are varying in different fluvial plains of the study area following the trend of Older Deltaic Plain (ODP) > Older Flood Plain (OFP) > Active Flood Plain (AFP). It has also been observed that arsenic contamination along the different geomorphic features follows the trend of abandoned channels > back swamps > other water bodies > swamps > cut-off meanders > meander scars > ponds > oxbow lakes > channel bar > point bars >channel islands. The present study indicates that the geomorphic features play a significant role in the mobilization of arsenic in shallow groundwater by supplying accumulated organic matter.

Spatial distribution and risk area assessment of Aphelenchoides besseyi using geostatistical approaches in Giridih district of Jharkhand, India.

Distributed widely across the rice growing regions of India, the rice leaf and bud nematode (Aphelenchoides besseyi Christie 1942) can cause substantial yield loss in rice. Whitening of leaf tips is the characteristics damage symptom of this nematode and therefore it is popularly referred to as the rice white tip nematode (RWTN). While information on the damage severity of RWTN is available from others parts of the country, to date, no information is available from the state of Jharkhand. In order to generate a detailed information on spatial distribution of this nematode and to identify infestation hotspots, extensive field sampling was conducted across the Giridih district of Jharkhand. In total, 163 samples with each sample consisting of 30 randomly chosen panicles from three nearby rice fields were collected across the district. Moran's I spatial autocorrelation test confirmed the presence of significant spatial clustering among the sampling locations. Optimized hotspot analysis found the presence of one significant hotspot in Dumri block and cold spots in adjoining areas of Gawan, Tisri, and Dhanwar blocks. Spatial interpolation techniques like inverse distance weighting (IDW) and ordinary kriging (OK) were employed to predict the population density at unsampled locations. Both IDW and OK resulted into generation of similar kind of maps where population density was found to be higher in Dumri, Giridih, Bengabad and some other pockets of the district. Finally, indicator kriging approach was employed which resulted into identifying both risk and nematode free areas. In risk areas, where the probability of the population density exceeding the economic threshold limit is high, immediate quarantine measures should be taken to prevent further dissemination of contaminated seeds. Our study provided a scientifically based decision method to devise preventive and curative protection measures against A. besseyi, a neglected pest of quarantine significance of rice in India.Distributed widely across the rice growing regions of India, the rice leaf and bud nematode (Aphelenchoides besseyi Christie 1942) can cause substantial yield loss in rice. Whitening of leaf tips is the characteristics damage symptom of this nematode and therefore it is popularly referred to as the rice white tip nematode (RWTN). While information on the damage severity of RWTN is available from others parts of the country, to date, no information is available from the state of Jharkhand. In order to generate a detailed information on spatial distribution of this nematode and to identify infestation hotspots, extensive field sampling was conducted across the Giridih district of Jharkhand. In total, 163 samples with each sample consisting of 30 randomly chosen panicles from three nearby rice fields were collected across the district. Moran's I spatial autocorrelation test confirmed the presence of significant spatial clustering among the sampling locations. Optimized hotspot analysis found the presence of one significant hotspot in Dumri block and cold spots in adjoining areas of Gawan, Tisri, and Dhanwar blocks. Spatial interpolation techniques like inverse distance weighting (IDW) and ordinary kriging (OK) were employed to predict the population density at unsampled locations. Both IDW and OK resulted into generation of similar kind of maps where population density was found to be higher in Dumri, Giridih, Bengabad and some other pockets of the district. Finally, indicator kriging approach was employed which resulted into identifying both risk and nematode free areas. In risk areas, where the probability of the population density exceeding the economic threshold limit is high, immediate quarantine measures should be taken to prevent further dissemination of contaminated seeds. Our study provided a scientifically based decision method to devise preventive and curative protection measures against A. besseyi, a neglected pest of quarantine significance of rice in India.

Microscopic Understanding of the Effect of Ionic Liquid on Protein from Molecular Simulation Studies.

We have performed molecular dynamics (MD) simulations of the protein α-lactalbumin in aqueous solution containing the ionic liquid (IL) 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM][BF4]) as the cosolvent at different concentrations. Attempts have been made to obtain quantitative understanding of the effects of the IL on the conformational features of the protein as well as the distributions of the IL and water around it. The calculations revealed enhanced rigidity of the protein with reduced conformational fluctuations and increasingly correlated local motions in the presence of the IL. Nonuniform relative population of the BMIM+ and BF4- ions at the protein surface with respect to that in the bulk solution has been observed. It is demonstrated that exchange of water by the IL around the protein results in rearrangement of the hydrogen bond network at the interface with breaking of protein-water hydrogen bonds and formation of protein-IL hydrogen bonds. Importantly, it is found that the protein forms increased number of stronger salt bridges in the presence of IL. This shows that the formation of a greater number of such stronger salt bridges is the origin behind the enhanced rigidity of the protein in the presence of the IL.