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.

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.

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.

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.

Relation between the localization length and level repulsion in 2D Anderson localization.

We report on the relation between the localization length and level-spacing characteristics of two-dimensional (2D) optical localizing systems. Using the tight-binding model over a wide range of disorder, we compute spectro-spatial features of Anderson localized modes. The spectra allow us to estimate the level-spacing statistics while the localization length $ \xi $ξ is computed from the eigenvectors. We use a hybrid interpolating function to fit the level-spacing distribution, whose repulsion exponent $ \beta $ß varies continuously between 0 and 1, with the former representing Poissonian statistics and the latter approximating the Wigner-Dyson distribution. We find that the $ (\xi ,\beta ) $(ξ,ß) scatter points occupy a well-defined nonlinear locus that is well fit by a sigmoidal function, implying that the localization length of a 2D disordered medium can be estimated by spectral means using the level-spacing statistics. This technique is also immune to dissipation since the repulsion exponent is insensitive to level widths, in the limit of weak dissipation.

Reduction in generalized conductance with increasing gain in amplifying Anderson-localized systems.

The consequences of a nonconservative environment on the transport of photons under conditions of Anderson localization in a disordered system are a topic of great interest. In this work, we experimentally demonstrate the systematic decrease in the localization length of a quasi-one-dimensional localizing system when gain is added to it. We quantify the generalized conductance of the system using the variance of the fluctuations in the localized eigenfunctions and show a decrease in conductance with gain. We theoretically model this system using a combination of transfer matrix calculations and rate equations for a two-level lasing system and find very good qualitative agreement with the experimental results. We show that the generalized conductance in higher disorder can be emulated in weak disorder using the appropriate gain. The decreasing conductance is explained using the reduced probability of outcoupling of photons relative to their peak position within the system.

Necklace-State-Mediated Anomalous Enhancement of Transport in Anderson-Localized non-Hermitian Hybrid Systems.

Non-Hermiticity is known to manifest interesting modifications in the transport properties of complex systems. We report an intriguing regime of transport of hybrid quasiparticles in a non-Hermitian setting. We calculate the probability of transport, quantified by the Thouless conductance, of hybrid plasmons under varying degrees of disorder. With increasing disorder, we initially observe an expected decrease in average transmission, followed by an anomalous rise at localizing disorder. The behavior originates from the confluence of hybridization and non-Hermiticity, in which the former realizes the aggregation of eigenvalues migrating under disorder, while the latter enables energy transfer between the eigenmodes. We find that the enhanced transmission is mediated by quasiparticle hopping over various Anderson-localized states within the so-formed necklace states. We note that, in this scenario, all configurations exhibit the formation of necklace states and enhanced transport, unlike the conventionally known behavior of necklace states which only occurs in rare configurations.

Heterogeneous Dynamical Environment at the Interface of a Protein-DNA Complex.

Binding between protein and DNA is an essential process to regulate different biological activities. Two puzzling questions in protein-DNA recognition are (i) how the protein's binding domain identifies the DNA sequence in an aqueous solution and (ii) how the formation of the complex alters the dynamical environment around it. In this work, we present results obtained from molecular dynamics simulations of the N-terminal α-helical domain of the λ-repressor protein (in dimeric form) bound to the corresponding operator DNA. Effects of formation of the complex in modifying the microscopic dynamics of water as well as the kinetics of hydrogen bonds at the interface have been explored. Locally heterogeneous restricted water motions at the complex interface have been observed, the extent of restriction being more significant around the directly bound residues of the protein and the DNA. In particular, the calculation revealed the existence of significantly constrained motionally restricted water layer that can form either bridges around the directly bound residues of the protein and DNA or are engaged in forming water-mediated contacts between a fraction of the unbound residues. More importantly, it is observed that the restricted water motion around the complex is correlated with the hydrogen bond relaxation time scale at the interface. It is further demonstrated that the kinetics of water-water hydrogen bonds involving the bridged water are influenced more due to complex formation.

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.

Redox Cascades and Making of a C-C Bond: 1,2-Benzodiazinyl Radicals and a Copper Complex of a Benzodiazine.

Two 1,2-benzodiazinyl radicals, cinnolinyl radicals by name, were successfully isolated by cascade routes using 1,4-naphthoquinone as a precursor. Reaction of 1,4-naphthoquinone with hydrazine hydrate promotes a (5e + 5H+) redox cascade affording benzo[ g]naphtho[1,2- c]cinnolinyl-7,12,14-trione (Cn•) in 69% yields, while the similar reaction with 2-hydrazinopyridine is a (7e + 7H+) oxidative cascade and furnishes N-pyridinecinnolinyl radical (PyCn•). The cascades are composed of C-N and C-C bond making reactions. The neutral even alternate arenes are always diamagnetic; thus, the isolation of Cn• and PyCn• is a breakthrough. The Cn•/Cn- and PyCn•/PyCn- redox couples are reversible, and the reaction of Cn• with [CuI(PPh3)3Cl] in the presence of hydrazine hydrate and Et3N affords a Cn- complex of copper(I), [(Cn-)CuI(PPh3)2] (1). Similar to phenalenyl radical, PyCn• exists in three redox states, PyCn+, PyCn•, and PyCn-, in a smaller potential range (-0.30 V to -0.60 V vs Fc+/Fc couple) and can be used as an oxidant as well as a reductant. PyCn• acts as a catalyst for the oxidative cleavages of benzil to benzoic and 2,2'-pyridil to picolinic acids in methanol in the presence of air. The molecular and electronic structures of Cn•, PyCn•, and 1·1/2MeOH were confirmed by single crystal X-ray crystallography, EPR spectroscopy, and DFT calculations.

Ambient electrospray deposition Raman spectroscopy (AESD RS) using soft landed preformed silver nanoparticles for rapid and sensitive analysis.

We introduce a technique called ambient electrospray deposition Raman spectroscopy (AESD RS) for rapid and sensitive surface-enhanced Raman scattering (SERS) based detection of analytes using a miniature Raman spectrometer. Using electrospray, soft landing of preformed silver nanoparticles (AgNPs) was performed for 30-40 seconds for different concentrations of analytes deposited on conducting glass slides. Using AESD RS, SERS signals were collected within 4-6 minutes, including sample preparation. Transmission electron microscopy (TEM) and dark-field microscopy (DFM) were used to characterize the preformed AgNPs before and after electrospray. We achieved the nanomolar and micromolar detection of p-mercaptobenzoic acid (p-MBA) and 2,4-dinitrotoluene (2,4-DNT), respectively. In this work, 0.3 µL of preformed AgNPs were used, which is ∼33 times less in volume than the quantity needed for conventional SERS. Quantitation of unknown concentration of analytes was also possible. A similar amount of electrosprayed AgNPs was utilized to characterize Escherichia coli (E. coli) bacteria of different concentrations. Viability of bacteria was tested using fluorescence microscopic imaging. Besides reduced analysis time and improved reproducibility of the data in every analysis, which is generally difficult in SERS, the amount of AgNPs required is an order of magnitude lower in this method. This method could also be used to probe the real-time changes in molecular and biological species under ambient conditions.

Flexibility of the Binding Regions of a Protein-DNA Complex and the Structure and Ordering of Interfacial Water.

Noncovalent interactions between protein and DNA are important to comprehend different biological activities in living organisms. One important issue is how the protein identifies the target DNA and the influence of the resulting protein-DNA complex on the hydration environment around it. In this study, we have carried out atomistic molecular dynamics simulations of the protein-DNA complex formed by the dimeric form of the α-helical N-terminal domain of the λ-repressor protein with its operator DNA. Local heterogeneous flexibilities of the residues of the protein and the DNA components that are involved in binding and the microscopic structure and ordering of water around those have been investigated in detail. The calculations revealed concurrent existence of highly ordered as well as disordered water molecules at the interface. It is found that a fraction of doubly coordinated water molecules exhibit high degree of ordering at the interface, while the randomly oriented ones are coordinated with three water molecules. The effect has been found to be more around the protein and DNA residues that are in contact in the complexed state. We believe that such highly ordered two-coordinated water molecules are likely to act as an adhesive to facilitate the formation of a protein-DNA complex and maintain its structural stability.

Carbon and Tin-Based Polyacrylonitrile Hybrid Architecture Solid Phase Microextraction Fiber for the Detection and Quantification of Antibiotic Compounds in Aqueous Environmental Systems.

In this study, the detection and quantification of multiple classes of antibiotics in water matrices are proposed using a lab-made solid phase microextraction (SPME) fiber coupled with high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). The lab-made fiber was prepared using a graphene oxide (G), carbon nanotubes (C), and titanium dioxide (T) composite, namely GCT, with polyacrylonitrile (PAN) as supporting material. The detected antibiotics were enrofloxacin, sulfathiazole, erythromycin, and trimethoprim. The custom-made fiber was found to be superior compared with a commercial C18 fiber. The excellent reproducibility and lower intra-fiber relative standard deviations (RSDs 1.8% to 6.8%) and inter-fiber RSDs (4.5% to 8.8%) made it an ideal candidate for the detection of traces of antibiotics in real environmental samples. The proposed validated method provides a satisfactory limit of detection and good linear ranges with higher (>0.99) coefficient of determination in the aqueous system. Application of the method was made in different real water systems such as river, pond and tap water using the standard spiking method. Excellent sensitivity, reproducibility, lower amount of sample detection and higher recovery was found in a real water sample. Therefore, the extraction method was successfully applied to the detection and quantification of multiple classes of antibiotics in different aqueous systems with satisfactory results.

A Redox-Active Cascade Precursor: Isolation of a Zwitterionic Triphenylphosphonio-Hydrazyl Radical and an Indazolo-Indazole Derivative.

A redox-active [ML] unit (M = CoII and MnII; LH2 = N'-(1,4-dioxo-1,4-dihydronaphthalen-2-yl)benzohydrazide) defined as a cascade precursor that undergoes a multicomponent redox reaction comprising of a C-N bond formation, tautomerization, oxidation, C-C coupling, demetalation, and affording 6,14-dibenzoylbenzo[f]benzo[5,6]indazolo[3a,3-c]indazole-5,8,13,16-tetraone (IndL2) is reported. Conversion of LH2 → IndL2 in air is overall a (6H++6e) oxidation reaction, and it opens a route for the syntheses of bioactive diarylindazolo[3a,3-c]indazole derivatives. The reaction occurs via a radical coupling reaction, and the radical intermediate was isolated as a triphenylphosphonio adduct. In presence of PPh3 the [ML] unit promotes a reaction that involves a C-P bond formation, tautomerization, and oxidation to yield a stable zwitterionic triphenylphosphonio-hydrazyl radical (PPh3L±â€¢). Conversion of LH2 → PPh3L±â€¢ is a (3H++3e) oxidation reaction. To authenticate the [ML] unit, in addition to the IndL2, a zinc(II) complex, [(L3)ZnII(H2O)Cl]·2MeOH (1·2MeOH), was successfully isolated (L3H = a pyridazine derivative of 1,4 naphthoquinone) from a reaction of LH2 with hydrated ZnCl2. Conversion of 3LH2 → 1 is also a multicomponent (6H++6e) oxidation reaction promoted by zinc(II) ion via a radical intermediate. Facile oxidation of [L2-] to [L•-] that was considered as an intermediate of these conversions was confirmed by isolating a 1,4 naphthoquinone-benzhydrazyl radical (LH•) complex, [(LH•)ZnII(H2O)Cl2] (2H•). The intermediates of LH2 → IndL2, LH2 → PPh3L±â€¢, and 3LH2 → 1 conversions were analyzed by electrospray ionization mass spectroscopy. The molecular and electronic structures of PPh3L±â€¢, IndL2, 1·2MeOH, and 2H• were confirmed by single-crystal X-ray crystallography, electron paramagnetic resonance spectroscopy, and density functional theory calculations.

Molecular and Electronic Structures of Ruthenium Complexes Containing an ONS-Coordinated Open-Shell π Radical and an Oxidative Aromatic Ring Cleavage Reaction.

The coordination chemistry of 2,4-di-tert-butyl-6-[(2-mercaptophenyl)amino]phenol (LONSH3), which was isolated as a diaryl disulfide form, (LONSH2)2, with a Ru ion is disclosed. It was established that the trianionic LONS3- is redox-noninnocent and undergoes oxidation to either a closed-shell singlet (CSS), LONS-, or an open-shell π-radical state, LONS•2-, and the reactivities of the [RuII(LONS•2-)] and [RuII(LONS-)] states are different. The reaction of (LONSH2)2 with [Ru(PPh3)3Cl2] in toluene in the presence of PPh3 affords a ruthenium complex of the type trans-[Ru(LONS)(PPh3)2Cl] (1), while the similar reaction with [Ru(PPh3)3(H)(CO)Cl] yields a LONS•2- complex of ruthenium(II) of the type trans-[RuII(LONS•2-)(PPh3)2(CO)] (2). 1 is a resonance hybrid of the [RuII(LONS-)Cl] and [RuIII(LONS•2-)Cl] states. It is established that 2 incorporating an open-shell π-radical state, [RuII(LONS•2-)(CO)], reacts with an in situ generated superoxide ion and promotes an oxidative aromatic ring cleavage reaction, yielding a α-N-arylimino-ω-ketocarboxylate (LNS2-) complex of the type [RuII(LNS2-)(PPh3)(CO)]2 (4), while 1 having a CSS state, [RuII(LONS-)Cl], is inert in similar conditions. Notably, 2 does not react with O2 molecule but reacts with KO2 in the presence of excess PPh3, affording 4. The redox reaction of (LONSH2)2 with [Ru(PPh3)3Cl2] in ethanol in air is different, leading to the oxidation of LONS to a quinone sulfoxide derivative (LONSO0) as in cis-[RuII(LONSO0)(PPh3)Cl2] (3), via 1 as an intermediate. The molecular and electronic structures of 1-4 were established by single-crystal X-ray crystallography, electron paramagnetic resonance spectroscopy, electrochemical measurements, and density functional theory calculations. 1+ is a resonance hybrid of [RuIII(LONS-)(PPh3)2Cl ↔ RuIV(LONS•2-)(PPh3)2Cl]+ states, 2- is a LONS3- complex of ruthenium(II), [RuII(LONS3-)(PPh3)2(CO)]-, and 2+ is a ruthenium(II) complex of LONS- of the type [RuII(LONS-)(PPh3)2(CO)]+, where 35% diradical character of the LONS- ligand was predicted.

Cobalt Ion Promoted Redox Cascade: A Route to Spiro Oxazine-Oxazepine Derivatives and a Dinuclear Cobalt(III) Complex of an N-(1,4-Naphthoquinone)-o-aminophenol Derivative.

The study discloses that the redox activity of N-(1,4-naphthoquinone)-o-aminophenol derivatives (LRH2) containing a (phenol)-NH-(1,4-naphthoquinone) fragment is notably different from that of a (phenol)-NH-(phenol) precursor. The former is a platform for a redox cascade. LRH2 is redox noninnocent and exists in Cat-N-(1,4-naphthoquinone)(2-) (LR 2-) and SQ-N-(1,4-naphthoquinone) (LR •-) states in the complexes. Reactions of LRH2 with cobalt(II) salts in MeOH in air promote a cascade affording spiro oxazine-oxazepine derivatives (OXLR) in good yields, when R = H, Me, tBu. Spiro oxazine-oxazepine derivatives are bioactive, and such a molecule has so far not been isolated by a schematic route. In this context this cascade is significant. Dimerization of LRH2 → OXLR in MeOH is a (6H+ + 6e) oxidation reaction and is composed of formations of four covalent bonds and 6-exo-trig and 7-endo-trig cyclization based on C-O coupling reactions, where MeOH is the source of a proton and the ester function. It was established that the active cascade precursor is [(LMe •-)CoIIICl2] (A). Notably, formation of a spiro derivative was not detected in CH3CN and the reaction ends up furnishing A. The route of the reaction is tunable by R, when R = NO2, it is a (2e + 4H+) oxidation reaction affording a dinuclear LR 2- complex of cobalt(III) of the type [(LNO2 2-)2CoIII2(OMe)2(H2O)2] (1) in good yields. No cascade occurs with zinc(II) ion even in MeOH and produces a LMe •- complex of type [(LMe •-)ZnIICl2] (2). The intermediate A and 2 exhibit strong EPR signals at g = 2.008 and 1.999, confrming the existence of LMe •- coordinated to low-spin cobalt(III) and zinc(II) ions. The intermediates of LRH2 → OXLR conversion were analyzed by ESI mass spectrometry. The molecular geometries of OXLR and 1 were confirmed by X-ray crystallography, and the spectral features were elucidated by TD DFT calculations.

Microscopic understanding of the conformational features of a protein-DNA complex.

Protein-DNA interactions play crucial roles in different biological processes. Binding of a protein to its target DNA is the key step at different stages of genetic activities. In this article, we have carried out atomistic molecular dynamics simulations to understand the microscopic conformational and dynamical features of the N-terminal domain of the λ-repressor protein and its operator DNA in their complexed state. The calculations revealed that the overall flexibility of the protein and the DNA components reduces due to complex formation. In particular, increased ordering of the DNA sugar rings bound to the protein is found to be associated with modified ring puckering. Attempts have been made to study the effect of complexation on the internal motions of the protein and the DNA components. It is demonstrated that the non-uniform ordering of the side chains of lysine residues in the consensus sequence leads to differential behavior of the two monomers of the homodimeric protein.

Radical and Non-Radical States of the [Os(PIQ)] Core (PIQ = 9,10-Phenanthreneiminoquinone): Iminosemiquinone to Iminoquinone Conversion Promoted o-Metalation Reaction.

The coordination and redox chemistry of 9,10-phenanthreneiminoquinone (PIQ) with osmium ion authenticating the [Os(II)(PIQ(•-))], [Os(III)(PIQ(•-))], [Os(III)(C,N-PIQ)], [Os(III)(PIQ)], and [Os(III)(PIQ(2-)) ] states of the [Os(PIQ)] core in the complexes of types trans-[Os(II)(PIQ(•-))(PPh3)2(CO)Br] (1), trans-[Os(III)(PIQ(•-))(PPh3)2Br2] (2), trans-[Os(III)(C,N-PIQ)(PPh3)2Br2]·2CH2Cl2 (3·2CH2Cl2), trans-[Os(III)(C,N-PIQ(Br))(PPh3)2Br2]·2CH2Cl2 (4·2CH2Cl2), trans-[Os(III)(C,N-PIQ(Cl2))(PPh3)2Br2] (6), trans-[Os(III)(PIQ(•-))(PPh3)2Br2](+)1/2I3(-)1/2Br(-) (1(+)1/2I3(-)1/2Br(-)), [Os(III)(PIQ)(PPh3)2Br2](+) (2(+)), and [Os(III)(PIQ(2-))(PPh3)2Br2](-) (2(-)) are reported (PIQ(•-) = 9,10-phenanthreneiminosemiquinonate anion radical; C,N-PIQ = ortho-metalated PIQ, C,N-PIQ(Br) = ortho-metalated 4-bromo PIQ, and C,N-PIQ(Cl2) = ortho-metalated 3,4-dichloro PIQ). Reduction of PIQ by [Os(II)(PPh3)3(H)(CO)Br] affords 1, while the reaction of PIQ with [Os(II)(PPh3)3Br2] furnishes 2. Oxidation of 1 with I2 affords 1(+)1/2I3(-)1/2Br(-), while the similar reactions of 2 with X2 (X = I, Br, Cl) produce the ortho-metalated derivatives 3·2CH2Cl2, 4·2CH2Cl2, and 6. PIQ and PIQ(2-) complexes of osmium(III), 2(+) and 2(-), are generated by constant-potential electrolysis. However, 2(+) ion is unstable in solution and slowly converts to 3 and partially hydrolyzes to trans-[Os(III)(PQ(•-))(PPh3)2Br2] (2PQ), a PQ(•-) analogue of 2. Conversion of 2(+) → 3 in solution excludes the formation of aryl halide as an intermediate for this unique ortho-metalation reaction at 295 K, where PIQ acts as a redox-noninnocent ambidentate ligand. In the complexes, the PIQ(•-) state where the atomic spin is more localized on the nitrogen atom is stable and is more abundant. The reaction of 2PQ, with I2 does not promote any ortho-metalation reaction and yields a PQ complex of type trans-[Os(III)(PQ)(PPh3)2Br2](+)I5(-)·2CH2Cl2 (5(+)I5(-)·2CH2Cl2). The molecular and electronic structures of 1-4, 6, 1(+), and 5(+) were established by different spectra, single-crystal X-ray bond parameters, cyclic voltammetry, and DFT calculations.

Biosorptive uptake of ibuprofen by steam activated biochar derived from mung bean husk: Equilibrium, kinetics, thermodynamics, modeling and eco-toxicological studies.

The present study explores the use of steam activated mung bean husk biochar (SA-MBHB) as a potential sorbent for the removal of non-steroidal and anti-inflammatory drug ibuprofen from aqueous solution. SA-MBHB was characterized by SEM, FTIR, BET, TGA, point of zero charge (pHPZC) and UV-Vis spectrophotometer. The relation between removal percentages of ibuprofen and parameters such as adsorbent dose (0.05 g-250 g), contact time (5 min-210 min), pH (2-10), speed of agitation (40-280 rpm), temperature (293-308 K) and initial ibuprofen concentration (5-100 ppm) was investigated and optimized by a series of batch sorption experiments. The optimized conditions achieved were: adsorbent dose 0.1 g/L, agitation speed 200 rpm, pH 2, initial ibuprofen concentration 20 mg L(-1), equilibrium time 120 min and temperature 20 °C for more than 99% adsorptive removal of ibuprofen. The equilibrium adsorption data were well fitted into the Langmuir isotherm model while kinetic data suggested the removal process to follow pseudo second order reaction. The adsorption phenomena were optimized and simulated by using response surface methodology (RSM) and artificial neural network (ANN). Effect of process variables viz. dose, agitation speed and pH on the sorbed amount of IBP was studied through a 2(3) full factorial central composite design (CCD). The comparative analysis was done for ibuprofen removal by constructing ANN model training using same experimental matrix of CCD. The growth of Scenedesmus abundans was also observed to be affected by the IBP solution whereas the biochar treated with IBP solution did not significantly affect the growth of the Scenedesmus abundans. The results revealed that SA-MBHB could be a cost-effective, efficient and non-hazardous adsorbent for the removal of ibuprofen from aqueous solution.