Conformation-selective coordination-driven self-assembly of a ditopic donor with Pd-II acceptors

Coordination-driven self-assembly of 3-(5-(pyridin-3-yl)-1H-1,2,4-triazol-3-yl)pyridine (L) was investigated with 90 degrees cis-blocked Pd(II) acceptors and tetratopic Pd(NO3)(2). Although the ligand is capable of binding in several different conformations (acting as a ditopic donor through the pyridyl nitrogens), the experimental results (including X-ray structures) showed that it adopts a particular conformation when it binds with 90 degrees cis-blocked Pd(II) acceptors (two available sites) to yield 2 + 2] self-assembled macrocycles. On the other hand, with Pd(NO3)(2) (where four available sites are present) a different conformer of the same donor was selectively bound to form a molecular cubic cage. The experimental findings were corroborated well with the density functional theory (B3LYP) calculations. The tetratopic Pd(NO3)(2) yielded a 6 + 12] self-assembled Pd6L12 molecular cube, which contains a potential void occupied by nitrate and perchlorate ions. Being a triazole based ligand, the free space inside the cage is enriched with several sp(2) hybridised nitrogen atoms with lone pairs of electrons to act as Lewis basic sites. Knoevenagel condensation reactions of several aromatic aldehydes with active methylene compounds were successfully performed in reasonably high yields in the presence of the cage.

Amperometric acetylcholinesterase biosensor for pesticides monitoring utilising iron oxide nanoparticles and poly(indole-5-carboxylic acid)

A new electrochemical sensing device was constructed for determination of pesticides. In this report, acetylcholinesterase was bioconjugated onto hybrid nanocomposite, i.e. iron oxide nanoparticles and poly(indole-5-carboxylic acid) (Fe(3)O(4)NPs/Pin5COOH) was deposited electrochemically on glassy carbon electrode. Fe(3)O(4)NPs was showed as an amplified sensing interface at lower voltage which makes the sensor more sensitive and specific. The enzyme inhibition by pesticides was detected within concentrations ranges between 0.1-60 and 1.5-70 nM for malathion and chlorpyrifos, respectively, under optimal experimental conditions (sodium phosphate buffer, pH 7.0 and 25 degrees C). Biosensor determined the pesticides level in water samples (spiked) with satisfactory accuracy (96%-100%). Sensor showed good storage stability and retained 50% of its initial activity within 70 days at 4 degrees C.

The X Chromosome of Hemipteran Insects: Conservation, Dosage Compensation and Sex-Biased Expression

Insects of the order Hemiptera (true bugs) use a wide range of mechanisms of sex determination, including genetic sex determination, paternal genome elimination, and haplodiploidy. Genetic sex determination, the prevalent mode, is generally controlled by a pair of XY sex chromosomes or by an XX/XO system, but different configurations that include additional sex chromosomes are also present. Although this diversity of sex determining systems has been extensively studied at the cytogenetic level, only the X chromosome of the model pea aphid Acyrthosiphon pisum has been analyzed at the genomic level, and little is known about X chromosome biology in the rest of the order. In this study, we take advantage of published DNA- and RNA-seq data from three additional Hemiptera species to perform a comparative analysis of the gene content and expression of the X chromosome throughout this clade. We find that, despite showing evidence of dosage compensation, the X chromosomes of these species show female-biased expression, and a deficit of male-biased genes, in direct contrast to the pea aphid X. We further detect an excess of shared gene content between these very distant species, suggesting that despite the diversity of sex determining systems, the same chromosomal element is used as the X throughout a large portion of the order.

Phase boundary at x=0.03 and its anomalous influence on the structure and properties in the lead-free piezoelectric (1-x)Na1/2Bi1/2TiO3-(x)BaTiO3

The complexity associated with local structures continues to pose challenges with regard to the understanding of the structure-property relationship in Na1/2Bi1/2TiO3-based lead-free piezoceramics. (1-x)Na1/2Bi1/2TiO3-(x)BaTiO3 is an extensively studied system because of its interesting piezoelectric properties. Recently, a room temperature phase boundary was reported at x = 0.03 in this system Ma et al., Adv. Funct. Mater. 23, 5261 (2013)]. In the present work we have examined this subtle phase boundary using x-ray diffraction, neutron diffraction, dielectric measurements as a function of composition (x < 0.06), temperature, and electric field. Our results show that this boundary separates an R3c + Cc-like structural state for x < 0.03 from an R3c+ cubiclike structural state for 0.03 <= x <= 0.05 in the unpoled specimens. This phase boundary is characterized by an anomalous reduction in the depolarization temperature, and a suppression of the tetragonal distortion of the high temperature P4bm phase. Our results also provide the clue to understand the pathway leading to the cubiclike structure of the critical composition x = 0.06, known for its highest piezoelectric response.

Structural studies on a non-toxic homologue of type II RIPs from bitter gourd: Molecular basis of non-toxicity, conformational selection and glycan structure

The structures of nine independent crystals of bitter gourd seed lectin (BGSL), a non-toxic homologue of type II RIPs, and its sugar complexes have been determined. The four-chain, two-fold symmetric, protein is made up of two identical two-chain modules, each consisting of a catalytic chain and a lectin chain, connected by a disulphide bridge. The lectin chain is made up of two domains. Each domain carries a carbohydrate binding site in type II RIPs of known structure. BGSL has a sugar binding site only on one domain, thus impairing its interaction at the cell surface. The adenine binding site in the catalytic chain is defective. Thus, defects in sugar binding as well as adenine binding appear to contribute to the non-toxicity of the lectin. The plasticity of the molecule is mainly caused by the presence of two possible well defined conformations of a surface loop in the lectin chain. One of them is chosen in the sugar complexes, in a case of conformational selection, as the chosen conformation facilitates an additional interaction with the sugar, involving an arginyl residue in the loop. The N-glycosylation of the lectin involves a plant-specific glycan while that in toxic type II RIPs of known structure involves a glycan which is animal as well as plant specific.

Continuum in the X-Z-Y Weak Bonds: Z= Main Group Elements

The Continuum in the variation of the X-Z bond length change from blue-shifting to red-shifting through zero-shifting in the X-Z---Y complex is inevitable. This has been analyzed by ab-initio molecular orbital calculations using Z= Hydrogen, Halogens, Chalcogens, and Pnicogens as prototypical examples. Our analysis revealed that, the competition between negative hyperconjugation within the donor (X-Z) molecule and Charge Transfer (CT) from the acceptor (Y) molecule is the primary reason for the X-Z bond length change. Here, we report that, the proper tuning of X-and Y-group for a particular Z-can change the blue-shifting nature of X-Z bond to zero-shifting and further to red-shifting. This observation led to the proposal of a continuum in the variation of the X-Z bond length during the formation of X-Z---Y complex. The varying number of orbitals and electrons available around the Z-atom differentiates various classes of weak interactions and leads to interactions dramatically different from the H-Bond. Our explanations based on the model of anti-bonding orbitals can be transferred from one class of weak interactions to another. We further take the idea of continuum to the nature of chemical bonding in general. (C) 2015 Wiley Periodicals, Inc.

On the Structural Stability of Melt Spun Ribbons of Fe95-x Zr (x) B4Cu1 (x=7 and 9) Alloys and Correlation with Their Magnetic Properties

Melt spun ribbons of Fe95-x Zr (x) B4Cu1 with x = 7 (Z7B4) and 9 (Z9B4) alloys have been prepared, and their structure and magnetic properties have been evaluated using XRD, DSC, TEM, VSM, and Mossbauer spectroscopy. The glass forming ability (GFA) of both alloys has been calculated theoretically using thermodynamical parameters, and Z9B4 alloy is found to possess higher GFA than that of Z7B4 alloy which is validated by XRD results. On annealing, the amorphous Z7B4 ribbon crystallizes into nanocrystalline alpha-Fe, whereas amorphous Z9B4 ribbon shows two-stage crystallization process, first partially to bcc solid solution which is then transformed to nanocrystalline alpha-Fe and Fe2Zr phases exhibiting bimodal distribution. A detailed phase analysis using Mossbauer spectroscopy through hyperfine field distribution of phases has been carried out to understand the crystallization behavior of Z7B4 and Z9B4 alloy ribbons. In order to understand the phase transformation behavior of Z7B4 and Z9B4 ribbons, molar Gibbs free energies of amorphous, alpha-Fe, and Fe2Zr phases have been evaluated. It is found that in case of Z7B4, alpha-Fe is always a stable phase, whereas Fe2Zr is stable at higher temperature for Z9B4. (C) The Minerals, Metals & Materials Society and ASM International 2015

Origin of giant dielectric constant and conductivity behavior in Zn1-xMgxO (0 <= x <= 0.1) ceramics

Zn1-xMgxO ( <= x <= 0.1) ceramics were fabricated by conventional solid-state reaction of co-precipitated zinc oxide and magnesium hydroxide nanoparticles. Structural and morphological properties of the fabricated ceramics were studied using X-ray diffraction and scanning electron microscopic analysis. The dielectric measurements of the ceramics were carried out as a function of frequency and temperature respectively. Interestingly, Mg doped ZnO (MZO) samples exhibited colossal dielectric response (similar to 1 x 10(4) at 1 kHz) with Debye like relaxation. The detailed dielectric studies and thermal analyses showed that the unusual dielectric response of the samples were originated from the defected grain and grain boundary (GB) conductivity relaxations due to the absorbed atmospheric water vapor (moisture). Impedance spectroscopy was employed to determine the defected grain and GB resistances, capacitances and which supported Maxwell-Wagner type relaxation phenomena. (C) 2015 Elsevier Ltd. All rights reserved.

Macropores generated during shrinkage in two paddy soils using X-ray micro-computed tomography

Soil shrinkage curve represents a decrease of total porosity or an increase of bulk density with water loss. However, our knowledge of the dynamics of pores and their geometry during soil shrinkage is scarce, partially due to lack of reliable methods for determining soil pores in relation to change in soil water. This study aimed to investigate the dynamics of macropores (>30 mu m) of paddy soils during shrinkage. Two, paddy soils, which were sampled from one paddy field cultivated for 20 years (YPF) and the other one for over 100 years (OPF), represented difference in crack geometry in the field. Macropore parameters (volume, connectivity, and orientation of pores) and soil shrinkage parameters were determined on the same undisturbed soil cores by X-ray microtomography and shrinkage curve, respectively. Macroporosity was on average four times larger in the YPF than in the OPF whereas the shrinkage capacity was lower in the YPF as compared to the OPF (0.09 vs. 0.15 COLE). Soil shrinkage increased the volume of pores by 3.7% in the YPF and by 1.6% in the OPF as well as their connectivity. The formation of macropores occurred mostly in the proportional shrinkage phase. As a result, the slope of the proportional shrinkage phase was smaller in the YPF (0.65) than in the OPF (0.89). New macropores were cracks and extended pre-existing pores in the range of 225-1215 pm size without any preferential orientation. This work provides image evidences that in paddy soils with high shrinkage capacity more macropores are generated in the soil presenting a smaller proportional shrinkage slope. (C) 2015 Elsevier B.V. All rights reserved.

On the Gaussian Many-to-One X Channel

In this paper, the Gaussian many-to-one X channel (XC), which is a special case of general multiuser XC, is studied. In the Gaussian many-to-one XC, communication links exist between all transmitters and one of the receivers, along with a communication link between each transmitter and its corresponding receiver. As per the XC assumption, transmission of messages is allowed on all the links of the channel. This communication model is different from the corresponding manyto- one interference channel (IC). Transmission strategies, which involve using Gaussian codebooks and treating interference from a subset of transmitters as noise, are formulated for the above channel. Sum-rate is used as the criterion of optimality for evaluating the strategies. Initially, a 3 x 3 many-to-one XC is considered and three transmission strategies are analyzed. The first two strategies are shown to achieve sum-rate capacity under certain channel conditions. For the third strategy, a sum-rate outer bound is derived and the gap between the outer bound and the achieved rate is characterized. These results are later extended to the K x K case. Next, a region in which the many-to-one XC can be operated as a many-to-one IC without the loss of sum-rate is identified. Furthermore, in the above region, it is shown that using Gaussian codebooks and treating interference as noise achieve a rate point that is within K/2 -1 bits from the sum-rate capacity. Subsequently, some implications of the above results to the Gaussian many-to-one IC are discussed. Transmission strategies for the many-to-one IC are formulated, and channel conditions under which the strategies achieve sum-rate capacity are obtained. A region where the sum-rate capacity can be characterized to within K/2 -1 bits is also identified. Finally, the regions where the derived channel conditions are satisfied for each strategy are illustrated for a 3 x 3 many-to-one XC and the corresponding many-to-one IC.

Investigations into the structural and down-shifting and up-conversion luminescence properties of Ba2Na1-3xErxNb5O15 (0 <= x <= 0.06) nanocrystalline phosphor synthesized via sol-gel route

The present work deals with the structural and efficient down-shifting (DS) and up-conversion (UC) luminescence properties of erbium ion (Er3+) doped nanocrystalline barium sodium niobate (Ba2Na1-3xErxNb5O15, where x = 0, 0.02, 0.04 and 0.06) powders synthesized via novel citrate-based sol-gel route. The monophasic nature of the title compound was confirmed via x-ray powder diffraction followed by FT-IR studies. High-resolution transmission electron microscopy (HRTEM) facilitated the establishment of the nanocrystalline phase and the morphology of the crystallites. The Kubelka-Munk function, based on diffused reflectance studies and carried out on nano-sized crystallites, was employed to obtain the optical band-gap. The synthesized nanophosphor showed efficient DS/PL-photoluminescence and UC luminescence properties, which have not yet been reported so far in this material. The material emits intense DS green emission on excitation with 378 nm radiation. Interestingly, the material gives intense UC emission in the visible region dominated by green emission and relatively weak red emission on 976 nm excitation (NIR laser excitation). Such a dual-mode emitting nanophosphor could be very useful in display devices and for many other applications.

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.

Evolution of Jahn-Teller distortion, transport and dielectric properties with doping in perovskite NdFe1-xMnxO3 (0 <= x <= 1) compounds

We have carried out dielectric and transport measurements in NdFe1-xMnxO3 (0 <= x <= 1) series of compounds and studied the variation of activation energy due to a change in Mn concentration. Despite similar ionic radii in Mn3+ and Fe3+, large variation is observed in the lattice parameters and a crossover from dynamic to static Jahn-Teller distortion is discernible. The Fe/Mn-O-Fe/Mn bond angle on the ab plane shows an anomalous change with doping. With an increase in the Mn content, the bond angle decreases until x = 0.6; beyond this, it starts rising until x = 0.8 and again falls after that. A similar trend is observed in activation energies estimated from both transport and dielectric relaxation by assuming a small polaron hopping (SPH) model. Impedance spectroscopy measurements delineate grain and grain boundary contributions separately both of which follow the SPH model. Frequency variation of the dielectric constant is in agreement with the modified Debye law from which relaxation dispersion is estimated.

DIFFUSE X-RAY EMISSION FROM STAR-FORMING GALAXIES

We study the diffuse X-ray luminosity (L-X) of star-forming galaxies using two-dimensional axisymmetric hydrodynamical simulations and analytical considerations of supernovae-(SNe-) driven galactic outflows. We find that the mass loading of the outflows, a crucial parameter for determining the X-ray luminosity, is constrained by the availability of gas in the central star-forming region, and a competition between cooling and expansion. We show that the allowed range of the mass loading factor can explain the observed scaling of L-X with star formation rate (SFR) as L-X alpha SFR2 for SFR greater than or similar to 1 M-circle dot yr(-1), and a flatter relation at low SFRs. We also show that the emission from the hot circumgalactic medium (CGM) in the halo of massive galaxies can explain the large scatter in the L-X-SFR relation for low SFRs (less than or similar to few M-circle dot yr(-1)). Our results suggest that galaxies with small SFRs and large diffuse X-ray luminosities are excellent candidates for the detection of the elusive CGM.

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.