Template-free coordination-driven self-assembly of discrete hexanuclear prismatic cages employing half-sandwich octahedral Ru-2(II) acceptors and triimidazole donors

Coordination-driven self-assembly of dinuclear half-sandwich p-cymene ruthenium(II) complexes Ru-2(mu-eta(4)-C2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) and Ru-2(mu-eta(4)-C6H2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) separately with imidazole-based tritopic donors (L-1-L-2) in methanol yielded a series of hexanuclear 3+2] trigonal prismatic cages (2-5), respectively L-1 = 1,3,5-tris(imidazole-1-yl) benzene; L-2 = 4,4',4 `'-tris(imidazole-1-yl) triphenylamine]. All the self-assembled cages 2-5 were characterized by various spectroscopic techniques (multinuclear NMR, Infra-red and ESI-MS) and their sizes, shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) computation. Despite the possibility due to the free rotation of donor sites of imidazole ligands, of two different atropoisomeric prismatic cages (C-3h or C-s) and polymeric product, the self-selection of single (C(3)h) conformational isomeric cages as the only product is a noteworthy observation. (C) 2015 Elsevier B.V. All rights reserved.

Ferromagnetism and the effect of free charge carriers on electric polarization in the double perovskite Y2NiMnO6

The double perovskite Y2NiMnO6 displays ferromagnetic transition at T-c approximate to 81 K. The ferromagnetic order at low temperature is confirmed by the saturation value of magnetization (Ms) and also validated by the refined ordered magnetic moment values extracted from neutron powder diffraction data at 10 K. This way, the dominant Mn4+ and Ni2+ cationic ordering is confirmed. The cation-ordered P2(1)/n nuclear structure is revealed by neutron powder diffraction studies at 300 and 10 K. Analysis of the frequency-dependent dielectric constant and equivalent circuit analysis of impedance data take into account the bulk contribution to the total dielectric constant. This reveals an anomaly which coincides with the ferromagnetic transition temperature (T-c). Pyrocurrent measurements register a current flow with onset near T-c and a peak at 57 K that shifts with temperature ramp rate. The extrinsic nature of the observed pyrocurrent is established by employing a special protocol measurement. It is realized that the origin is due to reorientation of electric dipoles created by the free charge carriers and not by spontaneous electric polarization at variance with recently reported magnetism-driven ferroelectricity in this material.

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.

Relaxor ferroelectricity and electric-field-driven structural transformation in the giant lead-free piezoelectric (Ba,Ca)(Ti, Zr)O-3

There is great interest in lead-free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O-3 (15/10BCTZ) because of its exceptionally large piezoelectric response Liu and Ren, Phys. Rev. Lett. 103, 257602 (2009)]. In this paper, we have analyzed the nature of: (i) crystallographic phase coexistence at room temperature, (ii) temperature-and field-induced phase transformation to throw light on the atomistic mechanisms associated with the large piezoelectric response of this system. A detailed temperature-dependent dielectric and lattice thermal expansion study proved that the system exhibits a weak dielectric relaxation, characteristic of a relaxor ferroelectric material on the verge of exhibiting a normal ferroelectric-paraelectric transformation. Careful structural analysis revealed that a ferroelectric state at room temperature is composed of three phase coexistences, tetragonal (P4mm)+ orthorhombic (Amm2) + rhombohedral (R3m). We also demonstrate that the giant piezoresponse is associated with a significant fraction of the tetragonal phase transforming to rhombohedral. It is argued that the polar nanoregions associated with relaxor ferroelectricity amplify the piezoresponse by providing an additional degree of intrinsic structural inhomogeneity to the system.

Efficient coupled polynomial interpolation scheme for out-of-plane free vibration analysis of curved beams

The performance of two curved beam finite element models based on coupled polynomial displacement fields is investigated for out-of-plane vibration of arches. These two-noded beam models employ curvilinear strain definitions and have three degrees of freedom per node namely, out-of-plane translation (v), out-of-plane bending rotation (theta(z)) and torsion rotation (theta(s)). The coupled polynomial interpolation fields are derived independently for Timoshenko and Euler-Bernoulli beam elements using the force-moment equilibrium equations. Numerical performance of these elements for constrained and unconstrained arches is compared with the conventional curved beam models which are based on independent polynomial fields. The formulation is shown to be free from any spurious constraints in the limit of `flexureless torsion' and `torsionless flexure' and hence devoid of flexure and torsion locking. The resulting stiffness and consistent mass matrices generated from the coupled displacement models show excellent convergence of natural frequencies in locking regimes. The accuracy of the shear flexibility added to the elements is also demonstrated. The coupled polynomial models are shown to perform consistently over a wide range of flexure-to-shear (EI/GA) and flexure-to-torsion (EI/GJ) stiffness ratios and are inherently devoid of flexure, torsion and shear locking phenomena. (C) 2015 Elsevier B.V. All rights reserved.

Electric field and temperature dependence of the local structural disorder in the lead-free ferroelectric Na0.5Bi0.5TiO3: An EXAFS study

The complex nature of the structural disorder in the lead-free ferroelectric Na1/2Bi1/2TiO3 has a profound impact on the perceived global structure and polar properties. In this paper, we have investigated the effect of electric field and temperature on the local structure around theBi and Ti atoms using extended x-ray absorption fine structure. Detailed analysis revealed that poling brings about a noticeable change in the bond distances associated with the Bi-coordination sphere, whereas the Ti coordination remains unaffected. We also observed discontinuity in the Bi-O bond lengths across the depolarization temperature of the poled specimen. These results establish that the disappearance of the monoclinic-like (Cc) global distortion, along with the drastic suppression of the short-ranged in-phase octahedral tilt after poling B. N. Rao et al., Phys. Rev. B 88, 224103 (2013)] is a result of the readjustment of theA-O bonds by the electric field, so as to be in conformity with the rhombohedral R3c structure.

Transition metal-free Minisci reaction promoted by NCS, and TBHP: acylation of heteroarenes

A method for acylation for heteroarenes under metal-free conditions has been described using NCS as an additive and TBHP as an oxidant. This method has been successfully employed in acylation of a variety of aldehyde with heteroarenes. The application of the method has been illustrated in synthesizing isoquinoline derived natural products. This strategy provides an efficient, mild and inexpensive method for acylation of heteroarenes. (C) 2015 Elsevier Ltd. All rights reserved.

Reagent-switch controlled metal-free intermolecular geminal diamination and aminooxygenation of vinylarenes

We report here the first general method for the geminal diamination and an intermolecular metal-free, geminal aminooxygenation of vinylarenes using hypervalent iodine reagent. A new m-CPBA mediated geminal aminooxygenation is also reported. A novel reagent-switch for the control of migrating group by controlling the two independent geminal addition paths is developed. Deuterium labelling studies and the control studies have provided unambiguous evidences for the phenyl migration and hydride migration in the oxidative geminal difunctionalization process mediated by Phl(OCOCF3)(2) and m-CPBA, respectively through a semi-pinacol rearrangement. (C) 2016 Elsevier Ltd. All rights reserved.

Molecular Cage Impregnated Palladium Nanoparticles: Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides

Two shape-persistent covalent cages (CC1(r) and CC2(r)) have been devised from triphenyl amine-based trialdehydes and cyclohexane diamine building blocks utilizing the dynamic imine chemistry followed by imine bond reduction. The cage compounds have been characterized by several spectroscopic techniques which suggest that CC1(r) and CC2(r) are 2+3] and 8+12] self-assembled architectures, respectively. These state-of-the-art molecules have a porous interior and stable aromatic backbone with multiple palladium binding sites to engineer the controlled synthesis and stabilization of ultrafine palladium nanoparticles (PdNPs). As-synthesized cage-embedded PdNPs have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and powder X-ray diffraction (PXRD). Inductively coupled plasma optical emission spectrometry reveals that Pd@CC1(r) and Pd@CC2(r) have 40 and 25 wt% palladium loading, respectively. On the basis of TEM analysis, it has been estimated that as small as similar to 1.8 nm PdNPs could be stabilized inside the CC1(r), while larger CC2(r) could stabilize similar to 3.7 nm NPs. In contrast, reduction of palladium salts in the absence of the cages form structure less agglomerates. The well-dispersed cage-embedded NPs exhibit efficient catalytic performance in the cyanation of aryl halides under heterogeneous, additive-free condition. Moreover, these materials have excellent stability and recyclability without any agglomeration of PdNPs after several cycles.

A Perspective on Computer Assisted Assessment Techniques for Short Free-Text Answers

Computer Assisted Assessment (CAA) has been existing for several years now. While some forms of CAA do not require sophisticated text understanding (e.g., multiple choice questions), there are also student answers that consist of free text and require analysis of text in the answer. Research towards the latter till date has concentrated on two main sub-tasks: (i) grading of essays, which is done mainly by checking the style, correctness of grammar, and coherence of the essay and (ii) assessment of short free-text answers. In this paper, we present a structured view of relevant research in automated assessment techniques for short free-text answers. We review papers spanning the last 15 years of research with emphasis on recent papers. Our main objectives are two folds. First we present the survey in a structured way by segregating information on dataset, problem formulation, techniques, and evaluation measures. Second we present a discussion on some of the potential future directions in this domain which we hope would be helpful for researchers.

Electrical and Plasmonic Properties of Ligand-Free Sn4+-Doped In2O3 (ITO) Nanocrystals

Sn4+-doped In2O3 (ITO) is a benchmark transparent conducting oxide material. We prepared ligand-free but colloidal ITO (8nm, 10% Sn4+) nanocrystals (NCs) by using a post-synthesis surface-modification reaction. (CH3)(3)OBF4 removes the native oleylamine ligand from NC surfaces to give ligand-free, positively charged NCs that form a colloidal dispersion in polar solvents. Both oleylamine-capped and ligand-free ITO NCs exhibit intense absorption peaks, due to localized surface plasmon resonance (LSPR) at around =1950nm. Compared with oleylamine-capped NCs, the electrical resistivity of ligand-free ITO NCs is lower by an order of magnitude (approximate to 35mcm(-1)). Resistivity over a wide range of temperatures can be consistently described as a composite of metallic ITO grains embedded in an insulating matrix by using a simple equivalent circuit, which provides an insight into the conduction mechanism in these systems.

Structural, Optical, and Piezoelectric Response of Lead-Free Ba0.95Mg0.05Zr0.1Ti0.9O3 Nanocrystalline Powder

Nanocrystalline powders of Ba1-xMgxZr0.1Ti0.9O3 (x = 0.025-0.1) were synthesized via citrate assisted sol-gel method. Interestingly, the one with x = 0.05 in the system Ba1-xMgxZr0.1Ti0.9O3 exhibited fairly good piezoelectric response aside from the other physical properties. The phase and structural confirmation of synthesized powder was established by X-ray powder diffraction (XRD) and Raman Spectroscopic techniques. Two distinct Raman bands i.e., 303 and 723 cm(-1) characteristic of tetragonal phase were observed. Thermogravimetric analysis (TGA) was performed to evaluate the phase decomposition of the as-synthesized Ba0.95Mg0.05Zr0.1Ti0.9O3 sample as a function of temperature. The average crystallite size associated with Ba0.95Mg0.05Zr0.1Ti0.9O3 was calculated using Scherrer formula based on the XRD data and was found to be 25 nm. However, Scanning and Transmission Electron Microscopy studies revealed the average crystallite size to be in the range of 30-40 nm, respectively. Kubelka-Munk function was employed to determine the optical band gap of these nanocrystallites. A piezoelectric response of 26 pm/V was observed for Ba0.95Mg0.05Zr0.1Ti0.9O3 nanocrystal by Piezoresponse Force Microscopy (PFM) technique. Photoluminescence (PL) study carried out on these nanocrystals exhibited a blue emission (470 nm) at room temperature.

Long-period modulated structure and electric-field-induced structural transformation in Na0.5Bi0.5TiO3-based lead-free piezoelectrics

Na0.5Bi0.5TiO3- based lead-free piezoelectrics exhibiting giant piezostrain are technologically interesting materials for actuator applications. The lack of clarity with regard to the structure of the nonpolar phase of this system has hindered the understanding of the structural mechanism associated with the giant piezostrain and other related phenomena. In this paper, we have investigated the structure and field-induced phase transformation behavior of a model system (0.94 - x) Na0.5Bi0.5TiO3-0.06BaTiO(3)-xK(0.5)Na(0.5)NbO(3) (0.0 <= x <= 0.025). A detailed structural analysis using neutron powder diffraction revealed that the nonpolar phase is neither cubic nor a mixture of rhombohedral (R3c) and tetragonal (P4bm) phases as commonly reported in literature but exhibits a long-period modulated structure, which is most probably of the type root 2 x root 2 x n with n = 16. Our results suggest that the giant piezoelectric strain is associated with a field-induced phase transformation of the long-period modulated structure to rhombohedral R3c structure above a critical field. We also demonstrate that the giant piezostrain is lost if the system retains a fraction of the field-induced R3c phase. A possible correlation among depolarization temperature, giant piezostrain, and its electrical fatigue behavior has also been indicated.

Polarization Self-Modulation Phenomenon in a Free Oscillated Nd: YAG Laser

Polarization self-modulation effect in a free oscillated Nd:YAG laser is investigated after a quarter wave plate is introduced independently in the two positions of the cavity. As described in the previous experiments, the intensity components in the orthogonal directions are modulated with a period of the round-trip time or twice. Different pulse shapes reveal that the seed field from the spontaneous emission is not uniform and seems to be stochastic for each pulse.

Simulation of Free-Surface Flow in a Tank Using the Navier-Stokes Model and Unstructured Finite Volume Method

Modelling free-surface flow has very important applications in many engineering areas such as oil transportation and offshore structures. Current research focuses on the modelling of free surface flow in a tank by solving the Navier-Stokes equation. An unstructured finite volume method is used to discretize the governing equations. The free surface is tracked by dynamically adapting the mesh and making it always surface conforming. A mesh-smoothing scheme based on the spring analogy is also implemented to ensure mesh quality throughout the computaiton. Studies are performed on the sloshing response of a liquid in an elastic container subjected to various excitation frequencies. Further investigations are also carried out on the critical frequency that leads to large deformation of the tank walls. Another numerical simulation involves the free-surface flow past as submerged obstacle placed in the tank to show the flow separation and vortices. All these cases demonstrate the capability of this numerical method in modelling complicated practical problems.