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.

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.

Electrically driven intracellular and extracellular nanomanipulators evoke neurogenic/cardiomyogenic differentiation in human mesenchymal stem cells

Nanomechanical intervention through electroactuation is an effective strategy to guide stem cell differentiation for tissue engineering and regenerative medicine. In the present study, we elucidate that physical forces exerted by electroactuated gold nanoparticles (GNPs) have a strong influence in regulating the lineage commitment of human mesenchymal stem cells (hMSCs). A novel platform that combines intracellular and extracellular GNPs as nano-manipulators was designed to trigger neurogenic/cardiomyogenic differentiation in hMSCs, in electric field stimulated culture condition. In order to mimic the native microenvironment of nerve and cardiac tissues, hMSCs were treated with physiologically relevant direct current electric field (DC EF) or pulsed electric field (PEF) stimuli, respectively. When exposed to regular intermittent cycles of DC EF stimuli, majority of the GNP actuated hMSCs acquired longer filopodial extensions with multiple branch-points possessing neural-like architecture. Such morphological changes were consistent with higher mRNA expression level for neural-specific markers. On the other hand, PEF elicited cardiomyogenic differentiation, which is commensurate with the tubelike morphological alterations along with the upregulation of cardiac specific markers. The observed effect was significantly promoted even by intracellular actuation and was found to be substrate independent. Further, we have substantiated the participation of oxidative signaling, G0/G1 cell cycle arrest and intracellular calcium Ca2+] elevation as the key upstream regulators dictating GNP assisted hMSC differentiation. Thus, by adopting dual stimulation protocols, we could successfully divert the DC EF exposed cells to differentiate predominantly into neural-like cells and PEF treated cells into cardiomyogenic-like cells, via nanoactuation of GNPs. Such a novel multifaceted approach can be exploited to combat tissue loss following brain injury or heart failure. (C) 2015 Elsevier Ltd. All rights reserved.

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.

Weakly corrected numerical solutions to stochastically driven nonlinear dynamical systems

A method to weakly correct the solutions of stochastically driven nonlinear dynamical systems, herein numerically approximated through the Eule-Maruyama (EM) time-marching map, is proposed. An essential feature of the method is a change of measures that aims at rendering the EM-approximated solution measurable with respect to the filtration generated by an appropriately defined error process. Using Ito's formula and adopting a Monte Carlo (MC) setup, it is shown that the correction term may be additively applied to the realizations of the numerically integrated trajectories. Numerical evidence, presently gathered via applications of the proposed method to a few nonlinear mechanical oscillators and a semi-discrete form of a 1-D Burger's equation, lends credence to the remarkably improved numerical accuracy of the corrected solutions even with relatively large time step sizes. (C) 2015 Elsevier Inc. All rights reserved.

Dynamos driven by weak thermal convection and heterogeneous outer boundary heat flux

We use numerical dynamo models with heterogeneous core-mantle boundary (CMB) heat flux to show that lower mantle lateral thermal variability may help support a dynamo under weak thermal convection. In our reference models with homogeneous CMB heat flux, convection is either marginally supercritical or absent, always below the threshold for dynamo onset. We find that lateral CMB heat flux variations organize the flow in the core into patterns that favour the growth of an early magnetic field. Heat flux patterns symmetric about the equator produce non-reversing magnetic fields, whereas anti-symmetric patterns produce polarity reversals. Our results may explain the existence of the geodynamo prior to inner core nucleation under a tight energy budget. Furthermore, in order to sustain a strong geomagnetic field, the lower mantle thermal distribution was likely dominantly symmetric about the equator. (C) 2015 Elsevier B.V. All rights reserved.

An efficient design of serial and parallel memory using Quantum dot cellular automata

Quantum cellular automata (QCA) is a new technology in the nanometer scale and has been considered as one of the alternative to CMOS technology. In this paper, we describe the design and layout of a serial memory and parallel memory, showing the layout of individual memory cells. Assuming that we can fabricate cells which are separated by 10nm, memory capacities of over 1.6 Gbit/cm2 can be achieved. Simulations on the proposed memories were carried out using QCADesigner, a layout and simulation tool for QCA. During the design, we have tried to reduce the number of cells as well as to reduce the area which is found to be 86.16sq mm and 0.12 nm2 area with the QCA based memory cell. We have also achieved an increase in efficiency by 40%.These circuits are the building block of nano processors and provide us to understand the nano devices of the future.

Crystal structure of a tripeptide containing aminocyclododecane carboxylic acid: a supramolecular twisted parallel -sheet in crystals

The crystal structure of a tripeptide Boc-Leu-Val-Ac(12)c-OMe (1) is determined, which incorporates a bulky 1-aminocyclododecane-1-carboxylic acid (Ac(12)c) side chain. The peptide adopts a semi-extended backbone conformation for Leu and Val residues, while the backbone torsion angles of the C-,C--dialkylated residue Ac(12)c are in the helical region of the Ramachandran map. The molecular packing of 1 revealed a unique supramolecular twisted parallel -sheet coiling into a helical architecture in crystals, with the bulky hydrophobic Ac(12)c side chains projecting outward the helical column. This arrangement resembles the packing of peptide helices in crystal structures. Although short oligopeptides often assemble as parallel or anti-parallel -sheet in crystals, twisted or helical -sheet formation has been observed in a few examples of dipeptide crystal structures. Peptide 1 presents the first example of a tripeptide showing twisted -sheet assembly in crystals. Copyright (c) 2016 European Peptide Society and John Wiley & Sons, Ltd.

Crystal structure of a tripeptide containing aminocyclododecane carboxylic acid: a supramolecular twisted parallel -sheet in crystals

The crystal structure of a tripeptide Boc-Leu-Val-Ac(12)c-OMe (1) is determined, which incorporates a bulky 1-aminocyclododecane-1-carboxylic acid (Ac(12)c) side chain. The peptide adopts a semi-extended backbone conformation for Leu and Val residues, while the backbone torsion angles of the C-,C--dialkylated residue Ac(12)c are in the helical region of the Ramachandran map. The molecular packing of 1 revealed a unique supramolecular twisted parallel -sheet coiling into a helical architecture in crystals, with the bulky hydrophobic Ac(12)c side chains projecting outward the helical column. This arrangement resembles the packing of peptide helices in crystal structures. Although short oligopeptides often assemble as parallel or anti-parallel -sheet in crystals, twisted or helical -sheet formation has been observed in a few examples of dipeptide crystal structures. Peptide 1 presents the first example of a tripeptide showing twisted -sheet assembly in crystals. Copyright (c) 2016 European Peptide Society and John Wiley & Sons, Ltd.

A dilation-driven vortex flow in sheared granular materials explains a rheometric anomaly

Granular flows occur widely in nature and industry, yet a continuum description that captures their important features is yet not at hand. Recent experiments on granular materials sheared in a cylindrical Couette device revealed a puzzling anomaly, wherein all components of the stress rise nearly exponentially with depth. Here we show, using particle dynamics simulations and imaging experiments, that the stress anomaly arises from a remarkable vortex flow. For the entire range of fill heights explored, we observe a single toroidal vortex that spans the entire Couette cell and whose sense is opposite to the uppermost Taylor vortex in a fluid. We show that the vortex is driven by a combination of shear-induced dilation, a phenomenon that has no analogue in fluids, and gravity flow. Dilatancy is an important feature of granular mechanics, but not adequately incorporated in existing models.

Numerical study of driven flows of shear thinning viscoelastic fluids in rectangular cavities

In this work, we present a numerical study of flow of shear thinning viscoelastic fluids in rectangular lid driven cavities for a wide range of aspect ratios (depth to width ratio) varying from 1/16 to 4. In particular, the effect of elasticity, inertia, model parameters and polymer concentration on flow features in rectangular driven cavity has been studied for two shear thinning viscoelastic fluids, namely, Giesekus and linear PTT. We perform numerical simulations using the symmetric square root representation of the conformation tensor to stabilize the numerical scheme against the high Weissenberg number problem. The variation in flow structures associated with merging and splitting of elongated vortices in shallow cavities and coalescence of corner eddies to yield a second primary vortex in deep cavities with respect to the variation in flow parameters is discussed. We discuss the effect of the dominant eigenvalues and the corresponding eigenvectors on the location of the primary eddy in the cavity. We also demonstrate, by performing numerical simulations for shallow and deep cavities, that where the Deborah number (based on convective time scale) characterizes the elastic behaviour of the fluid in deep cavities, Weissenberg number (based on shear rate) should be used for shallow cavities. (C) 2016 Elsevier B.V. All rights reserved.

PIB: Profiling Influential Blogger in Online Social Networks, A Knowledge Driven Data Mining Approach

Online Social Networks (OSNs) facilitate to create and spread information easily and rapidly, influencing others to participate and propagandize. This work proposes a novel method of profiling Influential Blogger (IB) based on the activities performed on one's blog documents who influences various other bloggers in Social Blog Network (SBN). After constructing a social blogging site, a SBN is analyzed with appropriate parameters to get the Influential Blog Power (IBP) of each blogger in the network and demonstrate that profiling IB is adequate and accurate. The proposed Profiling Influential Blogger (PIB) Algorithm survival rate of IB is high and stable. (C) 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

COST AND PERFORMANCE TRADEOFFS OF ALTERNATIVE SOLAR-DRIVEN S-CO2 BRAYTON CYCLE CONFIGURATIONS

This paper evaluates cost and performance tradeoffs of alternative supercritical carbon dioxide (s-CO2) closed-loop Brayton cycle configurations with a concentrated solar heat source. Alternative s-CO2 power cycle configurations include simple, recompression, cascaded, and partial cooling cycles. Results show that the simple closed-loop Brayton cycle yielded the lowest power-block component costs while allowing variable temperature differentials across the s-CO2 heating source, depending on the level of recuperation. Lower temperature differentials led to higher sensible storage costs, but cycle configurations with lower temperature differentials (higher recuperation) yielded higher cycle efficiencies and lower solar collector and receiver costs. The cycles with higher efficiencies (simple recuperated, recompression, and partial cooling) yielded the lowest overall solar and power-block component costs for a prescribed power output.

Numerical Investigation of Richtmyer-Meshkov Instability Driven by Cylindrical Shocks

In this paper, a numerical method with high order accuracy and high resolution was developed to simulate the Richtmyer-Meshkov(RM) instability driven by cylindrical shock waves. Compressible Euler equations in cylindrical coordinate were adopted for the cylindrical geometry and a third order accurate group control scheme was adopted to discretize the equations. Moreover, an adaptive grid technique was developed to refine the grid near the moving interface to improve the resolution of numerical solutions. The results of simulation exhibited the evolution process of RM instability, and the effect of Atwood number was studied. The larger the absolute value of Atwood number, the larger the perturbation amplitude. The nonlinear effect manifests more evidently in cylindrical geometry. The shock reflected from the pole center accelerates the interface for the second time, considerably complicating the interface evolution process, and such phenomena of reshock and secondary shock were studied.