Charge-transfer-driven inclusion of neutral TCNQ molecules in the galleries of a layered double hydroxide: an experimental and computational study

The layered double hydroxides (LDH) or anionic clays are an important class of ion-exchange materials. They consist of positively charged brucite-like inorganic sheets with charge-compensating exchangeable anions in the interlamellar space. Here we show how neutral TCNQ (7,7,8,8-tetracyanoquinodimethane) molecules can be included within the galleries of an LDH. To do so, we exploit the fact that TCNQ is a good electron acceptor that forms donor acceptor complexes with a variety of donors. The electron donor aniline was intercalated into a Mg-Al LDH as p-aminobenzoate (AB) ions by a conventional ion-exchange reaction. We show here that neutral TCNQ molecules may be driven into the galleries of the layered solid by charge-transfer complex formation with the intercalated p-aminobenzoate anions. We use diffraction and spectroscopic measurements in combination with molecular dynamics simulations and quantum chemical calculations to establish the nature of interactions and arrangement of the charge-transfer complex within the galleries of the layered double hydroxide. Electrostatic interactions between the TCNQ molecules and the anchored AB ions, subsequent to charge transfer, are the driving force for the inclusion of TCNQ molecules in the galleries of the LDH.

Freezing of the octahedral tilt near ferromagnetic transition and appearance of a glassy phase at low temperature driven by the tilt instabilities in SrRuO3

The emergence of low temperature glassy phase in widely known itinerant ferromagnet SrRuO3 is remotely understood. In order to understand this aspect, we have undertaken a detailed temperature dependent (5-250 K) neutron diffraction study. We observe a freezing of the octahedral tilt near the ferromagnetic transition and an unusual deviation in the octahedral tilt near the onset of low temperature spin glass like phase. A reduction of the ordered magnetic moment and a decline in the total integrated magnetic intensity is observed around the temperature where the glassy behaviour starts to appear. The magnetotransport study also reveals the possibility for an additional magnetic ordering by demonstrating a peak in magnetoresistance at the low temperature side as well. The neutron diffraction study presented here provides useful information to understand the observed unusual low temperature magnetic phenomena in SrRuO3.

1.5 V battery driven reduced graphene oxide-silver nanostructure coated carbon foam (rGO-Ag-CF) for the purification of drinking water

A porous carbon foam (CF) electrode modified with a reduced graphene oxide-Ag (rGO-Ag) nanocomposite has been fabricated to purify water. It can perform as an antibacterial device by killing pathogenic microbes with the aid of a 1.5 V battery, with very little power consumption. The device is recycled ten times with good performance for long term usage. It is shown that the device may be implemented as a fast water purifier to deactivate the pathogens in drinking water.

A relational contract for water demand management

For necessary goods like water, under supply constraints, fairness considerations lead to negative externalities. The objective of this paper is to design an infinite horizon contract or relational contract (a type of long-term contract) that ensures self-enforcing (instead of court-enforced) behaviour by the agents to mitigate the externality due to fairness issues. In this contract, the consumer is induced to consume at firm-supply level using the threat of higher fair price for future time periods. The pricing mechanism, computed in this paper, internalizes the externality and is shown to be economically efficient and provides revenue sufficiency.

Lead-free piezoelectric system (Na0.5Bi0.5)TiO3-BaTiO3: Equilibrium structures and irreversible structural transformations driven by electric field and mechanical impact

The structure-property correlation in the lead-free piezoelectric (1 - x)(Na0.5Bi0.5)TiO3-(x)BaTiO3 has been systematically investigated in detail as a function of composition (0 < x <= 0.11), temperature, electric field, and mechanical impact by Raman scattering, ferroelectric, piezoelectric measurement, x-ray, and neutron powder diffraction methods. Although x-ray diffraction study revealed three distinct composition ranges characterizing different structural features in the equilibrium state at room temperature: (i) monoclinic (Cc) + rhombohedral (R3c) for the precritical compositions, 0 <= x <= 0.05, (ii) cubiclike for 0.06 <= x <= 0.0675, and (iii) morphotropic phase boundary (MPB) like for 0.07 <= x < 0.10, Raman and neutron powder diffraction studies revealed identical symmetry for the cubiclike and the MPB compositions. The cubiclike structure undergoes irreversible phase separation by electric poling as well as by pure mechanical impact. This cubiclike phase exhibits relaxor ferroelectricity in its equilibrium state. The short coherence length (similar to 50A degrees) of the out-of-phase octahedral tilts does not allow the normal ferroelectric state to develop below the dipolar freezing temperature, forcing the system to remain in a dipolar glass state at room temperature. Electric poling helps the dipolar glass state to transform to a normal ferroelectric state with a concomitant enhancement in the correlation length of the out-of-phase octahedral tilt.

Magnetohydrodynamic stability of stochastically driven accretion flows

We investigate the evolution of magnetohydrodynamic (or hydromagnetic as coined by Chandrasekhar) perturbations in the presence of stochastic noise in rotating shear flows. The particular emphasis is the flows whose angular velocity decreases but specific angular momentum increases with increasing radial coordinate. Such flows, however, are Rayleigh stable but must be turbulent in order to explain astrophysical observed data and, hence, reveal a mismatch between the linear theory and observations and experiments. The mismatch seems to have been resolved, at least in certain regimes, in the presence of a weak magnetic field, revealing magnetorotational instability. The present work explores the effects of stochastic noise on such magnetohydrodynamic flows, in order to resolve the above mismatch generically for the hot flows. We essentially concentrate on a small section of such a flow which is nothing but a plane shear flow supplemented by the Coriolis effect, mimicking a small section of an astrophysical accretion disk around a compact object. It is found that such stochastically driven flows exhibit large temporal and spatial autocorrelations and cross-correlations of perturbation and, hence, large energy dissipations of perturbation, which generate instability. Interestingly, autocorrelations and cross-correlations appear independent of background angular velocity profiles, which are Rayleigh stable, indicating their universality. This work initiates our attempt to understand the evolution of three-dimensional hydromagnetic perturbations in rotating shear flows in the presence of stochastic noise.

Single electron transfer-driven multi-dimensional signal read-out function of TCNQ as an ``off-the-shelf'' detector for cyanide

Herein we report the first applications of TCNQ as a rapid and highly sensitive off-the-shelf cyanide detector. As a proof-of-concept, we have applied a kinetically selective single-electron transfer (SET) from cyanide to deep-lying LUMO orbitals of TCNQ to generate a persistently stable radical anion (TCNQ(center dot-)), under ambient condition. In contrast to the known cyanide sensors that operate with limited signal outputs, TCNQ(center dot-) offers a unique multiple signaling platform. The signal readability is facilitated through multichannel absorption in the UV-vis-NIR region and scattering-based spectroscopic methods like Raman spectroscopy and hyper Rayleigh scattering techniques. Particularly notable is the application of the intense 840 nm NIR absorption band to detect cyanide. This can be useful for avoiding background interference in the UV-vis region predominant in biological samples. We also demonstrate the fabrication of a practical electronic device with TCNQ as a detector. The device generates multiorder enhancement in current with cyanide because of the formation of the conductive TCNQ(center dot-).

Certificate-less on-demand public key management (CLPKM) for self-organized MANETs

In this paper, we have proposed a novel certificate-less on-demand public key management (CLPKM) protocol for self-organized MANETs. The protocol works on flat network architecture, and distinguishes between authentication layer and routing layer of the network. We put an upper limit on the length of verification route and use the end-to-end trust value of a route to evaluate its strength. The end-to-end trust value is used by the protocol to select the most trusted verification route for accomplishing public key verification. Also, the protocol uses MAC function instead of RSA certificates to perform public key verification. By doing this, the protocol saves considerable computation power, bandwidth and storage space. The saved storage space is utilized by the protocol to keep a number of pre-established routes in the network nodes, which helps in reducing the average verification delay of the protocol. Analysis and simulation results confirm the effectiveness of the proposed protocol.

A Nearly Exact Reformulation of the Girsanov Linearization for Stochastically Driven Nonlinear Oscillators

The Girsanov linearization method (GLM), proposed earlier in Saha, N., and Roy, D., 2007, ``The Girsanov Linearisation Method for Stochastically Driven Nonlinear Oscillators,'' J. Appl. Mech., 74, pp. 885-897, is reformulated to arrive at a nearly exact, semianalytical, weak and explicit scheme for nonlinear mechanical oscillators under additive stochastic excitations. At the heart of the reformulated linearization is a temporally localized rejection sampling strategy that, combined with a resampling scheme, enables selecting from and appropriately modifying an ensemble of locally linearized trajectories while weakly applying the Girsanov correction (the Radon-Nikodym derivative) for the linearization errors. The semianalyticity is due to an explicit linearization of the nonlinear drift terms and it plays a crucial role in keeping the Radon-Nikodym derivative ``nearly bounded'' above by the inverse of the linearization time step (which means that only a subset of linearized trajectories with low, yet finite, probability exceeds this bound). Drift linearization is conveniently accomplished via the first few (lower order) terms in the associated stochastic (Ito) Taylor expansion to exclude (multiple) stochastic integrals from the numerical treatment. Similarly, the Radon-Nikodym derivative, which is a strictly positive, exponential (super-) martingale, is converted to a canonical form and evaluated over each time step without directly computing the stochastic integrals appearing in its argument. Through their numeric implementations for a few low-dimensional nonlinear oscillators, the proposed variants of the scheme, presently referred to as the Girsanov corrected linearization method (GCLM), are shown to exhibit remarkably higher numerical accuracy over a much larger range of the time step size than is possible with the local drift-linearization schemes on their own.

Experimental investigation of a thermoacoustic refrigerator driven by a standing wave twin thermoacoustic prime mover

The objective of this study is to analyse the performance of thermoacoustic refrigerator (TAR) measured in terms of hot end temperature and temperature difference across refrigerator stack with two different spacing namely 0.4 mm and 0.8 mm and stack used in refrigerating section was made of low thermal conductivity materials namely Mylar sheet and photographic film & the experiments were carried out at 1 MPa pressure using helium as working fluid. High powered acoustic wave with frequency of 460 Hz and pressure amplitude of congruent to 0.07 MPa was obtained from twin thermoacoustic prime mover (TAPM) and this acoustic wave produced temperature difference of 16 degrees C across the Mylar sheet stack made of 0.4 mm spacing in refrigerator section. From this study, it has been inferred that twin TAPM can act as efficient drive for TAR. (C) 2013 Elsevier Ltd and IIR. All rights reserved.

Template-free multicomponent coordination-driven self-assembly of Pd(II)/Pt(II) molecular cages

Recent years have seen a tremendous increase in the interest for constructing hollowed-out molecular frameworks, for their potential uses. Metal-ligand coordination-driven self-assembly has provided multitudes of opportunities in the formation of molecular architectures of desired shapes and sizes, with the help of the information already coded in the components. This article summarizes the recent developments in the construction of multicomponent molecular cages through this process, with a focus on the decreasing relevance of templates, and use of these systems in catalysis/host-guest chemistry.

The translation initiation factor DAP5 promotes IRES-driven translation of p53 mRNA

Translational regulation of the p53 mRNA can determine the ratio between p53 and its N-terminal truncated isoforms and therefore has a significant role in determining p53-regulated signaling pathways. Although its importance in cell fate decisions has been demonstrated repeatedly, little is known about the regulatory mechanisms that determine this ratio. Two internal ribosome entry sites (IRESs) residing within the 5'UTR and the coding sequence of p53 mRNA drive the translation of full-length p53 and Delta 40p53 isoform, respectively. Here, we report that DAP5, a translation initiation factor shown to positively regulate the translation of various IRES containing mRNAs, promotes IRES-driven translation of p53 mRNA. Upon DAP5 depletion, p53 and Delta 40p53 protein levels were decreased, with a greater effect on the N-terminal truncated isoform. Functional analysis using bicistronic vectors driving the expression of a reporter gene from each of these two IRESs indicated that DAP5 preferentially promotes translation from the second IRES residing in the coding sequence. Furthermore, p53 mRNA expressed from a plasmid carrying this second IRES was selectively shifted to lighter polysomes upon DAP5 knockdown. Consequently, Delta 40p53 protein levels and the subsequent transcriptional activation of the 14-3-3 sigma gene, a known target of Delta 40p53, were strongly reduced. In addition, we show here that DAP5 interacts with p53 IRES elements in in vitro and in vivo binding studies, proving for the first time that DAP5 directly binds a target mRNA. Thus, through its ability to regulate IRES-dependent translation of the p53 mRNA, DAP5 may control the ratio between different p53 isoforms encoded by a single mRNA.

Structural Evolution and Phase Stability of Hume-Rothery Phase in a Mechanically Driven Nanostructured Ag-15 at. pct Sn Alloy

The paper reports phase evolution in mechanically driven Ag-15 at. pct Sn alloy powder starting with elemental powders in order to establish the feasibility of designing nanocomposites of a Ag-Sn solid solution. This alloy lies in the phase field of the hexagonal zeta-phase which is a well-known Hume-Rothery electron compound with an electron-to-atom ratio of about 1.45 and hexagonal crystal structure (a = 0.2966 nm, c = 0.4782 nm). Through a systematic use of X-ray diffraction and transmission electron microscopy, the results establish the formation of the zeta-phase which co-exists with the Ag solid solution during the initial phase of milling. Mechanical milling for long duration (55 hours) destabilizes the zeta-phase. A complete solid solution of Ag with a grain size of similar to 8 nm could be achieved after 60 hours of milling. Additional milling can induce decomposition of the solid solution that results in a reappearance of zeta-phase. We present a detailed thermodynamic calculation which indicates that complete Ag solid solution of the present alloy composition would be possible if the crystallites size can be reduced below a certain critical size. In particular, we show that both Ag and zeta-phase grain sizes need to be taken into account for determining the metastable equilibrium and the phase change that has been experimentally observed. Finally, we argue that recrystallization processes set a limit to the achievable size of the nanoparticles with metastable Ag solid solution.

Detonation-driven-shock wave interactions with perforated plates

The study of detonations and their interactions is vital for the understanding of the high-speed flow physics involved and the ultimate goal of controlling their detrimental effects. However, producing safe and repeatable detonations within the laboratory can be quite challenging, leading to the use of computational studies which ultimately require experimental data for their validation. The objective of this study is to examine the induced flow field from the interaction of a shock front and accompanying products of combustion, produced from the detonation taking place within a non-electrical tube lined with explosive material, with porous plates with varying porosities, 0.7-9.7%. State of the art high-speed schlieren photography alongside high-resolution pressure measurements is used to visualise the induced flow field and examine the attenuation effects which occur at different porosities. The detonation tube is placed at different distances from the plates' surface, 0-30 mm, and the pressure at the rear of the plate is recorded and compared. The results indicate that depending on the level of porosity and the Mach number of the precursor shock front secondary reflected and transmitted shock waves are formed through the coalescence of compression waves. With reduced porosity, the plates act almost as a solid surface, therefore the shock propagates faster along its surface.

Nanoparticle-Driven Intermolecular Cooperativity and Miscibility in Polystyrene/Poly(vinyl methyl ether) Blends

The effect of silver nanoparticles (nAg) in PS/PVME polystyrene/poly(vinyl methyl ether)] blends was studied with respect to the evolution of morphology, demixing temperature, and segmental dynamics. In the early stage of demixing, PVME developed an interconnected network that coarsened in the late stage. The nAg induced miscibility in the blends as supported by shear rheological measurements. The physicochemical processes that drive phase separation in blends also led to migration of nAg to the PVME phase as supported by AFM. The segmental dynamics was greatly influenced by the presence of nAg due to the specific interaction of nAg with PVME. Slower dynamics and an increase in intermolecular cooperativity in the presence of nAg further supported the role of nAg in delaying the phase separation processes and augmenting the demixing temperature in the blends. Different theoretical models were assessed to gain insight into the dynamic heterogeneity in PS/PVME blends at different length scales.