Diaminotriazine substituted diphenyl ether: reversible structural transformation and solvent dependent solid state fluorescence

The effect of molecular shape and position of hydrogen bonding functionality in the solid state structural self-assembly was investigated using diaminotriazine substituted diphenyl ether based positional isomers (1-5). The molecular shape was modulated by changing diaminotriazine position that produced channel supramolecular structures in 1, 3 and 5. There exists a direct correlation between the molecular shape and three dimensional structures; more linear molecules resulted in close-packing whereas molecules with a labyrinthine topology formed a channel structure. Supramolecular aspects pertaining to the influence of solvent of crystallization in structure formation and reversible structural transformation in solid state were also explored. 1-5 exhibited tunable solid state fluorescence (lambda(max) = 437-496 nm) depending on the diaminotriazine substitutional position and 3 showed solvent-dependent solid state fluorescence. The present study describes the generation of a supramolecular channel structure with functional properties such as tunable fluorescence by varying the position of hydrogen bond functionality and solvent of crystallization.

Revisiting borylanilines: unique solid-state structures and insight into photophysical properties

The structure and photophysical properties of two known borylanilines, 4-(dimesitylboryl)aniline (1) and 4-(dimesitylboryl)-3,5-dimethylaniline (2), have been investigated. 1 and 2 have similar donor and acceptor centers but differ in their molecular conformations. Compounds 1 and 2 have been structurally characterized, and they exhibit a rare form of intermolecular N-H - - -pi electrostatic interactions. The structure and photophysical properties of 1 and 2 are discussed in the context of computational results.

Tradeoff of average service cost and average delay for the state dependent M/M/1 queue

The optimal tradeoff between average service cost rate and average delay, is addressed for a M/M/1 queueing model with queue-length dependent service rates, chosen from a finite set. We provide an asymptotic characterization of the minimum average delay, when the average service cost rate is a small positive quantity V more than the minimum average service cost rate required for stability. We show that depending on the value of the arrival rate, the assumed service cost rate function, and the possible values of the service rates, the minimum average delay either a) increases only to a finite value, b) increases without bound as log(1/V), or c) increases without bound as 1/V, when V down arrow 0. We apply the analysis to a flow-level resource allocation model for a wireless downlink. We also investigate the asymptotic tradeoff for a sequence of policies which are obtained from an approximate fluid model for the M/M/1 queue.

Ancilla-assisted quantum state tomography in multiqubit registers

The standard method of quantum state tomography (QST) relies on the measurement of a set of noncommuting observables, realized in a series of independent experiments. Ancilla-assisted QST (AAQST) proposed by Nieuwenhuizen and co-workers Phys. Rev. Lett. 92, 120402 (2004)] greatly reduces the number of independent measurements by exploiting an ancilla register in a known initial state. In suitable conditions AAQST allows mapping out density matrix of an input register in a single experiment. Here we describe methods for explicit construction of AAQST experiments in multiqubit registers. We also report nuclear magnetic resonance studies on AAQST of (i) a two-qubit input register using a one-qubit ancilla in an isotropic liquid-state system and (ii) a three-qubit input register using a two-qubit ancilla register in a partially oriented system. The experimental results confirm the effectiveness of AAQST in such multiqubit registers.

State estimation in power systems using linear model infinity norm-based trust region approach

State estimation is one of the most important functions in an energy control centre. An computationally efficient state estimator which is free from numerical instability/ill-conditioning is essential for security assessment of electric power grid. Whereas approaches to successfully overcome the numerical ill-conditioning issues have been proposed, an efficient algorithm for addressing the convergence issues in the presence of topological errors is yet to be evolved. Trust region (TR) methods have been successfully employed to overcome the divergence problem to certain extent. In this study, case studies are presented where the conventional algorithms including the existing TR methods would fail to converge. A linearised model-based TR method for successfully overcoming the convergence issues is proposed. On the computational front, unlike the existing TR methods for state estimation which employ quadratic models, the proposed linear model-based estimator is computationally efficient because the model minimiser can be computed in a single step. The model minimiser at each step is computed by minimising the linearised model in the presence of TR and measurement mismatch constraints. The infinity norm is used to define the geometry of the TR. Measurement mismatch constraints are employed to improve the accuracy. The proposed algorithm is compared with the quadratic model-based TR algorithm with case studies on the IEEE 30-bus system, 205-bus and 514-bus equivalent systems of part of Indian grid.

Transition in subicular burst firing neurons from epileptiform activity to suppressed state by feedforward inhibition

The subiculum, a para-hippocampal structure positioned between the cornu ammonis 1 subfield and the entorhinal cortex, has been implicated in temporal lobe epilepsy in human patients and in animal models of epilepsy. The structure is characterized by the presence of a significant population of burst firing neurons that has been shown previously to lead epileptiform activity locally. Phase transitions in epileptiform activity in neurons following a prolonged challenge with an epileptogenic stimulus has been shown in other brain structures, but not in the subiculum. Considering the importance of the subicular burst firing neurons in the propagation of epileptiform activity to the entorhinal cortex, we have explored the phenomenon of phase transitions in the burst firing neurons of the subiculum in an in vitro rat brain slice model of epileptogenesis. Whole-cell patch-clamp and extracellular field recordings revealed a distinct phenomenon in the subiculum wherein an early hyperexcitable state was followed by a late suppressed state upon continuous perfusion with epileptogenic 4-aminopyridine and magnesium-free medium. The suppressed state was characterized by inhibitory post-synaptic potentials in pyramidal excitatory neurons and bursting activity in local fast-spiking interneurons at a frequency of 0.1-0.8Hz. The inhibitory post-synaptic potentials were mediated by GABA(A) receptors that coincided with excitatory synaptic inputs to attenuate action potential discharge. These inhibitory post-synaptic potentials ceased following a cut between the cornu ammonis 1 and subiculum. The suppression of epileptiform activity in the subiculum thus represents a homeostatic response towards the induced hyperexcitability. Our results suggest the importance of feedforward inhibition in exerting this homeostatic control.

A new 3D cadmium(II) coordination polymer having mu(4)-oxalato, mu-aquo and mu-chlorido bridges: crystal structure, solid state fluorescence and thermal behavior

A new 3D cadmium(II) coordination polymer, Cd(C2O4)(0.5)Cl(H2O)](n) (1) has been synthesized from a mixture of CdCl2. H2O and (NH4)(2)C2O4 in a slightly acidic pH. Its molecular structure was determined by single crystal X-ray diffraction which reveals that the new polymeric structure consists of simultaneous mu(4)-oxalato, mu-aquo, and mu-chlorido bridges between the metal centers, embedded in distorted pentagonal bipyramidal geometries. On thermal analysis compound exhibits high thermal stability up to 330 degrees C. Compound 1 also exhibits strong fluorescent emission. (c) 2013 Elsevier B.V. All rights reserved.

Tuning the solid state emission of meso-Me3SiC6H4 BODIPYs by tuning their solid state structure

A series of new BODIPYs (4-9) with bulky meso-trimethylsilylphenyl substitution were synthesized. The effect of the substituent's position on the emission properties of the BODIPYs was investigated in detail both in solution and solid state. The new BODIPYs exhibit emission in single crystals and in thin films. The logical increment of steric crowding in the compounds resulted in a periodic change in their conformational flexibility as evident from their F-19 NMR spectra, which in turn led to an increase of fluorescence in solution, thin films and single crystals.

Maltose Binding Protein Is Partially Structured in Its Molten Globule State

Seven double cysteine mutants of maltose binding protein (MBP) were generated with one each in the active cleft at position 298 and the second cysteine distributed over both domains of the protein. These cysteines were spin labeled and distances between the labels in biradical pairs determined by pulsed double electron-electron resonance (DEER) measurements. The values were compared with theoretical predictions of distances between the labels in biradicals constructed by molecular modeling from the crystal structure of MBP without maltose and were found to be in excellent agreement. MBP is in a molten globule state at pH 3.3 and is known to still bind its substrate maltose. The nitroxide spin label was sufficiently stable under these conditions. In preliminary experiments, DEER measurements were carried out with one of the mutants yielding a broad distance distribution as was to be expected if there is no explicit tertiary structure and the individual helices pointing into all possible directions.

Metastable morphotropic phase boundary state in the multiferroic BiFeO3-PbTiO3

Temperature-time study of the magnetoelectric multiferroic (1-x)BiFeO3-(x)PbTiO3 by x-ray and electron diffraction on the reported morphotropic phase boundary (MPB) compositions revealed that this MPB does not correspond to the equilibrium state. The MPB like state is rather of metastable nature and arise due to kinetic arrest of metastable rhombohedral (R3c) phase, along with the equilibrium tetragonal (P4mm) phase. The life time of the metastable R3c nuclei is very sensitive to composition and temperature, and nearly diverges at x -> 0.27. The MPB like state appears only if the system is cooled before the metastable R3c nuclei could vanish. These findings resolve the long standing controversy with regard to seemingly erratic phase formation behaviour reported by different groups and provides a rational basis for developing genuine equilibrium MPB compositions in this system for better piezoelectric properties. (C) 2013 AIP Publishing LLC.

Asynchronous Measurement of Transient Phase-Shift Resulting From RF Receiver State-Change

In a wireless receiver, a down-converted RF signal undergoes a transient phase shift, when the gain state is changed to adjust for varying conditions in transmission and propagation. A method is developed, in which such phase shifts are detected asynchronously, and their undesirable effects on the bit error rate are corrected. The method was developed for and used in, the system-level characterization and calibration of a 65-nm CMOS UHF receiver. The phase-shifts associated with specific gain-state transitions were measured within a test framework, and used in the baseband signal processing blocks to compensate for errors, whenever the receiver anticipated a gain-state transition.

Assessing resilience and state-transition models with historical records of cheatgrass Bromus tectorum invasion in North American sagebrush-steppe

1. Resilience-based approaches are increasingly being called upon to inform ecosystem management, particularly in arid and semi-arid regions. This requires management frameworks that can assess ecosystem dynamics, both within and between alternative states, at relevant time scales. 2. We analysed long-term vegetation records from two representative sites in the North American sagebrush-steppe ecosystem, spanning nine decades, to determine if empirical patterns were consistent with resilience theory, and to determine if cheatgrass Bromus tectorum invasion led to thresholds as currently envisioned by expert-based state-and-transition models (STM). These data span the entire history of cheatgrass invasion at these sites and provide a unique opportunity to assess the impacts of biotic invasion on ecosystem resilience. 3. We used univariate and multivariate statistical tools to identify unique plant communities and document the magnitude, frequency and directionality of community transitions through time. Community transitions were characterized by 37-47% dissimilarity in species composition, they were not evenly distributed through time, their frequency was not correlated with precipitation, and they could not be readily attributed to fire or grazing. Instead, at both sites, the majority of community transitions occurred within an 8-10year period of increasing cheatgrass density, became infrequent after cheatgrass density peaked, and thereafter transition frequency declined. 4. Greater cheatgrass density, replacement of native species and indication of asymmetry in community transitions suggest that thresholds may have been exceeded in response to cheatgrass invasion at one site (more arid), but not at the other site (less arid). Asymmetry in the direction of community transitions also identified communities that were at-risk' of cheatgrass invasion, as well as potential restoration pathways for recovery of pre-invasion states. 5. Synthesis and applications. These results illustrate the complexities associated with threshold identification, and indicate that criteria describing the frequency, magnitude, directionality and temporal scale of community transitions may provide greater insight into resilience theory and its application for ecosystem management. These criteria are likely to vary across biogeographic regions that are susceptible to cheatgrass invasion, and necessitate more in-depth assessments of thresholds and alternative states, than currently available.

Model-checking bisimulation-based information flow properties for infinite state sstems

Bisimulation-based information flow properties were introduced by Focardi and Gorrieri [1] as a way of specifying security properties for transition system models. These properties were shown to be decidable for finite-state systems. In this paper, we study the problem of verifying these properties for some well-known classes of infinite state systems. We show that all the properties are undecidable for each of these classes of systems.

Dynamic state estimation for identifying earthquake support motions in instrumented structures

The problem of identification of multi-component and (or) spatially varying earthquake support motions based on measured responses in instrumented structures is considered. The governing equations of motion are cast in the state space form and a time domain solution to the input identification problem is developed based on the Kalman and particle filtering methods. The method allows for noise in measured responses, imperfections in mathematical model for the structure, and possible nonlinear behavior of the structure. The unknown support motions are treated as hypothetical additional system states and a prior model for these motions are taken to be given in terms of white noise processes. For linear systems, the solution is developed within the Kalman filtering framework while, for nonlinear systems, the Monte Carlo simulation based particle filtering tools are employed. In the latter case, the question of controlling sampling variance based on the idea of Rao-Blackwellization is also explored. Illustrative examples include identification of multi-component and spatially varying support motions in linear/nonlinear structures.

An adaptive modulation scheme for two-user fading MAC with quantized fade state feedback

For transmission over the two-user Gaussian Multiple Access Channel with fading and finite constellation at the inputs, we propose a scheme which uses only quantized knowledge of fade state at users with the feedback overhead being nominal. One of the users rotates its constellation without varying the transmit power to adapt to the existing channel conditions, in order to meet certain pre-determined minimum Euclidean distance requirement in the equivalent constellation at the destination. The optimal modulation scheme has been described for the case when both the users use symmetric M-PSK constellations at the input, where M = 2λ, λ being a positive integer. The strategy has been illustrated by considering examples where both the users use QPSK signal set at the input. It is shown that the proposed scheme has considerable better error performance compared to the conventional non-adaptive scheme, at the cost of a feedback overhead of just [log2 (M2/8 - M/4 + 2)] + 1 bits, for the M-PSK case.