Coordination-driven self-assembly of 2D-metallamacrocycles using a shape-selective Pt(2)(II)-organometallic 90 degrees acceptor: design, synthesis and sensing study

Synthesis of a series of two-dimensional metallamacrocycles via coordination-driven self-assembly of a shape-selective Pt(2)(II)-molecular building unit incorporating carbazole-ethynyl functionality is described. An equimolar (1 : 1) combination of a Pt(2)(II)-organometallic 90 degrees acceptor, 1, with rigid linear ditopic donors (L(a) and L(b)) afforded [4 + 4] self-assembled octanuclear molecular squares, 2 and 3, in quantitative yields, respectively [L(a) = 4,4'-bipyridine; L(b) = trans-1,2-bis(4-pyridyl)ethylene]. Conversely, a similar treatment of 1 with an amide-based unsymmetrical flexible ditopic donor, L(c), resulted in the formation of a [2 + 2] self-sorted molecular rhomboid (4a) as a single product [L(c) = N-(4-pyridyl)isonicotinamide]. Despite the possibility of several linkage isomeric macrocycles (rhomboid, triangle and square) due to the different connectivity of L(c), the formation of a single and symmetrical molecular rhomboid (4a) as the only product is an interesting observation. All the self-assembled macrocycles (2, 3 and 4a) were fully characterized by multinuclear NMR ((1)H and (31)P) and ESI-MS analysis. Further structural insights about the size and shape of the macrocycles were obtained through energy minimization using density functional theory (DFT) calculations. Decoration of the starting carbazole building unit with Pt-ethynyl functionality enriches the assemblies to be more p-electron rich and luminescent in nature. Macrocycles 2 and 3 could sense the presence of electron deficient nitroaromatics in solution by quenching of the initial intensity upon gradual addition of picric acid (PA). They exhibited the largest quenching response with high selectivity for nitroaromatics compared to several other electron deficient aromatics tested.

Real-time monitoring of critical nodes with minimal number of Phasor Measurement Units

This paper presents a method for placement of Phasor Measurement Units, ensuring the monitoring of vulnerable buses which are obtained based on transient stability analysis of the overall system. Real-time monitoring of phase angles across different nodes, which indicates the proximity to instability, the very purpose will be well defined if the PMUs are placed at buses which are more vulnerable. The issue is to identify the key buses where the PMUs should be placed when the transient stability prediction is taken into account considering various disturbances. Integer Linear Programming technique with equality and inequality constraints is used to find out the optimal placement set with key buses identified from transient stability analysis. Results on IEEE-14 bus system are presented to illustrate the proposed approach.

An Online Actor-Critic Algorithm with Function Approximation for Constrained Markov Decision Processes

We develop an online actor-critic reinforcement learning algorithm with function approximation for a problem of control under inequality constraints. We consider the long-run average cost Markov decision process (MDP) framework in which both the objective and the constraint functions are suitable policy-dependent long-run averages of certain sample path functions. The Lagrange multiplier method is used to handle the inequality constraints. We prove the asymptotic almost sure convergence of our algorithm to a locally optimal solution. We also provide the results of numerical experiments on a problem of routing in a multi-stage queueing network with constraints on long-run average queue lengths. We observe that our algorithm exhibits good performance on this setting and converges to a feasible point.

Studies on Ultra Wideband Triangular Patch Antennas for Imaging Applications

This paper presents simulation and experimental studies on the characterization of ultra wideband antennas for imaging applications. Various configurations of antennas were simulated for their time and frequency domain characteristics with special emphasis on flat responses for group delay and gain versus frequency. Parametric studies reported here showed that locating the capacitive feed strip near the vertex of the triangle gave better response in these respects. An antenna with operating frequency from 2.9GHz to 4.1GHz was fabricated and measured.

Electrochemical determination of thermodynamic properties of DyRhO3 and phase relations in the system Dy-Rh-O

Thermodynamic properties of Dysprosium rhodite (DyRhO3) are measured in the temperature range from 900 to 1,300 K using a solid-state electrochemical cell incorporating yttria-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of DyRhO3 with O-type perovskite structure from its components binary oxides, Dysprosia with C-rare earth structure and beta-Rh2O3 with orthorhombic structure, can be represented by the equation: Delta G(f(OX))(O) (+/- 182)/J mol(-1) = -52710+3.821(T/K). By using the thermodynamic data for DyRhO3 from experiment and auxiliary data for other phases from the literature, the phase relations in the system Dy-Rh-O are computed. Thermodynamic data for intermetallic phases in the binary system Dy-Rh, required for constructing the chemical potential diagrams, are evaluated using calorimetric data available in the literature for three intermetallics and Miedema's model, consistent with the phase diagram. The results are presented in the form of Gibbs triangle, oxygen potential-composition diagram, and three-dimensional chemical potential diagram at 1,273 K. Temperature-composition diagrams at constant oxygen partial pressures are also developed. The decomposition temperature of DyRhO3 is 1,732 (+/- 2.5) K in pure oxygen and 1,624 (+/- 2.5) K and in air at standard pressure.

Simplified implementation of space vector PWM strategies for a three level inverter

Space vector based PWM strategies for three-level inverters have a broader choice of switching sequences to generate the required reference vector than triangle comparison based PWM techniques. However, space vector based PWM involves numerous steps which are computationally intensive. A simplified algorithm is proposed here, which is shown to reduce the computation time significantly. The developed algorithm is used to implement synchronous and asynchronous conventional space vector PWM, synchronized modified space vector PWM and an asynchronous advanced bus-clamping PWM technique on a low-cost dsPIC digital controller. Experimental results are presented for a comparative evaluation of the performance of different PWM methods.

Acto-myosin contractility rotates the cell nucleus

The nucleus of the eukaryotic cell functions amidst active cytoskeletal �laments, but its response to the stresses carried by these �laments is largely unexplored. We report here the results of studies of the translational and rotational dynamics of the nuclei of single �broblast cells, with the e�ects of cell migration suppressed by plating onto �bronectin-coated micro-fabricated patterns. Patterns of the same area but di�erent shapes and/or aspect ratio were used to study the e�ect of cell geometry on the dynamics. On circles, squares and equilateral triangles, the nucleus undergoes persistent rotational motion, while on high-aspect-ratio rectangles of the same area it moves only back and forth. The circle and the triangle showed respectively the largest and the smallest angular speed. We show that our observations can be understood through a hydrodynamic approach in which the nucleus is treated as a highly viscous inclusion residing in a less viscous uid of orientable �laments endowed with active stresses. Lowering actin contractility selectively by introducing blebbistatin at low concentrations drastically reduced the speed and persistence time of the angular motion of the nucleus. Time-lapse imaging of actin revealed a correlated hydrodynamic ow around the nucleus, with pro�le and magnitude consistent with the results of our theoretical approach. Coherent intracellular ows and consequent nuclear rotation thus appear to be a generic property that cells must balance by speci�c mechanisms in order to maintain nuclear homeostasis

A novel Q-learning algorithm with function approximation for constrained Markov decision processes

We present a novel multi-timescale Q-learning algorithm for average cost control in a Markov decision process subject to multiple inequality constraints. We formulate a relaxed version of this problem through the Lagrange multiplier method. Our algorithm is different from Q-learning in that it updates two parameters - a Q-value parameter and a policy parameter. The Q-value parameter is updated on a slower time scale as compared to the policy parameter. Whereas Q-learning with function approximation can diverge in some cases, our algorithm is seen to be convergent as a result of the aforementioned timescale separation. We show the results of experiments on a problem of constrained routing in a multistage queueing network. Our algorithm is seen to exhibit good performance and the various inequality constraints are seen to be satisfied upon convergence of the algorithm.

Robust formulations for clustering-based large-scale classification

Chebyshev-inequality-based convex relaxations of Chance-Constrained Programs (CCPs) are shown to be useful for learning classifiers on massive datasets. In particular, an algorithm that integrates efficient clustering procedures and CCP approaches for computing classifiers on large datasets is proposed. The key idea is to identify high density regions or clusters from individual class conditional densities and then use a CCP formulation to learn a classifier on the clusters. The CCP formulation ensures that most of the data points in a cluster are correctly classified by employing a Chebyshev-inequality-based convex relaxation. This relaxation is heavily dependent on the second-order statistics. However, this formulation and in general such relaxations that depend on the second-order moments are susceptible to moment estimation errors. One of the contributions of the paper is to propose several formulations that are robust to such errors. In particular a generic way of making such formulations robust to moment estimation errors is illustrated using two novel confidence sets. An important contribution is to show that when either of the confidence sets is employed, for the special case of a spherical normal distribution of clusters, the robust variant of the formulation can be posed as a second-order cone program. Empirical results show that the robust formulations achieve accuracies comparable to that with true moments, even when moment estimates are erroneous. Results also illustrate the benefits of employing the proposed methodology for robust classification of large-scale datasets.

Minimum uncertainty and entanglement

We address the question, does a system A being entangled with another system B, put any constraints on the Heisenberg uncertainty relation (or the Schrodinger-Robertson inequality)? We find that the equality of the uncertainty relation cannot be reached for any two noncommuting observables, for finite dimensional Hilbert spaces if the Schmidt rank of the entangled state is maximal. One consequence is that the lower bound of the uncertainty relation can never be attained for any two observables for qubits, if the state is entangled. For infinite-dimensional Hilbert space too, we show that there is a class of physically interesting entangled states for which no two noncommuting observables can attain the minimum uncertainty equality.

MINIMUM UNCERTAINTY AND ENTANGLEMENT

We address the question, does a system A being entangled with another system B, put any constraints on the Heisenberg uncertainty relation (or the Schrodinger-Robertson inequality)? We find that the equality of the uncertainty relation cannot be reached for any two noncommuting observables, for finite dimensional Hilbert spaces if the Schmidt rank of the entangled state is maximal. One consequence is that the lower bound of the uncertainty relation can never be attained for any two observables for qubits, if the state is entangled. For infinite-dimensional Hilbert space too, we show that there is a class of physically interesting entangled states for which no two noncommuting observables can attain the minimum uncertainty equality.

Estimation of Probabilistic Bounds on Phase CPI and Relevance in WCET Analysis

Estimating program worst case execution time(WCET) accurately and efficiently is a challenging task. Several programs exhibit phase behavior wherein cycles per instruction (CPI) varies in phases during execution. Recent work has suggested the use of phases in such programs to estimate WCET with minimal instrumentation. However the suggested model uses a function of mean CPI that has no probabilistic guarantees. We propose to use Chebyshev's inequality that can be applied to any arbitrary distribution of CPI samples, to probabilistically bound CPI of a phase. Applying Chebyshev's inequality to phases that exhibit high CPI variation leads to pessimistic upper bounds. We propose a mechanism that refines such phases into sub-phases based on program counter(PC) signatures collected using profiling and also allows the user to control variance of CPI within a sub-phase. We describe a WCET analyzer built on these lines and evaluate it with standard WCET and embedded benchmark suites on two different architectures for three chosen probabilities, p={0.9, 0.95 and 0.99}. For p= 0.99, refinement based on PC signatures alone, reduces average pessimism of WCET estimate by 36%(77%) on Arch1 (Arch2). Compared to Chronos, an open source static WCET analyzer, the average improvement in estimates obtained by refinement is 5%(125%) on Arch1 (Arch2). On limiting variance of CPI within a sub-phase to {50%, 10%, 5% and 1%} of its original value, average accuracy of WCET estimate improves further to {9%, 11%, 12% and 13%} respectively, on Arch1. On Arch2, average accuracy of WCET improves to 159% when CPI variance is limited to 50% of its original value and improvement is marginal beyond that point.

Role of dicarboxylate linkers in Mn-III-salicylaldoximate based extended structures: synthesis, structures, and magnetic behavior

Four new oxo-centered Mn-III-salicylaldoximate triangle-based extended complexes (Mn6O2)-O-III(salox)(6)(EtOH)(4)(phda)](n)(saloxH(2))(n)(2H(2)O)(n) (1), (Mn6O2)-O-III(salox)(6)(MeOH)(5)(5-I-isoph)](n)(3MeOH)(n) (2), (Mn6O2)-O-III(salox)(6)(MeOH)(4)(H2O) (5-N-3-isoph)](n)(4MeOH)(n) (3) and (Mn3NaO)-Na-III(salox)(3)(MeOH)(4)(5-NO2-isoph)](n)(MeOH)(n) (H2O)(n) (4) salox=salicylaldoximate, phda=1,3-phenylenediacetate, isoph=isophthalate] have been synthesized under similar reaction conditions. Single crystal X-ray structures show that in 1, only one type of Mn-6 cluster is arranged in 1D, whereas in 2 and 3 there are two types of clusters, differing in the way the triangle units are joined and assembled. In complex4, however, the basic building structure is heteronuclear and based on Mn-3 units extended in 2D. Susceptibility measurements (dc and ac) over a wide range of temperatures and fields show that the complexes1, 2, and 3 behave as single molecule magnets (SMMs) with S=4ground state, while 4 is dominantly antiferromagnetic with a ground spin state S=2. Density functional theory calculations have been performed on model complexes to provide a qualitative theoretical interpretation for their overall magnetic behavior.

Infinitely divisible metrics and curvature inequalities for operators in the Cowen-Douglas class

The curvature (T)(w) of a contraction T in the Cowen-Douglas class B-1() is bounded above by the curvature (S*)(w) of the backward shift operator. However, in general, an operator satisfying the curvature inequality need not be contractive. In this paper, we characterize a slightly smaller class of contractions using a stronger form of the curvature inequality. Along the way, we find conditions on the metric of the holomorphic Hermitian vector bundle E-T corresponding to the operator T in the Cowen-Douglas class B-1() which ensures negative definiteness of the curvature function. We obtain a generalization for commuting tuples of operators in the class B-1() for a bounded domain in C-m.

Harmonic Analysis of DC-Link Capacitor Current in Sinusoidally Modulated Neutral-Point-Clamped Inverter

The voltage ripple and power loss in the DC-capacitor of a voltage source inverter depend on the harmonic currents flowing through the capacitor. This paper presents double Fourier series based harmonic analysis of DC capacitor current in a three-level neutral point clamped inverter, modulated with sine-triangle PWM. The analytical results are validated experimentally on a 5-kVA three-level inverter prototype. The results of the analysis are used for predicting the power loss in the DC capacitor.