Self-assembly of discrete metallamacrocycles employing half-sandwich octahedral diruthenium(II) building units and imidazole-based ligands

Equimolar combination of a series of binuclear half-sandwich p-cymene ruthenium(II) building units Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1a](OTf)(2), Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)( MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1b](OTf)(2) and Ru-2(mu-eta(4)-C6H2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1c](OTf)(2) separately with imidazole-based ditopic ligands (L-1-L-2) in methanol yielded a series of tetranuclear metallamacrocycles 2-7](OTf)(4), respectively L-1 = 1,4-bis(imidazole-1-yl)benzene; L-2 = 4,4'-bis(imidazole-1-yl)biphenyl; OTf- = O3SCF3-]. Similarly, the reaction of Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)2](OTf)(2) 1a](OTf)(2) with a triazine-based tritopic ligand 1,3,5-tris(imidazole-1-yl) triazine (L3) in 3: 2 M ratio afforded an unexpected tetranuclear macrocycle 8](OTf)(4) instead of an expected trigonal prismatic cage 8a](OTf)(6). All the self-assembled macrocycles 2-8](OTf)(4) were isolated in moderate to high yields and were fully characterized by multinuclear H-1, F-19] NMR, IR and electrospray ionization mass spectrometry (ESI-MS). In addition, X-ray diffraction study on the single crystals of 3](OTf)(4) and 8](OTf)(4) also indicated the formation 2 + 2] self-assembled macrocycles. Despite the possibility of formation of different conformational isomeric macrocycles (syn-and anti) and polymeric product due to free rotation of ligand sites of imidazole linkers, the selective formation of single conformational isomer (anti) as the only product is quite interesting. Furthermore, the photo-and electrochemical properties of these assemblies have been studied using UV/Vis absorption and cyclic voltammetry analysis. (c) 2013 Elsevier B.V. All rights reserved.

Three-Dimensional Study of Natural Convection in a Horizontal Channel With Discrete Heaters on One of Its Vertical Walls

Three-dimensional natural convection in a horizontal channel with an array of discrete flush-mounted heaters on one of its vertical walls is numerically studied. Effects of thermal conductivities of substrate and heaters and convection on outer sides of the channel walls on heat transfer are examined. The substrate affects heat transfer in a wider range of thermal conductivities than do the heaters. At lower heater thermal conductivities a higher heat portion is transferred by direct convection from the heaters to the adjacent coolant. However, higher substrate conductivity is associated with higher heat portion transferred through the substrate. The innermost heater column is found to become the hottest heater column due to the lower coolant accessibility. The heat transfer in the channel is strongly influenced by convection on the outer sides of the channel walls. Correlations are presented for dimensionless temperature maximum and average Nusselt number.

Cubic Sieve Congruence of the Discrete Logarithm Problem, and fractional part sequences

The Cubic Sieve Method for solving the Discrete Logarithm Problem in prime fields requires a nontrivial solution to the Cubic Sieve Congruence (CSC) x(3) equivalent to y(2)z (mod p), where p is a given prime number. A nontrivial solution must also satisfy x(3) not equal y(2)z and 1 <= x, y, z < p(alpha), where alpha is a given real number such that 1/3 < alpha <= 1/2. The CSC problem is to find an efficient algorithm to obtain a nontrivial solution to CSC. CSC can be parametrized as x equivalent to v(2)z (mod p) and y equivalent to v(3)z (mod p). In this paper, we give a deterministic polynomial-time (O(ln(3) p) bit-operations) algorithm to determine, for a given v, a nontrivial solution to CSC, if one exists. Previously it took (O) over tilde (p(alpha)) time in the worst case to determine this. We relate the CSC problem to the gap problem of fractional part sequences, where we need to determine the non-negative integers N satisfying the fractional part inequality {theta N} < phi (theta and phi are given real numbers). The correspondence between the CSC problem and the gap problem is that determining the parameter z in the former problem corresponds to determining N in the latter problem. We also show in the alpha = 1/2 case of CSC that for a certain class of primes the CSC problem can be solved deterministically in <(O)over tilde>(p(1/3)) time compared to the previous best of (O) over tilde (p(1/2)). It is empirically observed that about one out of three primes is covered by the above class. (C) 2013 Elsevier B.V. All rights reserved.

Discrete time second order sliding mode observer for uncertain linear multi-output system

This paper presents a second order sliding mode observer (SOSMO) design for discrete time uncertain linear multi-output system. The design procedure is effective for both matched and unmatched bounded uncertainties and/or disturbances. A second order sliding function and corresponding sliding manifold for discrete time system are defined similar to the lines of continuous time counterpart. A boundary layer concept is employed to avoid switching across the defined sliding manifold and the sliding trajectory is confined to a boundary layer once it converges to it. The condition for existence of convergent quasi-sliding mode (QSM) is derived. The observer estimation errors satisfying given stability conditions converge to an ultimate finite bound (within the specified boundary layer) with thickness O(T-2) where T is the sampling period. A relation between sliding mode gain and boundary layer is established for the existence of second order discrete sliding motion. The design strategy is very simple to apply and is demonstrated for three examples with different class of disturbances (matched and unmatched) to show the effectiveness of the design. Simulation results to show the robustness with respect to the measurement noise are given for SOSMO and the performance is compared with pseudo-linear Kalman filter (PLKF). (C) 2013 Published by Elsevier Ltd. on behalf of The Franklin Institute

Multi Label Classification of Discrete Data

The paper describes an algorithm for multi-label classification. Since a pattern can belong to more than one class, the task of classifying a test pattern is a challenging one. We propose a new algorithm to carry out multi-label classification which works for discrete data. We have implemented the algorithm and presented the results for different multi-label data sets. The results have been compared with the algorithm multi-label KNN or ML-KNN and found to give good results.

Kinetically stabilized C-60-toluene solvate nanostructures with a discrete absorption edge enabling supramolecular topotactic molecular exchange

Nanosized fullerene solvates have attracted widespread research attention due to recent interesting discoveries. A particular type of solvate is limited to a fixed number of solvents and designing new solvates within the same family is a fundamental challenge. Here we demonstrate that the hexagonal closed packed (HCP) phase of C-60 solvates, formed with m-xylene, can also be stabilized using toluene. Contrary to the notion on their instability, these can be stabilized from minutes up to months by tuning the occupancy of solvent molecules. Due to high stability, we could record their absorption edge, and measure excitonic life-time, which has not been reported for any C-60 solvate. Despite being solid, absorbance spectrum of the solvates is similar in appearance to that of C-60 in solution. A new absorption band appears at 673 nm. The fluorescence lifetime at 760 nm is similar to 1.2 ns, suggesting an excited state unaffected by solvent-C-60 interaction. Finally, we utilized the unstable set of HCP solvates to exchange with a second solvent by a topotactic exchange mechanism, which rendered near permanent stability to the otherwise few minutes stable solvates. This is also the first example of topotactic exchange in supramolecular crystal, which is widely known in ionic solids. (C) 2014 Elsevier Ltd. All rights reserved.

Discrete Vortex Method-Based Model for Ground-Effect Studies

A discrete vortex method-based model has been proposed for two-dimensional/three-dimensional ground-effect prediction. The model merely requires two-dimensional sectional aerodynamics in free flight. This free-flight data can be obtained either from experiments or a high-fidelity computational fluid dynamics solver. The first step of this two-step model involves a constrained optimization procedure that modifies the vortex distribution on the camber line as obtained from a discrete vortex method to match the free-flight data from experiments/computational fluid dynamics. In the second step, the vortex distribution thus obtained is further modified to account for the presence of the ground plane within a discrete vortex method-based framework. Whereas the predictability of the lift appears as a natural extension, the drag predictability within a potential flow framework is achieved through the introduction of what are referred to as drag panels. The need for the use of the generalized Kutta-Joukowski theorem is emphasized. The extension of the model to three dimensions is by the way of using the numerical lifting-line theory that allows for wing sweep. The model is extensively validated for both two-dimensional and three-dimensional ground-effect studies. The work also demonstrates the ability of the model to predict lift and drag coefficients of a high-lift wing in ground effect to about 2 and 8% accuracy, respectively, as compared to the results obtained using a Reynolds-averaged Navier-Stokes solver involving grids with several million volumes. The model shows a lot of promise in design, particularly during the early phase.

Linear Index Coding and Representable Discrete Polymatroids

Discrete polymatroids are the multi-set analogue of matroids. In this paper, we explore the connections between linear index coding and representable discrete polymatroids. The index coding problem involves a sender which generates a set of messages X = {x(1), x(2), ... x(k)} and a set of receivers R which demand messages. A receiver R is an element of R is specified by the tuple (x, H) where x. X is the message demanded by R and H subset of X \textbackslash {x} is the side information possessed by R. It is first shown that a linear solution to an index coding problem exists if and only if there exists a representable discrete polymatroid satisfying certain conditions which are determined by the index coding problem considered. El Rouayheb et. al. showed that the problem of finding a multi-linear representation for a matroid can be reduced to finding a perfect linear index coding solution for an index coding problem obtained from that matroid. Multi-linear representation of a matroid can be viewed as a special case of representation of an appropriate discrete polymatroid. We generalize the result of El Rouayheb et. al. by showing that the problem of finding a representation for a discrete polymatroid can be reduced to finding a perfect linear index coding solution for an index coding problem obtained from that discrete polymatroid.

Discrete-Rate Adaptation and Selection in Energy Harvesting Wireless Systems

In a system with energy harvesting (EH) nodes, the design focus shifts from minimizing energy consumption by infrequently transmitting less information to making the best use of available energy to efficiently deliver data while adhering to the fundamental energy neutrality constraint. We address the problem of maximizing the throughput of a system consisting of rate-adaptive EH nodes that transmit to a destination. Unlike related literature, we focus on the practically important discrete-rate adaptation model. First, for a single EH node, we propose a discrete-rate adaptation rule and prove its optimality for a general class of stationary and ergodic EH and fading processes. We then study a general system with multiple EH nodes in which one is opportunistically selected to transmit. We first derive a novel and throughput-optimal joint selection and rate adaptation rule (TOJSRA) when the nodes are subject to a weaker average power constraint. We then propose a novel rule for a multi-EH node system that is based on TOJSRA, and we prove its optimality for stationary and ergodic EH and fading processes. We also model the various energy overheads of the EH nodes and characterize their effect on the adaptation policy and the system throughput.

Self-Assembled Discrete Molecules for Sensing Nitroaromatics

Efficient sensing of trace amount nitroaromatic (NAC) explosives has become a major research focus in recent time due to concerns over national security as well as their role as environment pollutants. NO2-containing electron-deficient aromatic compounds, such as picric acid (PA), trinitrotoluene (TNT), and dinitrotoluene (DNT), are the common constituents of many commercially available chemical explosives. In this article, we have summarized our recent developments on the rational design of electron-rich self-assembled discrete molecular sensors and their efficacy in sensing nitroaromatics both in solution as well as in vapor phase. Several p-electron-rich fluorescent metallacycles (squares, rectangles, and tweezers/pincers) and metallacages (trigonal and tetragonal prisms) have been synthesized by means of metal-ligand coordination-bonding interactions, with enough internal space to accommodate electron-deficient nitroaromatics at the molecular level by multiple supramolecular interactions. Such interactions subsequently result in the detectable fluorescence quenching of sensors even in the presence of trace quantities of nitroaromatics. The fascinating sensing characteristics of molecular architectures discussed in this article may enable future development of improved sensors for nitroaromatic explosives.

Voice source characterization using pitch synchronous discrete cosine transform for speaker identification

A characterization of the voice source (VS) signal by the pitch synchronous (PS) discrete cosine transform (DCT) is proposed. With the integrated linear prediction residual (ILPR) as the VS estimate, the PS DCT of the ILPR is evaluated as a feature vector for speaker identification (SID). On TIMIT and YOHO databases, using a Gaussian mixture model (GMM)-based classifier, it performs on par with existing VS-based features. On the NIST 2003 database, fusion with a GMM-based classifier using MFCC features improves the identification accuracy by 12% in absolute terms, proving that the proposed characterization has good promise as a feature for SID studies. (C) 2015 Acoustical Society of America

Alternative Formulation of the Discrete Linear Quadratic Regulator (DLQR)

In this paper, an alternative apriori and aposteriori formulation has been derived for the discrete linear quadratic regulator (DLQR) in a manner analogous to that used in the discrete Kalman filter. It has been shown that the formulation seamlessly fits into the available formulation of the DLQR and the equivalent terms in the existing formulation and the proposed formulation have been identified. Thereafter, the significance of this alternative formulation has been interpreted in terms of the sensitivity of the controller performances to any changes in the states or to changes in the control inputs. The implications of this alternative formulation to adaptive controller tuning have also been discussed.

Reservoir Operation with Fuzzy State Variables for Irrigation of Multiple Crops

This paper presents the development and application of a stochastic dynamic programming model with fuzzy state variables for irrigation of multiple crops. A fuzzy stochastic dynamic programming (FSDP) model is developed in which the reservoir storage and soil moisture of the crops are considered as fuzzy numbers, and the reservoir inflow is considered as a stochastic variable. The model is formulated with an objective of minimizing crop yield deficits, resulting in optimal water allocations to the crops by maintaining storage continuity and soil moisture balance. The standard fuzzy arithmetic method is used to solve all arithmetic equations with fuzzy numbers, and the fuzzy ranking method is used to compare two or more fuzzy numbers. The reservoir operation model is integrated with a daily-based water allocation model, which results in daily temporal variations of allocated water, soil moisture, and crop deficits. A case study of an existing Bhadra reservoir in Karnataka, India, is chosen for the model application. The FSDP is a more realistic model because it considers the uncertainty in discretization of state variables. The results obtained using the FSDP model are found to be more acceptable for the case study than those of the classical stochastic dynamic model and the standard operating model, in terms of 10-day releases from the reservoir and evapotranspiration deficit. (C) 2015 American Society of Civil Engineers.

Cybernetic Modeling Revisited: A Method for Inferring the Cybernetic Variables u(i) from Experimental Data

The cybernetic modeling framework for the growth of microorganisms provides for an elegant methodology to account for the unknown regulatory phenomena through the use of cybernetic variables for enzyme induction and activity. In this paper, we revisit the assumption of limited resources for enzyme induction (Sigma u(i) = 1) used in the cybernetic modeling framework by presenting a methodology for inferring the individual cybernetic variables u(i) from experimental data. We use this methodology to infer u(i) during the simultaneous consumption of glycerol and lactose by Escherichia coli and then model the fitness trade-offs involved in the recently discovered predictive regulation strategy of microorganisms.

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.