Thermal decomposition of haloethanols: single pulse shock tube and ab initio studies

This paper reports single pulse shock tube and ab initio studies on thermal decomposition of 2-fluoro and 2-chloroethanol at T=1000–1200 K. Both molecules have HX (X = F/Cl) and H2O molecular elimination channels. The CH3CHO formed by HX elimination is chemically active and undergoes secondary decomposition resulting in the formation of CH4, C2H6, and C2H4. A detailed kinetic simulation indicates that the formation of C2H4 could not be quantitatively explained as arising exclusively from secondary CH3CHO decomposition. Contributions from primary radical processes need to be considered to explain C2H4 quantitatively. Ab initio calculations on HX and H2O elimination reactions from the haloethanols at HF, MP2, and DFT levels with various basis sets up to 6/311++G**are reported. It is pointed out that due to strong correlations between A and Eα, comparison of these two parameters between experimental and theoretical results could be misleading.

Effect of convection and viscoelasticity on spinodal decomposition in fluids

Current analytical work on the effect of convection and viscoelasticity on the early and late stages of spinodal decomposition is briefly described. In the early stages, the effect of viscoelastic stresses was analysed using a simple Maxwell model for the stress, which was incorporated in the Langevin equation for the momentum field. The viscoelastic stresses are found to enhance the rate of decomposition. In the late stages, the pattern formed depends on the relative composition of the two species. Droplet spinodal decomposition occurs when the concentration of one of the species is small. Convective transport does not have a significant effect on the growth of a single droplet, but it does result in an attractive interaction between non - Brownian droplets which could lead to coalescence. The effect of convective transport for the growth of random interfaces in a near symmetric quench was analysed using an 'area distribution function', which gives the distribution of surface area of the interface in curvature space. It was found that the curvature of the interface decreases proportional to t in the late stages of spinodal decomposition, and the surface area also decreases proportional to t.

Determining optimum subband edges for signal compression

The coding gain in subband coding, a popular technique for achieving signal compression, depends on how the input signal spectrum is decomposed into subbands. The optimality of such decomposition is conventionally addressed by designing appropriate filter banks. The issue of optimal decomposition of the input spectrum is addressed by choosing the set of band that, for a given number of bands, will achieve maximum coding gain. A set of necessary conditions for such optimality is derived, and an algorithm to determine the optimal band edges is then proposed. These band edges along with ideal filters, achieve the upper bound of coding gain for a given number of bands. It is shown that with ideal filters, as well as with realizable filters for some given effective length, such a decomposition system performs better than the conventional nonuniform binary tree-structured decomposition in some cases for AR sources as well as images

Modified Adomian decomposition method for fracture of laminated uni-directional composites

In this paper, the well-known Adomian Decomposition Method (ADM) is modified to solve the fracture laminated multi-directional problems. The results are compared with the existing analytical/exact or experimental method. The already known existing ADM is modified to improve the accuracy and convergence. Thus, the modified method is named as Modified Adomian Decomposition Method (MADM). The results fromMADM are found to converge very quickly, simple to apply for fracture(singularity) problems and are more accurate compared to experimental and analytical methods. MADM is quite efficient and is practically well-suited for use in these problems. Several examples are given to check the reliability of the present method. In the present paper, the principle of the decomposition method is described, and its advantages form the analyses of fracture of laminated uni-directional composites.

An invariant subspace-based approach to the random eigenvalue problem of systems with clustered spectrum

The repeated or closely spaced eigenvalues and corresponding eigenvectors of a matrix are usually very sensitive to a perturbation of the matrix, which makes capturing the behavior of these eigenpairs very difficult. Similar difficulty is encountered in solving the random eigenvalue problem when a matrix with random elements has a set of clustered eigenvalues in its mean. In addition, the methods to solve the random eigenvalue problem often differ in characterizing the problem, which leads to different interpretations of the solution. Thus, the solutions obtained from different methods become mathematically incomparable. These two issues, the difficulty of solving and the non-unique characterization, are addressed here. A different approach is used where instead of tracking a few individual eigenpairs, the corresponding invariant subspace is tracked. The spectral stochastic finite element method is used for analysis, where the polynomial chaos expansion is used to represent the random eigenvalues and eigenvectors. However, the main concept of tracking the invariant subspace remains mostly independent of any such representation. The approach is successfully implemented in response prediction of a system with repeated natural frequencies. It is found that tracking only an invariant subspace could be sufficient to build a modal-based reduced-order model of the system. Copyright (C) 2012 John Wiley & Sons, Ltd.

Chiral discrimination and the measurement of enantiomeric excess from a severely overcrowded NMR spectrum

NMR spectroscopic chiral visualization, unambiguous assignment of peaks pertaining to R and S enantiomers and the subsequent measurement of enantiomeric composition demands a highly resolved spectrum. The method fails when the spectrum is severely overcrowded or highly complex, thereby hampering the determination of enantiomeric excess. In order to circumvent such problems we propose the utility of pure shift spectrum obtained by resolving the chemical shift and coupling information in two orthogonal dimensions. The skew projected spectrum yields singlet's at the respective chemical shift positions, permitting the unravelling of the superimposed spectral transitions for each enantiomer and measurement of enantiomeric composition. (C) 2012 Elsevier B. V. All rights reserved.

Cadmium deoxycholate: a new and efficient precursor for highly luminescent CdSe nanocrystals

We have demonstrated that cadmium deoxycholate (1), a Cd-salt, provides a convenient and inexpensive route to high quality CdSe nanocrystals with photoluminescence (PL) in the blue to red region of the visible spectrum, with reproducible quantum yields as high as similar to 47%. Owing to the high thermal stability of the bile acid based cadmium precursor (decomposition point: 332 degrees C), it was possible to achieve high injection and growth temperatures (similar to 300 degrees C) for the nanocrystals, which was essential for obtaining larger CdSe nanocrystals emitting in the red region (625-650 nm) with a sharp full width at half maximum (FWHM) (23 nm) and multiple (6-7) excitonic absorption features. The as-prepared CdSe nanocrystals synthesized from cadmium deoxycholate represent a series of highly efficient emitters with pure colours and controllable sizes, shapes and structures.

Error exponent analysis of energy-based bayesian spectrum sensing under fading channels

This paper analyzes the error exponents in Bayesian decentralized spectrum sensing, i.e., the detection of occupancy of the primary spectrum by a cognitive radio, with probability of error as the performance metric. At the individual sensors, the error exponents of a Central Limit Theorem (CLT) based detection scheme are analyzed. At the fusion center, a K-out-of-N rule is employed to arrive at the overall decision. It is shown that, in the presence of fading, for a fixed number of sensors, the error exponents with respect to the number of observations at both the individual sensors as well as at the fusion center are zero. This motivates the development of the error exponent with a certain probability as a novel metric that can be used to compare different detection schemes in the presence of fading. The metric is useful, for example, in answering the question of whether to sense for a pilot tone in a narrow band (and suffer Rayleigh fading) or to sense the entire wide-band signal (and suffer log-normal shadowing), in terms of the error exponent performance. The error exponents with a certain probability at both the individual sensors and at the fusion center are derived, with both Rayleigh as well as log-normal shadow fading. Numerical results are used to illustrate and provide a visual feel for the theoretical expressions obtained.

Cooperative distributed sequential spectrum sensing

We consider cooperative spectrum sensing for cognitive radios. We develop an energy efficient detector with low detection delay using sequential hypothesis testing. Sequential Probability Ratio Test (SPRT) is used at both the local nodes and the fusion center. We also analyse the performance of this algorithm and compare with the simulations. Modelling uncertainties in the distribution parameters are considered. Slow fading with and without perfect channel state information at the cognitive radios is taken into account.

A novel algorithm for cooperative distributed sequential spectrum sensing in Cognitive Radio

This paper considers cooperative spectrum sensing in Cognitive Radios. In our previous work we have developed DualSPRT, a distributed algorithm for cooperative spectrum sensing using Sequential Probability Ratio Test (SPRT) at the Cognitive Radios as well as at the fusion center. This algorithm works well, but is not optimal. In this paper we propose an improved algorithm- SPRT-CSPRT, which is motivated from Cumulative Sum Procedures (CUSUM). We analyse it theoretically. We also modify this algorithm to handle uncertainties in SNR's and fading.

SpecNet: Spectrum Sensing Sans Frontieres

While the under-utilization of licensed spectrum based on measurement studies conducted in a few developed countries has spurred lots of interest in opportunistic spectrum access, there exists no infrastructure today for measuring real-time spectrum occupancy across vast geographical regions. In this paper, we present the design and implementation of SpecNet, a first-of-its-kind platform that allows spectrum analyzers around the world to be networked and efficiently used in a coordinated manner for spectrum measurement as well as implementa- tion and evaluation of distributed sensing applications. We demonstrate the value of SpecNet through three applications: 1) remote spectrum measurement, 2) primary transmitter coverage estimation and 3) Spectrum-Cop that quickly identifies and localizes transmitters in a frequency range and geographic region of interest.

Cooperative distributed sequential spectrum sensing

We consider cooperative spectrum sensing for cognitive radios. We develop an energy efficient detector with low detection delay using sequential hypothesis testing. Sequential Probability Ratio Test (SPRT) is used at both the local nodes and the fusion center. We also analyse the performance of this algorithm and compare with the simulations. Modelling uncertainties in the distribution parameters are considered. Slow fading with and without perfect channel state information at the cognitive radios is taken into account.

Heat Shock Protein 90 Inhibitors as Broad Spectrum Anti-Infectives

Combating stress is one of the prime requirements for any organism. For parasitic microbes, stress levels are highest during the growth inside the host. Their survival depends on their ability to acclimatize and adapt to new environmental conditions. Robust cellular machinery for stress response is, therefore, both critical and essential especially for pathogenic microorganisms. Microbes have cleverly exploited stress proteins as virulence factors for pathogenesis in their hosts. Owing to its ability to sense and respond to the stress conditions, Heat shock protein 90 (Hsp90) is one of the key stress proteins utilized by parasitic microbes. There are growing evidences for the critical role played by Hsp90 in the growth of pathogenic organisms like Candida, Giardia, Plasmodium, Trypanosoma, and others. This review, therefore, explores potential of exploiting Hsp90 as a target for the treatment of infectious diseases. This molecular chaperone has already gained attention as an effective anti-cancer drug target. As a result, a lot of research has been done at laboratory, preclinical and clinical levels for several Hsp90 inhibitors as potential anti-cancer drugs. In addition, lot of data pertaining to toxicity studies, pharmacokinetics and pharmacodynamics studies, dosage regime, drug related toxicities, dose limiting toxicities as well as adverse drug reactions are available for Hsp90 inhibitors. Therefore, repurposing/repositioning strategies are also being explored for these compounds which have gone through advanced stage clinical trials. This review presents a comprehensive summary of current status of development of Hsp90 as a drug target and its inhibitors as candidate anti-infectives. A particular emphasis is laid on the possibility of repositioning strategies coupled with pharmaceutical solutions required for fulfilling needs for ever growing pharmaceutical infectious disease market.