Thermal Rearrangement of Azido Ketones into Oxazoles via Azirines: One-Pot, Metal-Free Heteroannulation to Functionalized 1,3-Oxazoles

alpha-Azidoacetophenones were converted into 2-aryl-1,3-oxazole-4-carbaldehydes through rearrangement of the carbon framework upon exposure to DMF/POCl3. The unprecedented rearrangement occurs via alkenyl azides and 2H-azirines. A mechanism for this unusual reaction was proposed and evidenced.

Simulation of Deformation Texture Evolution During Multi Axial Forging of Interstitial Free Steel

Bulk texture measurement of multi-axial forged body center cubic interstitial free steel performed in this study using x-ray and neutron diffraction indicated the presence of a strong {101}aOE (c) 111 > single texture component. Viscoplastic self-consistent simulations could successfully predict the formation of this texture component by incorporating the complicated strain path followed during this process and assuming the activity of {101}aOE (c) 111 > slip system. In addition, a first-order estimate of mechanical properties in terms of highly anisotropic yield locus and Lankford parameter was also obtained from the simulations.

Spectral zero-crossings: localization properties and application to epoch extraction in speech signals

We analyze the spectral zero-crossing rate (SZCR) properties of transient signals and show that SZCR contains accurate localization information about the transient. For a train of pulses containing transient events, the SZCR computed on a sliding window basis is useful in locating the impulse locations accurately. We present the properties of SZCR on standard stylized signal models and then show how it may be used to estimate the epochs in speech signals. We also present comparisons with some state-of-the-art techniques that are based on the group-delay function. Experiments on real speech show that the proposed SZCR technique is better than other group-delay-based epoch detectors. In the presence of noise, a comparison with the zero-frequency filtering technique (ZFF) and Dynamic programming projected Phase-Slope Algorithm (DYPSA) showed that performance of the SZCR technique is better than DYPSA and inferior to that of ZFF. For highpass-filtered speech, where ZFF performance suffers drastically, the identification rates of SZCR are better than those of DYPSA.

A risk-estimation-based formulation for speech enhancement and its relation to Wiener filtering

The goal of speech enhancement algorithms is to provide an estimate of clean speech starting from noisy observations. The often-employed cost function is the mean square error (MSE). However, the MSE can never be computed in practice. Therefore, it becomes necessary to find practical alternatives to the MSE. In image denoising problems, the cost function (also referred to as risk) is often replaced by an unbiased estimator. Motivated by this approach, we reformulate the problem of speech enhancement from the perspective of risk minimization. Some recent contributions in risk estimation have employed Stein's unbiased risk estimator (SURE) together with a parametric denoising function, which is a linear expansion of threshold/bases (LET). We show that the first-order case of SURE-LET results in a Wiener-filter type solution if the denoising function is made frequency-dependent. We also provide enhancement results obtained with both techniques and characterize the improvement by means of local as well as global SNR calculations.

A generalized Stein's estimation approach to speech enhancement based on perceptual criteria

We address the problem of speech enhancement using a risk- estimation approach. In particular, we propose the use the Stein’s unbiased risk estimator (SURE) for solving the problem. The need for a suitable finite-sample risk estimator arises because the actual risks invariably depend on the unknown ground truth. We consider the popular mean-squared error (MSE) criterion first, and then compare it against the perceptually-motivated Itakura-Saito (IS) distortion, by deriving unbiased estimators of the corresponding risks. We use a generalized SURE (GSURE) development, recently proposed by Eldar for MSE. We consider dependent observation models from the exponential family with an additive noise model,and derive an unbiased estimator for the risk corresponding to the IS distortion, which is non-quadratic. This serves to address the speech enhancement problem in a more general setting. Experimental results illustrate that the IS metric is efficient in suppressing musical noise, which affects the MSE-enhanced speech. However, in terms of global signal-to-noise ratio (SNR), the minimum MSE solution gives better results.

Sub-band envelope approach to obtain instants of significant excitation in speech

In this paper, we propose a new sub-band approach to estimate the glottal activity. The method is based on the spectral harmonicity and the sub-band temporal properties of voiced speech. We propose a method to represent glottal excitation signal using sub-band temporal envelope. Instants of maximum glottal excitation or Glottal Closure Instants (GCI) are extracted from the estimated glottal excitation pattern and the result is compared with a standard GCI computation method, DYPSA [1]. The performance of the algorithm is also compared for the noisy signal and it is shown that the proposed method is less variant to GCI estimation under noisy conditions compared to DYPSA. The algorithm is evaluated on the CMU-ARCTIC database.

Sex and physiological state influence the rate of resource acquisition and monopolisation in urban free-ranging dogs, Canis familiaris

In animal populations, the constraints of energy and time can cause intraspecific variation in foraging behaviour. The proximate developmental mediators of such variation are often the mechanisms underlying perception and associative learning. Here, experience-dependent changes in foraging behaviour and their consequences were investigated in an urban population of free-ranging dogs, Canis familiaris by continually challenging them with the task of food extraction from specially crafted packets. Typically, males and pregnant/lactating (PL) females extracted food using the sophisticated `gap widening' technique, whereas non-pregnant/non-lactating (NPNL) females, the relatively underdeveloped `rip opening' technique. In contrast to most males and PL females (and a few NPNL females) that repeatedly used the gap widening technique and improved their performance in food extraction with experience, most NPNL females (and a few males and PL females) non-preferentially used the two extraction techniques and did not improve over successive trials. Furthermore, the ability of dogs to sophisticatedly extract food was positively related to their ability to improve their performance with experience. Collectively, these findings demonstrate that factors such as sex and physiological state can cause differences among individuals in the likelihood of learning new information and hence, in the rate of resource acquisition and monopolization.

Model-free simulations for compressible mixing layer

Confined supersonic mixing layer is explored through model-free simulations. Both two- and three-dimensional spatio-temporal simulations were carried out employing higher order finite difference scheme as well as finite volume scheme based on open source software (OpenFOAM) to understand the effect of three-dimensionality on the development of mixing layer. It is observed that although the instantaneous structures exhibit three-dimensional features, the average pressure and velocities are predominantly two-dimensional. The computed wall pressures match well with experimental results fairly well, although three-dimensional simulation underpredicts the wall pressure in the downstream direction. The self-similarity of the velocity profiles is obtained within the duct length for all the simulations. Although the mixing layer thicknesses differ among different simulations, their growth rate is nearly the same. Significant differences are observed for species and temperature distribution between two- and three-dimensional calculations, and two-dimensional calculations do not match the experimental observation of smooth variations in species mass fraction profiles as reported in literature. Reynolds stress distribution for three-dimensional calculations show profiles with less peak values compared to two-dimensional calculations; while normal stress anisotropy is higher for three-dimensional case.

Surfactant free, non-aqueous method, for the deposition of ZnO nanoparticle thin films on Si(100) substrate with tunable ultraviolet (UV) emission

We report, strong ultraviolet (UV) emission from ZnO nanoparticle thin film obtained by a green synthesis, where the film is formed by the microwave irradiation of the alcohol solution of the precursor. The deposition is carried out in non-aqueous medium without the use of any surfactant, and the film formation is quick (5 min). The film is uniform comprising of mono-disperse nanoparticles having a narrow size distribution (15-22 nm), and that cover over an entire area (625 mm(2)) of the substrate. The growth rate is comparatively high (30-70 nm/min). It is possible to tune the morphology of the films and the UV emission by varying the process parameters. The growth mechanism is discussed precisely and schematic of the growth process is provided.

Free energy barriers for homogeneous crystal nucleation in a eutectic system of binary hard spheres

In this study, the free energy barriers for homogeneous crystal nucleation in a system that exhibits a eutectic point are computed using Monte Carlo simulations. The system studied is a binary hard sphere mixture with a diameter ratio of 0.85 between the smaller and larger hard spheres. The simulations of crystal nucleation are performed for the entire range of fluid compositions. The free energy barrier is found to be the highest near the eutectic point and is nearly five times that for the pure fluid, which slows down the nucleation rate by a factor of 10(-31). These free energy barriers are some of highest ever computed using simulations. For most of the conditions studied, the composition of the critical nucleus corresponds to either one of the two thermodynamically stable solid phases. However, near the eutectic point, the nucleation barrier is lowest for the formation of the metastable random hexagonal closed packed (rhcp) solid phase with composition lying in the two-phase region of the phase diagram. The fluid to solid phase transition is hypothesized to proceed via formation of a metastable rhcp phase followed by a phase separation into respective stable fcc solid phases.

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.

Joint pitch-analysis formant-synthesis framework for CS recovery of speech

A joint analysis-synthesis framework is developed for the compressive sensing (CS) recovery of speech signals. The signal is assumed to be sparse in the residual domain with the linear prediction filter used as the sparse transformation. Importantly this transform is not known apriori, since estimating the predictor filter requires the knowledge of the signal. Two prediction filters, one comb filter for pitch and another all pole formant filter are needed to induce maximum sparsity. An iterative method is proposed for the estimation of both the prediction filters and the signal itself. Formant prediction filter is used as the synthesis transform, while the pitch filter is used to model the periodicity in the residual excitation signal, in the analysis mode. Significant improvement in the LLR measure is seen over the previously reported formant filter estimation.

Automatic speech segmentation using probabilistic latent component modeling

Latent variable methods, such as PLCA (Probabilistic Latent Component Analysis) have been successfully used for analysis of non-negative signal representations. In this paper, we formulate PLCS (Probabilistic Latent Component Segmentation), which models each time frame of a spectrogram as a spectral distribution. Given the signal spectrogram, the segmentation boundaries are estimated using a maximum-likelihood approach. For an efficient solution, the algorithm imposes a hard constraint that each segment is modelled by a single latent component. The hard constraint facilitates the solution of ML boundary estimation using dynamic programming. The PLCS framework does not impose a parametric assumption unlike earlier ML segmentation techniques. PLCS can be naturally extended to model coarticulation between successive phones. Experiments on the TIMIT corpus show that the proposed technique is promising compared to most state of the art speech segmentation algorithms.

Polymorphic phase boundaries and enhanced piezoelectric response in extended composition range in the lead free ferroelectric BaTi1-xZrxO3

Neutron powder diffraction study of Ba(Ti1-xZrx)O-3 at close composition intervals has revealed coexistence of ferroelectric phases: orthorhombic (Amm2) + tetragonal (P4mm) for 0.02 <= x <= 0.05 and rhombohedral (R3m) + orthorhombic (Amm2) for 0.07 <= x < 0.09. These compositions exhibit relatively enhanced piezoelectric properties as compared to their single phase counterparts outside this composition region, confirming the polymorphic phase boundary nature of the phase coexistence regions. (C) 2013 AIP Publishing LLC.

Efficient gradient-free simplex method for estimation of optical properties in image-guided diffuse optical tomography

Typical image-guided diffuse optical tomographic image reconstruction procedures involve reduction of the number of optical parameters to be reconstructed equal to the number of distinct regions identified in the structural information provided by the traditional imaging modality. This makes the image reconstruction problem less ill-posed compared to traditional underdetermined cases. Still, the methods that are deployed in this case are same as those used for traditional diffuse optical image reconstruction, which involves a regularization term as well as computation of the Jacobian. A gradient-free Nelder-Mead simplex method is proposed here to perform the image reconstruction procedure and is shown to provide solutions that closely match ones obtained using established methods, even in highly noisy data. The proposed method also has the distinct advantage of being more efficient owing to being regularization free, involving only repeated forward calculations. (C) 2013 Society of Photo-Optical Instrumentation Engineers (SPIE)