Synthesis, Spectral Characterization, Crystal Structure and Thermal Behavior of Tert-butyl 2,2-bis(2,4-dinitrophenyl)ethanoate

Tert-butyl 2,2-bis(2,4-dinitrophenyl)ethanoate was prepared from the ethanolic solution of 1-chloro-2,4-dinitrobenzene, tert-butyl 3-oxobutanoate and triethylamine. Acetyl group in tert-butyl 3-oxobutanoate has cleaved off during the formation of the title molecule. UV-VIS, IR, 1H NMR, 13C NMR, Proton-Proton COSY data and single crystal XRD results support the proposed structure. Flammability test, impact sensitivity test and TG/DTA studies at different heating rates on the synthesized molecule imply that it is an insensitive high energy density material.

Intermolecular charge transfer and vibrational analysis of hydrogen bonding in acetazolamide

In the present work the structural and spectral characteristics of acetazolamide have been studied by methods of infrared, Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by density functional theory (DFT) employing B3LYP with complete relaxation in the potential energy surface using 6-311++G(d,p) basis set. Based on these results, we have discussed the correlation between the vibrational modes and the structure of the dimers of acetazolamide. The calculated vibrational spectra of three dimers of acetazolamide have been compared with observed spectra, and the assignment of observed bands was carried out using potential energy distribution. The observed spectra agree well with the values computed from the OFT. A comparison of observed and calculated vibrational spectra clearly shows the effect of hydrogen bonding. The frequency shifts observed for the different dimers are in accord with the hydrogen bonding in acetazolamide. Natural bond orbital (NBO) analyses reflect the charge transfer interaction in the individual hydrogen bond units and the stability of different dimers of acetazolamide. (C) 2012 Elsevier B.V. All rights reserved.

Influence of the Blade Hub Geometry on the Performance of Low-Head Axial Flow Turbines

The influence of geometric parameters, such as blade profile and hub geometry on axial flow turbines for micro hydro application remains poorly characterized. This paper first introduces a holistic theoretical model for studying the hydraulic phenomenon resulting from geometric modification to the blades. It then describes modification carried out on two runner stages, of which one has untwisted blades and the other has twisted blades obtained by modifying the inlet hub. The experimental results showed that the performance of the untwisted blade runner was satisfactory with a maximum efficiency of 68%. However, positive effects of twisted blades were clearly evident with an efficiency rise of more than 2%. This study also looks into the possible limitations of the model and suggests the extension of the experimental work and the use of computational tools to conduct a progressive validation of all experimental findings, especially on the flow physics within the hub region and the slip phenomena. The paper finally underlines the importance of developing a standardization philosophy for axial flow turbines specific for micro hydro requirements. DOI:10.1061/(ASCE)EY.1943-7897.0000060. (C) 2012 American Society of Civil Engineers.

Spectral analysis on SL(2, R)

Let G be the group . For this group we prove a version of Schwartz's theorem on spectral analysis for the group G. We find the sharp range of Lebesgue spaces L (p) (G) for which a smooth function is not mean periodic unless it is a cusp form. Failure of the Schwartz-like theorem is also proved when C (a)(G) is replaced by L (p) (G) with suitable p. We show that the last result is linked with the failure of the Wiener-tauberian theorem for G.

Spectral moment sum rules for the retarded Green's function and self-energy of the inhomogeneous Bose-Hubbard model in equilibrium and nonequilibrium

We derive exact expressions for the zeroth and the first three spectral moment sum rules for the retarded Green's function and for the zeroth and the first spectral moment sum rules for the retarded self-energy of the inhomogeneous Bose-Hubbard model in nonequilibrium, when the local on-site repulsion and the chemical potential are time-dependent, and in the presence of an external time-dependent electromagnetic field. We also evaluate these expressions for the homogeneous case in equilibrium, where all time dependence and external fields vanish. Unlike similar sum rules for the Fermi-Hubbard model, in the Bose-Hubbard model case, the sum rules often depend on expectation values that cannot be determined simply from parameters in the Hamiltonian like the interaction strength and chemical potential but require knowledge of equal-time many-body expectation values from some other source. We show how one can approximately evaluate these expectation values for the Mott-insulating phase in a systematic strong-coupling expansion in powers of the hopping divided by the interaction. We compare the exact moment relations to the calculated moments of spectral functions determined from a variety of different numerical approximations and use them to benchmark their accuracy. DOI: 10.1103/PhysRevA.87.013628

Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

Four dinuclear bis(mu-Cl) bridged copper(II) complexes, Cu-2(mu-Cl)(2)(L-X)(2)](ClO4)(2) (L-X = N,N-bis(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L-X ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH2) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu-t-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

Spectral-spatial MODIS image analysis using swarm intelligence algorithms and region based segmentation for flood assessment

This paper discusses an approach for river mapping and flood evaluation based on multi-temporal time-series analysis of satellite images utilizing pixel spectral information for image clustering and region based segmentation for extracting water covered regions. MODIS satellite images are analyzed at two stages: before flood and during flood. Multi-temporal MODIS images are processed in two steps. In the first step, clustering algorithms such as Genetic Algorithm (GA) and Particle Swarm Optimization (PSO) are used to distinguish the water regions from the non-water based on spectral information. These algorithms are chosen since they are quite efficient in solving multi-modal optimization problems. These classified images are then segmented using spatial features of the water region to extract the river. From the results obtained, we evaluate the performance of the methods and conclude that incorporating region based image segmentation along with clustering algorithms provides accurate and reliable approach for the extraction of water covered region.

Spectral-envelope and group-delay models for transient signals—applications to castanets and stop consonants

We present a novel approach to represent transients using spectral-domain amplitude-modulated/frequency -modulated (AM-FM) functions. The model is applied to the real and imaginary parts of the Fourier transform (FT) of the transient. The suitability of the model lies in the observation that since transients are well-localized in time, the real and imaginary parts of the Fourier spectrum have a modulation structure. The spectral AM is the envelope and the spectral FM is the group delay function. The group delay is estimated using spectral zero-crossings and the spectral envelope is estimated using a coherent demodulator. We show that the proposed technique is robust to additive noise. We present applications of the proposed technique to castanets and stop-consonants in speech.

Geometry of static balancing during posture transition

The interaction between the digital human model (DHM) and environment typically occurs in two distinct modes; one, when the DHM maintains contacts with the environment using its self weight, wherein associated reaction forces at the interface due to gravity are unidirectional; two, when the DHM applies both tension and compression on the environment through anchoring. For static balancing in first mode of interaction, it is sufficient to maintain the projection of the centre of mass (COM) inside the convex region induced by the weight supporting segments of the body on a horizontal plane. In DHM, static balancing is required while performing specified tasks such as reach, manipulation and locomotion; otherwise the simulations would not be realistic. This paper establishes the geometric relationships that must be satisfied for maintaining static balance while altering the support configurations for a given posture and altering the posture for a given support condition. For a given location of the COM for a system supported by multiple point contacts, the conditions for simultaneous withdrawal of a specified set of contacts have been determined in terms of the convex hulls of the subsets of the points of contact. When the projection of COM must move beyond the existing support for performing some task, new supports must be enabled for maintaining static balance. This support seeking behavior could also manifest while planning for reduction of support stresses. Feasibility of such a support depends upon the availability of necessary features in the environment. Geometric conditions necessary for selection of new support on horizontal,inclined and vertical surfaces within the workspace of the DHM for such dynamic scenario have been derived. The concepts developed are demonstrated using the cases of sit-to-stand posture transition for manipulation of COM within the convex supporting polygon, and statically stable walking gaits for support seeking within the kinematic capabilities of the DHM. The theory developed helps in making the DHM realize appropriate behaviors in diverse scenarios autonomously.

Palladium(II) complexes as biologically potent metallo-drugs: Synthesis, spectral characterization, DNA interaction studies and antibacterial activity

Four novel mononuclear Pd(II) complexes have been synthesized with the biologically active Schiff base ligands (L-1-L-4) derived from 3-amino-2-methyl-4(3H)-quinazolinone. The structure of the complexes has been proposed by elemental analysis, molar conductance, IR, H-1 NMR, mass, UV-Vis spectrometric and thermal studies. The investigation of interaction of the complexes with calf thymus DNA (CT-DNA) has been performed with absorption and fluorescence spectroscopic studies. The nuclease activity was done using pUC19 supercoiled DNA by gel-electrophoresis. All the ligands and their Pd(II) complexes have also been screened for their antibacterial activity by discolor diffusion technique. (C) 2013 Elsevier B.V. All rights reserved.

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.

Some questions on integral geometry on noncompact symmetric spaces of higher rank

Let be a noncompact symmetric space of higher rank. We consider two types of averages of functions: one, over level sets of the heat kernel on and the other, over geodesic spheres. We prove injectivity results for functions in which extend the results in Pati and Sitaram (Sankya Ser A 62:419-424, 2000).

Synthesis, antimicrobial, DNA-binding and photonuclease studies of Cobalt(III) and Nickel(II) Schiff base complexes

New metal complexes of the type M(nih)(L)](PF6)(n)center dot xAH(2)O and M(nih)(2)](PF6)center dot xH(2)O (where M = Co(III) or Ni(II), L = 1,10-phenanthroline (phen)/or 2,2' bipyridine (bpy), nih = 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone, n = 2 or 1 and x = 3 or 2) have been synthesized and characterized by elemental analysis, magnetic, IR and H-1 NMR spectral data. The electronic and magnetic moment 2.97-3.07 B.M. data infers octahedral geometry for all the complexes. The IR data reveals that Schiff base (nih) form coordination bond with the metal ion through azomethine-nitrogen, phenolic-oxygen and carbonyl-oxygen in a tridentate fashion. In addition, DNA-binding properties of these six metal complexes were investigated using absorption spectroscopy, viscosity measurements and thermal denaturation methods. The results indicated that the nickel(II) complex strongly bind with calf-thymus DNA with intrinsic DNA binding constant K-b value of 4.9 x 10(4) M-1 for (3), 4.2 x 10(4) M-1 for (4), presumably via an intercalation mechanism compared to cobalt(III) complex with K-b value of 4.6 x 10(4) M-1 (1) and 4.1 x 10(4) M-1 (2). The DNA Photoclevage experiment shows that, the complexes act as effective DNA cleavage agent. (C) 2012 Elsevier B.V. All rights reserved.

Spectral-envelope-group-delay models for transients

Transient signals such as plosives in speech or Castanets in audio do not have a specific modulation or periodic structure in time domain. However, in the spectral domain they exhibit a prominent modulation structure, which is a direct consequence of their narrow time localization. Based on this observation, a spectral-domain AM-FM model for transients is proposed. The spectral AM-FM model is built starting from real spectral zero-crossings. The AM and FM correspond to the spectral envelope (SE) and group delay (GD), respectively. Taking into account the modulation structure and spectral continuity, a local polynomial regression technique is proposed to estimate the GD function from the real spectral zeros. The SE is estimated based on the phase function computed from the estimated GD. Since the GD estimation is parametric, the degree of smoothness can be controlled directly. Simulation results based on synthetic transient signals generated using a beta density function are presented to analyze the noise-robustness of the SEGD model. Three specific applications are considered: (1) SEGD based modeling of Castanet sounds; (2) appropriateness of the model for transient compression; and (3) determining glottal closure instants in speech using a short-time SEGD model of the linear prediction residue.