Chiral synthons from campholenaldehyde: enantiospecific synthesis of diquinane and linear triquinanes

Enantiospecific syntheses of diquinane and linear triquinanes were accomplished, starting from the readily available alpha-campholenaldehyde employing a Nazarov reaction as the key step. (C) 2010 Elsevier Ltd. All rights reserved.

Convergence feedback and unstable low frequency oscillations in a simple coupled ocean‐atmosphere model

The role of convergence feedback on the stability of a coupled ocean‐atmosphere system is studied using model III of Hirst (1986). It is shown that the unstable coupled mode found by Hirst is greatly modified by the convergence feedback. If the convergence feedback strength exceeds a critical value, several new unstable intraseasonal modes are also introduced. These modes have very weak dependence on the wave number. These results may explain the behaviour of some coupled models and to some extent provide a mechanism for the observed aperiodicity of the El‐Nino and Southern Oscillation (ENSO) events.

Non-linear Dynamic Analysis of a Piezoelectrically Actuated Flapping Wing

An energy method is used in order to derive the non-linear equations of motion of a smart flapping wing. Flapping wing is actuated from the root by a PZT unimorph in the piezofan configuration. Dynamic characteristics of the wing, having the same size as dragonfly Aeshna Multicolor, are analyzed using numerical simulations. It is shown that flapping angle variations of the smart flapping wing are similar to the actual dragonfly wing for a specific feasible voltage. An unsteady aerodynamic model based on modified strip theory is used to obtain the aerodynamic forces. It is found that the smart wing generates sufficient lift to support its own weight and carry a small payload. It is therefore a potential candidate for flapping wing of micro air vehicles.

Geometrically simple linear weirs using circular quadrants

A detailed theoretical analysis of flow through a quadrant plate weir is made in the light of the generalized theory of proportional weirs, using a numerical optimization procedure. It is shown that the flow through the quadrant plate weir has a linear discharge-head relationship valid for certain ranges of head. It is shown that the weir is associated with a reference plane or datum from which all heads are reckoned.Further, it is shown that the measuring range of the quadrant plate weir can be considerably enhanced by extending the tangents to the quadrants at the terminals of the quadrant plate weir. The importance of this weir (when the datum of the weir lies below its crest) as an outlet weir for grit chambers is highlighted. Experiments show excellent agreement with the theory by giving a constant average coefficient of discharge.

Influence of cross-correlation between dipolar and chemical shift anisotropy relaxation mechanisms upon the transverse relaxation rates of 15N in macromolecules

Heteronuclear multiple-quantum coherence relaxation rate are calculated for the individual transitions of the S spin in an AIS nuclear spin system assuming that the heteronucleus (S spin) has relaxation contributions from both intramolecular dipole-dipole and chemical shift anisotropy relaxation. The individual multiplet components of the heteronuclear zero- and double-quantum coherences are shown to have different transverse relaxation rates. The cross-correlation between the two relaxation mechanisms is shown to be the dominant cause of the calculated differential line broadening. Experimental data are presented using as an example a uniformly 15N labelled sample of human epidermal growth factor.

Sonochemical synthesis of Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta nanocrystallites: oxygen storage material, CO oxidation and water gas shift catalyst

Nanocrystalline Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta of similar to 4 nm sizes were synthesized by a sonochemical method using diethyletriamine (DETA) as a complexing agent. Compounds were characterized by powder X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS) and transmission electron microscopy (TEM). Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta crystallize in fluorite structure where Fe is in +3, Ce is in +4 and Pd is in +2 oxidation state. Due to substitution of smaller Fe3+ ion in CeO2, lattice oxygen is activated and 33% Fe substituted CeO2 i.e. Ce0.67Fe0.33O1.835 reversibly releases 0.31O] up to 600 degrees C which is higher or comparable to the oxygen storage capacity of CeO2-ZrO2 based solid solutions (Catal. Today 2002, 74, 225-234). Due to interaction of redox potentials of Pd2+/0(0.89 V) and Fe3+/2+ (0.77 V) with Ce4+/3+ (1.61 V), Pd ion accelerates the electron transfer from Fe2+ to Ce4+ in Ce0.65Fe0.33Pd0.02O1.815, making it a high oxygen storage material as well as a highly active catalyst for CO oxidation and water gas shift reaction. The activation energy for CO oxidation with Ce0.65Fe0.33Pd0.02O1.815 is found to be as low as 38 kJ mol(-1). Ce0.67Fe0.33O1.835 and Ce0.65Fe0.33Pd0.02O1.815 have also shown high activity for the water gas shift reaction. CO conversion to CO2 is 100% H-2 specific with these catalysts and conversion rate was found to be as high 27.2 mu moles g(-1) s(-1) and the activation energy was found to be 46.4 kJ mol(-1) for Ce0.65Fe0.33Pd0.02O1.815.

Nucleosomes on linear duplex DNA allow homologous pairing but prevent strand exchange promoted by RecA protein

To understand the molecular basis of gene targeting, we have studied interactions of nucleoprotein filaments comprised of single-stranded DNA and RecA protein with chromatin templates reconstituted from linear duplex DNA and histones. We observed that for the chromatin templates with histone/DNA mass ratios of 0.8 and 1.6, the efficiency of homologous pairing was indistinguishable from that of naked duplex DNA but strand exchange was repressed. In contrast, the chromatin templates with a histone/DNA mass ratio of 9.0 supported neither homologous pairing nor strand exchange. The addition of histone H1, in stoichiometric amounts, to chromatin templates quells homologous pairing. The pairing of chromatin templates with nucleoprotein filaments of RecA protein-single-stranded DNA proceeded without the production of detectable networks of DNA, suggesting that coaggregates are unlikely to be the intermediates in homologous pairing. The application of these observations to strategies for gene targeting and their implications for models of genetic recombination are discussed.

A New Liquid Level Sensor for Process-Control Applications

Many process-control systems are air-operated. In such an environment, it would be desirable and economical to use pneumatic sensors. Bubble-back pressure sensors perform quite satisfactorily, but in case of viscous inflammable and slurry-like liquids with a tendency to froth, this level sensor is inadequate. The method suggested in this paper utilizes a pneumatic capacitor, one boundary of which is formed by the liquid level, to modulate a fluid amplifier feedback oscillator. The absence of moving parts and economy obtained makes this method attractive for process-control applications. The system has been mathematically modeled and simulated on an IBM 360/44 digital computer. Experimental values compare fairly well with the theoretical results. For the range tested, the sensor is found to have a linear frequency variation with the liquid level Extended running in the laboratory shows that the system is very reliable. This system has been found insensitive to temperature variations of up to 15ðC.

A formate bridged Ni(II) sheet and its 3D analogue in presence of a linear organic linker: Synthesis, crystal structure and magnetic properties

Reaction of formamide with Ni(NO3)(2)center dot 6H(2)O under hydrothermal condition in a mixture of MeOH/H2O forms a two-dimensional formate bridged sheet Ni(HCOO)(2)(MeOH)(2) (1). X-ray structure analysis reveals the conversion of formamide to formate which acts as a bridging ligand in complex 1 where the axial sites of Ni(II) are occupied by methanol used as a solvent. An analogous reaction in presence of 4,4'-bipyridyl (4,4'-bipy) yielded a three-dimensional structure Ni(HCOO)(2)(4,4'-bpy) (2). DC magnetic measurements as a function of temperature and field established the presence of spontaneous magnetization with T-c (Curie temperature) = 17 and 20.8 K in 1 and 2, respectively, which can be attributed due to spin-canting. DFT calculations were performed to corroborate the magnetic results of 1 and 2. (C) 2010 Elsevier Ltd. All rights reserved.

Polarization studies in electromagnetic scattering by small Solar-system particles

In remote-sensing studies, particles that are comparable to the wavelength exhibit characteristic features in electromagnetic scattering, especially in the degree of linear polarization. These features vary with the physical properties of the particles, such as shape, size, refractive index, and orientation. In the thesis, the direct problem of computing the unknown scattered quantities using the known properties of the particles and the incident radiation is solved at both optical and radar spectral regions in a unique way. The internal electromagnetic fields of wavelength-scale particles are analyzed by using both novel and established methods to show how the internal fields are related to the scattered fields in the far zone. This is achieved by using the tools and methods that were developed specifically to reveal the internal field structure of particles and to study the mechanisms that relate the structure to the scattering characteristics of those particles. It is shown that, for spherical particles, the internal field is a combination of a forward propagating wave with the apparent wavelength determined by the refractive index of the particle, and a standing wave pattern with the apparent wavelength the same as for the incident wave. Due to the surface curvature and dielectric nature of the particle, the incident wave front undergoes a phase shift, and the resulting internal wave is focused mostly at the forward part of the particle similar to an optical lens. This focusing is also seen for irregular particles. It is concluded that, for both spherical and nonspherical particles, the interference at the far field between the partial waves that originate from these concentrated areas in the particle interior, is responsible for the specific polarization features that are common for wavelength-scale particles, such as negative values and local extrema in the degree of linear polarization, asymmetry of the phase function, and enhancement of intensity near the backscattering direction. The papers presented in this thesis solve the direct problem for particles with both simple and irregular shapes to demonstrate that these interference mechanisms are common for all dielectric wavelength-scale particles. Furthermore, it is shown that these mechanisms can be applied to both regolith particles in the optical wavelengths and hydrometeors at microwave frequencies. An advantage from this kind of study is that it does not matter whether the observation is active (e.g., polarimetric radar) or passive (e.g., optical telescope). In both cases, the internal field is computed for two mutually perpendicular incident polarizations, so that the polarization characteristics can then be analyzed according to the relation between these fields and the scattered far field.

An optimal local approximation algorithm for max-min linear programs

In a max-min LP, the objective is to maximise ω subject to Ax ≤ 1, Cx ≥ ω1, and x ≥ 0 for nonnegative matrices A and C. We present a local algorithm (constant-time distributed algorithm) for approximating max-min LPs. The approximation ratio of our algorithm is the best possible for any local algorithm; there is a matching unconditional lower bound.

Epoch extraction from linear prediction residual for identification of closed glottis interval

In voiced speech analysis epochal information is useful in accurate estimation of pitch periods and the frequency response of the vocal tract system. Ideally, linear prediction (LP) residual should give impulses at epochs. However, there are often ambiguities in the direct use of LP residual since samples of either polarity occur around epochs. Further, since the digital inverse filter does not compensate the phase response of the vocal tract system exactly, there is an uncertainty in the estimated epoch position. In this paper we present an interpretation of LP residual by considering the effect of the following factors: 1) the shape of glottal pulses, 2) inaccurate estimation of formants and bandwidths, 3) phase angles of formants at the instants of excitation, and 4) zeros in the vocal tract system. A method for the unambiguous identification of epochs from LP residual is then presented. The accuracy of the method is tested by comparing the results with the epochs obtained from the estimated glottal pulse shapes for several vowel segments. The method is used to identify the closed glottis interval for the estimation of the true frequency response of the vocal tract system.

Design of clutter-rejecting compact pulse bursts with amplitude modulation and frequency-shift keying

A method is presented for the design of compact pulse burst signals, with amplitude and frequency stepping between individual pulses, for optimum rejection of radar clutter distributed arbitrarily in range. The method is illustrated by an example. It is shown that amplitude stepping plays a useful role only when the reciprocal of the individual pulse width is not insignificant compared to the bandwidth permitted to the signal. As an important and useful subclass of the amplitude-and-frequency-stepped signals, constant amplitude FSK bursts are studied and the extent of loss of clutter performance due to amplitude flattening is evaluated.