Transport properties of phosphomolybdate and phosphotungstate glasses

The d.c. conductivity of phosphomolybdate and phosphotungstate glasses is discussed. The conductivity of these glasses is due to the hopping of electrons between two valence states (Mo5+ to Mo6+ or W5+ W6+). In some of the glasses, the activation energy itself is found to be a function of temperature. This appears to be due to thermally activated and variable-range hopping mechanisms operating in different temperature regimes. The relation between conductivity and the [M5+]/[Mtotal](M ≡ Mo, W) ratio does not show any systematic variation. This anomaly can be understood using the structural models of these glasses. In contrast, Mott's theory and the Triberis and Friedman model have been used to obtain conductivity parameters such as the percolation distance Rij and 2agrRij (agr is the tunnelling probability). The conductivity parameter 2agrRij is quite useful to resolve the controversy regarding the tunnelling term exp(2agrRij) existing in the literature. For low values of 2agrRij, it is shown that the exp (2agrRij) term is very significant.

Supramolecular Chirality in Organogels: A Detailed Spectroscopic, Morphological, and Rheological Investigation of Gels (and Xerogels) Derived from Alkyl Pyrenyl Urethanes

This Article addresses the formation of chiral supramolecular structures in the organogels derived from chiral organogelator 1R (or 2R), and its mixtures with its enantiomer (1S) and achiral analogue 3 by extensive circular dichroism (CD) spectroscopic measurements. Morphological analysis by atomic force microscopy (AFM) and scanning electron microscopy (SEM) were complemented by the measurements of their bulk properties by thermal stability and rheological studies. Specific molecular recognition events (1/3 vs 2/3) and solvent effects (isooctane vs dodecane) were found to be critical in the formation of chiral aggregates. Theoretical studies were also carried out to understand the interactions responsible for the formation of the superstructures.

Disorder-driven electronic localization and phase separation in superconducting Fe1+yTe0.5Se0.5 single crystals

We have investigated the influence of Fe excess on the electrical transport and magnetism of Fe1+yTe0.5Se0.5 (y=0.04 and 0.09) single crystals. Both compositions exhibit resistively determined superconducting transitions (T-c) with an onset temperature of about 15 K. From the width of the superconducting transition and the magnitude of the lower critical field H-c1, it is inferred that excess of Fe suppresses superconductivity. The linear and nonlinear responses of the ac susceptibility show that the superconducting state for these compositions is inhomogeneous. A possible origin of this phase separation is a magnetic coupling between Fe excess occupying interstitial sites in the chalcogen planes and those in the Fe-square lattice. The temperature derivative of the resistivity d(rho)/d(T) in the temperature range T-c < T < T-a with T-a being the temperature of a magnetic anomaly, changes from positive to negative with increasing Fe. A log 1/T divergence of the resistivity above T-c in the sample with higher amount of Fe suggests a disorder-driven electronic localization.

Probing the role of the C-H center dot center dot center dot O hydrogen bond stabilized polypeptide chain reversal at the C-terminus of designed peptide helices. Structural characterization of three decapeptides

The structural characterization in crystals of three designed decapeptides containing a double D-segment at the C-terminus is described. The crystal structures of the peptides Boc-Leu-Aib-Val-Xxx-Leu-Aib-Val- (D)Ala-(D)Leu-Aib-OMe, (Xxx = Gly 2, (D)Ala 3, Aib 4) have been determined and compared with those reported earlier for peptide 1 (Xxx = Ala) and the all L analogue Boc-Leu-Aib-Val-Ala-Leu-Aib-Val-Ala-Leu-Aib-OMe, which yielded a perfect right-handed a-helical structure. Peptides 1 and 2 reveal a right-handed helical segment spanning residues 1 to 7, ending in a Schellman motif with Ala(8) functioning as the terminating residue. Polypeptide chain reversal occurs at residue 9, a novel feature that appears to be the consequence of a C-(HO)-O-... hydrogen bond between residue 4 (CH)-H-alpha and residue 9 CO groups. The structures of peptides 3 and 4, which lack the pro R hydrogen at the C-alpha atom of residue 4, are dramatically different. Peptide 3 adopts a right-handed helical conformation over the 1 to 7 segment. Residues 8 and 9 adopt at conformations forming a C-terminus type I' beta-turn, corresponding to an incipient left-handed twist of the polypeptide chain. In peptide 4, helix termination occurs at Aib(6), with residues 6 to 9 forming a left-handed helix, resulting in a structure that accommodates direct fusion of two helical segments of opposite twist. Peptides 3 and 4 provide examples of chiral residues occurring in the less favored sense of helical twist; (D)Ala(4) in peptide 3 adopts an alpha(R) conformation, while (L)Val(7) in 4 adopts an alpha(L) conformation. The structural comparison of the decapeptides reported here provides evidence for the role of specific C-(HO)-O-... hydrogen bonds in stabilizing chain reversals at helix termini, which may be relevant in aligning contiguous helical and strand segments in polypeptide structures.

Uniformly accelerated observer in Moyal spacetime

In Minkowski space, an accelerated reference frame may be defined as one that is related to an inertial frame by a sequence of instantaneous Lorentz transformations. Such an accelerated observer sees a causal horizon, and the quantum vacuum of the inertial observer appears thermal to the accelerated observer, also known as the Unruh effect. We argue that an accelerating frame may be similarly defined (i.e. as a sequence of instantaneous Lorentz transformations) in noncommutative Moyal spacetime, and discuss the twisted quantum field theory appropriate for such an accelerated observer. Our analysis shows that there are several new features in the case of noncommutative spacetime: chiral massless fields in (1 + 1) dimensions have a qualitatively different behavior compared to massive fields. In addition, the vacuum of the inertial observer is no longer an equilibrium thermal state of the accelerating observer, and the Bose-Einstein distribution acquires.-dependent corrections.

Structure, dielectric, and magnetic properties of Sr2TiMnO6 ceramics

Sr2TiMnO6, a double perovskite associated with high degree of B-site cation disorder was investigated in detail for its structural, magnetic, and dielectric properties. Though x-ray powder diffraction analysis confirms its cubic structure, first order Raman scattering and infrared reflectivity spectra indicate a breaking of the local cubic symmetry. The magnetization study reveals an anomaly at 14 K owing to a ferrimagnetic/canted antiferromagneticlike ordering arising from local Mn-O-Mn clusters. Saturated M-H hysteresis loops obtained at 5 K also reflect the weak ferromagnetic exchange interactions present in the system and an approximate estimation of Mn3+/Mn4+ was done using the magnetization data for the samples sintered at different temperatures. The conductivity and dielectric behavior of this system has been investigated in a broad temperature range of 10 to 300 K. Intrinsic permittivity was obtained only below 100 K whereas giant permittivity due to conductivity and Maxwell-Wagner polarization was observed at higher temperatures. X-ray photoemission studies further confirmed the presence of mixed oxidation states of Mn and the valence band spectra analysis was carried out in detail. (C) 2010 American Institute of Physics. doi: 10.1063/1.3500369]

Visualization of enantiomers and determination of homo- and hetero-nuclear residual dipolar and scalar couplings: The natural abundant C-13 edited J/D-resolved NMR techniques

The simple two dimensional C-13-satellite J/D-resolved experiments have been proposed for the visualization of enantiomers, extraction of homo- and hetero-nuclear residual dipolar couplings and also H-1 chemical shift differences between the enantiomers in the anisotropic medium. The significant advantages of the techniques are in the determination of scalar couplings of bigger organic molecules. The scalar couplings specific to a second abundant spin such as F-19 can be selectively extracted from the severely overlapped spectrum. The methodologies are demonstrated on a chiral molecule aligned in the chiral liquid crystal medium and two different organic molecules in the isotropic solutions. (C) 2010 Elsevier B.V. All rights reserved.

Critical phenomena in electrical resistance of binary liquids: A study of the frequency dependence

The electrical resistance is measured in two binary liquid systems CS2 + CH3NO2 and n-C7H16 + CH3OH in the critical region as a function of frequency from 10 Hz to 100 kHz. The critical exponent b ≈ 0.35 in the singularity of dR/dT α (T - Tc)−b near Tc has no appreciable dependence upon the frequency. Thus any contribution from dielectric dispersion to the critical resistivity is not appreciable. The universal behaviour of the dR/dT anomaly does not seem to be followed in binary liquid systems.

Dielectric relaxation in bismuth layer-structured BaBi4Ti4O15 ferroelectric ceramics

The dielectric properties of BaBi4Ti4O15 ceramics were investigated as a function of frequency (10(2)-10(6) Hz) at various temperatures (30 degrees C-470 degrees C), covering the phase transition temperature. Two different conduction mechanisms were obtained by fitting the complex impedance data to Cole-Cole equation. The grain and grain boundary resistivities were found to follow the Arrhenius law associated with activation energies: E-g similar to 1.12 eV below T-m and E-g similar to 0.70 eV above T-m for the grain conduction; and E-gb similar to 0.93 eV below T-m and E-gb similar to 0.71 eV above T-m for the grain boundary conduction. Relaxation times extracted using imaginary part of complex impedance Z `'(omega) and modulus M `'(omega) were also found to follow the Arrhenius law and showed an anomaly around the phase transition temperature. The frequency dependence of conductivity was interpreted in terms of the jump relaxation model and was fitted to the double power law. (C) 2010 Elsevier B. V. All rights reserved.

Synthesis of Reduced Metabolites of Isoflavonoids, and their Enantiomeric Forms

Isoflavonoids are naturally occurring plant derived biochemicals, which act as phytoalexins. Isoflavonoids are of interest due to their estrogenic and other potential physiological properties, particularly in mammals that typically consume isoflavonoid rich nutrients such as soy and red clover. The literature review of this thesis mainly focuses on the reduced metabolites of hydroxy and/or methoxy substituted isoflavones with four groups: isoflavan-4-ols, isoflav-3-enes, isoflavans and α-methyldeoxybenzoins (1,2-diarylpropan-1-ones), which are all reduced metabolites of food derived isoflavones in mammals. Related isoflavan-4-ones are briefly discussed. Results of an extensive survey of the literature concerning the synthesis of polyhydroxy- or methoxysubstituted isoflavonoids and especially asymmetric approaches are discussed. The experimental section describes new synthetic methods to prepare polyphenolic reduced isoflavonoid structures such as isoflav-3-enes, isoflavan-4-ones, cis- and trans-isoflavan-4-ols, 1,2-diarylpropan-1-ones and isoflavans by various hydride reagents and hydrogenations. The specific reactivity differences of various hydride reagents toward isoflavonoids are discussed. The first enantioselective synthesis of natural (S)-(-)-equol and the opposite enantiomer (R)-(+)-equol is also described by the asymmetric iridium PHOX catalysed hydrogenation of isoflav-3-enes. Both of these equol enantiomers are found to possess biological activity in mammals due to estrogen receptor binding activity. The natural enantiomer prefers estrogen receptor β and the R-enantiomer prefers the estrogen receptor α. Also the precursor, isoflav-3-ene, is found to possess positive biological effects on mammals. In connection with the synthetic work, the (S)-(-)-equol was discovered from serum of ewes after isoflavone rich red clover feeding. The chiral HPLC method was developed to identify natural equol enantiomer for the first time in this species. The first synthesis of natural isoflavonoid (R)-(-)-angolensin and its enantiomer (S)-(+)-angolensin is desribed by the use of recyclable chiral auxiliaries (chiral pseudoephedrines). The method offers a general approach also to other natural polyphenolic 1,2-diarylpropan-1-ones and to further study isoflavonoid metabolism in human and other mammals. The absolute configurations of these new chiral isoflavonoid metabolites were determined by X-ray spectroscopy. Also thorough NMR and MS analysis of synthesised structures are presented.

Demixing of severely overlapped H-1 NMR resonances and interpretation of anomalous intensity pattern of dipolar coupled A(3) spins in a weakly aligning medium

We report a single C-13 spin edited selective proton-proton correlation experiment to decipher overcrowded 13C coupled proton NMR spectra of weakly dipolar coupled spin systems. The experiment unravels the masked C-13 satellites in proton spectrum and permits the measurement of one bond carbon-proton residual dipolar couplings in I3S and for each diastereotopic proton in I2S groups. It also provides all the possible homonuclear proton-proton residual couplings which are otherwise difficult to extract from the broad and featureless one dimensional H-1 spectrum, in addition to enantiodifferentiation in a chiral molecule. Employment of heteronuclear (C-13) decoupling in the evolution period results in complete demixing of overlapped signals from enantiomers. The observed anomalous intensity pattern in strongly dipolar coupled methyl protons in methyl selective correlation experiment has been interpreted using polarization operator formalism. (C) 2010 Elsevier Inc. All rights reserved.

Optimal explicit guidance of multistage launch vehicle along three-dimensional trajectory

Details of an efficient optimal closed-loop guidance algorithm for a three-dimensional launch are presented with simulation results. Two types of orbital injections, with either true anomaly or argument of perigee being free at injection, are considered. The resulting steering-angle profile under the assumption of uniform gravity lies in a canted plane which transforms a three-dimensional problem into an equivalent two-dimensional one. Effects of thrust are estimated using a series in a recursive way. Encke's method is used to predict the trajectory during powered flight and then to compute the changes due to actual gravity using two gravity-related vectors. Guidance parameters are evaluated using the linear differential correction method. Optimality of the algorithm is tested against a standard ground-based trajectory optimization package. The performance of the algorithm is tested for accuracy, robustness, and efficiency for a sun-synchronous mission involving guidance for a multistage vehicle that requires large pitch and yaw maneuver. To demonstrate applicability of the algorithm to a range of missions, injection into a geostationary transfer orbit is also considered. The performance of the present algorithm is found to be much better than others.

Gauge-invariant reformulation of theories with second-class constraints

Given a classical dynamical theory with second-class constraints, it is sometimes possible to construct another theory with first-class constraints, i.e., a gauge-invariant one, which is physically equivalent to the first theory. We identify some conditions under which this may be done, explaining the general principles and working out several examples. Field theoretic applications include the chiral Schwinger model and the non-linear sigma model. An interesting connection with the work of Faddeev and Shatashvili is pointed out.

The German Military Entrepreneur Ernst von Mansfeld and His Conduct of Asymmetrical Warfare in the Thirty Years War

The dissertation examines aspects of asymmetrical warfare in the war-making of the German military entrepreneur Ernst von Mansfeld during his involvement in the Thirty Years War. Due to the nature of the inquiry, which combines history with military-political theory, the methodological approach of the dissertation is interdisciplinary. The theoretical framework used is that of asymmetrical warfare. The primary sources used in the dissertation are mostly political pamphlets and newsletters. Other sources include letters, documents, and contemporaneous chronicles. The secondary sources are divided into two categories, literature on the history of the Thirty Years War and textbooks covering the theory of asymmetrical warfare. The first category includes biographical works on Ernst von Mansfeld, as well as general histories of the Thirty Years War and seventeenth-century warfare. The second category combines military theory and political science. The structure of the dissertation consists of eight lead chapters, including an introduction and conclusion. The introduction covers the theoretical approach and aims of the dissertation, and provides a brief overlook of the sources and previous research on Ernst von Mansfeld and asymmetrical warfare in the Thirty Years War. The second chapter covers aspects of Mansfeld s asymmetrical warfare from the perspective of operational art. The third chapter investigates the illegal and immoral aspects of Mansfeld s war-making. The fourth chapter compares the differing methods by which Mansfeld and his enemies raised and financed their armies. The fifth chapter investigates Mansfeld s involvement in indirect warfare. The sixth chapter presents Mansfeld as an object and an agent of image and information war. The seventh chapter looks into the counter-reactions, which Mansfeld s asymmetrical warfare provoked from his enemies. The eighth chapter offers a conclusion of the findings. The dissertation argues that asymmetrical warfare presented itself in all the aforementioned areas of Mansfeld s conduct during the Thirty Years War. The operational asymmetry arose from the freedom of movement that Mansfeld enjoyed, while his enemies were constrained by the limits of positional warfare. As a non-state operator Mansfeld was also free to flout the rules of seventeenth-century warfare, which his enemies could not do with equal ease. The raising and financing of military forces was another source of asymmetry, because the nature of early seventeenth-century warfare favoured private military entrepreneurs rather than embryonic fiscal-military states. The dissertation also argues that other powers fought their own asymmetrical and indirect wars against the Habsburgs through Mansfeld s agency. Image and information were asymmetrical weapons, which were both aimed against Mansfeld and utilized by him. Finally, Mansfeld s asymmetrical threat forced the Habsburgs to adapt to his methods, which ultimately lead to the formation of a subcontracted Imperial Army under the management and leadership of Albrecht von Wallenstein. Therefore Mansfeld s asymmetrical warfare ultimately paved way for the kind of state-monopolized, organised, and symmetrical warfare that has prevailed from 1648 onwards. The conclusion is that Mansfeld s conduct in the Thirty Years War matched the criteria for asymmetrical warfare. While traditional historiography treated Mansfeld as an anomaly in the age of European state formation, his asymmetrical warfare has begun to bear resemblance to the contemporary conflicts, where nation states no longer hold the monopoly of violence.

Aperiodic Variability in the Cane-Zebiak Model: A Diagnostic Study

The finite predictability of the coupled ocean-atmosphere system is determined by its aperiodic variability. To gain insight regarding the predictability of such a system, a series of diagnostic studies has been carried out to investigate the role of convergence feedback in producing the aperiodic behavior of the standard version of the Cane-Zebiak model. In this model, an increase in sea surface temperature (SST) increases atmospheric heating by enhancing local evaporation (SST anomaly feedback) and low-level convergence (convergence feedback). The convergence feedback is a nonlinear function of the background mean convergence field. For the set of standard parameters used in the model, it is shown that the convergence feedback contributes importantly to the aperiodic behaviour of the model. As the strength of the convergence feedback is increased from zero to its standard value, the model variability goes from a periodic regime to an aperiodic regime through a broadening of the frequency spectrum around the basic periodicity of about 4 years. Examination of the forcing associated with the convergence feedback reveals that it is intermittent, with relatively large amplitude only during 2 or 3 months in the early part of the calendar year. This seasonality in the efficiency of the convergence feedback is related to the strong seasonality of the mean convergence over the eastern Pacific. It is shown that if the mean convergence field is fixed at its March value, aperiodic behavior is produced even in the absence of annual cycles in the other mean fields. On the, other hand, if the mean convergence field is fixed at its September value, the coupled model evolution remains close to periodic, even in the presence of the annual cycle in the other fields. The role of convergence feedback on the aperiodic variability of the model for other parameter regimes is also examined. It is shown that a range exists in the strength of the SST anomaly feedback for which the model variability is aperiodic even without the convergence feedback. It appears that in the absence of convergence feedback, enhancement of the strength of the air-sea coupling in the model through other physical processes also results in aperiodicity in the model.