The unusual formation of methyl alpha-(5,6-dimethoxycarbonyl-2,3-dimethoxyazepin-7-ylidene)-alpha-[5-methoxycarbonyl-2,3-dimethoxypyrid-6-yl)acetate during the pyrolysis of ''azido-meta-hemipinate'' - First example of a reaction involving a concomitant ring expansion and ring extrusion

he ortho methoxycarbonyl substituent constitutes a sole exception in the ring closure reactions of ortho substituted aryl azides, as it provides no rate acceleration to this reaction. Pyrolysis of ''azido-meta-hemipinate'', an aryl azide containing such a substituent, led us to the title compound, a new azepinylidenepyridylacetic ester, whose structure has been established unambiguously by a single crystal X-ray diffraction study. This is the first report of a reaction involving both a ring expansion to an azaheptafulvalene and a ring extrusion to a pyridyl ring residue.

DNA targeting polyaza macrobicyclic dizinc(II) complexes promoting high in vitro caspase dependent anti-proliferative activity against human carcinoma cancer cells

A series of macrobicyclic dizinc(II) complexes Zn2L1-2B](ClO4)(4) (1-6) have been synthesized and characterized (L1-2 are polyaza macrobicyclic binucleating ligands, and B is the N,N-donor heterocyclic base (viz. 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)). The DNA and protein binding, DNA hydrolysis and anticancer activity of these complexes were investigated. The interactions of complexes 1-6 with calf thymus DNA were studied by spectroscopic techniques, including absorption, fluorescence and CD spectroscopy. The DNA binding constant values of the complexes were found to range from 2.80 x 10(5) to 5.25 x 10(5) M-1, and the binding affinities are in the following order: 3 > 6 > 2 > 5 > 1 > 4. All the dizinc(II) complexes 1-6 are found to effectively promote the hydrolytic cleavage of plasmid pBR322 DNA under anaerobic and aerobic conditions. Kinetic data for DNA hydrolysis promoted by 3 and 6 under physiological conditions give observed rate constants (k(obs)) of 5.56 +/- 0.1 and 5.12 +/- 0.2 h(-1), respectively, showing a 10(7)-fold rate acceleration over the uncatalyzed reaction of dsDNA. Remarkably, the macrobicyclic dizinc(II) complexes 1-6 bind and cleave bovine serum albumin (BSA), and effectively promote the caspase-3 and caspase-9 dependent deaths of HeLa and BeWo cancer cells. The cytotoxicity of the complexes was further confirmed by lactate dehydrogenase enzyme levels in cancer cell lysate and content media.

DNA and protein targeting 1,2,4-triazole based water soluble dinickel(II) complexes enhances antiproliferation and lactate dehydrogenase inhibition

Water soluble dinickel(II) complexes Ni-2(L)(2)(1-2)](NO3)(4) (1-2), where L1-2 are triazole based dinucleating ligands, were synthesized and characterized. The DNA binding, protein binding, DNA hydrolysis and anticancer properties were investigated. The interactions of complexes 1 and 2 with calf thymus DNA were studied by spectroscopic techniques, including absorption and fluorescence spectroscopy. The DNA binding constant values of the complexes 1 and 2 were found to be 2.36 x 10(5) and 4.87 x 10(5) M-1 and the binding affinities are in the following order: 2 > 1. Both the dinickel(II) complexes 1 and 2, promoted the hydrolytic cleavage of plasmid pBR322 DNA under both anaerobic and aerobic conditions. Kinetic data for DNA hydrolysis promoted by 1 and 2 under physiological conditions give the observed rate constants (k(obs)) of 5.05 +/- 0.2 and 5.65 +/- 0.1 h(-1), respectively, which shows 10(8)-fold rate acceleration over the uncatalyzed reaction of ds-DNA. Meanwhile, the interactions of the complex with BSA have also been studied by spectroscopy. Both the complexes 1 and 2 display strong binding propensity and the binding constant (K-b), number of binding sites (n) were obtained are 0.71 x 10(6) 1.47] and 5.62 x 10(6) 1.98] M-1, respectively. The complexes 1 and 2 also promoted the apoptosis against human carcinoma (HeLa, and BeWo) cancer cells. Cytotoxicity of the complexes was further confirmed by lactate dehydrogenase enzyme level in cancer cell lysate and content media. (c) 2013 Elsevier Ltd. All rights reserved.

Effects of Ultrafast Solvation on the Rate of Adiabatic Outer-Sphere Electron Transfer Reactions

Recent studies have demonstrated that solvation dynamics in many common dipolar liquids contain an initial, ultrafast Gaussian component which may contribute even more than 60% to the total solvation energy. It is also known that adiabatic electron transfer reactions often probe the high-frequency components of the relevant solvent friction (Hynes, J. T. J. Phys. Chem. 1986, 90, 3701). In this paper, we present a theoretical study of the effects of the ultrafast solvent polar modes on the adiabatic electron transfer reactions by using the formalism of Hynes. Calculations have been carried out for a model system and also for water and acetonitrile. It is found that, in general, the ultrafast modes can greatly enhance the rate of electron transfer, even by more than an order of magnitude, over the rate obtained by using only the slow overdamped modes usually considered. For water, this acceleration of the rate can be attributed to the high-frequency intermolecular vibrational and librational modes. For a weakly adiabatic reaction, the rate is virtually indistinguishable from the rate predicted by the Marcus transition state theory. Another important result is that even in this case of ultrafast underdamped solvation, energy diffusion appears to be efficient so that electron transfer reaction in water is controlled essentially by the barrier crossing dynamics. This is because the reactant well frequency is-directly proportional to the rate of the initial Gaussian decay of the solvation time correlation function. As a result, the value of the friction at the reactant well frequency rarely falls below the value required for the Kramers turnover except when the polarizability of the water molecules may be neglected. On the other hand, in acetonitrile, the rate of electron transfer reaction is found to be controlled by the energy diffusion dynamics, although a significant contribution to the rate comes also from the barrier crossing rate. Therefore, the present study calls for a need to understand the relaxation of the high-frequency modes in dipolar liquids.

State estimation of spiralling target using UKF with generalized sinusoidal target acceleration model

Hit-to-kill interception of high velocity spiraling target requires accurate state estimation of relative kinematic parameters describing spiralling motion. In this pa- per, spiraling target motion is captured by representing target acceleration through sinusoidal function in inertial frame. A nine state unscented Kalman filter (UKF) formulation is presented here with three relative positions, three relative velocities, spiraling frequency of target, inverse of ballistic coefficient and maneuvering coef-ficient. A key advantage of the target model presented here is that it is of generic nature and can capture spiraling as well as pure ballistic motions without any change of tuning parameters. Extensive Six-DOF simulation experiments, which includes a modified PN guidance and dynamic inversion based autopilot, show that near Hit-to-Kill performance can be obtained with noisy RF seeker measurements of gimbal angles, gimbal angle rates, range and range rate.

Slow Slip Acceleration beneath Andaman Islands Triggered by the 11 April 2012 Indian Ocean Earthquakes

The M-w 8.6 and 8.2 strike-slip earthquakes that struck the northeast Indian Ocean on 11 April 2012 resulted in coseismic deformation both at near and distant sites. The slip distribution, deduced using seismic-wave analysis for the orthogonal faults that ruptured during these earthquakes, is sufficient to predict the coseismic displacements at the Global Positioning System (GPS) sites, such as NTUS, PALK, and CUSV, but fall short at four continuous sites in the Andaman Islands region. Slip modeling, for times prior to the events, suggests that the lower portion of the thrust fault beneath the Andaman Islands has been slipping at least at the rate of 40 cm/yr, in response to the 2004 Sumatra-Andaman coseismic stress change. Modeling of GPS displacements suggests that the en echelon and orthogonal fault ruptures of the 2012 intraplate oceanic earthquakes could have possibly accelerated the ongoing slow slip, along the lower portion of the thrust fault beneath the islands with a month-long slip of 4-10 cm. The misfit to the coseismic GPS displacements along the Andaman Islands could be improved with a better source model, assuming that no local process contributed to this anomaly.

Probabilistic seismic hazard analysis for Bangalore

This article presents the results of probabilistic seismic hazard analysis (PSHA) for Bangalore, South India. Analyses have been carried out considering the seismotectonic parameters of the region covering a radius of 350 km keeping Bangalore as the center. Seismic hazard parameter `b' has been evaluated considering the available earthquake data using (1) Gutenberg-Richter (G-R) relationship and (2) Kijko and Sellevoll (1989, 1992) method utilizing extreme and complete catalogs. The `b' parameter was estimated to be 0.62 to 0.98 from G-R relation and 0.87 +/- A 0.03 from Kijko and Sellevoll method. The results obtained are a little higher than the `b' values published earlier for southern India. Further, probabilistic seismic hazard analysis for Bangalore region has been carried out considering six seismogenic sources. From the analysis, mean annual rate of exceedance and cumulative probability hazard curve for peak ground acceleration (PGA) and spectral acceleration (Sa) have been generated. The quantified hazard values in terms of the rock level peak ground acceleration (PGA) are mapped for 10% probability of exceedance in 50 years on a grid size of 0.5 km x 0.5 km. In addition, Uniform Hazard Response Spectrum (UHRS) at rock level is also developed for the 5% damping corresponding to 10% probability of exceedance in 50 years. The peak ground acceleration (PGA) value of 0.121 g obtained from the present investigation is slightly lower (but comparable) than the PGA values obtained from the deterministic seismic hazard analysis (DSHA) for the same area. However, the PGA value obtained in the current investigation is higher than PGA values reported in the global seismic hazard assessment program (GSHAP) maps of Bhatia et al. (1999) for the shield area.

Free Energy Gap Dependence of the Electron-Transfer Rate from the Inverted to the Normal Region

numerical study of the free energy gap (FEG) dependence of the electron-transfer rate in polar solvents is presented. This study is based on the generalized multidimensional hybrid model, which not only includes the solvent polarization and the molecular vibration modes, but also the biphasic polar response of the solvent. The free energy gap dependence is found to be sensitive to several factors, including the solvent relaxation rate, the electronic coupling between the surfaces, the frequency of the high-frequency quantum vibrational mode, and the magnitude of the solvent reorganization energy. It is shown that in some cases solvent relaxation can play an important role even in the Marcus normal regime. The minimal hybrid model involves a large number of parameters, giving rise to a diverse non-Marcus FEG behavior which is often determined collectively by these parameters. The model gives the linear free energy gap dependence of the logarithmic rate over a substantial range of FEG, spanning from the normal to the inverted regime. However, even for favorable values of the relevant parameters, a linear free energy gap dependence of the rate could be obtained only over a range of 5000-6000 cm(-1) (compared to the experimentally observed range of 10000 cm(-1) reported by Benniston et al.). The present work suggests several extensions/generalizations of the hybrid model which might be necessary to fully understand the observed free energy gap dependence.

Optimal barrier subdivision for Kramers' escape rate

We examine the effect of subdividing the potential barrier along the reaction coordinate on Kramers' escape rate for a model potential. Using the known supersymmetric potential approach, we show the existence of an optimal number of subdivisions that maximizes the rate.

Oxygen transfer and energy dissipation rate in surface aerator

The dissipation rate of turbulent kinetic energy (epsilon) is a key parameter for mixing in surface aerators. In particular, determination epsilon across the impeller stream, where the most intensive mixing takes place, is essential to ascertain that an appropriate degree of mixing is achieved. Present work by using commercial software VisiMix (R) calculates the energy dissipation rate in geometrically similar unbaffled surface aeration systems in order to scale-up the oxygen transfer process. It is found that in geometrically similar system, oxygen transfer rate is uniquely correlated with dissipation rate of energy. Simulation or scale-up equation governing oxygen transfer rate and dissipation rate of energy has been developed in the present work.

Oxygen transfer and energy dissipation rate in surface aerator

The dissipation rate of turbulent kinetic energy(e)is a key parameter for mixing in surface aerators. In particular, determination e across the impeller stream, where the most intensive mixing takes place, is essential to ascertain that an appropriate degree of mixing is achieved. Present work by using commercial software VisiMix calculates the energy dissipation rate in geometrically similar unbaffled surface aeration systems in order to scale-up the oxygen transfer process. It is found that in geometrically similar system,oxygen transfer rate is uniquely correlated with dissipation rate of energy. Simulation or scale-up equation governing oxygen transfer rate and dissipation rate of energy has been developed in the present work.

Synergy between tribo-oxidation and strain rate response on governing the dry sliding wear behavior of titanium.

The present work provides an insight into the dry sliding wear behavior of titanium based on synergy between tribo-oxidation and strain rate response. Pin-on-disc tribometer was used to characterize the friction and wear behavior of titanium pin in sliding contact with polycrystalline alumina disk under ambient and vacuum condition. The sliding speed was varied from 0.01 to 1.4 ms(-1), normal load was varied from 15.3 to 76 N and with a sliding distance of 1500 m. It was seen that dry sliding wear behavior of titanium was governed by combination of tribo-oxidation and strain rate response in near surface region of titanium. Strain rate response of titanium was recorded by conducting uni-axial compression tests at constant true strain rate of 100 s(-1) in the temperature range from 298 to 873 K. Coefficient of friction and wear rate were reduced with increased sliding speed from 0.01 to 1.0 ms(-1). This is attributed to the formation of in situ self lubricating oxide film (TiO) and reduction in the intensity of adiabatic shear band cracking in the near surface region. This trend was confirmed by performing series of dry sliding tests under vacuum condition of 2 x 10(-4) Torr. Characterization tools such as optical microscopy, scanning electron microscopy, and X-ray diffractometer provided evidence of such processes. These experimental findings can be applied to enhance the dry sliding wear behavior of titanium with proper choice of operating conditions such as sliding speed, normal load, and environment.

Influence of clofibrate administration on the rate of synthesis of macromolecules in regenerating rat liver

Administration of the antihypercholesterolaemic drug clofibrate stimulates the rates of synthesis of nucleic acids and proteins in rat liver. The biosynthesis of mitochondrial proteins also is enhanced by the drug. In drug-fed animals, the rates of incorporation in vivo of radioactive precursors into DNA, RNA and proteins are stimulated even when the liver undergoes regeneration following partial hepatectomy. The rate of synthesis of mitochondrial proteins in the regenerative phase is higher in clofibrate-fed animals. These effects are consistent with the hepatomegalic and mitochondria-proliferating property of the drug.

Extrapolation and series acceleration procedures: Hard spheres and discs as illustrations

Three new procedures - in the context of estimation of virial coefficients and summation of the partial virial series for hard discs and hard spheres - are proposed. They are based on the parametrised Euler transformation, a novel resummation, identity and the ε-convergence methods respectively. A comparison with other estimates (molecular dynamics, graph theory and empirical methods) reveals satisfactory agreement.

Systematic Construction of Linear Transform Based Full-Diversity, Rate-One Space-Time Frequency Codes

In this paper, we generalize the existing rate-one space frequency (SF) and space-time frequency (STF) code constructions. The objective of this exercise is to provide a systematic design of full-diversity STF codes with high coding gain. Under this generalization, STF codes are formulated as linear transformations of data. Conditions on these linear transforms are then derived so that the resulting STF codes achieve full diversity and high coding gain with a moderate decoding complexity. Many of these conditions involve channel parameters like delay profile (DP) and temporal correlation. When these quantities are not available at the transmitter, design of codes that exploit full diversity on channels with arbitrary DIP and temporal correlation is considered. Complete characterization of a class of such robust codes is provided and their bit error rate (BER) performance is evaluated. On the other hand, when channel DIP and temporal correlation are available at the transmitter, linear transforms are optimized to maximize the coding gain of full-diversity STF codes. BER performance of such optimized codes is shown to be better than those of existing codes.