Simultaneous Detection of Two Triplets: A Time-Resolved Resonance Raman Study

Solvents are known to affect the triplet state structure and reactivity. In this paper, we have employed time-resolved resonance Raman (TR3) spectroscopy to understand solvent-induced subtle structural changes in the lowest excited triplet state of thioxanthone. Density functional theory (DFT) combined with the self-consistent reaction field (SCRF) implicit solvation model has been used to calculate the vibrational frequencies in the solvents. Here, we report a unique observation of the coexistence of two triplets, which has been substantiated by the probe wavelength-dependent Raman experiments. The coexistence of two triplets has been further supported by photoreduction experiments carried out at various temperatures.

Predatory Fish Select for Coordinated Collective Motion in Virtual Prey

Movement in animal groups is highly varied and ranges from seemingly disordered motion in swarms to coordinated aligned motion in flocks and schools. These social interactions are often thought to reduce risk from predators, despite a lack of direct evidence. We investigated risk-related selection for collective motion by allowing real predators ( bluegill sunfish) to hunt mobile virtual prey. By fusing simulated and real animal behavior, we isolated predator effects while controlling for confounding factors. Prey with a tendency to be attracted toward, and to align direction of travel with, near neighbors tended to form mobile coordinated groups and were rarely attacked. These results demonstrate that collective motion could evolve as a response to predation, without prey being able to detect and respond to predators.

Albedo enhancement over land to counteract global warming: impacts on hydrological cycle

A recent modelling study has shown that precipitation and runoff over land would increase when the reflectivity of marine clouds is increased to counter global warming. This implies that large scale albedo enhancement over land could lead to a decrease in runoff over land. In this study, we perform simulations using NCAR CAM3.1 that have implications for Solar Radiation Management geoengineering schemes that increase the albedo over land. We find that an increase in reflectivity over land that mitigates the global mean warming from a doubling of CO2 leads to a large residual warming in the southern hemisphere and cooling in the northern hemisphere since most of the land is located in northern hemisphere. Precipitation and runoff over land decrease by 13.4 and 22.3%, respectively, because of a large residual sinking motion over land triggered by albedo enhancement over land. Soil water content also declines when albedo over land is enhanced. The simulated magnitude of hydrological changes over land are much larger when compared to changes over oceans in the recent marine cloud albedo enhancement study since the radiative forcing over land needed (-8.2 W m(-2)) to counter global mean radiative forcing from a doubling of CO2 (3.3 W m(-2)) is approximately twice the forcing needed over the oceans (-4.2 W m(-2)). Our results imply that albedo enhancement over oceans produce climates closer to the unperturbed climate state than do albedo changes on land when the consequences on land hydrology are considered. Our study also has important implications for any intentional or unintentional large scale changes in land surface albedo such as deforestation/afforestation/reforestation, air pollution, and desert and urban albedo modification.

Directional motion of impacting drops on dual-textured surfaces

In this work, we analyze the directional movement of impacting liquid drops on dual-textured solid surfaces comprising two different surface morphologies: a textured surface and a smooth surface. The dynamics of liquid drops impacting onto the junction line between the two parts of the dual-textured surfaces is studied experimentally for varying drop impact velocity. The dual-textured surfaces used here featured a variation in their textures' geometrical parameters as well as their surface chemistry. Two types of liquid drop differing in their surface tension were used. The impact process develops a net horizontal drop velocity towards the higher-wettability surface portion and results in a bulk movement of the impacting drop liquid. The final distance moved by the impacting drop from the junction line decreases with increasing impacting drop Weber number We. A fully theoretical model, employing a balance of forces acting at the drop contact line as well as energy conservation, is formulated to determine the variation, with We, of net horizontal drop velocity and subsequent movement of the impacting drop on the dual-textured surfaces.

Ex Situ X-ray Diffraction, X-ray Absorption Near Edge Structure, Electron Spin Resonance, and Transmission Electron Microscopy Study of the Hydrothermal Crystallization of Vanadium Oxide Nanotubes: An Insight into the Mechanism of Formation

The nucleation and growth of vanadium oxide nanotubes (VOx-NT) have been followed by a combination of numerous ex situ techniques. long the hydrothermal process. Intermediate solid phases extracted at different reaction times have been characterized by powder X-ray diffraction, scanning and transmission electron microscopy, electron spin resonance, and V-K edge :X-ray absorption near-edge structure spectroscopy. The supernatant vanadate solutions extracted during the hydrothermal treatment have been studied by liquid V-51 NMR and flame. spectroscopy. For short durations of the hydrothermal synthesis, the initial V2O5-surfactant intercalate. is progressively transformed into VOx-NT whose crystallization starts to be detected after a hydrothermal treatment of 24 h. Upon heating from 24 h to 7 days, VOx-NT are obtained in larger amount and with an improved crystallinity. The detection of soluble amines and cyclic metavanadate V4O12](4-) in the supernatant solution along the hydrothermal process suggests that VOx-NT result from a dissolution precipitation mechanism. Metavanadate species V4O12](4-) could behave as molecular precursors in the polymerization reactions leading to VOx-NT.

Subdiffusion in hair bundle dynamics: The role of protein conformational fluctuations

The detection of sound signals in vertebrates involves a complex network of different mechano-sensory elements in the inner ear. An especially important element in this network is the hair bundle, an antenna-like array of stereocilia containing gated ion channels that operate under the control of one or more adaptation motors. Deflections of the hair bundle by sound vibrations or thermal fluctuations transiently open the ion channels, allowing the flow of ions through them, and producing an electrical signal in the process, eventually causing the sensation of hearing. Recent high frequency (0.1-10 kHz) measurements by Kozlov et al. Proc. Natl. Acad. Sci. U. S. A. 109, 2896 (2012)] of the power spectrum and the mean square displacement of the thermal fluctuations of the hair bundle suggest that in this regime the dynamics of the hair bundle are subdiffusive. This finding has been explained in terms of the simple Brownian motion of a filament connecting neighboring stereocilia (the tip link), which is modeled as a viscoelastic spring. In the present paper, the diffusive anomalies of the hair bundle are ascribed to tip link fluctuations that evolve by fractional Brownian motion, which originates in fractional Gaussian noise and is characterized by a power law memory. The predictions of this model for the power spectrum of the hair bundle and its mean square displacement are consistent with the experimental data and the known properties of the tip link. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4768902]

The Coil-to-Helix Transition in IlvN Regulates the Allosteric Control of Escherichia coli Acetohydroxyacid Synthase I

The solution structure of IlvN, the regulatory subunit of Escherichia coil acetohydroxyacid synthase I, in the valine-bound form has been determined using high-resolution multidimensional, multinuclear nuclear magnetic resonance (NMR) methods. IlvN in the presence or absence of the effector molecule is present as a 22.5 kDa dimeric molecule. The ensemble of 20 low-energy structures shows a backbone root-mean-square deviation of 0.73 +/- 0.13 angstrom and a root-mean-square deviation of 1.16 +/- 0.13 angstrom for all heavy atoms. Furthermore, more than 98% of the backbone phi and psi dihedral angles occupy the allowed and additionally allowed regions of the Ramachandran map, which is indicative of the fact that the structures are of high stereochemical quality. Each protomer exhibits a beta alpha beta beta alpha beta alpha topology that is a characteristic feature of the ACT domain seen in metabolic enzymes. In the valine-bound form, IlvN exists apparently as a single conformer. In the free form, IlvN exists as a mixture of conformational states that are in intermediate exchange on the NMR time scale. Thus, a large shift in the conformational equilibrium is observed upon going from the free form to the bound form. The structure of the valine-bound form of IlvN was found to be similar to that of the ACT domain of the unliganded form of IlvH. Comparisons of the structures of the unliganded forms of these proteins suggest significant differences. The structural and conformational properties of IlvN determined here have allowed a better understanding of the mechanism of regulation of branched chain amino acid biosynthesis.

Minimum power consumption for drag reduction on a circular cylinder by tangential surface motion

We investigate the effect of a prescribed tangential velocity on the drag force on a circular cylinder in a spanwise uniform cross flow. Using a combination of theoretical and numerical techniques we make an attempt at determining the optimal tangential velocity profiles which will reduce the drag force acting on the cylindrical body while minimizing the net power consumption characterized through a non-dimensional power loss coefficient (C-PL). A striking conclusion of our analysis is that the tangential velocity associated with the potential flow, which completely suppresses the drag force, is not optimal for both small and large, but finite Reynolds number. When inertial effects are negligible (R e << 1), theoretical analysis based on two-dimensional Oseen equations gives us the optimal tangential velocity profile which leads to energetically efficient drag reduction. Furthermore, in the limit of zero Reynolds number (Re -> 0), minimum power loss is achieved for a tangential velocity profile corresponding to a shear-free perfect slip boundary. At finite Re, results from numerical simulations indicate that perfect slip is not optimum and a further reduction in drag can be achieved for reduced power consumption. A gradual increase in the strength of a tangential velocity which involves only the first reflectionally symmetric mode leads to a monotonic reduction in drag and eventual thrust production. Simulations reveal the existence of an optimal strength for which the power consumption attains a minima. At a Reynolds number of 100, minimum value of the power loss coefficient (C-PL = 0.37) is obtained when the maximum in tangential surface velocity is about one and a half times the free stream uniform velocity corresponding to a percentage drag reduction of approximately 77 %; C-PL = 0.42 and 0.50 for perfect slip and potential flow cases, respectively. Our results suggest that potential flow tangential velocity enables energetically efficient propulsion at all Reynolds numbers but optimal drag reduction only for Re -> infinity. The two-dimensional strategy of reducing drag while minimizing net power consumption is shown to be effective in three dimensions via numerical simulation of flow past an infinite circular cylinder at a Reynolds number of 300. Finally a strategy of reducing drag, suitable for practical implementation and amenable to experimental testing, through piecewise constant tangential velocities distributed along the cylinder periphery is proposed and analysed.

Effect of chlorine substitution on triplet state structure of thioxanthone: A time-resolved resonance Raman study

Substitution plays an important role in determining the triplet state reactivity. In this paper, we have studied the effect of chlorine substitution on the triplet state structure and the reactivity of thioxanthone (TX). We have employed time-resolved resonance Raman technique to understand the structure of the lowest triplet excited state of 2-chlorothioxanthone (CTX). The experimental findings have been corroborated with the computational results using density functional theory. Akin to the parent compound (TX), coexistence of two lowest triplet states has been observed in case of CTX, which has been substantiated using resonant probe wavelength dependence study. The relative contribution of 3n-pi* to 3 pi-pi* to the equilibrated triplet state has been found to be more for CTX compared to TX suggesting increase in the triplet state reactivity after the substitution. The above observation has been further supported by the flash photolysis experiments. Copyright (C) 2013 John Wiley & Sons, Ltd.

Asymptotics of the invariant measure in mean field models with jumps

We consider the asymptotics of the invariant measure for the process of spatial distribution of N coupled Markov chains in the limit of a large number of chains. Each chain reflects the stochastic evolution of one particle. The chains are coupled through the dependence of transition rates on the spatial distribution of particles in the various states. Our model is a caricature for medium access interactions in wireless local area networks. Our model is also applicable in the study of spread of epidemics in a network. The limiting process satisfies a deterministic ordinary differential equation called the McKean-Vlasov equation. When this differential equation has a unique globally asymptotically stable equilibrium, the spatial distribution converges weakly to this equilibrium. Using a control-theoretic approach, we examine the question of a large deviation from this equilibrium.

Automatic road extraction using high resolution satellite images based on Level Set and Mean Shift methods

Analysis of high resolution satellite images has been an important research topic for urban analysis. One of the important features of urban areas in urban analysis is the automatic road network extraction. Two approaches for road extraction based on Level Set and Mean Shift methods are proposed. From an original image it is difficult and computationally expensive to extract roads due to presences of other road-like features with straight edges. The image is preprocessed to improve the tolerance by reducing the noise (the buildings, parking lots, vegetation regions and other open spaces) and roads are first extracted as elongated regions, nonlinear noise segments are removed using a median filter (based on the fact that road networks constitute large number of small linear structures). Then road extraction is performed using Level Set and Mean Shift method. Finally the accuracy for the road extracted images is evaluated based on quality measures. The 1m resolution IKONOS data has been used for the experiment.

Motion segmentation using curve fitting on Lagrangian particle trajectories

In this paper we present a segmentation algorithm to extract foreground object motion in a moving camera scenario without any preprocessing step such as tracking selected features, video alignment, or foreground segmentation. By viewing it as a curve fitting problem on advected particle trajectories, we use RANSAC to find the polynomial that best fits the camera motion and identify all trajectories that correspond to the camera motion. The remaining trajectories are those due to the foreground motion. By using the superposition principle, we subtract the motion due to camera from foreground trajectories and obtain the true object-induced trajectories. We show that our method performs on par with state-of-the-art technique, with an execution time speed-up of 10x-40x. We compare the results on real-world datasets such as UCF-ARG, UCF Sports and Liris-HARL. We further show that it can be used toper-form video alignment.

Electronic energy transfer between long-range resonance states of 3-mercaptopropionic acid capped CdTe quantum dots in aqueous media

We demonstrate electronic energy transfer between resonance states of 2 and 2.8 nm CdTe quantum dots in aqueous media using steady-state photoluminescence spectroscopy without using any external linker molecule. With increasing concentration of larger dots, there is subsequent quenching of luminescence in smaller dots accompanied by the enhancement of luminescence in larger dots. Our experimental evidence suggests that there is long-range resonance energy transfer among electronic excitations, specifically from the electronically confined states of the smaller dots to the higher excited states of the larger dots.

Electron paramagnetic resonance, magnetic and electrical properties of CoFe2O4 nanoparticles

CoFe2O4 nanoparticles were prepared by solution combustion method. The nanoparticle are characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). PXRD reveals single phase, cubic spinel structure with Fd (3) over barm (227) space group. SEM micrograph shows the particles are agglomerated and porous in nature. Electron paramagnetic resonance spectrum exhibits a broad resonance signal g=2.150 and is attributed to super exchange between Fe3+ and Co2+. Magnetization values of CoFe2O4 nanoparticle are lower when compared to the literature values of bulk samples. This can be attributed to the surface spin canting due to large surface-to-volume ratio for a nanoscale system. The variation of dielectric constant, dielectric loss, loss tangent and AC conductivity of as-synthesized nano CoFe2O4 particles at room temperature as a function of frequency has been studied. The magnetic and dielectric properties of the samples show that they are suitable for electronic and biomedical applications.