Temperature-Induced Reversible First-Order Single Crystal to Single Crystal Phase Transition in Boc-gamma(4)(R)Val-Val-OH: Interplay of Enthalpy and Entropy

Crystals of Boc-gamma y(4)(R)Val-Val-OH undergo a reversible first-order single crystal to single crystal phase transition at T-c approximate to 205 K from the orthorhombic space group P22(1)2(1) (Z' = 1) to the monoclinic space group P2(1) (Z' = 2) with a hysteresis of similar to 2.1 K. The low-temperature monoclinic form is best described as a nonmerohedral twin with similar to 50% contributions from its two components. The thermal behavior of the dipeptide crystals was characterized by differential scanning calorimetry experiments. Visual changes in birefringence of the sample during heating and cooling cycles on a hot-stage microscope with polarized light supported the phase transition. Variable-temperature unit cell check measurements from 300 to 100 K showed discontinuity in the volume and cell parameters near the transition temperature, supporting the first-order behavior. A detailed comparison of the room-temperature orthorhombic form with the low-temperature (100 K) monoclinic form revealed that the strong hydrogen-bonding motif is retained in both crystal systems, whereas the non-covalent interactions involving side chains of the dipeptide differ significantly, leading to a small change in molecular conformation in the monoclinic form as well as a small reorientation of the molecules along the ac plane. A rigid-body thermal motion analysis (translation, libration, screw; correlation of translation and libration) was performed to study the crystal entropy. The reversible nature of the phase transition is probably the result of an interplay between enthalpy and entropy: the low-temperature monoclinic form is enthalpically favored, whereas the room-temperature orthorhombic form is entropically favored.

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

Two novel triads based on a diketopyrrolopyrrole (DPP) central core and two 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) units attached by thiophene rings have been synthesised having high molar extinction coefficients. These triads were characterised and used as donor materials in small molecule, solution processable organic solar cells. Both triads were blended with PC71BM as an acceptor in different ratios by wt% and their photovoltaic properties were studied. For both the triads a modest photovoltaic performance was observed, having an efficiency of 0.65%. Moreover, in order to understand the ground and excited state properties and vertical absorption profile of DPP and BODIPY units within the triads, theoretical DFT and TDDFT calculations were performed.

An island called India: phylogenetic patterns across multiple taxonomic groups reveal endemic radiations

Island systems from around the world have provided fascinating opportunities for studies pertaining to various evolutionary processes. One recurring feature of isolated islands is the presence of endemic radiations. In this regard, the Indian subcontinent is an interesting entity given it has been an island during much of its history following separation from Madagascar and currently is isolated from much of Eurasia by the Himalayas in the north and the Indian Ocean in the south. Not surprisingly, recent molecular studies on a number of endemic taxa from India have reported endemic radiations. These studies suggest that the uniqueness of Indian biota is not just due to its diverse origin, but also due to evolution in isolation. The isolation of India has generated some peculiarities typically seen on oceanic islands. However, these patterns might be confined to, groups with low dispersal ability.

The X-C---Y (X = O/F, Y = O, S, F, Cl, Br, N, P,) Carbon bond and hydrophobic interactions

While the tetrahedral face of methane has an electron rich centre and can act as a hydrogen bond acceptor, substitution of one of its hydrogens with some electron withdrawing group (such as -F/OH) can make the opposite face electron deficient. Electrostatic potential calculations confirm this and high level quantum calculations show interactions between the positive face of methanol/methyl fluoride and electron rich centers of other molecules such as H2O. Analysis of the wave functions of atoms in molecules shows the presence of an unusual C···Y interaction, which could be called 'carbon bonding'. NBO analysis and vibrational frequency shifts confirm the presence of this interaction. Given the properties of alkyl groups bonded to electronegative elements in biological molecules, such interactions could play a significant role, which is yet to be recognized. This and similar interactions could give an enthalpic contribution to what is called the 'hydrophobic interactions'.

X-Ha center dot center dot center dot C hydrogen bonds in n-alkane-HX (X = F, OH) complexes are stronger than C-Ha <-X hydrogen bonds

Computational study of X-Ha <-C and C-Ha <-X hydrogen bonds in n-alkane-HX complexes (X =F,OH, alkane =propane, butane, pentane) has been carried out in this work. Ab initio and density functional theories were used for this study. For n-alkane-H2O complexes both Oa <-H-C and O-Ha <-C hydrogen bonded complex have been found, while for n-alkane-HF complexes, our attempt to optimize Fa <-H-C H-bond was not successful. Like most of the hydrogen bonded systems, strong correlation between binding energy and stretching frequency of H-F and O-H stretching mode was observed. The values of electron density and Laplacian of electron density are within the accepted range for hydrogen bonds. In all these cases, X-Ha <-C hydrogen bonds are found to be stronger than C-Ha <-X hydrogen bonds.

Efficient visible light photocatalytic activity and enhanced stability of BiOBr/Cd(OH)(2) heterostructures

Novel BioBr/Cd(OH)(2) heterostructures were synthesized by a facile chemical bath method under ambient conditions. A series of BiOBr/Cd(OH)(2) heterostructures were obtained by tuning the Bi/Cd molar ratios. The obtained heterostructures were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). Optical properties were studied by UV-visible spectroscopy, diffuse reflectance spectroscopy and photoluminescence (PL). Photocatalytic studies on rhodamine B (RhB) under visible light irradiation showed that the heterostructures are very efficient photocatalysts in mild basic medium. Scavenger test studies confirmed that the photogenerated holes and superoxide radicals (O-2(center dot-)) are the main active species responsible for RhB degradation. Comparison of photoluminescence (PL) intensity suggested that an inhibited charge recombination is crucial for the degradation process over these photocatalysts. Moreover, relative positioning of the valence and conduction band edges of the semiconductors, O-2/O-2(center dot-) and (OH)-O-center dot/H2O redox potentials and HOMO-LUMO levels of RhB appear to be responsible for the hole-specificity of degradation. Photocatalytic recycling experiments indicated the high stability of the catalysts in the reaction medium without any significant loss of activity. This study hence concludes that the heterojunction constructed between Cd(OH)(2) and BiOBr interfaces play a crucial role in influencing the charge carrier dynamics and subsequent photocatalytic activity.

QUANTITATIVE OH PLANAR LASER INDUCED FLUORESCENCE DIAGNOSTICS OF SYNGAS AND METHANE COMBUSTION IN A CAVITY COMBUSTOR

The current work reports quantitative OH species concentration in the cavity of a trapped vortex combustor (TVC) in the context of mixing and flame stabilization studies using both syngas and methane fuels. Planar laser induced fluorescence (PLIF) measurements of OH radical obtained using a Nd: YAG pumped dye laser are quantified using a flat flame McKenna burner. The momentum flux ratio (MFR), defined as the ratio of the cavity fuel jet momentum to that of the guide vane air stream, is observed to be a key governing parameter. At high MFRs similar to 4.5, the flame front is observed to form at the interface of the fuel jet and the air jet stream. This is substantiated by velocity vector field measurements. For syngas, as the MFR is lowered to similar to 0.3, the fuel-air mixing increases and a flame front is formed at the bottom and downstream edge of the cavity where a stratified charge is present. This trend is observed for different velocities at similar equivalence ratios. In case of methane combustion in the cavity, where the MFRs employed are extremely low at similar to 0.01, a different mechanism is observed. A fuel-rich mixture is now observed at the center of the cavity and this mixture undergoes combustion. On further increase of the cavity equivalence ratio, the rich mixture exceeds the flammability limit and forms a thin reaction zone at the interface with air stream. As a consequence, a shear layer flame at the top of the cavity interface with the mainstream is also observed. The equivalence ratio in the cavity also determines the combustion characteristics in the case of fuel-air mixtures that are formed as a result of the mixing. Overall, flame stabilization mechanisms have been proposed, which account for the wide range of MFRs and premixing in the mainstream as well.

Groups constrain the use of risky habitat by individuals: a new cost to sociality?

Predation risk can strongly constrain how individuals use time and space. Grouping is known to reduce an individual's time investment in costly antipredator behaviours. Whether grouping might similarly provide a spatial release from antipredator behaviour and allow individuals to use risky habitat more and, thus, improve their access to resources is poorly known. We used mosquito larvae, Aedes aegypti, to test the hypothesis that grouping facilitates the use of high-risk habitat. We provided two habitats, one darker, low-risk and one lighter, high-risk, and measured the relative time spent in the latter by solitary larvae versus larvae in small groups. We tested larvae reared under different resource levels, and thus presumed to vary in body condition, because condition is known to influence risk taking. We also varied the degree of contrast in habitat structure. We predicted that individuals in groups should use high-risk habitat more than solitary individuals allowing for influences of body condition and contrast in habitat structure. Grouping strongly influenced the time spent in the high-risk habitat, but, contrary to our expectation, individuals in groups spent less time in the high-risk habitat than solitary individuals. Furthermore, solitary individuals considerably increased the proportion of time spent in the high-risk habitat over time, whereas individuals in groups did not. Both solitary individuals and those in groups showed a small increase over time in their use of riskier locations within each habitat. The differences between solitary individuals and those in groups held across all resource and contrast conditions. Grouping may, thus, carry a poorly understood cost of constraining habitat use. This cost may arise because movement traits important for maintaining group cohesion (a result of strong selection on grouping) can act to exaggerate an individual preference for low-risk habitat. Further research is needed to examine the interplay between grouping, individual movement and habitat use traits in environments heterogeneous in risk and resources. (C) 2015 The Association for the Study of Animal Behaviour. Published by Elsevier Ltd. All rights reserved.

Social optimum in social groups with give-and-take criterion

We consider a Social Group' of networked nodes, seeking a universe' of segments. Each node has a subset of the universe and access to an expensive resource for downloading data. Nodes can also acquire the universe by exchanging copies of segments among themselves, at low cost, using inter-node links. While exchanges over inter-node links ensure minimum cost, some nodes in the group try to exploit the system. We term such nodes as non-reciprocating nodes' and prohibit such behavior by proposing the give-and-take' criterion, where exchange is allowed if each node has segments unavailable with the other. Under this criterion, we consider the problem of maximizing the number of nodes with the universe at the end of local exchanges. First, we present a randomized algorithm that is shown to be optimal in the asymptotic regime. Then, we present greedy links algorithm, which performs well for most of the scenarios and yields an optimal result when the number of nodes is four. The polygon algorithm is proposed, which yields an optimal result when each of the nodes has a unique segment. After presenting some intuitive algorithms (e.g., greedy incremental algorithm and rarest first algorithm), we compare the performances of all proposed algorithms with the optimal. Copyright (c) 2015 John Wiley & Sons, Ltd.

Implementación de HyD [Hidroxicolecalciferol (25-OH-D3)] en la dieta de pollos de engorde como profilaxis de osteopatías, enfatizando en el sindrome del hueso negro, Granja Trinidad-1, Tip Top industrial

El objetivo del experimento fue evaluar el efecto del Hidroxicolecalciferol [HyD (25 –OH- D3)] en pollos de engorde, atraves de porcentajes de ceniza, calcio, fosforo y diagnostico de síndrome de hueso negro, se evaluaron dos tratamientos ( HyD y Testigo) con seis repeticiones para cada uno en dos tiempos a los 21 y 35 días de edad en análisis de ceniza, calcio y fosforo para lo cual se extrajo una tibia por pollo, dichos análisis resultaron con diferencias no significativas en ambas edades, las evaluaciones dieron como resultado que de los 21 día a los 35 días disminuyen su valor, ceniza baja de 43.8% a 36.8% en el testigo y de 42.4% a 37.7% en HyD, calcio de 15.6% a 13.4% para el testigo y de 16% a 14.5% para HyD de igual manera para los porcentaje de fosforo de 21 a 35 días con 7.6% a 6.5% para testigo y 7.5% a 6.7% para HyD. A los 35 días los resultados son mayores en el grupo HyD, 37.7% HyD,36.8% testigo en ceniza, calcio 14.5% HyD, testigo 13.4% y fosforo 6.7% HyD , 6.5% para testigo, las diferencias de 21 a 35 días son notorias y conservan la parte proporcional en que los porcentajes estan en ceniza calcio y fosforo, pero estas disminuyen para una misma variable de los 21 días de edad a los 35, sin encontrar diferencia significativas. A los 35 días se realizo análisis de síndrome de hueso negro con un total de 22 repeticiones por tratamiento, la extracción de dicha muestra (tibia) se realizo en planta de proceso, el análisis determino diferencias entre las aves muestreadas dando los mejores resultados aquellas que fueron alimentadas con Hidroxicolecalciferol [HyD (25 –OH- D3)], se observo en los resultados que en el grupo con HyD alcanzo un 91% de individuos sanos superando significativamente al testigo que solo llego a un 77% de individuos sanos, empleando un grado de libertad y 0.05 de significancia, lo que indica diminución de la presencia del síndrome de hueso negro, producto del HyD, empleando la línea genética Cobb 500, y alimentando los pollos del día cero al día 21 con diferencias de tratamiento e igual alimento del día 22 al día 35.

The effects of introducing ester linking groups on the flexoelectro-optic properties of symmetric bimesogens

In the chiral nematic phase, flexoelectricity can give rise to an interesting electrooptic switching effect, known as flexoelectro-optic switching. Flexoelectro-optic switching gives a fast v-shaped switching regime. Previous studies show that symmetric bimesogens are particularly suited for flexoelectro-optic switching. By introducing two ester linking groups into the molecular structure of a symmetric bimesogen, it was hypothesised that the flexoelectric properties will be enhanced significantly because of the resulting increase in the dipole moment of the molecules. This was found to be the correct; however, the inclusion of ester linking groups reduced the liquid crystallinity of the material.

Models and algorithms for detection and tracking of coordinated groups

In this paper, we describe models and algorithms for detection and tracking of group and individual targets. We develop two novel group dynamical models, within a continuous time setting, that aim to mimic behavioural properties of groups. We also describe two possible ways of modeling interactions between closely using Markov Random Field (MRF) and repulsive forces. These can be combined together with a group structure transition model to create realistic evolving group models. We use a Markov Chain Monte Carlo (MCMC)-Particles Algorithm to perform sequential inference. Computer simulations demonstrate the ability of the algorithm to detect and track targets within groups, as well as infer the correct group structure over time. ©2008 IEEE.

Curvature and wrinkling of premixed flame kernels-comparisons of OH PLIF and DNS data

The effects of curvature and wrinkling on the growth of turbulent premixed flame kernels were studied using both two-dimensional OH Planar Laser-Induced Fluorescence (PLIF) and three-dimensional Direct Numerical Simulation (DNS). Comparisons of results between the two approaches showed a high level of agreement, providing confidence in the simplified chemistry treatment employed in the DNS, and indicating that chemistry might have only a limited influence on the evolution of the freely propagating flame. The usefulness of PLIF in providing data over a wide parameter range was illustrated using statistics obtained from both CH4/air and H2/air mixtures, which show markedly different behavior due to their different thermo-diffusive properties. The results provided a demonstration of the combined power of PLIF and DNS for flame investigation. Each technique compensate for the weaknesses of the other, and to reinforce the strengths of both.