J-Edited Pure Shift NMR for the Facile Measurement of (n)J(HH) for Specific Protons

We report a novel 1D J-edited pure shift NMR experiment (J-PSHIFT) that was constructed from a pseudo 2D experiment for the direct measurement of proton-proton scalar couplings. The experiment gives homonuclear broad-band H-1-decoupled H-1 NMR spectra, which provide a single peak for chemically distinct protons, and only retain the homonuclear-scalar-coupled doublet pattern at the chemical-shift positions of the protons in the coupled network of a specific proton. This permits the direct and unambiguous measurement of the magnitudes of the couplings. The incorporation of a 1D selective correlation spectroscopy (COSY)/ total correlation spectroscopy (TOCSY) block in lieu of the initial selective pulse, results in the exclusive detection of the correlated spectrum of a specific proton.

Effects of hydrogen bonding on amide-proton chemical shift anisotropy in a proline-containing model peptide

Longitudinal relaxation due to cross-correlation between dipolar ((HN-1H alpha)-H-1) and amide-proton chemical shift anisotropy (H-1(N) CSA) has been measured in a model tripeptide Piv-(L)Pro-(L)Pro-(L)Phe-OMe. The peptide bond across diproline segment is known to undergo cis/trans isomerization and only in the cis form does the lone Phe amide-proton become involved in intramolecular hydrogen bonding. The strength of the cross correlated relaxation interference is found to be significantly different between cis and trans forms, and this difference is shown as an influence of intramolecular hydrogen bonding on the amide-proton CSA. (C) 2015 Elsevier B.V. All rights reserved.

Negative hyperconjugation and red-, blue- or zero-shift in X-Z center dot center dot center dot Y complexes

A generalized explanation is provided for the existence of the red-and blue-shifting nature of X-Z bonds (Z = H, halogens, chalcogens, pnicogens, etc.) in X-Z center dot center dot center dot Y complexes based on computational studies on a selected set of weakly bonded complexes and analysis of existing literature data. The additional electrons and orbitals available on Z in comparison to H make for dramatic differences between the H-bond and the rest of the Z-bonds. The nature of the X-group and its influence on the X-Z bond length in the parent X-Z molecule largely controls the change in the X-Z bond length on X-Z center dot center dot center dot Y bond formation; the Y-group usually influences only the magnitude of the effects controlled by X. The major factors which control the X-Z bond length change are: (a) negative hyperconjugative donation of electron density from X-group to X-Z sigma* antibonding molecular orbital (ABMO) in the parent X-Z, (b) induced negative hyperconjugation from the lone pair of electrons on Z to the antibonding orbitals of the X-group, and (c) charge transfer (CT) from the Y-group to the X-Z sigma* orbital. The exchange repulsion from the Y-group that shifts partial electron density at the X-Z sigma* ABMO back to X leads to blue-shifting and the CT from the Y-group to the sigma* ABMO of X-Z leads to red-shifting. The balance between these two opposing forces decides red-, zero- or blue-shifting. A continuum of behaviour of X-Z bond length variation is inevitable in X-Z center dot center dot center dot Y complexes.

Spatio-temporal correlations in aqueous systems: computational studies of static and dynamic heterogeneity by 2D-IR spectroscopy

Local heterogeneity is ubiquitous in natural aqueous systems. It can be caused locally by external biomolecular subsystems like proteins, DNA, micelles and reverse micelles, nanoscopic materials etc., but can also be intrinsic to the thermodynamic nature of the aqueous solution itself (like binary mixtures or at the gas-liquid interface). The altered dynamics of water in the presence of such diverse surfaces has attracted considerable attention in recent years. As these interfaces are quite narrow, only a few molecular layers thick, they are hard to study by conventional methods. The recent development of two dimensional infra-red (2D-IR) spectroscopy allows us to estimate length and time scales of such dynamics fairly accurately. In this work, we present a series of interesting studies employing two dimensional infra-red spectroscopy (2D-IR) to investigate (i) the heterogeneous dynamics of water inside reverse micelles of varying sizes, (ii) supercritical water near the Widom line that is known to exhibit pronounced density fluctuations and also study (iii) the collective and local polarization fluctuation of water molecules in the presence of several different proteins. The spatio-temporal correlation of confined water molecules inside reverse micelles of varying sizes is well captured through the spectral diffusion of corresponding 2D-IR spectra. In the case of supercritical water also, we observe a strong signature of dynamic heterogeneity from the elongated nature of the 2D-IR spectra. In this case the relaxation is ultrafast. We find remarkable agreement between the different tools employed to study the relaxation of density heterogeneity. For aqueous protein solutions, we find that the calculated dielectric constant of the respective systems unanimously shows a noticeable increment compared to that of neat water. However, the `effective' dielectric constant for successive layers shows significant variation, with the layer adjacent to the protein having a much lower value. Relaxation is also slowest at the surface. We find that the dielectric constant achieves the bulk value at distances more than 3 nm from the surface of the protein.

Dynamics of 3D view invariance in monkey inferotemporal cortex

Rotations in depth are challenging for object vision because features can appear, disappear, be stretched or compressed. Yet we easily recognize objects across views. Are the underlying representations view invariant or dependent? This question has been intensely debated in human vision, but the neuronal representations remain poorly understood. Here, we show that for naturalistic objects, neurons in the monkey inferotemporal (IT) cortex undergo a dynamic transition in time, whereby they are initially sensitive to viewpoint and later encode view-invariant object identity. This transition depended on two aspects of object structure: it was strongest when objects foreshortened strongly across views and were similar to each other. View invariance in IT neurons was present even when objects were reduced to silhouettes, suggesting that it can arise through similarity between external contours of objects across views. Our results elucidate the viewpoint debate by showing that view invariance arises dynamically in IT neurons out of a representation that is initially view dependent.

Retrieval and Multi-scale Validation of Soil Moisture from Multi-temporal SAR Data in a Semi-Arid Tropical Region

The current study presents an algorithm to retrieve surface Soil Moisture (SM) from multi-temporal Synthetic Aperture Radar (SAR) data. The developed algorithm is based on the Cumulative Density Function (CDF) transformation of multi-temporal RADARSAT-2 backscatter coefficient (BC) to obtain relative SM values, and then converts relative SM values into absolute SM values using soil information. The algorithm is tested in a semi-arid tropical region in South India using 30 satellite images of RADARSAT-2, SMOS L2 SM products, and 1262 SM field measurements in 50 plots spanning over 4 years. The validation with the field data showed the ability of the developed algorithm to retrieve SM with RMSE ranging from 0.02 to 0.06 m(3)/m(3) for the majority of plots. Comparison with the SMOS SM showed a good temporal behaviour with RMSE of approximately 0.05 m(3)/m(3) and a correlation coefficient of approximately 0.9. The developed model is compared and found to be better than the change detection and delta index model. The approach does not require calibration of any parameter to obtain relative SM and hence can easily be extended to any region having time series of SAR data available.

DETERMINATION OF THE MASS OF IGR J17091-3624 FROM ``SPECTRO-TEMPORAL'' VARIATIONS DURING THE ONSET PHASE OF THE 2011 OUTBURST

The 2011 outburst of the black hole candidate IGR J17091-3624 followed the canonical track of state transitions along with the evolution of quasi-periodic oscillation (QPO) frequencies before it began exhibiting various variability classes similar to GRS 1915+105. We use this canonical evolution of spectral and temporal properties to determine the mass of IGR J17091-3624, using three different methods: photon index (Gamma)-QPO frequency (nu) correlation, QPO frequency (nu)-time (day) evolution, and broadband spectral modeling based on two-component advective flow (TCAF). We provide a combined mass estimate for the source using a naive Bayes based joint likelihood approach. This gives a probable mass range of 11.8 M-circle dot-13.7 M-circle dot. Considering each individual estimate and taking the lowermost and uppermost bounds among all three methods, we get a mass range of 8.7 M-circle dot-15.6 M-circle dot with 90% confidence. We discuss the possible implications of our findings in the context of two-component accretion flow.

Dynamics of history-dependent epidemics in temporal networks

The structural properties of temporal networks often influence the dynamical processes that occur on these networks, e.g., bursty interaction patterns have been shown to slow down epidemics. In this paper, we investigate the effect of link lifetimes on the spread of history-dependent epidemics. We formulate an analytically tractable activity-driven temporal network model that explicitly incorporates link lifetimes. For Markovian link lifetimes, we use mean-field analysis for computing the epidemic threshold, while the effect of non-Markovian link lifetimes is studied using simulations. Furthermore, we also study the effect of negative correlation between the number of links spawned by an individual and the lifetimes of those links. Such negative correlations may arise due to the finite cognitive capacity of the individuals. Our investigations reveal that heavy-tailed link lifetimes slow down the epidemic, while negative correlations can reduce epidemic prevalence. We believe that our results help shed light on the role of link lifetimes in modulating diffusion processes on temporal networks.

Exact Phase Retrieval in Principal Shift-Invariant Spaces

We address the problem of phase retrieval from Fourier transform magnitude spectrum for continuous-time signals that lie in a shift-invariant space spanned by integer shifts of a generator kernel. The phase retrieval problem for such signals is formulated as one of reconstructing the combining coefficients in the shift-invariant basis expansion. We develop sufficient conditions on the coefficients and the bases to guarantee exact phase retrieval, by which we mean reconstruction up to a global phase factor. We present a new class of discrete-domain signals that are not necessarily minimum-phase, but allow for exact phase retrieval from their Fourier magnitude spectra. We also establish Hilbert transform relations between log-magnitude and phase spectra for this class of discrete signals. It turns out that the corresponding continuous-domain counterparts need not satisfy a Hilbert transform relation; notwithstanding, the continuous-domain signals can be reconstructed from their Fourier magnitude spectra. We validate the reconstruction guarantees through simulations for some important classes of signals such as bandlimited signals and piecewise-smooth signals. We also present an application of the proposed phase retrieval technique for artifact-free signal reconstruction in frequency-domain optical-coherence tomography (FDOCT).

Gauge invariance in the theoretical description of time-resolved angle-resolved pump/probe photoemission spectroscopy

Nonequilibrium calculations in the presence of an electric field are usually performed in a gauge, and need to be transformed to reveal the gauge-invariant observables. In this work, we discuss the issue of gauge invariance in the context of time-resolved angle-resolved pump/probe photoemission. If the probe is applied while the pump is still on, one must ensure that the calculations of the observed photocurrent are gauge invariant. We also discuss the requirement of the photoemission signal to be positive and the relationship of this constraint to gauge invariance. We end by discussing some technical details related to the perturbative derivation of the photoemission spectra, which involve processes where the pump pulse photoemits electrons due to nonequilibrium effects.

Spatio-temporal Map Formation Based on a Potential Function

We revisit the problem of temporal self organization using activity diffusion based on the neural gas (NGAS) algorithm. Using a potential function formulation motivated by a spatio-temporal metric, we derive an adaptation rule for dynamic vector quantization of data. Simulations results show that our algorithm learns the input distribution and time correlation much faster compared to the static neural gas method over the same data sequence under similar training conditions.

Evaluación temporal y espacial en el bosque de Pinus oocarpa Schiede y su impacto sobre la fijación de carbono en el municipio de Dipilto

El objetivo de este estudio fue a nalizar el cambio de uso de suelo durante un periodo de 18 años en las áreas de bosque de pino y su influencia en la fijación de bióxido de carbono en el Municipio de Dipilto, Nueva Segovia . Se seleccionaron 3 Fincas : San Martín, El Sarrete y Campofresco que presentaron estados de desarrollo: bosque maduro, bosque joven y bosque en regeneración. Se establecieron 9 parcelas temporales (con predominancia P. oocarpa ), utilizándose una parcela temporal para cada es tado d esarrollo. En cada estado de desarrollo se derribó un árbol tipo, se separó en tallo, ramas y follaje. La mayor par te de biomasa seca se encuentra en la finca San Martin con 99.12 Mg/ha estado en desarrollo maduro , estado en desarrollo joven con 77.70 Mg/ ha y estado en desarrollo regeneración 38.63 Mg/ha . El Factor de expansión de biomasa en San Martin 1.59 esta do en desarrollo regeneración, El Sarrete para el estado en desarrollo maduro 1 .40 y finca Campofresco 1.27 estado desarrollo joven . El total de ca rbono almacenado lo presentó San Martín para el estado en desarrollo maduro con 27.13 Mg/ha , joven 22.06 Mg/ha y estado en desarrollo regeneraci ón con 9.82 Mg/ha . El contenido de carbono en el suelo 826.89 Mg/ha regeneración, 503.96 Mg/ha Joven , 294.55 Mg/ ha maduro en San Martín de 0 a 20 cm de profundidad. En un 38.49 % de esa área se emitieron entre 0 - 15 Mg/ha . Emisiones de 26 - 30 Mg/ha se presentaron en un 17.8 1 % del área. Existe un 48.19 % del área total que fijo rangos de 26 - 30 Mg/ha y un 38. 49 % de las áreas fij aron entre 0 - 15 Mg /ha . Se encontró un balance neto positivo de 2925. 2 1 hectáreas, de las cuales 1981.25 hectáreas fijaron rangos de 26 - 30 Mg/ha, 606.06 hectáre as fijaron en un rango entre 0 - 15 Mg /ha y el rango 16 - 25 Mg/ha 337.89 hect áreas .

The convection during NaClO3 crystal growth observed by the phase shift interferometer

An optical diagnostic system consisting of the Mach-Zehnder interferometer with the phase shift device and an image processor has been developed for the study of the kinetics of the crystal growing process. The dissolution and crystallization process of NaClO3 crystal has been investigated. The concentration distributions around a growing and dissolving crystal have been obtained by using phase-shift of four-steps theory for the interpretation of the interferograms. The convection (a plume flow) has been visualized and analyzed in the process of the crystal growth. The experiment demonstrates that the buoyancy convection dominates the growth rate of the crystal growing face on the ground-based experiment.

Numerical Investigation on Laser Transformation Hardening with Different Temporal Pulse Shapes

A 3-D numerical model for pulsed laser transformation hardening (LTH) is developed using the finite element method. In this model, laser spatial and temporal intensity distribution, temperature-dependent thermophysical properties of material, and multi-phase transformations are considered. The influence of laser temporal pulse shape on connectivity of hardened zone, maximum surface temperature of material and hardening depth is numerically investigated at different pulse energy levels. Results indicate that these hardening parameters are strongly dependent on the temporal pulse shape. For the rectangular temporal pulse shape, the temperature field obtained from this model is in excellent agreement with analytical solution, and the predicted hardening depth is favorably compared with experimental one. It should be pointed out that appropriate temporal pulse shape should be selected according to pulse energy level in order to achieve desirable hardening quality under certain laser spatial intensity distribution.

Biomasa y nutrientes de arboles de sombra temporal y permanente en sistemas agroforestales con Coffea arabiga L de cinco años en el Pacifico de Nicaragua

Chavarria, E; Hernández, J. 2,006. Biomasa y nutrientes de árboles de sombra temporal y permanente en sistemas agroforestales con Coffea arabiga L de 5 años en el pacífico de Nicaragua. La presente investigación se realizó en sistemas agroforestales con café (Coffea arábiga L.) en el Municipio de Masatepe, Nicaragua, determinando el aporte de biomasa y los contenidos de N, P, K, Ca y Mg. de la sombra temporal y permanente. Se evaluaron dos factores de estudio en un diseño de bloques completamente al azar con arreglo de parcelas subdivididas: A) Tipo de sombra: temporal estableciéndose de forma homogénea y mixtas, especies de leguminosas más no leguminosas para sombra de café como Cajanus cajan y Ricinus communis y en sombra permanente, especies de árboles leguminosas y/o maderables (Inga laurina, Simarouba glauca, Samanea saman, Tabebuia rosea) y una parcela de café a pleno sol, distribuidas en parcelas grandes; B) Los niveles de insumos: Convencional Intensivo (CI) y Convencional Extensivo (CE), Orgánico Intensivo (OI) y Orgánico Extensivo (OE); relativos a aportes de nutrientes, manejo de enfermedades, malezas e insectos dañinos. La biomasa de sombra temporal se cuantificó en 2,002 por podas y 2,003 por eliminación de la misma. También se cuantificó la biomasa en la sombra permanente por podas en 2,004 y de raleo 2,005. La biomasa total por especie y tratamientos en sombra temporal y permanente, se obtuvieron a partir de los componentes hojas, tallos menores a 2 cm, tallos mayores de 2 cm de diámetro y tronco. Se tomó una muestra de biomasa fresca por tratamiento, se secó al horno a temperaturas de 65 ºC, para obtener el contenido de materia seca. A este mismo material, se procedió a la determinación de las concentraciones de los elementos minerales anteriormente mencionados. Los resultados obtenidos mostraron que la especie de sombra temporal no leguminosa Higuera (Ricinus communis) presentó el mayor aporte de materia seca con 4,356 kg ha-1 en dos años (2,002 + 2,003), representando también los mayores contenidos de N, P, K, Ca y Mg con 82, 28, 165, 68 y 57 kg ha-1 respectivamente. Respecto a las especies de sombra permanente, sometidas al manejo de poda el nivel de sombra Il+Sg produce los mayores aportes de MS con 5,695.66 kg ha-1 a-1 de los cuales el 39 % se recicla en el sistema, este mismo tipo de sombra aporta al sistema los mayores contenidos de N, P, K, Ca y Mg con 64, 55, 55, 66 y 36 % respectivamente. En el manejo de raleo el tipo de sombra que produjo mayor cantidad de MS es Sg+Tr con 9,096.89 kg ha-1 a-1 aportando al sistema el 45 %, este mismo tipo de sombra aporta al sistema las mayores cantidades de N, P, K, Ca y Mg con 67, 54, 70, 80 y 44 % respectivamente. Los porcentaje restante de materia seca y nutrientes tanto en poda y raleo correspondiente a tallos mayores de 2 cm de diámetro, es extraído del sistema como leña y postes respectivamente.