Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N-'-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (+/-) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.

Large scale features and assessment of spatial scale correspondence between TMPA and IMD rainfall datasets over Indian landmass

Daily rainfall datasets of 10 years (1998-2007) of Tropical Rainfall Measuring Mission (TRMM) Multi-satellite Precipitation Analysis (TMPA) version 6 and India Meteorological Department (IMD) gridded rain gauge have been compared over the Indian landmass, both in large and small spatial scales. On the larger spatial scale, the pattern correlation between the two datasets on daily scales during individual years of the study period is ranging from 0.4 to 0.7. The correlation improved significantly (similar to 0.9) when the study was confined to specific wet and dry spells each of about 5-8 days. Wavelet analysis of intraseasonal oscillations (ISO) of the southwest monsoon rainfall show the percentage contribution of the major two modes (30-50 days and 10-20 days), to be ranging respectively between similar to 30-40% and 5-10% for the various years. Analysis of inter-annual variability shows the satellite data to be underestimating seasonal rainfall by similar to 110 mm during southwest monsoon and overestimating by similar to 150 mm during northeast monsoon season. At high spatio-temporal scales, viz., 1 degrees x1 degrees grid, TMPA data do not correspond to ground truth. We have proposed here a new analysis procedure to assess the minimum spatial scale at which the two datasets are compatible with each other. This has been done by studying the contribution to total seasonal rainfall from different rainfall rate windows (at 1 mm intervals) on different spatial scales (at daily time scale). The compatibility spatial scale is seen to be beyond 5 degrees x5 degrees average spatial scale over the Indian landmass. This will help to decide the usability of TMPA products, if averaged at appropriate spatial scales, for specific process studies, e.g., cloud scale, meso scale or synoptic scale.

Linear and nonlinear optical properties of expanded porphyrins: a DMRG study

We study absorption spectra and two photon absorption coefficient of expanded porphyrins (EPs) by the density matrix renormalization group (DMRG) technique. We employ the Pariser-Parr-Pople (PPP) Hamiltonian which includes long-range electron-electron interactions. We find that, in the 4n+2 EPs, there are two prominent low-lying one-photon excitations, while in 4n EPs, there is only one such excitation. We also find that 4n+2 EPs have large two-photon absorption cross sections compared to 4n EPs. The charge density rearrangement in the one-photon excited state is mostly at the pyrrole nitrogen site and at the meso carbon sites. In the two-photon states, the charge density rearrangement occurs mostly at the aza-ring sites. In the one-photon state, the C-C bond length in aza rings shows a tendency to become uniform. In the two-photon state, the bond distortions are on C-N bonds of the pyrrole ring and the adjoining C-C bonds which connect the pyrrole ring to the aza or meso carbon sites.

Effect of substituent position on optical properties of boron-dipyrromethane isomers

Three isomeric meso-SiMe3C6H4 substituted BODIPYs have been synthesized and their optical properties studied. The constitutional isomers show similar absorption properties but vastly different emissive properties as a result of their different conformational flexibility. Fluorine-19 NMR study is used to unravel the conformational state of the BODIPY isomers at a molecular level. (C) 2013 Elsevier B. V. All rights reserved.

Simulations and experiments in punching spring-steel devices with sub-millimeter features

This work demonstrates the feasibility of mesoscale (100 μm to mm) punching of multiple holes of intricate shapes in metals. Analytical modeling, finite element (FE)simulation, and experimentations are used in this work. Two dimensional FE simulations in ABAQUS were done with an assumed material modeling and plane-strain condition. A known analytical model was used and compared with the ABAQUS simulation results to understand the effects of clearance between the punch and the die. FE simulation in ABAQUS was done for different clearances and corner radii at punch, die, and holder. A set of punches and dies were used to punch out a miniature spring-steel gripper. Comparison of compliant grippers manufactured by wire-cut electro discharge machining(EDM) and punching shows that realizing sharp interior and re-entrant corners by punching is not easy to achieve. Punching of circular holes with 5 mm and 2.5 mm diameter is achieved. The possibility of realizing meso-scale parts with complicated shapes through punching is demonstrated in this work; and some strategies are suggested for improvement.

Factors affecting distribution of fish within a tidally drained mangrove forest in the Andaman and Nicobar Islands, India

Mangrove forests in meso-tidal areas are completely drained during low tides, forming only temporary habitats for fish. We hypothesised that in such temporary habitats, where stranding risks are high, distance from tidal creeks that provided access to inundated areas during receding tides would be the primary determinant of fish distribution. Factors such as depth, root density and shade were hypothesised to have secondary effects. We tested these hypotheses in a tidally drained mangrove patch in the Andaman Islands, India. Using stake nets, we measured fish abundance and species richness relative to distance from creeks, root density/m(2), shade, water depth and size (total length) of fish. We also predicted that larger fish (including potential predators) would be closer to creeks, as they faced a greater chance of mortality if stranded. Thus we conducted tethering trials to examine if predation would be greater close to the creeks. Generalised linear mixed effects models showed that fish abundance was negatively influenced by increasing creek distance interacting with fish size and positively influenced by depth. Quantile regression analysis showed that species richness was limited by increasing creek distance. Proportion of predation was greatest close to the creeks (0-25 m) and declined with increasing distance. Abundance was also low very close to the creeks, suggesting that close to the creeks predation pressure may be an important determinant of fish abundance. The overall pattern however indicates that access to permanently inundated areas, may be an important determinant of fish distribution in tidally drained mangrove forests.

Archean tectonics and crustal evolution of the Biligiri Rangan Block, southern India

The Southern Granulite Terrain in India is a collage of crustal blocks ranging in age from Archean to Neoproterozoic. This study investigate the tectonic evolution of one of the northernmost block- the Biligiri Block (BRB) through a multidisciplinary approach involving field investigation, petrographic studies, LA-ICPMS zircon U-Pb geochronology, Hf isotopic analyses, metamorphic P-T phase diagram computations, and crustal thickness modeling. The garnet bearing quartzofeldspathic gneiss from the central BRB preserve Mesoarchean magmatic zircons with ages between 3207 and 2806 Ma and positive epsilon Hf value (+2.7) which possibly indicates vestiges of a Mesoarchean primitive continental crust. The occurrence of quartzite-iron formation intercalation as well as ultramafic lenses along the western boundary of the BRB is interpreted to indicate that the Kollegal structural lineament is a possible paleo-suture. Phase diagram computation of a metagabbro from the southwestern periphery of the Kollegal suture zone reveals high-pressure (similar to 18.5 kbar) and medium-temperature (similar to 840 degrees C) metamorphism, likely during eastward subduction of the Western Dharwar oceanic crust beneath the Mesoarchean BRB. In the model presented here, slab subduction, melting and underplating processes generated arc magmatism and subsequent charnockitization within the BRB between ca. 2650 Ma and ca. 2498 Ma. These results thus reveal Meso- to Neoarchean tectonic evolution of the BRB. The spatial variation of crustal thickness, derived from flexure inversion technique, provides additional constraints on the tectonic linkage of the BRB with its surrounding terrains. In conjunction with published data, the Moyar and the Kollegal suture zones are considered to mark the trace of ocean closure along which the Nilgiri and Biligiri Rangan Blocks accreted on to the Western Dharwar Craton. (C) 2016 Elsevier B.V. All rights reserved.

Contingent sensitivity to configuration in a nonlinear evolution system

A trans-scopic sensitivity of macroscopic failure to slight differentiation in the meso-scopic structure of a system with nonlinear evolution is reported. A periodical chain following a non-local load-sharing evolution was applied as a propotype in failure study. The results demonstrate that there is a transition region composed of globally stable (GS) and evolution induced catastrophic (EIC) modes. That is different from a critical threshold as predicted by percolation and renormalization group theories. Moreover, the EIC mode shows a distinctive sample specific behaviour. For instance, some neighbouring initial states may evolve into completely different final states, though different initial states can evolve into the same final states. As an example, a marginal configuration of EIC mode, a quasi-Fibonacci skeleton, is constructed.

Evolution induced catastrophe in a nonlinear dynamical model of material failure

In order to study the failure of disordered materials, the ensemble evolution of a nonlinear chain model was examined by using a stochastic slice sampling method. The following results were obtained. (1) Sample-specific behavior, i.e. evolutions are different from sample to sample in some cases under the same macroscopic conditions, is observed for various load-sharing rules except in the globally mean field theory. The evolution according to the cluster load-sharing rule, which reflects the interaction between broken clusters, cannot be predicted by a simple criterion from the initial damage pattern and even then is most complicated. (2) A binary failure probability, its transitional region, where globally stable (GS) modes and evolution-induced catastrophic (EIC) modes coexist, and the corresponding scaling laws are fundamental to the failure. There is a sensitive zone in the vicinity of the boundary between the GS and EIC regions in phase space, where a slight stochastic increment in damage can trigger a radical transition from GS to EIC. (3) The distribution of strength is obtained from the binary failure probability. This, like sample-specificity, originates from a trans-scale sensitivity linking meso-scopic and macroscopic phenomena. (4) Strong fluctuations in stress distribution different from that of GS modes may be assumed as a precursor of evolution-induced catastrophe (EIC).

Evaluación de rendimiento en el cultivo de soja aplicando fosfitos y micronutrientes

Resumen: Lo que se pretende reflejar en este trabajo es la importancia del uso de fosfitos y micronutrientes en el cultivo de soja. El cultivo de esta oleaginosa se ha ido incrementando a lo largo de los últimos años de la mano de la siembra directa, de la genética, del paquete tecnológico para su implantación y protección y del manejo realizado por los profesionales del agro. Este crecimiento en superficie en detrimento de los demás cultivos extensivos que deberían formar parte de la rotación, hizo de la oleaginosa en varias zonas un monocultivo. Esto sumado a la falta de rotación de activos fue generando problemas dentro de los cuales podemos citar: malezas de difícil control, alta presión de enfermedades y plagas. La fertilización, en la generalidad de los casos, está por debajo de los requerimientos por tonelada lograda, generando extracción de macro y micro elementos y agotando los niveles de estos mismos en el perfil edáfico. El aporte de macronutrientes está dado principalmente por fósforo (no en todas las zonas). Asimismo, en algunas zonas dependiendo las deficiencias agregan potasio, azufre y calcio. Así todo se fertiliza por debajo de los rindes objetivos perseguidos, lo cual se comprende que cuando los cultivos superan los mismos, se está haciendo una extracción mayor del sistema suelo que los aportes generados. Lo ideal es realizar un muestreo de cada lote y ambiente, verificar los niveles de nutrientes disponibles y fertilizar pensado en contemplar el rinde perseguido y entregar al sistema suelo un poco más, de manera de hacer una producción no solo rentable en el corto plazo sino sustentable en el tiempo, cuidando el capital suelo. Los macro y meso nutrientes son aportados vía fertilización de base o fondo y la manera más eficiente de aportar los micro elementos, es vía fertilización foliar. Los fosfitos son desde el punto de vista sanitario, la herramienta ideal y complementaria de los fungicidas. Son derivados del ácido fosforoso y tienen dos formas de acción contra los hongos fitopatógenos. Una forma indirecta, aumentando el nivel de defensas de las plantas o Fitoalexinas, impidiendo que las esporas germinen en tejido susceptible. Y una acción directa como fungicidas contra los pseudohongos u Oomicetes. Recordar que los triazoles son una excelente herramienta para controlar hongos verdaderos (Ascomicetes, Basidiomicetes y Deuteromicetes) al igual que las estrobirulinas, pero ambos activos no son específicos para Oomicetes. Generalmente, los fosfitos van combinados con diferentes cationes, que a su vez le confieren diferentes modos de actuar, por ejemplo el fosfito de cobre, actúa desde el punto de vista sanitario elevando las defensas y además presenta el catión cobre como elemento fungistático y bactericida. En el mercado existen diferentes tipos de fosfitos y formas de acción según catión acompañante. Hay fosfitos de Cu, Al, K, Mn, Ca, ect. Uno de los puntos más importantes de los fosfitos es que se translocan vía xilema y floema, llegando rápidamente a los diferentes sitios de la planta. Los fungicidas a diferencia de los fosfitos no pueden realizar la misma labor. Los fungicidas protegen al follaje tratado, pero no al nuevo emergente y el movimiento de los activos se da desde donde impacta la gota asperjada en sentido ascendente, ósea acrópeto, mientras que los fosfitos al recorrer toda la planta realizan una protección integral de la misma. Además, los fosfitos, presentan efecto sinérgico con los fungicidas potenciando la acción de estos. Colaboran en el engrosamiento de tejidos de raíz y tallo, fortaleciéndolos contra el ataque de patógenos. Son de rápida absorción e impactan positivamente en la formación de destinos, como flores y frutos, y fuentes de reservas como raíz. No disponen de valor nutricional para los cultivos extensivos anuales, ya que presentan un tiempo de degradación que excede al desarrollo de estos mismos. Este trabajo, se desarrolla implementando el diseño completamente aleatorio, en el cual la variable respuesta (rendimiento) puede depender de la influencia de un único factor (aplicación de fitoestimulantes), de forma que el resto de las causas de variación se engloban en el error experimental. Se compara los tratamientos contra el testigo, y se hace análisis de la variancia con un nivel de significación del 5%. Dentro de la variable respuesta se analiza el rendimiento en kg/ha. Teniendo en cuenta para este análisis los siguientes datos: 1) Número de granos 2) Peso de 1000 granos Este ensayo consta de cuatro tratamientos y tres repeticiones en un mismo estado fenológico (V10 R2) del cultivo.

Threshold diversity and trans-scales sensitivity in a finite nonlinear evolution model of materials failure

We present a slice-sampling method and study the ensemble evolution of a large finite nonlinear system in order to model materials failure. There is a transitional region of failure probability. Its size effect is expressed by a slowly decaying scaling law. In a meso-macroscopic range (similar to 10(5)) in realistic failure, the diversity cannot be ignored. Sensitivity to mesoscopic details governs the phenomena. (C) 1997 Published by Elsevier Science B.V.

PICES Press, Vol. 12, No. 2, July 2004

The future of PICES [pdf, 1.7 MB] Paris by day - Symposium on "Quantative ecosystem indicators in fisheries management" [pdf, 0.2 MB] The Bering Sea: Current status and recent events [pdf, 0.4 MB] The state of the western North Pacific in the second half of 2003 [pdf, 0.7 MB] The state of the eastern North Pacific entering spring 2004 [pdf, 0.4 MB] PICES-IFEP Workshop on "In-situ iron enrichment experiments in the eastern and western subarctic Pacific" [pdf, 1.4 MB] Canadian SOLAS/PICES-IFEP session on "Response of the upper ocean to meso-scale iron enrichment" [pdf, 0.3 MB] Fisheries and ecosystem responses to recent regime shifts [pdf, 0.8 MB] PICES Interns [pdf, 0.8 MB] Did a regime shift occur in 1998 around Japan?- Highlights from a symposium addressing this question [pdf, 0.8 MB] The Global Ocean Carbon Observing System - Connecting national programs and regional networks [pdf, 1.7 MB] The North Pacific Ecosystem Metadatabase [pdf, 1.2 MB] International GLOBEC Symposium on "Climate variability and Sub-Arctic marine ecosystems" [pdf, 0.2 MB] PICES Calendar [pdf, 0.2 MB] PICES/GLOBEC Symposium on "Climate variability and ecosystem impacts on the North pacific: A basin-scale synthesis" [pdf, 0.2 MB]

“Deborah Numbers”, Coupling Multiple Space and Time Scales and Governing Damage Evolution to Failure

Two different spatial levels are involved concerning damage accumulation to eventual failure. nucleation and growth rates of microdamage nN* and V*. It is found that the trans-scale length ratio c*/L does not directly affect the process. Instead, two independent dimensionless numbers: the trans-scale one * * ( V*)including the * **5 * N c V including mesoscopic parameters only, play the key role in the process of damage accumulation to failure. The above implies that there are three time scales involved in the process: the macroscopic imposed time scale tim = /a and two meso-scopic time scales, nucleation and growth of damage, (* *4) N N t =1 n c and tV=c*/V*. Clearly, the dimensionless number De*=tV/tim refers to the ratio of microdamage growth time scale over the macroscopically imposed time scale. So, analogous to the definition of Deborah number as the ratio of relaxation time over external one in rheology. Let De be the imposed Deborah number while De represents the competition and coupling between the microdamage growth and the macroscopically imposed wave loading. In stress-wave induced tensile failure (spallation) De* < 1, this means that microdamage has enough time to grow during the macroscopic wave loading. Thus, the microdamage growth appears to be the predominate mechanism governing the failure. Moreover, the dimensionless number D* = tV/tN characterizes the ratio of two intrinsic mesoscopic time scales: growth over nucleation. Similarly let D be the “intrinsic Deborah number”. Both time scales are relevant to intrinsic relaxation rather than imposed one. Furthermore, the intrinsic Deborah number D* implies a certain characteristic damage. In particular, it is derived that D* is a proper indicator of macroscopic critical damage to damage localization, like D* ∼ (10–3~10–2) in spallation. More importantly, we found that this small intrinsic Deborah number D* indicates the energy partition of microdamage dissipation over bulk plastic work. This explains why spallation can not be formulated by macroscopic energy criterion and must be treated by multi-scale analysis.

Mechanics of metallic foams: A fractal approach

A fractal approach was proposed to investigate the meso structures and size effect of metallic foams: For a series At foams of different relative densities, the information dimension method was applied to measure meso structures. The generalized sierpinski carpet was introduced to map the meso structures of the foam according to specific dimension. The results show that the fractal-based model can not only reveal the variation of yield strength with specimen size, but also bridge the meso structures and mechanical proper-ties of Al foams directly. Key words: metallic foams; fractal; size effect; meso structures

Distribution and sighting frequency of reef fishes in the Florida Keys National Marine Sanctuary

This study analyzed species richness, distribution, and sighting frequency of selected reef fishes to describe species assemblage composition, abundance, and spatial distribution patterns among sites and regions (Upper Keys, Middle Keys, Lower Keys, and Dry Tortugas) within the Florida Keys National Marine Sanctuary (FKNMS) barrier reef ecosystem. Data were obtained from the Reef Environmental Education Foundation (REEF) Fish Survey Project, a volunteer fish-monitoring program. A total of 4,324 visual fish surveys conducted at 112 sites throughout the FKNMS were used in these analyses. The data set contained sighting information on 341 fish species comprising 68 families. Species richness was generally highest in the Upper Keys sites (maximum was 220 species at Molasses Reef) and lowest in the Dry Tortugas sites. Encounter rates differed among regions, with the Dry Tortugas having the highest rate, potentially a result of differences in the evenness in fishes and the lower diversity of habitat types in the Dry Tortugas region. Geographic coverage maps were developed for 29 frequently observed species. Fourteen of these species showed significant regional variation in mean sighting frequency (%SF). Six species had significantly lower mean %SF and eight species had significantly higher mean %SF in the Dry Tortugas compared with other regions. Hierarchical clustering based on species composition (presence-absence) and species % SF revealed interesting patterns of similarities among sites that varied across spatial scales. Results presented here indicate that phenomena affecting reef fish composition in the FKNMS operate at multiple spatial scales, including a biogeographic scale that defines the character of the region as a whole, a reef scale (~50-100 km) that include meso-scale physical oceanographic processes and regional variation in reef structure and associated reef habitats, and a local scale that includes level of protection, cross-shelf location and a suite of physical characteristics of a given reef. It is likely that at both regional and local scales, species habitat requirements strongly influence the patterns revealed in this study, and are particularly limiting for species that are less frequently observed in the Dry Tortugas. The results of this report serve as a benchmark for the current status of the reef fishes in the FKNMS. In addition, these data provide the basis for analyses on reserve effects and the biogeographic coupling of benthic habitats and fish assemblages that are currently underway. (PDF contains 61 pages.)