Nanoindentation as a probe for mechanically-induced molecular migration in layered organic donor-acceptor complexes

Nanoindentation and scratch experiments on 1:1 donor-acceptor complexes, 1 and 2, of 1,2,4,5-tetracyanobenzene with pyrene and phenanthrene, respectively, reveal long-range molecular layer gliding and large interaction anisotropy. Due to the layered arrangements in these crystals, these experiments that apply stress in particular directions result in the breaking of interlayer interactions, thus allowing molecular sheets to glide over one another with ease. Complex 1 has a layered crystal packing wherein the layers are 68° skew under the (002) face and the interlayer space is stabilized by van der Waals interactions. Upon indenting this surface with a Berkovich tip, pile-up of material was observed on just one side of the indenter due to the close angular alignment of the layers with the half angle of the indenter tip (65.35°). The interfacial differences in the elastic modulus (21 ) and hardness (16 ) demonstrate the anisotropic nature of crystal packing. In 2, the molecular stacks are arranged in a staggered manner; there is no layer arrangement, and the interlayer stabilization involves C-H�N hydrogen bonds and ��� interactions. This results in a higher modulus (20 ) for (020) as compared to (001), although the anisotropy in hardness is minimal (4 ). The anisotropy within a face was analyzed using AFM image scans and the coefficient of friction of four orthogonal nanoscratches on the cleavage planes of 1 and 2. A higher friction coefficient was obtained for 2 as compared to 1 even in the cleavage direction due to the presence of hydrogen bonds in the interlayer region making the tip movement more hindered. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Regulation of S100A2 expression by TGF-beta-induced MEK/ERK signalling and its role in cell migration/invasion

S100A2, an EF hand calcium-binding protein, is a potential biomarker in several cancers and is also a TGF-beta (transforming growth factor-beta)-regulated gene in melanoma and lung cancer cells. However, the mechanism of S100A2 regulation by TGF-beta and its significance in cancer progression remains largely unknown. In the present study we report the mechanism of S100A2 regulation by TGF-beta and its possible role in TGF-beta-mediated tumour promotion. Characterization of the S100A2 promoter revealed an AP-1 (activator protein-1) element at positions -1161 to -1151 as being the most critical factor for the TGF-beta 1 response. Chromatin immunoprecipitation and electrophoretic mobility-shift assays confirmed the functional binding of the AP-1 complex, predominantly JunB, to the S100A2 promoter in response to TGF-beta 1 in HaCaT keratinocytes. JunB overexpression markedly stimulated the S100A2 promoter which was blocked by the dominant-negative JunB and MEK1 MAPK (mitogen-activated protein kinase)/ERK (extracellular-signal-regulated kinase) kinase 1] inhibitor, PD98059. Intriguingly, despite the presence of a putative SMAD-binding element, S100A2 regulation by TGF-beta 1 was found to be SMAD3 independent. Interestingly, p53 protein and TGF-beta 1 show synergistic regulation of the S100A2 promoter. Finally, knockdown of S100A2 expression compromised TGF-beta 1-induced cell migration and invasion of Hep3B cells. Together our findings highlight an important link between the TGF-beta 1-induced MAPK and p53 signalling pathways in the regulation of S100A2 expression and pro-tumorigenic actions.

Impacts of climate change on regional water resources

Water is the most important medium through which climate change influences human life. Rising temperatures together with regional changes in precipitation patterns are some of the impacts of climate change that have implications on water availability, frequency and intensity of floods and droughts, soil moisture, water quality, water supply and water demands for irrigation and hydropower generation. In this article we provide an introduction to the emerging field of hydrologic impacts of climate change with a focus on water availability, water quality and irrigation demands. Climate change estimates on regional or local spatial scales are burdened with a considerable amount of uncertainty, stemming from various sources such as climate models, downscaling and hydrological models used in the impact assessments and uncertainty in the downscaling relationships. The present article summarizes the recent advances on uncertainty modeling and regional impacts of climate change for the Mahanadi and Tunga-Bhadra Rivers in India.

Numerical simulations of CO2 migration during charnockite genesis

Charnockite is considered to be generated either through the dehydration of granitic magma by CO2 purging or by solid-state dehydration through CO2 metasomatism during granulite facies metamorphism. To understand the extent of dehydration, CO2 migration is quantitatively modeled in silicate melt and metasomatic fluid as a function of temperature, H2O wt%, pressure, basal CO2 flux and dynamic viscosity. Numerical simulations show that CO2 advection through porous and permeable high-grade metamorphic rocks can generate dehydrated patches close to the CO2 flow path, as illustrated by the occurrences of ``incipient charnockites.'' CO2 reaction-front velocity constrained by field observations is 0.69 km/m.y., a reasonable value, which matches well with other studies. On the other hand, temperature, rate of cooling, and basal CO2 flux are the critical parameters affecting CO2 diffusion through a silicate melt. CO2 diffusion through silicate melt can only occur at temperature greater than 840 degrees C and during slow cooling (<= 3.7 x 10(-5) degrees C/yr), features that are typical of magma emplacement in the lower crust. Stalling of CO2 fluxing at similar to 840 degrees C explains why some deep-level plutons contain both hydrous and anhydrous (charnockitic) mineral assemblages. CO2 diffusion through silicate melt is virtually insensitive to pressure. Addition of CO2 basal flux facilitates episodic dehydrated melt migration by generating fracture pathways.

Regional impacts of climate change on irrigation water demands

This paper presents an approach to model the expected impacts of climate change on irrigation water demand in a reservoir command area. A statistical downscaling model and an evapotranspiration model are used with a general circulation model (GCM) output to predict the anticipated change in the monthly irrigation water requirement of a crop. Specifically, we quantify the likely changes in irrigation water demands at a location in the command area, as a response to the projected changes in precipitation and evapotranspiration at that location. Statistical downscaling with a canonical correlation analysis is carried out to develop the future scenarios of meteorological variables (rainfall, relative humidity (RH), wind speed (U-2), radiation, maximum (Tmax) and minimum (Tmin) temperatures) starting with simulations provided by a GCM for a specified emission scenario. The medium resolution Model for Interdisciplinary Research on Climate GCM is used with the A1B scenario, to assess the likely changes in irrigation demands for paddy, sugarcane, permanent garden and semidry crops over the command area of Bhadra reservoir, India. Results from the downscaling model suggest that the monthly rainfall is likely to increase in the reservoir command area. RH, Tmax and Tmin are also projected to increase with small changes in U-2. Consequently, the reference evapotranspiration, modeled by the Penman-Monteith equation, is predicted to increase. The irrigation requirements are assessed on monthly scale at nine selected locations encompassing the Bhadra reservoir command area. The irrigation requirements are projected to increase, in most cases, suggesting that the effect of projected increase in rainfall on the irrigation demands is offset by the effect due to projected increase/change in other meteorological variables (viz., Tmax and Tmin, solar radiation, RH and U-2). The irrigation demand assessment study carried out at a river basin will be useful for future irrigation management systems. Copyright (c) 2012 John Wiley & Sons, Ltd.

Regional variations in the nonlinearity and anisotropy of bovine aortic elastin

Arterial walls have a regular and lamellar organization of elastin present as concentric fenestrated networks in the media. In contrast, elastin networks are longitudinally oriented in layers adjacent to the media. In a previous model exploring the biomechanics of arterial elastin, we had proposed a microstructurally motivated strain energy function modeled using orthotropic material symmetry. Using mechanical experiments, we showed that the neo-Hookean term had a dominant contribution to the overall form of the strain energy function. In contrast, invariants corresponding to the two fiber families had smaller contributions. To extend these investigations, we use biaxial force-controlled experiments to quantify regional variations in the anisotropy and nonlinearity of elastin isolated from bovine aortic tissues proximal and distal to the heart. Results from this study show that tissue nonlinearity significantly increases distal to the heart as compared to proximally located regions (). Distally located samples also have a trend for increased anisotropy (), with the circumferential direction stiffer than the longitudinal, as compared to an isotropic and relatively linear response for proximally located elastin samples. These results are consistent with the underlying tissue histology from proximally located samples that had higher optical density (), fiber thickness (), and trend for lower tortuosity () in elastin fibers as compared to the thinner and highly undulating elastin fibers isolated from distally located samples. Our studies suggest that it is important to consider elastin fiber orientations in investigations that use microstructure-based models to describe the contributions of elastin and collagen to arterial mechanics.

Computational Study of the Migration of Rhenium from One Enantioface of an Olefin to the Other Facilitated by (C-H)center dot center dot center dot Re Interactions

The migration of a metal atom in a metal olefin complex from one pi face of the olefin to the opposite pi face has been rarely documented. Gladysz and co-workers showed that such a movement is indeed possible in monosubstituted chiral Re olefin complexes, resulting in diastereomerization. Interestingly, this isomerization occurred without dissociation, and on the basis of kinetic isotope effects, the involvement of a trans C-H bond was indicated. Either oxidative addition or an agostic interaction of the vinylic C-H(D) bond with the metal could account for the experimentally observed kinetic isotope effect. In this study we compute the free energy of activation for the migration of Re from one enantioface of the olefin to the other through various pathways. On the basis of DFT calculations at the B3LYP level we show that a trans (C-H)center dot center dot center dot Re interaction and trans C-H oxidative addition provide a nondissociative path for the diastereomerization. The trans (C-H)center dot center dot center dot Re interaction path is computed to be more favorable by 2.3 kcal mol(-1) than the oxidative addition path. While direct experimental evidence was not able to discount the migration of the metal through the formation of a eta(2)-arene complex (conducted tour mechanism), computational results at the B3LYP level show that it is energetically more expensive. Surprisingly, a similar analysis carried out at the M06 level computes a lower energy path for the conducted tour mechanism and is not consistent with the experimental isotope effects observed. Metal-(C-H) interactions and oxidative additions of the metal into C-H bonds are closely separated in energy and might contribute to unusual fluxional processes such as this diastereomerization.

Formulation of a mathematical approach to regional frequency analysis

Estimation of design quantiles of hydrometeorological variables at critical locations in river basins is necessary for hydrological applications. To arrive at reliable estimates for locations (sites) where no or limited records are available, various regional frequency analysis (RFA) procedures have been developed over the past five decades. The most widely used procedure is based on index-flood approach and L-moments. It assumes that values of scale and shape parameters of frequency distribution are identical across all the sites in a homogeneous region. In real-world scenario, this assumption may not be valid even if a region is statistically homogeneous. To address this issue, a novel mathematical approach is proposed. It involves (i) identification of an appropriate frequency distribution to fit the random variable being analyzed for homogeneous region, (ii) use of a proposed transformation mechanism to map observations of the variable from original space to a dimensionless space where the form of distribution does not change, and variation in values of its parameters is minimal across sites, (iii) construction of a growth curve in the dimensionless space, and (iv) mapping the curve to the original space for the target site by applying inverse transformation to arrive at required quantile(s) for the site. Effectiveness of the proposed approach (PA) in predicting quantiles for ungauged sites is demonstrated through Monte Carlo simulation experiments considering five frequency distributions that are widely used in RFA, and by case study on watersheds in conterminous United States. Results indicate that the PA outperforms methods based on index-flood approach.

Spectral Migration of Fluorescence in Graphene Oxide Aqueous Dispersions: Evidence for Excited-State Proton Transfer

Aqueous dispersions of graphene oxide (GO) exhibit strong pH-dependent fluorescence in the visible that originates, in part, from the oxygenated functionalities present. Here we examine the spectral migration on nanosecond time-scales of the pH dependent features in the fluorescence spectra. We show, from time-resolved emission spectra (TRES) constructed from the wavelength dependent fluorescence decay curves, that the migration is associated with excited state proton transfer. Both `intramolecular' and `intermolecular' transfer involving the quasi-molecular oxygenated aromatic fragments are observed. As a prerequisite to the time-resolved measurements, we have correlated the changes in the steady state fluorescence spectra with the sequence of dissociation events that occur in GO dispersions at different values of pH.

Development of a regional model for the North Indian Ocean

We have developed a one-way nested Indian Ocean regional model. The model combines the National Oceanic and Atmospheric Administration (NOAA) Geophysical Fluid Dynamics Laboratory's (GFDL) Modular Ocean Model (MOM4p1) at global climate model resolution (nominally one degree), and a regional Indian Ocean MOM4p1 configuration with 25 km horizontal resolution and 1 m vertical resolution near the surface. Inter-annual global simulations with Coordinated Ocean-Ice Reference Experiments (CORE-II) surface forcing over years 1992-2005 provide surface boundary conditions. We show that relative to the global simulation, (i) biases in upper ocean temperature, salinity and mixed layer depth are reduced, (ii) sea surface height and upper ocean circulation are closer to observations, and (iii) improvements in model simulation can be attributed to refined resolution, more realistic topography and inclusion of seasonal river runoff. Notably, the surface salinity bias is reduced to less than 0.1 psu over the Bay of Bengal using relatively weak restoring to observations, and the model simulates the strong, shallow halocline often observed in the North Bay of Bengal. There is marked improvement in subsurface salinity and temperature, as well as mixed layer depth in the Bay of Bengal. Major seasonal signatures in observed sea surface height anomaly in the tropical Indian Ocean, including the coastal waveguide around the Indian peninsula, are simulated with great fidelity. The use of realistic topography and seasonal river runoff brings the three dimensional structure of the East India Coastal Current and West India Coastal Current much closer to observations. As a result, the incursion of low salinity Bay of Bengal water into the southeastern Arabian Sea is more realistic. (C) 2013 Elsevier Ltd. All rights reserved.

Regional flood frequency analysis using kernel- based fuzzy clustering approach

Regionalization approaches are widely used in water resources engineering to identify hydrologically homogeneous groups of watersheds that are referred to as regions. Pooled information from sites (depicting watersheds) in a region forms the basis to estimate quantiles associated with hydrological extreme events at ungauged/sparsely gauged sites in the region. Conventional regionalization approaches can be effective when watersheds (data points) corresponding to different regions can be separated using straight lines or linear planes in the space of watershed related attributes. In this paper, a kernel-based Fuzzy c-means (KFCM) clustering approach is presented for use in situations where such linear separation of regions cannot be accomplished. The approach uses kernel-based functions to map the data points from the attribute space to a higher-dimensional space where they can be separated into regions by linear planes. A procedure to determine optimal number of regions with the KFCM approach is suggested. Further, formulations to estimate flood quantiles at ungauged sites with the approach are developed. Effectiveness of the approach is demonstrated through Monte-Carlo simulation experiments and a case study on watersheds in United States. Comparison of results with those based on conventional Fuzzy c-means clustering, Region-of-influence approach and a prior study indicate that KFCM approach outperforms the other approaches in forming regions that are closer to being statistically homogeneous and in estimating flood quantiles at ungauged sites. Key Points -list-0001'' list-type=''plain''> -item id=''wrcr20861-li-0001''>Kernel-based regionalization approach is presented for flood frequency analysis -item id=''wrcr20861-li-0002''>Kernel procedure to estimate flood quantiles at ungauged sites is developed -item id=''wrcr20861-li-0003''>A set of fuzzy regions is delineated in Ohio, USA

Mining Unit Tests for Discovery and Migration of Math APIs

Today's programming languages are supported by powerful third-party APIs. For a given application domain, it is common to have many competing APIs that provide similar functionality. Programmer productivity therefore depends heavily on the programmer's ability to discover suitable APIs both during an initial coding phase, as well as during software maintenance. The aim of this work is to support the discovery and migration of math APIs. Math APIs are at the heart of many application domains ranging from machine learning to scientific computations. Our approach, called MATHFINDER, combines executable specifications of mathematical computations with unit tests (operational specifications) of API methods. Given a math expression, MATHFINDER synthesizes pseudo-code comprised of API methods to compute the expression by mining unit tests of the API methods. We present a sequential version of our unit test mining algorithm and also design a more scalable data-parallel version. We perform extensive evaluation of MATHFINDER (1) for API discovery, where math algorithms are to be implemented from scratch and (2) for API migration, where client programs utilizing a math API are to be migrated to another API. We evaluated the precision and recall of MATHFINDER on a diverse collection of math expressions, culled from algorithms used in a wide range of application areas such as control systems and structural dynamics. In a user study to evaluate the productivity gains obtained by using MATHFINDER for API discovery, the programmers who used MATHFINDER finished their programming tasks twice as fast as their counterparts who used the usual techniques like web and code search, IDE code completion, and manual inspection of library documentation. For the problem of API migration, as a case study, we used MATHFINDER to migrate Weka, a popular machine learning library. Overall, our evaluation shows that MATHFINDER is easy to use, provides highly precise results across several math APIs and application domains even with a small number of unit tests per method, and scales to large collections of unit tests.

Evaluating Methods to Predict Streamflow at Ungauged Sites using Regional Flow Duration Curves: A Case Study

Precise information on streamflows is of major importance for planning and monitoring of water resources schemes related to hydro power, water supply, irrigation, flood control, and for maintaining ecosystem. Engineers encounter challenges when streamflow data are either unavailable or inadequate at target locations. To address these challenges, there have been efforts to develop methodologies that facilitate prediction of streamflow at ungauged sites. Conventionally, time intensive and data exhaustive rainfall-runoff models are used to arrive at streamflow at ungauged sites. Most recent studies show improved methods based on regionalization using Flow Duration Curves (FDCs). A FDC is a graphical representation of streamflow variability, which is a plot between streamflow values and their corresponding exceedance probabilities that are determined using a plotting position formula. It provides information on the percentage of time any specified magnitude of streamflow is equaled or exceeded. The present study assesses the effectiveness of two methods to predict streamflow at ungauged sites by application to catchments in Mahanadi river basin, India. The methods considered are (i) Regional flow duration curve method, and (ii) Area Ratio method. The first method involves (a) the development of regression relationships between percentile flows and attributes of catchments in the study area, (b) use of the relationships to construct regional FDC for the ungauged site, and (c) use of a spatial interpolation technique to decode information in FDC to construct streamflow time series for the ungauged site. Area ratio method is conventionally used to transfer streamflow related information from gauged sites to ungauged sites. Attributes that have been considered for the analysis include variables representing hydrology, climatology, topography, land-use/land- cover and soil properties corresponding to catchments in the study area. Effectiveness of the presented methods is assessed using jack knife cross-validation. Conclusions based on the study are presented and discussed. (C) 2015 The Authors. Published by Elsevier B.V.