Dual Binding Site Assisted Chromogenic and Fluorogenic Recognition and Discrimination of Fluoride and Cyanide by a Peripherally Borylated Metalloporphyrin: Overcoming Anion Interference in Organoboron Based Sensors

Peripherally triarylborane decorated porphyrin (2) and its Zn(II) complex (3) have been synthesized. Compound 3 contains of two different Lewis acidic binding sites (Zn(II) and boron center). Unlike all previously known triarylborane based sensors, the optical responses of 3 toward fluoride and cyanide are distinctively different, thus enabling the discrimination of these two interfering anions. Metalloporphyrin 3 shows a multiple channel fluorogenic response toward fluoride and cyanide and also a selective visual colorimetric response toward cyanide. By comparison with model systems and from detailed photophysical studies on 2 and 3, we conclude that the preferential binding of fluoride occurs at the peripheral borane moieties resulting in the cessation of the EET (electronic energy transfer) process from borane to porphyrin core and with negligible negetive cooperative effects. On the other hand, cyanide binding occurs at the Zn(II) core leading to drastic changes in its absorption behavior which can be followed by the naked eye. Such changes are not observed when the boryl substituent is absent (e.g., Zn-TPP and TPP). Compounds 2 and 3 were also found to be capable of extracting fluoride from aqueous medium.

Development of design charts for stress intensity factors at tips of multi-site cracks in unstiffened curved panels

Multi-site damage need to be addressed and evaluated in order to assess the integrity of aging aircraft structures. One of the problems recognized in the recent times is the effect of interaction between two or more cracks in the close neighborhood in such structures. The present paper deals with such a problem and presents numerical estimates of stress intensity factors at a crack tip in an un-stiffened curved panel with a secondary crack in the vicinity of a primary crack. The results are presented in the form of design charts. These results should be useful in evaluation in the damage tolerance evaluation of aircraft structures with multi-site damage. (C) 2014 Elsevier Ltd. All rights reserved.

Multi-site downscaling of maximum and minimum daily temperature using support vector machine

Climate change impact assessment studies involve downscaling large-scale atmospheric predictor variables (LSAPVs) simulated by general circulation models (GCMs) to site-scale meteorological variables. This article presents a least-square support vector machine (LS-SVM)-based methodology for multi-site downscaling of maximum and minimum daily temperature series. The methodology involves (1) delineation of sites in the study area into clusters based on correlation structure of predictands, (2) downscaling LSAPVs to monthly time series of predictands at a representative site identified in each of the clusters, (3) translation of the downscaled information in each cluster from the representative site to that at other sites using LS-SVM inter-site regression relationships, and (4) disaggregation of the information at each site from monthly to daily time scale using k-nearest neighbour disaggregation methodology. Effectiveness of the methodology is demonstrated by application to data pertaining to four sites in the catchment of Beas river basin, India. Simulations of Canadian coupled global climate model (CGCM3.1/T63) for four IPCC SRES scenarios namely A1B, A2, B1 and COMMIT were downscaled to future projections of the predictands in the study area. Comparison of results with those based on recently proposed multivariate multiple linear regression (MMLR) based downscaling method and multi-site multivariate statistical downscaling (MMSD) method indicate that the proposed method is promising and it can be considered as a feasible choice in statistical downscaling studies. The performance of the method in downscaling daily minimum temperature was found to be better when compared with that in downscaling daily maximum temperature. Results indicate an increase in annual average maximum and minimum temperatures at all the sites for A1B, A2 and B1 scenarios. The projected increment is high for A2 scenario, and it is followed by that for A1B, B1 and COMMIT scenarios. Projections, in general, indicated an increase in mean monthly maximum and minimum temperatures during January to February and October to December.

Robust dielectric properties of B-site size-disordered hexagonal Ln(2)CuTiO(6) (Ln = Y, Dy, Ho, Er, and Yb)

Hexagonal Ln(2)CuTiO(6) (Ln = Y, Dy, Ho, Er, and Yb) exhibits a rare combination of interesting dielectric properties, in the form of relatively large dielectric constants (epsilon' > 30), low losses, and extremely small temperature and frequency dependencies, over large ranges of temperature and frequency Choudhury et al., Appl. Phys. Lett. 96, 162903 (2010) and Choudhury et al., Phys. Rev. B 82, 134203 (2010)], making these compounds promising as high-k dielectric materials. The authors present a brief review of the existing literature on this interesting class of oxides, complimenting it with spectroscopic data in conjunction with first-principles calculation results, revealing a novel mechanism underlying these robust dielectric properties. These show that the large size differences in Cu2+ and Ti4+ at the B-site, aided by an inherent random distribution of CuO5 and TiO5 polyhedral units, frustrates the ferroelectric instability, inherent to the noncentrosymmetric P6(3) cm space group of this system, and gives rise to the observed relatively large dielectric constant values. Additionally, the phononic contributions to the dielectric constant are dominated primarily by mid-frequency (>100 cm(-1)) polar modes, involving mainly Ti4+ 3d(0) ions. In contrast, the soft polar phonon modes with frequencies typically less than 100 cm(-1), usually responsible for dielectric properties of materials, are found to be associated with non-d(0) Cu2+ ions and to contribute very little, giving rise to the remarkable temperature stability of dielectric properties of these compounds. (C) 2014 American Vacuum Society.

Whole exome sequencing identifies a novel splice-site mutation in ADAMTS17 in an Indian family with Weill-Marchesani syndrome

Purpose: Weill-Marchesani syndrome (WMS) is a rare connective tissue disorder, characterized by short stature, micro-spherophakic lens, and stubby hands and feet (brachydactyly). WMS is caused by mutations in the FBN1, ADAMTS10, and LTBP2 genes. Mutations in the LTBP2 and ADAMTS17 genes cause a WMS-like syndrome, in which the affected individuals show major features of WMS but do not display brachydactyly and joint stiffness. The main purpose of our study was to determine the genetic cause of WMS in an Indian family. Methods: Whole exome sequencing (WES) was used to identify the genetic cause of WMS in the family. The cosegregation of the mutation was determined with Sanger sequencing. Reverse transcription (RT)-PCR analysis was used to assess the effect of a splice-site mutation on splicing of the ADAMTS17 transcript. Results: The WES analysis identified a homozygous novel splice-site mutation c.873+1G>T in a known WMS-like syndrome gene, ADAMTS17, in the family. RT-PCR analysis in the patient showed that exon 5 was skipped, which resulted in the deletion of 28 amino acids in the ADAMTS17 protein. Conclusions: The mutation in the WMS-like syndrome gene ADAMTS17 also causes WMS in an Indian family. The present study will be helpful in genetic diagnosis of this family and increases the number of mutations of this gene to six.

Community-managed forests and wildlife-friendly agriculture play a subsidiary but not substitutive role to protected areas for the endangered Asian elephant

Global conservation policy is increasingly debating the feasibility of reconciling wildlife conservation and human resource requirements in land uses outside protected areas (PAs). However, there are few quantitative assessments of whether or to what extent these `wildlife-friendly' land uses fulfill a fundamental function of PAs-to separate biodiversity from anthropogenic threats. We distinguish the role of wildlife-friendly land uses as being (a) subsidiary, whereby they augment PAs with secondary habitat, or (b) substitutive, wherein they provide comparable habitat to PAs. We tested our hypotheses by investigating the influence of land use and human presence on space-use intensity of the endangered Asian elephant (Elephas maximus) in a fragmented landscape comprising PAs and wildlife-friendly land uses. We applied multistate occupancy models to spatial data on elephant occurrence to estimate and model the overall probability of elephants using a site, and the conditional probability of high-intensity use given that elephants use a site. The probability of elephants using a site regardless of intensity did not vary between PAs and wildlife-friendly land uses. However, high-intensity use declined with distance to PM, and this effect was accentuated by an increase in village density. Therefore, while wildlife-friendly land uses did play a subsidiary conservation role, their potential to substitute for PAs was offset by a strong human presence. Our findings demonstrate the need to evaluate the role of wildlife-friendly land uses in landscape-scale conservation; for species that have conflicting resource requirements with people, PAs are likely to provide crucial refuge from growing anthropogenic threats. (C) 2014 Elsevier Ltd. All rights reserved.

Dynamic Site Characterization and Correlation of Shear Wave Velocity with Standard Penetration Test `N' Values for the City of Agartala, Tripura State, India

Seismic site characterization is the basic requirement for seismic microzonation and site response studies of an area. Site characterization helps to gauge the average dynamic properties of soil deposits and thus helps to evaluate the surface level response. This paper presents a seismic site characterization of Agartala city, the capital of Tripura state, in the northeast of India. Seismically, Agartala city is situated in the Bengal Basin zone which is classified as a highly active seismic zone, assigned by Indian seismic code BIS-1893, Indian Standard Criteria for Earthquake Resistant Design of Structures, Part-1 General Provisions and Buildings. According to the Bureau of Indian Standards, New Delhi (2002), it is the highest seismic level (zone-V) in the country. The city is very close to the Sylhet fault (Bangladesh) where two major earthquakes (M (w) > 7) have occurred in the past and affected severely this city and the whole of northeast India. In order to perform site response evaluation, a series of geophysical tests at 27 locations were conducted using the multichannel analysis of surface waves (MASW) technique, which is an advanced method for obtaining shear wave velocity (V (s)) profiles from in situ measurements. Similarly, standard penetration test (SPT-N) bore log data sets have been obtained from the Urban Development Department, Govt. of Tripura. In the collected data sets, out of 50 bore logs, 27 were selected which are close to the MASW test locations and used for further study. Both the data sets (V (s) profiles with depth and SPT-N bore log profiles) have been used to calculate the average shear wave velocity (V (s)30) and average SPT-N values for the upper 30 m depth of the subsurface soil profiles. These were used for site classification of the study area recommended by the National Earthquake Hazard Reduction Program (NEHRP) manual. The average V (s)30 and SPT-N classified the study area as seismic site class D and E categories, indicating that the city is susceptible to site effects and liquefaction. Further, the different data set combinations between V (s) and SPT-N (corrected and uncorrected) values have been used to develop site-specific correlation equations by statistical regression, as `V (s)' is a function of SPT-N value (corrected and uncorrected), considered with or without depth. However, after considering the data set pairs, a probabilistic approach has also been presented to develop a correlation using a quantile-quantile (Q-Q) plot. A comparison has also been made with the well known published correlations (for all soils) available in the literature. The present correlations closely agree with the other equations, but, comparatively, the correlation of shear wave velocity with the variation of depth and uncorrected SPT-N values provides a more suitable predicting model. Also the Q-Q plot agrees with all the other equations. In the absence of in situ measurements, the present correlations could be used to measure V (s) profiles of the study area for site response studies.

Distribution, Demography, and Conservation of Lion-tailed Macaques (Macaca silenus) in the Anamalai Hills Landscape, Western Ghats, India

The status of the endemic and endangered lion-tailed macaque (Macaca silenus) has not been properly assessed in several regions of the Western Ghats of southern India. We conducted a study in Parambikulam Forest Reserve in the state of Kerala to determine the distribution, demography, and status of lion-tailed macaques. We laid 5km(2) grid cells on the map of the study area (644km(2)) and made four replicated walks in each grid cell using GPS. We gathered data on lion-tailed macaque group locations, demography, and site covariates including trail length, duration of walk, proportion of evergreen forest, height of tallest trees, and human disturbance index. We also performed occupancy modeling using PRESENCE ver. 3.0. We estimated a minimum of 17 groups of macaques in these hills. Low detection and occupancy probabilities indicated a low density of lion-tailed macaques in the study area. Height of the tallest trees correlated positively whereas human disturbance and proportion of evergreen forest correlated negatively with occupancy in grid cells. We also used data from earlier studies carried out in the surrounding Anamalai Tiger Reserve and Nelliyampathy Hills to discuss the conservation status in the large Anamalai Hills Landscape. This landscape harbors an estimated population of 1108 individuals of lion-tailed macaques, which is about one third of the entire estimated wild population of this species. A conservation plan for this landscape could be used as a model for conservation in other regions of the Western Ghats.

Off-site impacts of agricultural composting: role of terrestrially derived organic matter in structuring aquatic microbial communities and their metabolic potential

While considered as sustainable and low-cost agricultural amendments, the impacts of organic fertilizers on downstream aquatic microbial communities remain poorly documented. We investigated the quantity and quality of the dissolved organic matter leaching from agricultural soil amended with compost, vermicompost or biochar and assessed their effects on lake microbial communities, in terms of viral and bacterial abundances, community structure and metabolic potential. The addition of compost and vermicompost significantly increased the amount of dissolved organic carbon in the leachate compared with soil alone. Leachates from these additions, either with or without biochar, were highly bioavailable to aquatic microbial communities, although reducing the metabolic potential of the community and harbouring more specific communities. Although not affecting bacterial richness or taxonomic distributions, the specific addition of biochar affected the original lake bacterial communities, resulting in a strongly different community. This could be partly explained by viral burst and converging bacterial abundances throughout the samples. These results underline the necessity to include off-site impacts of agricultural amendments when considering their cascading effect on downstream aquatic ecosystems.

Estimating the volume of glaciers in the Himalayan-Karakoram region using different methods

Ice volume estimates are crucial for assessing water reserves stored in glaciers. Due to its large glacier coverage, such estimates are of particular interest for the Himalayan-Karakoram (HK) region. In this study, different existing methodologies are used to estimate the ice reserves: three area-volume relations, one slope-dependent volume estimation method, and two ice-thickness distribution models are applied to a recent, detailed, and complete glacier inventory of the HK region, spanning over the period 2000-2010 and revealing an ice coverage of 40 775 km(2). An uncertainty and sensitivity assessment is performed to investigate the influence of the observed glacier area and important model parameters on the resulting total ice volume. Results of the two ice-thickness distribution models are validated with local ice-thickness measurements at six glaciers. The resulting ice volumes for the entire HK region range from 2955 to 4737 km(3), depending on the approach. This range is lower than most previous estimates. Results from the ice thickness distribution models and the slope-dependent thickness estimations agree well with measured local ice thicknesses. However, total volume estimates from area-related relations are larger than those from other approaches. The study provides evidence on the significant effect of the selected method on results and underlines the importance of a careful and critical evaluation.

Identifying regions for conservation of sloth bears through occupancy modelling in north-eastern Karnataka, India

In the absence of information on species in decline with contracting ranges, management should emphasize remaining populations and protection of their habitats. Threatened by anthropogenic pressure including habitat degradation and loss, sloth bears (Melursus ursinus) in India have become limited in range, habitat, and population size. We identified ecological and anthropogenic determinants of occurrence within an occupancy framework to evaluate habitat suitability of non-protected regions (with sloth bears) in northeastern Karnataka, India. We employed a systematic sampling methodology to yield presence absence data to examine a priori hypotheses of determinants that affected occupancy. These covariates were broadly classified as habitat or anthropogenic factors. Mean number of termite mounds and trees positively influenced sloth bear occupancy, and grazing pressure expounded by mean number of livestock dung affected it negatively. Also, mean percentage of shrub coverage had no impact on bear inhabitance. The best fitting model further predicted habitats in Bukkasagara, Agoli, and Benakal reserved forests to have 38%, 75%, and 88%, respectively, of their sampled grid cells with high occupancies (>0.70) albeit little or no legal protection. We recommend a conservation strategy that includes protection of vegetation stand-structure, maintenance of soil moisture, and enrichment of habitat for the long-term welfare of this species.

Estimates of site response based on spectral ratio between horizontal and vertical components of ambient vibrations in the source zone of 2001 Bhuj earthquake

We investigated the site response characteristics of Kachchh rift basin over the meizoseismal area of the 2001, Mw 7.6, Bhuj (NW India) earthquake using the spectral ratio of the horizontal and vertical components of ambient vibrations. Using the available knowledge on the regional geology of Kachchh and well documented ground responses from the earthquake, we evaluated the H/V curves pattern across sediment filled valleys and uplifted areas generally characterized by weathered sandstones. Although our HIV curves showed a largely fuzzy nature, we found that the hierarchical clustering method was useful for comparing large numbers of response curves and identifying the areas with similar responses. Broad and plateau shaped peaks of a cluster of curves within the valley region suggests the possibility of basin effects within valley. Fundamental resonance frequencies (f(0)) are found in the narrow range of 0.1-2.3 Hz and their spatial distribution demarcated the uplifted regions from the valleys. In contrary, low HIV peak amplitudes (A(0) = 2-4) were observed on the uplifted areas and varying values (2-9) were found within valleys. Compared to the amplification factors, the liquefaction indices (kg) were able to effectively indicate the areas which experienced severe liquefaction. The amplification ranges obtained in the current study were found to be comparable to those obtained from earthquake data for a limited number of seismic stations located on uplifted areas; however the values on the valley region may not reflect their true amplification potential due to basin effects. Our study highlights the practical usefulness as well as limitations of the HIV method to study complex geological settings as Kachchh. (C) 2014 Elsevier Ltd. All rights reserved.

High Temperatures Result in Smaller Nurseries which Lower Reproduction of Pollinators and Parasites in a Brood Site Pollination Mutualism

In a nursery pollination mutualism, we asked whether environmental factors affected reproduction of mutualistic pollinators, non-mutualistic parasites and seed production via seasonal changes in plant traits such as inflorescence size and within-tree reproductive phenology. We examined seasonal variation in reproduction in Ficus racemosa community members that utilise enclosed inflorescences called syconia as nurseries. Temperature, relative humidity and rainfall defined four seasons: winter; hot days, cold nights; summer and wet seasons. Syconium volumes were highest in winter and lowest in summer, and affected syconium contents positively across all seasons. Greater transpiration from the nurseries was possibly responsible for smaller syconia in summer. The 3-5 degrees C increase in mean temperatures between the cooler seasons and summer reduced fig wasp reproduction and increased seed production nearly two-fold. Yet, seed and pollinator progeny production were never negatively related in any season confirming the mutualistic fig-pollinator association across seasons. Non-pollinator parasites affected seed production negatively in some seasons, but had a surprisingly positive relationship with pollinators in most seasons. While within-tree reproductive phenology did not vary across seasons, its effect on syconium inhabitants varied with season. In all seasons, within-tree reproductive asynchrony affected parasite reproduction negatively, whereas it had a positive effect on pollinator reproduction in winter and a negative effect in summer. Seasonally variable syconium volumes probably caused the differential effect of within-tree reproductive phenology on pollinator reproduction. Within-tree reproductive asynchrony itself was positively affected by intra-tree variation in syconium contents and volume, creating a unique feedback loop which varied across seasons. Therefore, nursery size affected fig wasp reproduction, seed production and within-tree reproductive phenology via the feedback cycle in this system. Climatic factors affecting plant reproductive traits cause biotic relationships between plants, mutualists and parasites to vary seasonally and must be accorded greater attention, especially in the context of climate change.

Genome wide chromatin occupancy of mrhl RNA and its role in gene regulation in mouse spermatogonial cells

Mrhl RNA is a nuclear lncRNA encoded in the mouse genome and negatively regulates Wnt signaling in spermatogonial cells through p68/Ddx5 RNA helicase. Mrhl RNA is present in the chromatin fraction of mouse spermatogonial Gc1-Spg cells and genome wide chromatin occupancy of mrhl RNA by ChOP (Chromatin oligo affinity precipitation) technique identified 1370 statistically significant genomic loci. Among these, genes at 37 genomic loci also showed altered expression pattern upon mrhl RNA down regulation which are referred to as GRPAM (Genes Regulated by Physical Association of Mrhl RNA). p68 interacted with mrhl RNA in chromatin at these GRPAM loci. p68 silencing drastically reduced mrhl RNA occupancy at 27 GRPAM loci and also perturbed the expression of GRPAM suggesting a role for p68 mediated mrhl RNA occupancy in regulating GRPAM expression. Wnt3a ligand treatment of Gc1-Spg cells down regulated mrhl RNA expression and also perturbed expression of these 27 GRPAM genes that included genes regulating Wnt signaling pathway and spermatogenesis, one of them being Sox8, a developmentally important transcription factor. We also identified interacting proteins of mrhl RNA associated chromatin fraction which included Pc4, a chromatin organizer protein and hnRNP A/B and hnRNP A2/B1 which have been shown to be associated with lincRNA-Cox2 function in gene regulation. Our findings in the Gc1-Spg cell line also correlate with the results from analysis of mouse testicular tissue which further highlights the in vivo physiological significance of mrhl RNA in the context of gene regulation during mammalian spermatogenesis.

Using long time series of agricultural-derived nitrates for estimating catchment transit times

The estimation of water and solute transit times in catchments is crucial for predicting the response of hydrosystems to external forcings (climatic or anthropogenic). The hydrogeochemical signatures of tracers (either natural or anthropogenic) in streams have been widely used to estimate transit times in catchments as they integrate the various processes at stake. However, most of these tracers are well suited for catchments with mean transit times lower than about 4-5 years. Since the second half of the 20th century, the intensification of agriculture led to a general increase of the nitrogen load in rivers. As nitrate is mainly transported by groundwater in agricultural catchments, this signal can be used to estimate transit times greater than several years, even if nitrate is not a conservative tracer. Conceptual hydrological models can be used to estimate catchment transit times provided their consistency is demonstrated, based on their ability to simulate the stream chemical signatures at various time scales and catchment internal processes such as N storage in groundwater. The objective of this study was to assess if a conceptual lumped model was able to simulate the observed patterns of nitrogen concentration, at various time scales, from seasonal to pluriannual and thus if it was relevant to estimate the nitrogen transit times in headwater catchments. A conceptual lumped model, representing shallow groundwater flow as two parallel linear stores with double porosity, and riparian processes by a constant nitrogen removal function, was applied on two paired agricultural catchments which belong to the Research Observatory ORE AgrHys. The Global Likelihood Uncertainty Estimation (GLUE) approach was used to estimate parameter values and uncertainties. The model performance was assessed on (i) its ability to simulate the contrasted patterns of stream flow and stream nitrate concentrations at seasonal and inter-annual time scales, (ii) its ability to simulate the patterns observed in groundwater at the same temporal scales, and (iii) the consistency of long-term simulations using the calibrated model and the general pattern of the nitrate concentration increase in the region since the beginning of the intensification of agriculture in the 1960s. The simulated nitrate transit times were found more sensitive to climate variability than to parameter uncertainty, and average values were found to be consistent with results from others studies in the same region involving modeling and groundwater dating. This study shows that a simple model can be used to simulate the main dynamics of nitrogen in an intensively polluted catchment and then be used to estimate the transit times of these pollutants in the system which is crucial to guide mitigation plans design and assessment. (C) 2015 Elsevier B.V. All rights reserved.