Reactivity studies of highly electrophilic ruthenium complexes

The 16-electron, coordinatively unsaturated, dicationic ruthenium complex Ru(P(OH)(2)(OMe))(dppe)(2)]OTf](2) (1a) brings about the heterolysis of the C-H bond in phenylacetylene to afford the phenylacetylide complex trans-Ru(C CPh)(P(OH)(2)(OMe))(dppe)(2)]OTf] (2). The phenylacetylide complex undergoes hydrogenation to give a ruthenium hydride complex trans-Ru(H)(P(OH)(2)(OMe))(dppe)(2)]OTf] (3) and phenylacetylene via the addition of H-2 across the Ru-C bond. The 16-electron complex also reacts with HSiCl3 quite vigorously to yield a chloride complex trans-Ru(Cl)(P(OH)(2)(OMe))(dppe)(2)]OTf] (4). On the other hand, the other coordinatively unsaturated ruthenium complex Ru(P(OH)(3))(dppe)(2)]OTf](2) (1b) reacts with a base N-benzylideneaniline to afford a phosphonate complex Ru(P(O)(OH)(2))(dppe)(2)]OTf] (5) via the abstraction of one of the protons of the P(OH)(3) ligand by the base. The phenylacetylide, chloride, and the phosphonate complexes have been structurally characterized. The phosphonate complex reacts with H-2 to afford the corresponding dihydrogen complex trans-Ru(eta(2)-H-2)(P(O)(OH)(2))(dppe)(2)]OTf] (5-H2). The intact nature of the H-H bond in this species was established using variable temperature H-1 spin-lattice relaxation time measurements and the observation of a significant J(H,D) coupling in the HD isotopomer trans-Ru(eta(2)-HD)(P(O)(OH)(2))(dppe)(2)]OTf] (5-HD). (C) 2010 Elsevier B. V. All rights reserved.

Production process of Scots pine.

The accompanying collective research report is the result of the research project in 1986­90 between The Finnish Academy and the former Soviet Academy of Sciences. The project was organized around common field work in Finland and in the former Soviet Union and theoretical analyses of tree growth determining processes. Based on theoretical analyses, dynamic stand growth models were made and their parameters were determined utilizing the field results. Annual cycle affects the tree growth. Our theoretical approach was based on adaptation to local climate conditions from Lapland to South Russia. The initiation of growth was described as a simple low and high temperature accumulation driven model. Linking the theoretical model with long term temperature data allowed us to analyze what type of temperature response produced favorable outcome in different climates. Initiation of growth consumes the carbohydrate reserves in plants. We measured the dynamics of insoluble and soluble sugars in the very northern and Karelian conditions. Clear cyclical pattern was observed but the differences between locations were surprisingly small. Analysis of field measurements of CO2 exchange showed that irradiance is the dominating factor causing variation in photosynthetic rate in natural conditions during summer. The effect of other factors is so small that they can be omitted without any considerable loss of accuracy. A special experiment carried out in Hyytiälä showed that the needle living space, defined as the ratio between the shoot cylindric volume and needle surface area, correlates with the shoot photosynthesis. The penetration of irradiance into Scots pine canopy is a complicated phenomenon because of the movement of the sun on the sky and the complicated structure of branches and needles. A moderately simple but balanced forest radiation regime submodel was constructed. It consists of the tree crown and forest structure, the gap probability calculation and the consideration of spatial and temporal variation of radiation inside the forest. The common field excursions in different geographical regions resulted in a lot of experimental data of regularities of woody structures. The water transport seems to be a good common factor to analyse these properties of tree structure. There are evident regressions between cross-sectional areas measured at different locations along the water pathway from fine roots to needles. The observed regressions have clear geographical trends. For example, the same cross-sectional area can support three times higher needle mass in South Russia than in Lapland. Geographical trends can also be seen in shoot and needle structure. Analysis of data published by several Russian authors show, that one ton of needles transpire 42 ton of water a year. This annual amount of transpiration seems to be independent of geographical location, year and site conditions. The produced theoretical and experimental material is utilised in the development of stand growth model that describes the growth and development of Scots pine stands in Finland and the former Soviet Union. The core of the model is carbon and nutrient balances. This means that carbon obtained in photosynthesis is consumed for growth and maintenance and nutrients are taken according to the metabolic needs. The annual photosynthetic production by trees in the stand is determined as a function of irradiance and shading during the active period. The utilisation of the annual photosynthetic production to the growth of different components of trees is based on structural regularities. Since the fundamental metabolic processes are the same in all locations the same growth model structure can be applied in the large range of Scots pine. The annual photosynthetic production and structural regularities determining the allocation of resources have geographical features. The common field measurements enable the application of the model to the analysis of growth and development of stands growing on the five locations of experiments. The model enables the analysis of geographical differences in the growth of Scots pine. For example, the annual photosynthetic production of a 100-year-old stand at Voronez is 3.5 times higher than in Lapland. The share consumed to needle growth (30 %) and to growth of branches (5 %) seems to be the same in all locations. In contrast, the share of fine roots is decreasing when moving from north to south. It is 20 % in Lapland, 15 % in Hyytiälä Central Finland and Kentjärvi Karelia and 15 % in Voronez South Russia. The stem masses (115­113 ton/ha) are rather similar in Hyytiälä, Kentjärvi and Voronez, but rather low (50 ton/ha) in Lapland. In Voronez the height of the trees reach 29 m being in Hyytiälä and Kentjärvi 22 m and in Lapland only 14 m. The present approach enables utilization of structural and functional knowledge, gained in places of intensive research, in the analysis of growth and development of any stand. This opens new possibilities for growth research and also for applications in forestry practice.

Catalytic performance of highly dispersed Ni/TiO2 for dry and steam reforming of methane

The present study reports a sonochemical-assisted synthesis of a highly active and coke resistant Ni/TiO2 catalyst for dry and steam reforming of methane. The catalyst was characterized using XRD, TEM, XPS, BET analyzer and TGA/DTA techniques. The TEM analysis showed that Ni nanoparticles were uniformly dispersed on TiO2 surface with a narrow size distribution. The catalyst prepared via this approach exhibited excellent activity and stability for both the reactions compared to the reference catalyst prepared from the conventional wet impregnation method. For dry reforming, 86% CH4 conversion and 84% CO2 conversion was obtained at 700 degrees C. Nearly 92% CH4 conversion and 77% CO selectivity was observed under a H2O/CH4 ratio of 1.2 at 700 degrees C for the steam reforming reaction. In particular, the present catalyst is extremely active and resistant to coke formation for steam reforming at low steam/carbon ratios. There is no significant modification of Ni particles size and no coke deposition, even after a long term reaction, demonstrating its potential applicability as an industrial reformate for hydrogen production. The detailed kinetic studies have been presented for steam reforming and the mechanism involving Langmuir-Hinshelwood kinetics with adsorptive dissociation of CH4 as a rate determining step has been used to correlate the experimental data.

New fish populations as evidence of climate chage in former dry areas of the Pampa Region ( Southern South America).

Water bodies located at 34º 58' S, 62º 58' W formed after 1980 by 30 % increasing rainfall during the last half century, were colonized by ten fish species which are a subset of the commonest species living in the pampasic lagunas. These new populations imply a displacement of the West of Pampasian fishes to areas of the western basins previously lacking fish.

Prospects for fish culture in char areas of Bangladesh

Fish production is considered in the barren chars or sandy land masses created through siltation along river banks and deltas in Bangladesh. The prospects for fish culture in ponds and cages or pen culture in rivers and canals are examined. The socioeconomic implications of fish culture as a livelihood source for communities living in char areas are also discussed.

A preliminary report on Chanos fry surveys carried out in the brackish water areas of Mannar, Puttalam and Negombo

This paper records the results of the Chanos fry surveys carried out in Mannar, Puttalam and Negombo lagoon areas since 1967, and gives a summary of the earlier surveys. The maximum amount of Chanos fry was obtained from Mannar area during April and May. All three areas have their main commercial fry season in April and May with a second commercially negligible season in October–November. The quantity of fry collected has been utilized to evaluate the potential fry production figures. Mannar 400,000,000 fry/annum. Puttalam 200,000,000 fry/annum. It would be extremely difficult to estimate the number of eggs laid, the larvae hatched and the fry available each year along the coastal areas of Ceylon. It is necessary to obtain biological, meteorological and oceanographical data so as to provide a basis for the prediction and estimation of fry populations in the coastal waters of Ceylon. The suggested ideal season for commercial catches of Chanos fry is April–May with operations to be carried out simultaneously all along the west coast.

Economics of pond fish culture in some selected areas of Bangladesh

A simple costs and return analysis was done to determine the profitability of pond fish culture in three selected thanas namely Nertakona Sadar, Purbadhala and Kendua under Netrakona district. Cobb-douglas production function model was used to estimate the contribution of key variables to the production process of pond fish culture. It was found that cost of pond fish production was Tk. 10,103/ha/yr and the per hectare fish yield was 943 kgl/yr and the average gross and net return were Tk. 49,515 and Tk. 39,412 respectively. It was found that medium and small farms had the higher yield because of efficient use of production inputs compared to large farms. It was also observed that ownership of pond, number of species and human labour had negative impact on pond fish output, while depth of pond water, farm size, fish seed, fertilizer and artificial feed had significant positive effects on pond fish output.

Ecological imbalances in the coastal areas of Pakistan and Karachi Harbour

The marine environment of Pakistan has been described in the context of three main regions : the Indus delta and its creek system, the Karachi coastal region, and the Balochistan coast. The creeks, contrary to concerns, do receive adequate discharges of freshwater. On site observations indicate that freshwater continues flowing into them during the lean water periods and dilutes the seawater there. A major factor for the loss of mangrove forests as well as ecological disturbances in the Indus delta is loss of the silt load resulting in erosion of its mudflats. The ecological disturbance has been aggravated by allowing camels to browse the mangroves. The tree branches and trunks, having been denuded of leaves are felled for firewood. Evidence is presented to show that while indiscriminate removal of its mangrove trees is responsible for the loss of large tracts of mangrove forests, overharvesting of fisheries resources has depleted the river of some valuable fishes that were available from the delta area. Municipal and industrial effluents discharged into the Lyari and Malir rivers and responsible for land-based pollution at the Karachi coast and the harbour. The following are the three major areas receiving land-based pollution and whose environmental conditions have been examined in detail: (l) the Manora channel, located on the estuary of the Lyari river and serving as the main harbour, has vast areas forming its western and eastern backwaters characterized by mud flats and mangroves. The discharge of industrial wastewater from the S.I.T.E. and municipal effluents from the northern and central districts into the Lyari has turned this river into an open drain. This, in turn, has caused a negative impact on the environment of the port, fish harbour, and the adjacent beaches. (2) The Gizri creek receives industrial and municipal effluents from the Malir river as well as from several industries and power stations. The highly degraded discharges from the Malir have negatively impacted the environment in this creek. (3) The coastline between the Manora channel and Gizri creek where the untreated municipal effluents are discharged by the southern districts of Karachi, is responsible for the degraded environment of the Chinna creek, and also of the beaches and the harbour. The Balochistan coast is relatively safe from land-based pollution, mainly because of the lack of industrial, urban or agricultural activity, except the Hingol river system where some agricultural activities have been initiated.

Factor intensity and economic returns of alternate shrimp crop and shrimp-salt farming in the coastal areas of Bangladesh

The paper examines the factor intensity and economic returns of alternate shrimp-crop and shrimp-salt farming in the coastal areas of Bangladesh. Data were collected from 30 shrimp-crop and 30 shrimp-salt farmers, 30 shrimp farmers and 30 rice farmers from three selected coastal districts of Bangladesh. Cobb-Douglas production function model was used to determine the effect of various factors on alternate shrimp-crop farming. The chosen variables were stocking of juveniles, paddy seed, labour, fertilizers, feed and farm size of respective type of farming. The results indicated that the production function exhibited increasing remrns to scale for alternate shrimp-rice, alternate shrimp-salt and year round shrimp farming while it indicated decreasing returns for year round rice farming. Economic analysis of same system of farming indicated that higher amount of input use produced higher level of yield, gross return and net return for each type of production system.

Culture practices of freshwater giant prawn in some selected areas of Mymensingh

A study was conducted to examine the culture practices of freshwater giant prawn, Macrobrachium rosenbergii in some selected areas of Mymensingh. Based on a sample of 100 farmers from three different upazila, namely Phulpur, Gouripur and Ishwargonj in Mymensingh district, 94% of farmers cultured prawn with fish in their pond. Only 6% of farmers cultured prawn, fish and dike crops for higher economic return. The culture period is typically nine months; hatchery produced post-larvae were stocked from May to June and harvested from November to January. Per hectare production of prawn, 375 kg/yr was very low because the farmers followed simple culture method. Most of the farmers made a profit of Tk. 68,403/ha/yr and the major costs incurred were for purchasing prawn seed and feed. The culture of prawn in pond system is technically possible under different conditions though expansion of small-scale prawn farming mainly depends on reduction of production costs. Future targets could be integration of pond prawn culture with other agricultural activities especially dike cropping and rice production in the monsoon.

Shifting rice farming to fish culture in some selected areas of Mymensingh, Bangladesh: the process, conflicts and impacts

The evolutionary process of converting low-lying paddy fields into fish farms and its impact on agrarian communities in some selected areas of Mymensingh district were studied. This study was conducted through participatory rural appraisal (PRA) covering 12 villages from each of selected upazillas viz. Fulpur and Haluaghat of Mymensing [sic] district. A total of 12 PRA sessions were conducted where 90 farmers participated during 29 July to 26 August 2004. It is seen that the use of low-lying paddy fields was mostly confined to Broadcast Aman (B. Aman) rice production until 1960s. With the introduction of modern rice farming technology, the farmers started to produce Boro rice in Rabi season and B. Aman rice in Kharif season. With the passage of time, aquaculture technologies have been evolved and the farmers realized that fish farming is more profitable than rice cultivation, and then they started to utilize their paddy fields for alternate rice-fish farming and rice-cum-fish farming. Now a days, aquaculture based crop production system is in practice in more than 25% of the low-lying paddy fields. Conversion of rice fields in to fish ponds has brought up a change in the livelihood patterns of the rural farmers. The areas where the farmers involved themselves in the new production systems were fingerling collection, transportation and marketing of fry and fingerlings. During 1960s to 1970s, a few people used to culture fish in the permanent ponds for their own consumption, the species produced were rohu, catla, mrigal, ghainna, long whiskered catfish, freshwater shark (boal), snake head (shol) etc. Small fishes like climbing perch, stinging catfish, walking catfish, barb, minnows etc. were available in the rice fields during monsoon season. In 1980s to mid 1990s, some rice fields were converted into fish ponds and the people started to produce fish for commercial purposes. When rice-fish farming became profitable, a large number of people started converting their rice fields in to rice-fish culture ponds. Culture of some exotic fishes like silver carp, tilapia, grass carp, silver barb etc. also started in the paddy fields. Higher income from fish farming contributed positively in improving the housing, sanitation and education system in the study areas. It is seen that the medium and medium high lands were only used for alternate rice fish farming. The net income was high in any fish based cropping system that motivated the farmers to introduce fish based cropping system in the low-lying inland areas. As a result, the regional as well as communal income disparities occurred. However, the extraction of ground water became common during the dry period as the water was used for both rice and fish farming. Mass conversion of paddy fields into rice-fish culture ponds caused water logging in the study areas. In most cases, the participated farmers mentioned that they could be easily benefited by producing fish with T. Aman or only fish during the monsoon season. They agreed that this was an impressive technology to them and they could generate employment opportunities throughout the year. Finally, the social, economic and technical problems which are acting as constraints to rapid expansion of fish production system were reported from the interviewee.

Preparation of highly dispersed gold microparticles and their electrocatalytic activity for the oxidation of formaldehyde

The electrochemical preparation of highly dispersed Au microparticles on the surfaces of glassy carbon (GC) electrodes and their electrocatalytic activities for the oxidation of formaldehyde were studied. It was found that the reduction of Au3+ to Au is controlled by diffusion and the formation mechanism of Au microparticles on the GC surfaces corresponds to an instantaneous nucleation and diffusion-controlled three dimensional growth process. The particle size is about 80-90 nm in diameter after the electrochemical ageing treatment. These highly dispersed Au microparticles have high surface areas and exhibit better electrocatalytic activity than that of bulk-form Au toward the electrochemical oxidation of formaldehyde in alkaline media.

A dimensionless number for understanding the evolutionary dynamics of antigenically variable RNA viruses.

Antigenically variable RNA viruses are significant contributors to the burden of infectious disease worldwide. One reason for their ubiquity is their ability to escape herd immunity through rapid antigenic evolution and thereby to reinfect previously infected hosts. However, the ways in which these viruses evolve antigenically are highly diverse. Some have only limited diversity in the long-run, with every emergence of a new antigenic variant coupled with a replacement of the older variant. Other viruses rapidly accumulate antigenic diversity over time. Others still exhibit dynamics that can be considered evolutionary intermediates between these two extremes. Here, we present a theoretical framework that aims to understand these differences in evolutionary patterns by considering a virus's epidemiological dynamics in a given host population. Our framework, based on a dimensionless number, probabilistically anticipates patterns of viral antigenic diversification and thereby quantifies a virus's evolutionary potential. It is therefore similar in spirit to the basic reproduction number, the well-known dimensionless number which quantifies a pathogen's reproductive potential. We further outline how our theoretical framework can be applied to empirical viral systems, using influenza A/H3N2 as a case study. We end with predictions of our framework and work that remains to be done to further integrate viral evolutionary dynamics with disease ecology.

Applying species distribution modelling to identify areas of high conservation value for endangered species: A case study using Margaritifera margaritifera (L.)

The development and implementation of a population supplementation and restoration plan for any endangered species should involve an understanding of the species’ habitat requirements prior to the release of any captive bred individuals. The freshwater pearl mussel, Margaritifera margaritifera, has undergone dramatic declines over the last century and is now globally endangered. In Northern Ireland, the release of captive bred individuals is being used to support wild populations and repatriate the species in areas where it once existed. We employed a combination of maximum entropy modelling (MAXENT) and Generalized Linear Mixed Models (GLMM) to identify ecological parameters necessary to support wild populations using GIS-based landscape scale and ground-truthed habitat scale environmental parameters. The GIS-based landscape scale model suggested that mussel occurrence was associated with altitude and soil characteristics including the carbon, clay, sand, and silt content. Notably, mussels were associated with a relatively narrow band of variance indicating that M. margaritifera has a highly specific landscape niche. The ground-truthed habitat scale model suggested that mussel occurrence was associated with stable consolidated substrates, the extent of bankside trees, presence of indicative macrophyte species and fast flowing water. We propose a three phase conservation strategy for M. margaritifera identifying suitable areas within rivers that (i) have a high conservation value yet needing habitat restoration at a local level, (ii) sites for population supplementation of existing populations and (iii) sites for species reintroduction to rivers where the mussel historically occurred but is now locally extinct. A combined analytical approach including GIS-based landscape scale and ground-truthed habitat scale models provides a robust method by which suitable release sites can be identified for the population supplementation and restoration of an endangered species. Our results will be highly influential in the future management of M. margaritifera in Northern Ireland.