A versatile ternary ionic complex for chiral discrimination of molecules with diverse functionalities using H-1 NMR

This study reports a simple, efficient and versatile protocol developed for NMR spectroscopic enantiodiscrimination of molecules containing diverse functional -groups, such as amino alcohols, secondary alcohols, cyanohydrins, oxazolidones, diols, thiones and epoxides, using a phosphorous based three component mixture. The simple mixing and shaking of enantiopure 1,1'-binaphthyt-2,2'-diyl hydrogenphosphate (BNPA), 4-(dimethylamino)pyridine (DMAP) and a chiral analyte in the solvent CDCl3 served as a chiral solvating agent and resulted in well dispersed peaks for each enantiomer in the H-1 NMR spectrum. Discrimination could be achieved not only for the proton at the chiral centre, but also for multiple proton sites. The devised approach also permitted the precise measurement of the enantiomeric excess (ee).

Semiconductor to metal transition in bilayer phosphorene under normal compressive strain

Phosphorene, a two-dimensional analog of black phosphorous, has been a subject of immense interest recently, due to its high carrier mobilities and a tunable bandgap. So far, tunability has been predicted to be obtained with very high compressive/tensile in-plane strains, and vertical electric field, which are difficult to achieve experimentally. Here, we show using density functional theory based calculations the possibility of tuning electronic properties by applying normal compressive strain in bilayer phosphorene. A complete and fully reversible semiconductor to metal transition has been observed at similar to 13.35% strain, which can be easily realized experimentally. Furthermore, a direct to indirect bandgap transition has also been observed at similar to 3% strain, which is a signature of unique band-gap modulation pattern in this material. The absence of negative frequencies in phonon spectra as a function of strain demonstrates the structural integrity of the sheets at relatively higher strain range. The carrier mobilities and effective masses also do not change significantly as a function of strain, keeping the transport properties nearly unchanged. This inherent ease of tunability of electronic properties without affecting the excellent transport properties of phosphorene sheets is expected to pave way for further fundamental research leading to phosphorene-based multi-physics devices.

A Synoptic View of a Coastal Plain Estuary.

During October, 1972 the Patuxent River Estuary was monitored intensively and synoptically over two tidal cycles to determine the spatial and temporal patterns of various hydrodynamic, chemical and biological features. Forty-one depths at eleven stations along nine transects were sampled simultaneously at hourly intervals for salinity, temperature, dissolved oxygen, chlorohyll a, particulate nitrogen, nitrate, nitrite, total kjeldahl nitrogen, ammonia, particulate carbohydrate, dissolved organic carbon, total hydrolizable phosphorous, dissolved inorganic phosphorous, suspended sediment, particle size distribution, and zooplankton. Tidal velocity was continuously monitored at each depth by recording current meters. Riverine input and meteorological conditions were relatively stable for two weeks preceeding the deployment. This communication describes the calculation of the intrinsic rates of change of the observed variables from their measured distributions in the Estuary. The steady-state, one-dimensional equation of species continuity is employed to separate the advection and tidal dispersion of a hydrodynamically passive substance frbm its intrinsic rate of change at point. A new spatial transform is introduced for the purpose of interpolation and extrapolation of data.The intrinsic rate of change profiles reveal a region of heavy bloom activity in the upper estuary and a secondary bloom near the point in the River that most of the suspended material settles out. The changes in ammonia and nitrates are highly correlated to the productivity patterns. Phosphorous rates are less closely correlated to productivity. The perturbations that the Chalk Point steam electric power plant have on the heat and oxygen balances are easily discernible.

Toxic blue-green algae: The "problem" in perspective

The incidence of blue-green algal blooms and surface scum-formation are certainly not new phenomena. Many British and European authors have been faithfully describing the unmistakable symptoms of blue-green algal scums for over 800 years. There is no disputing that blue-green algal toxins are extremely harmful. Three quite separate categories of compound have been separated: neurotoxins; hepatotoxins and lipopolysaccharides. There is a popular association between blue-green algae and eutrophication. Certainly the main nuisance species - of Microcystis, Anabaena and Aphanizomenon are rare in oligotrophic lakes and reservoirs. Several approaches have been proposed for the control of blue-green algae. Distinction is made between methods for discharging algae already present (eg algicides; straw bales; viruses; parasitic fungi and herbivorous ciliates), and methods for averting an anticipated abundance in the future (phosphorous control, artificial circulation etc).

Transformação de metanol em olefinas leves catalisada por zeólitas HZSM-5

A reação de transformação de MeOH em olefinas leves foi investigada sobre zeólitas HZSM-5 com razões SiO2/Al2O3 (SAR) iguais a 30, 80 e 280. As propriedades ácidas e texturais da amostra com SAR 30 foram modificadas por impregnação com ácido fosfórico. A caracterização físico-química das amostras foi realizada empregando-se as técnicas de FRX, fisissorção de N2, DRX, DTP de NH3 e IV com adsorção de piridina. O desempenho catalítico das mesmas foi comparado tanto em condições reacionais similares (mesma T, pressão parcial de MeOH e WHSV) como em condições de isoconversão. Verificou-se, que quanto maior a SAR da zeólita, menor a densidade total e a força dos sítios ácidos presentes, sendo este efeito mais significativo para os sítios de Brönsted. O efeito do aumento da SAR favoreceu a estabilidade catalítica e a formação de olefinas leves, principalmente propeno. No caso das amostras contendo fósforo, foi observada uma redução linear na área específica BET e no volume de microporos com o aumento do teor de fósforo. Estes resultados, aliados aos obtidos por DRX, sugerem que a redução mais significativa na área específica e no volume de microporos pode ser associada à redução na cristalinidade e à formação de espécies amorfas contendo fósforo, que bloqueariam a estrutura porosa da zeólita. Não se observou alteração significativa na força dos sítios fracos, enquanto a força dos sítios fortes diminuiu significativamente. As amostras apresentando menor SAR e menor teor de fósforo foram mais ativas. Por outro lado, em condições de isoconversão de 916%, a amostra mais seletiva à formação de olefinas foi aquela com maior SAR. Dentre as amostras impregnadas, aquela contendo 4% de fósforo foi a mais seletiva a propeno, enquanto a que continha 6% foi mais seletiva a eteno. A amostra com SAR igual a 280 foi investigada variando-se a temperatura de reação (400, 500 e 540C) e a pressão parcial de metanol (0,038; 0,083 e 0,123 atm), através de um planejamento experimental do tipo Box-Benhnken (32). O rendimento otimizado em olefinas leves foi alcançado a 480C e 0,08 atm. O modelo proposto descreveu bem os dados experimentais e evidenciou a existência de uma faixa ótima de temperatura para maximização do rendimento em propeno e eteno, o qual foi também afetado pela pressão parcial de MeOH na faixa estudada. Palavras-chave: ZSM-5, olefinas, propeno, eteno, processo MTO, fósforo.

Stillwaters monitoring programme. Summary results 2004 and 2005

This is the Stillwaters monitoring programme. Summary results 2004 and 2005 from the Environment Agency North West. This report focuses on the 5th year of winter monitoring analysis in 14 stillwaters in Cheshire. The 14 stillwaters analysed are: Comber Mere, Oss Mere, Marbury Big Mere, Chapel Mere, Bar Mere, Oak Mere, Hatch Mere, Black Lake, Betley Mere, Tabley Mere, Melchett Mere, Tatton Mere, Rostherne Mere and Mere mere. Nutrient availability in the stillwaters analysed is used to look into the productivity of the waterbody. Bank-side water samples were taken for nutrients (Nitrogen and Phosphorous) and chlorophyll. A YSI multi-parameter sonde measures temperature, pH, specific conductivity and dissolved oxygen (% saturation).

Increased toxicity of Karenia brevis during phosphate limited growth: ecological and evolutionary implications

Karenia brevis is the dominant toxic red tide algal species in the Gulf of Mexico. It produces potent neurotoxins (brevetoxins [PbTxs]), which negatively impact human and animal health, local economies, and ecosystem function. Field measurements have shown that cellular brevetoxin contents vary from 1–68 pg/cell but the source of this variability is uncertain. Increases in cellular toxicity caused by nutrient-limitation and inter-strain differences have been observed in many algal species. This study examined the effect of P-limitation of growth rate on cellular toxin concentrations in five Karenia brevis strains from different geographic locations. Phosphorous was selected because of evidence for regional P-limitation of algal growth in the Gulf of Mexico. Depending on the isolate, P-limited cells had 2.3- to 7.3-fold higher PbTx per cell than P-replete cells. The percent of cellular carbon associated with brevetoxins (%C-PbTx) was ~ 0.7 to 2.1% in P-replete cells, but increased to 1.6–5% under P-limitation. Because PbTxs are potent anti-grazing compounds, this increased investment in PbTxs should enhance cellular survival during periods of nutrient-limited growth. The %C-PbTx was inversely related to the specific growth rate in both the nutrient-replete and P-limited cultures of all strains. This inverse relationship is consistent with an evolutionary tradeoff between carbon investment in PbTxs and other grazing defenses, and C investment in growth and reproduction. In aquatic environments where nutrient supply and grazing pressure often vary on different temporal and spatial scales, this tradeoff would be selectively advantageous as it would result in increased net population growth rates. The variation in PbTx/cell values observed in this study can account for the range of values observed in the field, including the highest values, which are not observed under N-limitation. These results suggest P-limitation is an important factor regulating cellular toxicity and adverse impacts during at least some K. brevis blooms.

Selective biochemical studies in a freshwater prawn, Macrobrachium nobilli(Crustecea: Palaemodinae)

Calcium and phosphorous contents of abdomen and cheliped muscles of juvenile, male and female Macrobrchium nobilii were determined from field collected samples. In all the three groups calcium concentration was higher in chelipeds while the phosphorous content was more in abdomen muscles than in the chelipeds. However between three groups the calcium content varied significantly both in the abdomen and cheliped muscles (Pphosphorous content differed (P

Euglenophytes in aquaculture ponds - their ecology and role in fish production

The ecology of euglenophytes and their role in fish production were studied in 12 small earthen ponds beside the Faculty of Fisheries, BAU from July to November 2001. Four experiments each with three replications were conducted and those were as follows: pond treated with both poultry droppings and cowdung (T1); pond treated with only poultry droppings (T2), and pond treated with only poultry droppings (T3), while the control (T4) where no organic manure was applied. Fishes comprising of rohu (Labeo rohita), catla ( Catla catla), mrigal ( Cirrhinus cirrhosus), silver carp (Hypophthalmichthys molitrix) and silver barb (Barbonymus gonionotus) were stocked at the same stocking density of (10,621 fish/ha) and species ratio (1:1:1:2:2). The stocked fishes were fed with a common supplemental diet comprising of mustard oil cake and rice polish (1:1) at the rate of 4% of body weight per day. The highest cell density of euglenophytes was found in the ponds of T2, where poultry droppings were applied and was followed by T1, where both poultry droppings and cow dung were applied. Higher temperature, nitrate-nitrogen, phosphate-phosphorous and acidic pH were found to be conducive for the bloom of noxious euglenophytes. The bloom was found to use up most of the nutrients resulting in reduction in the growth of beneficial plankters and planktivorous fishes. The SGR (%/day) of catla, rohu and mrigal was lower during heavy bloom period while that of silver carp and silver barb were comparatively higher. The mortality of fishes in a pond of T2 during the bloom period was possibly due to formation of anoxic situation (dissolved oxygen level as low as 0.34 mg/1) in the early mornings through bacterial decomposition of the settled dead individuals or due to the combined effect of anoxic situation and toxic metabolite secretion by the euglenophytes.

Fish-makhana (Euryale salisb) integration: a case study of sustainable aquafarming system in north Bihar

The paper deals with a technique to synchronize two crops, fish and makhana (Euryale ferox Salisb) in a pond. In such eco-friendly integration both crops are mutually benefited. Decomposed plant parts of makhana crop form organic matter that releases nutrients in the water to enhance plankton population. Organic detritus not only acts as food for bottom dwelling fishes (mrigal and common carp) but also provides a suitable substratum for the growth of zooplankton, insect larvae, nematodes and gastropods. Fishes contribute to the control of makhana pests. Their faecal matter acts as organic manure for makhana crop. Plankton population fluctuated between 1260 u/l to 4030 u/l in the control pond and 1630 u/l to 4722 u/l in the experimental pond. During the grand growth period of makhana crop (April to July) the dissolved oxygen content fluctuated between 5.02 mg/l to 6.68 mg/l in the covered areas and 6.04 mg/l to 6.92 mg/l in uncovered areas. Makhana leaves acting as blanket barrier over the water surface brought down the D.O. content in the covered areas of the pond. Free CO sub(2) content showed wider fluctuation in the experimental pond (25.2 mg/l to 30.9 mg/l) than in the control pond (25.1 mg/l to 28.6 mg/l). This could be due to decomposition of plant parts of the presiding crop lying as debris at the pond bottom. Autochthonous supply of nutrients enhanced the content of nitrogen, phosphorous and organic carbon in the soil of experimental pond. The experimental pond covering an area of 0.40 ha yielded 852 kg fish and 200 kg pops whereas the control pond covering the same area produced 777 kg fish only. The net profit per ha came out to be Rs.1,04,700 and Rs. 66,200 in integrated and non-integrated system respectively. Owing to crop diversification, the present integrated system was found to be more viable than the non-integrated system in terms of production and net profit.

Understanding nutrient loading and sources in the Bay of Bengal Large Marine Ecosystem

Inputs of nitrogen, phosphorous and dissolved silica from watersheds draining into the Bay of Bengal Large Marine Ecosystem are calculated for the present day and predictions made for 2030 and 2050 are presented. The major sources are identified and the Indicator of Coastal Eutrophication (ICEP) is calculated.

Investigation on the ecological impact of constructing and activities of petrochemical industries of petrochemical special economic zone of Mahshahr on the abundance and diversity of macrobenthic fauna in Jafari Creek, north-west of the Persian Gulf

The impact of Petrochemical Special Economic Zone (PETZONE) activities on the health status of Jafari Creek was studied by assessing the changes in macroinvertebrate assemblages in nine sites during September 2006- January 2008. Furthermore to evaluate the ecological status of the Jafari Creek the WFD indices (i.e. AMBI, M-AMBI) were used. The relationship between spatial pattern of macro invertebrate assemblages and ambient factors (i.e. water temperature, salinity, pH, dissolved oxygen, turbidity, electrical conductivity, total dissolved solid, total hardness, total nitrogen, ammonia, total phosphorous, chemical oxygen demand, biological oxygen demand, sediment grain size distribution, sediment organic content, heavy metals contents) was measured. Background Enrichment indices, Contamination factor and Contamination degree, were used to assess the health status in the study area based on Nickel, Lead, Cadmium and Mercury contents of the sediments. The macrobenthic communities had a low diversity and were dominated by opportunistic taxa, and the AMBI and M-AMBI indices need to be calibrated before using in Persian Gulf and its coastal waters. The BIO-ENV analysis identified pH, dissolved oxygen, TDS, and the total organic content of sediments as the major environmental variables influencing the infaunal pattern. This suggests that management should attempt to ensure minimal disturbance to environmental variables underlying the spatial variation in macroinvertebrate assemblages. Background Enrichment indices showed that the health of Jafari Creek has declined over time due to the constant discharge of heavy metals to the Creek system. Furthermore WQS index shows that the quality condition of the water column in Jafari Creek, regard to the calculated number (3) is week. These indices also identified a significant degree of pollution in the study area. The decrease in the ecological potential of Jafari Creek was best highlighted by the alteration in macrobenthic assemblages.

Assessment effects of cage culture on nitrogen and phosphorus dynamics in relation to fallowing in a shallow lake in China

Nitrogen and phosphorus dynamics in relation to fallowing in a fish cage farm was investigated in a shallow lake in China. Four sampling sites were set: beneath the cages, at the cage sides, and 50 and 100 m east of the cage farm. Total nitrogen (TN) and total phosphorus (TP) in lake water and sediment were analyzed during a 2-year rearing cycle. The cage culture had a fish yield of 16.3-39.2 tonnes in the study period. Based on the mass balance equation, 1533-3084 kg TN and 339-697 kg TP were contributed to the lake environment. Nitrogen and phosphorous concentrations showed greater increase in the first culture period than in the second rearing cycle. No obvious changes were found at the sampling sites 50 and 100 m east of the cages during the study periods. Main impacts were found close to the cages (beneath the cages and at the cage side); the sampling points at the cage side showed relatively high TN and TP sedimentation. After 3 months of fallowing, water TN and TP decreased significantly but the sediment TN and TP contents remained high. Therefore, recovery seems to happen during fallowing but attention should be paid to whether the culture continues to operate in the future.

Performance and mechanism of phosphorus removal in an integrated vertical flow constructed wetland treating eutrophic lake water

Phosphorus removal performance and a possible mechanism for the phosphorus removal from an eutrophic lake water were investigated using a medium-scale integrated vertical constructed wetland (combined vertical and reverse-vertical systems) from April, 11, 2001 to September, 28, 2004. Environmental factors affecting phosphorus removal and release profiles were monitored simultaneously under hydraulic loads from 400 to 2000 mm per day. The phosphorus removal rate varied with the environmental conditions. The removal rate for acidic influent water was superior to that for alkaline influent water. The substrate in the wetland chamber acted as a buffer to regulate the pH value of the water sample. As regards the water temperature, no significant differences were observed for the removal rate of total phosphorus (TP) and soluble reactive phosphorus (SRP) between low (lower than 15 degrees C) medium (16-25 degrees C) and high temperature (higher than 26 degrees C) conditions. Under a hydraulic load of 400 mm per day, the removal rate reached over 70%, the highest value achieved in this work. In addition, the highest hydraulic load of 2000 mm/d did not result in the lowest removal rate, as had been expected. After a two-year high hydraulic load test, the removal rate decreased significantly. Phosphorous release from the substrate was examined using a spatial sampling method. Depth profiles of total phosphorus and different states of phosphorus present in the substrate were recorded. This further study demonstrated that binding of phosphorus by iron and calcium might be another major factor in the removal and release of TP and SRP in this wetland system. The distribution of the speciated phosphorus showed that the amount of phosphorus captured in the substrate of the down-flow chamber was significantly higher than that captured in the up-flow chamber, suggesting that the up-flow chamber was the main source of phosphorus release in this constructed wetland.

Ni silicide nanowires analysis by atom probe tomography

The Ni silicide formed at low temperature on Si nanowire has been analyzed by atom probe tomography (APT) thanks to a special technique for sample preparation. A method of preparation has been developed using the focused ion beam (FIB) for the APT analysis of nanowires (NWs). This method allow for the measurement of the radial distribution when a NW is cut, buried in a protective metal matrix, and finally mounted on the APT support post. This method was used for phosphorous doped Si NWs with or without a silicide shell, and allows obtaining the concentration and distribution of chemical elements in three-dimensions (3D) in the radial direction of the NWs. The distribution of atoms in the NWs has been measured including dopants and Au contamination. These measurements show that δ-Ni2Si phase is formed on Si NW, Au is found as cluster at the Ni/δ-Ni2Si interface and P is segregated at the δ-Ni2Si/ Si NW interface. The results obtained on NWs after silicidation were compared with the silicide on the Si substrate, showing that the same silicide phase δ-Ni2Si formed in both cases (NWs and substrate). © 2013 Elsevier B.V. All rights reserved.