A comparison of the DNMR behaviour of methyl 5,6-bis(2-methoxyphenyl)-1,4-dimethyl-7-oxobicyclo[2.2.1]hept-5-en-2-endo-carboxylate and its 7-oxa analogue

Methyl 5,6-Bis(2-methoxyphenyt)-1,4-dimethyl-7-oxobicyclo[2.2.1]hept-5-en-2-endo-carboxylate, a moderately crowded norbornenone ester, exhibits complex VT-DNMR behaviour. A similar behaviour is not seen in its 7-oxa analogue, showing that conformational transmission from position 7 has a crucial influence on the distance parameters that govern the dynamic processes involving the substituents on the bicycloheptene framework.

Theory of polymer breaking under tension

We consider the breaking of a polymer molecule which is fixed at one end and is acted upon by a force at the other. The polymer is assumed to be a linear chain joined together by bonds which satisfy the Morse potential. The applied force is found to modify the Morse potential so that the minimum becomes metastable. Breaking is just the decay of this metastable bond, by causing it to go over the barrier. Increasing the force causes the potential to become more and more distorted and eventually leads to the disappearance of the barrier. The limiting force at which the barrier disappears is D(e)a/2,D-e with a the parameters characterizing the Morse potential. The rate of breaking is first calculated using multidimensional quantum transition state theory. We use the harmonic approximation to account for vibrations of all the units. It includes tunneling contributions to the rate, but is valid only above a certain critical temperature. It is possible to get an analytical expression for the rate of breaking. We have calculated the rate of breaking for a model, which mimics polyethylene. First we calculate the rate of breaking of a single bond, without worrying about the other bonds. Inclusion of other bonds under the harmonic approximation is found to lower this rate by at the most one order of magnitude. Quantum effects are found to increase the rate of breaking and are significant only at temperatures less than 150 K. At 300 K, the calculations predict a bond in polyethylene to have a lifetime of only seconds at a force which is only half the limiting force. Calculations were also done using the Lennard-Jones potential. The results for Lennard-Jones and Morse potentials were rather different, due to the different long-range behaviors of the two potentials. A calculation including friction was carried out, at the classical level, by assuming that each atom of the chain is coupled to its own collection of harmonic oscillators. Comparison of the results with the simulations of Oliveira and Taylor [J. Chem. Phys. 101, 10 118 (1994)] showed the rate to be two to three orders of magnitude higher. As a possible explanation of discrepancy, we consider the translational motion of the ends of the broken chains. Using a continuum approximation for the chain, we find that in the absence of friction, the rate of the process can be limited by the rate at which the two broken ends separate from one another and the lowering of the rate is at the most a factor of 2, for the parameters used in the simulation (for polyethylene). In the presence of friction, we find that the rate can be lowered by one to two orders of magnitude, making our results to be in reasonable agreement with the simulations.

The role of defects in carrier type reversal in bismuth doped Ge-Se glasses by photoluminescence spectroscopy

The role played by defects in bringing out n-type conduction in Ge20Se80-xBix and Ge20Se70-xBixTe10 glasses is using investigated photoluminescence (PL) spectroscopy. It was found that for both the systems, the compositions at lower Bi content exhibit luminescence with fine features associated while the compositions that show n-type conduction do not exhibit luminescence. The identification of the associated fine features, carried out by deconvoluting the experimental spectra, reveals that Bi addition brings out a relative diminishing in D+ defects as compared to D- ones. The study gives an overall indication for the role played by native defects in bringing out n-type conduction in Bi-doped glasses.

Estimation of groundwater recharge of shallow aquifer on humid environment in Yaounde, Cameroon using hybrid water-fluctuation and hydrochemistry methods

A study of environmental chloride and groundwater balance has been carried out in order to estimate their relative value for measuring average groundwater recharge under a humid climatic environment with a relatively shallow water table. The hybrid water fluctuation method allowed the split of the hydrologic year into two seasons of recharge (wet season) and no recharge (dry season) to appraise specific yield during the dry season and, second, to estimate recharge from the water table rise during the wet season. This well elaborated and suitable method has then been used as a standard to assess the effectiveness of the chloride method under forest humid climatic environment. Effective specific yield of 0.08 was obtained for the study area. It reflects an effective basin-wide process and is insensitive to local heterogeneities in the aquifer system. The hybrid water fluctuation method gives an average recharge value of 87.14 mm/year at the basin scale, which represents 5.7% of the annual rainfall. Recharge value estimated based on the chloride method varies between 16.24 and 236.95 mm/year with an average value of 108.45 mm/year. It represents 7% of the mean annual precipitation. The discrepancy observed between recharge value estimated by the hybrid water fluctuation and the chloride mass balance methods appears to be very important, which could imply the ineffectiveness of the chloride mass balance method for this present humid environment.

Mechanism of enhanced corrosion of alumina graphite refractories near slag/metal interface

All refractories show enhanced corrosion near the slag/metal interface due to Marangoni and convective flows. However, in the case of oxide refractories containing graphite flakes, corrosion is severe due to periodic oscillations in the contact angle at the slag/metal interface, resulting in cyclic dissolution of oxide and graphite into the slag and metal, respectively. Alumina--graphite (AG) refractories should be used only where they are not in simultaneous contact with slag (flux) and low carbon steel.

A thermodynamic interpretation of the zonal arrangement of minerals in the bedded manganese deposits of the Noda tamagawa mine, Japan

Calculated phase relations in the system MnOSi02-C02-02 were used to propose a thermodynamic explanation for the thermal metamorphism of rhodochrosite beds lying between chert strata. The metamorphic MnOS i 0 2 minerals are arranged in order quartz(chert), rhodonite. tephroite and manganosite-hausmannite-pyrochroite rhodonite across the ore bed. The calculation covered temperatures up to 1000 K and pressures up to 5 kb. The zoning was interpreted as the result of a continuous rise in metamorphic temperature. The equilibrium partner of rhodochrosite changed from rhodonite through manganosite. Across the ore bed there are gradients in the chemical potential of MnO and SiO2 but fugacities of volatlle components such as C02. 02 and H20 were probably uniform at any given time and location during formation of the zones. Assuming that the total pressure and the fugacity of C02 were at 1.4 kb and 1.0 1 b. respectively. rhodonite. tephroite and manganosite would have formed at 472. 478 and 629 K.

La-Doped Ba2In2O5 Electrolyte: Pechini Synthesis, Microstructure, Electrical Conductivity, and Application for CO Gas Sensing

Dense (Ba1―xLax)2In2O5+x (BLIO) electrolytes with different compositions (x = 0.4, 0.5, 0.6) were fabricated using powders obtained by the Pechini method. The formation of BLIO powders was investigated by using X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. The calcination temperature and time were optimized. The sintered (Ba1―xLax)2In2O5+x electrolytes showed a relative density greater than ∼97%, and the major phase of three electrolyte compositions was indexed as a cubic perovskite. The electrical conductivity of BLIO ceramics at elevated temperatures in air was measured by ac-impedance spectroscopy. The activation energies for conduction in BLIO were 102 kJ mol―1 between 473 and 666 K and 118 kJ mol―1 between 769 and 873 K, which are comparable to that for 8 mol % yttria-stabilized cubic zirconia. Mixed-potential gas sensors utilizing BLIO-based electrolytes exhibited good sensitivity to different CO concentrations from ∼100 to ∼500 ppm and excellent selectivity to methane at around 873 K.

Ecological and Socio Economic Assesment of Varthur Wetlnd, Bengaluru (India)

Wetlands are the most productive ecosystems, recognized globally for its vital role in sustaining a wide array of biodiversity and provide goods and services. However despite their important role in maintaining the ecology and economy, wetlands in India are endangered by inattention and lack of appreciation for their role. Increased anthropogenic activities such as intense agriculture practices, indiscriminate disposal of industrial effluents and sewage wastes have altered the physical, chemical as well as biological integrity of the ecosystem. This has resulted in the ecological degradation, which is evident from the current ecosystem valuation of Varthur wetland. Global valuation of coastal wetland ecosystem shows a total of 14,785/ha US$ annual economic value. An earlier study of relatively pristine wetland in Bangalore shows the value of Rs. 10,435/ha/day while the polluted wetland shows the value of Rs.20/ha/day. In contrast to this, Varthur, a sewage fed wetland has a value of Rs.118.9/ha/day. The pollutants and subsequent contamination of the wetland has telling effects such as disappearance of native species, dominance of invasive exotic species (such as African catfish), in addition to profuse breeding of disease vectors and pathogens. Water quality analysis revealed of high phosphates (4.22-5.76 ppm) level in addition to the enhanced BOD (119-140 ppm) and decreased DO (0-1.06 ppm). The amplified decline of ecosystem goods and services with degradation of water quality necessitates the implementation of sustainable management strategies to recover the lost wetland benefits.

Ecological and socio-economic assessment of Varthur wetland, Bengaluru (India)

Wetlands are the most productive ecosystems, recognized globally for its vital role in sustaining a wide array of biodiversity and provide goods and services. However despite their important role in maintaining the ecology and economy, wetlands in India are endangered by inattention and lack of appreciation for their role. Increased anthropogenic activities such as intense agriculture practices, indiscriminate disposal of industrial effluents and sewage wastes have altered the physical, chemical as well as biological integrity of the ecosystem. This has resulted in the ecological degradation, which is evident from the current ecosystem valuation of Varthur wetland. Global valuation of coastal wetland ecosystem shows a total of 14,785/ha US$ annual economic value. An earlier study of relatively pristine wetland in Bangalore shows the value of Rs. 10,435/ha/day while the polluted wetland shows the value of Rs.20/ha/day. In contrast to this, Varthur, a sewage fed wetland has a value of Rs.118.9/ha/day. The pollutants and subsequent contamination of the wetland has telling effects such as disappearance of native species, dominance of invasive exotic species (such as African catfish), in addition to profuse breeding of disease vectors and pathogens. Water quality analysis revealed of high phosphates (4.22-5.76 ppm) level in addition to the enhanced BOD (119-140 ppm) and decreased DO (0-1.06 ppm). The amplified decline of ecosystem goods and services with degradation of water quality necessitates the implementation of sustainable management strategies to recover the lost wetland benefits.

Development of novel multiple quantummethodologies for the analyses of complex protonNMR spectra of scalar coupled spins

One of the significant advancements in Nuclear Magnetic Resonance spectroscopy (NMR) in combating the problem of spectral complexity for deriving the structure and conformational information is the incorporation of additional dimension and to spread the information content in a two dimensional space. This approach together with the manipulation of the dynamics of nuclear spins permitted the designing of appropriate pulse sequences leading to the evolution of diverse multidimensional NMR experiments. The desired spectral information can now be extracted in a simplified and an orchestrated manner. The indirect detection of multiple quantum (MQ) NMR frequencies is a step in this direction. The MQ technique has been extensively used in the study of molecules aligned in liquid crystalline media to reduce spectral complexity and to determine molecular geometries. Unlike in dipolar coupled systems, the size of the network of scalar coupled spins is not big in isotropic solutions and the MQ 1H detection is not routinely employed,although there are specific examples of spin topology filtering. In this brief review, we discuss our recent studies on the development and application of multiple quantum correlation and resolved techniques for the analyses of proton NMR spectra of scalar coupled spins.

Synthesis of beta-arabinofuranoside glycolipids, studies of their binding to surfactant protein-A and effect on sliding motilities of M. smegmatis

Surfactant protein A (SP-A), which is a lung innate immune system component, is known to bind glycolipids present at the cell surface of a mycobacterial pathogen. Lipoarabinomannan (LAM), a component of mycobacterial thick, waxy cell wall, is one of the glycolipid ligands for SP-A. In order to assess binding of synthetic glycolipids with SP-A and the glycosidic linkage preferences for the interaction, beta-arabinofuranoside trisaccharide glycolipids constituted with beta-(1 -> 2), beta-(1 -> 3) and beta-(1 -> 2), beta-(1 -> 5) linkages relevant to LAM were synthesized through chemical glycosylations. The efficacies of synthetic glycolipids to interact with SP-A were assessed by using the surface plasmon resonance (SPR) technique, from which association-dissociation rate constants and equilibrium binding constants were derived. The equilibrium binding constants of the interaction of two constitutionally varying beta-arabinofuranoside glycolipids with SP-A were found to be in the millimolar range. A comparison of the results with few alpha-anomeric arabinofuranoside glycolipids showed that glycolipids with beta-anomeric linkages were having relatively lower equilibrium binding constants than those with alpha-anomeric linkages in binding to the protein, whereas oligosaccharides alone, without lipidic chains, exhibited higher equilibrium binding constants. Further, the synthetic compounds inhibited the growth of mycobacteria and affected sliding motilities of the bacteria, although to an extent relatively lesser than that of synthetic compounds constituted with alpha-anomeric linkages.