Synthesis and characterization of photo-crosslinkable main-chain liquid-crystalline polymers containing bis(benzylidene)cycloalkanone units

A series of new photo-crosslinkable main-chain liquid-crystalline polymers containing bis(benzylidene)cycloalkanone units have been studied. These units in the polymers function as mesogens as well as photoactive centres. Polyesters with three different bis(4-hydroxybenzylidene)cycloalkanones corresponding to three cycloalkanones, namely cyclopentanone, cyclohexanone and cycloheptanone, have been prepared. Three dicarboxylic acids with ether linkages, which were derived from oligoethylene oxides, namely triethylene glycol, tetraethylene glycol and pentaethylene glycol, have been used as spacers in these polymers. Polymerization was carried out by both solution and interfacial polycondensation; the latter method gave high-molecular-weight polymers. Structural characterizations were done by ultra-violet, infra-red and H-1 nuclear magnetic resonance spectroscopy. Liquid-crystalline properties were studied by differential scanning calorimetry and polarized-light optical microscopy. These polymers show a nematic mesophase. Liquid-crystalline transition temperatures were correlated with polymer structure. The decrease in transition temperature with increase in cycloalkanone ring size was explained in terms of the change in geometrical anisotropy of bis(benzylidene)cycloalkanone units. MNDO (modified neglect of differential overlap) calculations were performed on the model compounds, bis(4-acetyloxybenzylidene)cycloalkanone to elucidate the geometrical variation of the mesogenic units with cycloalkanone ring size. Studies of photolysis reveal the two kinds of photoreactions that proceed in these polymer systems, namely photoisomerization and photo-crosslinking. The former reaction disrupts the parallel stacking of the chromophores and is reflected as an increase in the ultra-violet spectral intensity. The favourability of these two reactions depends on the mobility of the polymer chains. When the photolysis was done below T-g, photo-crosslinking dominates over photoisomerization. Above T-g, photoisomerization is followed by photo-crosslinking. The photosensitivity of the polymers decreases with increase in size of the cycloalkanone ring.

I*(P-2(1/2)) production from CH3I photodissociation at 236 nm

The quantum yield of I*((2)p(1/2)) production from CH3I photolysis at 236 nm in the gas phase has been measured as 0.69 +/- 0.03. The implication is that direct excitation to the (1)Q(1) excited state is significant at this wavelength. The dynamics of I* formation at other excitation energies covering the entire A-band of absorption of CH3I has been discussed in the light of this measurement.

Photodissociation dynamics of CH2ICl at 222, 236, 266, 280, and-304 nm

Dynamics of I*(P-2(1/2)) formation from CH2ICl dissociation has-been investigated at five different ultraviolet excitation wavelengths, e.g., 222, 236, 266, 280, and similar to304 nm. The quantum yield of I*((2)p(1/2)) production, phi*, has been measured by monitoring nascent I(P-2(3/2)) and I* concentrations using a resonance enhanced multiphoton ionization detection scheme. The measured quantum yield as a function of excitation energy follows the same trend as that of methyl iodide except at 236 run. The photodissociation dynamics of CH2ICl also involves three upper states similar to methyl iodide, and a qualitative correlation diagram has been constructed to account for the observed quantum yield. From the difference in behavior at 236 nm, it appears that the crossing region between the two excited states ((3)Q(0) and (1)Q(1)) is located near the exit valley away from the Franck Condon excitation region. The B- and C-band transitions do not participate in the dynamics, and the perturbation of the methyl iodide states due to Cl-I interaction is relatively weak at the photolysis wavelengths employed in this investigation.

A Macroscopic Model for First Return Stroke of Lightning

A lightning return stroke model for a downward flash is proposed. The model includes underlying physical phenomena governing return stroke evolution, namely, electric field due to charge distributed along the leader and cloud, transient enhancement of series channel conductance at the bridging regime, and the nonlinear variation of channel conductance, which supports the return stroke current evolution. Thermal effects of free burning arc at the stroke wave front and its impact on channel conductance are studied. A first-order arc model for determining the dynamic channel conductance along with a field-dependent conductivity for corona sheath is used in the model. The model predicts consistent current propagation along the channel with regard to current amplitude and return stroke velocity. The model is also capable of predicting the remote electromagnetic fields that are consistent with the experimental observations.

Simulation Blocks for TOSSIM-T2"

We develop several hardware and software simulation blocks for the TinyOS-2 (TOSSIM-T2) simulator. The choice of simulated hardware platform is the popular MICA2 mote. While the hardware simulation elements comprise of radio and external flash memory, the software blocks include an environment noise model, packet delivery model and an energy estimator block for the complete system. The hardware radio block uses the software environment noise model to sample the noise floor.The packet delivery model is built by establishing the SNR-PRR curve for the MICA2 system. The energy estimator block models energy consumption by Micro Controller Unit(MCU), Radio,LEDs, and external flash memory. Using the manufacturer’s data sheets we provide an estimate of the energy consumed by the hardware during transmission, reception and also track several of the MCUs states with the associated energy consumption. To study the effectiveness of this work, we take a case study of a paper presented in [1]. We obtain three sets of results for energy consumption through mathematical analysis, simulation using the blocks built into PowerTossim-T2 and finally laboratory measurements. Since there is a significant match between these result sets, we propose our blocks for T2 community to effectively test their application energy requirements and node life times.

Present status of Gottigere Tank : Indicator of Decision maker’s apathy

Gottigere lake with a water spread area of about 14.98 ha is located in the Bellandur Lake catchment of the South Pennar River basin. In recent years, this lake catchment has been subjected to environmental stress mainly due to the rampant unplanned developmental activities in the catchment. The functional ability of the ecosystem is impaired due to structural changes in the ecosystem. This is evident from poor water quality, breeding of disease vectors, contamination of groundwater in the catchment, frequent flooding in the catchment due to topography alteration, decline in groundwater table, erosion in lake bed, etc. The development plans of the region (current as well as the proposed) ignore the integrated planning approaches considering all components of the ecosystem. Serious threats to the sustainability of the region due to lack of holistic approaches in aquatic resources management are land use changes (removal of vegetation cover, etc.), point and non-point sources of pollution impairing water quality, dumping of solid waste (building waste, etc.). Conservation of lake ecosystem is possible only when the physical and chemical integrity of its catchment is maintained. Alteration in the catchment either due to land use changes (leading to paved surface area from vegetation cover), alteration in topography, construction of roads in the immediate vicinity are detrimental to water yield in the catchment and hence, the sustenance of the lake. Open spaces in the form of lakes and parks aid as kidney and lung in an urban ecosystem, which maintain the health of the people residing in the locality. Identification of core buffer zones and conservation of buffer zones (500 to 1000 m from shore) is to be taken up on priority for conservation and sustainable management of Bangalore lakes. Bangalore is located over a ridge delineating four watersheds, viz. Hebbal, Koramangala, Challaghatta and Vrishabhavathi. Lakes and tanks are an integral part of natural drainage and help in retaining water during rainfall, which otherwise get drained off as flash floods. Each lake harvests rainwater from its catchment and surplus flows downstream spilling into the next lake in the chain. The topography of Bangalore has uniquely supported the creation of a large number of lakes. These lakes form chains, being a series of impoundments across streams. This emphasises the interconnectivity among Bangalore lakes, which has to be retained to prevent Bangalore from flooding or from water scarcity. The main source of replenishment of groundwater is the rainfall. The slope of the terrain allows most of the rainwater to flow as run-off. With the steep gradients available in the major valleys of Bangalore, the rainwater will flow out of the city within four to five hours. Only a small fraction of the rainwater infiltrates into the soil. The infiltration of water into the subsoil has declined with more and more buildings and paved road being constructed in the city. Thus the natural drainage of Bangalore is governed by flows from the central ridge to all lower contours and is connected with various tanks and ponds. There are no major rivers flowing in Bangalore and there is an urgent need to sustain these vital ecosystems through proper conservation and management measures. The proposed peripheral ring road connecting Hosur Road (NH 7) and Mysore Road (SH 17) at Gottigere lake falls within the buffer zone of the lake. This would alter the catchment integrity and hence water yield affecting flora, fauna and local people, and ultimately lead to the disappearance of Gottigere lake. Developmental activities in lake catchments, which has altered lake’s ecological integrity is in violation of the Indian Fisheries Act – 1857, the Indian Forest Act – 1927, Wildlife (Protection) Act – 1972, Water (Prevention and Control of Pollution) Act – 1974, Water (Prevention and Control of Pollution) Act – 1977, Forest (Conservation Act) – 1980, Environmental (Protection) Act – 1986, Wildlife (Protection) Amendment Act – 1991 and National Conservation Strategy and Policy Statement on Environment and Development – 1992. Considering 65% decline of waterbodies in Bangalore (during last three decades), decision makers should immediately take preventive measures to ensure that lake ecosystems are not affected. This report discusses the impacts due to the proposed infrastructure developmental activities in the vicinity of Gottigere tank.

A homobimetallic complex of chromium(0) with a sigma-borane component

The synthesis, characterization, and reactivity of a chromium(0) complex bearing an amine-borane moiety (eta(6)-C(6)H(5)CH(2)NMe(2)center dot BH(3))Cr(CO)(3) (2) is reported. Photolysis of complex 2 results in the elimination of a CO ligand followed by the formation of an intramolecular sigma-borane complex (eta(1)-(eta(6)- C(6)H(5)CH(2)NMe(2)center dot BH(2)-H))Cr(CO)(2) (3). This species was characterized in solution by NMR spectroscopy. Reaction of complex 2 with photochemically generated (OC)(5)Cr(THF) affords a novel homobimetallic sigma-borane complex (OC)(3)Cr(eta(6)-C(6)H(5)CH(2)NMe(2)center dot BH(2)-H-Cr(CO)(5)) (4), wherein one of the BH moieties is bound to the chromium center in an eta(1)-fashion. The sigma-borane complex 4 was isolated in moderate to good yield (72%). The BH(3) fragment in the complexes 3 and 4 are highly dynamic involving exchange of the BH hydrogen bound to the metal with the terminal BH hydrogen atoms. The dynamics has been studied using variable-temperature NMR spectroscopy. Complexes 2 and 4 have been characterized by X-ray crystallography.

Some characteristics of tropical lightning

An integrated and generalized account of the characteristics of lightning flashes observed in the tropics is presented, along with features of tropical lightning which differ from flashes at other latitudes. Several years of lightning recordings were made at two locations in India by using the electromagnetic radiation of the flash in a suitable radio band. The distances of thunder audibility, the number of thunders/hr, the peak flash rate, the flash duration, the time interval between flashes, the duration of flashing activity of a cloud, the number of cells in the lifetime of the cloud, etc. were all found to follow log-normal distributions. Fewer cells were observed to occur in temperate regions, and thunder was found to be associated with ground flashes only.

Studies on electrical switching behavior and optical band gap of amorphous Ge-Te-Sn thin films

Amorphous thin film Ge15Te85-xSnx (1 <= x <= 5) and Ge17Te83-xSnx (1 <= x <= 4) switching devices have been deposited in sandwich geometry using a flash evaporation technique, with aluminum as the top and bottom electrodes. Electrical switching studies indicate that these films exhibit memory type electrical switching behavior. The switching fields for both the series of samples have been found to decrease with increase in Sn concentration, which confirms that the metallicity effect on switching fields/voltages, commonly seen in bulk glassy chalcogenides, is valid in amorphous chalcogenide thin films also. In addition, there is no manifestation of rigidity percolation in the composition dependence of switching fields of Ge15Te85-xSnx and Ge17Te83-xSnx amorphous thin film samples. The observed composition dependence of switching fields of amorphous Ge15Te85-xSnx and Ge17Te83-xSnx thin films has been understood on the basis of Chemically Ordered Network model. The optical band gap for these samples, calculated from the absorption spectra, has been found to exhibit a decreasing trend with increasing Sn concentration, which is consistent with the composition dependence of switching fields.

Visible light photocatalytic inactivation of Escherichia coli with combustion synthesized TiO2

The photocatalytic inactivation of Escherichia coil was studied with combustion synthesized TiO2 photocatalysts in the presence of visible light. A series of 400W lamps irradiating in the visible region of the solar spectrum was used. The effect of various parameters, such as catalyst loading, light intensity, presence of inorganic ions, addition of hydrogen peroxide and pH, on the photocatalytic inactivation of E. coil was investigated. Photolysis alone had a small effect on inactivation while the dark experiment resulted in no inactivation and Ag/TiO2 showed the maximum inactivation. At a catalyst loading of 0.25 g/L, all the combustion synthesized catalysts showed better inactivation of E. coil compared to commercial Degussa P-25 (DP-25) TiO2 catalyst. An improved inactivation was observed with increasing lamp intensity and addition of H2O2. A negative effect on inactivation was observed by addition of inorganic ions such as HCO3-, SO42-, Cl-, NO3-, Na+, K+ and Ca2+. The photocatalytic inactivation of E. coli remained unaltered at different pH of the solution. The inactivation of E. coli was modeled with power law kinetics and was observed to follow first order kinetics. (C) 2012 Elsevier B.V. All rights reserved.

Electrical switching studies on amorphous Ge‐Te‐Sn thin films

Electrical switching studies on amorphous Ge17Te83−xSnx thin films (1 ≤ x ≤ 4) has been done to find their suitability for Phase Change Memory application; Bulk ingots in glassy form are prepared using conventional melt quenching technique and the thin films are coated using flash evaporation technique. Samples are found to exhibit memory type of electrical switching behavior. The switching voltages of Ge17Te83−xSnx thin films have been found to decrease with increase in Sn concentration. The comparatively lower switching voltages of Ge17Te83−xSnx samples, make them suitable candidates for phase change memory applications.

Photoelectrochemical oxidation of p-nitrophenol on an expanded graphite-TiO2 electrode

In the quest for more efficient photoanodes in the photoelectrochemical oxidation processes for organic pollutant degradation and mineralisation in water treatment, we present the synthesis, characterisation and photoelectrochemical application of expanded graphite-TiO2 composite (EG-TiO2) prepared using the sol-gel method with organically modified silicate. The Brunauer-Emmett-Teller surface area analyser, ultraviolet-visible diffuse reflectance, scanning electron microscopy, energy dispersive spectroscopy, X-ray diffractometry, Raman spectrometry and X-ray photoelectron spectroscopy were employed for the characterisation of the composites. The applicability of the EG-TiO2 as photoanode material was investigated by the photoelectrochemical degradation of p-nitrophenol as a target pollutant in a 0.1 M Na2SO4 (pH 7) solution at a current density of 5 mA cm(-2). After optimising the TiO2 loading, initial p-nitrophenol concentration, pH and current density, a removal efficiency of 62% with an apparent kinetic rate constant of 10.4 x 10(-3) min(-1) was obtained for the photoelectrochemical process as compared to electrochemical oxidation and photolysis, where removal efficiencies of 6% and 24% were obtained respectively after 90 min. Furthermore, the EG-TiO2 electrode was able to withstand high current density due to its high stability. The EG-TiO2 electrode was also used to degrade 0.3 x 10(-4) M methylene blue and 0.1 x 10(-4) M Eosin Yellowish, leading to 94% and 47% removal efficiency within 120 reaction time. This confirms the suitability of the EG-TiO2 electrode to degrade other organic pollutants.

Temperature dependence of resistance and crystallization in amorphous Si15Te85-xGex thin films

Amorphous thin chalcogenide Si15Te85-xGex films (x: 5, 9, 10, 11, 12) are prepared by flash evaporation and the temperature dependence of resistance of these films has been studied in the temperature range 25-250 degrees C. All the compositions show a linear variation of resistance in this temperature range. Apart from the linear variation, a sharp reduction in resistance at one or at two distinct temperatures (T-TR1/T-TR2) is seen. Thin films annealed at these temperatures, when subjected to X-ray diffraction studies suggest that the dominant crystalline phase at T-TR1 and at T-TR2 is the same and the two dips are associated with varying levels of crystallization. This is also reflected in the atomic force microscopic (AFM) study. Further, the resistance of these two phases shows no drift when the films are annealed for varying lengths of time (10 min to 120 min) suggesting the stability of the phases.

A divide and conquer strategy for scaling weather simulations with multiple regions of interest

Accurate and timely prediction of weather phenomena, such as hurricanes and flash floods, require high-fidelity compute intensive simulations of multiple finer regions of interest within a coarse simulation domain. Current weather applications execute these nested simulations sequentially using all the available processors, which is sub-optimal due to their sub-linear scalability. In this work, we present a strategy for parallel execution of multiple nested domain simulations based on partitioning the 2-D processor grid into disjoint rectangular regions associated with each domain. We propose a novel combination of performance prediction, processor allocation methods and topology-aware mapping of the regions on torus interconnects. Experiments on IBM Blue Gene systems using WRF show that the proposed strategies result in performance improvement of up to 33% with topology-oblivious mapping and up to additional 7% with topology-aware mapping over the default sequential strategy.