Inter and intra crystalline ion exchange equilibria in the system Fe Cr Al O

The tie lines delineating ion-exchange equilibria between FeCr2O4FeAl2O4 spinel solid solution and Cr2O3Al2O3 solid solution with corundum structure have been determined at 1373 K by electron microprobe and EDAX point count analysis of oxide phases equilibrated with metallic iron. Activities in the spinel solid solution are derived from the tie lines and the thermodynamic data on Cr2O3Al2O3 solid solution available in the literature. The oxygen potentials corresponding to the tie-line composition of oxide phases in equilibrium with metallic iron were measured using solid oxide galvanic cells with CaOZrO2 and Y2O3ThO2 electrolytes. These electrochemical measurements also yield activities in the spinel solid solution, in good agreement with those obtained from tie lines. The activity-composition relationship in the spinel solid solution is analysed in terms of the intra-crystalline ion exchange between the tetrahedral and octahedral sites of the spinel structures. The ion exchange is governed by site-preference energies of the cations and the entropy of cations mixing on each site.

An improved X-ray structural analysis for determining cation distribution in ZnFe2O4 and ZnFe2O4- Fe3O4 solid solutions

The distribution of zinc cation between crystallographically nonequivalent positions in ZnFe204 has been determined by anomalous X-ray scattering near the Zn K absorption edge. Measured intensity ratio with two energies close to the edge can be quantitatively explained only by assigning all zinc cations to the tetrahedral position in the approximately cubic close packed array of oxygen ions. A similar conclusion has also been reached for ZnxFe3-x04 solid solutions with x = 0.73, 0.54 and 0.35 employing the improved X-ray method. This is consistent with the EXAFS results which indicate an almost unchanged environmental structure around zinc cation in these solid solutions.

Monograph on Essentials in Limnology and GIS

Aquatic ecosystems are dynamic and depend on various interdependent and inter-related factors that are vital for their existence and in maintaining the ecological balance. Various anthropogenic activities have impaired ecological conditions in many ecosystems. This monograph gives an account of the essentials in limnology, which helps in understanding the nature and extent of the problems and also provides an insight into the use of Geographic Information System as an effective tool for resource inventorying, monitoring and management. The monograph consists of four chapters, and the first one gives an overall view of the inland aquatic bodies as complex ecological systems. It begins with the formation of lakes, and the various physical, chemical and biological factors that determine these ecosystems. The physical factors covered include morphometry, density, light, etc., and the lake chemistry determined by various anions and cations are discussed in detail. The biological parameters include phytoplankton, zooplankton, waterfowl and fish communities that play an important role in freshwater biodiversity, and are presented with diagrams for easy understanding. The monograph gives an in depth view of the lake zones, productivity, and seasonal changes in the lake community with various energy relationships. The concept of food chain and food web in an aquatic ecosystem is also presented with illustrations. Lastly, the various anthropogenic activities that have deteriorated the quality of water are listed with the restoration strategies.

Controls on intense silicate weathering in a tropical river, southwestern India

The Silicate Weathering Rate (SWR) and associated Carbon dioxide Consumption Rate (CCR) in tropical silicate terrain is assessed through a study of the major ion chemistry in a small west flowing river of Peninsular India, the Nethravati River. The specific features of the river basin are high mean annual rainfall and temperature, high runoff and a Precambrian basement composed of granitic-gneiss, charnockite and minor metasediments. The water samples (n = 56) were collected from three locations along the Nethravati River and from two of its tributaries over a period of twelve months. Chemical Weathering Rate (CWR) for the entire watershed is calculated by applying rainwater correction using river chloride as a tracer. Chemical Weathering Rate in the Nethravati watershed is estimated to 44 t.km(-2).y(-1) encompassing a SWR of 42 t.km(-2).y(-1) and a maximum carbonate contribution of 2 t.km(-2).y(-1). This SWR is among the highest reported for granito-gneissic terrains. The assessed CCR is 2.9 . 10(5) mol.km(-2).y(-1). The weathering index (Re). calculated from molecular ratios of dissolved cations and silica in the river, suggests an intense silicate weathering leading to kaolinite-gibbsite precipitation in the weathering covers. The intense SWR and CCR could be due to the combination of high runoff and temperature along with the thickness and nature of the weathering cover. The comparison of silicate weathering fluxes with other watersheds reveals that under similar morpho-climatic settings basalt weathering would be 2.5 times higher than the granite-gneissic rocks. (C) 2012 Elsevier B.V. All rights reserved.

In Situ Electrochemical Polymerization at Air-Water Interface: Surface-Pressure-Induced, Graphene-Oxide-Assisted Preferential Orientation of Polyaniline

In situ electrochemical polymerization of aniline in a Langmuir trough under applied surface pressure assists in the preferential orientation of polyaniline (PANI) in planar polaronic structure. Exfoliated graphene oxide (EGO) spread on water surface is used to bring anilinium cations present in the subphase to air-water interface through electrostatic interactions. Subsequent electrochemical polymerization of aniline under applied surface pressure in the Schaefer mode results in EGO/PANT composite with PANT in planar polaronic form. The orientation of PANI is confirmed by electrochemical and Raman spectroscopic studies. This technique opens up possibilities of 2-D polymerization at the air-water interface. Electrochemical sensing of hydrogen peroxide is used to differentiate the activity of planar and coiled forms of PANI toward electrocatalytic reactions.

Accommodating Unwelcome Guests in Inorganic Layered Hosts: Inclusion of Chloranil in a Layered Double Hydroxide

The host-guest chemistry of most inorganic layered solids is limited to ion-exchange reactions. The guest species are either cations or anions to compensate for the charge deficit, either positive or negative, of the inorganic layers. Here, we outline a strategy to include neutral molecules like ortho- and para-chloranil, that are known to be good acceptors in donor-acceptor or charge-transfer complexes, within the galleries of a layered solid. We have succeeded in including neutral ortho- and para-chloranil molecules within the galleries of an Mg-Al layered double hydroxide (LDH) by using charge-transfer interactions with preintercalated p-aminobenzoate ions as the driving force. The p-aminobenzoate ions are introduced in the Mg-Al LDH via ion exchange. The intercalated LDH can adsorb ortho- and para-chloranil from chloroform solutions by forming charge-transfer complexes with the p-aminobenzoate anions present in the galleries. We use X-ray diffraction, spectroscopy, and molecular dynamics simulations to establish the nature of interactions and arrangement of the charge-transfer complex within the galleries of the layered double hydroxide.

Structural and mechanistic investigations on Salmonella typhimurium acetate kinase (AckA): identification of a putative ligand binding pocket at the dimeric interface

Background: Bacteria such as Escherichia coli and Salmonella typhimurium can utilize acetate as the sole source of carbon and energy. Acetate kinase (AckA) and phosphotransacetylase (Pta), key enzymes of acetate utilization pathway, regulate flux of metabolites in glycolysis, gluconeogenesis, TCA cycle, glyoxylate bypass and fatty acid metabolism. Results: Here we report kinetic characterization of S. typhimurium AckA (StAckA) and structures of its unliganded (Form-I, 2.70 angstrom resolution) and citrate-bound (Form-II, 1.90 angstrom resolution) forms. The enzyme showed broad substrate specificity with k(cat)/K-m in the order of acetate > propionate > formate. Further, the K-m for acetyl-phosphate was significantly lower than for acetate and the enzyme could catalyze the reverse reaction (i.e. ATP synthesis) more efficiently. ATP and Mg2+ could be substituted by other nucleoside 5'-triphosphates (GTP, UTP and CTP) and divalent cations (Mn2+ and Co2+), respectively. Form-I StAckA represents the first structural report of an unliganded AckA. StAckA protomer consists of two domains with characteristic beta beta beta alpha beta alpha beta alpha topology of ASKHA superfamily of proteins. These domains adopt an intermediate conformation compared to that of open and closed forms of ligand-bound Methanosarcina thermophila AckA (MtAckA). Spectroscopic and structural analyses of StAckA further suggested occurrence of inter-domain motion upon ligand-binding. Unexpectedly, Form-II StAckA structure showed a drastic change in the conformation of residues 230-300 compared to that of Form-I. Further investigation revealed electron density corresponding to a citrate molecule in a pocket located at the dimeric interface of Form-II StAckA. Interestingly, a similar dimeric interface pocket lined with largely conserved residues could be identified in Form-I StAckA as well as in other enzymes homologous to AckA suggesting that ligand binding at this pocket may influence the function of these enzymes. Conclusions: The biochemical and structural characterization of StAckA reported here provides insights into the biochemical specificity, overall fold, thermal stability, molecular basis of ligand binding and inter-domain motion in AckA family of enzymes. Dramatic conformational differences observed between unliganded and citrate-bound forms of StAckA led to identification of a putative ligand-binding pocket at the dimeric interface of StAckA with implications for enzymatic function.

Naphthylhydrazone based selective and sensitive chemosensors for Cu2+ and their application in bioimaging

Two new hydroxynaphthyl-hydrazone based fluorogenic chemosensors R-1 and R-2 have been synthesized by Schiff base condensation of Tris(4-formylphenyl)amine with 1-hydroxynaphthalene-2-hydrazide and 1-hydroxynaphthalene-2-carbohydrazone, respectively. They are examined as highly selective and sensitive receptors for Cu2+ ions in aqueous medium. Electronic absorption as well as fluorescence titration studies of receptors R-1 and R-2 with different metal cations in H2O/CH3CN medium showed highly selective and very rapid (< 2 min) binding affinity towards Cu2+ ions even in the presence of other commonly coexisting metal ions such as Na+, K+, Mg2+, Ca2+, Mn2+, Fe2+, Co2+, Ni2+, Zn2+, Cd2+ and Hg2+. Quantification of the fluorescence titration analysis indicated that these newly synthesized receptors (R-1 and R-2) can indicate the presence of Cu2+ ions even at very low concentrations of 598 and 676 ppt, respectively. In addition, the propensity of these receptors as bio-imaging fluorescent probes to detect Cu2+ ions in human cervical HeLa cancer cell lines and their cytotoxicity against HeLa cells have been investigated.

Electrical transport characteristics of ZnO-Bi2O3-B2O3 glasses

Optically clear glasses in the ZnO-Bi2O3-B2O3 (ZBBO) system were fabricated via the conventional melt-quenching technique. Dielectric constant and loss measurements carried out on ZBBO glasses unraveled nearly frequency (1 kHz-10 MHz)-independent dielectric characteristics associated with significantly low loss (D = 0.004). However, weak temperature response was found with temperature coefficient of dielectric constant 18 +/- 4 ppm A degrees C-1 in the 35-250 A degrees C temperature range. The conduction and relaxation phenomena were rationalized using universal AC conductivity power law and modulus formalism respectively. The activation energy for relaxation determined using imaginary parts of modulus peaks was 2.54 eV which was close to that of the DC conduction implying the involvement of similar energy barriers in both the processes. Stretched and power exponents were temperature dependent. The relaxation and conduction in these glasses were attributed to the hoping and migration of Bi3+ cations in their own and different local environment.

Force Biased Molecular Dynamics Simulation Study of Effect of Dendrimer Generation on Interaction with DNA

We have studied the effect of dendrimer generation on the interaction between dsDNA and the PAMAM dendrimer using force biased simulation of dsDNA with three generations of dendrimer: G3, G4, and G5. Our results for the potential of mean force (PMF) and the dendrimer asphericity along the binding pathway, combined with visualization of the simulations, demonstrate that dendrimer generation has a pronounced impact on the interaction. The PMF increases linearly with increasing generation of the dendrimer. While, in agreement with previous results, we see an increase in the extent to which the dendrimer bends the dsDNA with increasing dendrimer generation, we also see that the deformation of the dendrimer is greater with smaller generation of the dendrimer. The larger dendrimer forces the dsDNA to conform to its structure, while the smaller dendrimer is forced to conform to the structure of the dsDNA. Monitoring the number of bound cations at different values of force bias distance shows the expected effect of ions being expelled when the dendrimer binds dsDNA.

Effect of iodine concentration on the photovoltaic properties of dye sensitized solar cells for various I-2/LiI ratios

In the present study, the effect of iodine concentration on the photovoltaic properties of dye sensitized solar cells (DSSC) based on TiO2 nanoparticles for three different ratios of lithium iodide (LiI) and iodine (I-2) has been investigated. The electron transport properties and interfacial recombination kinetics have been evaluated by electrochemical impedance spectroscopy (EIS). It is found that increasing the concentration of lithium iodide for all ratios of iodine and lithium iodide decreases the open-circuit voltage (V-oc) whereas short circuit current density (J(sc)) and fill factor (FF) shows improvement. The reduction in V-oc and increment in J(sc) is ascribed to the higher concentration of absorptive Li+ cations which shifts the conduction band edge of TiO2 positively. The increase in FF is due to the reduction in electron transport resistance (R-omega) of the cell. In addition for all the ratios of LiI/I-2 increasing the concentration of I-2 decreases the V-oc which is attributed to the increased recombination with tri-iodide ions (I-3(-)) as verified from the low recombination resistance (R-k) and electron lifetime (tau) values obtained by EIS analysis. (C) 2012 Elsevier Ltd. All rights reserved.

A dynamic bandwidth allocation scheme for interactive multimedia applications over cellular networks

Cellular networks played key role in enabling high level of bandwidth for users by employing traditional methods such as guaranteed QoS based on application category at radio access stratum level for various classes of QoSs. Also, the newer multimode phones (e.g., phones that support LTE (Long Term Evolution standard), UMTS, GSM, WIFI all at once) are capable to use multiple access methods simulta- neously and can perform seamless handover among various supported technologies to remain connected. With various types of applications (including interactive ones) running on these devices, which in turn have different QoS requirements, this work discusses as how QoS (measured in terms of user level response time, delay, jitter and transmission rate) can be achieved for interactive applications using dynamic bandwidth allocation schemes over cellular networks. In this work, we propose a dynamic bandwidth allocation scheme for interactive multimedia applications with/without background load in the cellular networks. The system has been simulated for many application types running in parallel and it has been observed that if interactive applications are to be provided with decent response time, a periodic overhauling of policy at admission control has to be done by taking into account history, criticality of applications. The results demonstrate that interactive appli- cations can be provided with good service if policy database at admission control is reviewed dynamically.

Hydrothermal synthesis and characterization of bis(4,4 `-bipyridinium) dodecatungstosilicate dihydrate

Hydrothermal synthesis and structural characterization of a new organic polyoxometalate, namely, bis(4,4'-bipyridinium) dodecatungstosilicate dihydrate, 4,4'-bipyH(2)](2)SiW12O40]center dot 2H(2)O (1) is reported. The crystal structure of (1) consists of a SiW12O40](4-) Keggin anion situated on a two-fold axis, two unique 4,4'-bipyridinium cations, one of which is situated on a two-fold axis, and two independent lattice water molecules. The cations and anions are linked by H-bonding.

Hydrodynamic energy harvesting using an ionic polymer-metal composite stack for underwater applications

Ionic Polymer Metal Composites (IPMCs) are a class of Electro-Active Polymers (EAPs) consisting of a base polymer (usually Nafion), sandwiched between thin films of electrodes and an electrolyte. Apart from fuel cell like proton exchange process in Nafion, these IPMCs can act both as an actuator and a sensor. Typically, IPMCs have been known for their applications in fuel cell technology and in artificial muscles for robots. However, more recently, sensing properties of IPMC have opened up possibilities of mechanical energy harvesting. In this paper, we consider a bi-layer stack of IPMC membranes where fluid flow induced cyclic oscillation allows collection of electronic charge across a pair of functionalized electrode on the surface of IPMC layers/stacks. IPMCs work well in hydrated environment; more specifically, in presence of an electrolyte, and therefore, have great potential in underwater applications like hydrodynamic energy harvesting. Hydrodynamic forces produce bending deformation, which can induce transport of cations via polymer chains of the base polymer of Nafion or PTFE. In our experimental set-up, the deformation is induced into the array of IPMC membranes immersed in electrolyte by water waves caused by a plunger connected to a stepper motor. The frequency and amplitude of the water waves is controlled by the stepper motor through a micro-controller. The generated electric power is measured across a resistive load. Few orders of magnitude increase in the harvested power density is observed. Analytical modeling approach used for power and efficiency calculations are discussed. The observed electro-mechanical performance promises a host of underwater energy harvesting applications.

Imaging Intracellular Zinc by Using a Glyoxal Bis(4-methyl-4-phenyl-3-thiosemicarbazone) Ligand

The ligand glyoxal bis(4-methyl-4-phenyl-3-thiosemicarbazone) (GTSCH2) is shown to be a selective fluorescence turn-on sensor for zinc ions (Zn2+). This sensor is easy to synthesize, exhibits excellent sensitivity and selectivity towards Zn2+ over other physiologically relevant cations, and has sub-nanomolar binding affinity. It displays maximum fluorescence response to Zn2+ when the metal/ligand ratio is 1:1 and displays stable fluorescence over a broad pH range. The potential of GTSCH2 to image Zn2+ inside the cell was demonstrated in MCF-7 cells (human breast cancer cell line) by using flow cytometry and confocal fluorescence microscopy. Cell viability studies reveal that the probe is biocompatible and suitable for cellular applications.