Three-Dimensional Nanoarchitecture of BiFeO3 Anchored TiO2 Nanotube Arrays for Electrochemical Energy Storage and Solar Energy Conversion

Here, we report the synthesis of TiO2/BiFeO3 nano-heterostnicture (NH) arrays by anchoring BiFeO3 (BFO) particles on on TiO2 nanotube surface and investigate their pseudocapacitive and photoelectrochemical properties considering their applications in green energy fields. The unique TiO2/BFO NHs have been demonstrated both as energy conversion and storage materials. The capacitive behavior of the NHs has been found to be significantly higher than that of the pristine TiO2 NTs, which is mainly due to the anchoring of redox active BFO nanoparticles. A specific capacitance of about 440 F g(-1) has been achieved for this NHs at a current density of 1.1 A g(-1) with similar to 80% capacity retention at a current density of 2.5 A g(-1). The NHs also exhibit high energy and power performance (energy density of 46.5 Wh kg(-1) and power density of 1.2 kW kg(-1) at a current density of 2.5 A g(-1)) with moderate cycling stability (92% capacity retention after 1200 cycles). Photoelectrochemical investigation reveals that the photocurrent density of the NHs is almost 480% higher than the corresponding dark current and it shows significantly improved photoswitching performance as compared to pure TiO2 nanotubes, which has been demonstrated based the interfacial type-II band alignment between TiO2 and BFO.

Interplay of electrostatics and lipid packing determines the binding of charged polymer coated nanoparticles to model membranes

Understanding of nanoparticle-membrane interactions is useful for various applications of nanoparticles like drug delivery and imaging. Here we report on the studies of interaction between hydrophilic charged polymer coated semiconductor quantum dot nanoparticles with model lipid membranes. Atomic force microscopy and X-ray reflectivity measurements suggest that cationic nanoparticles bind and penetrate bilayers of zwitterionic lipids. Penetration and binding depend on the extent of lipid packing and result in the disruption of the lipid bilayer accompanied by enhanced lipid diffusion. On the other hand, anionic nanoparticles show minimal membrane binding although, curiously, their interaction leads to reduction in lipid diffusivity. It is suggested that the enhanced binding of cationic QDs at higher lipid packing can be understood in terms of the effective surface potential of the bilayers which is tunable through membrane lipid packing. Our results bring forth the subtle interplay of membrane lipid packing and electrostatics which determine nanoparticle binding and penetration of model membranes with further implications for real cell membranes.

Cell-Membrane-Mimicking Lipid-Coated Nanoparticles Confer Raman Enhancement to Membrane Proteins and Reveal Membrane-Attached Amyloid-beta Conformation

Identifying the structures of membrane bound proteins is critical to understanding their function in healthy and diseased states. We introduce a surface enhanced Raman spectroscopy technique which can determine the conformation of membrane-bound proteins, at low micromolar concentrations, and also in the presence of a substantial membrane-free fraction. Unlike conventional surface enhanced Raman spectroscopy, our approach does not require immobilization of molecules, as it uses spontaneous binding of proteins to lipid bilayer-encapsulated Ag nanoparticles. We apply this technique to probe membrane-attached oligomers of Amyloid-beta(40) (A beta(40)), whose conformation is keenly sought in the context of Alzheimer's disease. Isotope-shifts in the Raman spectra help us obtain secondary structure information at the level of individual residues. Our results show the presence of a beta-turn, flanked by two beta-sheet regions. We use solid-state NMR data to confirm the presence of the beta-sheets in these regions. In the membrane-attached oligomer, we find a strongly contrasting and near-orthogonal orientation of the backbone H-bonds compared to what is found in the mature, less-toxic A beta fibrils. Significantly, this allows a ``porin'' like beta-barrel structure, providing a structural basis for proposed mechanisms of A beta oligomer toxicity.

Estimation of activation energy for electroporation and pore growth rate in liquid crystalline and gel phases of lipid bilayers using molecular dynamics simulations

Molecular dynamics simulations of electroporation in POPC and DPPC lipid bilayers have been carried out at different temperatures ranging from 230 K to 350 K for varying electric fields. The dynamics of pore formation, including threshold field, pore initiation time, pore growth rate, and pore closure rate after the field is switched off, was studied in both the gel and liquid crystalline (L-alpha) phases of the bilayers. Using an Arrhenius model of pore initiation kinetics, the activation energy for pore opening was estimated to be 25.6 kJ mol(-1) and 32.6 kJ mol(-1) in the L-alpha phase of POPC and DPPC lipids respectively at a field strength of 0.32 V nm(-1). The activation energy decreases to 24.2 kJ mol(-1) and 23.7 kJ mol(-1) respectively at a higher field strength of 1.1 V nm(-1). At temperatures below the melting point, the activation energy in the gel phase of POPC and DPPC increases to 28.8 kJ mol(-1) and 34.4 kJ mol(-1) respectively at the same field of 1.1 V nm(-1). The pore closing time was found to be higher in the gel than in the L-alpha phase. The pore growth rate increases linearly with temperature and quadratically with field, consistent with viscosity limited growth models.

Plasmonic Lipid Bilayer Membranes for Enhanced Detection Sensitivity of Biolabeling Fluorophores

Plasmonics based sensing, using the surface plasmon resonance of metal nanoparticles, has been effectively demonstrated in various applications. Extending this methodology to cell and artificial lipid bilayer membranes is extremely beneficial in enhancing the sensitivity of the detection of binding and cellular transport of molecules across such membranes. Here, the creation of an artificial plasmonic biomembrane template is demonstrated and used to show the enhanced detection sensitivity of certain widely used biomarker molecules. The efficacy of these templates is explained in terms of the ability of the hydrophobic polymer grafted gold nanoparticles used to organize, penetrate, and fluidize the membranes. The enhancement of photoluminescence of the dye molecules used occurs over a reasonably large spectral range as compared to the plasmon resonance of gold nanoparticles. The results could, possibly, be extended to cellular membranes with relevant modifications, as well as to the detection of any other biological molecule appropriately labeled with fluorescent dye molecules, and demonstrate the versatility of these plasmonic bioinspired platforms as potential biochemical sensors.

First principles DFT investigation Of Yttrium-decorated Boron-Nitride Nanotube: Electronic Structure and Hydrogen Storage

The electronic structure and hydrogen storage capability of Yttrium-doped BNNTs has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site in the center of the hexagonal ring with a binding energy of 0.8048eV. Decorating by Y makes the system half-metallic and magnetic with a magnetic moment of 1.0 mu(B). Y decorated Boron-Nitride (8,0) nanotube can adsorb up to five hydrogen molecules whose average binding energy is computed as 0.5044eV. All the hydrogen molecules are adsorbed with an average desorption temperature of 644.708 K. Taking that the Y atoms can be placed only in alternate hexagons, the implied wt% comes out to be 5.31%, a relatively acceptable value for hydrogen storage materials. Thus, this system can serve as potential hydrogen storage medium.

Hydrogen energy future with formic acid: a renewable chemical hydrogen storage system

Formic acid, the simplest carboxylic acid, is found in nature or can be easily synthesized in the laboratory (major by-product of some second generation biorefinery processes); it is also an important chemical due to its myriad applications in pharmaceuticals and industry. In recent years, formic acid has been used as an important fuel either without reformation (in direct formic acid fuel cells, DFAFCs) or with reformation (as a potential chemical hydrogen storage material). Owing to the better efficiency of DFAFCs compared to several other PEMFCs and reversible hydrogen storage systems, formic acid could serve as one of the better fuels for portable devices, vehicles and other energy-related applications in the future. This perspective is focused on recent developments in the use of formic acid as a reversible source for hydrogen storage. Recent developments in this direction will likely give access to a variety of low-cost and highly efficient rechargeable hydrogen fuel cells within the next few years by the use of suitable homogeneous metal complex/heterogeneous metal nanoparticle-based catalysts under ambient reaction conditions. The production of formic acid from atmospheric CO2 (a greenhouse gas) will decrease the CO2 content and may be helpful in reducing global warming.

Rayleigh-Taylor instability in a thermocline based thermal storage tank

Numerical simulations are performed to study the stability characteristics of a molten salt thermocline storage unit. Perturbations are introduced into a stable flow field in such a way as to make the top-fluid heavier than the fluid at the bottom, thereby causing a possible instability in the system. The evolution pattern of the various disturbances are examined in detail. Disturbances applied for short duration get decayed before they could reach the thermocline, whereas medium and long duration disturbances evolve into a ``falling spike'' or ``stalactite-like'' structure and destabilize the thermocline. Rayleigh Taylor instability is observed inside the storage tank. The effect of the duration, velocity and temperature of the disturbance on thermocline thickness and penetration length are studied. A quadratic time dependence of penetration length was observed. New perspectives on thermocline breakdown phenomena are obtained from the numerical flow field. (C) 2015 Elsevier Masson SAS. All rights reserved.

Experimental solubilities of two lipid derivatives in supercritical carbon dioxide and new correlations based on activity coefficient models

The solubilities of two lipid derivatives, geranyl butyrate and 10-undecen-1-ol, in SCCO2 (supercritical carbon dioxide) were measured at different operating conditions of temperature (308.15 to 333.15 K) and pressure (10 to 18 MPa). The solubilities (in mole fraction) ranged from 2.1 x 10(-3) to 23.2 x 10(-3) for geranyl butyrate and 2.2 x 10(-3) to 25.0 x 10(-3) for 10-undecen-1-ol, respectively. The solubility data showed a retrograde behavior in the pressure and temperature range investigated. Various combinations of association and solution theory along with different activity coefficient models were developed. The experimental data for the solubilities of 21 liquid solutes along with geranyl butyrate and 10-undecen-1-ol were correlated using both the newly derived models and the existing models. The average deviation of the correlation of the new models was below 15%.

SMO: An Integrated Approach to Intra-array and Inter-array Storage Optimization

The polyhedral model provides an expressive intermediate representation that is convenient for the analysis and subsequent transformation of affine loop nests. Several heuristics exist for achieving complex program transformations in this model. However, there is also considerable scope to utilize this model to tackle the problem of automatic memory footprint optimization. In this paper, we present a new automatic storage optimization technique which can be used to achieve both intra-array as well as inter-array storage reuse with a pre-determined schedule for the computation. Our approach works by finding statement-wise storage partitioning hyper planes that partition a unified global array space so that values with overlapping live ranges are not mapped to the same partition. Our heuristic is driven by a fourfold objective function which not only minimizes the dimensionality and storage requirements of arrays required for each high-level statement, but also maximizes inter statement storage reuse. The storage mappings obtained using our heuristic can be asymptotically better than those obtained by any existing technique. We implement our technique and demonstrate its practical impact by evaluating its effectiveness on several benchmarks chosen from the domains of image processing, stencil computations, and high-performance computing.