Highly efficient WO3-ZnO mixed oxides for photocatalysis

Monoclinic nanocuboid WO3 enhanced the photocatalyst efficiency of quasi nanobelt zinc oxide for dye degradation in the presence of visible light radiation. Combustion synthesized ZnO resulted in a belt-like morphology through in situ cluster formation of near spherical particles but homogenously disperses and strongly adheres to nanocuboid WO3 during physical mixing. Cationic methylene blue (MB) and anionic orange G (OG) undergo degradation through a charge transfer mechanism in the presence of WO3-ZnO (1 : 9 weight percentage ratio) mixture. The photocatalytic reaction was enhanced due to the reduction in the recombination of photogenerated electron-holes. The high degree of 90% degradation of both dyes is due to the activity of the mixed oxides, which is much higher than that obtained either with WO3 or ZnO individually.

Analysis of Entropy Generation During Mixed Convective Heat Transfer of Nanofluids Past a Rotating Circular Cylinder

The entropy generation due to mixed convective heat transfer of nanofluids past a rotating circular cylinder placed in a uniform cross stream is investigated via streamline upwind Petrov-Galerkin based finite element method. Nanosized copper (Cu) particles suspended in water are used with Prandtl number (Pr)=6.9. The computations are carried out at a representative Reynolds number (Re) of 100. The dimensionless cylinder rotation rate, a, is varied between 0 and 2. The range of nanoparticle volume fractions (phi) considered is 0 <= phi <= 5%. Effect of aiding buoyancy is brought about by considering two fixed values of the Richardson number (Ri) as 0.5 and 1.0. A new model for predicting the effective viscosity and thermal conductivity of dilute suspensions of nanoscale colloidal particles is presented. The model addresses the details of the agglomeration-deagglomeration in tune with the pertinent variations in the effective particulate dimensions, volume fractions, as well as the aggregate structure of the particulate system. The total entropy generation is found to decrease sharply with cylinder rotation rates and nanoparticle volume fractions. Increase in nanoparticle agglomeration shows decrease in heat transfer irreversibility. The Bejan number falls sharply with increase in alpha and phi.

Charge Transfer Induces Formation of Stimuli-Responsive, Chiral, Cohesive Vesicles-on-a-String that Eventually Turn into a Hydrogel

A charge transfer (CT) mediated two-component, multistimuli responsive supergelation involving a L-histidine-appended pyrenyl derivative (PyHisOMe) as a donor and an asymmetric bolaamphiphilic naphthalene-diimide (Asym-NDI) derivative as an acceptor in a 2: 1 mixture of H2O/MeOH was investigated. Asym-NDI alone self-assembled into pH-responsive vesicular nanostructures in water. Excellent selectivity in CT gel formation was achieved in terms of choosing amino acid appended pyrenyl donor scaffolds. Circular di-chroism and morphological studies suggested formation of chiral, interconnected vesicular assemblies resembling ``pearls-on-a-string'' from these CT mixed stacks. XRD studies revealed the formation of monolayer lipid membranes from these CT mixed stacks that eventually led to the formation of individual vesicles. Strong cohesive forces among the interconnected vesicles originate from the protrusion of the oxyethylene chains from the surfaces of the chiral vesicles.

Electron transfer statistics and thermal fluctuations in molecular junctions

We derive analytical expressions for probability distribution function (PDF) for electron transport in a simple model of quantum junction in presence of thermal fluctuations. Our approach is based on the large deviation theory combined with the generating function method. For large number of electrons transferred, the PDF is found to decay exponentially in the tails with different rates due to applied bias. This asymmetry in the PDF is related to the fluctuation theorem. Statistics of fluctuations are analyzed in terms of the Fano factor. Thermal fluctuations play a quantitative role in determining the statistics of electron transfer; they tend to suppress the average current while enhancing the fluctuations in particle transfer. This gives rise to both bunching and antibunching phenomena as determined by the Fano factor. The thermal fluctuations and shot noise compete with each other and determine the net (effective) statistics of particle transfer. Exact analytical expression is obtained for delay time distribution. The optimal values of the delay time between successive electron transfers can be lowered below the corresponding shot noise values by tuning the thermal effects. (C) 2015 AIP Publishing LLC.

Mitochondria-Targeting Photocytotoxic Ferrocenyl Conjugates of N-Alkylpyridinium Salts

Ferrocenyl (Fc) conjugates (1-3) of alkylpyridinium cations (E)-N-alkyl-4-2-(ferrocenyl)vinyl]pyridinium bromide (alkyl = n-butyl in 1, N,N,N-triethylbutan-1-aminium bromide in 2, and n-butyltriphenylphosphonium bromide in 3) were prepared and characterized, and their photocytotoxicities and cellular uptakes in HeLa cancer and 3T3 normal cells were studied. The species with a 4-methoxyphenyl moiety (4) instead of Fc was used as a control. The triphenylphosphonium-appended 3 was designed for specific delivery into the mitochondria of the cells. Compounds 1-3 showed metal-to-ligand charge-transfer bands at approximate to 550 nm in phosphate buffered saline (PBS). The Fc(+)/Fc and pyridinium core redox couples were observed at 0.75 and -1.2 V versus a saturated calomel electrode (SCE) in CH2Cl2/0.1 M (nBu(4)N)ClO4. Conjugate 3 showed a significantly higher photocytotoxicity in HeLa cancer cells IC50 = (1.3 +/- 0.2) M] than in normal 3T3 cells IC50 = (27.5 +/- 1.5) M] in visible light (400-700 nm). The positive role of the Fc moiety in 3 was evident from the inactive nature of 4. A JC-1 dye (5,5,6,6-tetrachloro-1,1,3,3-tetraethylbenzimidazolylcarbocyanine iodide) assay showed that 3 targets the mitochondria and induces apoptosis by the mitochondrial intrinsic pathway caused by reactive oxygen species (ROS). Annexin/propidium iodide studies showed that 3 induces apoptotic cell death in visible light by ROS generation, as evidenced from dichlorofluorescein diacetate assay. Compounds 1-3 exhibit DNA photocleavage activity through the formation of hydroxyl radicals.

New single-source precursor for bismuth sulfide and its use as low-cost counter electrode material for dye-sensitized solar cells

One new homoleptic Bi(dtc)(3)] (1) (dtc = 4-hydroxypiperdine dithiocarbamate) has been synthesized and characterized by microanalysis, IR, UV-Vis, H-1 and C-13 spectroscopy and X-ray crystallography. The photoluminescence spectrum for the compound in DMSO solution was recorded. The crystal structure of 1 displayed distorted octahedral geometry around the Bi(III) center bonded through sulfur atoms of the dithiocarbamate ligands. TGA indicates that the compound decomposes to a Bi and Bi-S phase system. The Bi and Bi-S obtained from decomposition of the compound have been characterized by pXRD, EDAX and SEM. Solvothermal decomposition of 1 in the absence and presence of two different capping agents yielded three morphologically different Bi2S3 systems which were deployed as counter-electrode in dye-sensitized solar cells (DSSCs). (C) 2015 Elsevier B.V. All rights reserved.

Comparative evaluation of inversion approaches of the radiative transfer model for estimation of crop biophysical parameters

The inversion of canopy reflectance models is widely used for the retrieval of vegetation properties from remote sensing. This study evaluates the retrieval of soybean biophysical variables of leaf area index, leaf chlorophyll content, canopy chlorophyll content, and equivalent leaf water thickness from proximal reflectance data integrated broadbands corresponding to moderate resolution imaging spectroradiometer, thematic mapper, and linear imaging self scanning sensors through inversion of the canopy radiative transfer model, PROSAIL. Three different inversion approaches namely the look-up table, genetic algorithm, and artificial neural network were used and performances were evaluated. Application of the genetic algorithm for crop parameter retrieval is a new attempt among the variety of optimization problems in remote sensing which have been successfully demonstrated in the present study. Its performance was as good as that of the look-up table approach and the artificial neural network was a poor performer. The general order of estimation accuracy for para-meters irrespective of inversion approaches was leaf area index > canopy chlorophyll content > leaf chlorophyll content > equivalent leaf water thickness. Performance of inversion was comparable for broadband reflectances of all three sensors in the optical region with insignificant differences in estimation accuracy among them.

Standardizing Patent Data Cleaning in a University Technology Transfer Office

There are multiple goals of a technology transfer office (TTO) based in a university system. Whilst commercialization is a critical goal, maintenance and cleaning of the TTO's database needs detailing. Literature in the area is scarce and only some researchers make reference to TTO data cleaning. During an attempt to understand the commercial strategy of a university TTO in Bangalore the challenge of data cleaning was encountered. This paper describes a case study of data cleaning at an Indian university based TTO. 382 patent records were analyzed in the study. The case study first describes the back ground of the university system. Second, the method to clean the data and the experiences encountered are highlighted. Insights drawn indicate that patent data cleaning in a TTO is a specialized area which needs attention. Overlooking this activity can have legal implications and may result in an inability to commercialize the patent. Two levels of patent data cleaning are discussed in this case study. Best practices of data cleaning in academic TTOs are discussed.

Efficient charge transfer and field-induced tunneling transport in hybrid composite device of organic semiconductor and cadmium telluride quantum dots

Temperature and photo-dependent current-voltage characteristics are investigated in thin film devices of a hybrid-composite comprising of organic semiconductor poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT: PSS) and cadmium telluride quantum dots (CdTe QDs). A detailed study of the charge injection mechanism in ITO/PEDOT: PSS-CdTe QDs/Al device exhibits a transition from direct tunneling to Fowler-Nordheim tunneling with increasing electric field due to formation of high barrier at the QD interface. In addition, the hybrid-composite exhibits a huge photoluminescence quenching compared to aboriginal CdTe QDs and high increment in photoconductivity (similar to 400%), which is attributed to the charge transfer phenomena. The effective barrier height (Phi(B) approximate to 0.68 eV) is estimated from the transition voltage and the possible origin of its variation with temperature and photo-illumination is discussed. (C) 2015 AIP Publishing LLC.

Targeted Modifications in Adeno-Associated Virus Serotype 8 Capsid Improves Its Hepatic Gene Transfer Efficiency In Vivo

Recombinant adeno-associated virus vectors based on serotype 8 (AAV8) have shown significant promise for liver-directed gene therapy. However, to overcome the vector dose dependent immunotoxicity seen with AAV8 vectors, it is important to develop better AAV8 vectors that provide enhanced gene expression at significantly low vector doses. Since it is known that AAV vectors during intracellular trafficking are targeted for destruction in the cytoplasm by the host-cellular kinase/ubiquitination/proteasomal machinery, we modified specific serine/threonine kinase or ubiquitination targets on the AAV8 capsid to augment its transduction efficiency. Point mutations at specific serine (S)/threonine (T)/lysine (K) residues were introduced in the AAV8 capsid at the positions equivalent to that of the effective AAV2 mutants, generated successfully earlier. Extensive structure analysis was carried out subsequently to evaluate the structural equivalence between the two serotypes. scAAV8 vectors with the wild-type (WT) and each one of the S/T -> Alanine (A) or K-Arginine (R) mutant capsids were evaluated for their liver transduction efficiency in C57BL/6 mice in vivo. Two of the AAV8-S -> A mutants (S279A and S671A), and a K137R mutant vector, demonstrated significantly higher enhanced green fluorescent protein (EGFP) transcript levels (similar to 9- to 46-fold) in the liver compared to animals that received WT-AAV8 vectors alone. The best performing AAV8 mutant (K137R) vector also had significantly reduced ubiquitination of the viral capsid, reduced activation of markers of innate immune response, and a concomitant two-fold reduction in the levels of neutralizing antibody formation in comparison to WT-AAV8 vectors. Vector bio-distribution studies revealed that the K137R mutant had a significantly higher and preferential transduction of the liver (106 vs. 7.7 vector copies/mouse diploid genome) when compared to WT-AAV8 vectors. To further study the utility of the K137R-AAV8 mutant in therapeutic gene transfer, we delivered human coagulation factor IX (h. FIX) under the control of liver-specific promoters (LP1 or hAAT) into C57BL/6 mice. The circulating levels of h. FIX: Ag were higher in all the K137R-AAV8 treated groups up to 8 weeks post-hepatic gene transfer. These studies demonstrate the feasibility of the use of this novel AAV8 vectors for potential gene therapy of hemophilia B.

Redox-Active Metal-Organic Frameworks: Highly Stable Charge-Separated States through Strut/Guest-to-Strut Electron Transfer

Molecular organization of donor and acceptor chromophores in self-assembled materials is of paramount interest in the field of photovoltaics or mimicry of natural light-harvesting systems. With this in mind, a redox-active porous interpenetrated metal-organic framework (MOF), {Cd(bpdc)(bpNDI)]4.5H(2)ODMF}(n) (1) has been constructed from a mixed chromophoric system. The -oxo-bridged secondary building unit, {Cd-2(-OCO)(2)}, guides the parallel alignment of bpNDI (N,N-di(4-pyridyl)-1,4,5,8-naphthalenediimide) acceptor linkers, which are tethered with bpdc (bpdcH(2)=4,4-biphenyldicarboxylic acid) linkers of another entangled net in the framework, resulting in photochromic behaviour through inter-net electron transfer. Encapsulation of electron-donating aromatic molecules in the electron-deficient channels of 1 leads to a perfect donor-acceptor co-facial organization, resulting in long-lived charge-separated states of bpNDI. Furthermore, 1 and guest encapsulated species are characterised through electrochemical studies for understanding of their redox properties.

Probing Ultrafast Photoinduced Electron Transfer to TiO2 from CdS Nanocrystals of Varying Crystallographic Phase Content

The photoinduced electron transfer processes in a nanoheterostructured semiconductor assembly are complex and depend on various parameters Of the constituents of the assembly. We present here the ultrafast electron transfer characteristics of an assembly comprised of a Wide band semiconductor, titanium dioxide (TiO2), attached to light-harvesting cadmium sulfide (CdS) nanotrystals of varying crystallographic phase content. Quantitative analysis of Synchrotron high-resolution X-ray. diffraction data of CdS nanocrystals precisely reveals the presence of both wurtzite and zinc blende phases in varying amounts. The,estimated content of crystal phases is observed to be strongly dependent on an important synthesis parameter, viz., the ratio of the two solvents. The biphasit nature of CdS influences directly the shape of the nanocrystal at long reaction times as well as the transfer of the photoexcited electrons from the CdS to TiO2 as obtained from transient absorption spectroscopy. A higher amount of zinc blende Phase is observed to be beneficial for fast electron transfer across the CdS-TiO2 interface. The electron transfer rate constant differs by one order of magnitude between the CdS nanocryStals and varies linearly with the fraction of the phases.

Robust, metallic Pd17Se15 and Pd7Se4 phases from a single source precursor and their use as counter electrodes in dye sensitized solar cells

Thin films of conducting palladium selenide phases (Pd17Se15 and Pd7Se4) are prepared using a single source molecular precursor by thermolysis. Varying the mole ratios of palladium and selenium precursors results in palladium organo-selenolate complexes which on thermolysis at different temperatures yield Pd17Se15 and Pd7Se4 phases that are very stable and adherent to the substrate. The organo-selenolate complexes are characterized using small angle XRD, Se-77 NMR and thermogravimetric analysis (TGA). The palladium selenide films are characterized by various techniques such as XRD, XPS, TEM and SEM. Electrical conductivities of the films are determined using the four probe method. The strong adherence of the films to glass substrates coupled with high corrosion resistant behavior towards strong acid and alkaline environments render them to be very effective as electrocatalysts. The catalytic activity towards the I-3(-)/I- redox couple, which is an important reaction in the regeneration of the dye in a dye-sensitized solar cell, is studied. Between the two phases, the Pd17Se15 film shows superior activity as the counter electrode for dye sensitized solar cells with a photocurrent conversion efficiency of 7.45%.

Structures of substrate- and nucleotide-bound propionate kinase from Salmonella typhimurium: substrate specificity and phosphate-transfer mechanism

Kinases are ubiquitous enzymes that are pivotal to many biochemical processes. There are contrasting views on the phosphoryl-transfer mechanism in propionate kinase, an enzyme that reversibly transfers a phosphoryl group from propionyl phosphate to ADP in the final step of non-oxidative catabolism of L-threonine to propionate. Here, X-ray crystal structures of propionate- and nucleotide-bound Salmonella typhimurium propionate kinase are reported at 1.8-2.0 angstrom resolution. Although the mode of nucleotide binding is comparable to those of other members of the ASKHA superfamily, propionate is bound at a distinct site deeper in the hydrophobic pocket defining the active site. The propionate carboxyl is at a distance of approximate to 5 angstrom from the -phosphate of the nucleotide, supporting a direct in-line transfer mechanism. The phosphoryl-transfer reaction is likely to occur via an associative S(N)2-like transition state that involves a pentagonal bipyramidal structure with the axial positions occupied by the nucleophile of the substrate and the O atom between the - and the -phosphates, respectively. The proximity of the strictly conserved His175 and Arg236 to the carboxyl group of the propionate and the -phosphate of ATP suggests their involvement in catalysis. Moreover, ligand binding does not induce global domain movement as reported in some other members of the ASKHA superfamily. Instead, residues Arg86, Asp143 and Pro116-Leu117-His118 that define the active-site pocket move towards the substrate and expel water molecules from the active site. The role of Ala88, previously proposed to be the residue determining substrate specificity, was examined by determining the crystal structures of the propionate-bound Ala88 mutants A88V and A88G. Kinetic analysis and structural data are consistent with a significant role of Ala88 in substrate-specificity determination. The active-site pocket-defining residues Arg86, Asp143 and the Pro116-Leu117-His118 segment are also likely to contribute to substrate specificity.