Anomalous Viscosity Reduction and Hydrodynamic Interactions of Polymeric Nanocolloids in Polymers

One of the central dogmas of fluid physics is the no-slip boundary condition, whose validity has come under scrutiny, especially in the fields of micro and nanofluidics. Although various studies show the violation of the no-slip condition its effect on flow of colloidal particles in viscous media has been rarely explored. Here we report unusually large reduction of effective viscosity experienced by polymeric nano colloids moving through a highly viscous and confined polymer, well above its glass transition temperature. The extent of reduction in effective interface viscosity increases with decreasing temperature and polymer film thickness. Concomitant with the reduction in effective viscosity we also observe apparent divergence of the wave vector dependent hydrodynamic interaction function of these colloids with an anomalous power law exponent of similar to 2 at the lowest temperatures and film thickness studied. Such strong hydrodynamic interactions are not expected for polymeric colloidal motion in polymer melts. We suggest hydrodynamics, especially slip present at the colloid-polymer interface which determines the observed reduction in interface viscosity and presence of strong hydrodynamic interactions.

Thermoelectric properties of Co substituted synthetic tetrahedrite

Transition metal atom (Co) substituted synthetic tetrahedrite compounds Cu12-xCoxSb4S13 (x = 0, 0.5, 1.0, 1.5, 2.0) were prepared by solid state synthesis. X-Ray Diffraction (XRD) patterns revealed tetrahedrite as the main phase, whereas for the compounds with x = 0, 0.5 a trace of impurity phase Cu3SbS4 was observed. The surface morphology showed a large grain size with low porosity, which indicated appropriate compaction for the hot pressed samples. The phase purity, as monitored by Electron Probe Micro Analysis (EPMA) is in good agreement with the XRD data. The elemental composition for all the compounds almost matched with the nominal composition. The X-ray Photoelectron Spectroscopy (XPS) data showed that Cu existed in both +1 and +2 states, while Sb exhibited +3 oxidation states. Elastic modulus and hardness showed a systematic variation with increasing Co content. The electrical resistivity and Seebeck coefficient increased with increase in the doping content due to the decrease in the number of carriers caused by the substitution of Co2+ on the Cu1+ site. The positive Seebeck coefficient for all samples indicates that the dominant carriers are holes. A combined effect of resistivity and Seebeck coefficient leads to the maximum power factor of 1.76 mW m(-1) K-2 at 673 K for Cu11.5Co0.5Sb4S13. This could be due to the optimization in the carrier concentration by the partial substitution of Co2+ on both the Cu1+ as well as Cu2+ site at the same doping levels, which is also supported by the XPS data. The total thermal conductivity systematically decreased with increase of doping content as it is mainly influenced by the decrease of carrier thermal conductivity. The maximum thermoelectric figure of merit zT = 0.98 was obtained at 673 K for Cu11.5Co0.5Sb4S13. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Detailed mechanism and kinetic study of CO oxidation on cobalt oxide surfaces

Co3O4 catalysts were prepared by combustion synthesis using different fuels glycine (G), ODH (O) and urea (U). Morphological changes of the materials were observed by using different fuels. The prepared catalysts were characterized by XRD, XPS, SEM, TEM, BET and DRIFTS analysis. All compounds showed 100% conversion of CO below 175C. The prepared catalysts exhibited very high stability and conversions did not decrease even after 50 h of continuous operation. The oxygen storage capacity (OSC) of materials was measured by H-2-TPR analysis. Co3O4-O is having high OSC among the synthesized catalysts. The activation energies of these catalysts were found to be in the range of 42.3-64.8 kJ mol(-1). With DRIFTS analysis, the surface carbonates, superoxide anions, adsorbed CO, O-2 species on the catalyst surface were found and this information was used to develop a detailed reaction pathway. A kinetic model was developed with the help of proposed mechanism and used to fit the data. (C) 2014 Elsevier B.V. All rights reserved.

Structural modification and enhanced magnetic properties with two phonon modes in Ca-Co codoped BiFeO3 nanoparticles

Bi1-xCaxFe1-xCoxO3 nanoparticles with x=0.0, 0.05, 0.10 and 0.15 were successfully synthesized by cost effective tartaric acid based sol gel route. The alkali earth metal Ca2+ ions and transition metal Co3+ ions codoping at A and B-sites of BiFeO3 results in structural distortion and phase transformation. Rietveld refinement of XRD patterns suggested the coexistence of rhombohedral and orthorhombic phases in codoped BiFeO3 samples. Both XRD and Raman scattering studies showed the compressive lattice distortion in the samples induced by codoping of Ca2+ and Co3+ ions. Two-phonon Raman spectra exhibited the improvement of magnetization in these samples. X-ray photoelectron spectroscopy (XPS) showed the dominancy of Fe3+ and Co3+ oxidation states along with the shifting of the binding energy of Bi 4f orbital which confirms the substitution Ca2+ at Bi-site. The magnetic study showed the enhancement in room temperature ferromagnetic behavior with co-substitution consistent with Rama analysis. The gradual change in line shape of electron spin resonance spectra indicated the local distortion induced by codoping. (C) 2015 Published by Elsevier Ltd and Techna Group S.r.l.

Modeling the co-transport of viruses and colloids in unsaturated porous media

A mathematical model is developed to simulate the co-transport of viruses and colloids in unsaturated porous media under steady-state flow conditions. The virus attachment to the mobile and immobile colloids is described using a linear reversible kinetic model. Colloid transport is assumed to be decoupled from virus transport; that is, we assume that colloids are not affected by the presence of attached viruses on their surface. The governing equations,are solved numerically using an alternating three-step operator splitting approach. The model is verified by fitting three sets of experimental data published in the literature: (1) Syngouna and Chrysikopoulos (2013) and (2) Walshe et al. (2010), both on the co-transport of viruses and clay colloids under saturated conditions, and (3) Syngouna and Cluysikopoulos (2015) for the co-transport of viruses and clay colloids under unsaturated conditions. We found a good agreement between observed and fitted breakthrough curves (BTCs) under both saturated and unsaturated conditions. Then, the developed model was used to simulate the co-transport of viruses and colloids in porous media under unsaturated conditions, with the aim of understanding the relative importance of various processes on the co-transport of viruses and colloids in unsaturated porous media. The virus retention in porous media in the presence of colloids is greater during unsaturated conditions as compared to the saturated conditions due to: (1) virus attachment to the air-water interface (AWI), and (2) co-deposition of colloids with attached viruses on its surface to the AWL A sensitivity analysis of the model to various parameters showed that the virus attachment to AWI is the most sensitive parameter affecting the BTCs of both free viruses and total mobile viruses and has a significant effect on all parts of the BTC. The free and the total mobile viruses BTCs are mainly influenced by parameters describing virus attachment to the AIM, virus interaction with mobile and immobile colloids, virus attachment to solid-water interface (SWI), and colloid interaction with SWI and AWL The virus BTC is relatively insensitive to parameters describing the maximum adsorption capacity of the AWI for colloids, inlet colloid concentration, virus detachment rate coefficient from the SW!, maximum adsorption capacity of the AWI for viruses and inlet virus concentration. (C) 2015 Elsevier B.V. All rights reserved.

Room temperature ferromagnetism and white light emissive CdS:Cr nanoparticles synthesized by chemical co-precipitation method

Undoped and Cr (3% and 5%) doped CdS nanoparticles were synthesized by chemical co-precipitation method. The synthesized nanocrystalline particles are characterized by energy dispersive X-ray analysis (EDAX), scanning electron microscope (SEM), X-ray Diffraction (XRD), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), photoluminescence (PL), Electron paramagnetic resonance (EPR), vibrating sample magnetometer (VSM) and Raman spectroscopy. XRD studies indicate that Cr doping in host CdS result a structural change from Cubic phase to mixed (cubic + hexagonal) phase. Due to quantum confinement effect, widening of the band gap is observed for undoped and Cr doped CdS nanoparticles compared to bulk CdS. The average particle size calculated from band gap values is in good agreement with the TEM study calculation and it is around 4-5 nm. A strong violet emission band consisting of two emission peaks is observed for undoped CdS nanoparticles, whereas for CdS:Cr nanoparticles, a broad emission band ranging from 420 nm to 730 nm with a maximum at similar to 587 nm is observed. The broad emission band is due to the overlapped emissions from variety of defects. EPR spectra of CdS:Cr samples reveal resonance signal at g = 2.143 corresponding to interacting Cr3+ ions. VSM studies indicate that the diamagnetic CdS nanoparticles are transform to ferromagnetic for 3% Cr3+ doping and the ferromagnetic nature is diminished with increasing the doping concentration to 5%. (C) 2015 Elsevier B.V. All rights reserved.

Organic-inorganic hybrid PtCo nanoparticle with high electrocatalytic activity and durability for oxygen reduction

In Pt-transition metal (TM) alloy catalysts, the electron transfer from the TM to Pt is retarded owing to the inevitable oxidation of the TM surface by oxygen. In addition, acidic electrolytes such as those employed in fuel cells accelerate the dissolution of the surface TM oxide, which leads to catalyst degradation. Herein, we propose a novel synthesis strategy that selectively modifies the electronic structure of surface Co atoms with N-containing polymers, resulting in highly active and durable PtCo nanoparticle catalysts useful for the oxygen reduction reaction (ORR). The polymer, which is functionalized on carbon black, selectively interacts with the Co precursor, resulting in Co-N bond formation on the PtCo nanoparticle surface. Electron transfer from Co to Pt in the PtCo nanoparticles modified by the polymer is enhanced by the increase in the difference in electronegativity between Pt and Co compared with that in bare PtCo nanoparticles with the TM surface oxides. In addition, the dissolution of Co and Pt is prevented by the selective passivation of surface Co atoms and the decrease in the O-binding energy of surface Pt atoms. As a result, the catalytic activity and durability of PtCo nanoparticles for the ORR are significantly improved by the electronic ensemble effects. The proposed organic/inorganic hybrid concept will provide new insights into the tuning of nanomaterials consisting of heterogeneous metallic elements for various electrochemical and chemical applications.

Role of (La, Gd) co-doping on the enhanced dielectric and magnetic properties of BiFeO3 ceramics

The effect of the La3+ and Gd3+ co-doping on the structure, electric and magnetic properties of BiFeO3 (BFO) ceramics are investigated. For the compositions (x=0 and 0 <= y <= 0.15) in the perovskite structured LaxGdyBi1-xFeO3 system, a tiny residual phase of Bi2Fe4O9 is noticed. Such a secondary phase is suppressed with the incorporation of `La' content (x). The magnitude of dielectric constant (epsilon(r) increases progressively by increasing the `La' content from x=0 to 0.15 with a remarkable decrease of dielectric loss. For x=0.15, the system LaxGdyBi1-x(x+y)FeO3 exhibits highest remanent magnetization (M-r) of 0.18 emu/g and coercive magnetic field (H-c) of similar to 1 Tin the presence of external magnetic field of 9 T at 300 K. The origin of enhanced dielectric and magnetic properties of LaxGdyBil (x+y)Fe03 and the role of doping elements, La3+, Gd3+ has been discussed. (C) 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Effect of solvents on the enzyme mediated degradation of copolymers

The biodegradation of polycaprolactone (PCL), polylactic acid (PLA), polyglycolide (PGA) and their copolymers, poly (lactide-co-glycolide) and poly (D, L-lactide-co-caprolactone) (PLCL) was investigated. The influence of different solvents on the degradation of these polymers at 37 degrees C in the presence of two different lipases namely Novozym 435 and the free lipase of porcine pancreas was investigated. The rate coefficients for the polymer degradation and enzyme deactivation were determined using continuous distribution kinetics. Among the homopolymers, the degradation of PGA was nearly an order of magnitude lower than that for PCL and PLA. The overall rate coefficients of the copolymers were higher than their respective homopolymers. Thus, PLCL degraded faster than either PCL or PLA. The degradation was highly dependent on the viscosity of the solvent used with the highest degradation observed in acetone. The degradation of the polymers in acetone was nearly twice that observed in dimethyl sulfoxide indicating that the degradation decreases with increase in the solvent viscosity. The degradation of the polymers in water-solvent mixtures indicated an optimal water content of 2.5 wt% of water.

CuIn1-xAlxSe2 Thin Films Grown by Co-Sputtering and Modified Selenization: Application in Flexible Solar Cells

Thin films of CuIn1-xAlxSe2 (CIAS) were grown on the flexible 10 micrometer thin stainless steel substrates, by dc co-sputtering from the elemental cathodes, followed by annealing with modified selenization. CuInAl alloyed precursor films were selenized both by noble gas assisted Se vapor transport in a tubular furnace and vacuum evaporation of Se in an evaporation chamber. CIAS thin films were optimized for better adhesion. X-ray diffraction, scanning electron microscopy, and UV-visible absorption spectroscopy were used to characterize the selenized films. The composition of CIAS films was varied by substituting In with Al in CuInSe2 (CIS) from 0 <= x <= 0.65 (x = Al/Al+In). Lattice parameters, average crystallite sizes, and compact density of the films, decreased when compared to CIS and (112) peak shifted to higher Bragg's angle, upon Al incorporation. The dislocation density and strain were found to increase with Al doping. Solar cells with SS/Mo/CIAS/CdS/iZnO: AZnO/Al configuration were fabricated and were tested for current-voltage characteristics for various `x' values, under Air Mass 1.5 Global one sun illumination. The best CIAS solar cell showed the efficiency of 6.8%, with x = 0.13, Eg = 1.17 eV, fill factor 45.04, and short circuit current density J(sc) 30 mA/cm(2).

Effect of solvents on the enzyme mediated degradation of copolymers

The biodegradation of polycaprolactone (PCL), polylactic acid (PLA), polyglycolide (PGA) and their copolymers, poly (lactide-co-glycolide) and poly (D, L-lactide-co-caprolactone) (PLCL) was investigated. The influence of different solvents on the degradation of these polymers at 37 degrees C in the presence of two different lipases namely Novozym 435 and the free lipase of porcine pancreas was investigated. The rate coefficients for the polymer degradation and enzyme deactivation were determined using continuous distribution kinetics. Among the homopolymers, the degradation of PGA was nearly an order of magnitude lower than that for PCL and PLA. The overall rate coefficients of the copolymers were higher than their respective homopolymers. Thus, PLCL degraded faster than either PCL or PLA. The degradation was highly dependent on the viscosity of the solvent used with the highest degradation observed in acetone. The degradation of the polymers in acetone was nearly twice that observed in dimethyl sulfoxide indicating that the degradation decreases with increase in the solvent viscosity. The degradation of the polymers in water-solvent mixtures indicated an optimal water content of 2.5 wt% of water.

CuIn1-xAlxSe2 Thin Films Grown by Co-Sputtering and Modified Selenization: Application in Flexible Solar Cells

Thin films of CuIn1-xAlxSe2 (CIAS) were grown on the flexible 10 micrometer thin stainless steel substrates, by dc co-sputtering from the elemental cathodes, followed by annealing with modified selenization. CuInAl alloyed precursor films were selenized both by noble gas assisted Se vapor transport in a tubular furnace and vacuum evaporation of Se in an evaporation chamber. CIAS thin films were optimized for better adhesion. X-ray diffraction, scanning electron microscopy, and UV-visible absorption spectroscopy were used to characterize the selenized films. The composition of CIAS films was varied by substituting In with Al in CuInSe2 (CIS) from 0 <= x <= 0.65 (x = Al/Al+In). Lattice parameters, average crystallite sizes, and compact density of the films, decreased when compared to CIS and (112) peak shifted to higher Bragg's angle, upon Al incorporation. The dislocation density and strain were found to increase with Al doping. Solar cells with SS/Mo/CIAS/CdS/iZnO: AZnO/Al configuration were fabricated and were tested for current-voltage characteristics for various `x' values, under Air Mass 1.5 Global one sun illumination. The best CIAS solar cell showed the efficiency of 6.8%, with x = 0.13, Eg = 1.17 eV, fill factor 45.04, and short circuit current density J(sc) 30 mA/cm(2).

Structural and Magnetic Properties of Amorphous Tb-Dy-Fe-Co Thin Films

This paper reports the effect of film thickness (50, 200, 400 and 800 nm) on the structural and magnetic properties of amorphous Tb-Dy-Fe-Co alloy thin films. All the films are found to exhibit perpendicular magnetic anisotropy (PMA) irrespective of the film thickness. The PMA is found to decrease with increase in film thickness due to the decrease in the magnetic texture and anisotropy energy. While the coercivity deduced from the out-of-plane magnetization curve increases with increasing film thickness, the in-plane coercivity exhibits weak thickness dependence. The irreversibility point in the thermo-magnetic curves obtained from field-cooled and zero-field-cooled measurements along the out-of-plane direction is found to shift towards higher temperature compared to the measurements in in-plane directions, indicating the presence of strong PMA.

Regulation of Acetate Metabolism and Acetyl Co-a Synthetase 1 (ACS1) Expression by Methanol Expression Regulator 1 (Mxr1p) in the Methylotrophic Yeast Pichia pastoris

Methanol expression regulator 1 (Mxr1p) is a zinc finger protein that regulates the expression of genes encoding enzymes of the methanol utilization pathway in the methylotrophic yeast Pichia pastoris by binding to Mxr1p response elements (MXREs) present in their promoters. Here we demonstrate that Mxr1p is a key regulator of acetate metabolism as well. Mxr1p is cytosolic in cells cultured in minimal medium containing a yeast nitrogen base, ammonium sulfate, and acetate (YNBA) but localizes to the nucleus of cells cultured in YNBA supplemented with glutamate or casamino acids as well as nutrient-rich medium containing yeast extract, peptone, and acetate (YPA). Deletion of Mxr1 retards the growth of P. pastoris cultured in YNBA supplemented with casamino acids as well as YPA. Mxr1p is a key regulator of ACS1 encoding acetyl-CoA synthetase in cells cultured in YPA. A truncated Mxr1p comprising 400 N-terminal amino acids activates ACS1 expression and enhances growth, indicating a crucial role for the N-terminal activation domain during acetate metabolism. The serine 215 residue, which is known to regulate the expression of Mxr1p-activated genes in a carbon source-dependent manner, has no role in the Mxr1p-mediated activation of ACS1 expression. The ACS1 promoter contains an Mxr1p response unit (MxRU) comprising two MXREs separated by a 30-bp spacer. Mutations that abrogate MxRU function in vivo abolish Mxr1p binding to MxRU in vitro. Mxr1p-dependent activation of ACS1 expression is most efficient in cells cultured in YPA. The fact that MXREs are conserved in genes outside of the methanol utilization pathway suggests that Mxr1p may be a key regulator of multiple metabolic pathways in P. pastoris.

Thermal co-reduction approach to vary size of silver nanoparticle: its microbial and cellular toxicology

In recent years, silver nanoparticles (AgNPs) have attracted considerable interest in the field of food, agriculture and pharmaceuticals mainly due to its antibacterial activity. AgNPs have also been reported to possess toxic behavior. The toxicological behavior of nanomaterials largely depends on its size and shape which ultimately depend on synthetic protocol. A systematic and detailed analysis for size variation of AgNP by thermal co-reduction approach and its efficacy toward microbial and cellular toxicological behavior is presented here. With the focus to explore the size-dependent toxicological variation, two different-sized NPs have been synthesized, i.e., 60 nm (Ag60) and 85 nm (Ag85). A detailed microbial toxicological evaluation has been performed by analyzing minimum inhibitory concentration (MIC), minimum bactericidal concentration (MBC), diameter of inhibition zone (DIZ), growth kinetics (GrK), and death kinetics (DeK). Comparative cytotoxicological behavior was analyzed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. It has been concluded by this study that the size of AgNPs can be varied, by varying the concentration of reactants and temperature called as ``thermal co-reduction'' approach, which is one of the suitable approaches to meet the same. Also, the smaller AgNP has shown more microbial and cellular toxicity.