Impact of metal binding on the antitumor activity and cellular imaging of a metal chelator cationic imidazopyridine derivative

A new water soluble cationic imidazopyridine species, viz. (1E)-1-((pyridin-2-yl)methyleneamino)-3-(3(pyridin-2-yl) imidazo1,5-a]pyridin-2(3H)-yl)propan-2-ol (1), as a metal chelator is prepared as its PF6 salt and characterized. Compound 1 shows fluorescence at 438 nm on excitation at 342 nm in Tris-HCl buffer giving a fluorescence quantum yield (phi) of 0.105 and a life-time of 5.4 ns. Compound 1, as an avid DNA minor groove binder, shows pUC19 DNA cleavage activity in UV-A light of 365 nm forming singlet oxygen species in a type-II pathway. The photonuclease potential of 1 gets enhanced in the presence of Fe2+, Cu2+ or Zn2+. Compound 1 itself displays anticancer activity in HeLa, HepG2 and Jurkat cells with an enhancement on addition of the metal ions. Photodynamic effect of 1 at 365 nm also gets enhanced in the presence of Fe2+ and Zn2+. Fluorescence-based cell cycle analysis shows a significant dead cell population in the sub-G1 phase of the cell cycle suggesting apoptosis via ROS generation. A significant change in the nuclear morphology is observed from Hoechst 33258 and an acridine orange/ethidium bromide (AO/EB) dual nuclear staining suggesting apoptosis in cells when treated with 1 alone or in the presence of the metal ions. Apoptosis is found to be caspase-dependent. Fluorescence imaging to monitor the distribution of 1 in cells shows that 1 in the presence of metal ions accumulates predominantly in the cytoplasm. Enhanced uptake of 1 into the cells within 12 h is observed in the presence of Fe2+ and Zn2+.

Microstructure evolution during solidification of DRMMCs (discontinuously reinforced metal matrix composites): State of art

Distribution of particle reinforcements in cast composites is determined by the morphology of the solidification front. Interestingly, during solidification, the morphology of the interface is intrinsically affected by the presence of dispersed reinforcements. Thus the dispersoid distribution and length scale of matrix microstructure is a result of the interplay between these two. A proper combination of material and process parameters can be used to obtain composites with tailored microstructures. This requires the generation of a broad data base and optimization of the complete solidification process. The length scale of soldification microtructure has a large influence on the mechanical properties of the composites. This presentation addresses the concept of a particle distribution map which can help in predicting particle distribution under different solidification conditions Future research directions have also been indicated.

Microstructure and properties of squeeze cast Cu-carbon fibre metal matrix composite

There have been reported attempts of producing Cu based MMCs employing solid phase routes. In this work, copper was reinforced with short carbon fibres by pressure infiltration (squeeze casting) of molten metal through dry-separated carbon fibres. The resulting MMC's microstructure revealed uniform distribution of fibres with minimum amount of clustering. Hardness values are considerably higher than that for the unreinforced matrix. Addition of carbon fibres has brought in strain in the crystal lattice of the matrix, resulting in higher microhardness of MMCs and improved wear resistance. Tensile strength values of MMCs at elevated temperatures are considerably higher than that of the unreinforced matrix processed under identical conditions. (C) 1999 Kluwer Academic Publishers.

Microstructural evolution in liquid metal processed Al-alloy/SiCp composites

Al-Zn-Mg/SiCP composites processed by a liquid metal processing (stir casting) technique have been microstructurally characterised in the as-cast and extruded conditions. Uniform distribution of SiCP is observed with few defects, such as particle clusters, which are due to partial wetting and associated gas porosity. The constituent particles are associated with SiCP although their composition remains unaffected compared with the control alloy. Hot extrusion of the composite using a shear type die showed banding of particles in the extruded direction with 9 vol.% composite. Such defects however, are not predominant in 18% SiCP extruded composites. The presence Of Mg2Si is detected at the particle matrix interface as well as in the matrix.

Study of temperature distribution along an artificially polluted insulator string

Insulator becomes wet partially or completely, and the pollution layer on it becomes conductive, when collecting pollutants for an extended period during dew, light rain, mist, fog or snow melting. Heavy rain is a complicated factor that it may wash away the pollution layer without initiating other stages of breakdown or it may bridge the gaps between sheds to promote flashover. The insulator with a conducting pollution layer being energized, can cause a surface leakage current to flow (also temperature-rise). As the surface conductivity is non-uniform, the conducting pollution layer becomes broken by dry bands (at spots of high current density), interrupting the flow of leakage current. Voltage across insulator gets concentrated across dry bands, and causes high electric stress and breakdown (dry band arcing). If the resistance of the insulator surface is sufficiently low, the dry band arcs can be propagated to bridge the terminals causing flashover. The present paper concerns the evaluation of the temperature distribution along the surface of an energized artificially polluted insulator string.

An improved method for calculating activities from distribution equilibria

The method of Gibbs-Duhem integration suggested by Speiser et al. has been modified to derive activities from distribution equilibria. It is shown that, in general, the activities of components in melts with a common anion can be calculated, without using their standard Gibbs energies of formation, from eqUilibrium ratios and the knowledge of activities in the metal phase. Moreover, if systems are so chosen that the concentration of one element in the metal phase lies in the Henry's law region (less than 1 %), information on activities in the metal phase is not required. Conversely, activities of elements in an alloy can be readily calculated from equilibrium distribution ratios alone, if the salt phase in equilibrium contains very small amounts of one element. Application of the method is illustrated using distribution ratios from the literature on AgCI-CuCI, AgBr-CuBr, and CuDo.5 -PbD systems. The results indicate that covalent bonding and van der Waals repulsive interactions in certain types of fused salt melts can significantly affect the thermodynamic properties of mixing.

A k-epsilon model for turbulent weld pool convection in gas metal arc welding process

In this paper, we present a modified k - epsilon model capable of addressing turbulent weld-pool convection in a GMAW process, taking into account the morphology of the phase change interface during a Gas Metal Arc Welding (GMAW) process. A three-dimensional turbulence mathematical model has been developed to study the heat transfer and fluid flow within the weld pool by considering the combined effect of three driving forces, viz., buoyancy, Lorentz force and surface tension (Marangoni convection). Mass and energy transports by the droplets are considered through the thermal analysis of the electrode. The falling droplet's heat addition to the molten pool is considered to be a volumetric heat source distributed in an imaginary cylindrical cavity ("cavity model") within the weld pool. This nature of heat source distribution takes into account the momentum and the thermal, energy of the falling droplets. The numerically predicted weld pool dimensions both from turbulence and laminar models are then compared with the experimental post-weld results sectioned across the weld axis. The above comparison enables us to analyze the overall effects of turbulent convection on the nature of heat and fluid flow and hence on the weld pool shape/size during the arc welding processes.

Flux tube model signals for baryon correlations in heavy ion collisions

The flux tube model offers a pictorial description of what happens during the deconfinement phase transition in QCD. The three-point vertices of a flux tube network lead to formation of baryons upon hadronization. Therefore, correlations in the baryon number distribution at the last scattering surface are related to the preceding pattern of the flux tube vertices in the quark-gluon plasma, and provide a signature of the nearby deconfinement phase transition. I discuss the nature of the expected signal, and how to extract it from the experimental data for heavy ion collisions at RHIC and LHC.

Modeling of Ascending/Descending Velocity of Metal Droplet Emulsified in Pb-Salt System

Metal-slag emulsion is an important process to enhance the reaction rate between the two phases; thus, it improves the heat and mass transfer of the process significantly. Various experimental studies have been carried out, and some system specific relations have been proposed by various investigators. A unified, theoretical study is lacking to model this complex phenomenon. Therefore, two simple models based on fundamental laws for metal droplet velocity (both ascending and descending) and bubble velocity, as well as its position at any instant of time, have been proposed. Analytical solutions have been obtained for the developed equations. Analytical solutions have been verified for the droplet velocity, traveling time, and size distribution in slag phase by performing high-temperature experiments in a Pb-salt system and comparing the obtained data with theory. The proposed model has also been verified with published experimental data for various liquid systems with a wide range of physical properties. A good agreement has been found between the analytical solution and the experimental and published data in all cases.

Threshold voltage modeling under size quantization for ultra-thin silicon double-gate metal-oxide-semiconductor field-effect transistor

We report on the threshold voltage modeling of ultra-thin (1 nm-5 nm) silicon body double-gate (DG) MOSFETs using self-consistent Poisson-Schrodinger solver (SCHRED). We define the threshold voltage (V th) of symmetric DG MOSFETs as the gate voltage at which the center potential (Φ c) saturates to Φ c (s a t), and analyze the effects of oxide thickness (t ox) and substrate doping (N A) variations on V th. The validity of this definition is demonstrated by comparing the results with the charge transition (from weak to strong inversion) based model using SCHRED simulations. In addition, it is also shown that the proposed V t h definition, electrically corresponds to a condition where the inversion layer capacitance (C i n v) is equal to the oxide capacitance (C o x) across a wide-range of substrate doping densities. A capacitance based analytical model based on the criteria C i n v C o x is proposed to compute Φ c (s a t), while accounting for band-gap widening. This is validated through comparisons with the Poisson-Schrodinger solution. Further, we show that at the threshold voltage condition, the electron distribution (n(x)) along the depth (x) of the silicon film makes a transition from a strong single peak at the center of the silicon film to the onset of a symmetric double-peak away from the center of the silicon film. © 2012 American Institute of Physics.

Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Photoelectron spectromicroscopy study of metal-insulator transition in NaxWO3

We have investigated the validity of percolation model, which is quite often invoked to explain the metal-insulator transition in sodium tungsten bronzes, NaxWO(3) by photoelectron spectromicroscopy. The spatially resolved direct spectromicroscopic probing on both the insulating and metallic phases of high quality single crystals of NaxWO(3) reveals the absence of any microscopic inhomogeneities embedded in the system within the experimental limit. Neither any metallic domains in the insulating host nor any insulating domains in the metallic host have been found to support the validity of percolation model to explain the metal-insulator transition in NaxWO(3). The possible origin of insulating phase in NaxWO(3) is due to the Anderson localization of all the states near E-F. The localization occurs because of the strong disorder arising from random distribution of Na+ ions in the WO3 lattice.

Structural, iono and thermoluminescence properties of heavy ion (100 MeV Si7+) bombarded Zn2SiO4:Sm3+ nanophosphor

Structural, iono (IL) and thermoluminescence (TL) studies of Zn2SiO4:Sm3+ (1-5 mol%) nanophosphor bombarded with swift heavy ions in the fluence range 3.91 x 10(12)-21.48 x 10(12) cm(-2) have been carried out. The average crystallite sizes for pristine and ion irradiated for 3.91 x 10(12) ions cm(-2) and 21.48 x 10(12) ions cm(-2) were found to be 34, 26 and 20 nm. With increase of ion fluence, the intensity of XRD peaks decreases and FWHM increases. The peak broadening indicates the stress induced point/clusters defects produced due to heavy ion irradiation. IL studies were carried out for different Sm3+ concentrations in Zn2SiO4 by irradiating with ion fluence of 15.62 x 10(12) ions cm(-2). The characteristic emission peaks at similar to 562, 599, 646 and 701 nm were recorded by exciting Si7+ ions in the fluence range 3.91 x 10(12)-21.48 x 10(12) ions cm(-2). These peaks were attributed to (4)G(5/2)-> H-6(5/2) (562 nm), (4)G(5/2)-> H-6(7/2) (599 nm), (4)G(5/2)-> H-6(9/2) (646 nm), and (4)G(5/2)-> H-6(5/2) (701 nm) transitions of Sm3+. The highest emission was recorded at 3 mol% of Sm3+ doped Zn2SiO4. TL studies were carried out for 3 mol% Sm3+ concentration in the fluence range 3.91 x 10(12)-21.48 x 10(12) ions cm(-2). Two U glow peaks at 152 and 223 degrees C were recorded. The kinetic parameters (E, b, and s), were estimated using Chen's peak shape method. Simple glow curve structure (223 degrees C), highly resistive, increase in TL. intensity up to 19.53 x 10(12) ions cm(-2), simple trap distribution makes Zn2SiO4:Sm3+ (3 mol%) phosphor highly useful in radiation dosimetry.

Role of interface curvature on stress distribution under indentation for ZrN/Zr multilayer coating

Contact damage in curved interface nano-layeredmetal/nitride (150 (ZrN)/10 (Zr) nm) multilayer is investigated in order to understand the role of interface morphology on contact damage under indentation. A finite element method (FEM) model was formulated with different wavelengths of 1000 nm, 500 nm, 250 nm and common height of 50 nm, which gives insight on the effect of different curvature on stress field generated under indentation. Elastic-plastic properties were assigned to the metal layer and substrate while the nitride layer was assigned perfectly elastic properties. Curved interface multilayers show delamination along the metal/nitride interface and vertical cracks emanating from the ends of the delamination. FEM revealed the presence of tensile stress normal to the interface even under the contact, along with tensile radial stresses, both present at the valley part of the curve, which leads to vertical cracks associated with interfacial delamination. Stress enhancement was seen to be relatively insensitive to curvature. (C) 2014 Elsevier B.V. All rights reserved.

Effect of metal oxidation state on FRET: a Cu(I) silent but selectively Cu(II) responsive fluorescent reporter and its bioimaging applications

Copper(II) and copper(I) complexes of a newly designed and crystallographically characterized Schiff base (HL) derived from rhodamine hydrazide and cinnamaldehyde were isolated in pure form formulated as Cu(L)(NO3)] (L-Cu) (1) and Cu(HL)(CH3CN)(H2O)]ClO4 (HL-Cu) (2), and characterized by physicochemical and spectroscopic tools. Interestingly, complex 1 but not 2 offers red fluorescence in solution state, and eventually HL behaves as a Cu(II) ions selective FRET based fluorosensor in HEPES buffer (1 mM, acetonitrile-water: 1/5, v/v) at 25 degrees C at biological pH with almost no interference of other competitive ions. The dependency of the FRET process on the +2 oxidation state of copper has been nicely supported by exhaustive experimental studies comprising electronic, fluorimetric, NMR titration, and theoretical calculations. The sensing ability of HL has been evaluated by the LOD value towards Cu(II) ions (83.7 nM) and short responsive time (5-10 s). Even the discrimination of copper(I) and copper(II) has also been done using only UV-Vis spectroscopic study. The efficacy of this bio-friendly probe has been determined by employing HL to detect the intercellular distribution of Cu(II) ions in HeLa cells by developing image under fluorescence microscope.