Mitochondria targeting Photocytotoxic Oxidovanadium( IV) Complexes of Curcumin and ( Acridinyl) dipyridophenazine in Visible Light

Oxidovanadium(IV) complexes, VO(acac)(L)Cl] (1), VO(cur)(L)Cl] (2), and VO(scur)(L)Cl] (3) {acac = acetylacetonate, cur = curcumin monoanion, scur = diglucosylcurcumin monoanion, L = 11-(9-acridinyl)dipyrido3, 2-a:2',3'-c]phenazine (acdppz)}, were prepared and characterized. The complexes are non-electrolytic in DMF and 1:1 electrolytic in aqueous DMF. The one-electron paramagnetic complexes showed a d-d band near 725 nm in aqueous DMF and green emission near 520 nm in aqueous DMSO. The complexes exhibited an irreversible V-IV/V-III redox response near -0.85 V versus SCE in aqueous DMF. The complexes showed good binding strengths to calf thymus DNA (K-b: 3.1x10(5)-9.6x10(5) M-1) and efficient pUC19 DNA photocleavage activity in red light of 705 and 785 nm by singlet oxygen (O-1(2)) pathway. Complexes 1 and 2 exhibited significant photocytotoxicity (IC50: 0.1-1.0 M) in visible light (400-700 nm) with low dark toxicity (IC50: >20 M) in HeLa and HaCaT cells. Complex 3 was cytotoxic in both light and dark. DNA ladder formation experiments indicated cell death via apoptotic pathway. Confocal microscopy done with 1 and 2 revealed primarily cytosolic localization of the complexes with significant presence of the complex in the mitochondria as evidenced from the imaging data using mitotracker red.

Three Dimensional Fluorescence Imaging Using Multiple Light-Sheet Microscopy

We developed a multiple light-sheet microscopy (MLSM) system capable of 3D fluorescence imaging. Employing spatial filter in the excitation arm of a SPIM system, we successfully generated multiple light-sheets. This improves upon the existing SPIM system and is capable of 3D volume imaging by simultaneously illuminating multiple planes in the sample. Theta detection geometry is employed for data acquisition from multiple specimen layers. This detection scheme inherits many advantages including, background reduction, cross-talk free fluorescence detection and high-resolution at long working distance. Using this technique, we generated 5 equi-intense light-sheets of thickness approximately 7: 5 mm with an inter-sheet separation of 15 mm. Moreover, the light-sheets generated by MLSM is found to be 2 times thinner than the state-of-art SPIM system. Imaging of fluorescently coated yeast cells of size 4 +/- 1 mm (encaged in Agarose gel-matrix) is achieved. Proposed imaging technique may accelerate the field of fluorescence microscopy, cell biology and biophotonics.

Model for triplet state engineering in organic light emitting diodes

Engineering the position of the lowest triplet state (T-1) relative to the first excited singlet state (S-1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. We have carried out model exact calculations of substituted polyene chains to understand the factors that affect the energy gap between S-1 and T-1. The factors studied are backbone dimerisation, different donor-acceptor substitutions, and twisted geometry. The largest system studied is an 18 carbon polyene which spans a Hilbert space of about 991 x 10(6). We show that for reverse intersystem crossing process, the best system involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. (C) 2014 AIP Publishing LLC.

Metal-metal charge transfer and interfacial charge transfer mechanism for the visible light photocatalytic activity of cerium and nitrogen co-doped TiO2

Nanosized cerium and nitrogen co-doped TiO2 (Ce-TiO2-xNx) was synthesized by sol gel method and characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), FESEM, Fourier transform infrared, N-2 adsorption and desorption methods, photoluminescence and ultraviolet-visible (UV-vis) DRS techniques. PXRD analysis shows the dopant decreases the crystallite sizes and slows the crystallization of the titania matrix. XPS confirm the existence of cerium ion in +3 or +4 state, and nitrogen in -3 state in Ce-TiO2-xNx. The modified surface of TiO2 provides highly active sites for the dyes at the periphery of the Ce-O-Ti interface and also inhibits Ce particles from sintering. UV-visible DRS studies show that the metal-metal charge transfer (MMCT) of Ti/Ce assembly (Ti4+/Ce3+ -> Ti3+/Ce4+) is responsible for the visible light photocatalytic activity. Photoluminescence was used to determine the effect of cerium ion on the electron-hole pair separation between the two interfaces Ce-TiO2-xNx and Ce2O3. This separation increases with the increase of cerium and nitrogen ion concentrations of doped samples. The degradation kinetics of methylene blue and methyl violet dyes in the presence of sol gel TiO2, Ce-TiO2-xNx and commercial Degussa P25 was determined. The higher visible light activity of Ce-TiO2-xNx was due to the participation of MMCT and interfacial charge transfer mechanism.

Mitigating UVA light induced reactivity of 6-thioguanine through formation of a Ru(II) half-sandwich complex

The organometallic complex of (eta(6)-cymene)Ru(II)Br with 6-thioguanine (6-TG) shows better photostability than the biologically active 6-thioguanine which is used as an immunosuppressant and as an anticancer agent.

Synthesis of self-light-scattering wrinkle structured ZnO photoanode by sol-gel method for dye-sensitized solar cells

A special morphological zinc oxide (ZnO) photoanode for dye-sensitized solar cell was fabricated by simple sol-gel drop casting technique. This film shows a wrinkled structure resembling the roots of banyan tree, which acts as an effective self scattering layer for harvesting more visible light and offers an easy transport path for photo-injected electrons. These ZnO electrode of low thickness (similar to 5 mu m) gained an enhanced short-circuit current density of 6.15 mA/cm(2), open-circuit voltage of 0.67 V, fill factor of 0.47 and overall conversion efficiency of 1.97 % under 1 sun illumination. This shows a high conversion efficiency and a superior performance than that of ZnO nanoparticle-based photoanode (eta similar to 1.13 %) of high thickness (similar to 8 mu m).

Fermi-Edge Transmission Resonance in Graphene Driven by a Single Coulomb Impurity

The interaction between the Fermi sea of conduction electrons and a nonadiabatic attractive impurity potential can lead to a power-law divergence in the tunneling probability of charge through the impurity. The resulting effect, known as the Fermi edge singularity (FES), constitutes one of the most fundamental many-body phenomena in quantum solid state physics. Here we report the first observation of FES for Dirac fermions in graphene driven by isolated Coulomb impurities in the conduction channel. In high-mobility graphene devices on hexagonal boron nitride substrates, the FES manifests in abrupt changes in conductance with a large magnitude approximate to e(2)/h at resonance, indicating total many-body screening of a local Coulomb impurity with fluctuating charge occupancy. Furthermore, we exploit the extreme sensitivity of graphene to individual Coulomb impurities and demonstrate a new defect-spectroscopy tool to investigate strongly correlated phases in graphene in the quantum Hall regime.

Ferrocenyl-L-amino acid copper(II) complexes showing remarkable photo-induced anticancer activity in visible light

Ferrocene-conjugated copper(II) complexes Cu(Fc-aa)(aip)](ClO4) (1-3) and (Cu(Fc-aa)(pyip)](ClO4) (4-6) of L-amino acid reduced Schiff bases (Fc-aa), 2-(9-anthryl)-1H-imidazo4,5-f]1,10]phenanthroline (aip) and 2-(1-pyrenyl)-1H-imidazo4,5-f] 1,10]phenanthroline (pyip), where Fc-aa is ferrocenylmethyl-L-tyrosine (Fc-Tyr in 1, 4), ferrocenylmethyl-L-tryptophan (Fc-Trp in 2, 5) and ferrocenylmethyl-L-methionine (Fc-Met in 3, 6), were prepared and characterized, and their photocytotoxicity was studied (Fc = ferrocenyl moiety). Phenyl analogues, viz. (Cu(Ph-Met)(aip)](ClO4) (7) and (Cu(Ph-Met)(pyip)](ClO4) (8), were prepared and used as control compounds. The bis-imidazophenanthroline copper(II) complexes, viz. (Cu(aip)(2)(NO3)](NO3) (9) and Cu(pyip)(2)(NO3)](NO3) (10), were also prepared and used as controls. Complexes 1-6 having a redox inactive cooper(II) center showed the Fc(+)-Fc redox couple at similar to 0.5 V vs. SCE in DMF-0.1 mol (Bu4N)-N-n](ClO4). The copper(II)-based d-d band was observed near 600 nm in DMF-Tris-HCl buffer (1 :1 v/v). The ferrocenyl complexes showed low dark toxicity, but remarkably high photocytotoxicity in human cervical HeLa and human breast adenocarcinoma MCF-7 cancer cells giving an excellent photo-dynamic effect while their phenyl analogues were inactive. The photo-exposure caused significant morphological changes in the cancer cells when compared to the non-irradiated ones. The photophysical processes were rationalized from the theoretical studies. Fluorescence microscopic images showed 3 and 6 localizing predominantly in the endoplasmic reticulum (ER) of the cancer cells, thus minimizing any undesirable effects involving nuclear DNA.

Microstructure Development, Nanomechanical, and Dynamic Compression Properties of Spark Plasma Sintered TiB2-Ti-Based Homogeneous and Bi-layered Composites

The growing threats due to increased use of small-caliber armor piercing projectiles demand the development of new light-weight body armor materials. In this context, TiB2 appears to be a promising ceramic material. However, poor sinterability and low fracture toughness remain two major issues for TiB2. In order to address these issues together, Ti as a sinter-aid is used to develop TiB2-(x wt pct Ti), (x = 10, 20) homogeneous composites and a bi-layered composite (BLC) with each layer having Ti content of 10 and 20 wt pct. The present study uniquely demonstrates the efficacy of two-stage spark plasma sintering route to develop dense TiB2-Ti composites with an excellent combination of nanoscale hardness (similar to 36 GPa) and indentation fracture toughness (similar to 12 MPa m(1/2)). In case of BLC, these properties are not compromised w.r.t. homogeneous composites, suggesting the retention of baseline material properties even in the bi-layer design due to optimal relief of residual stresses. The better indentation toughness of TiB2-(10 wt pct Ti) and TiB2-(20 wt pct Ti) composites can be attributed to the observed crack deflection/arrest, indicating better damage tolerance. Transmission electron microscope investigation reveals the presence of dense dislocation networks and deformation twins in alpha-Ti at the grain boundaries and triple pockets, surrounded by TiB2 grains. The dynamic strength of around 4 GPa has been measured using Split Hopkinson Pressure Bar tests in a reproducible manner at strain rates of the order of 600 s(-1). The damage progression under high strain rate has been investigated by acquiring real time images for the entire test duration using ultra-high speed imaging. An attempt has been made to establish microstructure-property correlation and a simple analysis based on Mohr-Coulomb theory is used to rationalize the measured strength properties.

Organic white-light emitting materials

Full-color emissive organic materials have attracted significant attention in recent years as key components in display and lighting devices based on OLEDs. An ideal white-light emitter demands simultaneous emission of red, green and blue with nearly similar distribution of intensities covering the entire region of visible spectra. However, the design of such white-light emitters is not straightforward. Mixing several emitters is seldom successful owing to the negative effects of intermolecular interactions and energy transfer processes. Nonetheless, these fundamental questions have been addressed in recent times by several research groups of vastly different expertise leading to a considerable progress in the field of organic white-light emitters. The designs cover a large area of the chemistry ranging from frustrated energy transfer to simple protonation or from designed self-assembly to simple mixing of materials. In this review, the concepts and rational approaches underlying the design of white-light emissive organic materials are described. (C) 2014 Elsevier Ltd. All rights reserved.

Frequency-domain stimulated and spontaneous light emission signals at molecular junctions

Using a diagrammatic superoperator formalism we calculate optical signals at molecular junctions where a single molecule is coupled to two metal leads which are held at different chemical potentials. The molecule starts in a nonequilibrium steady state whereby it continuously exchanges electrons with the leads with a constant electron flux. Expressions for frequency domain optical signals measured in response to continuous laser fields are derived by expanding the molecular correlation functions in terms of its many-body states. The nonunitary evolution of molecular states is described by the quantum master equation. (C) 2014 AIP Publishing LLC.

Organic solar cell by using vertically aligned nanostructured ZnO nanorods

A low temperature solution approach was employed to grow zinc oxide (ZnO) nanorods with various aspect ratios. Various sizes (diameter-10-25nm) of the nanorods were grown by changing the concentrations of the growth solution. The length (50nm-500nm) of nanorods was controlled using growth times. These one-dimensional (1D) nanostructures with direct paths for a charge transport with high surface area for light harvesting, are promising candidates for organic photovoltaics (OPV). The structural and optical properties of the prepared ZnO nanorods have been studied using SEM, XRD and UV-Vis absorption spectroscopy. Using as-grown ZnO inverted OPV was fabricated. ZnO nanorods were subjected to various doses of UV-ozone irradiation which led to improvement in transmission and hence enhanced device performance.

Generation of multiple sheets of light using spatial-filtering technique

We develop an optical system for generating multiple light sheets. This is enabled by employing a special class of spatial filters in a cylindrical lens geometry. The proposed binary filter placed at the back aperture of the cylindrical lens results in the generation of a periodic transverse pattern extending along the z axis (i.e., multiple light sheets). Experimental results confirm the generation of multiple light sheets of thickness 6.6 mu m with an intersheet spacing of 13.4 mu m. The proposed imaging technique may facilitate three-dimensional imaging in nano-optics, fluorescence microscopy, and nanobiology. (C) 2014 Optical Society of America

Application of lateral photovoltage towards contactless light beam induced current measurements and its dependence on the finite beam size

The nature of the signal due to light beam induced current (LBIC) at the remote contacts is verified as a lateral photovoltage for non-uniformly illuminated planar p-n junction devices; simulation and experimental results are presented. The limitations imposed by the ohmic contacts are successfully overcome by the introduction of capacitively coupled remote contacts, which yield similar results without any significant loss in the estimated material and device parameters. It is observed that the LBIC measurements introduce artefacts such as shift in peak position with increasing laser power. Simulation of LBIC signal as a function of characteristic length L-c of photo-generated carriers and for different beam diameters has resulted in the observed peak shifts, thus attributed to the finite size of the beam. Further, the idea of capacitively coupled contacts has been extended to contactless measurements using pressure contacts with an oxidized aluminium electrodes. This technique avoids the contagious sample processing steps, which may introduce unintentional defects and contaminants into the material and devices under observation. Thus, we present here, the remote contact LBIC as a practically non-destructive tool in the evaluation of device parameters and welcome its use during fabrication steps. (C) 2014 AIP Publishing LLC.