Mitochondria-Targeting Oxidovanadium(IV) Complex as a Near-IR Light Photocytotoxic Agent

Oxidovanadium(IV) complexes VO(L-1)(phen)]Cl (1) and VO(L-2)(L-3)]Cl (2), in which HL1 is 2-{(benzimidazol-2-yl)methylimino]-methyl}phenol (sal-ambmz), HL2 is 2-({1-(anthracen-9-yl)methyl]-benzimidazol-2-yl}methylimino)-met hyl]phenol (sal-an-ambmz), phen is 1,10-phenanthroline and L-3 is dipyrido3,2-a:2,3-c]phenazine (dppz) conjugated to a Gly-Gly-OMe dipeptide moiety, were prepared, characterized, and their DNA binding, photoinduced DNA-cleavage, and photocytotoxic properties were studied. Fluorescence microscopy studies were performed by using complex 2 in HeLa and HaCaT cells. Complex 1, structurally characterized by X-ray crystallography, has a vanadyl group in VO2N4 core with the VO2+ moiety bonded to N,N-donor phen and a N,N,O-donor Schiff base. Complex 2, having an anthracenyl fluorophore, showed fluorescence emission bands at 397, 419, and 443nm. The complexes are redox-active exhibiting the V(IV)/V(III) redox couple near -0.85V versus SCE in DMF 0.1M tetrabutylammonium perchlorate (TBAP). Complex 2, having a dipeptide moiety, showed specific binding towards poly(dAdT)(2) sequence. The dppz-Gly-Gly-OMe complex showed significant DNA photocleavage activity in red light of 705nm through a hydroxyl radical ((OH)-O-.) pathway. Complex 2 showed photocytotoxicity in HaCaT and HeLa cells in visible light (400-700nm) and red light (620-700nm), however, the complex was less toxic in the dark. Fluorescence microscopy revealed the localization of complex 2 primarily in mitochondria. Apoptosis was found to occur inside mitochondria (intrinsic pathway) caused by ROS generation.

Contrast in luminescence characteristics (intense UV to bright visible light) of ZnO nanostructures with the variation in microstructure

We report the controlled variation of luminescence of ZnO nanostructures from intense ultraviolet to bright visible light. Deliberate addition of surfactants in the reaction medium not only leads to growth anisotropy of ZnO, but also alters the luminescence property. ZnO nanoclusters comprising of very fine particles with crystallite sizes approximate to 15-22nm were prepared in a non-aqueous medium, either from a single alcohol or from their mixtures. Introduction of the aqueous solution of the surfactant helps in altering the microstructure of ZnO nanostructure to nanorods, nanodumb-bells as well as the luminescence property. The as-prepared powder material is found to be well crystallized. Defects introduced by the surfactant in aqueous medium play an important role in substantial transition in the optical luminescence. Chromaticity coordinates were found to lie in the yellow region of color space. This gives an impression of white light emission from ZnO nanocrystals, when excited by a blue laser. Oxygen vacancy is described as the major defect responsible for visible light emission as quantified by X-ray photoelectron spectroscopy and Raman analysis.

LHC constraints on light neutralino dark matter in the MSSM

Light neutralino dark matter can be achieved in the Minimal Supersymmetric Standard Model if staus are rather light, with mass around 100 GeV. We perform a detailed analysis of the relevant supersymmetric parameter space, including also the possibility of light selectons and smuons, and of light higgsino- or wino-like charginos. In addition to the latest limits from direct and indirect detection of dark matter, ATLAS and CMS constraints on electroweak-inos and on sleptons are taken into account using a ``simplified models'' framework. Measurements of the properties of the Higgs boson at 125 GeV, which constrain amongst others the invisible decay of the Higgs boson into a pair of neutralinos, are also implemented in the analysis. We show that viable neutralino dark matter can be achieved for masses as low as 15 GeV. In this case, light charginos close to the LEP bound are required in addition to light right-chiral staus. Significant deviations are observed in the couplings of the 125 GeV Higgs boson. These constitute a promising way to probe the light neutralino dark matter scenario in the next run of the LHC. (C) 2013 Elsevier B.V. All rights reserved.

Between photocatalysis and photosynthesis: Synchrotron spectroscopy methods on molecules and materials for solar hydrogen generation

Energy research is to a large extent materials research, encompassing the physics and chemistry of materials, including their synthesis, processing toward components and design toward architectures, allowing for their functionality as energy devices, extending toward their operation parameters and environment, including also their degradation, limited life, ultimate failure and potential recycling. In all these stages, X-ray and electron spectroscopy are helpful methods for analysis, characterization and diagnostics for the engineer and for the researcher working in basic science.This paper gives a short overview of experiments with X-ray and electron spectroscopy for solar energy and water splitting materials and addresses also the issue of solar fuel, a relatively new topic in energy research. The featured systems are iron oxide and tungsten oxide as photoanodes, and hydrogenases as molecular systems. We present surface and subsurface studies with ambient pressure XPS and hard X-ray XPS, resonant photoemission, light induced effects in resonant photoemission experiments and a photo-electrochemical in situ/operando NEXAFS experiment in a liquid cell, and nuclear resonant vibrational spectroscopy (NRVS). (C) 2012 Elsevier B.V. All rights reserved.

Temperature dependent magnetic ordering and electrical transport behavior of nano zinc ferrite from 20 to 800 K

The nano ZnFe2O4 compound was prepared by eco-friendly hydrothermal method. The characterization of the sample for its structure, morphology and composition were done by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), dynamic light scattering, Fourier transform infrared spectroscopy, zeta surface profiler and UV-Visible spectroscopy studies. The PXRD measurement reveals that the compound shows spinel cubic phase belong Fd (3) over barm (227) space group. Morphology of the compound from SEM and surface profile shows nearly spherical agglomerated particles with well defined grains and grain boundaries. The material shows the semiconducting behavior with E-g of 2.3 eV at room temperature (RT). The variation in the magnetic ordering was observed for wide range of temperature. The compound behaves like a soft magnetic material with ferrimagnetic at various temperatures except at RT. Both magnetic and EPR studies supports the superparamagnetic behavior of the the sample. The DC conductivity, dielectric and AC conductivity behavior of the 1000 degrees C pellets sintered for 2 h shows good frequency dependent transport properties. The present study facilitate in selecting the suitable materials for the nanoelectronics and spintronic applications. (C) 2013 Elsevier B.V. All rights reserved.

A Novel Design Method for SOGI-PLL for Minimum Settling Time and Low Unit Vector Distortion

Phase-locked loops (PLLs) are necessary in grid connected systems to obtain information about the frequency, amplitude and phase of the grid voltage. In stationary reference frame control, the unit vectors of PLLs are used for reference generation. It is important that the PLL performance is not affected significantly when grid voltage undergoes amplitude and frequency variations. In this paper, a novel design for the popular single-phase PLL topology, namely the second-order generalized integrator (SOGI) based PLL is proposed which achieves minimum settling time during grid voltage amplitude and frequency variations. The proposed design achieves a settling time of less than 27.7 ms. This design also ensures that the unit vectors generated by this PLL have a steady state THD of less than 1% during frequency variations of the grid voltage. The design of the SOGI-PLL based on the theoretical analysis is validated by experimental results.

Carbohydrate-Appended Tumor Targeting Iron(III) Complexes Showing Photocytotoxicity in Red Light

Glucose-appended photocytotoxic iron(III) complexes of a tridentate Schiff base phenolate ligand Fe(bpyag) (L)] (NO3) (1-3), where bpyag is N,N-bis(2- pyridylmethyl)-2-aminoethyl-beta-D-glucopyranoside and H2L is 3-(2-hydroxyphenylimino)-1-phenylbutan-1-one (H(2)phap) in 1, 3-(2-hydroxyphenylimino)-9-anthrylbutan-1-one (H(2)anap) 2, and 3- (2-hydroxyphenylimino)-1-pyrenylbutan-1-one (H(2)pyap) in 3, were synthesized and characterized. The complex Fe(dpma)(anapn(NO3) (4), having bis-(2-pyridylmethyl)benzylamine (dpma), in which the glucose moiety of bpyag is substituted by a phenyl group, was used as a control, and the complex Fe(dpma)(anap)](PF6) (4a) was structurally characterized by X-ray crystallography. The structure shows a FeN4O2 core in a distorted octahedral geometry. The high-spin iron(III) complexes with magnetic moment value of similar to 5.9 mu(B) showed a low-energy phenolate-to-Fe(III) charge-transfer (CT) absorption band as a shoulder near 500 nm with a tail extending to 700 nm and an irreversible Fe(III)-Fe(II) redox couple near -0.6 V versus saturated calomel electrode. The complexes are avid binders to calf thymus DNA and showed photocleavage of supercoiled pUC19 DNA in red (647 nm) and green (532 nm) light. Complexes 2 and 3 displayed significant photocytotoxicity in red light, with an IC50 value of similar to 20 mu M in HeLa and HaCaT cells, and no significant toxicity in dark. The cell death is via an apoptotic pathway, by generation of reactive oxygen species. Preferential internalization of the carbohydrate-appended complexes 2 and 3 was evidenced in HeLa cells as compared to the control complex 4. A 5-fold increase in the cellular uptake was observed for the active complexes in HeLa cells. The photophysical properties of the complexes are rationalized from the density functional theory calculations.

Spontaneous assembly of iridium nanochain-like structures: surface enhanced Raman scattering activity using visible light

A facile, environmentally friendly approach to synthesize branched Ir nanochain-like structures under mild conditions, using polyfunctional capping molecules in an aqueous medium is reported; the nanostructures exhibit a surface plasmon resonance peak (SPR) in the visible region and serve as an active substrate for surface enhanced Raman scattering studies.

Facile hydrothermal synthesis of carbon nanoparticles and possible application as white light phosphors and catalysts for the reduction of nitrophenol

We report a simple hydrothermal synthesis of highly reproducible carbon nanoparticles in a size range between 2 and 7 nmfroma single precursor sucrose without either surface passivating agents or acids and bases. The carbon nanoparticles can be used as white light phosphors, especially for ultraviolet light emitting diodes and metal-free catalyst for the reduction of nitrophenol.

Combinatorial Exploration of the Structural Landscape of Acid-Pyridine Cocrystals

The structural landscape of acid-pyridine cocrystals is explored by adopting a combinatorial matrix method with 4-substituted benzoic acids and 4-substituted pyridines. The choice of the system restricts the primary synthon to the robust acid-pyridine entity. This methodology accordingly provides hints toward the formation of secondary synthons. The pK(a) rule is validated in the landscape by taking all components of the matrix together and exploring it as a whole. Along with the global features, the exploration of landscapes reveals some local features. Apart from the identification of secondary synthons, it also sheds light on the propensity of hydration in cocrystals, synthon competition, and certain topological similarities. The method described here combines two approaches, namely, database analysis and high throughput crystallography, to extract more information with minimal extra experimental effort.

High Throughput, Low Latency, Memory Optimized 64K Point FFT Architecture using Novel Radix-4 Butterfly Unit

In this paper we propose a fully parallel 64K point radix-4(4) FFT processor. The radix-4(4) parallel unrolled architecture uses a novel radix-4 butterfly unit which takes all four inputs in parallel and can selectively produce one out of the four outputs. The radix-4(4) block can take all 256 inputs in parallel and can use the select control signals to generate one out of the 256 outputs. The resultant 64K point FFT processor shows significant reduction in intermediate memory but with increased hardware complexity. Compared to the state-of-art implementation 5], our architecture shows reduced latency with comparable throughput and area. The 64K point FFT architecture was synthesized using a 130nm CMOS technology which resulted in a throughput of 1.4 GSPS and latency of 47.7 mu s with a maximum clock frequency of 350MHz. When compared to 5], the latency is reduced by 303 mu s with 50.8% reduction in area.

New luminescent 2-methoxy-6-(4-methoxy-phenyl)-4-p-tolyl-nicotinonitrile: Synthesis, crystal structure, DFT and photophysical studies

In the current communication, we report the synthesis, spectroscopic, crystal structure, DFT and photophysical studies of a new nicotinonitrile derivative, viz. 2-methoxy-6-(4-methoxy-phenyl)-4-p-tolyl-nicotinonitrile (2) as a potential blue light emitting material. The compound 2 was synthesized in good yield via a simple route. The acquired spectral and elemental analysis data were in consistent with the chemical structure of 2. The single crystal study further confirms its three dimensional structure, molecular shape, and nature of short contacts. Its DFT calculations reveal that compound 2 possesses a non-planar structure and its theoretical IR spectral data are found to be in accordance with experimental values. In addition, its UV visible and fluorescence spectral measurements prove that the compound exhibits good absorption and fluorescence properties. Also, it shows positive solvatochromic effect when the solvent polarity was varied from non-polar to polar. (c) 2014 Elsevier B.V. All rights reserved.

A little more gauge mediation and the light Higgs mass

We consider minimal models of gauge mediated supersymmetry breaking with an extra U(1) factor in addition to the Standard Model gauge group. A U(1) charged, Standard Model singlet is assumed to be present which allows for an additional NMSSM like coupling, lambda HuHdS. The U(1) is assumed to be flavour universal. Anomaly cancellation in the MSSM sector requires additional coloured degrees of freedom. The S field can get a large vacuum expectation value along with consistent electroweak symmetry breaking. It is shown that the lightest CP even Higgs boson can attain mass of the order of 125 GeV. (C) 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/3.0/).

Iron(III) benzhydroxamates of dipicolylamines for photocytotoxicity in red light and cellular imaging

Benzhydroxamate (BHA) iron(III) complexes Fe(BHA)(L)ClICI (I, 2)], where L is (phenyl)dipicolylamine (phdpa in I) and (pyrenyl)dipicolylamine (pydpa in 2), were prepared and their photocytotoxicity in visible (400-700 nm) and red (600-720 nm) light was studied. Complex 1 was structurally characterized by X-ray crystallography. The complexes have high-spin iron(III) centers. Complex 2, with a pyrenyl fluorophore, was used for cellular imaging, showing both mitochondrial and nuclear localization in the fluorescence microscopic study. The complex exhibited photocytotoxicity in red light in HeLa cancer cells, giving IC50 value of 24.4(+/- 0.4) pM, but remained essentially non-toxic in the dark. The involvement of reactive oxygen species and an apoptotic nature of cell death were observed from the cellular studies. (C) 2014 Elsevier Ltd. All rights reserved.