Remarkable anticancer activity of ferrocenylterpyridine platinum(II) complexes in visible light with low dark toxicity

Ferrocenyl platinum(II) complexes (1-3), viz. Pt(Fc-tpy)Cl]Cl (1), Pt(Fc-tpy)(NPC)]Cl (2, HNPC = N-propargyl carbazole) and Pt(Fc-bpa)Cl]Cl (3), were prepared, characterized and their anti-proliferative properties in visible light in human keratinocyte (HaCaT) cell lines have been studied. Pt(Ph-tpy)Cl]Cl (4) was prepared and used as a control. Complexes 1 and 3, structurally characterized by X-ray crystallography, show distorted square-planar geometry for the platinum(II) centre. Complexes 1 and 2 having the Fc-tpy ligand showed an intense absorption band at similar to 590 nm. The ferrocenyl complexes are redox active showing the Fc(+)-Fc couple near 0.6 V vs. SCE in DMF-0.1 M tetrabutylammonium perchlorate (TBAP). Complexes 1-3 showed external binding to calf thymus DNA. Both 1 and 2 showed remarkable photocytotoxicity in HaCaT cell lines giving respective IC50 values of 9.8 and 12.0 mu M in visible light of 400-700 nm with low dark toxicity (IC50 > 60 mu M). Fluorescent imaging studies showed the spread of the complexes throughout the cell localising both in cytoplasm and the nucleus. The ferrocenyl complexes triggered apoptosis on light exposure as evidenced from the Annexin V-FITC/PI and DNA ladder formation assays. Spectral studies revealed the formation of ferrocenium ions upon photo-irradiation generating cytotoxic hydroxyl radicals via a Fenton type mechanism. The results are rationalized from a TDDFT study that shows involvement of ferrocene and the platinum coordinated terpyridine moiety as respective HOMO and LUMO.

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.

Regenerating codes: A reformulated storage-bandwidth trade-off and a new construction

In this paper, the storage-repair-bandwidth (SRB) trade-off curve of regenerating codes is reformulated to yield a tradeoff between two global parameters of practical relevance, namely information rate and repair rate. The new information-repair-rate (IRR) tradeoff provides a different and insightful perspective on regenerating codes. For example, it provides a new motivation for seeking to investigate constructions corresponding to the interior of the SRB tradeoff. Interestingly, each point on the SRB tradeoff corresponds to a curve in the IRR tradeoff setup. We characterize completely, functional repair under the IRR framework, while for exact repair, an achievable region is presented. In the second part of this paper, a rate-half regenerating code for the minimum storage regenerating point is constructed that draws upon the theory of invariant subspaces. While the parameters of this rate-half code are the same as those of the MISER code, the construction itself is quite different.

Surface freshwater storage and variability in the Amazon basin from multi-satellite observations, 1993-2007

The amount of water stored and moving through the surface water bodies of large river basins (river, floodplains, wetlands) plays a major role in the global water and biochemical cycles and is a critical parameter for water resources management. However, the spatiotemporal variations of these freshwater reservoirs are still widely unknown at the global scale. Here, we propose a hypsographic curve approach to estimate surface freshwater storage variations over the Amazon basin combining surface water extent from a multi-satellite-technique with topographic data from the Global Digital Elevation Model (GDEM) from Advance Spaceborne Thermal Emission and Reflection Radiometer (ASTER). Monthly surface water storage variations for 1993-2007 are presented, showing a strong seasonal and interannual variability, and are evaluated against in situ river discharge and precipitation. The basin-scale mean annual amplitude of similar to 1200 km(3) is in the range of previous estimates and contributes to about half of the Gravity Recovery And Climate Experiment (GRACE) total water storage variations. For the first time, we map the surface water volume anomaly during the extreme droughts of 1997 (October-November) and 2005 (September-October) and found that during these dry events the water stored in the river and floodplains of the Amazon basin was, respectively, similar to 230 (similar to 40%) and 210 (similar to 50%) km(3) below the 1993-2007 average. This new 15 year data set of surface water volume represents an unprecedented source of information for future hydrological or climate modeling of the Amazon. It is also a first step toward the development of such database at the global scale.

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.

Influence of exhaust gas heating and L/D ratios on the discharge efficiencies for an activated carbon natural gas storage system

A transient 2D axi-symmetric and lumped parameter (LP) model with constant outflow conditions have been developed to study the discharge capacity of an activated carbon bed. The predicted discharge times and variations in bed pressure and temperature are in good agreement with experimental results obtained from a 1.82 l adsorbed natural gas (ANG) storage system. Under ambient air conditions, a maximum temperature drop of 29.5 K and 45.5 K are predicted at the bed center for discharge rates of 1.0 l min(-1) and 5.0 l min(-1) respectively. The corresponding discharge efficiencies are 77% and 71.5% respectively with discharge efficiencies improving with decreasing outflow rates. Increasing the LID ratio from 1.9 to 7.8 had only a marginal increase in the discharge efficiency. Forced convection (exhaust gas) heating had a significant effect on the discharge efficiency, leading to efficiencies as high as 92.8% at a discharge of 1.0 l min(-1) and 88.7% at 5 l min(-1). Our study shows that the LP model can be reliably used to obtain discharge times due to the uniform pressure distributions in the bed. Temperature predictions with the LP model were more accurate at ambient conditions and higher discharge rates, due to greater uniformity in bed temperatures. For the low thermal conductivity carbon porous beds, our study shows that exhaust gas heating can be used as an effective and convenient strategy to improve the discharge characteristics and performance of an ANG system. (C) 2013 Elsevier Ltd. All rights reserved.

Green ionothermal synthesis of hierarchical nanostructures of SnS2 and their Li-ion storage properties

Flower-like hierarchical architectures of layered SnS2 have been synthesized ionothermally for the first time, using a water soluble EMIM]BF4 ionic liquid (IL) as the solvent medium. At lower reaction temperatures, the hierarchical structures are formed of few-layered polycrystalline 2D nanosheet-petals composed of randomly oriented nanoparticles of SnS2. The supramolecular networks of the IL serve as templates on which the nanoparticles of SnS2 are glued together by combined effects of hydrogen bonding, electrostatic, hydrophobic and imidazolium stacking interactions of the IL, giving rise to polycrystalline 2D nanosheet-petals. At higher reaction temperatures, single crystalline plate-like nanosheets with well-defined crystallographic facets are obtained due to rapid inter-particle diffusion across the IL. Efficient surface charge screening by the IL favors the aggregation of individual nanosheets to form hierarchical flower-like architectures of SnS2. The mechanistic aspects of the ionothermal bottom-up hierarchical assembly of SnS2 nanosheets are discussed in detail. Li-ion storage properties of the pristine SnS2 samples are examined and the electrochemical performance of the sample synthesized at higher temperatures is found to be comparable to that reported for pristine SnS2 samples in the literature.

Endoplasmic reticulum targeted chemotherapeutics: the remarkable photo-cytotoxicity of an oxovanadium(IV) vitamin-B6 complex in visible light

An oxovanadium(IV) vitamin-B6 Schiff base complex, viz. VO(HL)( acdppz)] Cl, having (acridinyl) dipyridophenazine (acdppz) shows specific localization to endoplasmic reticulum (ER) and remarkable apoptotic photocytotoxicity in visible light (400-700 nm) in HeLa and MCF-7 cancer cells (IC50 < 0.6 mu M) while being non-toxic in the dark and to MCF-10A normal cells (IC50 > 40 mu M).

Mitochondria-Targeted Photoinduced Anticancer Activity of Oxidovanadium( IV) Complexes of Curcumin in Visible Light

Oxidovanadium(IV) complexes VO(py-aebmz)(B)]Cl (1, 2) and VO(napth-py-aebmz)(cur)]Cl 3; py-aebmz = 2-(1H-benzimidazol-2-yl)-N-(pyridin-2-ylmethylene)ethanamine, HB = acetylacetone (Hacac, 1) and curcumin (Hcur, 2), napth-py-aebmz = naphthalimide conjugated to py-aebmz ] have been prepared, characterized and their photoinduced DNA cleavage activities and photocytotoxicities studied. Complexes 1-3 each exhibited an irreversible cyclic voltammetric response of the V-IV/V-III redox couple at around -0.85 V versus SCE in dmf/0.1 M tbap. The complexes showed DNA photocleavage activity in visible light of 454, 530 and 647 nm through hydroxyl radical and singlet oxygen pathways. Fluorescence microscopy data suggest mitochondrial localization of complex 3 bearing a naphthalimide with a two-fold increase in photocytotoxicity in HaCaT cells with an IC50 value of 6.3 M and a three-fold increase in MCF-7 cells with an IC50 of 5.4 M compared with complex 2. Both 2 and 3 were non-toxic in the dark.

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.

Enhancing hydrogen storage capacity of pyridine-based metal organic framework

Using first principles calculations, we show that the storage capacity as well as desorption temperature of MOFs can be significantly enhanced by decorating pyridine (a common linker in MOFs) by metal atoms. The storage capacity of metal-pyridine complexes are found to be dependent on the type of decorating metal atom. Among the 3d transition metal atoms, Sc turns out to be the most efficient storing unto four H-2 molecules. Most importantly, Sc does not suffer dimerisation on the surface of pyridine, keeping the storage capacity of every metal atom intact. Based on these findings, we propose a metal-decorated pyridine-based MOFs, which has potential to meet the required H-2 storage capacity for vehicular usage. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

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.

Evaluating methane storage targets: from powder samples to onboard storage systems

The development of a viable adsorbed natural gas onboard fuel system involves synthesizing materials that meet specific storage target requirements. We assess the impact on natural gas storage due to intermediate processes involved in taking a laboratory powder sample to an onboard packed or adsorbent bed module. We illustrate that reporting the V/V (volume of gas/volume of container) capacities based on powder adsorption data without accounting for losses due to pelletization and bed porosity, grossly overestimates the working storage capacity for a given material. Using data typically found for adsorbent materials that are carbon and MOF based materials, we show that in order to meet the Department of Energy targets of 180 V/V (equivalent STP) loading at 3.5 MPa and 298 K at the onboard packed bed level, the volumetric capacity of the pelletized sample should be at least 245 V/V and the corresponding gravimetric loading varies from 0.175 to 0.38 kg/kg for pellet densities ranging from 461.5 to 1,000 . With recent revision of the DOE target to 263 V/V at the onboard packed bed level, the volumetric loadings for the pelletized sample should be about 373 V/V.

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.