Synthesis, structural studies and catalytic activity of dioxidomolybdenum(VI) complexes with aroylhydrazones of naphthol-derivative

Reaction of the salicylhydrazone of 2-hydroxy-1-naphthaldehyde (H2L1), anthranylhydrazone of 2hydroxy-l-naphthaldehyde (H2L2), benzoylhydrazone of 2-hydroxy-1-acetonaphthone (H2L3) and anthranylhydrazone of 2-hydroxy-1-acetonaphthone (H2L4; general abbreviation H2L) with MoO2(acac)21 afforded a series of 5- and 6- coordinate Mo(VI) complexes of the type MoO2L1-2(ROH)] where R = C2H5 (1) and CH3 (2)], and MoO2L3-4] (3 and 4). The substrate binding capacity of 1 has been demonstrated by the formation of one mononuclear mixed-ligand dioxidomolybdenum complex MoO2L1(Q)] (where Q= gamma-picoline (la)). Molecular structure of all the complexes (I, la, 2,3 and 4) is determined by X-ray crystallography, demonstrating the dibasic tridentate behavior of ligands. All the complexes show two irreversible reductive responses within the potential window -0.73 to -1.08 V, due to Movl/Mov and Mov/Mow processes. Catalytic potential of these complexes was tested for the oxidation of benzoin using 30% aqueous H2O2 as an oxidant in methanol. At least four reaction products, benzoic acid, benzaldehydedimethylacetal, methyl benzoate and benzil were obtained with the 95-99% conversion under optimized reaction conditions. Oxidative bromination of salicylaldehyde, a functional mimic of haloperoxidases, in aqueous 1-1202/KEr in the presence of HC1O4 at room temperature has also been carried out successfully. (C) 2013 Elsevier Ltd. All rights reserved.

Characterization, charge transport and magnetic properties of multi-walled carbon nanotube-polyvinyl chloride nanocomposites

Multi-walled carbon nanotube (MWCNT)-polyvinyl chloride (PVC) nanocomposites, with MWCNT loading up to 44.4 weight percent (wt%), were prepared by the solvent mixing and casting method. Electron microscopy indicates high degree of dispersion of MWCNT in PVC matrix, achieved by ultrasonication without using any surfactants. Thermogravimetric analysis showed a significant monotonic enhancement in the thermal stability of nanocomposites by increasing the wt% of MWCNT. Electrical conductivity of nanocomposites followed the classical percolation theory and the conductivity prominently improved from 10(-7) to 9 S/cm as the MWCNT loading increased from 0.1 to 44.4 wt%. Low value of electrical percolation threshold similar to 0.2 wt% is achieved which is attributed to high aspect ratio and homogeneous dispersion of MWCNT in PVC. The analysis of the low temperature electrical resistivity data shows that sample of 1.9 wt% follows three dimensional variable range hopping model whereas higher wt% nanocomposite samples follow power law behavior. The magnetization versus applied field data for both bulk MWCNTs and nanocomposite of 44.4 wt% display ferromagnetic behavior with enhanced coercivities of 1.82 and 1.27 kOe at 10 K, respectively. The enhancement in coercivity is due to strong dipolar interaction and shape anisotropy of rod-shaped iron nanoparticles. (C) 2013 Elsevier B.V. All rights reserved.

Anomalous magnetism of Pr in PrCoAsO

Detailed magnetization and magneto-transport measurements studies are carried out to unearth the anomalous magnetism of Pr in PrCoAsO compound. The studied PrCoAsO sample is single phase and crystallized in the tetragonal structure with space group P4/nmm in analogy of ZrCuSiAs type compounds. Detailed magnetization measurements showed that Co moments in PrCoAsO exhibit weakly itinerant ferromagnetic Co spins ordering at below 80 K with a small magnetic moments of similar to 0.12 mu B/f.u. High temperatures Curie-Weiss fit, resulted in effective paramagnetic moment mu(eff) (exp) of 5.91 mu(B)/f.u., which can be theoretically assigned to 3d Co (3.88 mu(B)) and 4f Pr (3.58 mu(B)). Further, a positive Curie-Weiss temperature (Theta) of 136 K is seen, indicating predominant ferromagnetic interactions in PrCoAsO. Detailed transport measurements showed that PrCoAsO exhibit metallic behavior and negative magneto-resistance below ferro-magnetically (FM) ordered state. Surprisingly, the situation of PrCoAsO is similar to non magnetic La containing LaCoAsO and strikingly different than that as reported for magnetic Nd, Sm and Gd i.e., (Nd/Sm/Gd)CoAsO. The magnetic behavior of PrCoAsO being closed to LaCoAsO and strikingly different to that of (Nd/Sm/Gd)CoAsO is unusual. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Magnetic and dielectric interactions in nano zinc ferrite powder: Prepared by self-sustainable propellant chemistry technique

The structural, magnetic and dielectric properties of nano zinc ferrite prepared by the propellant chemistry technique are studied. The PXRD measurement at room temperature reveal that the compound is in cubic spinel phase, belong to the space group Fd (3) over barm. The unit cell parameters have been estimated from Rietveld refinement. The calculated force constants from FTIR spectrum corresponding to octahedral and tetrahedral sites at 375 and 542 cm(-1) are 6.61 x 10(2) and 3.77 x 10(2) N m(-1) respectively; these values are slightly higher compared to the other ferrite systems. Magnetic hysteresis and EPR spectra show superparamagnetic property nearly to room temperature due to comparison values between magnetic anisotropy energy and the thermal energy. The calculated values of saturation magnetization, remenant magnetization, coercive field and magnetic moment supports for the existence of multi domain particles in the sample. The temperature dependent magnetic field shows the spin freezing state at 30 K and the blocking temperature at above room temperature. The frequency dependent dielectric interactions show the variation of dielectric constant, dielectric loss and impedance as similar to other ferrite systems. The AC conductivity in the prepared sample is due to the presence of electrons, holes and polarons. The synthesized material is suitable for nano-electronics and biomedical applications. (C) 2014 Elsevier B.V. All rights reserved.

Synergistic effect of static magnetic field and HA-Fe3O4 magnetic composites on viability of S. aureus and E. coli bacteria

In addressing the issue of prosthetic infection, this work demonstrated the synergistic effect of the application of static magnetic field (SMF) and ferrimagnetic substrate properties on the bactericidal property in vitro. This aspect was studied using hydroxyapatite (HA)-xFe(3)O(4) (x=10, 20, and 40 wt.%) substrates, which have different saturation magnetization properties. During bacteria culture experiments, 100 mT SMF was applied to growth medium (with HA-xFe(3)O(4) substrate) in vitro for 30, 120, and 240 min. A combination of MTT assay, membrane rupture assays, live/dead assay, and fluorescence microscopic analysis showed that the bactericidal effect of SMF increases with the exposure duration as well as increasing Fe3O4 content in biomaterial substrates. Importantly, the synergistic bactericidal effect was found to be independent of bacterial cell type, as similar qualitative trend is measured with both gram negative Escherichia coli (E. coli) and gram positive Staphylococcus aureus (S. aureus) strains. The reduction in E. coli viability was 83% higher on HA-40 Wt % Fe3O4 composite after 4 h exposure to SMF as compared to nonexposed control. Interestingly, any statistically significant difference in ROS was not observed in bacterial growth medium after magnetic field exposure, indicating the absence of ROS enhancement due to magnetic field. Overall, this study illustrates significant role being played by magnetic substrate compositions towards bactericidal property than by magnetic field exposure alone. (c) 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 102B: 524-532, 2014.

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.

Synthesis and Characterization of CoFe2O4/Polyaniline Nanocomposites for Electromagnetic Interference Applications

The Cobalt ferrite (CoFe2O4) powders were synthesized by Co-precipitation method. The as prepared ferrite powders were incorporated into a polyaniline matrix at various volumetric ratios. The as prepared composites of ferrite and polyaniline powders were characterized using X-ray diffraction (XRD), transmission electron microscope (TEM). The particle size of CoFe2O4 is found to be 20 nm. The saturation magnetization (M-s) of all the composites was found to be decreasing with decrease of ferrite content, while coercivity (H-c) remained at the value corresponding to pure cobalt ferrite nanopowders. The complex permittivity (epsilon' and epsilon `') and permeability (mu' and mu `') of composite samples were measured in the range of 1 MHz to 1.1 GHz. The value of epsilon' and mu' found to be increased with ferrite volume concentration.

Modulation of glyceraldehyde-3-phosphate dehydrogenase activity by surface functionalized quantum dots

Enzymatic regulation is a fast and reliable diagnosis tool via identification and design of inhibitors for modulation of enzyme function. Previous reports on quantum dots (QDs)-enzyme interactions reveal a protein-surface recognition ability leading to promising applications in protein stabilization, protein delivery, bio-sensing and detection. However, the direct use of QDs to control enzyme inhibition has never been revealed to date. Here we show that a series of biocompatible surface-functionalized metal-chalcogenide QDs can be used as potent inhibitors for malignant cells through the modulation of enzyme activity, while normal cells remain unaffected. The in vitro activity of glyceraldehyde-3-phosphate dehydrogenase (GAPDH), an enzyme involved critically in the glycolysis of cancer cells, is inactivated selectively in a controlled way by the QDs at a significantly low concentration (nM). Cumulative kinetic studies delineate that the QDs undergo both reversible and irreversible inhibition mechanisms owing to the site-specific interactions, enabling control over the inhibition kinetics. These complementary loss-of-function probes may offer a novel route for rapid clinical diagnosis of malignant cells and biomedical applications.

Reentrant Superspin Glass Phase in a La0.82Ca0.18MnO3 Ferromagnetic Insulator

We report results of the magnetization and ac susceptibility measurements down to very low fields on a single crystal of the perovskite manganite, La-0.82 Ca-0.18 MnO3. This composition falls in the intriguing ferromagnetic insulator region of the manganite phase diagram. In contrast to earlier beliefs, our investigations reveal that magnetically (and in every other sense), this is a single- phase system with a ferromagnetic ordering temperature of around 170 K. However, this ferromagnetic state is magnetically frustrated, and the system exhibits pronounced glassy dynamics below 90 K. Based on measured dynamical properties, we propose that this quasi-long-ranged ferromagnetic phase, and the associated superspin glass behavior, is the true magnetic state of the system, rather than being a macroscopic mixture of ferromagnetic and antiferromagnetic phases, as often suggested. Our results provide an understanding of the quantum phase transition from an antiferromagnetic insulator to a ferromagnetic metal via this ferromagnetic state as a function of x in La1-xCaxMnO3, in terms of the possible formation of magnetic polarons.

Dielectric relaxation and anti-ferromagnetic coupling of BiEu03 and BiGd03

BiEuO3 (BE) and BiGdO3 (BG) are synthesized by the solid-state reaction technique. Rietveld refinement of the X-ray diffraction data shows that the samples are crystallized in cubic phase at room temperature having Fm3m symmetry with the lattice parameters of 5.4925(2) and 5.4712(2) A for BE and BG, respectively. Raman spectra of the samples are investigated to obtain the phonon modes of the samples. The dielectric properties of the samples are investigated in the frequency range from 42 Hz to 1.1 MHz and in the temperature range from 303 K to 673 K. An analysis of the real and imaginary parts of impedance is performed assuming a distribution of relaxation times as confirmed by the Cole-Cole plots. The frequency-dependent maxima in the loss tangent are found to obey an Arrhenius law with activation energy similar to 1 eV for both the samples. The frequency-dependent electrical data are also analyzed in the framework of conductivity formalism. Magnetization of the samples are measured under the field cooled (EC) and zero field cooled (ZFC) modes in the temperature range from 5 K to 300 K applying a magnetic Field of 500 Oe. The FC and ZFC susceptibilities show that BE is a Van Vleck paramagnetic material with antiferromagnetic coupling at low temperature whereas BG is an anti-ferromagnetic system. The results are substantiated by the M-11 loops of the materials taken at 5 K in the ZFC mode. (C) 2014 Elsevier B.V. All rights reserved

Structural and thermodynamic properties of Fe1.12Te with multiple phase transitions

The parent compound of iron chalcogenide superconductors, Fe1+yTe, with a range of excess Fe concentrations exhibits intriguing structural and magnetic properties. Here, the interplay of magnetic and structural properties of Fe1.12Te single crystals have been probed by low-temperature synchrotron X-ray powder diffraction, magnetization, and specific heat measurements. Thermodynamic measurements reveal two distinct phase transitions, considered unique to samples possessing excess Fe content in the range of 0.11 <= y <= 0.13. On cooling, an antiferromagnetic transition, T-N approximate to 57K is observed. A closer examination of powder diffraction data suggests that the transition at TN is not purely magnetic, but accompanied by the commencement of a structural phase transition from tetragonal to orthorhombic symmetry. This is followed by a second prominent first-order structural transition at T-S with T-S < T-N, where an onset of monoclinic distortion is observed. The results point to a strong magneto-structural coupling in this material. (C) 2014 AIP Publishing LLC.

Dynamics of a driven magneto-martensitic ribbon

We investigate the dynamics of a sinusoidally driven ferromagnetic martensitic ribbon by adopting a recently introduced model that involves strain and magnetization as order parameters. Retaining only the dominant mode of excitation we reduce the coupled set of partial differential equations for strain and magnetization to a set of coupled ordinary nonlinear equations for the strain and magnetization amplitudes. The equation for the strain amplitude takes the form of parametrically driven oscillator. Finite strain amplitude can only be induced beyond a critical value of the strength of the magnetic field. Chaotic response is seen for a range of values of all the physically interesting parameters. The nature of the bifurcations depends on the choice of temperature relative to the ordering of the Curie and the martensite transformation temperatures. We have studied the nature of response as a function of the strength and frequency of the magnetic field, and magneto-elastic coupling. In general, the bifurcation diagrams with respect to these parameters do not follow any standard route. The rich dynamics exhibited by the model is further illustrated by the presence of mixed mode oscillations seen for low frequencies. The geometric structure of the mixed mode oscillations in the phase space has an unusual deep crater structure with an outer and inner cone on which the orbits circulate. We suggest that these features should be seen in experiments on driven magneto-martensitic ribbons. (C) 2014 Elsevier B. V. All rights reserved.

Epitaxial Co metal thin film grown by pulsed laser deposition using oxide target

We report here the growth of epitaxial Co metal thin film on c-plane sapphire by pulsed laser deposition (RD) using Co:ZnO target utilizing the composition inhomogeneity of the corresponding plasma. Two distinct plasma composition regions have been observed using heavily alloyed Co0.6Zn0.4O target. The central and intense region of the plasma grows Co:ZnO film; the extreme tail grows only Co metal with no trace of either ZnO or Co oxide In between the two extremes, mixed phases (Co +Co-oxides +Co:ZnO) were observed. The Co metal thin film grown in this way shows room temperature ferromagnetism with large in plane magnetization similar to 1288 emu cm(-3) and a coerciviLy of similar to 230 Oe with applied field parallel to the film-substrate interface. Carrier density of the film is similar to 10(22) cm(-3). The film is epiLaxial single phase Co metal which is confirmed by both X-ray diffraction and transmission electron microscopy characierizaLions. Planar Hall Effect (PHE) and Magneto Optic Kerr Effect (MOKE) measurements confirm that the film possesses similar attributes of Co metal. The result shows that the epiLaxial Co metal thin film can be grown from its oxides in the PLD. (C) 2014 Elsevier B.V. All rights reserved.

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.

Magneto-structural study of the multiferroic BiFeo(3)-SrTiO3

The structural and magnetic study of the pseudo-binary multiferroic (1 x)BiFeO3 (x)SrTiO3 has been investigated as a function of composition and temperature. In contrary to the previous studies, detailed examination revealed that the reported anomaly in the magnetization at x-0.30 does not occur at the composition induced rhombohedral-cubic phase boundary, but within the rhombohedral phase itself. The rhombohedral to cubic transition occurs at x > 0.4. Evidence of magneto-elastic coupling near the Neel temperature and nucleation-growth mode of the rhombohedral-cubic transformation, with both the phases coexisting over a range of temperature was found. (C) 2014 Elsevier B.V. All rights reserved.