Structural modification and enhanced magnetic properties with two phonon modes in Ca-Co codoped BiFeO3 nanoparticles

Bi1-xCaxFe1-xCoxO3 nanoparticles with x=0.0, 0.05, 0.10 and 0.15 were successfully synthesized by cost effective tartaric acid based sol gel route. The alkali earth metal Ca2+ ions and transition metal Co3+ ions codoping at A and B-sites of BiFeO3 results in structural distortion and phase transformation. Rietveld refinement of XRD patterns suggested the coexistence of rhombohedral and orthorhombic phases in codoped BiFeO3 samples. Both XRD and Raman scattering studies showed the compressive lattice distortion in the samples induced by codoping of Ca2+ and Co3+ ions. Two-phonon Raman spectra exhibited the improvement of magnetization in these samples. X-ray photoelectron spectroscopy (XPS) showed the dominancy of Fe3+ and Co3+ oxidation states along with the shifting of the binding energy of Bi 4f orbital which confirms the substitution Ca2+ at Bi-site. The magnetic study showed the enhancement in room temperature ferromagnetic behavior with co-substitution consistent with Rama analysis. The gradual change in line shape of electron spin resonance spectra indicated the local distortion induced by codoping. (C) 2015 Published by Elsevier Ltd and Techna Group S.r.l.

Copper oxide nanoparticles: an antidermatophytic agent for Trichophyton spp.

Copper oxide (CuO) is one of the most important transition metal oxides due to its unique properties. It is used in various technological applications such as high critical temperature, superconductors, gas sensors, in photoconductive applications and so on. Recently, it has been used as an antimicrobial agent against various pathogenic bacteria. In the present investigation, we studied the structural and antidermatophytic properties of CuO nanoparticles (NPs) synthesized by a precipitation technique. Copper sulfate was used as a precursor and sodium hydroxide as a reducing agent. Scanning electron microscopy (SEM) showed flower-shaped CuO NPs and X-ray diffraction (XRD) pattern showed the crystalline nature of CuO NPs. These NPs were evaluated against two prevalent species of dermatophytes, i.e. Trichophyton rubrum and T. mentagrophytes by using the broth microdilution technique. Further, the NPs activity was also compared with synthetic sertaconazole. Although better antidermatophytic activity was exhibited with sertaconazole as compared to NPs, being synthetic, sertaconazole may not be preferred, as it shows different adverse effects. Trichophyton mentagrophytes is more susceptible to NPs than T. rubrum. A phylogenetic approach was applied for predicting differences in susceptibility of pathogens.

Visible light-induced cytotoxicity of a dinuclear iron(III) complex of curcumin with low-micromolar IC50 value in cancer cells

Photoactive metal complexes have emerged as potential candidates in the photodynamic therapy (PDT) of cancer. We present here the synthesis, characterization and visible light-triggered anticancer activity of two novel mixed-ligand oxo-bridged iron(III) complexes, viz., {Fe(L)(acac)}(2)(mu-O)](ClO4)(2) (1) and {Fe (L)(cur)}(2)(mu-O)](ClO4)(2) (2) where L is bis-(2-pyridylmethyl)-benzylamine, acac is acetylacetonate and cur is the monoanion of curcumin (bis(4-hydroxy-3-methoxyphenyl)-1,6-diene-3,5-dione). The crystal structure of complex 1 (as PF6 salt, 1a) shows distorted octahedral geometry of each iron(III) centre formed by the FeN3O3 core. The 1: 2 electrolytic complexes are stable in solution and retain their oxo-bridged identity in aqueous medium. Complex 2 has a strong absorption band in the visible region and shows promising photocytotoxicity in HeLa and MCF-7 cancer cells in visible light giving respective IC50 values of 3.1 +/- 0.4 lM and 4.9 +/- 0.5 lM while remains non-toxic in the dark (IC50 > 50 lM). The control complex 1 is inactive both in the light and dark. Complex 2 accumulates in cytoplasm of HeLa and MCF-7 cells as evidenced from fluorescence microscopy and triggers apoptotic cell death via light-assisted generation of reactive oxygen species (ROS). Taken together, complex 2 with its promising photocytotoxicity but negligible dark toxicity in cancer cells has significant photochemotherapeutic potential for applications in PDT. (C) 2015 Elsevier B.V. All rights reserved.

Organic-inorganic hybrid PtCo nanoparticle with high electrocatalytic activity and durability for oxygen reduction

In Pt-transition metal (TM) alloy catalysts, the electron transfer from the TM to Pt is retarded owing to the inevitable oxidation of the TM surface by oxygen. In addition, acidic electrolytes such as those employed in fuel cells accelerate the dissolution of the surface TM oxide, which leads to catalyst degradation. Herein, we propose a novel synthesis strategy that selectively modifies the electronic structure of surface Co atoms with N-containing polymers, resulting in highly active and durable PtCo nanoparticle catalysts useful for the oxygen reduction reaction (ORR). The polymer, which is functionalized on carbon black, selectively interacts with the Co precursor, resulting in Co-N bond formation on the PtCo nanoparticle surface. Electron transfer from Co to Pt in the PtCo nanoparticles modified by the polymer is enhanced by the increase in the difference in electronegativity between Pt and Co compared with that in bare PtCo nanoparticles with the TM surface oxides. In addition, the dissolution of Co and Pt is prevented by the selective passivation of surface Co atoms and the decrease in the O-binding energy of surface Pt atoms. As a result, the catalytic activity and durability of PtCo nanoparticles for the ORR are significantly improved by the electronic ensemble effects. The proposed organic/inorganic hybrid concept will provide new insights into the tuning of nanomaterials consisting of heterogeneous metallic elements for various electrochemical and chemical applications.

Optical-Phonon-Limited High-Field Transport in Layered Materials

An optical-phonon-limited velocity model has been employed to investigate high-field transport in a selection of layered 2-D materials for both, low-power logic switches with scaled supply voltages, and high-power, high-frequency transistors. Drain currents, effective electron velocities, and intrinsic cutoff frequencies as a function of carrier density have been predicted, thus providing a benchmark for the optical-phonon-limited high-field performance limits of these materials. The optical-phonon-limited carrier velocities for a selection of multi-layers of transition metal dichalcogenides and black phosphorus are found to be modest compared to their n-channel silicon counterparts, questioning the utility of biasing these devices in the source-injection dominated regime. h-BN, at the other end of the spectrum, is shown to be a very promising material for high-frequency, high-power devices, subject to the experimental realization of high carrier densities, primarily due to its large optical-phonon energy. Experimentally extracted saturation velocities from few-layer MoS2 devices show reasonable qualitative and quantitative agreement with the predicted values. The temperature dependence of the measured v(sat) is discussed and compared with the theoretically predicted dependence over a range of temperatures.

Characterization of silver-kaolinite (AgK): an adsorbent for long-lived I-129 species

Bentonite is a preferred buffer and backfill material for deep geological disposal of high-level nuclear waste (HLW). Bentonite does not retain anions by virtue of its negatively charged basal surface. Imparting anion retention ability to bentonite is important to enable the expansive clay to retain long-lived I-129 (iodine-129; half-life = 16 million years) species that may escape from the HLW geological repository. Silver-kaolinite (AgK) material is prepared as an additive to improve the iodide retention capacity of bentonite. The AgK is prepared by heating kaolinite-silver nitrate mix at 400 degrees C to study the kaolinite influence on the transition metal ion when reacting at its dehydroxylation temperature. Thermo gravimetric-Evolved Gas Detection analysis, X-ray diffraction analysis, X-ray photo electron spectroscopy and electron probe micro analysis indicated that silver occurs as AgO/Ag2O surface coating on thermally reacting kaolinite with silver nitrate at 400 degrees C.

NH3 adsorption on PtM (Fe, Co, Ni) surfaces: Cooperating effects of charge transfer, magnetic ordering and lattice strain

Adsorption of a molecule or group with an atom which is less electronegative than oxygen (0) and directly interacting with the surface is very relevant to development of PtM (M = 3d-transition metal) catalysts with high activity. Here, we present theoretical analysis of the adsorption of NH3 molecule (N being less electronegative than 0) on (111) surfaces of PtM (Fe, Co, Ni) alloys using the first principles density functional approach. We find that, while NH3-Pt interaction is stronger than that of NH3 with the elemental M-surfaces, it is weaker than the strength of interaction of NH3 with M-site on the surface of PtM alloy. (C) 2016 Published by Elsevier B.V.

Effects of pre-treatment and plasma enhancement on chemical vapor deposition of carbon nanotubes from ultra-thin catalyst films

We report a detailed study of surface-bound chemical vapor deposition of carbon nanotubes and nanofibers from evaporated transition metal catalysts exposed to ammonia diluted acetylene. We show that a reduction of the Fe/Co catalyst film thickness below 3 nm results into a transition from large diameter (> 40 nm), bamboo-like nanofibers to small diameter (similar to 5 nm) multi-walled carbon nanotubes. The nanostructuring of ultrathin catalyst films critically depends on the gas atmosphere, with the resulting island distribution initiating the carbon nucleation. Compared to purely thermal chemical vapor deposition, we find that, for small diameter nanotube growth, DC plasma assistance is detrimental to graphitization and sample homogeneity and cannot prevent an early catalyst poisoning. (c) 2006 Elsevier B.V. All rights reserved.

Domain structure of a Nd60Al10Fe20Co10 bulk metallic glass

Magnetic domain structure of Nd60Al10Fe20Co10 bulk metallic glass (BMG) has been studied by using magnetic-force microscopy. In the magnetic-force images it is shown that the exchange-interaction-type magnetic domains with a period of about 360 nm do exist in the BMG, which is believed to be associated with the appearance of hard-magnetic properties in this system. The existence of the large-scale domains demonstrates that the magnetic moments of a great deal of short-scale ordered atomic clusters in the BMG have been aligned by exchange coupling. Annealing at 715 K leads to partial crystallization of the BMG. However, the exchange coupling is stronger in the annealed sample, which is considered to arise from the increase of transition-metal concentration in the amorphous phase due to the precipitation of Nd crystalline phase.

Estudio de la reducción de SO2 con CH4 en presencia de O2 a altas temperaturas, sobre catalizador de Cr2O3 soportado en alúmina

Resumen: Se propone utilizar un óxido como el Cr2O3 como catalizador ya que se ha determinado anteriormente, en la primera etapa de esta investigación, (“Estudio comparativo de la retención de SO2 sobre óxidos de metales de transición soportados en alúmina”), que la retención de SO2 sobre su superficie es un proceso de quimisorción con formación de especies sulfito superficiales sobre sitios básicos y un proceso de óxido reducción del ión metálico. Apoya este mecanismo el hecho de que la cantidad de SO2 adsorbido es función de la temperatura. La mayor eficiencia del Cr2O3 puede explicarse en base a sus propiedades superficiales, lo cual ha sido utilizado en la segunda etapa de reacción de reducción, ya que se ha completado la etapa inicial de quimisorción. En la segunda etapa de esta investigación (“Estudio de la reacción de reducción de SO2 con CH4 a altas temperaturas sobre catalizador de Cr2O3 soportado en alúmina”), se apuntó al estudio de un nuevo tipo de sinergia entre propiedades ácido-base y propiedades redox en una misma superficie. Esta tercera etapa apuntó a determinar la influencia que tiene el O2 en este proceso, ya que el O2 se encuentra presente en las chimeneas industriales en las condiciones de reacción entre el SO2 y el CH4, y produce modificaciones en los parámetros de reacción. Se experimentó con diferentes masas de catalizador y flujos de los distintos gases, y se estudió la influencia de la presencia de oxígeno en la reacción y particularmente con diferentes flujos del mismo, y la posibilidad de regeneración del catalizador.

Estudio de la factibilidad de aplicación, a escala planta piloto, del catalizador Cr2O3, soportado en alúmina, en la reducción de emisión de SO2 a la atmósfera proveniente de fuentes fijas

Resumen: Se propone utilizar un óxido como el Cr2O3 como catalizador ya que se ha determinado anteriormente, en la primera etapa de esta investigación, (“Estudio comparativo de la retención de SO2 sobre óxidos de metales de transición soportados en alúmina”), que la retención de SO2 sobre su superficie es un proceso de quimisorción con formación de especies sulfito superficiales sobre sitios básicos y un proceso de óxido reducción del ión metálico. Apoya este mecanismo el hecho de que la cantidad de SO2 adsorbido es función de la temperatura. La mayor eficiencia del Cr2O3 puede explicarse en base a sus propiedades superficiales, lo cual ha sido utilizado en la segunda etapa de reacción de reducción, ya que se ha completado la etapa inicial de quimisorción. En la segunda etapa de esta investigación (“Estudio de la reacción de reducción de SO2 con CH4 a altas temperaturas sobre catalizador de Cr2O3 soportado en alúmina”), se apuntó al estudio de un nuevo tipo de sinergia entre propiedades ácido-base y propiedades redox en una misma superficie. La tercera etapa apuntó a determinar la influencia que tiene el O2 en este proceso, ya que el O2 se encuentra presente en las chimeneas industriales en las condiciones de reacción entre el SO2 y el CH4, y produce modificaciones en los parámetros de reacción. Se experimentó con diferentes masas de catalizador y flujos de los distintos gases, y se estudió la influencia de la presencia de oxígeno en la reacción y particularmente con diferentes flujos del mismo, y la posibilidad de regeneración del catalizador.En esta cuarta y última etapa se están estudiando los cambios que se producen en la reacción al pasar de escala laboratorio a planta piloto utilizando una columna de mayor diámetro construída en metal. A través de los datos experimentales se está estudiando, en conjunto con el INIFTA, la presencia de especies sulfito y sulfato sobre la superficie del soporte. Adicionalmente, por medio del programa VASP (Vienna Ab-initio Simulation Package), se analiza la interacción entre los reactivos gaseosos y el soporte.

A Study on iron-based amorphous alloys : alloy development, thermodynamics and soft magnetism

Metallic glass has since its debut been of great research interest due to its profound scientific significance. Magnetic metallic glasses are of special interest because of their promising technological applications. In this thesis, we introduced a novel series of Fe-based alloys and offer a holistic review of the physics and properties of these alloys. A systematic alloy development and optimization method was introduced, with experimental implementation on transition metal based alloying system. A deep understanding on the influencing factors of glass forming ability was brought up and discussed, based on classical nucleation theory. Experimental data of the new Fe-based amorphous alloys were interpreted to further analyze those influencing factors, including reduced glass transition temperature, fragility, and liquid-crystal interface free energy. Various treatments (fluxing, overheating, etc.) were discussed for their impacts on the alloying systems' thermodynamics and glass forming ability. Multiple experimental characterization methods were discussed to measure the alloys' soft magnetic properties. In addition to theoretical and experimental investigation, we also gave a detailed numerical analysis on the rapid-discharge-heating-and-forming platform. It is a novel experimental system which offers extremely fast heating rate for calorimetric characterization and alloy deformation.

Variable-angle electron spectroscopic studies of various polyatomic molecular systems

The complementary techniques of low-energy, variable-angle electron-impact spectroscopy and ultraviolet variable-angle photoelectron spectroscopy have been used to study the electronic spectroscopy and structure of several series of molecules. Electron-impact studies were performed at incident beam energies between 25 eV and 100 eV and at scattering angles ranging from 0° to 90°. The energy-loss regions from 0 eV to greater than 15 eV were studied. Photoelectron spectroscopic studies were conducted using a HeI radiation source and spectra were measured at scattering angles from 45° to 90°. The molecules studied were chosen because of their spectroscopic, chemical, and structural interest. The operation of a new electron-impact spectrometer with multiple-mode target source capability is described. This spectrometer has been used to investigate the spin-forbidden transitions in a number of molecular systems.

The electron-impact spectroscopy of the six chloro-substituted ethylenes has been studied over the energy-loss region from 0-15 eV. Spin-forbidden excitations corresponding to the π → π*, N → T transition have been observed at excitation energies ranging from 4.13 eV in vinyl chloride to 3.54 eV in tetrachloroethylene. Symmetry-forbidden transitions of the type π → np have been oberved in trans-dichloroethyene and tetrachlor oethylene. In addition, transitions to many states lying above the first ionization potential were observed for the first time. Many of these bands have been assigned to Rydberg series converging to higher ionization potentials. The trends observed in the measured transition energies for the π → π*, N → T, and N → V as well as the π → 3s excitation are discussed and compared to those observed in the methyl- and fluoro- substituted ethylenes.

The electron energy-loss spectra of the group VIb transition metal hexacarbonyls have been studied in the 0 eV to 15 eV region. The differential cross sections were obtained for several features in the 3-7 eV energy-loss region. The symmetry-forbidden nature of the ¹A_1g → ¹A_1g, 2t_2g(π) → 3t_2g(π*) transition in these compounds was confirmed by the high-energy, low-angle behavior of their relative intensities. Several low lying transitions have been assigned to ligand field transitions on the basis of the energy and angular behavior of the differential cross sections for these transitions. No transitions which could clearly be assigned to singlet → triplet excitations involving metal orbitals were located. A number of states lying above the first ionization potential have been observed for the first time. A number of features in the 6-14 eV energy-loss region of the spectra of these compounds correspond quite well to those observed in free CO.

A number of exploratory studies have been performed. The π → π*, N → T, singlet → triplet excitation has been located in vinyl bromide at 4.05 eV. We have also observed this transition at approximately 3.8 eV in a cis-/trans- mixture of the 1,2-dibromoethylenes. The low-angle spectrum of iron pentacarbonyl was measured over the energy-loss region extending from 2-12 eV. A number of transitions of 8 eV or greater excitation energy were observed for the first time. Cyclopropane was also studied at both high and low angles but no clear evidence for any spin- forbidden transitions was found. The electron-impact spectrum of the methyl radical resulting from the pyrolysis of tetramethyl tin was obtained at 100 eV incident energy and at 0° scattering angle. Transitions observed at 5.70 eV and 8.30 eV agree well with the previous optical results. In addition, a number of bands were observed in the 8-14 eV region which are most likely due to Rydberg transitions converging to the higher ionization potentials of this molecule. This is the first reported electron-impact spectrum of a polyatomic free radical.

Variable-angle photoelectron spectroscopic studies were performed on a series of three-membered-ring heterocyclic compounds. These compounds are of great interest due to their highly unusual structure. Photoelectron angular distributions using HeI radiation have been measured for the first time for ethylene oxide and ethyleneimine. The measured anisotropy parameters, β, along with those measured for cyclopropane were used to confirm the orbital correlations and photoelectron band assignments. No high values of β similar to those expected for alkene π orbitals were observed for the Walsh or Forster-Coulson-Moffit type orbitals.

The application of metallointercalators in recognition of and charge transport in nucleic acids

Metal complexes that utilize the 9,10-phenanthrene quinone diimine (phi) moiety bind to DNA through the major groove. These metallointercalators can recognize DNA sites and perform reactions on DNA as a substrate. The site-specific metallointercalator Λ-1-Rh(MGP)_2phi^(5+) competitively disrupts the major groove binding of a transcription factor, yAP-1, from an oligonucleotide that contains a common binding site. The demonstration that metal complexes can prevent transcription factor binding to DNA site-specifically is an important step in using metallointercalators as therapeutics.

The distinctive photochemistry of metallointercalators can also be applied to promote long range charge transport in DNA. Experiments using duplexes with regions 4 to 10 nucleotides long containing strictly adenine and thymine sequences of varying order showed that radical migration is more dependent on the sequence of bases, and less dependent on the distance between the guanine doublets. This result suggests that mechanistic proposals of long range charge transport must involve all the bases.

RNA/DNA hybrids show charge migration to guanines from a remote site, thus demonstrating that nucleic acid stacking other than B-form can serve as a radical bridge. Double crossover DNA assemblies also provide a medium for charge transport at distances up to 100 Å from the site of radical introduction by a tethered metal complex. This radical migration was found to be robust to mismatches, and limited to individual, electronically distinct base stacks. In single DNA crossover assemblies, which have considerably greater flexibility, charge migration proceeds to both base stacks due to conformational isomers not present in the rigid and tightly annealed double crossovers.

Finally, a rapid, efficient, gel-based technique was developed to investigate thymine dimer repair. Two oligonucleotides, one radioactively labeled, are photoligated via the bases of a thymine-thymine interface; reversal of this ligation is easily visualized by gel electrophoresis. This assay was used to show that the repair of thymine dimers from a distance through DNA charge transport can be accomplished with different photooxidants.

Thus, nucleic acids that support long range charge transport have been shown to include A-track DNA, RNA/DNA hybrids, and single and double crossovers, and a method for thymine dimer repair detection using charge transport was developed. These observations underscore and extend the remarkable finding that DNA can serve a medium for charge transport via the heteroaromatic base stack.

The electrical and magnetic properties of amorphous Pd-Cu-P alloys

The amorphous phases of the Pd-Cu-P system has been obtained using the technique of rapidly quenching from the liquid state. Broad maxima in the diffraction pattern were obtained in the X-ray diffraction studies which are indicative of a glass-like structure. The composition range over which the amorphous solid phase is retained for the Pd-Cu-P system is (Pd_100-xCu_x)₈₀P₂₀ with 10 ≤ x ≤ 50 and (Pd₆₅Cu₃₅)_100-yP_y with 15 ≤ y ≤ 24 and (Pd₆₀Cu₄₀)_100-yP_y with 15 ≤ y ≤ 24.

The electrical resistivity for the Pd-Cu-P alloys decreases with temperature as T² at low temperatures and as T at high temperatures up to the crystallization temperature. The structural scattering model of the resistivity proposed by Sinha and the spin-fluctuation resistivity model proposed by Hasegawa are re-examined in the light of the similarity of this result to the Pt-Ni-P and Pd-Ni-P systems. Objections are raised to these interpretations of the resistivity results and an alternate model is proposed consistent with the new results on Pd-Cu-P and the observation of similar effects in crystalline transition metal alloys. The observed negative temperature coefficients of resistivity in these amorphous alloys are thus interpreted as being due to the modification of the density of states with temperature through the electron-phonon interaction. The weak Pauli paramagnetism of the Pd-Cu-P, Pt-Ni-P and Pd-Ni-P alloys is interpreted as being modifications of the transition d-states as a result of the formation of strong transition metal-metalloid bonds rather than a large transfer of electrons from the glass former atoms (P in this case) to the d-band of the transition metal in a rigid band picture.