Synthesis of zero valent iron nanoparticles and application to removal of arsenic(III) and arsenic(V) from water

Recently nano scale zero valent iron particles (nZVI) have been considered as smart adsorbent for environmental and groundwater remediation. Although several synthetic methods are available for the preparation of nZVI, air stable nZVI are not available for remediation works. Further, challenges demand synthesis of nZVI without stabilizers and capping agents. A modified methodology for the synthesis of air stable nZVI has been developed without any capping agents and characterized by powder X-Ray Diffraction (XRD), Scanning Electron Microscopy Energy-dispersive X-Ray (SEM-EDS), Transmission Electron Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS). The results of the present study suggest that the synthetic nZVI are air-stable over a period of one year and consists of particles of 30-40 nm in diameter. Although a layer of less than 3 am thick oxide/hydroxide is observed by TEM and XPS, it appears to be due to oxidation of outer surface during analysis. Adsorption study has shown that the synthetic nZVI are more effective adsorbent than the commercial nZVI and can remove simultaneously arsenite As-III] and arsenate As-V] from water without prior reduction of As-V to As-III. The removal process is adsorptive rather than precipitative and the removal of As-III is greater than that of As-V.

Low temperature CO oxidation and water gas shift reaction over Pt/Pd substituted in Fe/TiO2 catalysts

We demonstrate the activity of Ti0.84Pt0.01Fe0.15O2-delta and Ti0.73Pd0.02Fe0.25O2-delta catalysts towards the CO oxidation and water gas shift (VMS) reaction. Both the catalysts were synthesized in the nano crystalline form by a low temperature sonochemical method and characterized by different techniques such as XRD, FT-Raman, TEM, FT-IR, XPS and BET surface analyzer. H-2-TPR results corroborate the intimate contact between noble metal and Fe ions in the both catalysts that facilitates the reducibility of the support. In the absence of feed CO2 and H-2, nearly 100% conversion of CO to CO2 with 100% H-2 selectivity was observed at 300 degrees C and 260 degrees C respectively, for Ti0.84Pt0.01Fe0.15O2-delta and Ti0.73Pd0.02Fe0.25O2-delta catalyst. However, the catalytic performance of Ti0.73Pd0.02Fe0.25O2-delta deteriorates in the presence of feed CO2 and H-2. The change in the support reducibility is the primary reason for the significant increase in the activity for CO oxidation and WGS reaction. The effect of Fe addition was more significant in Ti0.73Pd0.02Fe0.25O2-delta than Ti0.84Pt0.01Fe0.15O2-delta. Based on the spectroscopic evidences and surface phenomena, a hybrid reaction scheme utilizing both surface hydroxyl groups and the lattice oxygen was hypothesized over these catalysts for WGS reaction. The mechanisms based on the formate and redox pathway were used to fit the ldnetic data. The analysis of experimental data shows the redox mechanism is the dominant pathway over these catalysts. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Compositionally Graded Microstructure for Ag-Fe Nanoparticles

Ag-Fe nanoparticles with a highly Ag rich average composition were synthesized by the sonochemical route. Silver-iron system exhibits a wide miscibility gap in the bulk materials. Interestingly, a graded compositional profile along the nanoparticle radius was observed. Regions at and near the surface of the nanoparticle contained both Ag and Fe atoms. The composition got relatively deficient Fe towards the center of the particle with particle core made up of pure Ag. Alloying of Ag and Fe is confirmed by the absence of diffraction signal corresponding to pure Fe phase and presence of a paramagnetic phase in nanoparticles containing a diamagnetic (Ag) and ferromagnetic (Fe) elements.

Non-neutral evolution in non-LEE-encoded type III effectors of attaching and effacing Escherichia coli

Attaching and effacing Escherichia coli (AEEC) employ type III secretion system (T3SS) to secrete effector proteins into host cells and regulate their function. Here we have investigated T3SS genes of AEEC for non-neutral evolution. Our analysis revealed non-neutral evolution in three genes (nleE1, nleB2 and nleD) which encode effector proteins. These genes are located outside the locus of enterocyte effacement (LEE). In general, non-LEE effector genes show greater deviation from neutral evolution than LEE effector genes. These results suggest that effector genes located outside LEE are under greater selection pressure than those present in LEE. (C) 2012 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Synthesis, antimicrobial, DNA-binding and photonuclease studies of Cobalt(III) and Nickel(II) Schiff base complexes

New metal complexes of the type M(nih)(L)](PF6)(n)center dot xAH(2)O and M(nih)(2)](PF6)center dot xH(2)O (where M = Co(III) or Ni(II), L = 1,10-phenanthroline (phen)/or 2,2' bipyridine (bpy), nih = 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone, n = 2 or 1 and x = 3 or 2) have been synthesized and characterized by elemental analysis, magnetic, IR and H-1 NMR spectral data. The electronic and magnetic moment 2.97-3.07 B.M. data infers octahedral geometry for all the complexes. The IR data reveals that Schiff base (nih) form coordination bond with the metal ion through azomethine-nitrogen, phenolic-oxygen and carbonyl-oxygen in a tridentate fashion. In addition, DNA-binding properties of these six metal complexes were investigated using absorption spectroscopy, viscosity measurements and thermal denaturation methods. The results indicated that the nickel(II) complex strongly bind with calf-thymus DNA with intrinsic DNA binding constant K-b value of 4.9 x 10(4) M-1 for (3), 4.2 x 10(4) M-1 for (4), presumably via an intercalation mechanism compared to cobalt(III) complex with K-b value of 4.6 x 10(4) M-1 (1) and 4.1 x 10(4) M-1 (2). The DNA Photoclevage experiment shows that, the complexes act as effective DNA cleavage agent. (C) 2012 Elsevier B.V. All rights reserved.

Feasibility of laser-induced breakdown spectroscopy for the study of the temporal distribution of trace elements trapped in snow collected from greater himalayan range

The potential merit of laser-induced breakdown spectroscopy (LIBS) has been demonstrated for detection and quantification of trace pollutants trapped in snow/ice samples. In this technique, a high-power pulsed laser beam from Nd:YAG Laser (Model no. Surelite III-10, Continuum, Santa Clara, CA, USA) is focused on the surface of the target to generate plasma. The characteristic emissions from laser-generated plasma are collected and recorded by a fiber-coupled LIBS 2000+ (Ocean Optics, Santa Clara, CA, USA) spectrometer. The fingerprint of the constituents present in the sample is obtained by analyzing the spectral lines by using OOI LIBS software. Reliable detection of several elements like Zn, Al, Mg, Fe, Ca, C, N, H, and O in snow/ice samples collected from different locations (elevation) of Manali and several snow samples collected from the Greater Himalayan region (from a cold lab in Manali, India) in different months has been demonstrated. The calibration curve approach has been adopted for the quantitative analysis of these elements like Zn, Al, Fe, and Mg. Our results clearly demonstrate that the level of contamination is higher in those samples that were collected in the month of January in comparison to those collected in February and March.

Synthesis of nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) solid solution exhibiting high CO oxidation and water gas shift activity

Nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) has been synthesized using a low temperature sonication method and characterized using XRD, TEM, XPS and H-2-TPR. The potential application of both the solid solutions has been explored as exhaust catalysts by performing CO oxidation. The addition of Si- and Fe-in Ce0.95Ru0.05O2-delta greatly enhanced the reducibility of Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe), as indicated by the H-2-TPR study. The oxygen storage capacity has been used to correlate surface oxygen reactivity to the CO oxidation activity. Both the compounds reversibly release lattice oxygen and exhibit excellent CO oxidation activity with 99% conversion below 200 degrees C. A bifunctional reaction mechanism involving CO oxidation by the extraction of lattice oxygen and rejuvenation of oxide vacancy with gas feed O-2 has been used to correlate experimental data. The performance of both the solid solutions has also been investigated for energy application by performing the water gas shift reaction. The present catalysts are highly active and selective towards the hydrogen production and a lack of methanation activity is an important finding of present study.

Interdiffusion and solid solution strengthening in Ni-Co-Pt and Ni-Co-Fe ternary systems

Diffusion couple experiments are conducted in Co-Ni-Pt system at 1200 degrees C and in Co-Ni-Fe system at 1150 degrees C, by coupling binary alloys with the third element. Uphill diffusion is observed for both Co and Ni in Pt rich corner of the Co-Ni-Pt system, whereas in the Co-Ni-Fe system, it is observed for Co. Main and cross interdiffusion coefficients are calculated at the composition of intersection of two independent diffusion profiles. In both the systems, the main interdiffusion coefficients are positive over the whole composition range and the cross interdiffusion coefficients show both positive and negative values at different regions. Hardness measured by performing the nanoindentations on diffusion couples of both the systems shows the higher values at intermediate compositions.

Suppression Of Barkhausen Noise Due To Exchange Biasing In Fe-FeMn Bilalayers

Exchange biased Fe(FM)-FeMn(AFM) bilayers were grown by pulsed laser ablation in UHV and probed by SQUID magnetometer and planar Hall effect measurements. A suppression of barkhausen avalanches was observed during the switching of the bilayer when compared to that of pure Fe, which is indicative of a change in the reversal mechanism.

A model of coupled thermal, mechanical, and electrostatic field effects in III-N thin film heterostructures

A one-dimensional coupled multi-physics based model has been developed to accurately compute the effects of electrostatic, mechanical, and thermal field interactions on the electronic energy band structure in group III-nitrides thin film heterostructures. Earlier models reported in published literature assumes electro-mechanical field with uniform temperature thus neglecting self-heating. Also, the effects of diffused interface on the energy band structure were not studied. We include these effects in a self-consistent manner wherein the transport equation is introduced along with the electro-mechanical models, and the lattice structural variation as observed in experiments are introduced at the interface. Due to these effects, the electrostatic potential distribution in the heterostructure is altered. The electron and hole ground state energies decrease by 5% and 9%, respectively, at a relative temperature of 700 K, when compared with the results obtained from the previously reported electro-mechanical model assuming constant and uniform temperature distribution. A diffused interface decreases the ground state energy of electrons and holes by about 11% and 9%, respectively, at a relative temperature of 700 K when compared with the predictions based on uniform temperature based electro-mechanical model. (C) 2013 AIP Publishing LLC.

Fe as Hydrogen/Halogen Bond Acceptor in Square Pyramidal Fe(CO)(5)

Hydrogen bonded complexes formed between the square pyramidal Fe(CO)(5) with HX (X = F, Cl, Br), showing X-H center dot center dot center dot Fe interactions, have been investigated theoretically using density functional theory (DFT) including dispersion correction. Geometry, interaction energy, and large red shift of about 400 cm(-1) in the FIX stretching frequency confirm X-H center dot center dot center dot Fe hydrogen bond formation. In the (CO)(5)Fe center dot center dot center dot HBr complex, following the significant red shift, the HBr stretching mode is coupled with the carbonyl stretching modes. This clearly affects the correlation between frequency shift and binding energy, which is a hallmark of hydrogen bonds. Atoms in Molecule (AIM) theoretical analyses show the presence of a bond critical point between the iron and the hydrogen of FIX and significant mutual penetration. These X-H center dot center dot center dot Fe hydrogen bonds follow most but not all of the eight criteria proposed by Koch and Popelier (J. Phys. Chem. 1995, 99, 9747) based on their investigations on C-H center dot center dot center dot O hydrogen bonds. Natural bond orbital (NBO) analysis indicates charge transfer from the organometallic system to the hydrogen bond donor. However, there is no correlation between the extent of charge transfer and interaction,energy, contrary to what is proposed in the recent IUPAC recommendation (Pure Appl.. Chem. 2011, 83, 1637). The ``hydrogen bond radius'' for iron has been determined to be 1.60 +/- 0.02 angstrom, and not surprisingly it is between the covalent (127 angstrom) and van der Waals (2.0) radii of Fe. DFT and AIM theoretical studies reveal that Fe in square pyramidal Fe(CO)(5) can also form halogen bond with CIF and ClH as ``halogen bond donor''. Both these complexes show mutual penetration as well, though the Fe center dot center dot center dot Cl distance is closer to the sum of van der Waals radii of Fe and Cl in (CO)5Fe center dot center dot center dot ClH, and it is about 1 angstrom less in (CO)(5)Fe center dot center dot center dot ClF.

Thermoelectric properties of Fe(0.2)Co(3.8)Sbi(12-x)Te(x) skutterudites

Skutterudites Fe(0.)2Co(3.8)Sb(12),Te-x (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6) were synthesized by induction melting at 1273 K, followed by annealing at 923 K for 144 h. X-ray powder diffraction and electron microprobe analysis confirmed the presence of the skutterudite phase as the main phase. The temperature-dependent transport properties were measured for all the samples from 300 to 818 K. A positive Seebeck coefficient (holes are majority carriers) was obtained in Fe0.2Co3.8Sb 12 in the whole temperature range. Thermally excited carriers changed from n-type to p-type in Fe(0.)2Co(3.8)Sb(12),Te-x 19Te0.1 at 570 K, while in all the other samples, Fe(0.)2Co(3.8)Sb(12),Te-x (x = 0.2, 0.3, 0.4, 0.5, 0.6) exhibited negative Seebeck coefficients in the entire temperature range measured. Whereas for the alloys up to x = 0.2 (Fe(0.)2Co(3.8)Sb(12),Te-x ) the electrical resistivity decreased by charge compensation, it increased for x> 0.2 with an increase in Te content as a result of an increase in the electron concentration. The thermal conductivity decreased with Te substitution owing to carrier phonon scattering and point defect scattering. The maximum dimensionless thermoelectric figure of merit, ZT = 1.04 at 818 K, was obtained with an optimized Te content for Fe0.2Co3.8Sb1 1.5Te0.5 and a carrier concentration of,,J1/ =- 3.0 x 1020 CM-3 at room temperature. Thermal expansion (a = 8.8 x 10-6 K-1), as measured for Fe(0.)2Co(3.8)Sb(12),Te-x , compared well with that of undoped Co4Sb12. A further increase in the thermoelectric figure of merit up to ZT = 1.3 at 820 K was achieved for Fe(0.)2Co(3.8)Sb(12),Te-x , applying severe plastic deformation in terms of a high-pressure torsion process. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Inhibition of cancer cell proliferation and apoptosis-inducing activity of fungal taxol and its precursor baccatin III purified from endophytic Fusarium solani

Background: Taxol (generic name paclitaxel), a plant-derived antineoplastic agent, used widely against breast, ovarian and lung cancer, was originally isolated from the bark of the Pacific yew, Taxus brevifolia. The limited supply of the drug has prompted efforts to find alternative sources, such as chemical synthesis, tissue and cell cultures of the Taxus species both of which are expensive and yield low levels. Fermentation processes with microorganisms would be the methods of choice to lower the costs and increase yields. Previously we have reported that F. solani isolated from T. celebica produced taxol and its precursor baccatin III in liquid grown cultures J Biosci 33: 259-67, 2008. This study was performed to evaluate the inhibition of proliferation and induction of apoptosis of cancer cell lines by the fungal taxol and fungal baccatin III of F. solani isolated from T. celebica. Methods: Cell lines such as HeLa, HepG2, Jurkat, Ovcar3 and T47D were cultured individually and treated with fungal taxol, baccatin III with or without caspase inhibitors according to experimental requirements. Their efficacy on apoptotic induction was examined. Results: Both fungal taxol and baccatin III inhibited cell proliferation of a number of cancer cell lines with IC50 ranging from 0.005 to 0.2 mu M for fungal taxol and 2 to 5 mu M for fungal baccatin III. They also induced apoptosis in JR4-Jurkat cells with a possible involvement of anti-apoptotic Bcl2 and loss in mitochondrial membrane potential, and was unaffected by inhibitors of caspase-9,-2 or -3 but was prevented in presence of caspase-10 inhibitor. DNA fragmentation was also observed in cells treated with fungal taxol and baccatin III. Conclusions: The cytotoxic activity exhibited by fungal taxol and baccatin III involves the same mechanism, dependent on caspase-10 and membrane potential loss of mitochondria, with taxol having far greater cytotoxic potential.

Role of dicarboxylate linkers in Mn-III-salicylaldoximate based extended structures: synthesis, structures, and magnetic behavior

Four new oxo-centered Mn-III-salicylaldoximate triangle-based extended complexes (Mn6O2)-O-III(salox)(6)(EtOH)(4)(phda)](n)(saloxH(2))(n)(2H(2)O)(n) (1), (Mn6O2)-O-III(salox)(6)(MeOH)(5)(5-I-isoph)](n)(3MeOH)(n) (2), (Mn6O2)-O-III(salox)(6)(MeOH)(4)(H2O) (5-N-3-isoph)](n)(4MeOH)(n) (3) and (Mn3NaO)-Na-III(salox)(3)(MeOH)(4)(5-NO2-isoph)](n)(MeOH)(n) (H2O)(n) (4) salox=salicylaldoximate, phda=1,3-phenylenediacetate, isoph=isophthalate] have been synthesized under similar reaction conditions. Single crystal X-ray structures show that in 1, only one type of Mn-6 cluster is arranged in 1D, whereas in 2 and 3 there are two types of clusters, differing in the way the triangle units are joined and assembled. In complex4, however, the basic building structure is heteronuclear and based on Mn-3 units extended in 2D. Susceptibility measurements (dc and ac) over a wide range of temperatures and fields show that the complexes1, 2, and 3 behave as single molecule magnets (SMMs) with S=4ground state, while 4 is dominantly antiferromagnetic with a ground spin state S=2. Density functional theory calculations have been performed on model complexes to provide a qualitative theoretical interpretation for their overall magnetic behavior.

AIPE-active green phosphorescent iridium(III) complex impregnated test strips for the vapor-phase detection of 2,4,6-trinitrotoluene (TNT)

Detection of explosives, especially trinitrotoluene (TNT), is of utmost importance due to its highly explosive nature and environmental hazard. Therefore, detection of TNT has been a matter of great concern to the scientific community worldwide. Herein, a new aggregation-induced phosphorescent emission (AIPE)-active iridium(III) bis(2-(2,4-difluorophenyl)pyridinato-NC2') (2-(2-pyridyl)benzimidazolato-N,N') complex FIrPyBiz] has been developed and serves as a molecular probe for the detection of TNT in the vapor phase, solid phase, and aqueous media. In addition, phosphorescent test strips have been constructed by impregnating Whatman filter paper with aggregates of FIrPyBiz for trace detection of TNT in contact mode, with detection limits in nanograms, by taking advantage of the excited state interaction of AIPE-active phosphorescent iridium(III) complex with that of TNT and the associated photophysical properties.