A Histidine Aspartate Ionic Lock Gates the Iron Passage in Miniferritins from Mycobacterium smegmatis

Background: DNA-binding protein from starved cells (Dps) are nano-compartments that can oxidize and store iron rendering protection from free radicals. Results: A histidine-aspartate ionic cluster in mycobaterial Dps2 modulates the rate of iron entry and exit in these proteins. Conclusion: Substitutions that disrupt the cluster interface alter the iron uptake/release properties with localized structural changes. Significance: Identifying important gating residues can help in designing nano-delivery vehicles. Dps (DNA-binding protein from starved cells) are dodecameric assemblies belonging to the ferritin family that can bind DNA, carry out ferroxidation, and store iron in their shells. The ferritin-like trimeric pore harbors the channel for the entry and exit of iron. By representing the structure of Dps as a network we have identified a charge-driven interface formed by a histidine aspartate cluster at the pore interface unique to Mycobacterium smegmatis Dps protein, MsDps2. Site-directed mutagenesis was employed to generate mutants to disrupt the charged interactions. Kinetics of iron uptake/release of the wild type and mutants were compared. Crystal structures were solved at a resolution of 1.8-2.2 for the various mutants to compare structural alterations vis a vis the wild type protein. The substitutions at the pore interface resulted in alterations in the side chain conformations leading to an overall weakening of the interface network, especially in cases of substitutions that alter the charge at the pore interface. Contrary to earlier findings where conserved aspartate residues were found crucial for iron release, we propose here that in the case of MsDps2, it is the interplay of negative-positive potentials at the pore that enables proper functioning of the protein. In similar studies in ferritins, negative and positive patches near the iron exit pore were found to be important in iron uptake/release kinetics. The unique ionic cluster in MsDps2 makes it a suitable candidate to act as nano-delivery vehicle, as these gated pores can be manipulated to exhibit conformations allowing for slow or fast rates of iron release.

The Presence of Multiple Cellular Defects Associated with a Novel G50E Iron-Sulfur Cluster Scaffold Protein ( ISCU) Mutation Leads to Development of Mitochondrial Myopathy

Background: Muscle-specific deficiency of iron-sulfur (Fe-S) cluster scaffold protein (ISCU) leads to myopathy. Results: Cells carrying the myopathy-associated G50E ISCU mutation demonstrate impaired Fe-S cluster biogenesis and mitochondrial dysfunction. Conclusion: Reduced mitochondrial respiration as a result of diminished Fe-S cluster synthesis results in muscle weakness in myopathy patients. Significance: The molecular mechanism behind disease progression should provide invaluable information to combat ISCU myopathy. Iron-sulfur (Fe-S) clusters are versatile cofactors involved in regulating multiple physiological activities, including energy generation through cellular respiration. Initially, the Fe-S clusters are assembled on a conserved scaffold protein, iron-sulfur cluster scaffold protein (ISCU), in coordination with iron and sulfur donor proteins in human mitochondria. Loss of ISCU function leads to myopathy, characterized by muscle wasting and cardiac hypertrophy. In addition to the homozygous ISCU mutation (g.7044GC), compound heterozygous patients with severe myopathy have been identified to carry the c.149GA missense mutation converting the glycine 50 residue to glutamate. However, the physiological defects and molecular mechanism associated with G50E mutation have not been elucidated. In this report, we uncover mechanistic insights concerning how the G50E ISCU mutation in humans leads to the development of severe ISCU myopathy, using a human cell line and yeast as the model systems. The biochemical results highlight that the G50E mutation results in compromised interaction with the sulfur donor NFS1 and the J-protein HSCB, thus impairing the rate of Fe-S cluster synthesis. As a result, electron transport chain complexes show significant reduction in their redox properties, leading to loss of cellular respiration. Furthermore, the G50E mutant mitochondria display enhancement in iron level and reactive oxygen species, thereby causing oxidative stress leading to impairment in the mitochondrial functions. Thus, our findings provide compelling evidence that the respiration defect due to impaired biogenesis of Fe-S clusters in myopathy patients leads to manifestation of complex clinical symptoms.

Conducting polymer-carbon black nanocomposite sensor for volatile organic compounds and correlating sensor response by molecular dynamics

Volatile organic compounds (VOCs) are present in our every day used products such as plastics, cosmetics, air fresheners, paint, etc. The determination of amount of VOC present in atmosphere can be carried out via various sensors. In this work a nanocomposite of a novel thiophene based conducting polymer and carbon black is used as a volatile organic compound sensor. The fabricated 2 lead chemiresistor sensor was tested for vapours of toluene, acetone, cylcohexane, and carbon tetrachloride. The sensor responds to all the vapours, however, exhibit maximum response to toluene vapours. The sensor was evaluated for various concentrations of toluene. The lower limit of detection of the sensor is 15 +/- 10 ppm. The study of the effect of humidity on senor response to toluene showed that the response decreases at higher humidity conditions. The surface morphology of the nanocomposite was characterized by scanning electron microscopy. Diffuse reflectance spectroscopy was used to investigate the absorption of vapours by the nanocomposite film. Contact angle measurements were used to present the effect of water vapour on the toluene response of nanocomposite film. Solubility parameter of the conducting polymer is predicted by molecular dynamics. The sensing behaviour of the conducting polymer is correlated with solubility parameter of the polymer. Dispersion interaction of conducting polymer with toluene is believed to be the reason for the selective response towards toluene. (C) 2014 Elsevier B.V. All rights reserved.

Magnetism and superconductivity in Sb-doped binary and ternary iron chalcogenide single crystals

We report the single crystal growth of antimony doped Fe1+yTe and Fe1+yTe0.5Se0.5 (Fe1+ySbxTe1-x (x=0, 2%, 5%) and Fe1+yTe0.49Se0.49Sb0.02) by a modified horizontal Bridgman method. Growth parameters are optimized to obtain high quality single crystals. The antiferromagnetic (AFM) transition at T-N = 62.2 K which is a first order transition, shifts to lower temperature on doping in Fe1+yTe. Alternately when the chalcogen site of the ternary compound Fe1+yTe0.5Se0.5 is doped with Sb, superconductivity is preserved albeit the superconducting transition temperature (T-C) falls slightly and a concomitant reduction occurs in superconducting volume fraction. (C) 2013 Elsevier B.V. All rights reserved,

Phonon anomalies, orbital-ordering and electronic raman scattering in iron-pnictide Ca(Fe0.97Co0.03)(2)As-2: temperature-dependent Raman study

We report inelastic light scattering studies on Ca(Fe0.97Co0.03)(2)As-2 in a wide spectral range of 120-5200 cm(-1) from 5 to 300 K, covering the tetragonal to orthorhombic structural transition as well as magnetic transition at T-sm similar to 160 K. The mode frequencies of two first-order Raman modes B-1g and E-g, both involving the displacement of Fe atoms, show a sharp increase below T-sm. Concomitantly, the linewidths of all the first-order Raman modes show anomalous broadening below T-sm, attributed to strong spin-phonon coupling. The high frequency modes observed between 400 and 1200 cm(-1) are attributed to electronic Raman scattering involving the crystal field levels of d-orbitals of Fe2+. The splitting between xz and yz d-orbital levels is shown to be similar to 25 meV, which increases as temperature decreases below T-sm. A broad Raman band observed at similar to 3200 cm(-1) is assigned to two-magnon excitation of the itinerant Fe 3d antiferromagnet.

Iron(III) Catecholates for Cellular Imaging and Photocytotoxicity in Red Light

Iron(III) complexes Fe(L)(L') (NO3)]-in which L is phenyl-N, N-bis(pyridin-2-yl) methyl]methanamine (1), (anthracen-9-yl)N, N-bis(pyridin-2-yl) methyl] methanamine (2), (pyreny-1-yl)-N, N-bis(pyridin- 2-yl) methyl] methanamine (3-5), and L' is catecholate (1-3), 4-tert-butyl catecholate (4), and 4-(2-aminoethyl)benzene- 1,2-diolate (5)-were synthesized and their photocytotoxic proper-ties examined. The five electron-paramagnetic complexes displayed a FeIII/ Fe-II redox couple near similar to 0.4 V versus a saturated calomel electrode (SCE) in DMF/0.1m tetrabutylammonium perchlorate (TBAP). They showed unpre-cedented photocytotoxicity in red light (600-720 nm) to give IC50-15 mm in various cell lines by means of apoptosis to generate reactive oxygen species. They were ingested in the nucleus of HeLa and HaCaT cells in 4 h, thereby interacting favorably with calf thymus (ct)-DNA and photocleaving pUC19 DNA in red light of 785 nm to form hydroxyl radicals.

Hetero-tri-spin 2p-3d-4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo-Ligands: Synthesis, Structure, and Magnetic Properties

Employing nitronyl nitroxide lanthanide(III) complexes as metallo-ligands allowed the efficient and highly selective preparation of three series of unprecedented heterotri-spin (Cu Ln-radical) one-dimensional compounds. These 2p-3d-4f spin systems, namely Ln(3)Cu(hfac)II(NitPhOAII)41 (Ln(III)=Gd 1(Gd), Tb 1(Tb), Dy 1(Dy); NitPhOAII=2-(4'-allyloxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3- oxide), Ln(3)Cu(hfac)II(NitPhOPO4] (1-nrn=Gd 2Gd, Tb 2Tb, Dy 2(Dy), Ho 2HOf Yb 2yb; NitPhOPr= 2-(4'-propoxyphenyI)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) and Ln3Cu(hfac)II(NitPhOB441 (LnIm=Gd 3Gd, Tb 3Tb, Dy 3(Dy); NitPhOBz=2-(4'-benzyloxy- phenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) involve O-bound nitronyl nitroxide radicals as bridging ligands in chain structures with a Cu-Nit-Ln-Nit-Ln-Nit-Ln-Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal radical interactions take place in these heterotri-spin chain complexes, these and the next-neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single-chain magnet behavior.

Iron-carbon hybrid capacitor: A proof-of-concept study

In the present study, cost-intensive Ni electrode is replaced by high surface-area activated carbon (AC) cathode and the possibility of the Fe anode, used in Ni-Fe battery, to function as Fe-C hybrid capacitor has been examined. The electrochemical properties of Fe-C hybrid capacitor assembly are studied using cyclic voltammetry (CV) and galvanostatic charge-discharge cycles. Over 100 galvanostatic charge-discharge cycles for Fe-C hybrid capacitor are carried out and a maximum capacitance of 24 F g(-1) is observed.

Low temperature magnetoresistance and magnetization studies of iron encapsulated multiwall carbon nanotube/polyvinyl chloride composites

We present the experimental results of temperature dependent magnetoresistance (MR) and the magnetization studies of iron encapsulated multiwall carbon nanotube (MWCNT)/polyvinyl chloride (PVC) composites with different wt% of MWCNTs. Transmission electron microscopy characterization shows that MWCNTs are encapsulated with rod-shaped iron nanoparticles of aspect ratio of similar to 3. The MR behavior of 1.9 wt% MWCNT/PVC sample shows dominance of forward scattering and wave function shrinkage whereas, weak localization and electron-electron interactions explain the MR data of higher wt% samples (9.1, 16.6 and 44.4 wt%). The composites of 4.7 and 9.1 wt% exhibit ferromagnetic behavior at all temperatures with room temperature coercivities of similar to 1036 and 628 Oe, respectively. (C) 2014 Elsevier Ltd. All rights reserved.

Structural, magnetic and electrochemical investigation of novel binary Na2-x(Fe1-yMny)P2O7 (0 <= y <= 1) pyrophosphate compounds for rechargeable sodium-ion batteries

Pyrophosphate cathodes have been recently reported as a competent family of insertion compounds for sodium-ion batteries. In the current study, we have investigated the binary Na2 - x(Fe1 - yMny)P2O7 (0 <= y <= 1) pyrophosphate family, synthesized by the classical solid-state method. They form a continuous solid solution maintaining triclinic P-1 (#2) symmetry. The local structural coordination differs mainly by different degrees of Na site occupancy and preferential occupation of the Fe2 site by Mn. The structural and magnetic properties of these mixed-metal pyrophosphate phases have been studied. In each case, complete Fe3+/Fe2+ redox activity has been obtained centered at 3 V vs. Na. The Fe3+/Fe2+ redox process involves multiple steps between 2.5 and 3 V owing to Na-cation ordering during electrochemical cycling, which merge to form a broad single Fe3+/Fe2+ redox peak upon progressive Mn-doping. (C) 2014 Elsevier B.V. All rights reserved.

Morphological Evolution in Air-Stable Metallic Iron Nanostructures and Their Magnetic Study

Iron nanostructures with morphology ranging from discrete nanoparticles to nearly monodisperse hierarchical nanostructures have been successfully synthesized using solvated metal atom dispersion (SMAD) method. Such a morphological evolution was realized by tuning the molar ratio of ligand to metal. Surface energy minimization in confluence with strong magnetic interactions and ligand-based stabilization results in the formation of nanospheres of iron. The as-prepared amorphous iron nanostructures exhibit remarkably high coercivity in comparison to the discrete nanoparticles and bulk counterpart. Annealing the as-prepared amorphous Fe nanostructures under anaerobic conditions affords air-stable carbon-encapsulated Fe(0) and Fe3C nanostructures with retention of the morphology. The resulting nanostructures were thoroughly analyzed by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and Raman spectroscopy. TGA brought out that Fe3C nanostructures are more robust toward oxidation than those of a-Fe. Finally, detailed magnetic studies were carried out by superconducting quantum interference device (SQUID) magnetometer and it was found that the magnetic properties remain conserved even upon exposure of the annealed samples to ambient conditions for months.

High Proton Mobility, Solvent Induced Single Crystal to Single Crystal Structural Transformation, and Related Studies on a Family of Compounds Formed from Mn-3 Oxo-Clusters

The reaction between 4,4'-sulfonyldibenzoic acid (H(2)SDBA) and manganese under mild conditions resulted in the isolation of two new three-dimensional compounds, Mn-4(C14H8O6S)(4)(DMA)(2)]center dot 3DMA, I, and Mn-3(C14H8O6S)(3)(DMA)(2)(MeOH)]center dot DMA, IIa. Both structures have Mn-3 trimer oxo cluster units. While the Mn-3 oxoclusters are connected through octahedral manganese forming one-dimensional Mn-O-Mn chains in I, the Mn-3 units are isolated in IIa. The SDBA units connect the Mn-O-Mn chains and the Mn-3 clusters giving rise to the three-dimensional structure. Both compounds have coordinated and free solvent molecules. In IIa, two different solvent molecules are coordinated, of which one solvent can be reversibly exchanged by a variety of other similar solvents via a solvent-mediated single crystal to single crystal (SCSC) transformation. The free lattice DMA solvent molecules in I can be exchanged by water molecules resulting in hydrophilic channels. Proton conductivity studies on I reveals a high proton mobility with conductivity values of similar to 0.87 x 10(-3) Omega(-1) cm(-1) at 34 degrees C and 98% RH, which is comparable to some of the good proton conductivity values observed in inorganic coordination polymers. We have also shown structural transformation of I to IIa through a possible dissolution and recrystallization pathway. In addition, both I and IIa appear to transform to two other manganese compounds H3O]Mn-3(mu(3)-OH)(C14H8O6S)(3)(H2O)](DMF)(5) and H3O](2)Mn-7(mu 3-OH)(4)(C14H8O6S)(6)(H2O)(4)](H2O)(2)(DMF)(8) under suitable reaction conditions. We have partially substituted Co in place of Mn in the Mn-3 trimer clusters forming CoMn2(C14H8O6S)(3)(DMA)(2)(EtOH)]center dot DMA, III, a structure that is closely related to IIa. All the compounds reveal antiferromagnetic behavior. On heating, the cobalt substituted phase (compound III) forms a CoMn2O4 spinel phase with particle sizes in the nanometer range.

Facile green fabrication of iron-doped cubic ZrO2 nanoparticles by Phyllanthus acidus: Structural, photocatalytic and photoluminescent properties

Cubic ZrO2: Fe3+ (0.5-4 mol%) nanoparticles (NPs) were synthesized via bin-inspired, inexpensive and simple route using Phyllanthus acidus as fuel. PXRD, SEM, TEM, FTIR, UV absorption and PL studies were performed to ascertain the formation of NPs. Rietveld analysis confirmed the formation of cubic structure. The influence of Fe3+ on the structure, morphology, UV absorption, PL emission and photocatalytic activity of NPs were investigated. The CIE chromaticity coordinates (0.36, 0.41) show that NPs could be a promising candidate for white LEDs. The influence of Fe3+ on ZrO2 matrix for photocatalytic degradation of AO7 was evaluated under UVA and Sunlight irradiation. The enhanced photocatalytic activity of spherical shaped ZrO2: Fe3+ (2 mol%) under UVA light was attributed to dopant concentration, crystallite size, narrow band gap, textural properties and capability for reducing the electron-hole pair recombination. The trend of inhibitory effect in the presence of different radical scavengers were followed the order SO42- > Cl- > C2H5OH > HCO3- > CO32-. The recycling catalytic ability of the ZrO2: Fe3+ (2 mol%) was also evaluated with a negligible decrease in the degradation efficiency even after the sixth successive run. (C) 2014 Elsevier B.V. All rights reserved.

Effect of lateral substituent and chain length on mesomorphic properties of novel alkoxy benzyloxy benzoates of cyanophenyl rod-shaped compounds

Three novel homologous series of rod-shaped cyanophenyl alkoxy benzoate liquid crystalline compounds with lateral polar fluorine and chlorine substituent were prepared, and chemical structures of novel materials have been characterized by standard spectral technique and elemental analysis. The mesophase characterization was carried out using the combination of polarized optical microscopy and differential scanning calorimetry. All the compounds exhibit wide thermal range of enantiotropic SmA phase.

Significant photocytotoxic effect of an iron(III) complex of a Schiff base ligand derived from vitamin B-6 and thiosemicarbazide in visible light

Iron(III)-Schiff base complexes, namely, Fe(tsc-py)(2)](NO3) (1), Fe(tsc-acpy)(2)](NO3) (2) and Fe(tsc-VB6)(2)](NO3) (3), where tsc-py, tsc-acpy and tsc-VB6 are the respective Schiff bases derived from thiosemicarbazide (tsc) and pyridine-2-aldehyde (tsc-py), 2-acetyl pyridine (tsc-acpy) and vitamin B-6 (pyridoxal, tsc-VB6), have been prepared, structurally characterized and their photocytotoxicity studied in cancer HeLa cells. The single crystal X-ray structures of the complexes 1 and 2 show a distorted octahedral geometry formed by the FeN4S2 core. The low-spin and 1 : 1 electrolytic complexes display a broad absorption band in the visible region. Complexes 1 and 2, without any VB6 moiety are not cytotoxic under light or dark conditions. Complex 3 is significantly photocytotoxic under visible light of 400-700 nm giving an IC50 value of 22.5 mu M in HeLa cells with no dark toxicity (IC50 > 100 mu M). The photo-induced cell death is attributable to apoptotic pathways involving photo-assisted generation of intracellular ROS. The observed photocytotoxicity of complex 3 could be the result of its better photosensitizing property combined with its enhanced uptake into cancer cells via a VB6 transporting membrane carrier (VTC) mediated diffusion pathway due to the presence of the VB6 moiety compared to the two non-vitamin B-6 analogues, complexes 1 and 2.