Novel tetranuclear distorted open-cubane copper complex containing oximate bridges: Synthesis, crystal structure, DNA binding and cleavage activity

The synthesis, molecular structure, DNA binding and nuclease activity of Cu4O4 open-cubane tetranuclear copper(II) complex with 3-2-(ethyl amino)ethyl]imino]-2-butanoneoxime (HL) are reported for the first time. The neutral tetranuclear Cu4L4(ClO4)(4)] complex crystallizes in tetragonal space group P (4) over bar2(1)c with the unit cell parameters; a = 13.798(4) angstrom, b = 13.798(4) angstrom, c = 14.119(6) angstrom, V = 2688(16) angstrom(3), Z = 8, R = 0.0636. Symmetrically equivalent copper atoms exhibit a CuN3O3 elongated distorted octahedral coordination environment, with three nitrogen atoms of the L ligand and one oxime-oxygen atom of second L ligand at equatorial positions, one oxime-oxygen atom of the third L ligand and perchlorate oxygen at axial positions. The complex shows quasireversible cyclic voltammetric response at 0.805 V (Delta E-p = 277 mV) at 100 mV s (1) in DMF for the Cu(II)/Cu(I) redox couple. The binding study of the complex with calf-thymus DNA has been investigated using absorption spectrophotometry. The complex shows strong nuclease activity on stranded pBR 322 plasmid DNA in the presence of hydrogen peroxide and marginal nuclease activity in the presence of reducing agent (dithiothreitol). (C) 2012 Elsevier B. V. All rights reserved.

Cloning, expression, purification, and biochemical characterisation of the FIC motif containing protein of Mycobacterium tuberculosis

The role of FIC (Filamentation induced by cAMP)(2) domain containing proteins in the regulation of many vital pathways, mostly through the transfer of NMPs from NTPs to specific target proteins (NMPylation), in microorganisms, higher eukaryotes, and plants is emerging. The identity and function of FIC domain containing protein of the human pathogen, Mycobacterium tuberculosis, remains unknown. In this regard, M. tuberculosis fic gene (Mtfic) was cloned, overexpressed, and purified to homogeneity for its biochemical characterisation. It has the characteristic FIC motif, HPFREGNGRSTR (HPFxxGNGRxxR), spanning 144th to 155th residue. Neither the His-tagged nor the GST-tagged MtFic protein, overexpressed in Escherichia coil, nor expression of Mtfic in Mycobacterium smegmatis, yielded the protein in the soluble fraction. However, the maltose binding protein (MBP) tagged MtFic (MBP-MtFic) could be obtained partly in the soluble fraction. The cloned, overexpressed, and purified recombinant MBP-MtFic showed conversion of ATP, GTP, CTP, and UTP into AMP. GMP, CMP, and UMP, respectively. Sequence alignment with several FIC motif containing proteins, complemented with homology modeling on the FIC motif containing protein, VbhT of Bartonella schoenbuchensis as the template, showed conservation and interaction of residues constituting the FIC domain. Site-specific mutagenesis of the His144, or Glu148, or Asn150 of the FIC motif, or of Arg87 residue that constitutes the FIC domain, or complete deletion of the FIC motif, abolished the NTP to NMP conversion activity. The design of NMP formation assay using the recombinant, soluble MtFic would enable identification of its target substrate for NMPylation. (C) 2012 Elsevier Inc. All rights reserved.

An EQCM investigation of capacitance of MnO2 in electrolytes containing multivalent cations

MnO2 is electrochemically deposited on Au coated quartz crystal to study the electrochemical capacitance properties and to monitor the mass variations that accompany reversible adsorption/desorption of Na+, Mg2+ and La3+ ions during discharge/charge cycling. There is an increase in the values of specific capacitance of MnO2 with increase in charge of the cation in the electrolyte. Also, there is an increase in mass during discharge due to adsorption of cations from the electrolyte resulting from reduction of MnO2. Mass decreases during charging process due to desorption of cations. The magnitude of mass variation is approximately proportional to the atomic weight of the cationic element. (C) 2012 Elsevier B.V. All rights reserved.

The Structural Characterization of Folded Peptides Containing the Conformationally Constrained beta-Amino Acid Residue beta(2,2)Ac(6)c

Backbone alkylation has been shown to result in a dramatic reduction in the conformational space that is sterically accessible to a-amino acid residues in peptides. By extension, the presence of geminal dialkyl substituents at backbone atoms also restricts available conformational space for beta and ? residues. Five peptides containing the achiral beta 2,2-disubstituted beta-amino acid residue, 1-(aminomethyl)cyclohexanecarboxylic acid (beta 2,2Ac6c), have been structurally characterized in crystals by X-ray diffraction. The tripeptide Boc-Aib-beta 2,2Ac6c-Aib-OMe (1) adopts a novel fold stabilized by two intramolecular H-bonds (C11 and C9) of opposite directionality. The tetrapeptide Boc-Aib-beta 2,2Ac6c]2-OMe (2) and pentapeptide Boc-Aib-beta 2,2Ac6c]2-Aib-OMe (3) form short stretches of a hybrid a beta C11 helix stabilized by two and three intramolecular H-bonds, respectively. The structure of the dipeptide Boc-Aib-beta 2,2Ac6c-OMe (5) does not reveal any intramolecular H-bond. The aggregation pattern in the crystal provides an example of an extended conformation of the beta 2,2Ac6c residue, forming a polar sheet like H-bond. The protected derivative Ac-beta 2,2Ac6c-NHMe (4) adopts a locally folded gauche conformation about the C beta?Ca bonds (?=-55.7 degrees). Of the seven examples of beta 2,2Ac6c residues reported here, six adopt gauche conformations, a feature which promotes local folding when incorporated into peptides. A comparison between the conformational properties of beta 2,2Ac6c and beta 3,3Ac6c residues, in peptides, is presented. Backbone torsional parameters of H-bonded a beta/beta a turns are derived from the structures presented in this study and earlier reports.

Fabrication and characterization of micro-arc oxidized fluoride containing titania films on Cp Ti

The present study is focussed at establishing an appropriate electrolyte system for developing electrochemically stable and fluorine (F) containing titania (F-TiO2) films on Cp Ti by micro-arc oxidation (MAO) technique. To fabricate the F-TiO2 films on Cp Ti, different electrolyte solutions of chosen concentrations of tri-sodium orthophosphate (TSOP, Na3PO4 center dot I2H2O), potassium hydroxide (KOH) and various F-containing compounds such as ammonium fluoride (NH4F), potassium fluoride (KF), sodium fluoride (NaF) and potassium fluorotitanate (K2TiF6) are employed. The structural and morphological characteristics, thickness and elemental composition of the developed films have been assessed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The in-vitro electrochemical corrosion behavior of the films was studied under Kokubo simulated body fluid (SBF) environment by potentiodynamic polarization, long term potential measurement and electrochemical impedance spectroscopy (EIS) methods. The XRD and SEM-EDS results show that the rutile content in the films vary in the range of 15-37 wt% and the F and P contents in the films is found to be in the range of 2-3 at% and 2.9-4.7 at% respectively, suggesting that the anatase to rutile phase transformation and the incorporation of F and P into the films are significantly controlled by the respective electrolyte solution. The SEM elemental mapping results show that the electrolyte borne F and P elements are incorporated and distributed uniformly in all the films. Among all the films under study, the film developed with 5 g TSOP+2 g KOH+3 g K2TiF6 electrolyte system exhibits considerably improved in-vitro corrosion resistance and therefore best suited for biomedical applications. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Clay mineral liner system for leachates containing organic contaminants

A conventional liner with a good performance against inorganic contaminants with a minimal hydraulic conductivity does not usually perform well for retention/removal of leachates containing organic contaminants. Organic modification of clay can render the naturally organophobic clay tobe organophilic. Incorporation of modified organo clay along with unmodified inorganic clay in liner systems can overcome the inherent incompatibility of conventional liners to organic contaminants and can increase organic sorption. The performance of commercially available organo clay and natural bentonite and mixtures of them in different pore fluids has been studied. It is found that the properties of mixtures improve with increase in organically modified clay particularly in non aqueous fluids from the considerations of liner application.

Crystal-structure analysis of cis-X-pro-containing peptidomimetics: understanding the steric interactions at cis X-pro amide bonds

Catch the twist: The cis Piv-Pro conformer (Piv=pivaloyl) of peptides is no longer inaccessible. Any cis X-Pro tertiary-amide-bond conformer can be stabilized in crystals of peptides by accommodating the unavoidable distortion of the dihedral angle of the peptide bond to the carbonyl group of the Pro residue (see picture), in this case through ni−1→πi* interactions. Steric clashes were not observed in the cis Piv-Pro rotamers studied.

A new approach for understanding ion transport in glasses; example of complex alkali diborate glasses containing lead, bismuth and tellurium oxides

Mechanism of ion transport in glasses continues to be incompletely understood. Several of the theoretical models in vogue fail to rationalize conductivity behaviour when d.c. and a.c. measurements are considered together. While they seem to involve the presence of at least two components in d.c. activation energy, experiments fail to reveal that feature. Further, only minor importance is given to the influence of structure of the glass on the ionic conductivity behaviour. In this paper, we have examined several general aspects of ion transport taking the example of ionically conducting glasses in pseudo binary, yNa(2)B(4)O(7)center dot(1-y) M (a) O (b) (with y = 0 center dot 25-0 center dot 79 and M (a) O (b) = PbO, TeO2 and Bi2O3) system of glasses which have also been recently characterized. Ion transport in them has been studied in detail. We have proposed that non-bridging oxygen (NBO) participation is crucial to the understanding of the observed conductivity behaviour. NBO-BO switching is projected as the first important step in ion transport and alkali ion jump is a subsequent event with a characteristically lower barrier which is, therefore, not observed in any study. All important observations in d.c. and a.c. transport in glasses are found consistent with this model.

Mechanical properties of a metal-organic framework containing hydrogen-bonded bifluoride linkers

We report the mechanical properties of a framework structure, Cu2F(HF)(HF2)(pyz)(4)](SbF6)(2)](n) (pyz = pyrazine), in which Cu(pyz)(2)](2+) layers are pillared by HF2- anions containing the exceptionally strong F-H center dot center dot center dot F hydrogen bonds. Nanoindentation studies on single-crystals clearly demonstrate that such bonds are extremely robust and mechanically comparable with coordination bonds in this system.

Fine scale characterization of surface/subsurface and nanosized debris particles on worn Cu-10 % Pb nanocomposites

The identification of the damage mechanisms involved in the wear process demands the finer scale characterization of the surface, as well as the subsurface region of the wear scar region, and to this end, this article discusses the results obtained with Cu-10 wt% Pb-based metallic nanocomposites using a host of characterization techniques, including transmission electron microscopy and ion milling microscopy. Apart from finer scale characterization to understand deformation and cracking during the wear process, X-ray photoelectron spectroscopy analysis of wear debris confirms the occurrence of oxidation of Pb phase to Pb3O4. In order to understand the role of oxides on friction and wear, sliding wear tests in argon were also carried out and such tests did not result in the formation of any tribo-oxides, as confirmed using electron probe microanalysis. Conclusively, oxidative wear is attributed as the dominant wear mechanism in ambient conditions for Cu-10 wt% Pb composite.

Densification kinetics, phase assemblage and hardness of spark plasma sintered Cu-10 wt% TiB2 and Cu-10 wt% TiB2-10 wt% Pb composites

The present work demonstrates the synthesis of Cu-10 wt% TiB2 composites with a theoretical density of more than 90% by tailoring the spark plasma sintering (SPS) conditions in the temperature range of 400-700 degrees C. Interestingly, 10 wt% Pb addition to Cu-10 wt% TiB2 lowers the sinter density and the difference in the densification behavior of the investigated compositions was discussed in reference to the current profile recorded during a SPS cycle. The sintering kinetics and phase assemblage were also discussed in reference to surface melting of the constituents prior to bulk melting temperature, temperature dependent wettability of Pb on Cu, diffusion kinetics of Cu as well as the formation of various oxides. An important result is that a high hardness of around 2 GPa and relative density close to 92% qtheoretical was achieved for the Cu-10 wt% TiB2-10 wt% Pb composite, and such a combination has never been achieved before using any conventional processing route.

Ion transport studies in lithium phospho-molybdate glasses containing Cl- ion

Ion conducting glasses in xLiCl-20Li(2)O-(80-x) 0.80P(2)O(5)-0.20MoO(3)] glass system have been prepared over a wide range of composition (X = 5, 10, 15, 20 and 25 mol%). The electrical conductivity and dielectric relaxation of these glasses were analyzed using impedance spectroscopy in the frequency range of 10 Hz-10 MHz and in the temperature range of 313-353 K. D.c. activation energies extracted from Arrhenius plots using regression analysis, decreases with increasing LiCl mol%. A.c. conductivity data has been fitted to both single and double power law equation with both fixed and variable parameters. The increased conductivity in the present glass system has been correlated with the volume increasing effect and the coordination changes that occur due to structural modification resulting in the creation of non-bridging oxygens (NBO's) of the type O-Mo-O- bonds in the glass network. Dielectric relaxation mechanism in these glasses is analyzed using Kohlrausch-Williams-Watts (KWW) stretched exponential function and stretched exponent (beta) is found to be insensitive to temperature.

On the densification mechanisms and properties of Cu-Pb and Cu-Pb-TiB2 nanocomposites densified using spark plasma sintering

The present paper is aimed to understand the sub-processes triggered by rapid heating during spark plasma sintering as well as to assess the extent to which densification and properties of metallic materials can be enhanced using such superfast consolidation process. Using nanocrystalline Cu-Pb as a model system, the influence of Pb as well as TiB2 addition on the densification mechanisms and properties are discussed. Importantly, a high hardness of 2 GPa is achieved in Cu-based nanocomposites. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Stable hybrid containing haploid genomes of two obligate diploid Candida species

Candida albicans and Candida dubliniensis are diploid, predominantly asexual human-pathogenic yeasts. In this study, we constructed tetraploid (4n) strains of C. albicans of the same or different lineages by spheroplast fusion. Induction of chromosome loss in the tetraploid C. albicans generated diploid or near-diploid progeny strains but did not produce any haploid progeny. We also constructed stable heterotetraploid somatic hybrid strains (2n + 2n) of C. albicans and C. dubliniensis by spheroplast fusion. Heterodiploid (n + n) progeny hybrids were obtained after inducing chromosome loss in a stable heterotetraploid hybrid. To identify a subset of hybrid heterodiploid progeny strains carrying at least one copy of all chromosomes of both species, unique centromere sequences of various chromosomes of each species were used as markers in PCR analysis. The reduction of chromosome content was confirmed by a comparative genome hybridization (CGH) assay. The hybrid strains were found to be stably propagated. Chromatin immunoprecipitation (ChIP) assays with antibodies against centromere-specific histones (C. albicans Cse4/C. dubliniensis Cse4) revealed that the centromere identity of chromosomes of each species is maintained in the hybrid genomes of the heterotetraploid and heterodiploid strains. Thus, our results suggest that the diploid genome content is not obligatory for the survival of either C. albicans or C. dubliniensis. In keeping with the recent discovery of the existence of haploid C. albicans strains, the heterodiploid strains of our study can be excellent tools for further species-specific genome elimination, yielding true haploid progeny of C. albicans or C. dubliniensis in future.

Graphene composites containing chemically bonded metal oxides

Composites of graphene involving chemically bonded nano films of metal oxides have been prepared by reacting graphene containing surface oxygen functionalities with metal halide vapours followed by exposure to water vapour. The composites have been characterized by electron microscopy, atomic force microscopy and other techniques. Magnetite particles chemically bonded to graphene dispersible in various solvents have been prepared and they exhibit fairly high magnetization.