Ternary copper(II) complexes of thiosemicarbazones and heterocyclic bases showing N3OS coordination as models for the type-2 centers of copper monooxygenases

Six ternary copper(II) complexes of general formulation [CuLB] (1-6), where L is dianionic ONS-donor thiosemicarbazones derived from the condensation of salicylaldehyde with thiosemicarbazides and B is NN-donor heterocyclic bases like 2,2'-bipyridine, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline, are prepared from a reaction of copper(II) acetate hydrate with the heterocyclic base (B) and the thiosemicarbazone (H2L) in MeOH, and structurally characterized by X-ray diffraction technique. Crystal structures of the complexes display a distorted square-pyramidal (4 + 1) coordination geometry having the ONS-donor thiosemicarbazone bonded at the basal plane. The chelating heterocyclic bases exhibit axial-equatorial mode of bonding. The complexes are one-electron paramagnetic and they show axial X-band EPR spectra in DMF-toluene glass at 77 K giving g(parallel to)(A(parallel to)) and g(perpendicular to) values of similar to2.2 (175 x 10(-4) cm(-1)) and similar to2.0 indicating a {d(x2-y2)}(1) ground state. The complexes show a d-d band near 570 nm and a charge transfer band near 400 nm in DMF. The complexes are redox active and exhibit a quasireversible Cu(II)-Cu(I) couple in DMF-0.1 M tetrabutylammonium perchlorate near 0.1 V vs. SCE. They are catalytically active in the oxidation of ascorbic acid in presence of dioxygen. The complexes with a CuN3OS coordination model the ascorbate oxidation property of dopamine beta-hydroxylase and peptidylglycine a-hydroxylating monooxygeanase. (C) 2003 Elsevier Science B.V. All rights reserved.

Ligand-modulated Parallel Mechanical Unfolding Pathways of Maltose-binding Proteins

Protein folding and unfolding are complex phenomena, and it is accepted that multidomain proteins generally follow multiple pathways. Maltose-binding protein (MBP) is a large (a two-domain, 370-amino acid residue) bacterial periplasmic protein involved in maltose uptake. Despite the large size, it has been shown to exhibit an apparent two-state equilibrium unfolding in bulk experiments. Single-molecule studies can uncover rare events that are masked by averaging in bulk studies. Here, we use single-molecule force spectroscopy to study the mechanical unfolding pathways of MBP and its precursor protein (preMBP) in the presence and absence of ligands. Our results show that MBP exhibits kinetic partitioning on mechanical stretching and unfolds via two parallel pathways: one of them involves a mechanically stable intermediate (path I) whereas the other is devoid of it (path II). The apoMBP unfolds via path I in 62% of the mechanical unfolding events, and the remaining 38% follow path II. In the case of maltose-bound MBP, the protein unfolds via the intermediate in 79% of the cases, the remaining 21% via path II. Similarly, on binding to maltotriose, a ligand whose binding strength with the polyprotein is similar to that of maltose, the occurrence of the intermediate is comparable (82% via path I) with that of maltose. The precursor protein preMBP also shows a similar behavior upon mechanical unfolding. The percentages of molecules unfolding via path I are 53% in the apo form and 68% and 72% upon binding to maltose and maltotriose, respectively, for preMBP. These observations demonstrate that ligand binding can modulate the mechanical unfolding pathways of proteins by a kinetic partitioning mechanism. This could be a general mechanism in the unfolding of other large two-domain ligand-binding proteins of the bacterial periplasmic space.

Synthesis and DNA binding studies of Ni(II), Co(II), Cu(II) and Zn(II) metal complexes of N(1),N(5)-bis[pyridine-2-methylene]-thiocarbohydrazone Schiff-base ligand

The thiocarbohydrazone Schiff-base ligand with a nitrogen and sulphur donor was synthesized through condensation of pyridine-2-carbaldehyde and thiocarbohydrazide. Schiff-base ligands have the ability to conjugate with metal salts. A series of metal complexes with a general formula [MCl(2)(H(2)L)]center dot nH(2)O (M=Ni, Co, Cu and Zn) were synthesized by forming complexes of the N(1),N5-bis[pyridine-2-methylene]thiocarbohydrazone (H2L) Schiff-base ligand. These metal complexes and ligand were characterized by using ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FT-IR), (1)H and (13)C NMR spectroscopy and mass spectroscopy, physicochemical characterization, CHNS and conductivity. The biological activity of the synthesized ligand was investigated by using Escherichia coli DNA as target. The DNA interaction of the synthesized ligand and complexes on E. coli plasmid DNA was investigated in the aqueous medium by UV-Vis spectroscopy and the binding constant (K(b)) was calculated. The DNA binding studies showed that the metal complexes had an improved interaction due to trans-geometrical isomers of the complexes than ligand isomers in cis-positions. (C) 2011 Elsevier B.V. All rights reserved.

A Single-Crystal Study Of The Defect Chemistry And Transport-Properties Of Silver Selenide, Ag2+Delta-Se

Electronic and ionic conductivities of silver selenide crystal (Ag$_2+\delta$ Se) have been measured over a range of stoichiometry through the $\alpha - \beta$ transition by using solid state electrochemical techniques. In the high temperature $\beta$-phase Ag$_2$Se shows metallic behaviour of electronic conductivity for high values of $\delta$; with decrease in $\delta$, the conductivity of the material exhibits a transition. The magnitude of change in electronic conductivity at the $\alpha - \beta$ transition is also determined by stoichiometry. Ionic conductivity of the $\beta$-phase does not vary significantly with stochiometry. Ionic conductivity of the $\beta$-does not vary significantly with stoichiometry. A model to explain the observed transport properties has been suggested.

Complexes of rare-earth perchlorates with ditbutyl amides of di, tri and tetraglycolic acids

New complexes of lanthanide perchlorates with di-t-butyl amides of di, tri and tetraglycolic acids have been synthesised. The complexes have the general formula Ln(DiGA)3(ClO4)3; Ln(TriGA)2 (ClO4)3 and Ln(TetGA)2 (C1O4)3, where Ln = La-Yb and Y and DiGA = N,N′, di-t-butyl diglycolamide, TriGA N,N′, di-t-butyl triglycolamide and TetGA = N,N′ di-t-butyl tetraglycolamide, respectively. The complexes have been characterized by analysis, electrolytic conductance, infrared,1H and13C nuclear magnetic resonance and electronic spectral data.Infrared spectra indicate the coordination of all the available ether oxygens and the amide carbonyls in each of the ligands, to the metal ions. IR and conductance data show that the perchlorate groups in all the complexes are ionic.1H and13C NMR data support the IR data regarding the mode of coordination of ligands to the metal ions. Electronic spectral shapes have been interpreted in terms of nine, eight and ten coordination in DiGA, TriGA and TetGA complexes respectively.

Fault-Tolerant Average Execution Time Optimization for General Purpose Multi-Processor System-on Chips

Fault-tolerance is due to the semiconductor technology development important, not only for safety-critical systems but also for general-purpose (non-safety critical) systems. However, instead of guaranteeing that deadlines always are met, it is for general-purpose systems important to minimize the average execution time (AET) while ensuring fault-tolerance. For a given job and a soft (transient) error probability, we define mathematical formulas for AET that includes bus communication overhead for both voting (active replication) and rollback-recovery with checkpointing (RRC). And, for a given multi-processor system-on-chip (MPSoC), we define integer linear programming (ILP) models that minimize AET including bus communication overhead when: (1) selecting the number of checkpoints when using RRC, (2) finding the number of processors and job-to-processor assignment when using voting, and (3) defining fault-tolerance scheme (voting or RRC) per job and defining its usage for each job. Experiments demonstrate significant savings in AET.

10 Years of Click Chemistry: Synthesis and Applications of Ferrocene-Derived Triazoles

Click chemistry has played a significant role as a rapid and versatile strategy for conjugating two molecular fragments under very mild reaction conditions. Introduction of ferrocene-derived triazole systems using click chemistry has attracted enormous interest in various fields due to its potential applications in electrochemical techniques for detection and sensing. The present discussion focuses on the synthesis of ferrocene-triazole and the importance of using a CuAAC reaction for such conjugation. Applications of ferrocene-based click reactions in conjugate chemistry, asymmetric catalysis, medicinal chemistry, host-guest interactions, and materials chemistry have been highlighted.

Shape and size mimicry in the design of ternary molecular solids: towards a robust strategy for crystal engineering

2- and 5-methylresorcinol form co-crystals with 4,4'-bipyridine in which some of the bipyridine molecules are loosely bound. These molecules can be replaced with other molecules of a similar shape and size to give a general method for the engineering of a ternary co-crystal.

Physical chemistry of mixed conducting zirconia ceramics

Suivant la pression partielle d'oxygène, la zircone peut être conducteur ionique ou électronique. Mise au point de méthodes de mesures de f.é.m. permettant de s'affranchir des sources d'erreur introduites par ces propriétés.

Physical chemistry of the reduction of calcium oxide with aluminium in vacuum

The physical chemistry of "aluminothermic" reduction of calcium oxide in vacuum is analyzed. Basic thermodynamic data required for the analysis have been generated by a variety of experiments. These include activity measurements in liquid AI-Ca alloys and determination of the Gibbs energies of formation of calcium aluminates. These data have been correlated with phase relations in the Ca-AI-0 system at 1373 K. The various stages of reduction, the end products and the corresponding equilibrium partial pressures of calcium have been established from thermodynamic considerations. In principle, the recovery of calcium can be improved by reducing the pressure in the reactor. However,, the cost of a high vacuum system and the enhanced time for reduction needed to achieve higher yields makes such a practice uneconomic. Aluminum contamination of calcium also increases at low pressures. The best compromise is to carry the reduction up to the stage where 3CaO-Al,O, is formed as the product. This corresponds to an equilibrium calcium partial pressure of 31.3 Pa at 1373 K and 91.6 Pa at 1460 K. Calcium can be extracted at this pressure using mechanical pumps in approximately 8 to 15 hr, depending on the size and the fill ratio of the retort and porosity of the charge briquettes.

Zircon Sand--a Viable Alternative Moulding System for Titanium Castings

The experimental observations of casting titanium in sodium silicate bonded zircon sand mould are presented in this paper. Metal-mould reactions, in general, involved dissolution of oxides in liquid titanium resulting in contamination of the casting. Minimal metal-mould reactions occurred when titanium was cast in zircon sand mould containing about 7.5 wt% of ZrO2. It has been further shown that the metal-mould reaction is considerably reduced if moulds were fired at high temperatures (> 1273K). This ensured elimination of moisture from the mould and also resulted in some beneficial changes in the mould chemistry. The reduction in metal-mould reaction is reflected in the decrease in oxygen and hydrogen contamination and decrease in hardness. Thus microhardness profile and oxygen analysis seems to provide a good index for evaluation of severity of metal-mould reaction. The method has been demonstrated to be satisfactory for casting titanium components.