Influence of steric effect on the structural aspects of N,N `,N `'-triarylguanidine derived six-membered C,N] palladacycles

Guanidine derived six-membered C,N] palladacycles of the types (C,N)Pd(mu-OC(O)R)](2) (1a-d), (C,N)Pd(mu-Br)](2) (2a,b), cis-(C,N)PdBr(L)] (3a-d, 4, and 5), and ring contracted guanidine derived five-membered C,N] palladacycle, (C,N)PdBr(C NXy)] (6) were prepared in high yield following the established methods with a view aimed at understanding the influence of the substituents on the aryl rings of the guanidine upon the solid state structure and solution behaviour of palladacycles. Palladacycles were characterised by microanalytical, IR, NMR and mass spectral data. The molecular structures of 1a, 1c, 2a, 2b, 3a, 3c, 3d, and 4-6 were determined by single crystal X-ray diffraction data. Palladacycles 1a and 1c were shown to exist as a dimer in transoid in-in conformation in the solid state but as a mixture of a dimer in major proportion and a monomer (kappa(2)-O,O'-OAc) in solution as deduced from H-1 NMR data. Palladacycles 2a and 2b were shown to exist as a dimer in transoid conformation in the solid state but the former was shown to exist as a mixture of a dimer and presumably a trimer in solution as revealed by a variable temperature H-1 NMR data in conjunction with ESI-MS data. The cis configuration around the palladium atom in 3a, 3c, and 3d was ascribed to steric influence of the aryl moiety of =NAr unit and that in 4-6 was ascribed to antisymbiosis. The solution behaviour of 3d was studied by a variable concentration (VC) H-1 NMR data.

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.

Probing hemoglobin confinement inside submicron silica tubes using synchrotron SAXS and electrochemical response

The configuration of hemoglobin in solution and confined inside silica nanotubes has been studied using synchrotron small angle X-ray scattering and electrochemical activity. Confinement inside submicron tubes of silica aid in preventing protein aggregation, which is vividly observed for unconfined protein in solution. The radius of gyration (R-g) and size polydispersity (p) of confined hemoglobin was found to be lower than that in solution. This was also recently demonstrated in case of confined hemoglobin inside layered polymer capsules. The confined hemoglobin displayed a higher thermal stability with Rg and p showing negligible changes in the temperature range 25-75 degrees C. The differences in configuration between the confined and unconfined protein were reflected in their electrochemical activity. Reversible electrochemical response (from cyclic voltammograms) obtained in case of the confined hemoglobin, in contrary to the observance of only a cathodic response for the unconfined protein, gave direct indication of the differences between the residences of the electroactive heme center in a different orientation compared to that in solution state. The confined Hb showed loss of reversibility only at higher temperatures. The electron transfer coefficient (alpha) and electron transfer rate constant (k(s)) were also different, providing additional evidence regarding structural differences between the unconfined and confined states of hemoglobin. Thus, absence of any adverse effects due to confinement of proteins inside the inorganic matrices such as silica nanotubes opens up new prospects for utilizing inorganic matrices as protein ``encapsulators'', as well as sensors at varying temperatures.

Photoelectrochemical oxidation of p-nitrophenol on an expanded graphite-TiO2 electrode

In the quest for more efficient photoanodes in the photoelectrochemical oxidation processes for organic pollutant degradation and mineralisation in water treatment, we present the synthesis, characterisation and photoelectrochemical application of expanded graphite-TiO2 composite (EG-TiO2) prepared using the sol-gel method with organically modified silicate. The Brunauer-Emmett-Teller surface area analyser, ultraviolet-visible diffuse reflectance, scanning electron microscopy, energy dispersive spectroscopy, X-ray diffractometry, Raman spectrometry and X-ray photoelectron spectroscopy were employed for the characterisation of the composites. The applicability of the EG-TiO2 as photoanode material was investigated by the photoelectrochemical degradation of p-nitrophenol as a target pollutant in a 0.1 M Na2SO4 (pH 7) solution at a current density of 5 mA cm(-2). After optimising the TiO2 loading, initial p-nitrophenol concentration, pH and current density, a removal efficiency of 62% with an apparent kinetic rate constant of 10.4 x 10(-3) min(-1) was obtained for the photoelectrochemical process as compared to electrochemical oxidation and photolysis, where removal efficiencies of 6% and 24% were obtained respectively after 90 min. Furthermore, the EG-TiO2 electrode was able to withstand high current density due to its high stability. The EG-TiO2 electrode was also used to degrade 0.3 x 10(-4) M methylene blue and 0.1 x 10(-4) M Eosin Yellowish, leading to 94% and 47% removal efficiency within 120 reaction time. This confirms the suitability of the EG-TiO2 electrode to degrade other organic pollutants.

Exploring the color of transition metal ions in irregular coordination geometries: new colored inorganic oxides based on the spiroffite structure, Zn2-xMxTe3O8 (M = Co, Ni, Cu)

We describe the synthesis, crystal structures, and optical absorption spectra of transition metal substituted spiroffite derivatives, Zn2-xMxTe3O8 (M-II = Co, Ni, Cu; 0 < x <= 1.0). The oxides are readily synthesized by solid state reaction of stoichiometric mixtures of the constituent binaries at 620 degrees C. Reitveld refinement of the crystal structures from powder X-ray diffraction (XRD) data shows that the Zn/MO6 octahedra are strongly distorted, as in the parent Zn2Te3O8 structure, consisting of five relatively short Zn/M-II-O bonds (1.898-2.236 angstrom) and one longer Zn/M-II-O bond (2.356-2.519 angstrom). We have interpreted the unique colors and the optical absorption/diffuse reflectance spectra of Zn2-xMxTe3O8 in the visible, in terms of the observed/irregular coordination geometry of the Zn/M-II-O chromophores. We could not however prepare the fully substituted M2Te3O8 (M-II = Co, Ni, Cu) by the direct solid state reaction method. Density Functional Theory (DFT) modeling of the electronic structure of both the parent and the transition metal substituted derivatives provides new insights into the bonding and the role of transition metals toward the origin of color in these materials. We believe that transition metal substituted spiroffites Zn2-xMxTe3O8 reported here suggest new directions for the development of colored inorganic materials/pigments featuring irregular/distorted oxygen coordination polyhedra around transition metal ions.

Pristine nanomaterials: synthesis, stability and applications

Capping-free and linker-free nanostructures/hybrids possess superior properties due to the presence of pristine surfaces and interfaces. In this review, various methods for synthesizing pristine nanomaterials are presented along with the general principles involved in their morphology control. In wet chemical synthesis, the interplay between various reaction parameters results in diverse morphology. The fundamental principles behind the evolution of morphology including nanoporous aggregates of metals and other inorganic materials, 2D nanocrystals of metals is elucidated by capping-free methods in aqueous medium. In addition, strategies leading to the attachment of bare noble metal nanoparticles to functional oxide supports/reduced graphene oxide has been demonstrated which can serve as a simple solution for obtaining thermally stable and efficient supported catalysts with free surfaces. Solution based synthesis of linker-free oxide-semiconductor hybrids and capping-free metal nanowires on substrates are also discussed in this context with ZnO/CdS and ultrathin Au nanowires as examples. A simple and rapid microwave-assisted method is highlighted for obtaining such hybrids which can be employed for high-yield production of similar materials.

Selenium adsorption on Au(111) and Ag(111) surfaces: adsorbed selenium and selenide films

Results of a high resolution photoemission and electrochemistry study of Se adsorption Au(111) and Ag(111) surfaces performed by immersion of pristine samples into an aqeuous solution of Na2Se are presented. Cyclic voltammetry on Au shows formation of selenium adsorbed species and the structures observed in reductive desorption are to the atomic and polymeric species observed in XPS. In the case of Au(111) XPS spectra in the Se(3d) region indeed show two main features attributed to Se chemisorbed atomically and polymeric Se-8 features.' Smaller structures due to other types of Se conformations were also observed. The Au(4f) peak line, shape does not show core level, shifts: indicative of Au selenide formation the case of silver, XPS spectra for the Ag(3d) show a broadening of the peak and a deconvolution into Ag-B bulk like Ag-Se components shows that the Ag-Se is located at a lower binding energy, an effect similar to oxidation and sulfidation of Ag. The Se(3d) XPS spectrum is found to be substantially different from the Au case and dominated by atomic type Se due to the selenide, though a smaller intensity Se structure at an energy similar to the Se-8 structure for Au is also observed. Changes in the valence band region. related to Se adsorption are reported.

Carbonaceous nickel oxide nano-composites: as electrode materials in electrochemical capacitor applications

Carbonaceous nickel oxide powder samples have been synthesized from an adducted nickel beta-ketoester complex used as a ``single source precursor'' through a solution-based microwave-assisted chemical route. Comprehensive analysis of the resulting powder material has been carried out using various characterization techniques. These analysis reveal that, depending on the solvent used, either NiO/C or Ni/NiO/C composites are formed, wherein Ni and/or NiO nanocrystals are enveloped in amorphous carbon. As the components emerge from the same molecular source, the composites are homogeneous on a fine scale, making them promising electrode materials for supercapacitors. Electrochemical capacitive behavior of these oxide composites is studied in a three-electrode configuration. With a specific capacitance of 113 F g(-1), Ni/NiO/C is superior to NiO/C as capacitor electrode material, in 0.1 M Na2SO4 electrolyte. This is confirmed by impedance measurements, which show that charge-transfer resistance and equivalent series resistance are lower in Ni/NiO/C than in NiO/C, presumably because of the presence of metallic nickel in the former. The cyclic voltammograms are nearly rectangular and the electrodes display excellent cyclability in different electrolytes: Na2SO4, KOH and Ca(NO3)(2)center dot 4H(2)O. Specific capacitance as high as 143 F g(-1), is measured in Ca(NO3)(2)center dot 4H(2)O electrolyte.

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.

Solution nuclear magnetic resonance structure of the GATase subunit and structural Basis of the interaction between GATase and ATPPase subunits in a two-subunit-type GMPS from methanocaldococcus jannaschii

The solution structure of the monomeric glutamine amidotransferase (GATase) subunit of the Methanocaldococcus janaschii (Mj) guanosine monophosphate synthetase (GMPS) has been determined using high-resolution nuclear magnetic resonance methods. Gel filtration chromatography and N-15 backbone relaxation studies have shown that the Mj GATase subunit is present in solution as a 21 kDa (188-residue) monomer. The ensemble of 20 lowest-energy structures showed root-mean-square deviations of 0.35 +/- 0.06 angstrom for backbone atoms and 0.8 +/- 0.06 angstrom for all heavy atoms. Furthermore, 99.4% of the backbone dihedral angles are present in the allowed region of the Ramachandran map, indicating the stereochemical quality of the structure. The core of the tertiary structure of the GATase is composed of a seven-stranded mixed beta-sheet that is fenced by five alpha-helices. The Mj GATase is similar in structure to the Pyrococcus horikoshi (Ph) GATase subunit. Nuclear magnetic resonance (NMR) chemical shift perturbations and changes in line width were monitored to identify residues on GATase that were responsible for interaction with magnesium and the ATPPase subunit, respectively. These interaction studies showed that a common surface exists for the metal ion binding as well as for the protein-protein interaction. The dissociation constant for the GATase-Mg2+ interaction has been found to be similar to 1 mM, which implies that interaction is very weak and falls in the fast chemical exchange regime. The GATase-ATPPase interaction, on the other hand, falls in the intermediate chemical exchange regime on the NMR time scale. The implication of this interaction in terms of the regulation of the GATase activity of holo GMPS is discussed.

Crystal engineering: from molecule to crystal

How do molecules aggregate in solution, and how do these aggregates consolidate themselves in crystals? What is the relationship between the structure of a molecule and the structure of the crystal it forms? Why do some molecules adopt more than one crystal structure? Why do some crystal structures contain solvent? How does one design a crystal structure with a specified topology of molecules, or a specified coordination of molecules and/or ions, or with a specified property? What are the relationships between crystal structures and properties for molecular crystals? These are some of the questions that are being addressed today by the crystal engineering community, a group that draws from the larger communities of organic, inorganic, and physical chemists, crystallographers, and solid state scientists. This Perspective provides a brief historical introduction to crystal engineering itself and an assessment of the importance and utility of the supramolecular synthon, which is one of the most important concepts in the practical use and implementation of crystal design. It also provides a look to the future from the viewpoint of the author, and indicates some directions in which this field might be moving.

Six-membered C,N] cyclopalladated sym N,N `,N `'-tri(4-tolyl) guanidines: Synthesis, reactivity studies and structural aspects

Six-membered C,N] cyclopalladated sym N,N',N `'-tri(4-tolyl)guanidines, (ArNH)(2)C=NAr] (sym = symmetrical; Ar = 4-MeC6H4; LH24-tolyl) of the types (C,N)Pd(mu-OC(O)R)](2) (1 and 2), (C,N)Pd(mu-Br)](2) (3), cis-(C,N)PdLBr] (4-7), and (C,N)Pd(acac)] (8) were prepared in high yield by established methods with a view aimed at understanding the influence of the 4-tolyl substituent of the guanidine moiety upon the solution behaviour of 1-8. The composition of 1-8 was confirmed by elemental analysis, IR, and NMR spectroscopy, and mass spectrometry. The molecular structures of 1-6 were determined by single-crystal X-ray diffraction. Palladacycles 1-3 exist as a dimer in transoid conformation in the solid state while 4-6 exist as a monomer with cis configuration around the palladium atom as the Lewis base is placed cis to the Pd-C bond due to antisymbiosis. The NMR spectra of 1-8 revealed the presence of a single isomer in solution and this spectral feature is ascribed to the rapid inversion of the six-membered ``C,N]Pd'' ring due to the presence of sterically less hindered and more symmetrical 4-tolyl substituent in the =NAr unit of the guanidine moiety. (C) 2013 Elsevier B.V. All rights reserved.

Fast Eigen solution for homogeneous quadratic minimization with at most three constraints

We propose an eigenvalue based technique to solve the Homogeneous Quadratic Constrained Quadratic Programming problem (HQCQP) with at most three constraints which arise in many signal processing problems. Semi-Definite Relaxation (SDR) is the only known approach and is computationally intensive. We study the performance of the proposed fast eigen approach through simulations in the context of MIMO relays and show that the solution converges to the solution obtained using the SDR approach with significant reduction in complexity.

Tuning the solid state emission of meso-Me3SiC6H4 BODIPYs by tuning their solid state structure

A series of new BODIPYs (4-9) with bulky meso-trimethylsilylphenyl substitution were synthesized. The effect of the substituent's position on the emission properties of the BODIPYs was investigated in detail both in solution and solid state. The new BODIPYs exhibit emission in single crystals and in thin films. The logical increment of steric crowding in the compounds resulted in a periodic change in their conformational flexibility as evident from their F-19 NMR spectra, which in turn led to an increase of fluorescence in solution, thin films and single crystals.

Growth and characterization of L-histidinium 2-nitrobenzoate single crystals: A new NLO material

Crystals of a new nonlinear optical (NLO) material, viz., L-histidinium 2-nitrobenzoate (LHNB) (1) were grown by slow evaporation of an aqueous solution containing equimolar concentrations of L-histidine and 2-nitrobenzoic acid. The structure of the title compound which crystallizes in the non-centrosymmetric monoclinic space group P2(1) was elucidated using single crystal X-ray intensity data. The UV-Vis-NIR spectrum of 1 reveals its transparent nature while the vibrational spectra confirm the presence of the functional groups in 1. The thermal stability and second harmonic generation (SHG) conversion efficiency of 1 were also investigated. (C) 2012 Elsevier GmbH. All rights reserved.