Usefulness of in Situ Single Crystal to Single Crystal Transformation (SCSC) Studies in Understanding the Temperature-Dependent Dimensionality Cross-over and Structural Reorganization in Copper-Containing Metal-Organic Frameworks (MOFs)

Two copper-containing compounds [Cu(3)(mu(3)-OH)(2)-(H(2)O)(2){(SO(3))-C(6)H(3)-(COO)(2)}(CH(3)COO)] , I, and [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, II, were prepared using sulphoisophthalic and nitroisophthalic acids. The removal of the coordinated water molecules in the compounds was investigated using in situ single crystal to single crystal (SCSC) transformation studies, temperature-dependent powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). The efficacy of SCSC transformation studies were established by the observation of dimensionality cross-over from a two-dimensional (I) to a three-dimensional structure, Cu(6)(mu(3)-OH)(4){(SO(3))-C(6)H(3)-(COO)(2)}(2)(CH(3)COO)(2), Ia, during the removal of the coordinated water molecules. Compound H exhibited a structural reorganization forming Cu(5)(mu(2)-OH)(2){(NO(2))C(6)H(3)-(COO)(2))(4)], Ha, possessing trimeric (Cu(3)O(12)) and dimeric (Cu(2)O(8)) copper clusters. The PXRD studies indicate that the three-dimensional structure (Ia) is transient and unstable, reverting back to the more stable two-dimensional structure (I) on cooling to room temperature. Compound Ha appears to be more stable at room temperature. The rehydration/dehydration studies using a modified TGA setup suggest complete rehydration of the water molecules, indicating that the water molecules in both compounds are labile. A possible model for the observed changes in the structures has been proposed. Magnetic studies indicate changes in the exchanges between the copper centers in Ha, whereas no such behavior was observed in Ia.

Effect of gate-drain/source overlap on the noise in 90 nm N-channel metal oxide semiconductor field effect transistors

In this paper, we have studied the effect of gate-drain/source overlap (LOV) on the drain channel noise and induced gate current noise (SIg) in 90 nm N-channel metal oxide semiconductor field effect transistors using process and device simulations. As the change in overlap affects the gate tunneling leakage current, its effect on shot noise component of SIg has been taken into consideration. It has been shown that “control over LOV” allows us to get better noise performance from the device, i.e., it allows us to reduce noise figure, for a given leakage current constraint. LOV in the range of 0–10 nm is recommended for the 90 nm gate length transistors, in order to get the best performance in radio frequency applications.

Influence of two photon absorption induced free carriers on coherent polariton and phonon generation in ZnTe crystals

Combination of femtosecond Kerr, two photon absorption, and impulsive stimulated Raman scattering (ISRS) experiments have been carried out to investigate the effect of pulse energy and crystal temperature on the generation of coherent polaritons and phonons in 〈110〉 cut ZnTe single crystals of three different resistivities. We demonstrate that the effect of two photon induced free carriers on the creation of both the polaritons and phonons is largest at 4 K where the free carrier lifetime is enhanced. The temperature dependant ISRS on high and low purity ZnTe crystals allows us to unambiguously assign the phonon mode at 3.5 THz to the longitudinal acoustic mode at X-point in the Brillouin zone, LA(X).

Combined Raman and infrared investigation of the insulator-to-metal transition in NiS(2-x)Se(x) compounds

Ambient-condition Raman spectra were collected in the strongly correlated NiS(1-x)Se(x) pyrite (0 <= x <= 1.2). Two samples (x = 0 and x = 0.55) were studied as a function of pressure up to 10 GPa, and for the x = 0.55 sample the pressure dependence of the infrared reflectivity was also measured (0-10 GPa). This gave a complete picture of the optical response of that system on approaching the metallic state both by application of pressure and/or by Se alloying, which corresponds to a volume expansion. A peculiar nonmonotonic (V-shaped) volume dependence was found for the quasiparticle spectral weight of both pure and Se-doped compounds. In the x = 0.55 sample the vibrational frequencies of the chalcogen dimer show an anomalous volume dependence on entering the metallic phase. The abrupt softening observed, particularly significant for the Se-Se pair, indicates the relevant role of the softness of the Se-Se bond as previously suggested by theoretical calculations.

Electronic structure of early transition metal oxides, Ca1−xSrxVO3 and La1−xCaxVO3: What can we learn from photoelectron spectroscopy

Photoemission spectroscopy offers the unique possibility of mapping out the electronic structure of the occupied electron states. However, the extreme surface sensitivity of this technique ensures that only the surface and the near-surface regions of any sample are probed. An important question arises in this context—Is the electronic structure of the surface region the same as that of the bulk? We address this issue using two different series of vanadium oxides, Ca1−xSrxVO3 and La1−xCaxVO3. Our results clearly establish that the electronic structure of the surface region is drastically different from that of the bulk in both these cases. We provide a method to separate the two contributions: one arising from the near-surface region and the other representative of the bulk. This separation allows us to deduce some very unusual behaviors of the electronic structures in these systems.

(Dimethylamino)borylene and Related Complexes of Electron-Rich Metal Fragments: Generation of Nucleophile-Resistant Cations by Spontaneous Halide Ejection

Spontaneous halide ejection from a three-coordinate Lewis acid has been shown to offer a remarkable new route to cationic metal complexes featuring a linear, multiply bonded boron-donor Ligand. The exploitation of electron-rich [CpM(PR3)(2)] fragments within boryl systems of the type LnMB(hal)NR2 leads to the spontaneous formation in polar solvents of chemically robust borylene complexes, [LnM(BNR2)](+), with exceptionally low electrophilicity and short M-B bonds. This is reflected by M-B distances (ca. 1.80 angstrom for FeB systems) which are more akin to alkyl-/aryl-substituted borylene complexes and, perhaps most strikingly, by the very low exothermicity associated with the binding of pyridine to the two-coordinate boron center (Delta H = -7.4 kcal mol(-1), cf. -40.7 kcal mol(-1) for BCl3). Despite the strong pi electron release from the metal fragment implied by this suppressed reactivity and by such short M-B bonds, the barrier to rotation about the Fe=B bond in the unsymmetrical variant [CpFe(dmpe)(BN{C6H4OMe-4}Me)](+) is found to be very small (ca. 2.9 kcal mol(-1)). This apparent contradiction is rationalized by the orthogonal orientations of the HOMO and HOMO-2 orbitals of the [CpML2](+) fragment, which mean that the M-B pi interaction does not fall to zero even in the highest energy conformation.

Towards sustainability: a new, solid-state synthetic route for supported metal nanocatalysts

Noble metal ions like Pt(IV) and Pd(II) were impregnated on gamma-alumina and aerosol 300 silica surfaces. Reduction of these ions using ammonia borane in the solid state resulted in the formation of the respective metal nanoparticles embedded in BNHx polymer which is dispersed on the oxide support. Removal of the BNH polymer was accomplished by washing the samples repeatedly with methanol. In this process the polymer undergoes solvolysis to release H-2 accompanied by the formation of ammonium methoxy borate salt, which has been removed by repeated methanol washings. As a result, metal nanoparticles well dispersed on gamma-alumina and aerosol 300 silica were obtained. These samples have been characterized by a combination of techniques, including electron microscopy, powder X-ray diffraction, NMR spectroscopy and surface area analyser.

Some mechanisms of tribofilm formation in metal/metal and ceramic/metal sliding interactions

Tribological interaction often generates new structures and materials which form the interface between the sliding pair. The new material designated tribofilm here may be protective or tribologically deleterious. The tribofilm plays a major role in determining the friction and wear of the interaction. Here, we give three examples: mechanically mixed, chemically generated and thermally activated, of tribofilms formed in three different tribological systems and speculate on the mechanism of their formation.

Biosorption of heavy metal ions from aqueous and cyanide solutions using fungal biomass

A waste fungal biomass containing killed cells of Aspergillus niger was efficiently used in the removal of toxic metal ions such as nickel, calcium, iron and chromium from aqueous solutions. The role of different parameters such as initial metal ion concentration, solution pH and biomass concentration on biosorption capacity was established. The maximum metal uptake was found to be dependent on solution pH and increased with biomass loading upto 10g/L. The adsorption densities for various metal ions could be arranged as Ca>Cr (III)>Ni>Fe>Cr (VI). The effect of the presence of various metal ions in binary, ternary and quaternary combinations on biosorption was also assessed. Ni uptake was significantly affected, while that of Cr (VI) the least, in the presence of other metal ions. Uptake of base metals from an industrial cyanide effluent was studied using different species of fungi such as Aspergillus niger, Aspergillus terreus and Penicillium funiculosum and yeast such as Saccharomyces cerevisiae which were isolated from a gold mine. Traces of gold present in the cyanide effluent could be efficiently recovered. Among the four base metal contaminants present in the cyanide effluent, zinc was found to be most efficiently biosorbed, followed by iron, copper and lead. The role of both living and dead biomass on biosorption was distinguished and probable mechanisms illustrated.

Structure and properties of zinc alloy based metal matrix composites

Zinc-aluminium cast alloys (ZA alloys) exhibit good castability and mechanical properties but these alloys lack creep resistance and high temperature stability. One solution to improve these properties is to reinforce with ceramic particles or fibres, to result in MMCs. MMCs can be produced using casting technique involving infiltration. A systematic investigation was taken and this paper discusses the salient findings of the study on the ZA-27 alloy based MMCs produced through squeeze casting. (Reinforcing fibers: SAFFIL (chopped alumina) or mullite.)

A k-epsilon model for turbulent weld pool convection in gas metal arc welding process

In this paper, we present a modified k - epsilon model capable of addressing turbulent weld-pool convection in a GMAW process, taking into account the morphology of the phase change interface during a Gas Metal Arc Welding (GMAW) process. A three-dimensional turbulence mathematical model has been developed to study the heat transfer and fluid flow within the weld pool by considering the combined effect of three driving forces, viz., buoyancy, Lorentz force and surface tension (Marangoni convection). Mass and energy transports by the droplets are considered through the thermal analysis of the electrode. The falling droplet's heat addition to the molten pool is considered to be a volumetric heat source distributed in an imaginary cylindrical cavity ("cavity model") within the weld pool. This nature of heat source distribution takes into account the momentum and the thermal, energy of the falling droplets. The numerically predicted weld pool dimensions both from turbulence and laminar models are then compared with the experimental post-weld results sectioned across the weld axis. The above comparison enables us to analyze the overall effects of turbulent convection on the nature of heat and fluid flow and hence on the weld pool shape/size during the arc welding processes.

Enhanced photoluminescence of Gd2O3:Eu3+ nanophosphors with alkali (M = Li+, Na+, K+) metal ion co-doping

Gd1.95Eu0.4M0.01O3 (M = Li+ Na+ K+) nanophosphors have been synthesized by a low temperature solution combustion (LSC) method. Powder X-ray diffraction pattern (PXRD), scanning electron microscopy (SEM), UV-vis and photoluminescence (PL) measurements were carried out to characterize their structural and luminescent properties. The excitation and emission spectra indicated that the phosphor could be well excited by UV light (243 nm) and emit red light about 612 nm. The effect of alkali co-dopant on PL properties has been examined. The results showed that incorporation of Li+, Na+ and K+ in to Gd2O3:Eu3+ phosphor would lead to a remarkable increase of photoluminescence. The PL intensity of Gd2O3:Eu3+ phosphor was improved evidently by co-doping with Li+ ions whose radius is less than that of Gd3+ and hardly with Na+, K+ whose radius is larger than that of Gd3+. The effect of co-dopants on enhanced luminescence was mainly regarded as the result of a suitable local distortion of crystal field surrounding the Eu3+ activator. These results will play an important role in seeking some more effective co-dopants. (C) 2011 Published by Elsevier B.V.

Durable Transition-Metal-Carbide-Supported Pt-Ru Anodes for Direct Methanol Fuel Cells

Molybdenum carbide (MoC) and tungsten carbide (WC) are synthesized by direct carbonization method. PtRu catalysts supported on MoC, WC, and Vulcan XC-72R are prepared, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy in conjunction with electrochemistry. Electrochemical activities for the catalysts towards methanol electro-oxidation are studied by cyclic voltammetry. All the electro-catalysts are subjected to accelerated durability test (ADT). The electrochemical activity of carbide-supported electro-catalysts towards methanol electro-oxidation is found to be higher than carbon-supported catalysts before and after ADT. The study suggests that PtRu/MoC and PtRu/WC catalysts are more durable than PtRu/C. Direct methanol fuel cells (DMFCs) with PtRu/MoC and PtRu/WC anodes also exhibit higher performance than the DMFC with PtRu/C anode.

Synthesis, spectroscopic properties and biological evaluation of transition metal complexes of salicylhydrazone of anthranilhydrazide: X-ray crystal structure of copper complex

The transition metal complexes of salicylhydrazone of anthranilhydrazide (H2L) were synthesised. The structures of metal complexes were characterized by various spectroscopic [IR, NMR, UV-Vis, EPR], thermal and other physicochemical methods. The single-crystal X-ray diffraction study of [Cu(HL)Cl]center dot H2O reveal its orthorhombic system with space group P2(1)2(1)2 and Z=4. The copper center has a distorted square planar geometry with ONO and Cl as the donor atoms. The ligand and its metal chelates have been screened for their antimicrobial and anti-tubercular activities using serial dilution method. Metal complexes in general have exhibited better antibacterial and antifungal activity than the free ligand and in few cases better than the standard used. Among the bacterial strains used, the complexes are highly potent against Gram-positive strains compared to Gram-negative. Anti-tubercular activity exhibited by the Co(II) complex is comparable with the standard used. (C) 2011 Elsevier B. V. All rights reserved.

Efficiency enhancement in DSSC using metal nanoparticles: A size dependent study

The photoelectrode of Eosin-Y sensitised DSSC was modified by incorporating Au-nanoparticles to enhance the power conversion efficiency via scattering from surface plasmon polaritons. Size dependence of Au nanoparticle on conversion efficiency was performed in DSSC for the first time by varying the particle size from 20 to 94 nm. It was found that, the conversion efficiency is highly dependent on the size of the Au nanoparticles. For larger particles (>50 nm), the efficiency was found to be increased due to constructive interference between the transmitted and scattered waves from the Au nanoparticle while for smaller particles, the efficiency decreases due to destructive interference. Also a reduction in the V-oc was observed in general, due to the negative shifting of the TiO2 Fermi level on the adsorption of Au nanoparticle. This shift was negligible for larger particles. When 94 nm size particles were employed the conversion efficiency was doubled from 0.74% to 1.52%. This study points towards the application of the scattering effect of metal nanoparticle to enhance the conversion efficiency in DSSCs. (C) 2011 Elsevier Ltd. All rights reserved.