Synthesis and mesogenic behavior of metal-containing liquid crystalline networks

A new hydroxy functionalized liquid crystalline (LC) polyazomethine has been synthesized by the solution polycondensation of a dialdehyde with a diamine. The polymer was characterized by IR, H-1-, and C-13-NMR spectroscopy. Studies on the liquid crystalline properties reveal the nematic mesomorphic behavior. This polymer functions as a polymeric chelate and forms a three-dimensional network structure through the metal complexation. Influence of various metals and their concentration on the liquid crystalline behavior of the network has been studied. Networks up to 30 mol % of the metal show LC phase transitions; above this the transitions are suppressed and the network behaves like an LC thermoset. (C) 1996 John Wiley & Sons, Inc.

Impact of metal binding on the antitumor activity and cellular imaging of a metal chelator cationic imidazopyridine derivative

A new water soluble cationic imidazopyridine species, viz. (1E)-1-((pyridin-2-yl)methyleneamino)-3-(3(pyridin-2-yl) imidazo1,5-a]pyridin-2(3H)-yl)propan-2-ol (1), as a metal chelator is prepared as its PF6 salt and characterized. Compound 1 shows fluorescence at 438 nm on excitation at 342 nm in Tris-HCl buffer giving a fluorescence quantum yield (phi) of 0.105 and a life-time of 5.4 ns. Compound 1, as an avid DNA minor groove binder, shows pUC19 DNA cleavage activity in UV-A light of 365 nm forming singlet oxygen species in a type-II pathway. The photonuclease potential of 1 gets enhanced in the presence of Fe2+, Cu2+ or Zn2+. Compound 1 itself displays anticancer activity in HeLa, HepG2 and Jurkat cells with an enhancement on addition of the metal ions. Photodynamic effect of 1 at 365 nm also gets enhanced in the presence of Fe2+ and Zn2+. Fluorescence-based cell cycle analysis shows a significant dead cell population in the sub-G1 phase of the cell cycle suggesting apoptosis via ROS generation. A significant change in the nuclear morphology is observed from Hoechst 33258 and an acridine orange/ethidium bromide (AO/EB) dual nuclear staining suggesting apoptosis in cells when treated with 1 alone or in the presence of the metal ions. Apoptosis is found to be caspase-dependent. Fluorescence imaging to monitor the distribution of 1 in cells shows that 1 in the presence of metal ions accumulates predominantly in the cytoplasm. Enhanced uptake of 1 into the cells within 12 h is observed in the presence of Fe2+ and Zn2+.

Finite element simulations of ductile rupture in a constrained metal foil

A numerical study of the ductile rupture in a metal foil constrained between two stiff ceramic blocks is performed. The finite element analysis is carried out under the conditions of mode I, plane strain, small-scale yielding. The rate-independent version of the Gurson model that accounts for the ductile failure mechanisms of microvoid nucleation, growth and coalescence is employed to represent the behavior of the metal foil. Different distributions of void nucleating sites in the metal foil are considered for triggering the initiation of discrete voids. The results clearly show that far-field triaxiality-induced cavitation is the dominant failure mode when the spacing of the void nucleating sites is large. On the contrary, void coalescence near the notch tip is found to be the operative failure mechanism when closely spaced void nucleating sites are considered.

Oxidation of substituted benzylic hydrocarbons and naphthalenes by peroxydisulphate in the presence of metal ions

Oxidations of various substituted benzylic hydrocarbons with peroxydisulphate in the presence of metal ion catalysts like iron, nickel, copper, cobalt, silver and cerium were examined. Among the metal ions copper (II) catalysed reaction gives products in excellent yield, whereas oxidation of naphthalene and substituted naphthalenes gives low to moderate yield of the products with peroxydisulphate- copper (II).

Reentrant insulator-metal transition in the half-filled Hubbard model

Using the d=infinity or local-approximation approach to the half-filled Hubbard model on a compressible lattice, we present a detailed study of the transport and structural properties near the paramagnetic metal-insulator transition. The results describe qualitatively most of the observed data in V2O3, including the metal-insulator-metal crossover [Kuwamoto et al., Phys. Rev. B 22, 2626 (1980)]. In addition, we discuss an interesting and intrinsic reentrance feature in the resistivity of the half-filled Hubbard model at high temperatures.

Short-bite chiral diphosphazanes derived from (S)-?-methyl benzyl amine and their Pd, Pt and Rh metal complexes

New chiral diphosphazane ligands of the type Ph(2)PN(S-*CHMePh)PYY' {YY'= Ph(2) (2), O2C6H4 (3); Y= Ph, Y'= Cl {4a (SS), 4b (SR)}, N(2)C(3)HMe(2)-3,5 {5a (SR), 5b (SS)} are synthesised starting from a chiral aminophosphine, Ph(2)PNH(S-*CHMePh) (1). The structure of one of the diastereomer 5a has been confirmed by single crystal X-ray diffraction {Orthorhombic system, P2(1)2(1)2(1); a=10.456 (4), b=15.362 (7), c=17.379 (6) Angstrom, Z=4}. Transition metal mononuclear complexes [Rh{eta(2)-(Ph(2)P)(2)N- (S-*CHMePh)}(2)](+)(BF4)(-) (6), [PdCl2{eta(2)-(Ph(2)P)(2)N(S-*CHMePh)}] (7) and [PtCl2{eta(2)-(Ph(2)P)(2)N- (S-*CHMePh)}] (8) have also been synthesised. The structure of the palladium complex 7 is solved by X-ray crystallography {Orthorhombic system, P2(1)2(1)2(1); a=8.746 (2), b=18.086 (2), c=20.811 (3) Angstrom, Z=4}. All these compounds are characterised by micro analyses, IR and NMR spectroscopic data.

Synthesis of new transition metal nitrides, MWN2 (Mtriple bond; length as m-dashMn, Co, Ni)

We report the synthesis of ternary transition metal nitrides of the formula MWN(2) for M=Mn, Co, Ni by reaction of the corresponding MWO(4) with NH3 gas at 600-700 degrees C. MnWN2 is isostructural with the already-known FeWN2, crystallizing in a hexagonal structure (a=2.901(2), b=16.48(5) Angstrom) related to LiMoN2. CoWN2 and NiWN2 (which are isostructural amongst themselves) adopt a different hexagonal structure with a smaller c parameter. While the Mn and Fe nitrides are semiconducting, the Co and Ni nitrides are semimetallic.

The Metal-Nonmetal Transition: A Global Perspective

A wide range of condensed matter systems traverse the metal-nonmetal transition. These include doped semiconductors, metal-ammonia solutions, metal clusters, metal alloys, transition metal oxides, and superconducting cuprates. Certain simple criteria, such as those due to Herzfeld and Mott, have been highly successful in explaining the metallicity of materials. In this article, we demonstrate the amazing effectiveness of these criteria and examine them in the light of recent experimental findings. We then discuss the Limitations in our understanding of the phenomenon of the metal-nonmetal transition.

Dry sliding wear of Al alloy 2024-Al203 particle metal matrix composites

In the present investigation, Al 2024-15vol.%Al2O3 particulate (average size, 18 mu m) composites were fabricated using the liquid metallurgy route. The wear and friction characteristics of Al alloy 2024 and Al 2024-15vol.%Al2O3p, composite in the as-extruded and peak-aged conditions were studied using a pin-on-disc machine (with a steel disc as the counterface material). The worn surfaces, subsurfaces and the debris were analysed in a scanning electron microscope.The performance of the composite in the as-extruded condition is slightly inferior to that of the unreinforced alloy. However, in the T6 condition, although the wear rates of two materials are initially comparable, the unreinforced alloy seizes while the composite does not within the tested range employed. In the as-extruded condition, the presence of Al2O3 particles is not particularly beneficial as they fracture and result in extensive localized cracking and removal of material from the surface. In the peak-aged condition, however, while the unreinforced alloy exhibits severe plastic deformation and undergoes seizure, there is no significant change in the mechanism in the case of the composite. Except in the case of the peak-aged unreinforced alloy, worn surfaces of all other materials show the presence of an iron-rich layer.

Metal-insulator transition in perovskite oxides: Tunneling experiments

In this paper we have investigated the composition-driven metal-insulator (MI) transitions in two ABO3 classes of perovskite oxides (LaNixCo1-xO3 and NaxTayW1-yO3) in the composition range close to the critical region by using the tunneling technique. Two types of junctions (point-contact and planar) have been used for the investigation covering the temperature range 0.4 K

Production and properties of carbon fibre/particle reinforced cast metal matrix composites

Carbon fibres/particles can be satisfactory reinforcing material in polymer, ceramic and metal matrices. Carbon fibres/particles reinforced polymer matrix composites and ceramic matrix composites are being used extensively in critical areas of application, but carbon fibre - metal matrix composites have not reached that stage yet. This paper discusses the salient aspects of production and specific properties of carbon fibre/particle reinforced cast metal matrix composites. It is envisaged that these materials will find extensive applications where cost, weight and thermal expansion are the key factors.

Magnetic field-induced metal-insulator transitions in graphite and diluted magnetic semiconductors - Discussion

Two topical subjects related with the effect of magnetic field on electrical conduction and the metal-insulator transition are discussed. The first topic is an electronic phase transition in graphite, which is interpreted as a manifestation of a nestingtype instability inherent to a one-dimensional narrow Landau sub-band. The second topic is spin-dependent tranport in III-V based diluted magnetic semiconductors; in particular, a large negative magnetoresistance observed in the vicinity of metal-nonmetal transition.

Synthesis, Structures, and Magnetic Behavior of a Series of Copper(II) Azide Polymers of Cu-4 Building Clusters and Isolation of a New Hemiaminal Ether as the Metal Complex

Four new neutral copper azido polymers, Cu-4(N-3)(8)(L-1)(2)](n) (1), Cu-4(N-3)(8)(L-2)(2)](n) (2), Cu-4(N-3)(8)(L-3)(2)](n) (3), and Cu-9(N-3)(18)(L-4)(4)](n) (4) L1-4 are formed in situ by reacting pyridine-2-carboxaldehyde with 22-(methylamino)ethyl]pyridine (mapy, L-1), N,N-dimethylethylenediamine (N,N-dmen, L-2), N,N-diethylethylenediamine (N,N-deen, L-3), and N,N,2,2-tetramethylpropanediamine (N,N,2,2-tmpn, L-4)], have been synthesized by using 0.5 mol equiv of the chelating tridentate ligands with Cu-(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single-crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu-4(II) building blocks. The overall structure of 3 is two-dimensional, while the other three complexes are one-dimensional in nature. Complex 1 represents a unique example containing hemiaminal ether arrested by copper(R). Complexes 1 and 2 have a rare bridging azido pathway: both end-on and end-to-end bridging azides between a pair of Cu-II centers. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all four complexes. Density functional theory calculations (B3LYP functional) have been performed on complexes 1-3 to provide a qualitative theoretical interpretation of their overall ferromagnetic behavior.

Universal Stability and Temperature Dependent Phase Transformation in Group VIIIB-IB Transition Metal FCC Nanowires

Atomistic simulation of Ag, Al, Au, Cu, Ni, Pd, and Pt FCC metallic nanowires show a universal FCC -> HCP phase transformation below a critical cross-sectional size, which is reported for the first time in this paper. The newly observed HCP structure is also confirmed from previous experimental results. Above the critical cross-sectional size, initial < 100 >/{100} FCC metallic nanowires are found to be metastable. External thermal heating shows the transformation of metastable < 100 >/{100} FCC nanowires into < 110 >/{111} stable configuration. Size dependent metastability/instability is also correlated with initial residual stresses of the nanowire by use of molecular static simulation using the conjugant gradient method at a temperature of 0 K. It is found that a smaller cross-sectional dimension of an initial FCC nanowire shows instability due to higher initial residual stresses, and the nanowire is transformed into the novel HCP structure. The initial residual stress shows reduction with an increase in the cross-sectional size of the nanowires. A size dependent critical temperature is also reported for metastable FCC nanowires using molecular dynamic, to capture the < 110 >/{111} to < 100 >/{100} shape memory and pseudoelasticity.