A novel single pot synthesis of binuclear copper(II) complexes of macrocyclic and macroacyclic compartmental ligands: Structures and magnetic properties

Two binuclear copper(II) complexes one (complex 1) with a macrocyclic ligand (H(2)L1) and other (complex 2) with a macroacyclic (end-off type) compartmental ligand (HL2) have been synthesized from single pot template synthesis involving copper(II) nitrate, 1,2diaminoethane, 4-methyl-2,6-diformylphenol, and sodium azide. Structure analysis of complex I reveals that there are actually two half molecules present in the asymmetric unit and so two complexes (molecule-I and molecule-II) are present in unit cell, although they show slight differences. The two Cu(II) centers are in distorted square pyramidal coordination environment with two endogenous phenoxo bridges provided by the phenolate of H(2)L1 I having Cu-Cu separations of 2.9133(10) angstrom and 2.9103(10) in the two molecules. In complex 2 the coordination environments around two Cu(II) centers are asymmetric, Cu1 is in distorted square pyramidal environment whereas, the coordination environment around Cu2 is distorted octahedral. The two Cu(II) centers in complex 2 are connected by two different kinds of bridges, one is endogenous phenoxo bridge provided by the phenolate of the ligand HL2 and the other is exogenous azido bridge (mu-(1),(l) type) with Cu-Cu distance of 3.032(10) angstrom. Variable temperature magnetic studies show that two Cu(II) centers in both the complexes are strongly antiferromagnetically coupled with J = -625 +/- 5 cm(-1) and J = -188.6 +/- 1cm(-1) for complex 1 and 2, respectively. (C) 2006 Elsevier B.V. All rights reserved.

Inter-helical Interactions in Membrane Proteins: Analysis Based on the Local Backbone Geometry and the Side Chain Interactions

The availability of a significant number of the Structures of helical membrane proteins has prompted us to investigate the mode of helix-helix packing. In the present study, we have considered a dataset of alpha-helical membrane proteins representing Structures solved from all the known superfamilies. We have described the geometry of all the helical residues in terms of local coordinate axis at the backbone level. Significant inter-helical interactions have been considered as contacts by weighing the number of atom-atom contacts, including all the side-chain atoms. Such a definition of local axis and the contact criterion has allowed us to investigate the inter-helical interaction in a systematic and quantitative manner. We show that a single parameter (designated as alpha), which is derived from the parameters representing the Mutual orientation of local axes, is able to accurately Capture the details of helix-helix interaction. The analysis has been carried Out by dividing the dataset into parallel, anti-parallel, and perpendicular orientation of helices. The study indicates that a specific range of alpha value is preferred for interactions among the anti-parallel helices. Such a preference is also seen among interacting residues of parallel helices, however to a lesser extent. No such preference is seen in the case of perpendicular helices, the contacts that arise mainly due to the interaction Of Surface helices with the end of the trans-membrane helices. The Study Supports the prevailing view that the anti-parallel helices are well packed. However, the interactions between helices of parallel orientation are non-trivial. The packing in alpha-helical membrane proteins, which is systematically and rigorously investigated in this study, may prove to be useful in modeling of helical membrane proteins.

Effect of Al substitution on the magnetic properties of amorphous Fe73.5Cu1Mo3Si13.5-xAlxB9 alloy

We have synthesized FINEMET type amorphous Fe73.5Cu1Mo3Si13.5-xAlxB9 alloy by the single wheel melt spinning technique. The effect of Al substitution on the magnetic properties has been studied using a vibrating sample magnetometer, SQUID and Mossbauer spectroscopy. Magnetization and Curie temperature of the amorphous phase of the alloys were found to decrease with A] concentration. The results are attributed to the dilution effect of At on the magnetic moment of Fe and to the increase in Fe-Fe interaction distance resulting in the weakening of exchange interaction. (C) 2007 Elsevier B.V. All rights reserved.

Thermoelectric Power Under Strong Magnetic Field in Quantum Dots and Quantized Superlattices: Simplified Theory and Relative Comparison

In this paper, we study the thermoelectric power under strong magnetic field (TPSM) in quantum dots (QDs) of nonlinear optical, III-V, II-VI, GaP, Ge, Te, Graphite, PtSb2, zerogap, Lead Germanium Telluride, GaSb, stressed materials, Bismuth, IV-VI, II-V, Zinc and Cadmium diphosphides, Bi2Te3 and Antimony respectively. The TPSM in III-V, II-VI, IV-VI, HgTe/CdTe quantum well superlattices with graded interfaces and effective mass superlattices of the same materials together with the quantum dots of aforementioned superlattices have also been investigated in this context on the basis of respective carrier dispersion laws. It has been found that the TPSM for the said quantum dots oscillates with increasing thickness and decreases with increasing electron concentration in various manners and oscillates with film thickness, inverse quantizing magnetic field and impurity concentration for all types of superlattices with two entirely different signatures of quantization as appropriate in respective cases of the aforementioned quantized structures. The well known expression of the TPSM for wide-gap materials has been obtained as special case for our generalized analysis under certain limiting condition, and this compatibility is an indirect test of our generalized formalism. Besides, we have suggested the experimental method of determining the carrier contribution to elastic constants for nanostructured materials having arbitrary dispersion laws.

Influence of magnetic clusters on electrical and magnetic properties of In1-xMnxSb/GaAs dilute magnetic semiconductor grown by liquid phase epitaxy

In1-xMnxSb films have been grown with different Mn doping concentrations (x = 0.0085, 0.018, 0.029 and 0.04) beyond the equilibrium 14 solubility limit by liquid phase epitaxy. We have studied temperature dependent resistivity, the Hall effect, magnetoresistance and magnetization for all compositions. Saturation in magnetization observed even at room temperature suggests the existence of ferromagnetic clusters in the film which has been verified by scanning electron microscopy studies. The anomalous Hall coefficient is found to be negative. Remnant field present on the surface of the clusters seems to affect the anomalous Hall effect at very low fields (below 350 Gauss). In the zero field resistivity, a variable-range hopping conduction mechanism dominates below 3.5 K for all samples above which activated behavior is predominant. The temperature dependence of the magnetization measurement shows a magnetic ordering below 10 K which is consistent with electrical measurements. (c) 2007 Elsevier Ltd. All rights reserved.

Investigation of inter-ion interactions in N,N,N',N'-tetramethylethylenediammonium dithiocyanate via experimental and theoretical charge density studies

The crystal structure of the N,N,N',N'-tetramethylethylenediammonium dithiocyanate salt has been examined by experimental charge density studies from high-resolution X-ray diffraction data. The corresponding results are compared with multipole refinements, using theoretical structure factors obtained from a periodic density functional theory calculation at the B3LYP level with a 6-31G** basis set. The salt crystallizes in space group P (1) over bar and contains only a single ion pair with an inversion center in the cation. The salt has thus one unique classical N+-H center dot center dot center dot(NCS)(-) hydrogen bond but also has six other weaker interactions: four C-H center dot center dot center dot S, one C-H center dot center dot center dot N, and one C-H center dot center dot center dot C-pi. The nature of all these interactions has been examined topologically using Bader's quantum theory of "atoms in molecules" and all eight of the Koch-Popelier criteria. The experimental and theoretical approaches agree well and both show that the inter-ion interactions, even in this simplest of systems, play an integrated and complex role in the packing of the ions in the crystal. Electrostatic potential maps are derived from experimental charge densities. This is the first time such a system has been examined in detail by these methods.

Investigation of the local Fe magnetic moments at the grain boundaries of the Ca2FeReO6 double perovskite

The local Fe ferromagnetic (FM) moment at the grain boundaries of a ceramic sample of Ca2FeReO6 double perovskite was investigated by means of x-ray magnetic circular dichroism spectroscopy at the Fe L-2,L-3 edges and compared to the overall bulk magnetization. We found that, at the grain boundaries, the Fe FM moments at H=5 T are much smaller than expected and that the MxH curve is harder than in the bulk magnetization. These results suggest a larger degree of Fe/Re antisite disorder at the grain boundaries of this sample, shedding light into the intriguing nonmetallic resistivity behavior despite the reported presence of free carriers. (c) 2007 American Institute of Physics.

Electromechanical interactions in a carbon nanotube based thin film field emitting diode

Carbon nanotubes (CNTs) have emerged as promising candidates for biomedical x-ray devices and other applications of field emission. CNTs grown/deposited in a thin film are used as cathodes for field emission. In spite of the good performance of such cathodes, the procedure to estimate the device current is not straightforward and the required insight towards design optimization is not well developed. In this paper, we report an analysis aided by a computational model and experiments by which the process of evolution and self-assembly (reorientation) of CNTs is characterized and the device current is estimated. The modeling approach involves two steps: (i) a phenomenological description of the degradation and fragmentation of CNTs and (ii) a mechanics based modeling of electromechanical interaction among CNTs during field emission. A computational scheme is developed by which the states of CNTs are updated in a time incremental manner. Finally, the device current is obtained by using the Fowler–Nordheim equation for field emission and by integrating the current density over computational cells. A detailed analysis of the results reveals the deflected shapes of the CNTs in an ensemble and the extent to which the initial state of geometry and orientation angles affect the device current. Experimental results confirm these effects.

Experimental implementation of a three qubit quantum game with corrupt source using nuclear magnetic resonance quantum information processor

In a three player quantum `Dilemma' game each player takes independent decisions to maximize his/her individual gain. The optimal strategy in the quantum version of this game has a higher payoff compared to its classical counterpart. However, this advantage is lost if the initial qubits provided to the players are from a noisy source. We have experimentally implemented the three player quantum version of the `Dilemma' game as described by Johnson, [N.F. Johnson, Phys. Rev. A 63 (2001) 020302(R)] using nuclear magnetic resonance quantum information processor and have experimentally verified that the payoff of the quantum game for various levels of corruption matches the theoretical payoff. (c) 2007 Elsevier Inc. All rights reserved.

Probing the existing magnetic phases in Pr0.5Ca0.5MnO3 (PCMO) nanowires and nanoparticles: magnetization and magneto-transport investigations

We show from conventional magnetization measurements that the charge order (CO) is completely suppressed in 10 nm Pr0.5Ca0.5MnO3 (PCMO 10) nanoparticles. Novel magnetization measurements, designed by a special high field measurement protocol, show that the dominant ground state magnetic phase is ferromagnetic-metallic (FM-M), which is an equilibrium phase, which coexists with the residual charge ordered anti-ferromagnetic phase (CO AFM) (an arrested phase) and exhibits the characteristic features of a `magnetic glassy state' at low temperatures. It is observed that there is a drastic reduction in the field required to induce the AFM to FM transition (similar to 5-6 T) compared to their bulk counterpart(similar to 27 T); this phase transition is of first order in nature, broad, irreversible and the coexisting phases are tunable with the cooling field. Temperature-dependent magneto-transport data indicate the occurrence of a size-induced insulator-metal transition (TM-I) and anomalous resistive hysteresis (R-H) loops, pointing out the presence of a mixture of the FM-M phase and AFM-I phase.

Manifestation of geometric frustration on magnetic and thermodynamic properties of the pyrochlores Sm2X2O7 (X=Ti,Zr)

We present here magnetization, specific heat, and Raman studies on single-crystalline specimens of the first pyrochlore member Sm2Ti2O7 of the rare-earth titanate series. Its analogous compound Sm2Zr2O7 in the rare-earth zirconate series is also investigated in the polycrystalline form. The Sm spins in Sm2Ti2O7 remain unordered down to at least T=0.5 K. The absence of magnetic ordering is attributed to very small values of exchange (θcw∼−0.26 K) and dipolar interaction (μeff∼0.15 μB) between the Sm3+ spins in this pyrochlore. In contrast, the pyrochlore Sm2Zr2O7 is characterized by a relatively large value of Sm-Sm spin exchange (θcw∼−10 K); however, long-range ordering of the Sm3+ spins is not established at least down to T=0.67 K due to frustration of the Sm3+ spins on the pyrochlore lattice. The ground state of Sm3+ ions in both pyrochlores is a well-isolated Kramers doublet. The higher-lying crystal field excitations are observed in the low-frequency region of the Raman spectra of the two compounds recorded at T=10 K. At higher temperatures, the magnetic susceptibility of Sm2Ti2O7 shows a broad maximum at T=140 K, while that of Sm2Zr2O7 changes monotonically. Whereas Sm2Ti2O7 is a promising candidate for investigating spin fluctuations on a frustrated lattice, as indicated by our data, the properties of Sm2Zr2O7 seem to conform to a conventional scenario where geometrical frustration of the spin excludes their long-range ordering.

Magneto-transport and optical properties of diluted magnetic semiconductor Ga1-xMnxSb

We have studied magneto-transport and optical properties of Ga1-xMnxSb crystals (x = 0.01, 0.02, 0.03 and 0.04) grown by horizontal Bridgman method. Negative magnetoresistance and anomalous Hall effect have been observed below 10K. Temperature dependence of magnetization measurement shows a magnetic ordering below 10K which could arise from Ga1-xMnxSb alloy formation. Also, saturation in magnetization observed even at room temperature suggests the existence of ferromagnetic MnSb clusters. Reduction in band gap is observed with increasing Mn concentration in the crystals. Temperature dependence of band gap follows Bose-Einstein's model.

How Effective Is The Data On Co-Occurrence Of Domains In Multi-Domain Proteins In Prediction Of Protein-Protein Interactions?

We explore the fuse of information on co-occurrence of domains in multi-domain proteins in predicting protein-protein interactions. The basic premise of our work is the assumption that domains co-occurring in a polypeptide chain undergo either structural or functional interactions among themselves. In this study we use a template dataset of domains in multidomain proteins and predict protein-protein interactions in a target organism. We note that maximum number of correct predictions of interacting protein domain families (158) is made in S. cerevisiae when the dataset of closely related organisms is used as the template followed by the more diverse dataset of bacterial proteins (48) and a dataset of randomly chosen proteins (23). We conclude that use of multi-domain information from organisms closely-related to the target can aid prediction of interacting protein families.

Enhanced Tetrahedral Ordering of Water Molecules in Minor Grooves of DNA: Relative Role of DNA Rigidity, Nanoconfinement, and Surface Specific Interactions

Confinement and Surface specific interactions call induce Structures otherwise unstable at that temperature and pressure. Here we Study the groove specific water dynamics ill the nucleic acid sequences, poly-AT and poly-GC, in long B-DNA duplex chains by large scale atomistic molecular dynamics simulations, accompanied by thermodynamic analysis. While water dynamics in the major groove remains insensitive to the sequence differences, exactly the opposite is true for the minor groove water. Much slower water dynamics observed in the minor grooves (especially in the AT minor) call be attributed to all enhanced tetrahedral ordering (< t(h)>) of water. The largest value of < t(h)> in the AT minor groove is related to the spine of hydration found in X-ray Structure. The calculated configurational entropy (S-C) of the water molecules is found to be correlated with the self-diffusion coefficient of water in different region via Adam-Gibbs relation D = A exp(-B/TSC), and also with < t(h)>.

Supramolecular Organization in Tetra Aqua (mu-8-Hydroxyquinoline-5-sulfonate) Barium (II) and Ag center dot center dot center dot I Interactions in a Pseudopolymorphic Form of (7-Iodo-8-hydroxyquinoline-5-sulfonate) Silver (I) Monohydrate

The complexes, Ba (HQS) (H2O)(4) (HQS = 8-hydroxyquinoline-5-sulfonic acid) (1) and Ag (HIQS) (H2O) (Ferron = 7-iodo-8-hydroxyquinoline-5-sulfonic acid) (2) have been synthesized and characterized by X-ray diffraction analysis and spectroscopic studies. In compound 1, Ba2+ ion has a nine-coordinate monocapped antiprismatic geometry. In compound 2, Ag+ has distorted tetrahedral coordination and Ag center dot center dot center dot I interactions generate the supramolecular architectures. The complexes have been characterized by FT-IR and UV-Visible measurements. In both the structures, the inversion-related organic ligands are stacked over one another leading to three-dimensional networks.