Axial wave propagation in coupled nanorod system with nonlocal small scale effects

This article deals with the axial wave propagation properties of a coupled nanorod system with consideration of small scale effects. The nonlocal elasticity theory has been incorporated into classical rod/bar model to capture unique features of the coupled nanorods under the umbrella of continuum mechanics theory. Nonlocal rod model is developed for coupled nanorods. The strong effect of the nonlocal scale has been obtained which leads to substantially different wave behavior of nanorods from those of macroscopic rods. Explicit expressions are derived for wavenumber, cut-off frequency and escape frequency of nanorods. The analysis shows that the wave characteristics of nanorods are highly over estimated by the classical rod model, which ignores the effect of small-length scale. The studies also shows that the nonlocal scale parameter introduces certain band gap region in axial or longitudinal wave mode, where no wave propagation occurs. This is manifested in the spectrum cures as the region, where the wavenumber tends to infinite or wave speed tends to zero. The effect of the coupled spring stiffness is also capture in the present analysis. It has been also shown that the cut-off frequency increases as the stiffness of the coupled spring increases and also the coupled spring stiffness has no effect on escape frequency of the axial wave mode in the nanorod. This cut-off frequency is also independent of the nonlocal small scale parameter. The present study may bring in helpful insights while investigating multiple-nanorod-system-models for future nano-optomechanical systems applications. The results can also provide useful guidance for the study and design of the next generation of nanodevices that make use of the wave propagation properties of coupled single-walled carbon nanotubes or coupled nanorods. (C) 2011 Elsevier Ltd. All rights reserved.

Ferrocene-Conjugated L-Tryptophan Copper(II) Complexes of Phenanthroline Bases Showing DNA Photocleavage Activity and Cytotoxicity

Ferrocene-conjugated L-tryptophan (L-Trp) reduced Schiff base (Fc-TrpH) copper(II) complexes [Cu(Fc-Trp)(L)](ClO(4)) of phenanthroline bases (L), viz. 2,2'-bipyridine (bpy in 1), 1,10-phenanthroline (phen in 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq in 3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz in 4), were prepared and characterized and their photocytotoxicity studied. Cationic reduced Schiff base (Ph-TrpH) complexes [Cu(Ph-Trp)(L)(H(2)O)] (ClO(4)) (L = phen in 5; dppz in 6) having the ferrocenyl moiety replaced by a phenyl group and the Zn(II) analogue (7) of complex 4 were prepared and used as control species. The crystal structures of 1 and 5 with respective square-planar CuN(3)O and square-pyramidal CuN(3)O(2) coordination geometry show significantly different core structures. Complexes 1-4 exhibit a Cu(II)-Cu(I) redox couple near -0.1 V and the Fc(+)-Fc couple at similar to 0.5 V vs SCE in DMF-0.1 M [Bu(4)(n)N] (ClO(4)) (Fc = ferrocenyl moiety). The complexes display a copper(II)-based d-d band near 600 nm and a Fc-centered band at similar to 450 nm in DMF-Tris-HCl buffer. The complexes are efficient binders to calf thymus DNA. They are synthetic chemical nucleases in the presence of thiol or H(2)O(2), forming hydroxyl radicals. The photoactive complexes are cleavers of pUC19 DNA in visible light, forming hydroxyl radicals. Complexes 2-6 show photocytotoxicity in HeLa cancer cells, giving IC(50) values of 4.7, 10.2, 1.3, 4.8, and 4.3 mu M, respectively, in visible light with the appearance of apoptotic bodies. The complexes also show photocytotoxicity in MCF-7 cancer cells. Nuclear chromatin cleavage has been observed with acridine orange/ethidium bromide (AO/EB) dual staining with complex 4 in visible light. The complexes induce caspase-independent apoptosis in the HeLa cells.

Synthesis, Structure, Negative Thermal Expansion, and Photocatalytic Property of Mo Doped ZrV(2)O(7)

A new series of compounds identified in the phase diagram of ZrO(2)-V(2)O(8)-MoO(3) have been synthesized via the solution combustion method. Single crystals of one of the compounds in the series, ZrV(1.50)Mo(0.50)O(7.25), were grown by the melt-cool technique from the starting materials with double the MoO(3) quantity. The room temperature average crystal structure of the grown crystals was solved using the single crystal X-ray diffraction technique. The crystals belong to the cubic crystal system, space group Pa (3) over bar (No. 205) with a = 8.8969 (4) angstrom, V = 704.24 (6) angstrom(3), and Z = 4. The final R(1) value of 0.0213 was achieved for 288 independent reflections during the structure refinement. The Zr(4+) occupies the special position (4a) whereas V(5+) and Mo(6+) occupy two unique (8c) Wyckoff positions. Two fully occupied O atoms, (24d) and (4b), one partially occupied 0 atom (8c) have been identified for this molybdovanadate, which is a unique feature for these crystals. The structure is related to both ZrV(2)O(7) and cubic ZrMo(2)O(8). The temperature dependent single crystal studies show negative thermal expansion above 370 K. The compounds have been characterized by powder X-ray diffraction, solid-state UV-vis diffuse reflectance spectra, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The photocatalytic activity of these compounds has been investigated for the degradation of various dyes, and these compounds show specificity toward the degradation of non-azoic dyes.

Direct Infrared Absorption Spectroscopy of Benzene Dimer

The direct infrared (IR) absorption spectrum of benzene dimer formed in a free-jet expansion was recorded in the 3.3 mu m region for the first time. This has led to the observation of the C H stretching fundamental mode nu(13) (B(1u)), which is both IR and Raman forbidden in the monomer. Moreover, the IR forbidden and Raman allowed nu(7) (E(2g)) mode has been observed as well. These two modes were found to be red-shifted along with the IR allowed nu(20) (E(1u)) mode, as previously reported by Erlekam et al. [Erlekam; Frankowski; Meijer; Gert von Helden J. Chem. Phys. 2006, 124, 171101], using ion-dip spectroscopy, contrary to the blue-shift predicted earlier by theoretical studies. The observation of the nu(13) band indicates that the symmetry is reduced in the dimer, confirming the T-shaped structure observed by Erlekam et al. Our experimental results have not provided any direct evidence for the presence of the parallel displaced geometry, the main objective of the present work, as predicted by theoretical calculations.

Electrochemical copolymerization of thiophene derivatives; a precursor to photovoltaic devices

This work presents an electrochemical technique for the polymerization and copolymerization of thiophene derivatives like 7,9-dithiophene-2yl-8H-cyclopenta[a]acenaphthalene-8-one and 3-hexylthiophene. The structural characterization of chemically synthesized monomers and electro-chemically synthesized polymers was carried out by nuclear magnetic resonance and Fourier transform infrared spectroscopy. Thermal characterizations indicate that copolymer has increased thermal stability than that of homopolymer. Morphological studies of the polymerized films carried out by scanning electron microscopy shows network structure of copolymer. Optical properties of the homopolymers and copolymer were studied by UV-visible spectrometer and it was observed that band gap of copolymer is less than the homopolymers. HOMO and LUMO levels, band gap values of the respective polymers were also calculated from the cyclic voltammetry technique with various scan rates. By the peak current obtained from various scan rates shows that all polymerization reactions are diffusion controlled process. Charge transfer resistances of polymers were determined using Nyquist plots. Conductivity of synthesized polymers shows higher conductivity for copolymer than homopolymers. (C) 2011 Elsevier Ltd. All rights reserved.

Solute solute and solvent solute interactions in solid solutions of Cu+Sn, Au+Sn and Cu+Au+Sn alloys

The chemical potentials of tin in its α-solid solutions with Cu, Au and Cu + Au alloys have been measured using a gas-solid equilibration technique. The variation of the excess chemical potential of tin with its composition in the alloy is related to the solute-solute repulsive interaction, while the excess chemical potential at infinite dilution of the solute is a measure of solvent-solute interaction energies. It is shown that solute-solute interaction is primarily determined by the concentration of (s + p) electrons in the conduction band, although the interaction energies are smaller than those predicted by either the rigid band model or calculation based on Friedel oscillations in the potential function. Finally, the variation of the solvent-solute interaction with solvent composition in the ternary system can be accounted for in terms of a quasi-chemical treatment which takes into account the clustering of the solvent atoms around the solute.

Anomalous temperature dependence of phonons and photoluminescence bands in pyrochlore Er(2)Ti(2)O(7): signatures of structural deformation at 130 K

We report a Raman study of single crystal pyrochlore Er(2)Ti(2)O(7) as a function of temperature from 12 to 300 K. In addition to the phonons, various photoluminescence (PL) lines of Er(3+) in the visible range are also observed. Our Raman data show an anomalous red-shift of two phonons (one at similar to 200 cm(-1) and another at similar to 520 cm(-1)) upon cooling from room temperature which is attributed to phonon-phonon anharmonic interactions. However, the phonons at similar to 310, 330, and 690 cm(-1) initially show a blue-shift upon cooling from room temperature down to about 130 K, followed by a red-shift, indicating a structural deformation at similar to 130 K. The intensities of the PL bands associated with the transitions between the various levels of the ground state manifold ((4)I(15/2)) and the (2)H(11/2) as well as (4)S(3/2) excited state manifolds of Er(3+) show a change at similar to 130 K. Moreover, the temperature dependence of the peak position of the two PL bands shows a change in their slope (d(omega)/d(T)) at similar to 130 K, thus further strengthening the proposal of a structural deformation. The temperature dependence of the peak positions of the PL bands has been analyzed using the theory of optical dephasing in crystals.

Impact of metal on the DNA photocleavage activity and cytotoxicity of ferrocenyl terpyridine 3d metal complexes

Ferrocenyl terpyridine 3d metal complexes and their analogues, viz. [M(Fc-tpy)(2)](ClO(4))(2) (1-4), [Zn(Ph-tpy)(2)](ClO(4))(2) (5) and [Zn(Fc-dpa)(2)]X(2) (X = ClO(4), 6; PF6, 6a), where M = Fe(II) in 1, Co(II) in 2, Cu(II) in 3 and Zn(II) in 4, Fc-tpy is 4'-ferrocenyl-2,2': 6', 2 `'-terpyridine, Ph-tpy is 4'-phenyl-2,2': 6', 2 `'-terpyridine and Fc-dpa is ferrocenyl-N,N-dipicolylmethanamine, are prepared and their DNA binding and photocleavage activity in visible light studied. Complexes 2, 4, 5 and 6a that are structurally characterized by X-ray crystallography show distorted octahedral geometry with the terpyridyl ligands binding to the metal in a meridional fashion, with Fc-dpa in 6a showing a facial binding mode. The Fc-tpy complexes display a charge transfer band in the visible region. The ferrocenyl (Fc) complexes show a quasi-reversible Fc(+)-Fc redox couple within 0.48 to 0.66 V vs. SCE in DMF-0.1 M TBAP. The DNA binding constants of the complexes are similar to 10(4) M(-1). Thermal denaturation and viscometric data suggest DNA surface binding through electrostatic interaction by the positively charged complexes. Barring the Cu(II) complex 3, the complexes do not show any chemical nuclease activity in the presence of glutathione. Complexes 1-4 exhibit significant plasmid DNA photocleavage activity in visible light via a photoredox pathway. Complex 5, without the Fc moiety, does not show any DNA photocleavage activity. The Zn(II) complex 4 shows a significant PDT effect in HeLa cancer cells giving an IC(50) value of 7.5 mu M in visible light, while being less toxic in the dark (IC(50) = 49 mu M).

Design of compact low pass filter with wide stop band using tri-section stepped impedance resonator

This paper reports the design of a compact low pass filter (LPF) with wide stop band region using trisection stepped impedance resonators in microstrip medium. Experimental results of a low pass filter designed at 1 GHz have been compared against the analytical and EM simulation results for the validation of the design. Results are satisfactorily matching each other. The maximum insertion of the measured filter is 0.2 dB and minimum return loss is 13.5 dB over the pass band. The stop band rejection is better than 20 dB from 1.5 GHz to 4.2 GHz and hence wide stop band performance is achieved. Overall size of the filter is 30 mm x 20 mm x 0.78 mm which is 0.1 lambda x 0.066 lambda. x 0.0026 lambda at 1 GHz. (C) 2011 Elsevier GmbH. All rights reserved.

Effect of substrate bias voltage on the structure, electric and dielectric properties of TiO(2) thin films by DC magnetron sputtering

Titanium dioxide (TiO(2)) films have been deposited on glass and p-silicon (1 0 0) substrates by DC magnetron sputtering technique to investigate their structural, electrical and optical properties. The surface composition of the TiO(2) films has been analyzed by X-ray photoelectron spectroscopy. The TiO(2) films formed on unbiased substrates were amorphous. Application of negative bias voltage to the substrate transformed the amorphous TiO(2) into polycrystalline as confirmed by Raman spectroscopic studies. Thin film capacitors with configuration of Al/TiO(2)/p-Si have been fabricated. The leakage current density of unbiased films was 1 x10(-6) A/cm(2) at a gate bias voltage of 1.5 V and it was decreased to 1.41 x 10(-7) A/cm(2) with the increase of substrate bias voltage to -150 V owing to the increase in thickness of interfacial layer of SiO(2). Dielectric properties and AC electrical conductivity of the films were studied at various frequencies for unbiased and biased at -150 V. The capacitance at 1 MHz for unbiased films was 2.42 x 10(-10) F and it increased to 5.8 x 10(-10) F in the films formed at substrate bias voltage of -150 V. Dielectric constant of TiO(2) films were calculated from capacitance-voltage measurements at 1 MHz frequency. The dielectric constant of unbiased films was 6.2 while those formed at -150 V it increased to 19. The optical band gap of the films decreased from 3.50 to 3.42 eV with the increase of substrate bias voltage from 0 to -150 V. (C) 2011 Elsevier B. V. All rights reserved.

An Accurate Model for EESM and its Application to Analysis of CQI Feedback Schemes and Scheduling in LTE

The Effective Exponential SNR Mapping (EESM) is an indispensable tool for analyzing and simulating next generation orthogonal frequency division multiplexing (OFDM) based wireless systems. It converts the different gains of multiple subchannels, over which a codeword is transmitted, into a single effective flat-fading gain with the same codeword error rate. It facilitates link adaptation by helping each user to compute an accurate channel quality indicator (CQI), which is fed back to the base station to enable downlink rate adaptation and scheduling. However, the highly non-linear nature of EESM makes a performance analysis of adaptation and scheduling difficult; even the probability distribution of EESM is not known in closed-form. This paper shows that EESM can be accurately modeled as a lognormal random variable when the subchannel gains are Rayleigh distributed. The model is also valid when the subchannel gains are correlated in frequency or space. With some simplifying assumptions, the paper then develops a novel analysis of the performance of LTE's two CQI feedback schemes that use EESM to generate CQI. The comprehensive model and analysis quantify the joint effect of several critical components such as scheduler, multiple antenna mode, CQI feedback scheme, and EESM-based feedback averaging on the overall system throughput.