Versatile chelating behavior of benzil bis(thiosemicarbazone) in zinc, cadmium, and nickel complexes

Reactions of benzil bis(thiosemicarbazone), LH(6), with M(NO(3))(2).nH(2)O (M = Zn, Cd, and Ni), in the presence of LiOH.H(2)O, show the versatile behavior of this molecule. The structure of the ligand, with the thiosemicarbazone moieties on opposite sides of the carbon backbone, changes to form complexes by acting as a chelating molecule. Complexes of these metal ions with empirical formula [MLH(4)] were obtained, although they show different molecular structures depending on their coordinating preferences. The zinc complex is the first example of a crystalline coordination polymer in which a bis(thiosemicarbazone) acts as bridging ligand, through a nitrogen atom, giving a 1D polymeric structure. The coordination sphere is formed by the imine nitrogen and sulfur atoms, and the remaining position, in a square-based pyramid, is occupied by an amine group of another ligand. The cadmium derivative shows the same geometry around the metal ion but consists of a dinuclear structure with sulfur atoms acting as a bridge between the metal ions. However, in the nickel complex LH(6) acts as a N(2)S(2) ligand yielding a planar structure for the nickel atom. The ligand and its complexes have been characterized by X-ray crystallography, microanalysis, mass spectrometry, IR, (1)H, and (13)C NMR spectroscopies and for the cadmium complex by (113)Cd NMR in solution and in the solid state.     

Electrochemical investigations of baicalin and DNA–baicalin interactions

Baicalin is an anti-HIV drug purified from the traditional Chinese medicinal plant Scutellaria Baicalensis Georgi. Baicalin has proven to be electroactive at pyrolytic graphite (PG) electrodes. We thus studied its interaction with DNA via the electrochemical approach. We observed that the peak currents corresponding to the baicalin reduction–oxidation (redox) reaction significantly decrease upon the addition of DNA. With complementary ultraviolet/visible (UV/Vis) spectroscopic evidence, we suggest that baicalin binds to DNA through intercalation. This feature has enabled baicalin to discriminate between double-stranded DNA (dsDNA) and single-stranded DNA (ssDNA).Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Irradiation-induced magnetism in graphite: a density functional study

Recent experiments indicate that proton irradiation triggers ferromagnetism in originally nonmagnetic graphite samples while He ion bombardment has a much smaller effect. To understand the origin of irradiation-induced magnetism, we have performed spin-polarized density functional theory calculations of the magnetic properties of the defects which are most likely to appear under irradiation vacancies and vacancy-hydrogen complexes. Both defects are magnetic, but as for the latter we find that H adsorption on one of the vacancy dangling bonds gives rise to a magnetic moment double that of the naked vacancy. We show that for small irradiation doses vacancy-hydrogen complexes result in a macroscopic magnetic signal which agrees well with the experimental values.     

Nonexistence of abelian difference sets: Lander's conjecture for prime power orders

In 1963 Ryser conjectured that there are no circulant Hadamard matrices of order 4$"> and no cyclic difference sets whose order is not coprime to the group order. These conjectures are special cases of Lander's conjecture which asserts that there is no abelian group with a cyclic Sylow -subgroup containing a difference set of order divisible by . We verify Lander's conjecture for all difference sets whose order is a power of a prime greater than 3.

     

Ferroelectric properties of Bi3.25−x/3La0.75Ti3−xNbxO12 films prepared by pulsed laser deposition

Bi₄Ti₃O₁₂ (BiT), Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_4−x/3Ti_3−xNb_xO₁₂ (BTN) and Bi_3.25−x/3La_0.75Ti_3−xNb_xO₁₂ (BLTN) thin films have been prepared by pulsed laser deposition. BTN and BLTN films exhibit a maximum in the remanent polarization P_r at a Nb content x=0.018. At this Nb content, the BLTN film has a P_r value (25 μC/cm²) that is much higher than that of BiT and a coercive field similar to that of BiT. The polarization of this BLTN film is fatigue-free up to 10⁹ switching cycles. The high fatigue resistance is mainly due to the substitution of Bi³⁺ ions by La³⁺ ions at the A site and the enhanced P_r arises largely from the replacement of Ti⁴⁺ ions by Nb⁵⁺ ions at the B site. The mechanisms behind the effects of the substitution at the two sites are discussed.     

White organic light-emitting devices

In view of their potential applications in flat panel displays, organic light-emitting devices have attracted much attention in the past decade. A challenging target in this field is to realize full color display applications. One of the approaches proposed for these is combining white emission with color filters, where efficient and pure white emission (especially at high brightness) is necessary. In this paper, three kinds of white organic light-emitting devices with different structures and materials are fabricated and their characteristics are discussed.     

Effect of surface roughness on determination of bulk tissue optical parameters

Monte Carlo simulations have been conducted to investigate the effect of surface roughness on the inverse determination of bulk optical parameters. Results show that mus, mua, and g can be overestimated by an order of magnitude for thin slab tissue samples with a moderate index mismatch at the interfaces if typical surface roughness is neglected. Measurements of Intralipid samples between glass windows with smooth and rough surfaces have been carried out and agreement was found between the numerical and the experimental data. This study suggests that the surface roughness should be taken into account for both in vitro and in vivo determination of bulk tissue optical parameters.     

The shock formation distance in a bounded sound beam of finite amplitude

This paper investigates the shock formation distance in a bounded sound beam of finite amplitude by solving the Khokhlov-Zabolotskaya-Kuznetsov (KZK) equation using frequency-domain numerical method. Simulation results reveal that, besides the nonlinearity and absorption, the diffraction is another important factor that affects the shock formation of a bounded sound beam. More detailed discussions of the shock formation in a bounded sound beam, such as the waveform of sound pressure and the spatial distribution of shock formation, are also presented and compared for different parameters.     

Novel germanium-based magnetic semiconductors

Epitaxial synthesis and properties of novel Co and Mn-doped Ge magnetic semiconductors were studied. Epitaxial growth of high quality films with high doping concentrations has been stabilized by the use of two dopants. The magnetic and transport properties of the system exhibit high T(C) and large magnetoresistance effects that can be controlled systematically by the doping concentration. The maximum T(C) achieved in the semiconducting materials is approximately 270 K at a composition of Co0.12Mn0.03Ge0.85.     

Preparation and characterization of a poled nanocrystal and polymer composite PbTiO3/PEKc film for electro-optic applications

Composite thin films of PbTiO₃ nanocrystals and high-transparency PEKc polymer for applications in electro-optical devices were prepared using the spin coating technique. The size of the PbTiO₃ nanocrystals was estimated to be 30–40 nm using a transmission electron microscope. The transmission technique, a simple method for measuring the electro-optic coefficients of poled composite polymer films was developed. The electro-optic coefficient γ₃₃ of poled PbTiO₃/PEKc composite polymer films was measured to be 18.34 pm  V^-1 at 633 nm under room temperature. The index at 633 nm and the dielectric constant at 100 kHz under room temperature were determined to be 1.65248 and 7.32, respectively. The figure of merit F₂=n⁷γ²/ε was estimated to be 1546, showing very good electro-optical properties. Received: 5 February 2002 / Accepted: 12 March 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: +852/2788-7791, E-mail: eeytc@cityu.edu.hk