Ternary rare-earth alumo-silicides—single-crystal growth from Al flux, structural and physical properties

A number of rare-earth alumo-silicides (R-Al-Si) have been synthesized from the corresponding elements by high-temperature reactions, carried out in excess of aluminum to serve as a flux. Under these experimental conditions, large single crystals of all R-Al-Si ternary phases were readily produced. The crystal structures these ternaries adopt were studied by means of powder and single-crystal X-ray diffraction and were classified as follows: (1) the early rare-earths (R=La, Ce, Pr, Nd, Sm, Gd) yield RAl_xSi_2−x, x∼1, non-stoichiometric ternary derivatives of the body-centered α-ThSi₂-type; (2) the late rare-earths (R=Tb, Dy, Ho, Er, Tm) form stoichiometric R₂Al₃Si₂ compounds that crystallize in the C-centered monoclinic Y₂Al₃Si₂-type; (3) the divalent Eu and Yb produce EuAl₂Si₂ and YbAl₂Si₂ with the trigonal CaAl₂Si₂-type, whereas the last lanthanide element, Lu, forms LuAlSi with C-centered orthorhombic YAlGe-type. These structural trends are reviewed, and the evolution of the basic physical properties such as magnetism, heat capacity and electrical resistivity when moving across the series is described in detail.     

Synthesis and structural, spectroscopic and magnetic studies of two new polymorphs of Mn(SeO3)·H2O

Two new manganese(II) selenite polymorphs with formula Mn(SeO₃)·H₂O have been synthesized by slow evaporation from an aqueous solution. The crystal structure of both compounds (1) and (2) have been solved from X-ray diffraction data. The structure of (1) was determined from single-crystal X-ray diffraction techniques. The compound crystallizes in the Ama2 space group, with a=5.817(1), b=13.449(3), and Z=4. The structure of (2) has been solved from X-ray powder diffraction data. This phase crystallizes in the P2₁/n space group with unit-cell parameters of a=4.921(3), b=13.121(7), , β=90.03(2)° and Z=4. Both polymorphs exhibit a layered structure formed by isolated sheets of MnO₆ octahedra and (SeO₃)²⁻ trigonal pyramids in the (010) plane. These layers, which contain one manganese and selenium atom crystallographically independent, are formed by octahedra linked between them through the selenite oxoanions. The difference of both compounds consists in the stacking of the layers along the b-axis. The IR spectra show the characteristic bands of the selenite anion. Studies of luminescence performed at 6 K and diffuse reflectance spectroscopy have been carried out for both phases. The Dq and Racah (B and C) parameters, from luminescence and diffuse reflectance spectroscopy, are Dq=705, B=750, for (1) and Dq=720, B=745, for (2). The ESR spectra of both compounds are isotropic with g-values of 1.99(1). Magnetic measurements indicate the presence of antiferromagnetic couplings in both phases. The J-exchange parameters have been estimated by fitting the experimental magnetic data to a model for square-planar lattice. The values obtained are J/k=-0.83, −0.91 K and J^′/k=-0.97, −1.20 K, for polymorphs (1) and (2), respectively.     

Magnetic interactions in a series of paramagnetic Ln(III) complexes with a chelated imino nitroxide radical

The magnetic interactions in a new series of isostructural imino nitroxide radical lanthanide(III) complexes, [Ln(hfac)₃(IM2py)] (Ln = Gd–Yb: IM2py = 2-(2′-pyridyl)-4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-1-oxy; hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), are examined by considering the intrinsic paramagnetic contribution of the Ln(III) ion from the corresponding [Ln(hfac)₃(pybzim)] with a diamagnetic pybzim(2-(2-pyridyl)benzimidazole) ligand; the Ln(III)–IM2py interaction being antiferromagnetic for the 4f⁷ to 4f¹³ Ln(III) complexes and negligibly small for the other complexes. This series is the first example reverse to the previous cases for the series of Ln–Cu or Ln–aminoxyl(NIT) radical (4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-3-oxide-1-oxy) complexes, other than only a few examples of semiquinone Ln complexes. This reverse nature of the magnetic interaction, as compared with the NIT complexes, validates the empirical approach by O. Kahn et al. [Inorg. Chem. 38 (1999) 3692; J. Am. Chem. Soc. 122 (2000) 3413] in the spin-coupled systems for a series of Ln(III) complexes.     

Dielectric,magnetic and mechanical properties of ferrite composites

The dielectric and magnetic properties of carbonyl—iron (CI) and nickel zinc ferrite polymer composites were studied with respect to the ferrite particulate content and microwave frequency. From the experimental data and using empirical models that relate the composite dielectric and magnetic properties, the respective dielectric and magnetic properties of the neat fillers were estimated. The tensile properties of the particulate composites comprising CI were shown to follow qualitatively Mooney's equation for the elastic modulus. The tensile strength of an elastomeric polyurethane and PVC composites containing CI increased with particulate content, while the elongation to break decreased with filler content. SEM micrographs of tensile fracture surfaces indicated that somewhat better adhesion is obtained in the case of the polyurethane-based composites compared to the PVC ones.     

Nanowire‐Based Electrochemical Biosensors

We review recent advances in biosensors based on one‐dimensional (1‐D) nanostructure field‐effect transistors (FET). Specifically, we address the fabrication, functionalization, assembly/alignment and sensing applications of FET based on carbon nanotubes, silicon nanowires and conducting polymer nanowires. The advantages and disadvantages of various fabrication, functionalization, and assembling procedures of these nanosensors are reviewed and discussed. We evaluate how they have been used for detection of various biological molecules and how such devices have enabled the achievement of high sensitivity and selectivity with low detection limits. Finally, we conclude by highlighting some of the challenges researchers face in the 1‐D nanostructures research arena and also predict the direction toward which future research in this area might be directed.     

Bioelectrochemical Magnetic Immunosensing of Trichloropyridinol: A Potential Insecticide Biomarker

A fast, simple and sensitive bioelectrochemical magnetic immunosensing method is developed to monitor a potential insecticide biomarker, trichloropyridinol (TCP), in environmental sample. A magnet/glassy carbon (MGC) working electrode was used to accumulate immunocomplex associated magnetic beads and separate free and unbound reagents after liquid phase competitive immunoreaction among TCP antibody coated magnetic beads, TCP analyte and horseradish peroxidase (HRP) labeled TCP. The activity of HRP tracers was monitored by square‐wave voltammetry (SWV) by scanning electrocactive enzymatic product in the presence of 3,3′,5,5′‐tetramethylbenzidine dihydrochloride and hydrogen peroxide (TMB‐H₂O₂) substrate solution. The electrochemical signal of enzymatic product was greatly enhanced by dual accumulation events: magnetic accumulation of enzyme tracers bound magnetic beads and constant potential accumulation of enzymatic product. The voltammetric characteristics of substrate and enzymatic product were investigated, and the parameters of SWV analysis and immunoassay were optimized. Under the optimal conditions the immunosensor was used to measure as low as 5 ng L^?1 (ppt) TCP, which is 50‐fold lower than the value indicated by the manufacture of the TCP RaPID Assay kit (0.25 μg/L, colorimetric detection). The performance of the developed immunosensing system was successfully evaluated with river water samples spiked with TCP, indicating this convenient and sensitive technique offers great promise for decentralized environmental application. This technique could be readily used for detection of other environmental contaminants by developing specific antibodies against the contaminants and are expected to open new opportunities for environmental monitoring and public health.     

Thermal conductivity measurements on ferrofluids

The thermal conductivity of a number of ferrofluids consisting of colloidally dispersed Fe₃O₄ particles in diester, hydrocarbon, water and fluorcarbon carriers have been measured at 38°C. The variation in thermal conductivity with particle concentration is well described by Tareef's equation (1940). This has enabled the ratio of the physical to magnetic size to be determined and compared with estimates of the ratio obtained from electron micrographs and magnetic measurements.The fit between theory and experiment is particularly good for hydrocarbon carrier fluids giving the ratio of solid to magnetic radiusR _i/R _m=1.24±0.03 compared with the value obtained from magnetic data and electron micrographs of 1.19±0.07. The corresponding value from the fluids with a diester carrier ranges between 1.1<R _d/R _m<1.3 which is again consistent with microscopy and magnetic data.The application of a magnetic field of 0.1 T had no noticeable effect on the thermal conductivities of ferrofluids.     

Characterization of CNS disorders and evaluation of therapy using structural and functional MRI

Modern drug development requires technologies that allow rapid translation from the preclinical to the clinical stage. It is obvious that non-invasive imaging modalities such as magnetic resonance imaging (MRI) will play a central role in this regard. This article reviews the use of structural and functional MRI readouts for characterization of central nervous system (CNS) disorders and evaluation of the efficacy of potential CNS drugs. Examples comprise dementia of Alzheimer's type, cerebral ischemia, and neuroinflammation covering both clinical and preclinical aspects. In these examples MRI has been used to obtain relevant structural information on brain atrophy, on the location and extent of ischemic brain areas, and on the number and distribution of demyelinated plaques. These structural data are complemented by readouts assessing the functional consequences associated with the pathomorphological changes. In the last decade, MRI has evolved into a standard tool for the development of CNS drugs. With regard to target-specific/molecular imaging applications MRI is limited by its inherently low sensitivity; complementary imaging modalities utilizing optical and radionuclear reporter systems will thus be required.     

Influence of the preparation procedure on the properties of polyaniline based magnetic composites

A versatile process for the preparation of composite films consisting of magnetite (Fe₃O₄) nanoparticles embedded in a polyaniline (PANI) matrix is reported. Spectroscopic properties of polyaniline matrix (PANI-EB), polyaniline protonated with camphor sulfonic acid (PANI-CSA_0.5) PANI-ES and PANI/Fe₃O₄-CSA_0.5 composites were studied, both in the state of the solutions of m-cresol and in thin films processed from the same solvents. The results of these studies indicate that m-cresol can be used for PANI/Fe₃O₄ composite preparation. Such films show both reasonably high electrical conductivity and magnetic permeability. A controlled application of a magnetic field during the casting process resulted in the formation of the materials with an unusual combination of magnetic and transport properties. The obtained films show the behavior that can be explained by the presence of both ferromagnetic and paramagnetic phases. The superparamagnetic contribution, if any, is very small. Application of the external magnetic field during fabrication of the composites stimulates creation of the aggregates of magnetic particles which, although keeps conductivity at a relatively high level, leads to a small decrease of the conductivity value.     

Structure and Magnetic Properties of Nickel–Zinc Ferrite Nanoparticles Prepared by Glass Crystallization Method

Summary. The magnetic and microstructure properties of Fe₂O₃–0.4NiO–0.6ZnO–B₂O₃ glass system, which was subjected to heat treatment in order to induce a magnetic crystalline phase (Ni_0.4Zn_0.6-Fe₂O₄ crystals) within the glass matrix, were investigated. DSC measurement was performed to reveal the crystallization temperature of the prepared glass sample. The obtained samples, produced by heat treatment at 765°C for various times (1, 1.5, 2, and 3 h), were characterized by X-ray diffraction, IR spectra, transmission electron microscopy, and vibrating sample magnetometer. The results indicated the formation of spinel Ni–Zn ferrite in the glass matrix. Particles of the ferrite with sizes ranging from 28 to 120 nm depending on the sintering time were observed. The coercivity values for different heat-treatment samples were found to be in the range from 15.2 to 100 Oe. The combination of zinc content and sintering times leads to samples with saturation magnetization ranging from 12.25 to 17.82 emu/g.