Zur komplexchemie von 4-zentren-π-systemen : VIII. ESR-untersuchungen an heterobutadien-chelaten. I. Kalium-(diazabutadien-tetracarbonyl-metallate)

Glyoxal- and diacetyl-bis(imine)metal tetracarbonyls (RNCR′CR′NR)M(CO)₄ (M = Cr, Mo, W) are reduced with potassium in DME to give paramagnetic mono-anions. Their high-resolutior, ESR spectra show the hyperfine splittings of the magnetically active ligand atoms as well as the satellites of the metal isotopes ⁵³Cr,^95,97Mo and ¹⁸³W. The coupling constants are discussed with respect to π-bonding mechanisms.     

Sensitive determination of diquat by a kinetic method using the stopped-flow mixing technique

A simple, sensitive, selective, fast and inexpensive assay for the determination of diquat is proposed. The method is based on the reduction of the herbicide to a strongly fluorescent monocation radical with sodium dithionite. The initial rate of this reaction is directly proportional to the diquat concentration. The stopped-flow mixing technique was used because the kinetic data can be obtained in only 7 s, meaning that the method can be automated. The calibration graph is linear over the range 5-500 ng ml-1 and the precision (RSD) is close to 1.2%. The applicability of the method was demonstrated by determining the herbicide in different kinds of samples.     

Polymerization of 4-vinylpyridinium salts. III. A clarification of the mechanism of spontaneous polymerization

The mechanism of the spontaneous polymerization of 4-vinylpyiridine on quaternization or protonation has been investigated. Results indicate that initiation is caused by the nucleophilic attack of 4-vinylpyridine on the double bond of 4-vinylpyridinium ion. It was shown that halide ions do not contribute significantly to the initiation. In the case of acid salts of 4-vinylpyridine a hydrogen-transfer polymerization occurred to give an ionene polymer with pyridinium units in the main chain. The “matrix” polymerization of 4-vinylpyridine on poly(phosphoric acid) or poly(acrylic acid) also resulted in ionene formation. Conditions under which stable 4-vinylpyridinium salts can be obtained are discussed.     

Impact of silica environment on hyperfine interactions in 𝜖-Fe2O3 nanoparticles

Magnetic nanoparticles have found broad applications in medicine, especially for cell targeting and transport, and as contrast agents in MRI. Our samples of ??-Fe₂O₃ nanoparticles were prepared by annealing in silica matrix, which was leached off and the bare particles were then coated with amorphous silica layers of various thicknesses. The distribution of particle sizes was determined from the TEM pictures giving the average size ～20 nm and the thickness of silica coating ～5; 8; 12; 19 nm. The particles were further characterized by the XRPD and DC magnetic measurements. The nanoparticles consisted mainly of ??-Fe₂O₃ with admixtures of ～1 % of the α phase and less than 1 % of the γ phase. The hysteresis loops displayed coercivities of ～2 T at room temperature. The parameters of hyperfine interactions were derived from transmission Mössbauer spectra. Observed differences of hyperfine fields for nanoparticles in the matrix and the bare ones are ascribed to strains produced during cooling of the composite. This interpretation is supported by slight changes of their lattice parameters and increase of the elementary cell volume deduced from XRD. The temperature dependence of the magnetization indicated a two-step magnetic transition of the ??-Fe₂O₃ nanoparticles spread between ～85 K and ～150 K, which is slightly modified by remanent tensile stresses in the case of nanoparticles in the matrix. The subsequent coating of the bare particles by silica produced no further change in hyperfine parameters, which indicates that this procedure does not modify magnetic properties of nanoparticles.     

Effect of Finite Rise Time on the Strength of the Magnetic Field Generated in a Switched Plasma

The effect of a magnetized transient plasma on a circularly polarized source wave, when the rise time of the electron density profile is comparable to the source wave period, is considered. The H-formulation Green's function is developed to study the effect of a finite rise time on the generation of a wiggler magnetic field.     

Optical characterization of sol gel TiO<Subscript>2</Subscript> monoliths doped with Brilliant Green

Amorphous titanium dioxide monoliths doped with brilliant green (BG) were synthesized by the sol-gel process. The optical properties of the monoliths were characterized by Photoacoustic Spectroscopy and Photoluminescence Spectroscopy. The absorption spectra for the BG-doped TiO₂ monoliths exhibited two well defined absorption regions: a band below 400 nm corresponding to TiO₂ absorption and three absorption bands centered at 424 nm, 588 nm, and 632 nm due to brilliant green. While the undoped TiO₂ monoliths showed no luminescence, the doped samples showed a strong luminescence band at 673 nm, which increased its intensity for increasing organic dye doping.