Determination of silicon in biological samples by ICP-OES after non-oxidative decomposition under alkaline conditions.

A non-oxidative alkaline sample digestion procedure using tetramethylammonium hydroxide and a high pressure, microwave assisted autoclave digestion system was developed. The silicon concentrations of the digested samples were measured by inductively coupled axial plasma optical emission spectrometry (ICP-OES). Details of the digestion conditions as well as the optimised instrumental parameters for ICP-OES are described. The method was developed and tested using silicon-spiked ascorbic acid and applied to samples of animal tissue and organs. The total silicon content of two different reference materials, NIST 1577b Bovine liver and BCR 184 Bovine Muscle having neither certified nor informational values for Si was determined. The results obtained are compared with the results of independent methods such as wavelength dispersive x-ray fluorescence spectrometry (WDXRF) and solid sampling electrothermal atomic absorption spectrometry (ETAAS). The method described achieves a limit of detection of 2 mg kg(-1) using 100 mg of solid biological or organic material and covers a concentration range of up to 500 mg kg(-1).     

Chaotic patterns in a coupled oscillator-excitator biochemical cell system

In this paper we examine dynamical modes resulting from diffusion-like interaction of two model biochemical cells. Kinetics in each of the cells is given by the ICC model of calcium ions in the cytosol. Constraints for one of the cells are set so that it is excitable. One of the constraints in the other cell - a fraction of activated cell surface receptors-is varied so that the dynamics in the cell is either excitable or oscillatory or a stable focus. The cells are interacting via mass transfer and dynamics of the coupled system are studied as two parameters are varied-the fraction of activated receptors and the coupling strength. We find that (i) the excitator-excitator interaction does not lead to oscillatory patterns, (ii) the oscillator-excitator interaction leads to alternating phase-locked periodic and quasiperiodic regimes, well known from oscillator-oscillator interactions; torus breaking bifurcation generates chaos when the coupling strength is in an intermediate range, (iii) the focus-excitator interaction generates compound oscillations arranged as period adding sequences alternating with chaotic windows; the transition to chaos is accompanied by period doublings and folding of branches of periodic orbits and is associated with a Shilnikov homoclinic orbit. The nature of spontaneous self-organized oscillations in the focus-excitator range is discussed. (c) 1999 American Institute of Physics.     

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We show that for every odd integer p 1 there is an absolute positive constantc_p, so that the maximum cardinality of a set of vectors in Rⁿ such that the l_p distance between any pair is precisely 1, is at most c_p n log n. We prove some upper bounds for other l_p norms as well.     

Structural analysis of lignin by resonance Raman spectroscopy

Resonance Raman (RR) spectroscopy, combined with Kerr gated fluorescence rejection in the time domain, has recently elucidated lignin structure with unique sensitivity and selectivity. This promises structural studies of fluorescent natural macromolecules, such as lignin, which were previously not possible. Such studies rely on an improved understanding of the RR spectral behavior of lignin, which is today scarcely understood. We explain for the first time this behavior by a semi-empirical theory, and observe its pertinent features for lignin in vascular plants. We have used well-defined oxidative treatments as means of probing lignin structural elements, and show that RR sensitivity and selectivity depend crucially on excitation wavelength. Through the theory we relate these results to basic structural aspects of lignin. Spectra obtained by blue light laser excitation (400 nm) are dominated by low redox potential syringyl lignin groups, whereas lower photon energy (500 nm) decreases the selectivity markedly. RR bands depend on molecular structure but also on molecular environment. Thus charge transfer donor-acceptor interactions within lignin reduce the intensity of bands associated with electron rich moieties. New possibilities for basic and selective structural information on fluorescent natural materials, such as lignin, have thus appeared.     

Copper-catalyzed N-arylation of carbamate-protected hydrazones with organobismuthanes

Efficient copper(II) acetate-catalyzed N-arylation of carbamate-protected hydrazones was achieved under mild reaction conditions with organobismuthanes.     

Classical trajectories for two ring-shaped potentials

The present paper deals with the classical trajectories for two superintegrable systems: a system known in quantum chemistry as the Hartmann system and a system of potential use in quantum chemistry and nuclear physics. Both systems correspond to ring-shaped potentials. They admit two maximally superintegrable systems as limiting cases, viz., the isotropic harmonic oscillator system and the Coulomb–Kepler system in three dimensions. The planarity of the trajectories is studied in a systematic way. In general, the trajectories are quasi-periodic rather than periodic. A constraint condition allows to pass from quasi-periodic motions to periodic ones. When written in a quantum mechanical context, this constraint condition leads to new accidental degeneracies for the two systems studied. © 1992 John Wiley & Sons, Inc.     

Nucleation kinetics of folded chain crystals of polyethylene on active centers

Kinetic equations describing formation of nuclei of a new phase on active centers from supercooled melt taking into account exhaustion of active centers are solved numerically. Basic characteristics of nucleation process (total number of nuclei and nucleation rate) of folded chain crystals of polyethylene at low supercooling are determined and compared with measured data. Our model gives good coincidence with experimental measurements of the total number density of nuclei. Nucleation rate reaches some quasistationary limit at sufficiently long time, which is approximately 20% of the stationary nucleation rate determined by the standard way.     

Semiempirical estimates of the correlation energy in small clusters of hydrogen atoms

The Pamuk EPCE-F2σ method is applied to neutral and charged clusters composed from 2–9 hydrogen atoms. The range of applicability of the method is demonstrated with H₂, H ₃ ⁺ , and H₃ by comparing the results with the reported rigorous SCF and CI calculations. Predictions of the correlation energy were made for larger hydrogen atom systems, the emphasis being laid in the discussion on H₄, H ₅ ⁺ , and H₆.     

Neighboring group participation and rearrangement in hypobromous acid addition to 10β-vinyl-cholestanes

Hypobromous acid addition to the diol $\text{Ia}$ yields two epimeric dibromo 6β,19a-epoxides $\text{III}$ and $\text{IV}$ in a 83:17 ratio. Under the same conditions the 6β-acetoxy derivative $\text{Ib}$ gives three products: $\text{III}$ (46%), its epimer $\text{VII}$ (5%) and the spyrocyclic ketone $\text{V}$ (49%).     

Mesoionic dimethyl derivatives of some 1,2,4-triazinones. The course of the reaction of 3,5-dimethoxy, 3-methoxy-5-methylthio, 5-methoxy-3- methylthio and 3,5-bis(methylthio)-1,2,4-triazine with methyl iodide

Treatment of 3,5-dimethoxy-1,2,4-triazine ( 1a ) with methyl iodide was found to give depending on the reaction time triazinium iodide 2a , triaziniumolates 4a and 6a as well as methoxytriazinones 7a and 8a . Thermolysis of 2a gave triaziniumolates 4a and 6a . Reaction of 2a , 4a or methoxytriazinone 9a with methyl iodide in acetonitrile yielded as the sole product 6a . Reaction of 3-methoxy-5-methylthio-1,2,4-tri-azine (1b ) with methyl iodide gave triazinium iodide 2b and methylthio triazinone 7b . Hydrolysis of 2a,b afforded 4a . Reaction of 5-methoxy-3-methylthio-1,2,4-triazine ( 1c ) with methyl iodide gave triazinium iodide 2c , triaziniumolate 4b , triazinium iodide 5b and triazinone 8b . Hydrolysis of 2c yielded 4b and its thermolysis gave a mixture of 4b and 5b . Reaction of 2c , 4b and triazinone 9b with methyl iodide afforded 5b . Treatment of 3,5-bis(methylthio)-1,2,4-triazine ( 1d ) with methyl iodide was found to give a mixture of N1 and N2 methiodides 2d and 3d which gave on hydrolysis 4b and 8b , respectively. Methylation of 6-methyl derivatives 1c-g gave analogous results, however the proportions of N1 methylated products were lower and the reaction rates higher in comparison to their respective lower homologues 1a,c,d . The structures of the mesoionic dimethyl derivatives were assigned from uv, ir, ¹H nmr and electron impact mass spectra. The structural assignments were eventually confirmed by quantum chemical calculations of net charge distributions, bond lengths and ipso angles of the C5?O bonds.