Transition to Chaos in the Floating Half Zone Convection

The transition process from steady convection to chaos is experimentally studied in thermocapillary convections of floating half zone. The onset of temperature oscillations in the liquid bridge of floating half zone and further transitions of the temporal convective behaviour are detected by measuring the temperature in the liquid bridge. The fast Fourier transform reveals the frequency and amplitude characteristics of the flow transition. The experimental results indicate the existence of a sequence of period-doubling bifurcations that culminate in chaos. The measured Feigenbaum numbers are δ2 =4.69 and δ4 = 4.6, which are comparable with the theoretical asymptotic value δ=4.669.     

Obliquely propagating ion-acoustic shock waves in a degenerate quantum plasma

A theoretical investigation has been carried out on the propagation of non-linear ion-acoustic shock waves (IASHWs) in a magnetized degenerate quantum plasma system composed of inertial non-relativistic positively charged light and heavy ions, inertialess non-relativistically or ultra-relativistically degenerate electrons and positrons. The reductive perturbation method has been employed to derive the Burgers' equation. It has been observed that under consideration, our plasma model supports only positive potential shock structure. It is also found that the amplitude and steepness of the IASHWs have been significantly modified by the variation of ion kinematic viscosity, oblique angle, number density, and charge state of the plasma species. The results of our present investigation will be helpful for understanding the propagation of IASHWs in white dwarfs and neutron stars.     

Commensurability oscillations in NdBa2Cu3Oy single crystals

Commensurability between inter-vortex distance and crystal lattice constant is investigated by angular dependent magnetization in very pure twinned and twin-free NdBa₂ Cu₃ O_y single crystals. With increasing temperature the incommensurate states split up and become finally commensurate with half the vortex distance. These new commensurate states are related to a substructure of the intrinsic pinning potential within the unit cell and discussed with respect to temperature, field, anisotropy, and twin structure.     

Determining a 'safe' high-mass limit in matrix-assisted laser desorption/ionisation time-of-flight mass spectra of coal derived materials with reference to instrument noise

Three methods for determining a 'safe' estimate for high-mass limits of MALDI spectra of coal derived liquids were explored, using a sample of coal-tar pitch and its pyridine-insoluble fraction. Co-addition of increasing numbers of single-shot spectra (10, 30, 50 and 100 pulses) showed visually observable reductions in noise levels, consistent with robust and statistically meaningful signals. Three separate types of post-acquisition calculation were used to identify high-mass limits of the spectra. (i) A literature method indicated high-mass limits similar to those observed visually-as a shift from baseline at the highest masses, nearly 350 000 u for the coal tar pitch and about 390 000 u for its pyridine insoluble fraction. (ii) Comparing instrument signal with pre-selected multiples of the standard deviation, upper mass estimates of between 40-60 000 u for the coal-tar pitch and about 95 000 u for its pyridine-insoluble fraction were found. (iii) Calculation of the slope was used to identify 'lift-off' of the spectrum from baseline. The angle between the smoothed spectrum and the baseline was matched to a pre-selected value (e.g. 0.5 degrees and 1 degrees ). However, the arbitrary specification of the key parameter did not establish this last method on a firm basis. The choice of a criterion for estimating high-mass limits of MALDI spectra remains a semi-quantitative procedure; a reasonably conservative high-mass limit may be estimated by comparison of signal with five times the standard deviation. However, evaluation of size exclusion chromatograms of the present samples using polystyrene standards suggests that molecular mass distributions of pitch samples arrived at by MALDI mass spectrometry are, at least partly, determined by the limitations of available instruments. Copyright 1999 John Wiley & Sons, Ltd.     

Exploiting distinct molecular architectures of ultrathin films made with iron phthalocyanine for sensing

The possibility of generating distinct film properties from the same material is crucial for a number of applications, which can only be achieved by controlling the molecular architecture. In this paper we demonstrate as a proof-of-principle that ultrathin films produced from iron phthalocyanine (FePc) may be used to detect trace amounts of copper ions in water, where advantage was taken of the cross sensitivity of the sensing units that displayed distinct electrical properties. The ultrathin films were fabricated with three methods, namely physical vapor deposition (PVD), Langmuir-Blodgett (LB), and electrostatic layer-by-layer (LbL) techniques, where for the latter tetrasulfonated phthalocyanine was used (FeTsPc). PVD and LB films were more homogeneous than the LbL films at both microscopic and nanoscopic scales, according to results from micro-Raman spectroscopy and atomic force microscopy (AFM), respectively. From FTIR spectroscopy data, these more homogeneous films were found to have FePc molecules oriented preferentially, tilted in relation to the substrate surface, while FeTsPc molecules were isotropically distributed in the LbL films. Impedance spectroscopy measurements with films adsorbed onto interdigitated gold electrodes indicated that the electrical response depends on the type of film-forming method and varies with incorporation of copper ions in aqueous solutions. Using principal component analysis (PCA), we were able to exploit the cross sensitivity of the sensing units and detect copper ions (Cu(2+)) down to 0.2 mg/L, not only in ultrapure water but also in distilled and tap water. This level of sensitivity is sufficient for quality control of water for human consumption, with a fast, low-cost method.     

Syntheses and reactions of some fluorinated dienes,cyclobutenes and furans

There are many reports¹ of the pyrolysis of fluorinated organic compounds, including the defluorination of cyclic fluorocarbons over iron to give aromatic compounds. Extending this technique we have investigated the flow pyrolysis of some readily accessible unsaturated fluorocarbons, such as I, II, and III, and found these to be synthetically

useful routes to fluorinated dienes, cyclobutenes, and furans. Pyrolyses were carried out using a nitrogen flow over platinum, iron or caesium fluoride heated at 430–700°. The various products can all be rationalized in terms of intermediate allylic radicals, and the solid substrate influences which allylic radicals are formed.We are also investigating the chemistry of those now accessible compounds, such as IV, V, and VI, and some of the preliminary results are described.

For example the fluoride ion induced dimerisation of IV gave two major products VII and VIII via a particular interesting mechanism.

     

ChemInform Abstract: The Ground-State Potential Energy Surface of Diazene

has been studied by using a complete active space MCSCF wave function generated by distributing eight electrons among eight orbitals.