Continuous flow hydroformylation using supported ionic liquid phase catalysts with carbon dioxide as a carrier.

A supported ionic liquid phase (SILP) catalyst prepared from [PrMIM][Ph2P(3-C6H4SO3)] (PrMIM = 1-propyl-3-methylimidazolium), [Rh(CO)(2)(acac)] (acacH = 2,4-pentanedione) [OctMIM]NTf2 (OctMIM = 1-n-octyl-3-methylimidazolium, Tf = CF3SO2) and microporous silica has been used for the continuous flow hydroformylation of 1-octene in the presence of compressed CO2. Statistical experimental design was used to show that the reaction rate is neither much affected by the film thickness (IL loading) nor by the syngas: substrate ratio. However, a factor-dependent interaction between the syngas: substrate ratio and film thickness on the reaction rate was revealed. Increasing the substrate flow led to increased reaction rates but lower overall yields. One of the most important parameters proved to be the phase behaviour of the mobile phase, which was studied by varying the reaction pressure. At low CO2 pressures or when N-2 was used instead of CO2 rates were low because of poor gas diffusion to the catalytic sites in the SILP. Furthermore, leaching of IL and Rh was high because the substrate is liquid and the IL had been designed to dissolve in it. As the CO2 pressure was increased, the reaction rate increased and the IL and Rh leaching were reduced, because an expanded liquid phase developed. Due to its lower viscosity the expanded liquid allows better transport of gases to the catalyst and is a poorer solvent for the IL and the catalyst because of its reduced polarity. Above 100 bar (close to the transition to a single phase at 106 bar), the rate of reaction dropped again with increasing pressure because the flowing phase becomes a better and better solvent for the alkene, reducing its partitioning into the IL film. Under optimised conditions, the catalyst was shown to be stable over at least 40 h of continuous catalysis with a steady state turnover frequency (TOF, mol product (mol Rh)(-1)) of 500 h(-1) at low Rh leaching (0.2 ppm). The selectivity of the catalyst was not much affected by the variation of process parameters. The linear: branched (1:b) ratios were ca. 3, similar to that obtained using the very same catalyst in conventional organic solvents.

A low-energy core-collapse supernova without a hydrogen envelope

The final fate of massive stars depends on many factors. Theory suggests that some with initial masses greater than 25 to 30 solar masses end up as Wolf-Rayet stars, which are deficient in hydrogen in their outer layers because of mass loss through strong stellar winds. The most massive of these stars have cores which may form a black hole and theory predicts that the resulting explosion of some of them produces ejecta of low kinetic energy, a faint optical luminosity and a small mass fraction of radioactive nickel. An alternative origin for low-energy supernovae is the collapse of the oxygen-neon core of a star of 7-9 solar masses. No weak, hydrogen-deficient, core-collapse supernovae have hitherto been seen. Here we report that SN 2008ha is a faint hydrogen-poor supernova. We propose that other similar events have been observed but have been misclassified as peculiar thermonuclear supernovae (sometimes labelled SN 2002cx-like events). This discovery could link these faint supernovae to some long-duration gamma-ray bursts, because extremely faint, hydrogen-stripped core-collapse supernovae have been proposed to produce such long gamma-ray bursts, the afterglows of which do not show evidence of associated supernovae.

Towards Surface Plasmon Resonance biosensing combined with bioaffinity-assisted nano HILIC Liquid Chromatography Time-of-flight Mass Spectrometry identification of Paralytic Shellfish Poisons

The potential for coupling technologies to deliver new, improved forms of bioanalysis is still in its infancy. We review a number of examples in which coupling has been successful, with special emphasis on combining surface-plasmon-resonance biosensors with mass spectrometry. We give an overview of current progress towards combining biosensor-based bioanalysis with chemical analysis for confirmation of paralytic shellfish poisons that are marine toxins. This comprehensive approach could be an alternative to the official methods currently used (e.g., animal testing and high-performance liquid chromatography with fluorescence detection) and could serve as a model for many more such applications. (C) 2009 Elsevier Ltd. All rights reserved.

Ion-acoustic waves in a two-electron-temperatute plasma: oblique modulation and envelope excitations

Theoretical and numerical studies are carried out for the nonlinear amplitude modulation of ion-acoustic waves propagating in an unmagnetized, collisionless, three-component plasma composed of inertial positive ions moving in a background of two thermalized electron populations. Perturbations oblique to the carrier wave propagation direction have been considered. The stability analysis, based on a nonlinear Schrodinger-type equation, shows that the wave may become unstable; the stability criteria depend on the angle theta between the modulation and propagation directions. Different types of localized excitations (envelope solitary waves) are shown to exist in qualitative agreement with satellite observations in the magnetosphere.

Finite ion temperature effects on oblique modulational stability and envelope excitations of dust-ion acoustic waves

Theoretical and numerical investigations are carried out for the amplitude modulation of dust-ion acoustic waves (DIAW) propagating in an unmagnetized weakly coupled collisionless fully ionized plasma consisting of isothermal electrons, warm ions and charged dust grains. Modulation oblique (by an angle theta) to the carrier wave propagation direction is considered. The stability analysis, based on a nonlinear Schrodinger-type equation (NLSE), exhibits a sensitivity of the instability region to the modulation angle theta, the dust concentration and the ion temperature. It is found that the ion temperature may strongly modify the wave's stability profile, in qualitative agreement with previous results, obtained for an electron-ion plasma. The effect of the ion temperature on the formation of DIAW envelope excitations (envelope solitons) is also discussed.

Electron-acoustic plasma waves: Oblique modulation and envelope solitons

Theoretical and numerical studies are presented of the amplitude modulation of electron-acoustic waves (EAWs) propagating in space plasmas whose constituents are inertial cold electrons, Boltzmann distributed hot electrons, and stationary ions. Perturbations oblique to the carrier EAW propagation direction have been considered. The stability analysis, based on a nonlinear Schrodinger equation, reveals that the EAW may become unstable; the stability criteria depend on the angle theta between the modulation and propagation directions. Different types of localized EA excitations are shown to exist.

Modulated wave packets and envelope solitary structures in complex plasmas

A theoretical study is presented of the nonlinear amplitude modulation of waves propagating in unmagnetized plasmas contaminated by charged dust particles. Distinct well-known dusty plasma modes are explicitly considered, namely, the dust-acoustic wave, the dust-ion acoustic wave, and transverse dust-lattice waves. Using a multiple-scale technique, a nonlinear Schrodinger-type equation is derived, describing the evolution of the wave amplitude. A stability analysis reveals the possibility for modulational instability to occur, possibly leading to the formation of different types of envelope-localized excitations (solitary waves), under conditions which depend on the wave dispersion laws and intrinsic dusty plasma parameters.

Nonlinear Lagrangian theory of envelope electrostatic plasma waves in a two-electron-temperature plasma

An analytical model based on Lagrangian variables is presented for the description of ion-acoustic waves propagating in an unmagnetized, collisionless, three-component plasma composed of inertial positive ions and two thermalized electron populations, characterized by different temperatures. The wave's amplitude is shown to be modulationally unstable. Different types of localized envelope electrostatic excitations are shown to exist, and their forms are analytically and numerically investigated in terms of the plasma dispersion and nonlinearity laws. These results are in qualitative agreement with satellite observations in the magnetosphere. (C) 2004 American Institute of Physics.

Envelope solitons associated with electromagnetic waves in a magnetized pair plasma

The amplitude modulation of magnetic field-aligned circularly polarized electromagnetic (CPEM) waves in a magnetized pair plasma is reexamined. The nonlinear frequency shifts include the effects of the radiation pressure driven density and compressional magnetic field perturbations as well as relativistic particle mass variations. The dynamics of the modulated CPEM wave packets is governed by a nonlinear Schrodinger equation, which has attractive and repulsive interaction potentials for fast and slow CPEM waves. The modulational stability of a constant amplitude CPEM wave is studied by deriving a nonlinear dispersion from the cubic Schrodinger equation. The fast (slow) CPEM mode is modulationally unstable (stable). Possible stationary amplitude solutions of the modulated fast (slow) CPEM mode can be represented in the form of bright and dark/gray envelope electromagnetic soliton structures. Localized envelope excitations can be associated with the microstructures in pulsar magnetospheres and in laboratory pair magnetoplasmas. (C) 2005 American Institute of Physics.

Exact theory for localized envelope modulated electrostatic wavepackets in space and dusty plasmas

Abundant evidence for the occurrence of modulated envelope plasma wave packets is provided by recent satellite missions. These excitations are characterized by a slowly varying localized envelope structure, embedding the fast carrier wave, which appears to be the result of strong modulation of the wave amplitude. This modulation may be due to parametric interactions between different modes or, simply, to the nonlinear (self-)interaction of the carrier wave. A generic exact theory is presented in this study, for the nonlinear self-modulation of known electrostatic plasma modes, by employing a collisionless fluid model. Both cold (zero-temperature) and warm fluid descriptions are discussed and the results are compared. The (moderately) nonlinear oscillation regime is investigated by applying a multiple scale technique. The calculation leads to a Nonlinear Schrodinger-type Equation (NLSE), which describes the evolution of the slowly varying wave amplitude in time and space. The NLSE admits localized envelope (solitary wave) solutions of bright(pulses) or dark- (holes, voids) type, whose characteristics (maximum amplitude, width) depend on intrinsic plasma parameters. Effects like amplitude perturbation obliqueness (with respect to the propagation direction), finite temperature and defect (dust) concentration are explicitly considered. Relevance with similar highly localized modulated wave structures observed during recent satellite missions is discussed.

Modulated electrostatic modes in pair plasmas: Modulational stability profile and envelope excitations

A pair plasma consisting of two types of ions, possessing equal masses and opposite charges, is considered. The nonlinear propagation of modulated electrostatic wave packets is studied by employing a two-fluid plasma model. Considering propagation parallel to the external magnetic field, two distinct electrostatic modes are obtained, namely a quasiacoustic lower moddfe and a Langmuir-like, as optic-type upper one, in agreement with experimental observations and theoretical predictions. Considering small yet weakly nonlinear deviations from equilibrium, and adopting a multiple-scale technique, the basic set of model equations is reduced to a nonlinear Schrodinger equation for the slowly varying electric field perturbation amplitude. The analysis reveals that the lower (acoustic) mode is stable and may propagate in the form of a dark-type envelope soliton (a void) modulating a carrier wave packet, while the upper linear mode is intrinsically unstable, and may favor the formation of bright-type envelope soliton (pulse) modulated wave packets. These results are relevant to recent observations of electrostatic waves in pair-ion (fullerene) plasmas, and also with respect to electron-positron plasma emission in pulsar magnetospheres. (c) 2006 American Institute of Physics.

Electrostatic mode envelope excitations in e-p-i plasmas - application in warm pair ion plasmas with a small fraction of stationary ions

The nonlinear propagation of amplitude-modulated electrostatic wavepackets in an electron-positron-ion (e-p-i) plasma is considered, by employing a two-fluid plasma model. Considering propagation parallel to the external magnetic field, two distinct electrostatic modes are obtained, namely a quasi-thermal acoustic-like lower mode and a Langmuir-like optic-type upper one. These results equally apply in warm pair ion ( e. g. fullerene) plasmas contaminated by a small fraction of stationary ions ( or dust), in agreement with experimental observations and theoretical predictions in pair plasmas. Considering small yet weakly nonlinear deviations from equilibrium, and adopting a multiple-scales perturbation technique, the basic set of model equations is reduced to a nonlinear Schrodinger (NLS) equation for the slowly varying electric field perturbation amplitude. The analysis reveals that the lower ( acoustic) mode is mostly stable for large wavelengths, and may propagate in the form of a dark-type envelope soliton ( a void) modulating a carrier wavepacket, while the upper linear mode is intrinsically unstable, and thus favours the formation of bright-type envelope soliton ( pulse) modulated wavepackets. The stability ( instability) range for the acoustic ( Langmuir-like optic) mode shifts to larger wavenumbers as the positive-to-negative ion temperature ( density) ratio increases. These results may be of relevance in astrophysical contexts, where e-p-i plasmas are encountered, and may also serve as prediction of the behaviour of doped ( or dust-contaminated) fullerene plasmas, in the laboratory.

Oblique modulation of electrostatic modes and envelope excitations in pair-ion and electron-positron plasmas

The nonlinear amplitude modulation of electrostatic waves propagating in a collisionless two-component plasma consisting of negative and positive species of equal mass and absolute charge is investigated. Pair-ion (e.g., fullerene) and electron-positron (e-p) plasmas (neglecting recombination) are covered by this description. Amplitude perturbation oblique to the direction of propagation of the wave has been considered. Two distinct linear electrostatic modes exist, namely an acoustic lower mode and Langmuir-type optic-type upper one. The behavior of each of these modes is examined from the modulational stability point of view. The stability criteria are investigated, depending on the electrostatic carrier wave number, the angle theta between the modulation and propagation directions, and the positron-to-electron temperature ratio sigma. The analysis shows that modulated electrostatic wavepackets associated to the lower (acoustic) mode are unstable, for small values of carrier wave number k (i.e., for large wavelength lambda) and for finite (small) values of the angle theta (yet stable for higher theta), while those related to the upper (optic-like) mode are stable for large values of the angle theta only, in the same limit, yet nearly for all values of sigma. These results are of relevance in astrophysical contexts (e.g., in pulsar environments), where e-p plasmas are encountered, or in pair fullerene-ion plasmas, in laboratory. (c) 2006 American Institute of Physics.