Catalytic gasification of glycerol in supercritical water

The conversion of glycerol in supercritical water (SCW) was studied at 510-550 °C and a pressure of 350 bars using both a bed of inert and non-porous ZrO2 particles (hydrothermal experiments), and a bed of a 1% Ru/ZrO2 catalyst. Experiments were conducted with a glycerol concentration of 5 wt% in a continuous isothermal fixed-bed reactor at a residence time between 2 and 10 s. Hydrothermolysis of glycerol formed water-soluble products such as acetaldehyde, acetic acid, hydroxyacetone and acrolein, and gases like H2, CO and CO2. The catalyst enhanced the formation of acetic acid, inhibited the formation of acrolein, and promoted gasification of the glycerol decomposition products. Hydrogen and carbon oxides were the main gases produced in the catalytic experiments, with minor amounts of methane and ethylene. Complete glycerol conversion was achieved at a residence time of 8.5 s at 510 °C, and at around 5 s at 550 °C with the 1 wt% Ru/ZrO2 catalyst. The catalyst was not active enough to achieve complete gasification since high yields of primary products like acetic acid and acetaldehyde were still present. Carbon balances were between 80 and 60% in the catalytic experiments, decreasing continuously as the residence time was increased. This was attributed partially to the formation of methanol and acetaldehyde, which were not recovered and analyzed efficiently in our set-up, but also to the formation of carbon deposits. Carbon deposition was not observed on the catalyst particles but on the surface of the inert zirconia particles, especially at high residence time. This was related to the higher concentration of acetic acid and other acidic species in the catalytic experiments, which may polymerize to form tar-like carbon precursors. Because of carbon deposition, hydrogen yields were significantly lower than expected; for instance at 550 °C the hydrogen yield potential was only 50% of the stoichiometric value.

Catalytic tuning of phosphinoethane ligand. An improved catalyst for hydrocarbon

Report for the scientific sojourn carried out at the Department of Chemistry University of North Texas (USA) from September until November 2006. It includes the performance of two computational chemistry studies: an experimental and computational study toward the intra- and intermolecular hydroarylation of isonitriles and the development of an improved catalyst for hydrocarbon functionalization.

Conjugation of genetically-engineered protein phosphatases to magnetic particles for okadaic acid detection

This work presents the functional characterisation of a protein phosphatase 2A (PP2A) catalytic subunit obtained by genetic engineering and its conjugation to magnetic particles (MPs) via metal coordination chemistry for the subsequent development of assays for diarrheic lipophilic marine toxins. Colorimetric assays with free enzyme have allowed the determination of the best enzyme activity stabiliser, which is glycerol at 10%. They have also demonstrated that the recombinant enzyme can be as sensitive towards okadaic acid (OA) (LOD=2.3μg/L) and dinophysistoxin-1 (DTX-1) (LOD=15.2μg/L) as a commercial PP2A and, moreover, it has a higher operational stability, which makes possible to perform the protein phosphatase inhibition assay (PPIA) with a lower enzyme amount. Once conjugated to MPs, the PP2A catalytic subunit still retains its enzyme activity and it can also be inhibited by OA (LOD=30.1μg/L).

The complete Raman spectrum of nanometric SnO2 particles

The complete Raman spectrum of SnO2 nanoparticles in presented and analyzed. In addition to the "classical" modes observed in the rutile structure, two other regions shown Raman activity for nanoparticles. The Raman bands in the low-frequency region are attributed to acoustic modes associated with the vibration of the individual nanoparticle as a whole. The high-frequency region is activated by surface disorder. A detailed analysis of these regions and the changes in the normal modes of SnO2 are presented as a function nanoparticle size.

Flux and composition of settling particles across the continental margin of the Gulf of Lion: the role of dense shelf water cascading

Settling particles were collected using sediment traps deployed along three transects in the Lacaze-Duthiers and Cap de Creus canyons and the adjacent southern open slope from October 2005 to October 2006. The settling material was analyzed to obtain total mass fluxes and main constituent contents (organic matter, opal, calcium carbonate, and siliciclastics). Cascades of dense shelf water from the continental shelf edge to the lower continental slope occurred from January to March 2006. They were traced through strong negative near-bottom temperature anomalies and increased current speeds, and generated two intense pulses of mass fluxes in January and March 2006. This oceanographic phenomenon appeared as the major physical forcing of settling particles at almost all stations, and caused both high seasonal variability in mass fluxes and important qualitative changes in settling material. Fluxes during the dense shelf water cascading (DSWC) event ranged from 90.1 g m(-2) d(-1) at the middle Cap de Creus canyon (1000 m) to 3.2 g m(-2) d(-1) at the canyon mouth (1900 m). Fractions of organic matter, opal and calcium carbonate components increased seaward, thus diminishing the siliciclastic fraction. Temporal variability of the major components was larger in the canyon mouth and open slope sites, due to the mixed impact of dense shelf water cascading processes and the pelagic biological production. Results indicate that the cascading event remobilized and homogenized large amounts of material down canyon and southwardly along the continental slope contributing to a better understanding of the off-shelf particle transport and the internal dynamics of DSWC events.

From subdiffusion to superdiffusion of particles on solid surfaces

We present a numerical and partially analytical study of classical particles obeying a Langevin equation that describes diffusion on a surface modeled by a two-dimensional potential. The potential may be either periodic or random. Depending on the potential and the damping, we observe superdiffusion, large-step diffusion, diffusion, and subdiffusion. Superdiffusive behavior is associated with low damping and is in most cases transient, albeit often long. Subdiffusive behavior is associated with highly damped particles in random potentials. In some cases subdiffusive behavior persists over our entire simulation and may be characterized as metastable. In any case, we stress that this rich variety of behaviors emerges naturally from an ordinary Langevin equation for a system described by ordinary canonical Maxwell-Boltzmann statistics.

Inertial effects on reactive particles advected by turbulence

We study the problem of the advection of passive particles with inertia in a two-dimensional, synthetic, and stationary turbulent flow. The asymptotic analytical result and numerical simulations show the importance of inertial bias in collecting the particles preferentially in certain regions of the flow, depending on their density relative to that of the flow. We also study how these aggregates are affected when a simple chemical reaction mechanism is introduced through a Eulerian scheme. We find that inertia can be responsible for maintaining a stationary concentration pattern even under nonfavorable reactive conditions or destroying it under favorable ones.

Lattice-gas model of particles with orientational and positional degrees of freedom: Mean-field treatment

We consider a lattice-gas model of particles with internal orientational degrees of freedom. In addition to antiferromagnetic nearest-neighbor (NN) and next-nearest-neighbor (NNN) positional interactions we also consider NN and NNN interactions arising from the internal state of the particles. The system then shows positional and orientational ordering modes with associated phase transitions at Tp and To temperatures at which long-range positional and orientational ordering are, respectively, lost. We use mean-field techniques to obtain a general approach to the study of these systems. By considering particular forms of the orientational interaction function we study coupling effects between both phase transitions arising from the interplay between orientational and positional degrees of freedom. In mean-field approximation coupling effects appear only for the phase transition taking place at lower temperatures. The strength of the coupling depends on the value of the long-range order parameter that remains finite at that temperature.

Atomic structure of the nanocrystalline Si particles appearing in nanostructured Si thin films produced in low-temperature radiofrequency plasmas

Nanostructured Si thin films, also referred as polymorphous, were grown by plasma-enhanced chemical vapor deposition. The term "polymorphous" is used to define silicon material that consists of a two-phase mixture of amorphous and ordered Si. The plasma conditions were set to obtain Si thin films from the simultaneous deposition of radical and ordered nanoparticles. Here, a careful analysis by electron transmission microscopy and electron diffraction is reported with the aim to clarify the specific atomic structure of the nanocrystalline particles embedded in the films. Whatever the plasma conditions, the electron diffraction images always revealed the existence of a well-defined crystalline structure different from the diamondlike structure of Si. The formation of nanocrystallinelike films at low temperature is discussed. A Si face-cubic-centered structure is demonstrated here in nanocrystalline particles produced in low-pressure silane plasma at room temperature.

Erasing the glassy state in magnetic fine particles

BaFe10.4Co0.8Ti0.8O19 magnetic fine particles exhibit most of the features attributed to glassy behavior, e.g., irreversibility in the hysteresis loops and in the zero-field-cooling and field-cooling curves extends up to very high fields, and aging and magnetic training phenomena occur. However, the multivalley energy structure of the glassy state can be strongly modified by a field-cooling process at a moderate field. Slow relaxation experiments demonstrate that the intrinsic energy barriers of the individual particles dominate the behavior of the system at high cooling fields, while the energy states corresponding to collective glassy behavior play the dominant role at low cooling fields.

Reply to "Comment on 'Erasing glassy state in magnetic fine particles'"

The Comment affirms that no phase transition occurs in spin-glass systems with an applied magnetic field. However, only according to the droplet model is this result expected. Other models do not predict this result and, consequently, it is under current discussion. In addition, we show how the experimental results obtained in our system correspond to a cluster glass rather than to a true spin glass.