Modification of platinum surfaces by spontaneous deposition: Methanol oxidation electrocatalysis

The presence of a second metal on platinum surfaces affects the performance of methanol oxidation. However, most of the electrocatalytic reactions are studied by using electrochemically deposited platinum alloys, but in the case of spontaneous deposition the situation is not so clear since the surface distribution, stability and morphology are usually not well documented. The formation of surface decorated samples on mono- and poly-crystalline platinum is followed by electrochemical and spectroscopic techniques and analysis of their performance towards methanol adsorption and oxidation compared with that on pure platinum. Pt/Sn and Pt/Ru are of special interest because of their well-known performance in methanol fuel cells. Methanol oxidation on Pt(111)/Ru, Pt(111)/Sn and Pt(111) shows that ruthenium is the only one able to promote the reaction since the simultaneous dissolution of tin occurs and competes with the process of interest. The in situ infrared spectroscopy is used to compare methanol oxidation on Pt(111)/Ru and Pt(111) in acid media using p-polarized light. The formation of bridge bound carbon monoxide is inhibited in the presence of ruthenium ad-species, whereas on Pt(111) the three adsorption configurations are observed. Linear sweep polarization curves and Tafel slopes (calculated from steady state potentiostatic plots) for methanol oxidation are compared on polycrystalline surfaces modified by tin or ruthenium at different coverages. There is almost no change in the Tafel slopes due to the presence of the foreign metal except for Pt/Ru, where a 0.09 V decade⁻¹ slope was calculated below 0.55 V due to hydroxyl adsorbates on ruthenium islands. The anodic stripping of methanol residues on the three surfaces indicates a lower amount of carbon monoxide-type adsorbates on Pt/Ru, and the simultaneous tin dissolution process leading to residues oxidation on Pt/Sn electrodes.     

Clarification of a wheat straw‐derived medium with ion‐exchange resins for xylitol crystallization

BACKGROUND: Xylitol bioproduction from lignocellulosic residues comprises hydrolysis of the hemicellulose, detoxification of the hydrolysate, bioconversion of the xylose, and recovery of xylitol from the fermented hydrolysate. There are relatively few reports on xylitol recovery from fermented media. In the present study, ion‐exchange resins were used to clarify a fermented wheat straw hemicellulosic hydrolysate, which was then vacuum‐concentrated and submitted to cooling in the presence of ethanol for xylitol crystallization. RESULTS: Sequential adsorption into two anion‐exchange resins (A‐860S and A‐500PS) promoted considerable reductions in the content of soluble by‐products (up to 97.5%) and in medium coloration (99.5%). Vacuum concentration led to a dark‐colored viscous solution that inhibited xylitol crystallization. This inhibition could be overcome by mixing the concentrated medium with a commercial xylitol solution. Such a strategy led to xylitol crystals with up to 95.9% purity. The crystallization yield (43.5%) was close to that observed when using commercial xylitol solution (51.4%). CONCLUSION: The experimental data demonstrate the feasibility of using ion‐exchange resins followed by cooling in the presence of ethanol as a strategy to promote the fast recovery and purification of xylitol from hemicellulose‐derived fermentation media. Copyright © 2008 Society of Chemical Industry     

Rheological and drug‐release behaviour of a scleroglucan gel matrix at different drug loadings

The aim of this study was to investigate the drug‐loading effects on release and mechanical properties of a scleroglucan gel, with the intention of considering them in delivery systems formulations. The rheological and kinetic properties of a 2 % w/w scleroglucan gel matrix loaded with 0, 0.02, 0.04, 0.06, 0.2 and 0.4 % w/w of theophylline (Th, used as a model drug) were investigated. Rheological measurements were performed in a controlled‐stress rotational‐shear rheometer under isothermal conditions. For theophylline release from the gel a flat Franz cell was used and the kinetic parameters were derived applying a semi‐empirical power law. The influence of scleroglucan molar weight on kinetic and rheological behaviour was also studied. Results suggest two possible effects of drug loading on the gel network: in the 0.04–0.06 % w/w Th range a plasticizing effect and in the 0.2–0.4 % w/w Th range a rigidization effect. In the first range mentioned, the changes in the gel structural properties tested by means of rheological measurements are coincident with changes in drug‐release kinetics. Copyright © 2005 Society of Chemical Industry     

Alphorn: a remote procedure call environment for fault-tolerant,heterogeneous, distributed systems

Alphorn, a software environment for programming distributed computer systems, is described. Programs running on different computers, possibly of different types and running different operating systems, communicate in a client-server relationship by means of remote procedure calls. This efficient construct structures programs neatly. The paper covers distributed process control, Alphorn's object-based programming style, remote procedure calls, the service interface language, configuration, runtime and debugging, and fault tolerance support     

A shell for cooperating expert systems

Abstract: This paper describes a shell for cooperating expert systems that has been developed at the University of Porto. The main goal of this shell is two-fold: to generate a community of cooperative knowledge-based systems and to develop several special reasoning techniques which can be used under a distributed and cooperative paradigm. UPShell is able to convert a set of generated intelligent systems (ISs) into a community of cooperative ISs. In this first version it is already possible to generate different intelligent systems which are able to run 'simultaneously' as separate Unix processes and, using a message-passing mechanism, to communicate among themselves. They can be set to pursue an overall goal in a cooperative way. Moreover, several tasks can be given to each IS to be solved simultaneously, and the IS can switch from task to task according to dynamic priorities reflecting the urgency attached to the specific sub-tasks that emerge. The shell described here may also be used to test, within a distributed environment, some time-bounded reasoning techniques that are presently being developed. The paper has three main parts: a general overview of the UPShell (Section 1); a tutorial explaining, by means of examples, how to use the package (Section 2); and, finally, some considerations on the reasoning techniques used and future improvements (Sections 3–5).     

Toughening of Dental Porcelain by Tetragonal ZrO2 Additions

The effect on mechanical behavior of ZrO₂ additions to a dental porcelain was investigated. The ZrO₂ was introduced into the glassy matrix phase of the porcelain by refritting the all-glass porcelain constituent. X-ray diffraction indicated that a sizeable fraction of the ZrO₂ was retained in the tetragonal form after the porcelain was fired. Zirconia additions to the porcelain produced substantial improvements in fracture toughness, strength, and thermal shock resistance.