Mechanism of the skeletal isomerisation of linear butenes over ferrierite: analysis of side reactions

An investigation of the effect of reaction conditions on product distribution in the skeletal isomerisation reaction of linear butenes has been carried out. The main reaction routes over ferrierite have been identified. Beside the main product isobutene, major by-product formation occurs. The unwanted reactions include dimerisation of butene to form octenes, hydrogen transfer yielding small amounts of saturated C₃ and C₄ hydrocarbons and disproportionation producing propene and pentenes. The most abundant by-products were pentene and propene, though these were not formed in equimolar amounts as could be expected. Oligomerisation experiments of propene over ferrierite produced large amounts of butene and pentene, revealing the presence of adsorbed nonene. The cracking of this surface species to hexene and propene is the most likely reaction route for the excess propene formation. This additional path to propene formation operates mainly at temperatures above 623 K.     

An APL procedure to estimate genotype by environment interaction when two environments are considered

Genotype by environment interaction (GEI) is a relevant topic in many fields of applied biology. Normal parametric approaches following analysis of variance are not suitable when large differences between error variances within environments are present. We illustrate an APL program following Yamada's approach to estimate GEIs and ancillary statistics when two environments are considered. The choice of APL environment is based on its value as a useful tool in algorithm implementation and problem-solving. Its use is suggested in biological applications where matrix algebra is involved and an understanding of the computing complexity of problems is generally not required.     

Mobile positioning using wireless networks: possibilities and fundamental limitations based on available wireless network measurements

Positioning in wireless networks is mainly used for safety, gaming, and commercial services. It is expected to increase in popularity when emergency call services become mandatory as well as with the advent of more advanced location-based services and mobile gaming. In this article, we discuss and illustrate the possibilities and fundamental limitations associated with mobile positioning based on available wireless network measurements. The possibilities include a sensor fusion approach and model-based filtering, while the fundamental limitations provide hard bounds on the accuracy of position estimates, given the information in the measurements in the most favorable situation. The focus of this article is to illustrate the relation between performance requirements, such as those stated by the Federal Communications Commission (FCC), and the available measurements. Specific issues on accuracy limitation in each measurement, such as synchronization and multipath problems, are briefly commented upon. A geometrical example, as well as a realistic example adopted from a cell planning tool, are used for illustration.     

Comparison between photocatalytic ozonation and other oxidation processes for the removal of phenols from water

Photocatalytic ozonation (1O₃ + VUV + TiO₂), ozonation (O₃), catalytic ozonation (O₃ + TiO₂), ozone photolysis (O₃ + VUV), photocatalysis (TiO₂ + VUV) and photolysis (VUV) have been compared in terms of formation of intermediates, extent of, mineralization (TOC, COD, chloride, nitrate) and kinetics in the aqueous treatment of three phenols (phenol, p‐chlorophenol and p‐nitrophenol). In all cases, photocatalytic ozonation led to lower degradation times for chemical oxygen demand and total organic carbon removal. Intermediates formed were similar in the different oxidation systems with some exceptions. They can be classified into three different types: polyphenols (resorcinol, catechol, hydroquinone), unsaturated carboxylic acids (maleic and fumaric acids) and saturated carboxylic acids (glyoxylic, formic and oxalic acids). First order kinetic equations have been checked for the oxidation processes studied in the case of the parent compound. Rate constants of these systems have also been calculated. Copyright © 2005 Society of Chemical Industry     

Hypercoagulability and chronic atrial fibrillation: the role of markers of thrombin generation

BACKGROUND: We have studied 64 patients with congestive heart failure, half of them also with chronic nonvalvular atrial fibrillation (AF). Patients were also stratified according to a history of prior stroke. METHODS: The generation of thrombin was investigated by means of the molecular markers prothrombin fragment 1 + 2 (F1 + 2) and thrombin-antithrombin III complex (TAT), because AF patients may have a hypercoagulable state. There was only a trend toward higher values of TAT and F1 + 2 for AF patients, while subjects with previous stroke (irrespective of AF) had increased levels of the markers of thrombin generation (TAT stroke+ 18.95 +/- 5.15 vs TAT stroke- 8.34 +/- 2.41; F1 + 2 stroke+ 2.22 +/- 0.29 vs F1 + 2 stroke- 1.32 +/- 0.12). The presence of spontaneous echo contrast (SEC) within left atrium was also investigated in 32 AF patients by transesophageal echocardiography. RESULTS: TAT were significantly higher in subjects (n = 11) with SEC (TAT sec+ 37.5 +/- 13.41 vs TAT sec- 8.7 +/- 2.51, p = 0.008). CONCLUSIONS: Finally, when we grouped into 1) those with both AF and stroke, 2) AF alone, 3) stroke alone and 4) sinus rhythm without stroke, levels of F1 + 2 were higher (and marginally higher TAT) in patients with AF and stroke than in those without stroke, revealing that there is a true clotting activation state in these subjects.     

Characterisation and modelling of VBR video traffic

The impact of VBR video traffic characteristics on broadband network performance is analysed. In particular, the authors compare in a queue the behaviour of several models that adjust different statistical parameters of actual MPEG traces. It is proved that a good fit of the probability density function (PDF) is essential to approximate queuing behaviour while the effects of short range dependence (SRD) are of secondary importance and those of long range dependence (LRD) could be neglected for practical purposes if realistic scenarios, with strict QoS requirements, are considered     

Enhanced electron emission from phosphorus-doped diamond-cladsilicon field emitter arrays

Undoped and phosphorus (P)-doped diamond-clad Si field emitter arrays have been successfully fabricated using microwave plasma chemical vapor deposition (MPCVD) technology. The electron emission from the blunt diamond-clad microtips are much higher than those for the pure Si tips with sharp curvature due to a lower work function. Furthermore, the characteristics of emission current against applied voltage for the P-doped diamond-clad tips show superior emission at lower field to the undoped ones. After the examination of Auger electron spectroscopy (AES) and electrical characteristics of as-grown diamond, such a significant enhancement of the electron emission from the P-doped diamond-clad tips is attributed to a higher electron conductivity and defect densities