Support and precursor effects on the preparation of new heterogenized Pt/Sn catalysts for the selective hydroformylation of 1-pentene

New heterogenized Pt/Sn catalysts selective for the hydroformylation of 1-pentene have been synthesized. The complex cis-[PtCl₂(PPh₃)₂] and the SnCl₂.2H₂O or SnC₂O₄ precursors have been anchored on silica-, magnesia- and alumina-carriers. X-ray photoelectron spectroscopy was used to determine the surface composition and the nature of the anchored species. The hydroformylation activity was found to depend on the type of support and tin precursor used. Only the silica supported catalysts were active in the hydroformylation reaction. Samples prepared from SnCl₂-2H₂O were 200-fold more active than those prepared from SnC₂O₄. Selectivity ton-hexanal of the silica-supported catalyst prepared from SnCl₂-2H₂O was as high as 94.4% at 39.2% conversion of 1-pentene.     

Evidence of the vital role of the pore network on various catalytic conversions of N2O over Fe-silicalite and Fe-SBA-15 with the same iron constitution

Fe-silicalite and Fe-SBA-15 with similar iron content have been characterized by N₂ adsorption, small angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), scanning electron microscopy (SEM), high-resolution transmission electron micrographs (HRTEM), UV–vis–DRS and EPR, and tested in direct N₂O decomposition, N₂O reduction by CO and N₂O-mediated propane oxidative dehydrogenation. Both catalysts contain almost exclusively isolated Fe³⁺ sites of similar concentration and structure, which are, however, stabilized in markedly different pore geometries (intersecting channels of ca. 0.55 nm diameter in Fe-silicalite versus parallel linear pores of ca. 7.5 nm diameter in Fe-SBA-15). This aspect is of vital importance in order to exclusively ascribe different catalytic performances to the environment where the iron species are stabilized. Fe-silicalite revealed to be much more active than Fe-SBA-15 in all reactions studied. This clearly illustrates that the confinement of the iron species in pores of suitable geometry (structure and size) is essential to originate their remarkable catalytic properties. The large pores in ordered mesoporous materials apparently do not generate the required intimate contact between potentially active Fe sites and reactant molecules.     

Combustion synthesis and electrochemical characterisation of Pt–Ru–Ni anode electrocatalyst for PEMFC

The present work studies the synthesis by the combustion method of an anode catalyst for protonic exchange membrane fuel cell (PEMFC) employing two different fuels, that is, urea and sucrose. The unsupported pure solid solution Pt_0.6Ru_0.3Ni_0.1 was selected from a calculated and empirical ternary phase diagram, which was previously studied. Theoretically, this particular composition exhibited single-phase features without the presence of secondary phases as RuO₃ and NiO, regarding the oxygen partial pressure conditions generated during the combustion synthesis. In the X-ray diffraction (XRD) analysis of the nanoparticles synthesized by using two different fuels, a single-phase Pt_0.6Ru_0.3Ni_0.1 alloy was detected. However, the X-ray photoelectron spectroscopy (XPS) studies showed that the nanoparticles prepared could present an onion-shell structure, in the case of the sample synthesized with sucrose as fuel, the external layers are partially constituted by Ni hydroxides, which can exhibit an active role in the hydrogen oxidation reaction. The electrochemical behaviour of this unsupported catalyst was performed by preparing MEAs, which were evaluated using a I–V polarisation curve test. The results obtained indicated that the nanoparticles prepared by sucrose have better performance, 260 mW/cm², than those prepared using urea, 170 mW/cm². These results are discussed in relation with the hydrogen oxidation mechanism. The results obtained reveal combustion synthesis as an appropriate method for preparing PEMFC electrocatalysts, due to its versatility, simplicity and fastness.     

Biodegradable blend films based on two polysaccharide derivatives and their use as ibuprofen‐releasing matrices

Differential scanning calorimetry (DSC), FTIR, X‐ray diffraction (XRD), and viscosity methods were used to examine the miscibility, interaction, and degradability of cationic guar gum (GG) and sodium carboxymethylcellulose (NaCMC) in their blend films. The experiment results prove that there exist electrostatic interactions and hydrogen bonding between GG and NaCMC. Blend films degrade quicker than pure GG or NaCMC film. Furthermore, the degradation rate of blend films is related to the interactions between GG and NaCMC. Based on the research of blend films as the drug carriers for Ibuprofen, it is found that the blend composition, initial drug concentration, and pH value affect the drug release and the GG/NaCMC blend films have good sustained release performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3553–3559, 2007     

Leucinosis--a case of congenital metabolic disease in a child

Trasditional Chinese medicine is based on inductive-synthetic reasoning with regard to all life processes, in contrast to the causal-analytic orientation in our Western medicine. This philosophical approach is based on a system of comparisons (equivalents), referred to as Yin and Yang. Vital functions are seen as "energizing" processes, whereby the acupuncture points and the system of meridians are seen as a means of regulation for this "energy". A disturbed balance in this energy results in illness. The therapy according to the acupuncture method is to acheive a balance in the disturbed flow of energy by means of acupuncture points. By utilizing biophysical methods of measurement, it is possible to prove that a change in this energy takes place. The complex active principle which results in the effectiveness of acupuncture includes neurophysiological, biochemical and biophysical functional processes.     

Observation of a half-quantum-flux periodicity pattern in an rf SQUID with small critical currents

We have found experimentally that rf SQUID's working in a nonhysteretic mode with small critical currents give exactly at resonance and at very low rf bias a triangular pattern with a period equal to half of one elementary quantum of magnetic flux. We discuss a possible explanation of this peculiar result.     

Pigmentary glaucoma? Relations to megalocornea

The student population at Edinburgh University was surveyed in 1974 to collect data on women's menstrual cycles and to examine sources of individual differences in reporting symptoms associated with the cycle. 2542 non-oral contraceptive (OC) users and 756 OC users provided data. Both sets of respondents were questioned about the occurrence, both premenstrually and during menstruation, of 9 symptoms. The "physical" symptoms (stomachache, backache, nausea, fainting) were more often reported during menstruation, whereas the so-called "emotional" symptoms (lethargy, irritability, depression, tension, headache) had a greater prevalence premenstrually. When the 9 menstrual symptoms were broken down by students' fields of concentration, arts students were found to report more "emotional" symptoms than those in the sciences and professions (medicine and law). Further analysis showed that only and 1st born children were slightly less likely to report symptoms than those whose nearest sibling is 7 or more years older or younger or later born children. A similar trend was found for the reporting of illness in an earlier analysis of data from this sample. When cycle length and reqularity were analyzed together, women with long and regular cycles were found to have the lowest proportion reporting symptoms during menstruating with the exception of tension, nausea, and fainting, and women with short and irregular cycles had a correspondingly high incidence of all symptoms. In addition, women with more regular cycles were more likely to report infrequent recall of dreams than those with irregular cycles. Overall, the women who are most likely to report menstrual symptoms, especially those of an "emotional" character, are more likely to report other illnesses with emotional connotations, recall their dreams more frequently, show a preference for the arts, and tend to have been brought up with older siblings. This cluster of personality attributes defines an "expressive" personaltiy in contrast to the more "controlled" style of women at the other extreme.     

Gammagraphy of the carotid glomus

Using the colorant proteic complex labell with Tc-99 m. we visualize--by the first time--the carotideal glomus in the human in 6 volunteers and one patient with tumor. The results are very encorageous: the method was simple and safe (one single dose endovenously) and hardless (no radiotoxicity presents in 3 months of clinical and laboratory controls) and there is a good visualization by scan of carotideal bodies "in vivo", in human being. We think this new method and labell compound could be useful in research and medical diagnoses.     

Effect of prolactin suppression on gonadotrophic secretion in the puerperium

Serum levels of prolactin (PRL), FSH, LH and oestradiol-17 beta were determined by radioimmunoassay in 57 lactating women and in 20 women in whom lactation was inhibited by ergocryptine (CS-154). Women who breast fed their infants exhibited high PRL levels which abruptly declined within 48 h post-partum, and remained low for the duration of the study. Serum FSH was undetectable during the first week post-partum in lactating as well as in CB-154 treated women. Thereafter, lactating women showed increasing FSH levels which reached a maximum by the third week post-partum. These FSH values were higher in lactating women than in the CBS-154 treated group. In contrast, LH levels were higher in those women receiving CB-154. Serum oestradiol-17 beta remained in low levels throughout the study, and no difference was observed between the two groups of subjects. From these results it seems that: 1) inhibition of PRL secretion leads to a faster recovery of gonadotrophin secretion toward the "menstrual type", and 2) PRL suppression produces no effect on the ovarian oestrogen production.     

Synthesis, structure, and field emission properties of sulfur-doped nanocrystalline diamond

The synthesis and properties of sulfur-doped nanocrystalline diamond films were investigated. The films were deposited by hot-filament chemical vapor deposition on Mo substrates using methane, hydrogen, and hydrogen disulfide. The nanocrystalline nature of the material arises from the induction of continuous secondary nucleation in the chemical vapor deposition environment. Complementary characterization tools were employed in order to obtain a comprehensive and coherent understanding of the correlations between the structural and electronic properties. In particular, sulfur-doped nanocrystalline diamond films show n-type Hall conductivity, enhanced field emission properties, and insensitivity to ion radiation. It was found that n-type doping of the tetragonally-bonded carbon matrix together with a nano network of trigonally-bonded carbon are crucial elements for enhanced field emission from nanocrystalline diamond. These conclusions and the corresponding supporting evidence are discussed.