Dimethyl Ether as a Source of Reactive Species for Alkylation of Benzene

The co-reaction of dimethyl ether and benzene has been investigated on pure and promoted-ZSM-5 catalysts at 473–773 K. It was found that the addition of benzene to dimethyl ether markedly increased the formation of toluene, xylene and C₉ aromatics on ZSM-5 at and above 623 K. This feature is attributed to the reaction of benzene with the reactive hydrocarbon species formed in the decomposition of dimethyl ether on the acidic sites of ZSM-5 zeolite. The extent of the enhancement was further increased by ZnO and Mo₂C promoters.     

Hydrogen Formation in the Reactions of Methanol on Supported Au Catalysts

The adsorption and reactions of methanol have been investigated on Au metal supported by various oxides and carbon Norit of high surface area. Infrared spectroscopic studies revealed the dissociation of methanol at 300 K, which mainly occurs on the oxide-supports yielding methoxy species. The presence of Au already appeared in the increased amounts of desorbed products in the TPD spectra. The reaction pathway of the decomposition and the activity of the catalyst sensitively depend on the nature of the support. As regards the production of hydrogen the most effective catalyst is Au/CeO₂ followed by Au/MgO, Au/TiO₂ and Au/Norit. In contrast, on Au/Al₂O₃ the main process is the dehydration reaction yielding dimethyl ether. On Au/CeO₂ the decomposition of methanol starts above ~500 K and approaches total conversion at 723–773 K. The products are H₂ (~68%) and CO (~27%) with very small amounts of methane and CO₂. The decomposition of methanol follows the first order kinetics. The activation energy of this process is 87.0 kJ/mol. The selectivity of H₂ formation at 573–773 K was ~90%, this value increased to 97% using CH₃OH:H₂O (1:1) reacting mixture indicating the involvement of water in the reaction. No deactivation of Au catalysts was experienced at 773 K in ~10 h. It is assumed that the interface between Au and partially reduced ceria is responsible for the high activity of Au/CeO₂ catalyst.     

Surgical treatment of extratemporal epilepsy: clinical, radiologic, and histopathologic findings in 60 patients

PURPOSE AND METHODS: The aim of this study was to analyze clinical, radiologic, and histopathologic findings in 60 consecutive patients with medically intractable extratemporal epilepsy who were operated on between November 1987 and May 1993. RESULTS: Histologically, there were distinct structural abnormalities in 50 (83%) of the surgical specimens. Signal abnormalities on magnetic resonance imaging (MRI) were present in all patients with neoplastic lesions (n = 17) and in 94% of patients with nonneoplastic focal lesions (n = 32). Overall, structural abnormalities were detected by MRI in 47 (96%) of 49 patients with focal lesions. During a mean follow-up of 4 years, 30 (54%) patients remained completely seizure free, 11 (20%) had < or = 2 seizures per year, seven (12%) showed a seizure reduction of > or = 75%, and eight (14%) had < 75% reduction in seizure frequency. The fraction of seizure-free patients was 12 (80%) of 15 in patients with neoplastic lesions, 16 (52%) of 31 in patients with nonneoplastic focal lesions, and two (20%) of 10 for those without histopathologic abnormalities. The differences in seizure outcome between patients with and without focal lesions were statistically significant (p < 0.05), if seizure-free outcome was compared with persistent seizures. CONCLUSIONS: Focal lesions and particularly neoplasms are associated with improved postoperative seizure control compared with patients without histopathologic abnormalities. We advise caution in considering surgery to treat extratemporal epilepsy in patients who have normal MRI scans, because the outcome with the approach described in this study is poor in such cases.     

Effects of potassium on the chemisorption of CO2 and CO on the Mo2C/Mo(100) surface

The interaction of CO₂ with K-promoted Mo₂C/Mo(100) has been studied with high-resolution electron energy loss spectroscopy, work function measurements and temperature-programmed desorption. Pre-adsorbed potassium dramatically affects the adsorption behavior of CO₂ on the Mo₂C/Mo(100) surface. It increases the rate of adsorption, the binding energy of CO₂ and it induces the dissociation of CO₂ through the formation of negatively charged CO₂. Potassium adatoms also promote the dissociation of adsorbed CO over Mo₂C. This revised version was published online in July 2006 with corrections to the Cover Date.     

The oxidative dehydrogenation of ethane with CO2 over Mo2C/SiO2 catalyst

Mo₂C prepared on SiO₂ was found to be an effective catalyst for the dehydrogenation of ethane to produce ethylene in the presence of CO₂. The selectivity to ethylene at 850–923 K was 90–95% at an ethane conversion of 8–30%. With the increase of the temperature the dry reforming of ethane became also a significant process. It is assumed that the Mo oxycarbide formed in the reaction between CO₂ and Mo₂C plays an important role in the activation of ethane. This revised version was published online in July 2006 with corrections to the Cover Date.     

Formation and reactions of CH3 species over Mo2C/Mo(111) surface

The reaction pathways of adsorbed CH₃ on the Mo₂C/Mo(111) surface were investigated by means of temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HREELS). CH₃ fragments were produced by the dissociation of the corresponding iodo-compound. CH₃I adsorbs molecularly on Mo₂C at 90 K and dissociates at and above 140 K. The main products of the reaction of adsorbed CH₃ are hydrogen, methane and ethylene. The coupling into ethane was not observed. The results are discussed in relevance to the conversion of methane into benzene on Mo₂C deposited on ZSM-5. This revised version was published online in August 2006 with corrections to the Cover Date.     

Photolysis of HCOOH over Rh Deposited on Pure and N-Modified TiO2

Abstract  

The photo-induced vapor-phase decomposition of formic acid was investigated on pure, N-doped and Rh-promoted TiO₂. The bandgap of TiO₂ was narrowed by 0.82–1.04 eV as a result of the incorporation N into TiO₂. Adsorption of formic acid on pure TiO₂ produced strong absorption bands due to formate species, the intensity of which decreased by illumination. The photodecomposition of formic acid on pure TiO₂ at 300 K occurs to only a limited extent: on N-doped TiO₂, however, it is enhanced by a factor of 2–4. The N-modified TiO₂ catalyzes the photoreaction even in the visible light, which is attributed to the prevention of electron–hole recombination. The deposition of Rh on TiO₂ markedly increased the extent of photodecomposition. The conversion is complete in 200 min, while the extent of decomposition reaches only ~30% on pure TiO₂. The effect of Rh is explained by a better separation of charge carriers induced by illumination and by enhanced electron donation to the adsorbed formate species. On TiO₂ samples both the dehydrogenation and dehydration reactions occurred, on Rh/TiO₂ only a trace amount of CO was formed. Addition of water to formic acid eliminated this CO, but exerted no other influence on the occurrence the photoreaction.     

Adsorption and decomposition of ethanol on supported Au catalysts

The adsorption and reactions of ethanol are investigated on Au nanoparticles supported by various oxides and carbon Norit. The catalysts are characterized by means of XPS. Infrared spectroscopic studies reveal the dissociation of ethanol to ethoxy species at 300 K on all the oxidic supports. The role of Au is manifested in the enhanced formation of ethoxy species on Au/SiO₂, and in increased amounts of desorbed products in the TPD spectra. The supported Au particles mainly catalyse the dehydrogenation of ethanol, to produce hydrogen and acetaldehyde. An exception is Au/Al₂O₃, where the main process is dehydration to yield ethylene and dimethyl ether. C–C bond cleavage occurs to only a limited extent on all samples. As regards to the production of hydrogen, the most effective catalyst is Au/CeO₂, followed by Au/SiO₂, Au/Norit, Au/TiO₂ and Au/MgO. A fraction of acetaldehyde formed in the primary process on Au/CeO₂ is converted above 623 K into 2-pentanone and 3-penten-2-one. The decomposition of ethanol on Au/CeO₂ follows first-order kinetics. The activation energy of this process is 57.0 kJ/mol. No deactivation of Au/CeO₂ is observed during 10 h at 623 K. It is assumed that the interface between Au and partially reduced CeO₂ is responsible for the high activity of the Au/CeO₂ catalyst.     

Fusiform dilatations of the internal carotid artery following surgery for pediatric suprasellar tumors

Fusiform dilatations of the internal carotid artery (FDCA) represent a vascular complication following surgery for suprasellar tumors in children. In a long-term follow-up of 62 children we identified 7 children (11.3%) with a FDCA. In all children the FDCA was present within 15 months following surgery. It was not related to radiotherapy or a distinct histology. In 3 children the FDCA remained unchanged during the follow-up, in 3 children there was a progression and 1 child revealed a regression within 6 months. Clinically the FDCA was inapparent in all cases and not treated. In a follow-up study of an adult population who underwent surgery for suprasellar tumors no case of FDCA was encountered. Potential pathomechanisms and indications for treatment are discussed.     

Enlarged cerebrospinal fluid spaces in opiate-dependent male patients: a stereological CT study

Total knee arthroplasty was evaluated in 10 patients with post-traumatic osteoarthrosis secondary to work-related knee injuries (age- and sex-matched with 10 controls who had total knee arthroplasties for nonwork-related osteoarthrosis) to determine if Workers' Compensation status influenced treatment outcome. Using the Hospital for Special Surgery Knee Rating System (maximum possible score: 100), most recent follow-up scores averaged 64.1 for Workers' Compensation patients and 91.9 for controls. Subjective indices (pain, function) were significantly different between groups (p < 0.05), but objective indices (range of motion, strength, deformity, instability) were not. No significant differences were noted between groups on either immediate postoperative or most recent follow-up radiographs (which were assessed for alignment and radiolucencies at implant surfaces, respectively). Suboptimal outcomes can be anticipated in total knee arthroplasties performed on Workers' Compensation patients, particularly in cases where claims have not been settled at the time of surgery.