Investigation of the nature of the oxidant (selective and unselective) in/on a vanadyl pyrophosphate catalyst

The anaerobic oxidation of CO by a (VO)₂P₂O₇ catalyst has been used to investigate the nature of the oxidant (selective and unselective) in/on that material. Three peaks were observed in the rate of production of CO₂ - at 993, 1073 and 1093 K. The temperature of the maximum in the rate of production of the first CO₂ peak and the amount of oxygen associated with it are the same as that observed in the selective anaerobic oxidation of n-butane to butene and butadiene, but-1-ene to butadiene and furan and but-1,3-diene to dihydrofuran, furan and maleic anhydride. The interaction of CO with the (VO)₂P₂O₇ catalyst forming CO₂ at 993 K is therefore concluded to be with the selective oxygen. The total amount of oxygen removed by the CO from the (VO)₂P₂O₇ lattice (>5 monolayers) is about six times greater than that of the selective oxygen. The higher activation energies for the removal of the unselective oxygen accounts for the high selectivities (~80%) encountered commercially for the anaerobic oxidation of n-butane to maleic anhydride. Re-oxidation of the CO reduced (VO)₂P₂O₇ by N₂O quantitatively replaces all of the lattice oxygen removed by the formation of CO₂, but does not restore the original morphology. This revised version was published online in July 2006 with corrections to the Cover Date.     

Call to needle times after acute myocardial infarction in urban and rural areas in northeast Scotland: prospective observational study

OBJECTIVE: To determine call to needle times and consider how best to provide timely thrombolytic treatment for patients with acute myocardial infarction. DESIGN: Prospective observational study. SETTING: City, suburban, and country practices referring patients to a single district general hospital in northeast Scotland. SUBJECTS: 1046 patients with suspected acute myocardial infarction given thrombolytic treatment. MAIN OUTCOME MEASURES: Time from patients' calls for medical help until receipt of opiate or thrombolytic treatment, measured against a call to needle time of 90 minutes or less, as proposed by the British Heart Foundation. RESULTS: General practitioners were the first medical contact in 97% (528/544) of calls by country patients and 68% (340/502) of city and suburban patients. When opiate was given by general practitioners, median call to opiate time was about 30 minutes (95% within 90 minutes) in city, suburbs, and country; call to opiate delay was about 60 minutes in city and suburban patients calling "999" for an ambulance. One third of country patients received thrombolytic treatment from their general practitioners with a median call to thrombolysis time of 45 minutes (93% within 90 minutes); this compares with 150 minutes (5% within 90 minutes) when this treatment was deferred until after hospital admission. In the city and suburbs, no thrombolytic treatment was given outside hospital, and only a minority of patients received it within 90 minutes of calling; median call to thrombolysis time was 95 (46% within 90 minutes) minutes. CONCLUSIONS: The first medical contact after acute myocardial infarction is most commonly with a general practitioner. This contact provides the optimum opportunity to give thrombolytic treatment within the British Heart Foundation's guideline.     

Interactive story authoring: A viable form of creative expression for the classroom

The unprecedented growth in numbers of children playing computer games has stimulated discussion and research regarding what, if any, educational value these games have for teaching and learning. The research on this topic has primarily focused on children as players of computer games rather than builders/constructors of computer games. Recently, several game companies, such as BioWare Corp. and Bethesda Softworks, have released game story creation tools to the public, along with their games. However, a major obstacle to using these commercial tools is the level of programming experience required to create interactive game stories. In this paper, we demonstrate that a commercial game story construction tool, BioWare Corp.’s Aurora Toolset, can be augmented by our new tool, ScriptEase, to enable students in two grade ten English classes to successfully construct interactive game stories. We present evidence that describes the relationship between interactive story authoring and traditional story authoring, along with a series of factors that can potentially affect success at these activities: gender, creativity, intellectual ability, previous experiences with programming, time playing computer games, and time spent online. Results indicate that students can successfully construct sophisticated interactive stories with very little training. The results also show no gender differences in the quality of these interactive stories, regardless of programming experience or the amount of time per week playing computer games or participating in general online activities, although a subset of female students did show a slightly higher level of performance on interactive story authoring. In the educational context of this study, we show that ScriptEase provides an easy-to-use tool for interactive story authoring in a constructionist learning environment.     

Value of transthoracic echocardiography in predicting embolic events in active infective endocarditis. Duke Endocarditis Service

The purpose of this study was twofold: (1) to determine interobserver variability of echocardiographic characteristics of vegetations in patients with infective endocarditis, and (2) to assess the value of these vegetation characteristics in predicting embolic events. Although echocardiography contributes to the diagnosis of patients with infective endocarditis, its prognostic role in predicting embolic events is controversial. The echocardiograms of 41 patients with infective endocarditis were independently reviewed by 4 echocardiographers blinded to the clinical data. If a vegetation was present, the following characteristics were analyzed: involved site, size, mobility, shape, and pedunculated or sessile attachment. Each echocardiographer also made a "gestalt" estimate of embolic risk based on these vegetation characteristics. Interobserver agreement on vegetation characteristics and their relation to embolic events was then determined using kappa statistics and logistic regression analysis. Interobserver agreement was 98% with regard to echocardiographic vegetation presence and 97% with regard to the involved site. Of the 30 patients in whom vegetations were observed, complete observer agreement was achieved with regard to size in 22 (73%), mobility in 17 (57%), shape in 11 (37%), and attachment in 12 (40%). Vegetations with a maximal diameter of > 10 mm were associated with a 50% incidence of embolic events, compared with a 42% incidence of emboli in patients with vegetations measuring < or = 10 mm. Interobserver variability was great with respect to vegetation shape, mobility, and attachment characteristics. Echocardiographic vegetation characteristics were not helpful in defining the risk of embolic complications in patients with endocarditis.     

The effect of the duration of n-butane/air pretreatment on the morphology and reactivity of (VO)2P2O7 catalysts

Three vanadium pyrophosphate catalysts have been prepared by calcining vanadium hydrogen phosphate hemihydrate (VOHPO₄0.5H₂O, prepared in an organic medium) for different lengths of time (40, 100 and 132 h) in a n-butane (0.75%)/air mixture at 473 K. The catalysts were designated VPO40, VPO100 and VPO132. Increasing the duration of reaction with n-butane/air mixture led to an increase in the total surface area from 21.3 m²g^–1 (VPO40) to 24.9 m²g^–1(VPO100) and to 27.0 m²g^–1(VPO132). It also led to the complete removal of the VOPO₄ phase from catalysts VPO100 and VPO132, this VOPO₄ phase having seen as a minor component of catalyst VPO40. Scanning electron microscopy showed that longer periods of pretreatment in the n-butane/air mixture produced catalysts with increasing amounts of a characteristic rosette-type of agglomerate. Temperature-programmed reduction with H₂ resulted in the removal of 11 monolayers equivalent of oxygen from all three of these catalysts at a peak maximum temperature of 1000 K with the development of a second reduction peak at 1100 K which increases with increasing time of n-butane/air pretreatment. The morphology produced by extended pretreatment in the n-butane/air mixture at 673 K is therefore predisposed to reaction with H₂ (and probably with n-butane). Apparently paradoxically, increasing the duration of n-butane/air pretreatment results in catalysts which on temperature-programmed desorption desorb less oxygen.     

Upgrade of the MIT Linear Electrostatic Ion Accelerator (LEIA) for nuclear diagnostics development for Omega, Z and the NIF

The MIT Linear Electrostatic Ion Accelerator (LEIA) generates DD and D(3)He fusion products for the development of nuclear diagnostics for Omega, Z, and the National Ignition Facility (NIF). Significant improvements to the system in recent years are presented. Fusion reaction rates, as high as 10(7) s(-1) and 10(6) s(-1) for DD and D(3)He, respectively, are now well regulated with a new ion source and electronic gas control system. Charged fusion products are more accurately characterized, which allows for better calibration of existing nuclear diagnostics. In addition, in situ measurements of the on-target beam profile, made with a CCD camera, are used to determine the metrology of the fusion-product source for particle-counting applications. Finally, neutron diagnostics development has been facilitated by detailed Monte Carlo N-Particle Transport (MCNP) modeling of neutrons in the accelerator target chamber, which is used to correct for scattering within the system. These recent improvements have resulted in a versatile platform, which continues to support the existing nuclear diagnostics while simultaneously facilitating the development of new diagnostics in aid of the National Ignition Campaign at the National Ignition Facility.     

Linkages between facial expressions of anger and transient myocardial ischemia in men with coronary artery disease.

The authors examined whether facial expressions of emotion would predict changes in heart function. One hundred fifteen male patients with coronary artery disease underwent the Type A Structured Interview, during which time measures of transient myocardial ischemia (wall motion abnormality and left ventricular ejection fraction) were obtained. Facial behavior exhibited during the ischemia measurement period was videotaped and later coded by using the Facial Action Coding System (P. Ekman & W. V. Friesen, 1978). Those participants who exhibited ischemia showed significantly more anger expressions and nonenjoyment smiles than nonischemics. Cook–Medley Hostility scores did not vary with ischemic status. The findings have implications for understanding how anger and hostility differentially influence coronary heart disease risk. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Three-year experience with the White-Yu Endovascular GAD Graft for transluminal repair of aortic and iliac aneurysms

PURPOSE: To report a > 3-year experience with a modular, balloon-expandable endovascular graft used for aneurysm exclusion in the aorta and other arteries. METHODS: The customized White-Yu Endovascular GAD Graft, a woven polyester prosthesis with an intrinsic Elgiloy wire graft attachment system along the body of the graft, is a flexible endograft design available in straight, tapered, and bifurcated versions that can be delivered transluminally through 18F to 24F sheaths. RESULTS: Since July 1993, 93 patients have received the White-Yu endograft for treatment of 76 abdominal aortic, 3 thoracic aortic, 13 iliac, and 1 popliteal aneurysms. Of the 79 aortic procedures, 39 involved straight tube grafts, 20 were tapered aortoiliac models, and 20 were bifurcated devices. Success rates for tube grafts were 81% in the abdominal aorta and 100% for the thoracic aorta; 5 primary endoleaks (14%) and 2 conversions to surgery (5.6%) occurred with this graft type. Aortoiliac grafts were deployed successfully in 95% (19/20) of cases with 1 conversion (5%) due to thrombosis. Seventy-five percent of the bifurcated endograft procedures were successful, with 4 conversions (20%) for technical failures and 1 graft thrombosis. Four additional endografts were deployed to treat two primary and two secondary endoleaks in tube graft patients. Two access-related arterial injuries were treated surgically. There was one case of embolus to the distal femoral artery but no microembolization. Overall perioperative (30-day) mortality was 3.1%. Over a mean 18-month follow-up (range 2 to 39), no late graft thrombosis, stenosis, or graft migration has been seen on CT scans or X ray. Endoleak has not been detected in any aortoiliac or bifurcated graft. Aneurysm size has diminished consistently in successfully treated cases. CONCLUSIONS: The White-Yu endograft appears to offer a safe, efficacious, and minimally invasive means of excluding aneurysms from the circulation. Improvements in patient selection, surgical techniques, and equipment have reduced the incidence of endoleak and conversion to open repair over the course of the evaluation.     

On the mechanism of the selective oxidation of n-butane, but-1-ene and but-1,3-diene to maleic anhydride over a vanadyl pyrophosphate catalyst

The mechanism of the selective partial oxidation of n-butane, but-1-ene and but-1,3-diene over a vanadyl phosphate catalyst has been investigated by temperature-programmed desorption (TPD) and by anaerobic temperature-programmed oxidation (TPO). TPD showed lattice oxygen to be desorbed in two states at 998 and 1023 K. The anaerobic TPO of n-butane produced butene and butadiene at 1020 K; anaerobic TPO of but-1-ene produced butadiene and furan at 990 K and dehydrofuran at 965 K, while anaerobic TPO of but-1,3-diene produced dehydrofuran at 970 K, furan at 1002 K and maleic anhydride at 1148 K. The total amount of oxygen removed from the lattice in these anaerobic selective partial oxidations was the same as that evolved from the vanadyl phosphate catalyst by TPD. This, and the fact that the selective oxidation reactions occurred at the same temperature at which the oxygen evolves from the lattice, suggests that the lattice oxygen is uniquely selective when it appears at the surface of the catalyst. (Under identical conditions of flow rate, weight of catalyst, heating rate etc., the reaction of n-butane or of but-1,3-diene in air produced only CO₂ and H₂O.) This revised version was published online in July 2006 with corrections to the Cover Date.     

Local overexpression of thrombomodulin for in vivo prevention of arterial thrombosis in a rabbit model

Data from 213 cases of simultaneous carotid endarterectomy and coronary artery bypass grafting (CEN/CABG) were analyzed (1980-1996). There were 154 males (72.3%), and 59 females (27.7%), (mean age: 65. 6 years, range: 42-83). One hundred and thirty-two patients (62.0%) had angina, 58 (37.2%) had myocardial infarction, and 23 (10.8%) had congestive heart failure. Symptomatic cerebrovascular disease was present in 89 patients (41.7%). One hundred and twenty-two patients (57.2%) had three-vessel coronary artery disease, 41 (19.2%) had left main disease, and 27 (12.6%) had a low ejection fraction (ejection fraction /=75% diameter reduction) stenosis was present in 168 (78.8%) of the operated carotid arteries. The contralateral internal carotid artery was severely stenosed or occluded in 35 patients (16.4%). The hospital mortality rate was 5. 6% (12 patients). The cause of death was cardiac in ten patients (4. 6%), and neurologic in two (1%). Eleven patients (5.1%) developed a stroke postoperatively; eight strokes were ipsilateral to the operated artery, and six were permanent. Myocardial infarction occurred in five patients (2.3%). Independent predictors of early mortality were age >62 years, hypertension, and postoperative stroke (p < 0.05). Male sex was the only independent predictor of neurologic morbidity (p < 0.05). Late follow-up data were obtained for 163 (81.0%) patients (mean: 54.8 months, range: 1-168). Four (9. 3%) out of the 43 late deaths were attributed to strokes. There were three (1.8%) late ipsilateral strokes, and five (3.1%) contralateral strokes. The 5- and 10-year survival probabilities were 75 +/- 4%, and 52 +/- 6.9%. The freedom from late ipsilateral neurologic morbidity at 5 and 10 years were 97 +/- 1.7% and 90 +/- 4.0%, respectively. Taken together, the results indicate that combined carotid endarterectomy and coronary artery bypass grafting can be performed safely in this high-risk group of patients. Excellent long-term freedom from stroke can be expected.