Development and Characterization of Robust and Cost-Effective Catalysts for Selective Biomass Upgrading to Fuels and Chemicals by Deoxydehydration

The use of biomass-derived ligno-cellulose as a possible alternative source of fuels and chemicals to fossil-based hydrocarbons, however, biomass offers many challenges based on processing and its high oxygen content. One promising upgrading route is deoxydehydration, a reaction which combines a deoxygenation by a sacrificial reductant and dehydration in a single step to selectively convert vicinal diols into an olefin. This reaction is highly selective when using homogeneous oxo-rhenium catalysts, which can easily undergo the necessary changes in coordination and oxidation state, however the high cost of rhenium and difficulty of homogeneous catalyst recovery make these catalysts untenable for large scale biomass upgrading. This thesis details work in developing more robust and economical solid catalysts for deoxydehydration. A series of oxide-supported oxo-rhenium catalysts using silica, titania, alumina, iron oxide, and zirconia supports were synthesized and tested which demonstrated high activity and up to 95% selectivity. However, due to the liquid phase chemistry of the reaction, these catalysts demonstrated various propensities to deactivate over multiple runs through leaching of the active rhenium species. We observed that leaching was promoted by the presence of the diol. The severity of the leaching was dependent on not only the support, but the choice of reactant and solvent and after complete diol conversion, the leached rhenium would precipitate out of the reaction mixture, enabling a release and catch leaching mitigation strategy. In preliminary work using microporous zeolites as a support to inhibit leaching, it was found that the acid site of the zeolite provided an anchoring site for the oxo-rhenium species which reduced leaching, but also lowered selectivity due to side reactions catalyzed by the acid site. Vanadium, tungsten, molybdenum, and manganese catalysts were screened for deoxydehydration activity as low-cost alternatives to rhenium. The molybdenum catalysts were found to be the most promising, with the homogeneous ammonium heptamolybdate catalyst achieving 50% alkene yield and the oxide-supported molybdenum catalysts achieving 22% alkene yield using triphenylphosphine as the reductant. It was also found that the ammonium counterion in ammonium heptamolybdate promoted activity for molybdenum-catalyzed deoxydehydration

Sustained-release niacin induced acute liver failure: an autopsy report

Niacin, either alone or in combination with other anti-hyperlipidemic agents, safely and effectively addresses most lipid abnormalities in patients with mixed dyslipidemias. Niacin is the only available agent that significantly lowers lipoprotein (a) and has the greatest high density lipoprotein cholesterol-raising effects of all available agents. Despite niacin’s numerous beneficial lipid effects, patient compliance to long-term therapy is challenged by its common side effects which include nausea, pruritus, and vasodilatory flushing. The incidence of these unpleasant side effects in patients taking the Immediate Release (IR) form of the drug is close to 100 %. To avoid these side effects, Sustained Release (SR) formulations of the drug were created which lower the rate of nausea, flushing and pruritus markedly. Unfortunately, the SR form is associated with a high incidence of chemical hepatitis and rarely fulminant hepatic failure, which is not seen in patients taking the IR form. We report the autopsy findings of a 68 years old man who died of fulminant liver failure three weeks after switching from IR to SR form of niacin. All other toxic, infectious and autoimmune causes of liver failure were ruled out clinically. His liver biopsy one-week antemortem was consistent with chemical hepatitis, such as has been described for slow-release niacin. At autopsy the liver showed diffuse massive hepatic necrosis with no background fibrosis. SR Niacin is widely available over the counter; however, there is substantial scientific evidence that the drug is associated with potentially fatal hepatotoxicity

Autonomic physiological data associated with simulator discomfort

The development of a physiological monitoring capability for the Army's advanced helicopter simulator facility is reported. Additionally, preliminary physiological data is presented. Our objective was to demonstrate the sensitivity of physiological measures in this simulator to self-reported simulator sickness. The data suggested that heart period, hypergastria, and skin conductance level were more sensitive to simulator sickness than were vagal tone and normal electrogastric activity

The role of the maternal immune system in the regulation of human birth weight

This is the accepted manuscript version. It will be embargoed until 12 months after publication by RSC. The final version is available from RCS at http://rstb.royalsocietypublishing.org/content/370/1663/20140071.longHuman birth weight is subject to stabilizing selection. Large babies are at risk of obstetric complications such as obstructed labour, which endangers both mother and child. Small babies are also at risk with reduced survival. Fetal growth requires remodeling of maternal spiral arteries to provide an adequate maternal blood supply to the placenta. This arterial transformation is achieved by placental trophoblast cells, which invade into the uterine wall. Under invasion is associated with fetal growth restriction; but if invasion is excessive large babies can result. A growing body of evidence suggests that this process is controlled by interactions between KIR receptors expressed on maternal uterine NK cells (uNK) and their corresponding HLA-C ligands on invading trophoblast. Mothers with the KIR AA genotype and a fetus with a paternal HLA-C2 allele tend to have small babies, because this combination inhibits cytokine secretion by uNK. Mothers with the activating KIR2DS1 gene and an HLA-C2 fetus are more likely to have large babies. When KIR2DS1 binds to HLA-C2 this increases secretion of cytokines that enhance trophoblast invasion. We conclude that specific combinations of the highly polymorphic gene systems, KIR and HLAC, contribute to successful reproduction by maintaining birth weight between two extremes.This work was supported by funding from the Wellcome Trust [090108/Z/09/Z], [085992/Z/08/Z] and the British Heart Foundation [PG/09/077/27964]. This work was also supported by a Frederick National Laboratory for Cancer Research Contract [HHSN261200800001E] and by the Intramural Research Program of National Institutes of Health, Frederick National Laboratory, Center for Cancer Research. The authors also thank the Centre for Trophoblast Research, Cambridge for generous support

Escape Room: A Competency Validation Approach

Goal The purpose of the evidence-based practice initiative is to enhance annual competencies of clinical staff in the medical/surgical areas through innovative validation methods. Methods • Clinical Nurse Educators (CNEs) identified need for change with clinical staff annual competencies. • CNEs brainstormed new concepts for creating competencies. • In collaboration with the Unit Based Practice Councils (UBPC), a learning needs assessment was conducted in each of the four units. • Unit-based competencies were identified. • The concept of an escape room activity was adapted and tailored to meet the needs of competency validation (Figure 1). • A set up of different competency skill stations were designed separately for both Registered Nurses (RNs) and Clinical Partners (CPs). • Groups of 6 to 8 staff participated and completed the activity within a one and a half hour time frame. • A pre-test and post-test were conducted to measure knowledge before and after completion of the activity and an evaluation was completed by all staff. • A scale evaluation was used from very dissatisfied to very satisfied and for the 180 submitted evaluations 100% answered very satisfied. Outcomes • A total number of 120 RNs and 45 CPs completed the activity. • Total of 29 RN and 10 CP sessions were conducted over a period of 4 months. • RNs completed twelve and CPs completed five competencies. • The pre-test average scores measuring knowledge for the RNs were only 50% and post-test increased to 91%. The CPs pretest average scores were 42%and posttest increased to 92% (Figure 2). • Staff evaluations determined a 100% satisfaction rate. Discussion • The innovative method for measuring competency of RNs and CPs in the medical-surgical areas was initiated by the exploration of non-traditional strategies for engaging the team through active learning. • The nurse educators searched for modalities to demonstrate competency, improve nurse satisfaction, bridge the generational gaps of the staff, while saving cost associated with annual education. • The escape room competency validation approach proved to be a successful method where staff demonstrated skill proficiency and teamwork in an entertaining setting. • Staff felt glad to show competency in their role and reinforce current knowledge. Implications for Practice • Staff competency is essential to provide adequate care to patients. • Validation of staff’s ability to perform skills within their role has traditionally been designed based on staff’s lack of proficiency in performing a designated skill. • Clinical nurse educators need to find new learning strategies to engage clinical staff in active learning while increasing their level of competence. • Overall, increased competency and satisfaction may positively reflect an improvement of clinical outcomes

A demonstration of motion base design alternatives for the National Advanced Driving Simulator

A demonstration of the capability of NASA's Vertical Motion Simulator to simulate two alternative motion base designs for the National Advanced Driving simulator (NADS) is reported. The VMS is located at ARC. The motion base conditions used in this demonstration were as follows: (1) a large translational motion base; and (2) a motion base design with limited translational capability. The latter had translational capability representative of a typical synergistic motion platform. These alternatives were selected to test the prediction that large amplitude translational motion would result in a lower incidence or severity of simulator induced sickness (SIS) than would a limited translational motion base. A total of 10 drivers performed two tasks, slaloms and quick-stops, using each of the motion bases. Physiological, objective, and subjective measures were collected. No reliable differences in SIS between the motion base conditions was found in this demonstration. However, in light of the cost considerations and engineering challenges associated with implementing a large translation motion base, performance of a formal study is recommended

Nutritional Knowledge of NCAA Division I HBCU Student-Athletes

Obesity is a major public health problem. Nutrition education and promotion of healthy food choices may help students-athletes (SA) manage energy intake with some success. General nutrition knowledge may be lacking. Therefore, the purpose of this study was to assess nutrition knowledge of National Collegiate Athletic Association Division I SA at a historically black college or university (HBCU)