75 research outputs found

    Studies of Alternative Solvent Systems to Recycle Phase Selectively Soluble Catalysts

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    In recent years, the Bergbreiter group has investigated the synthesis and use of recyclable polymer-supported catalysts. If the polymer-supported catalyst has high phase selective solubility in certain solvents, the catalyst can often be separated from products with opposite phase selective solubility by using a biphasic separation. Thermomorphic systems, comprised of two solvents that are initially immiscible but that form one phase at elevated temperature, are used to run a reaction under homogeneous conditions and to separate the catalyst and the product in two phases afterward. This work details the use of polymer-supported dyes as catalyst surrogates to examine the phase selective solubility of catalyst supports in thermomorphic systems and to study how leaching of polymer-supported materials into a product phase can be minimized. These studies include the synthesis of a nonpolar phase selectively soluble PIB-supported naphthol azo dye and its use as a catalyst surrogate to study leaching into the polar phase of a heptane/methanol thermomorphic system. It was found that leaching of the PIB-supported dye into the methanol phase was effectively minimized by the addition of nontoxic and nonvolatile poly(α-olefins) (PAOs) as cosolvents. Furthermore, when PAOs were used as a replacement for heptane, PAOs did not appreciably leach into the polar solvent when DMF or methanol were used. The synthesis of a polar phase selective MPEG-supported dansyl fluorophore and its use as a catalyst surrogate to study the phase selective solubility of PEG supports in a heptane/DMF thermomorphic system is also described. The addition of MPEG as a polymer cosolvent did not affect the leaching of PEG-supported dansyl dyes into heptane when PEG supports with molecular weights of greater than 1000 Da were used. Thus, MPEG could serve as a green cosolvent for this system. Finally, the synthesis of a PIB-supported BINOL ligand is detailed. This ligand was prepared in a few steps and was tested in an N-arylation reaction. Although it showed very low reactivity in comparison with BINOL, similar PIB-supported ligands could be prepared and tested. The previous studies of alternative solvents can then be applied to the design of greener recycling systems for such polymer-supported materials

    Studies of Alternative Solvent Systems to Recycle Phase Selectively Soluble Catalysts

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    In recent years, the Bergbreiter group has investigated the synthesis and use of recyclable polymer-supported catalysts. If the polymer-supported catalyst has high phase selective solubility in certain solvents, the catalyst can often be separated from products with opposite phase selective solubility by using a biphasic separation. Thermomorphic systems, comprised of two solvents that are initially immiscible but that form one phase at elevated temperature, are used to run a reaction under homogeneous conditions and to separate the catalyst and the product in two phases afterward. This work details the use of polymer-supported dyes as catalyst surrogates to examine the phase selective solubility of catalyst supports in thermomorphic systems and to study how leaching of polymer-supported materials into a product phase can be minimized. These studies include the synthesis of a nonpolar phase selectively soluble PIB-supported naphthol azo dye and its use as a catalyst surrogate to study leaching into the polar phase of a heptane/methanol thermomorphic system. It was found that leaching of the PIB-supported dye into the methanol phase was effectively minimized by the addition of nontoxic and nonvolatile poly(α-olefins) (PAOs) as cosolvents. Furthermore, when PAOs were used as a replacement for heptane, PAOs did not appreciably leach into the polar solvent when DMF or methanol were used. The synthesis of a polar phase selective MPEG-supported dansyl fluorophore and its use as a catalyst surrogate to study the phase selective solubility of PEG supports in a heptane/DMF thermomorphic system is also described. The addition of MPEG as a polymer cosolvent did not affect the leaching of PEG-supported dansyl dyes into heptane when PEG supports with molecular weights of greater than 1000 Da were used. Thus, MPEG could serve as a green cosolvent for this system. Finally, the synthesis of a PIB-supported BINOL ligand is detailed. This ligand was prepared in a few steps and was tested in an N-arylation reaction. Although it showed very low reactivity in comparison with BINOL, similar PIB-supported ligands could be prepared and tested. The previous studies of alternative solvents can then be applied to the design of greener recycling systems for such polymer-supported materials

    The Textual Ecology of the Palimpsest: Environmental Entanglement of Present and Past

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    Utilizing the metaphor of the palimpsest, this paper looks at layering processes at work in the natural world and human perceptions of it, paying particular attention to the manifestations of the past visible in constructions in and of the landscape. History is made of constant reformations, in which pieces of the past make up the present. The palimpsest offers a useful tool for discussing a trans-temporal landscape. The layers of landscape construction go beyond the literal geological construction, encompassing human pasts and presents as well. Engaging the palimpsestuous layers at work in physical and textual landscape construction allows us to place human endeavours into more expansive notions of temporality

    The association Between Overnight Fasting and Body Mass index in Older adults: the interaction Between Duration and Timing

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    BACKGROUND: Circadian rhythms play an important role in the regulation of eating and fasting, and mistimed dietary intakes may be detrimental to metabolic health. Extended overnight fasting has been proposed as a strategy to better align the eating-fasting cycle with the internal circadian clock, and both observational and experimental studies have linked longer overnight fasting with lower body weight. However, it remains unclear if the timing of overnight fasting modifies the relationship between fasting duration and weight outcomes. METHODS: The current study included 495 men and 499 women age 50-74 years. Dietary intake over 12 months was assessed by 24-h dietary recalls every two months, and body-mass index was measured at the beginning, middle and end of the study. Logistic regression was used to estimate the relationship between overnight fasting duration and the likelihood of being overweight or obesity adjusted for multiple confounders, and assessed whether the relationship was modified by the timing of overnight fasting, measured as the midpoint of the fasting period. RESULTS: Among participants with early overnight fasting (midpoint \u3c 02:19 am), a longer fasting duration was associated with lower odds of overweight and obesity; while among those with late fasting (≥02:19 am), longer fasting was associated with higher odds of overweight and obesity. Specifically, when compared to the shortest quintile of overnight fasting duration, the longest quintile was associated with a 53% reduction in the odds of overweight and obesity in the early fasting group (OR = 0.47, 95% CI = 0.23, 0.97), but a 2.36-fold increase in the late fasting group (OR = 3.36, 95% CI = 1.48, 7.62). Additionally adjusting for dietary intakes during morning and late evening periods did not affect the observed associations. CONCLUSIONS: Longer overnight fasting was associated with a reduced likelihood of being overweight or obese, but only among those with an early timing of fasting

    Advanced Exploration Systems Logistics Reduction and Repurposing Trash-to-Gas and Heat Melt Compactor KSC

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    Topics covered: 1. Project Structure 2. "Trash to Gas" 3. "Smashing Trash! The Heat Melt Compactor" 4. "Heat Melt Compaction as an Effective Treatment for Eliminating Microorganisms from Solid Waste" Thermal degradation of trash reduces volume while creating water, carbon dioxide and ash. CO2 can be fed to Sabatier reactor for CH4 production to fuel LOX/LCH4 ascent vehicle. Optimal performance: HFWS, full temperature ramp to 500-600 C. Tar challenges exist. Catalysis: Dolomag did eliminate allene byproducts from the product stream. 2nd Gen Reactor Studies. Targeting power, mass, time efficiency. Gas separation, Catalysis to reduce tar formation. Microgravity effects. Downselect in August will determine where we should spend time optimizing the technology

    Validation of the Persistent Complex Bereavement Disorder (PCBD) Checklist: A Developmentally Informed Assessment Tool for Bereaved Youth

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    The inclusion of Persistent Complex Bereavement Disorder (PCBD) in the DSMâ 5 appendix signifies a call for research regarding the distinguishing features and clinical utility of proposed PCBD criteria. Rigorously constructed tools for assessing PCBD are lacking, especially for youth. This study evaluated the validity and clinical utility of the PCBD Checklist, a 39â item measure designed to assess PCBD criteria in youth aged 8 to18 years. Test construction procedures involved: (a) reviewing the literature regarding developmental manifestations of proposed criteria, (b) creating a developmentally informed item pool, (c) surveying an expert panel to evaluate the clarity and developmental appropriateness of candidate items, (d) conducting focus groups to evaluate the comprehensibility and acceptability of items, and (e) evaluating psychometric properties in 367 bereaved youth (Mage = 13.49, 55.0% female). The panel, clinicians, and youth provided favorable content validity and comprehensibility ratings for candidate items. As hypothesized, youth who met full PCBD criteria, Criterion B (e.g., preoccupation with the deceased and/or circumstances of the death), or Criterion C (e.g., reactive distress and/or social/identity disruption) reported higher posttraumatic stress and depressive symptoms than youth who did not meet these criteria, ηp2 = .07â .16. Youth who met Criterion C reported greater functional impairment than youth who did not, ηp2 = .08â .12. Youth who qualified for the â traumatic bereavement specifierâ reported more frequent posttraumatic stress symptoms than youth who did not, ηp2 = .04. Findings support the convergent, discriminant, and discriminantâ groups validity, developmental appropriateness, and clinical utility of the PCBD Checklist.ResumenValidación de Lista de verificación del Trastorno por Duelo Complejo Persistente (TDCP): Un informe del desarrollo de herramientas de medición para duelo en jóvenesLISTA DE CHEQUEO DE TRASTORNO DE DUELO COMPLEJO PERSISTENTELa inclusión del trastorno de duelo complejo persistente (TDCP en su sigla en español; PCBD en sus siglas en inglés) en el apéndice del DSMâ 5 significa un llamado para investigar en relación a las características distintivas y la utilidad clínica de los criterios propuestos para el TDCP. Se carece de herramientas rigurosamente construidas para evaluar TDCP, especialmente para jóvenes. Este estudio evalúa la validez y utilidad clínica de la lista de verificación de TPCP, una medida con 39 ítems diseñada para medir el criterio de TDCP en jóvenes de edades entre 8 a 18 años. El procedimiento de construcción del test involucró: (a) revisión de la literatura relacionada con manifestaciones desarrolladas del criterio propuesto; (b) creación de un pool de ítems informados para el desarrollo; (c) encuesta a un panel experto para evaluar la claridad y desarrollo apropiado de los ítems; (d) conducir grupos focales para evaluar la compresibilidad y aceptabilidad de los ítems; y (e) evaluación de propiedades psicométricas en 367 jóvenes en proceso de duelo (M edad = 13.49, 55.0% femenino). El panel, los clínicos y los jóvenes en proceso de duelo proveyeron una validez de contenido favorable y rangos de comprensibilidad para los ítems candidatos. Como se hipotetizó, los jóvenes que cumplieron el criterio completo de TDCP, criterio B (ej., preocupación por el fallecido y/o las circunstancias de la muerte) o el criterio C (ej., estrés reactivo y/o perturbación social/identidad) reportaron alto estrés postraumático y síntomas depresivos que los jóvenes que no cumplen este criterio, ηp2 = .07 a .16. Los jóvenes que no cumplieron el criterio C reportaron mayor deterioro funcional que los jóvenes que no lo cumplieron ηp2 = .08 a .12. Los jóvenes que calificaron para el â duelo traumático especificoâ reportaron mayor frecuencia de síntomas de estrés postraumático que jóvenes que no calificaron ηp2 = .04. 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    A multidisciplinary stroke clinic for outpatient care of veterans with cerebrovascular disease

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    Background: Managing cerebrovascular risk factors is complex and difficult. The objective of this program evaluation was to assess the effectiveness of an outpatient Multidisciplinary Stroke Clinic model for the clinical management of veterans with cerebrovascular disease or cerebrovascular risk factors. Methods: The Multidisciplinary Stroke Clinic provided care to veterans with cerebrovascular disease during a one-half day clinic visit with interdisciplinary evaluations and feedback from nursing, health psychology, rehabilitation medicine, internal medicine, and neurology. We conducted a program evaluation of the clinic by assessing clinical care outcomes, patient satisfaction, provider satisfaction, and costs. Results: We evaluated the care and outcomes of the first consecutive 162 patients who were cared for in the clinic. Patients had as many as six clinic visits. Systolic and diastolic blood pressure decreased: 137.2 ± 22.0 mm Hg versus 128.6 ± 19.8 mm Hg, P = 0.007 and 77.9 ± 14.8 mm Hg versus 72.0 ± 10.2 mm Hg, P = 0.004, respectively as did low-density lipoprotein (LDL)-cholesterol (101.9 ± 23.1 mg/dL versus 80.6 ± 25.0 mg/dL, P = 0.001). All patients had at least one major change recommended in their care management. Both patients and providers reported high satisfaction levels with the clinic. Veterans with stroke who were cared for in the clinic had similar or lower costs than veterans with stroke who were cared for elsewhere. Conclusion: A Multidisciplinary Stroke Clinic model provides incremental improvement in quality of care for complex patients with cerebrovascular disease at costs that are comparable to usual post-stroke care
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