Catalytic Processes Mediated by Metal−Organic Frameworks : Reactivity and Mechanistic Studies

The present thesis describes the development of heterogeneous catalytic methodologies using metal−organic frameworks (MOFs) as porous matrices for supporting transition metal catalysts. A wide spectrum of chemical reactions is covered. Following the introductory section (Chapter 1), the results are divided between one descriptive part (Chapter 2) and four experimental parts (Chapters 3–6). Chapter 2 provides a detailed account of MOFs and their role in heterogeneous catalysis. Specific synthesis methods and characterization techniques that may be unfamiliar to organic chemists are illustrated based on examples from this work. Pd-catalyzed heterogeneous C−C coupling and C−H functionalization reactions are studied in Chapter 3, with focus on their practical utility. A vast functional group tolerance is reported, allowing access to substrates of relevance for the pharmaceutical industry. Issues concerning the recyclability of MOF-supported catalysts, leaching and operation under continuous flow are discussed in detail. The following chapter explores puzzling questions regarding the nature of the catalytically active species and the pathways of deactivation for Pd@MOF catalysts. These questions are addressed through detailed mechanistic investigations which include in situ XRD and XAS data acquisition. For this purpose a custom reaction cell is also described in Chapter 4. The scope of Pd@MOF-catalyzed reactions is expanded in Chapter 5. A strategy for boosting the thermal and chemical robustness of MOF crystals is presented. Pd@MOF catalysts are coated with a protecting SiO2 layer, which improves their mechanical properties without impeding diffusion. The resulting nanocomposite is better suited to withstand the harsh conditions of aerobic oxidation reactions. In this chapter, the influence of the nanoparticles’ geometry over the catalyst’s selectivity is also investigated. While Chapters 3–5 dealt with Pd-catalyzed processes, Chapter 6 introduces hybrid materials based on first-row transition metals. Their reactivity is explored towards light-driven water splitting. The heterogenization process leads to stabilized active sites, facilitating the spectroscopic probing of intermediates in the catalytic cycle.

Aerobic and anaerobic test performance among elite male football players in different team positions

The purpose was to determine the magnitude of aerobic and anaerobic performance factors among elite male football players in different team positions. Thirty-nine players from the highest Swedish division classified as defenders (n=18), midfield players (n=12) or attackers (n=9) participated. Their mean (± sd) age, height and body mass (bm) were 24.4 (±4.7) years, 1.80 (±5.9)m and 79 (±7.6)kg, respectively. Running economy (RE) and anaerobic threshold (AT) was determined at 10, 12, 14, and 16km/h followed by tests of maximal oxygen uptake (VO2max). Maximal strength (1RM) and average power output (AP) was performed in squat lifting. Squat jump (SJ), counter-movement jump with free arm swing (CMJa), 45m maximal sprint and the Wingate test was performed. Average VO2max for the whole population (WP) was 57.0mL O2•kg-1min-1 . The average AT occurred at about 84% of VO2max. 1RM per kg bm0.67 was 11.9±1.3kg. Average squat power in the whole population at 40% 1RM was 70±9.5W per kg bm0.67 . SJ and CMJa were 38.6±3.8cm and 48.9±4.4cm, respectively. The average sprint time (45m) was 5.78± 0.16s. The AP in the Wingate test was 10.6±0.9W•kg-1 . The average maximal oxygen uptake among players in the highest Swedish division was lower compared to international elite players but the Swedish players were better off concerning the anaerobic threshold and in the anaerobic tests. No significant differences were revealed between defenders, midfielders or attackers concerning the tested parameters presented above.

Running economy and blood lactate accumulation in elite football players with high and low maximal aerobic power

The purpose was to determine running economy and lactate threshold among a selection of male elite football players with high and low aerobic power. Forty male elite football players from the highest Swedish division (“Allsvenskan”) participated in the study. In a test of running economy (RE) and blood lactate accumulation the participants ran four minutes each at 10, 12, 14, and 16 km•h-1 at horizontal level with one minute rest in between each four minutes interval. After the last sub-maximal speed level the participants got two minutes of rest before test of maximal oxygen uptake (VO2max). Players that had a maximal oxygen uptake lower than the average for the total population of 57.0 mL O2•kg-1•minute-1 were assigned to the low aerobic power group (LAP) (n=17). The players that had a VO2max equal to or higher than 57.0 mL O2•kg-1•minute-1 were selected for the high aerobic power group (HAP) (n=23). The VO2max was significantly different between the HAP and LAP group. The average RE, measured as oxygen uptake at 12, 14 and 16km•h-1 was significantly lower but the blood lactate concentration was significantly higher at 14 and 16 km•h-1 for theLAP group compared with the HAP group.

Aerobic and anaerobic test performance among elite male football players in different team positions

The purpose was to determine the magnitude of aerobic and anaerobic performance factors among elite male football players in different team positions. Thirty-nine players from the highest Swedish division classified as defenders (n=18), midfield players (n=12) or attackers (n=9) participated. Their mean (± sd) age, height and body mass (bm) were 24.4 (±4.7) years, 1.80 (±5.9)m and 79 (±7.6)kg, respectively. Running economy (RE) and anaerobic threshold (AT) was determined at 10, 12, 14, and 16km/h followed by tests of maximal oxygen uptake (VO2max). Maximal strength (1RM) and average power output (AP) was performed in squat lifting. Squat jump (SJ), counter-movement jump with free arm swing (CMJa), 45m maximal sprint and the Wingate test was performed. Average VO2max for the whole population (WP) was 57.0mL O2•kg-1min-1. The average AT occurred at about 84% of VO2max. 1RM per kg bm0.67 was 11.9±1.3kg. Average squat power in the whole population at 40% 1RM was70±9.5W per kg bm0.67. SJ and CMJa were 38.6±3.8cm and 48.9±4.4cm,respectively. The average sprint time (45m) was 5.78± 0.16s. The AP in the Wingate test was 10.6±0.9W•kg-1. The average maximal oxygen uptake among players in the highest Swedish division was lower compared to international elite players but the Swedish players were better off concerning the anaerobic threshold and in the anaerobic tests. No significant differences were revealed between defenders, midfielders or attackers concerning the tested parameters presented above.

Population Health Facility - Determination of Significance and Request for Comments on Scope of SEIS

The University is considering a proposal for site selection and construction of a new above and below grade building to create a physical convening space and compelling catalyst for Population Health endeavors across all three UW campuses, the region, and the world, creating a high profile marker for the UW’s commitment to Population Health, as outlined in President Ana Man Cauce’s May 2016 address to the community.

Effects of a 12-week aerobic exercise intervention on eating behaviour, food cravings and 7-day energy intake and energy expenditure in inactive men

This study examined effects of 12 weeks of moderate-intensity aerobic exercise on eating behaviour, food cravings and weekly energy intake and expenditure in inactive men. Eleven healthy men (mean ± SD: age, 26 ± 5 years; body mass index, 24.6 ± 3.8 kg/m2; maximum oxygen uptake, 43.1 ± 7.4 mL/kg/min) completed the 12-week supervised exercise programme. Body composition, health markers (e.g. blood pressure), eating behaviour, food cravings and weekly energy intake and expenditure were assessed before and after the exercise intervention. There were no intervention effects on weekly free-living energy intake (p=0.326, d=-0.12) and expenditure (p=0.799, d=0.04), or uncontrolled eating and emotional eating scores (p>0.05). However, there was a trend with a medium effect size (p=0.058, d=0.68) for cognitive restraint to be greater after the exercise intervention. Total food cravings (p=0.009, d=-1.19) and specific cravings of high-fat foods (p=0.023, d=-0.90), fast-food fats (p=0.009, d=-0.71) and carbohydrates/starches (p=0.009, d=-0.56) decreased from baseline to 12 weeks. Moreover, there was a trend with a large effect size for cravings of sweets (p=0.052, d=-0.86) to be lower after the exercise intervention. In summary, 12 weeks of moderate-intensity aerobic exercise reduced food cravings and increased cognitive restraint, however, these were not accompanied by changes in other eating behaviours and weekly energy intake and expenditure. The results indicate the importance of exercising for health improvements even when reductions in body mass are modest.

Cardiorespiratory fitness and aerobic performance adaptations to a 4-week sprint interval training in young healthy untrained females

Purpose The aim of this study was to test the effects of sprint interval training (SIT) on cardiorespiratory fitness and aerobic performance measures in young females. Methods Eight healthy, untrained females (age 21 ± 1 years; height 165 ± 5 cm; body mass 63 ± 6 kg) completed cycling peak oxygen uptake ( V˙O2V˙O2 peak), 10-km cycling time trial (TT) and critical power (CP) tests pre- and post-SIT. SIT protocol included 4 × 30-s “all-out” cycling efforts against 7 % body mass interspersed with 4 min of active recovery performed twice per week for 4 weeks (eight sessions in total). Results There was no significant difference in V˙O2V˙O2 peak following SIT compared to the control period (control period: 31.7 ± 3.0 ml kg−1 min−1; post-SIT: 30.9 ± 4.5 ml kg−1 min−1; p > 0.05), but SIT significantly improved time to exhaustion (TTE) (control period: 710 ± 101 s; post-SIT: 798 ± 127 s; p = 0.00), 10-km cycling TT (control period: 1055 ± 129 s; post-SIT: 997 ± 110 s; p = 0.004) and CP (control period: 1.8 ± 0.3 W kg−1; post-SIT: 2.3 ± 0.6 W kg−1; p = 0.01). Conclusions These results demonstrate that young untrained females are responsive to SIT as measured by TTE, 10-km cycling TT and CP tests. However, eight sessions of SIT over 4 weeks are not enough to provide sufficient training stimulus to increase V˙O2V˙O2 peak.

A neuroimaging investigation of the association between aerobic fitness, hippocampal volume and memory performance in preadolescent children

Because children are becoming increasingly overweight, unhealthy and unfit, understanding the neurocognitive benefits of an active lifestyle in childhood has important public health and educational implications. Animal research has indicated that aerobic exercise is related to increased cell proliferation and survival in the hippocampus as well as enhanced hippocampal-dependent learning and memory. Recent evidence extends this relationship to elderly humans by suggesting that high aerobic fitness levels in older adults are associated with increased hippocampal volume and superior memory performance. The present study aimed to further extend the link between fitness, hippocampal volume, and memory to a sample of preadolescent children. To this end, magnetic resonance imaging was employed to investigate whether high- and low-fit 9- and 10-year-old children showed differences in hippocampal volume and if the differences were related to performance on an item and relational memory task. Relational but not item memory is primarily supported by the hippocampus. Consistent with predictions, high-fit children showed greater bilateral hippocampal volumes. Furthermore, hippocampal volume was positively associated with performance on the relational but not the item memory task. The findings are the first to suggest that aerobic fitness can impact the structure and function of the developing human brain.

Guia de análises microbiológicas para cortes de aves in natura: elaboração e aplicação prática

An effective hygiene and sanitation inspection of meat and meat products is essential for its production and commercialization. For this reason, the national and international standards responsible for these products quality control employs microbiological analyses methods as quality control tools. In December of 2012, it was included in the Ministério da Agricultura Pecuária e Abastecimento (MAPA) website, a Microbiological Scope of food and water, which presents the replacement of some methods proposed by the Normative Instruction 62. Some of these methodologies are considered rapid, practical and convenient. However, other methodologies were still replaced by conventional ones, which presents disadvantages as incorrect interpretations of the microorganism phenotypical and biochemical characteristics, leading to the misinterpretation of test results. Therefore, the objective of this study is to develop a comprehensive, practical and illustrative guidebook of microbiological analysis for in natura poultry cuts. The methods addressed in this guide are the official standards analysis required by the poultry cuts legislation, which are the Escherichia coli count, the thermotolerant coliforms count, the aerobic plate count and the detection of Salmonella spp. The approached methodologies for these analysis will be the AOAC 998.08, the Normative Instruction 62 and the ISO 4833-1:2013 and ISO 6579:2002, respectively. In these events, it is expected to obtain an enlightening and approved guidebook evaluated by laboratory technicians, which will help reduce the analytical subjectivity leading to a more reliable interpretation of the test results.

Aerobic performance and morphological modifications after a 4 month physical activity training program in elderly women

Research clearly shows that physical activity (PA) is an important factor to develop and maintain good health and adequate body functions in older people. In this context, the purpose of this study was to determine aerobic performance and morphological modifications after a 4 month physical activity program (PAP) in elderly. METHODS Forty subjects divided in two groups (control, n=20; and experimental, n=20) were evaluated twice, at the beginning and after a 4-month-activity program period. This program called “+ age + health” consists of 3 week sessions of one hour each, based on walking and aerobic exercises. The control group had, at its first evaluation, the followings characteristics: average body mass 68kg±15, 28±5 BMI, 37%±5 body fat, 2.2kg±0.4 bone mass, 42%±9 lean body mass and did 129 repetitions ± 46 on a 2-Minute Step Test (2MST). The assessment of anthropometric and morphological variables was measured through an electrical bioimpedance scale (TANITA - BC 545). Aerobic endurance was evaluated from a 2MST.RESULTS In the control group only the percentage of body fat changed significantly, and increased over time. In the experimental group we found a positive relationship between PAP and the majority of morphological variables. The percentage of variation changed in: body fat (-4.3%±7.6, p=0.014), bone mass (2.4%±3.1, p=0.004) and 2MST (33.6%±63.1, p=0.023). In the remaining variables there were no significant modifications. The significant modification in 2MST after the activity period means that the aerobic performance can be improved in elderly, and attenuates the negative effects of age. Moreover, the benefits of PAP can be seen by positive alterations registered in lean body mass and in the percentage of body fat.

Plasma inflammatory biomarkers response to aerobic versus resisted exercise training for chronic obstructive pulmonary disease patients.

Background: Chronic obstructive pulmonary disease (COPD) is a main risk for morbidity, associated with alterations in systemic inflammation. Recent studies proved that morbidity and mortality of COPD is related to systemic inflammation as it contributes to the pathogenesis of atherosclerosis and cardiovascular disease. However, increase of inflammatory cytokines adversely affects quality of life, alteration in ventilatory and skeletal muscles functions. Moreover, exercise training has many beneficial effects in correction of the adverse effects of COPD. Objective: This study aimed to compare the response of inflammatory cytokines of COPD to aerobic versus resisted exercises. Materials and methods: One hundred COPD diseased patients participated in this study and were randomly included in two groups; the first group received aerobic exercise, whereas the second group received resisted exercise training for 12 weeks. Results: The mean values of TNF-α, Il-2, IL-4, IL-6 and CRP were significantly decreased in both groups. Also; there was a significant difference between both groups at the end of the study with more reduction in patients who received aerobic exercise training. Conclusion: Aerobic exercise is more appropriate than resisted exercise training in modulating inflammatory cytokines level in patients with chronic obstructive pulmonary disease.

Aerobic endurance in HIV-positive young adults and HIV-negative controls in Malawi

Background Aerobic endurance is an important aspect of physical fitness that enables individuals living with HIV to endure in the work place as well as in agricultural operations in order to earn a living and improve their quality of life. However, despite high HIV prevalence rates, the aerobic endurance status of young Malawians living with HIV remains unknown. The objective of this study was to determine the difference in VO2max between HIV-negative and HIV-positive individuals in Blantyre, Malawi. Methods Fifty five participants (17 males and 38 females) who have HIV and were not taking antiretroviral medication and 78 HIV-negative participants (45 males and 33 females) performed the Rockport submaximal treadmill exercise test. Measures of body weight, post-exercise heart rate and time to walk one mile were obtained and used to predict VO2max. Comparisons between groups were adjusted for age differences using analysis of covariance (ANCOVA). Results VO2max was significantly lower in HIV-positive subjects [31.1, 28.7 - 33.5mL.kg-1.min-1(mean, 95% CI)] compared with HIV-negative subjects [56.2, 54.3 - 58.1mL.kg-1.min-1]. Conclusion Aerobic endurance was markedly reduced in HIV-positive participants compared with HIV-negative participants. Findings of the current study implicate factors associated with the HIV infection as contributors to a decreased aerobic endurance in people living with HIV.

Socio-economic status, growth, physical activity and fitness: the Madeira growth study

Within a country social conditions change over time and these conditions vary from country to country. The associations between these conditions, somatic growth, physical activity and fitness reflect these changes. Aim: The study documented variation in somatic growth, physical activity and fitness associated with socio-economic status (SES). Subjects and methods: The study involved 507 subjects (256 boys and 251 girls) from the Madeira Growth Study, a mixed longitudinal study of five cohorts (8, 10, 12, 14 and 16 years of age) followed at yearly intervals over 3 years (1996–1998). A total of 1493 observations were made. Anthropometric measurements included lengths, body mass, skeletal breadths, girths and skinfolds. Physical activity and SES were collected via questionnaire and interview. Physical fitness was assessed using the Eurofit test battery. Variation in somatic growth, physical activity and physical fitness by SES (high, average and low) was tested with analysis of variance. Results: Significant differences between SES groups were observed for height, body mass and skinfolds. Boys and girls from high SES groups were taller, heavier and fatter (subscapular and triceps skinfolds) than their peers from average and low SES groups. At some age intervals, the high SES group had larger skeletal breadths (girls) and girths (boys and girls) than low SES. Small SES differences were observed for physical activity (sport and leisure-time indices). SES was significantly associated with physical fitness. At some age levels, boys from the low SES group performed better for muscular and aerobic endurance whereas girls from the high SES group performed better for power. Conclusion: Considerable variation in somatic growth and physical fitness in association with SES has been demonstrated, but little association was found for physical activity.

Tracking of fatness during childhood, adolescence and young adulthood: a 7-year follow-up study in Madeira Island, Portugal

Aims: Investigating tracking of fatness from childhood to adolescence, early adolescence to young adulthood and late adolescence to young adulthood. Subjects and methods: Participants from the Madeira Growth Study were followed during an average period of 7.2 years. Height, body mass, skin-folds and circumferences were measured, nine health- and performance-related tests were administered and the Baecke questionnaire was used to assess physical activity. Skeletal maturity was estimated using the TW3 method. Results: The prevalence of overweight plus obesity ranged from 8.2–20.0% at baseline and from 20.4–40.0% at followup, in boys. Corresponding percentages for girls were 10.6– 12.0% and 13.2–18.0%. Inter-age correlations for fatness indicators ranged from 0.43–0.77. BMI, waist circumference and sum of skin-folds at 8, 12 and 16-years old were the main predictors of these variables at 15, 19 and 23-years old, respectively. Strength, muscular endurance and aerobic fitness were negatively related to body fatness. Physical activity and maturation were independently associated with adolescent (15 years) and young adult (19 years) fatness. Conclusions: Over 7.2 years, tracking was moderate-to-high for fatness. Variance was explained by fatness indicators and to a small extent by physical fitness, physical activity and maturation.