ERP and cardiovascular correlates of source memory discrimination in older and younger adults /

There is much evidence to support an age-related decline in source memory ability. However, the underlying mechanisms responsible for this decline are not well understood. The current study was carried out to determine the electrophysiological correlates of source memory discrimination in younger and older adults. Event-related potentials (ERPs) and continuous electrocardiographic (ECG) data were collected from younger (M= 21 years) and older (M= 71 years) adults during a source memory task. Older adults were more likely to make source memory errors for recently repeated, non-target words than were younger adults. Moreover, their ERP records for correct trials showed an increased amplitude in the late positive (LP) component (400-800 msec) for the most recently presented, non-target stimuli relative to the LP noted for target items. Younger adults showed an opposite pattern, with a large LP component for target items, and a much smaller LP component for the recently repeated non-target items. Computation of parasympathetic activity in the vagus nerve was performed on the ECG data (Porges, 1985). The resulting measure, vagal tone, was used as an index of physiological responsivity. The vagal tone index of physiological responsivity was negatively related to the LP amplitude for the most recently repeated, non-target words in both groups, after accounting for age effects. The ERP data support the hypothesis that the tendency to make source memory errors on the part of older adults is related to the ability to selectively control attentional processes during task performance. Furthermore, the relationship between vagal tone and ERP reactivity suggests that there is a physiological basis to the heightened reactivity measured in the LP response to recently repeated non-target items such that, under decreased physiological resources, there is an impairment in the ability to selectively inhibit bottom-up, stimulus based properties in favour of task-related goals in older adults. The inconsistency of these results with other explanatory models of source memory deficits is discussed. It is concluded that the data are consistent with a physiological reactivity model requiring inhibition of reactivity to irrelevant, but perceptually-fluent, stimuli.

Cardiovascular health risk profiling of Niagara Region grade 9 students : implications for elementary curriculum /

The purpose of this study was to determine if Ontario's health and physical education curriculum contributes sufficiently to ensure the health of our children and young adults. To determine the curriculum effect, the health risk profile of Niagara Region's grade 9 students was compared to Canada's adolescent population. All subjects completed a "Heart Health Lifestyle" survey and were measured for height, weight, percent body fat, blood pressure, and total cholesterol and performed the 20-metre shuttle run test as part of their physical and health education classes. The Niagara Region grade 9 population had a healthy risk profile. Aerobic power was inversely related, and cholesterol levels were positively associated to body mass index and percent body fat in the whole group analysis. These results indicate that physical education can offer unique and essential aspects allowing individuals a means to learn and control body movements and keep physically fit while providing protection against modern disease. Ontario's health and physical education curriculum does contribute to the health of our children and adolescents; however, there is a need to implement a stronger mandate for daily vigorous physical activity.

Physiological reactivity and the perception of emotional stimuli as they relate to social adaptive functioning after traumatic brain injury / y Melonie Jane Hopkins.

Traumatic brain injury (TBI) often affects social adaptive functioning and these changes in social adaptability are usually associated with general damage to the frontal cortex. Recent evidence suggests that certain neurons within the orbitofrontal cortex appear to be specialized for the processing of faces and facial expressions. The orbitofrontal cortex also appears to be involved in self-initiated somatic activation to emotionally-charged stimuli. According to Somatic Marker Theory (Damasio, 1994), the reduced physiological activation fails to provide an individual with appropriate somatic cues to personally-relevant stimuli and this, in turn, may result in maladaptive behaviour. Given the susceptibility of the orbitofrontal cortex in TBI, it was hypothesized that impaired perception and reactivity to socially-relevant information might be responsible for some of the social difficulties encountered after TBL Fifteen persons who sustained a moderate to severe brain injury were compared to age and education matched Control participants. In the first study, both groups were presented with photographs of models displaying the major emotions and either asked to identify the emotions or simply view the faces passively. In a second study, participants were asked to select cards from decks that varied in terms of how much money could be won or lost. Those decks with higher losses were considered to be high-risk decks. Electrodermal activity was measured concurrently in both situations. Relative to Controls, TBI participants were found to have difficulty identifying expressions of surprise, sadness, anger, and fear. TBI persons were also found to be under-reactive, as measured by electrodermal activity, while passively viewing slides of negative expressions. No group difference,in reactivity to high-risk card decks was observed. The ability to identify emotions in the face and electrodermal reactivity to faces and to high-risk decks in the card game were examined in relationship to social monitoring and empathy as described by family members or friends on the Brock Adaptive Functioning Questionnaire (BAFQ). Difficulties identifying negative expressions (i.e., sadness, anger, fear, and disgust) predicted problems in monitoring social situations. As well, a modest relationship was observed between hypo-arousal to negative faces and problems with social monitoring. Finally, hypo-arousal in the anticipation of risk during the card game related to problems in empathy. In summary, these data are consistent with the view that alterations in the ability to perceive emotional expressions in the face and the disruption in arousal to personally-relevant information may be accounting for some of the difficulties in social adaptation often observed in persons who have sustained a TBI. Furthermore, these data provide modest support for Damasio's Somatic Marker Theory in that physiological reactivity to socially-relevant information has some value in predicting social function. Therefore, the assessment of TBI persons, particularly those with adaptive behavioural problems, should be expanded to determine whether alterations in perception and reactivity to socially-relevant stimuli have occurred. When this is the case, rehabilitative strategies aimed more specifically at these difficulties should be considered.

Reactivity characteristics of cytochrome c, cytochrome oxidase and the electrostatic cytochrome c - cytochrome oxidase complex /

The mechanism whereby cytochrome £ oxidase catalyses elec-. tron transfer from cytochrome £ to oxygen remains an unsolved problem. Polarographic and spectrophotometric activity measurements of purified, particulate and soluble forms of beef heart mitochondrial cytochrome c oxidase presented in this thesis confirm the following characteristics of the steady-state kinetics with respect to cytochrome £: (1) oxidation of ferrocytochrome c is first order under all conditions. -(2) The relationship between sustrate concentration and velocity is of the Michaelis-Menten type over a limited range of substrate. concentrations at high ionic strength. (3) ~he reaction rate is independent from oxygen concentration until very low levels of oxygen. (4) "Biphasic" kinetic plots of enzyme activity as a function of substrate concentration are found when the range of cytochrome c concentrations is extended; the biphasicity ~ is more apparent in low ionic strength buffer. These results imply two binding sites for cytochrome £ on the oxidase; one of high affinity and one of low affinity with Km values of 1.0 pM and 3.0 pM, respectively, under low ionic strength conditions. (5) Inhibition of the enzymic rate by azide is non-c~mpetitive with respect to cytochrome £ under all conditions indicating an internal electron transfer step, and not binding or dissociation of £ from the enzyme is rate limiting. The "tight" binding of cytochrome '£ to cytochrome c oxidase is confirmed in column chromatographic experiments. The complex has a cytochrome £:oxidase ratio of 1.0 and is dissociated in media of high ionic strength. Stopped-flow spectrophotometric studies of the reduction of equimolar mixtures and complexes of cytochrome c and the oxidase were initiated in an attempt to assess the functional relevance of such a complex. Two alternative routes -for reduction of the oxidase, under conditions where the predominant species is the £ - aa3 complex, are postulated; (i) electron transfer via tightly bound cytochrome £, (ii) electron transfer via a small population of free cytochrome c interacting at the "loose" binding site implied from kinetic studies. It is impossible to conclude, based on the results obtained, which path is responsible for the reduction of cytochrome a. The rate of reduction by various reductants of free cytochrome £ in high and low ionic strength and of cytochrome £ electrostatically bound to cytochrome oxidase was investigated. Ascorbate, a negatively charged reagent, reduces free cytochrome £ with a rate constant dependent on ionic strength, whereas neutral reagents TMPD and DAD were relatively unaffected by ionic strength in their reduction of cytochrome c. The zwitterion cysteine behaved similarly to uncharged reductants DAD and TI~PD in exhibiting only a marginal response to ionic strength. Ascorbate reduces bound cytochrome £ only slowly, but DAD and TMPD reduce bound cytochrome £ rapidly. Reduction of cytochrome £ by DAD and TMPD in the £ - aa3 complex was enhanced lO-fold over DAD reduction of free £ and 4-fold over TMPD reduction of free c. Thus, the importance of ionic strength on the reactivity of cytochrome £ was observed with the general conclusion being that on the cytochrome £ molecule areas for anion (ie. phosphate) binding, ascorbate reduction and complexation to the oxidase overlap. The increased reducibility for bound cytochrome £ by reductants DAD and TMPD supports a suggested conformational change of electrostatically bound c compare.d to free .£. In addition, analysis of electron distribution between cytochromes £ and a in the complex suggest that the midpotential of cytochrome ~ changes with the redox state of the oxidase. Such evidence supports models of the oxidase which suggest interactions within the enzyme (or c - enzyme complex) result in altered midpoint potentials of the redox centers.

The cardiovascular hemodynamic responses to various levels of orthostatic stress in children

The ability of the cardiovascular system to quickly and efficiently adapt to an orthostatic stress is vital for the human body to function on earth. The way in which the various aspects of the cardiovascular system work together to counteract an orthostatic stress has been previously quantified in the adult population. However, there are still many unknowns surrounding the topic of how the cardiovascular system functions to cope with this same stress in children. The purpose of this study was to describe the cardiovascular hemodynamic adaptations to various levels of orthostatic stress induced using a lower body negative pressure (LBNP) chamber in pre-pubertal boys. A secondary purpose was to determine indices of baroreceptor sensitivity (BRS) at both rest and during low levels of LBNP in this same pediatric sample. Finally, this study aimed to compare the relative responses to LBNP between the children and adults. To complete the study 20 healthy pre-pubertal boys and adult males (9.3 ± 1.1 and 23 ± 1.8 years of age respectively) were recruited and randomly exposed to three levels of LBNP (15, 20 and 25 mmHg). At rest and during the application of the LBNP heart rate (HR), manual and bcat-by-beat systolic (SBP), diastolic (DBP) and mean arterial blood pressure (MAP) were monitored continuously. Aortic diameter was measured at rest and peak aortic blood velocity (PV) was recorded continuously for at least I minute during each baseline and LBNP condition. From the raw data HR, stroke volume (SV), cardiac output (Q), total peripheral resistance (TPR), low frequency baroreceptor sensitivity (LF BRS), high frequency baroreceptor sensitivity (HF BRS) and LFIIIF ratio were calculated. At rest, llR wa'i higher and SBP, SV, Q and LF/HF ratio were lower in the children compared to the adult males (pgJ.05). In response to the increasing LEN!> IIR and TPR increased, and LF BRS. SV and Q decreased in the adult group (pSf).05). while the same levels of LBNP caused an increase in TPR and a decrease in SBP, SV and Q in the children (pSf).05). Although not significant, the LF/HF ratio in the adult group showed an increasing trend in response to increased negative pressure (p=O.088). As for resting BRS, there were no significant differences in LF or HF BRS between the children and the adults despite a tendency for both measures to be 18% lower in the children. Also the LF/HF ratio was almost significantly greater in the adults compared to the children (p=O.057). In addition, a comparison between the relative adult and child responses to LBNP yielded no significant group by level interactions. This result should be taken with caution though, as the low sample size and high measurement variability generated very low statistical power for this analysis. In conclusion, the results of this study suggest that the hemodynamic adaptations to an orthostatic stress were less pronounced in the prepubertal males, most likely due to an underdeveloped autonomic system. These results need to be strengthened by further research before any implications can be derived for health care purposes.

The roles of ERK1/2 and PI3K in abnormal vascular functions in angiotensin II-infused hypertensive rats

Background: Ang II plays a major role in cardiovascular regulation. Recently, it has become apparent that vascular superoxide anion may play an important role in hypertension development. Treatment with antisense NAD(P)H oxidase or SOD decreased BP in Ang II-infused rats. Wang et al recently reported mice which lack one of the subunits of NAD(P)H oxidase developed hypertension at a much lower extent when compared to the wild type animals infused with Ang II, indicating that superoxide anion contributes to elevation in BP in the Ang II-infused hypertensive model. In the Ang II-infused hypertensive model, altered reactivity of blood vessels is often associated with the elevation of systolic blood pressure. We have observed abnormal tension development and impaired endothelium-dependent relaxation in the isolated aorta of Ang II-infused and DOCA-salt hypertensive rats. Recently, several other cellular signal molecules, including ERK1I2 and PI3K, have been determined to play important roles in the regulation of smooth muscle contraction and relaxation. ERKl/2 and PI3K pathways are also reported to contribute to Ang II induced cell growth, hypertrophy, remodeling and contraction. Moreover, these signaling pathways have shown ROS-sensitive properties. Therefore, the aim of the present study is to investigate the roles of ERKl12 and PI3K in vascular oxidative stress, spontaneous tone and impaired endothelium relaxation in Ang II-infused hypertensive model. Hypothesis: We hypothesize that the activation of ERKl12 and PI3K are elevated in response to an Ang II infusion for 6 days. The elevated activation of phospho-ERKl/2 and PI3K mediated the increased level of vascular superoxide anion, the abnormal vascular contraction and impaired endothelium-dependent vascular relaxation in Ang II-infused hypertensive rats. Methods: Vascular superoxide anion level is measured by lucigenin chemiluminescence. Spontaneous tone and ACh-induced endothelium-dependent relaxation was measured by isometric tension recording in organ chamber. The activity of ERK pathway will be measured by its Western blot of phosphorylation of ERK. PI3K activity was evaluated indirectly by Western blot of the phosphorylation of PDKl, a downstream protein of PI3K signaling pathway. The role of each pathway was also addressed via comparing the responses to the specific inhibitors. Results: Superoxide anion was markedly increased in the isolated thoracic aorta from Ang II-infused rats. There was spontaneous tone developed in rings from Ang II-induced hypertensive but not sham-operated normotensive rats. ACh-induced endothelium-dependent relaxation function is impaired in Ang II-infused hypertensive rats. Superoxide dismutase and NAD(P)H oxidase inhibitor, apocynin, inhibited the abnormal spontaneous tone and ameliorated impaired endothelium-dependent relaxation. The expression of phopho-ERKII2 was enhanced in Ang II-infused rats, indicating the activity of ERK1I2 could be increased. MEK1I2 inhibitors, PD98059 and U126, but not their inactive analogues, SB203580 and U124, significantly reduced the vascular superoxide anion in aortas from Ang II-infused rats. The MEK1I2 inhibitors reduced the spontaneous tone and improved the impaired endothelium-dependent relaxation in aorta of hypertension. These findings supported the role of ERKII2 signaling pathway in vascular oxidative stress, spontaneous tone and impaired endothelium-dependent relaxation in Ang II-infused hypertensive rats. The amount of phospho-PDK, a downstream protein of PI3K was increased in Ang II rats indicating the activity of PI3K activity was elevated. Strikingly, PI3K significantly inhibited the increase of superoxide anion level, abnormal spontaneous tone and restored endothelium-dependent relaxation in Ang II-infused hypertensive rats. These findings indicated the important role of PI3K in Ang II-infused hypertensive rats. Conclusion: ERKII2 and PI3K signaling pathways are sustained activated in Ang II-infused hypertensive rats. The activated ERKII2 and PI3K mediate the increase of vascular superoxide anion level, vascular abnormal spontaneous tone and impaired endothelium-dependent relaxation.

Effect of diurnal cycling temperatures on cardiovascular- ventilatory function in statically-acclimated rainbow trout, Salmo gairdneri

Four groups of rainbow trout, Salmo gairdneri, were acclimated to 2°, 10°, and 18°e, and to a diurnal temperature cycle (100 ± 4°C). To evaluate the influence of cycling temperatures in terms of an immediate as opposed to acclimatory response various ventilatory-cardiovascular rate functions were observed for trout, either acclimated to cycling temperatures or acclimated to constant temperatures and exposed to a diurnal temperature cycle for the first time (10° ± 4°C for trout acclimated to 10°C; 18°+ 4°C for trout acclimated to l8°e). Gill resistance and the cardiac to ventilatory rate ratio were then calculated. Following a post preparatory recovery period of 36 hr, measurements were made over a 48 hour period with the first 24 hours being at constant temperature in the case of statically-acclimated fish followed by 24 hours under cyclic temperature conditions. Trout exhibited marked changes in oxygen consumption (Vo ) with temp- 2 erature both between acclimation groups, and in response to the diurnal temperature cycle. This increase in oxygen uptake appears to have been achieved by adjustment of ventilatory and, to some extent, cardiovascular activity. Trout exhibited significant changes in ventilatory rate (VR), stroke volume (Vsv), and flow (VG) in response to temperature. Marked changes in cardiac rate were also observed. These findings are discussed in relation to their importance in convective oxygen transport via water and blood at the gills and tissues. Trout also exhibited marked changes in pressure waveforms associated with the action of the resp; ratory pumps with temperature. Mean differenti a 1 pressure increased with temperature as did gill resistance and utilization. This data is discussed in relation to its importance in diffusive oxygen transport and the conditions for gas exchange at the gills. With one exception, rainbow trout were able to respond to changes in oxygen demand and availability associated with changes in temperature by means of adjustments in ventilation, and possibly pafusion, and the conditions for gas exchange at the gills. Trout acclimated to 18°C, however, and exposed to high cyclic temperatures, showed signs of the ventilatory and cardiovascular distress problems commonly associated with low circulating levels of oxygen in the blood. It appears these trout were unable to fully meet the oxygen requirements associated with c~ling temperatures above 18°C. These findings were discussed in relation to possible limitations in the cardiovascular-ventilatory response at high temperatures. The response of trout acclimated to cycling temperatures was generally similar to that for trout acclimated to constant temperatures and exposed to cycling temperatures for the first time. This result suggested that both groups of fish may have been acclimated to a similar thermal range, regardless of the acclimation regime employed. Such a phenomenon would allow trout of either acclimation group to respond equally well to the imposed temperature cycle. Rainbow trout showed no evidence of significant diurnal rhythm in any parameters observed at constant temperatures (2°, 10°, and 18° C), and under a 12/12 light-dark photoperiod regime. This was not taken to indicate an absence of circadian rhythms in these trout, but rather a deficiency in the recording methods used in the study.

Effect of iron on reactivity of vanillin in wine models /

Phenolic compounds are important components of grapes and wines. They have been found to have important roles in grape and wine systems and properties that are beneficial for human health. Vanillin (3-methoxy-4-hydroxybenzaldehyde) is a phenolic compound coming from the oxidative degradation of lignin in oak-barrels during the aging of wine. Vanillin is an important flavour component of wine and its concentration in wine influences significantly the aroma and flavour of wine. The concentration of vanillin in wine is affected by various factors including the presence of metal ions. In this work, by using HPLC, HPLC-MS, and MS technologies, iron (III) cations were found to affect the oxidation of vanillin in a model system of wine, and the product of the oxidation was identified as divanillin. The mechanism of the redox reaction between vanillin and Fe^"^ is thought to follow that of other phenol oxidations. Increasing the concentration of Fe ^ in the model system accelerates divanillin production. The best pH condition for the divanillin production in the system is the range of 3.0 ~ 3.5. Increasing temperature from 20°C to 40°C accelerates the divanillin production. Divanillin was found to exist in three commercial red wines in this work. Keeping the storage temperature cool and decreasing the contact of grapes and wines with iron are two major measures suggested by this work in order to decrease the oxidation of vanillin during the making and aging of wine.

Participants' perceptions of their involvement in a cardiovascular disease risk factor reduction program

A cardiovascular disease risk factor reduction program was implemented in the Niagara region. To gain an understanding of this program from the participants ' perspective, 10 participants of the program were interviewed to document their perceptions of what they learned in the program, their perceptions of their behaviour change and their perceptions of factors that facilitated or impeded any behaviour change. The learning style inventory and PET test were also given to the participants to further understand their perceptions. Findings unique to this study highlighted aspects of the andragogical model, self-directed learning theory, learning style preference and psychological type that were prominent in the participants' comments and perspectives. Implications for practice, theory development and further research are suggested.

The influence of recreational ball hockey play on cardiovascular risk factors in sedentary males

Introduction: The prevalence of coronary artery disease (CAD) is ever increasing in western industrialized societies. An individuals overall risk for CAD may be quantified by integrating a number of factors including, but not limited to, cardiorespiratory fitness, body composition, blood lipid profile and blood pressure. It might be expected that interventions aimed at improving any or all of these independent factors might improve an individual 's overall risk. To this end, the influence of standard endurance type exercise on cardiorespiratory fitness, body composition, blood lipids and blood pressure, and by extension the reduction of coronary risk factors, is well documented. On the other hand, interval training (IT) has been shown to provide an extremely powerful stimulus for improving indices of cardiorespiratory function but the influence of this training type on coronary risk factors is unknown. Moreover, the vast majority of studies investigating the effects of IT on fitness have used laboratory type training protocols. As a result of this, the influence of participation in interval-type recreational sports on cardiorespiratory fitness and coronary risk factors is unknown. Aims: The aim of the present study was to evaluate the effectiveness of recreational ball hockey, a sport associated with interval-type activity patterns, on indices of aerobic function and coronary risk factors in sedentary men in the approximate age range of 30 - 60 years. Individual risk factors were compiled into an overall coronary risk factor score using the Framingham Point Scale (FPS). Methods: Twenty-four sedentary males (age range 30 - 60) participated in the study. Subject activity level was assessed apriori using questionnaire responses. All subjects (experimental and control) were assessed to have been inactive and sedentary prior to participation in the study. The experimental group (43 ± 3 years; 90 ± 3 kg) (n = 11) participated in one season of recreational ball hockey (our surrogate for IT). Member of this group played a total of 16 games during an 11 week span. During this time, the control group (43 ± 2 years; 89 ± 2 kg) (n = 11) performed no training and continued with their sedentary lifestyle. Prior to and following the ball hockey season, experimental and control subjects were tested for the following variables: 1) cardiorespiratory fitness (as V02 Max) 2) blood lipid profile 3) body composition 5) waist to hip ratio 6) blood glucose levels and 7) blood pressure. Subject V02 Max was assessed using the Rockport submaximal walking test on an indoor track. To assess body composition we determined body mass ratio (BMI), % body fat, % lean body mass and waist to hip ratio. The blood lipid profile included high density lipoprotein, low density lipoprotein and total cholesterol levels; in addition, the ratio of total cholesterol to high density was calculated. Blood triglycerides were also assessed. All data were analyzed using independent t - tests and all data are expressed as mean ± standard error. Statistical significance was accepted at p :S 0.05. Results: Pre-test values for all variables were similar between the experimental and control group. Moreover, although the intervention used in this study was associated with changes in some variables for subjects in the experimental group, subjects in the control group did not exhibit any changes over the same time period. BODY COMPOSITION: The % body fat of experimental subjects decreased by 4.6 ± 0.5%, from 28.1 ± 2.6 to 26.9 ± 2.5 % while that of the control group was unchanged at 22.7 ± 1.4 and 22.2 ± 1.3 %. However, lean body mass of experimental and control subjects did not change at 64.3 ± 1.3 versus 66.1 ± 1.3 kg and 65.5 ± 0.8 versus 64.7 ± 0.8 kg, respectively. In terms of body mass index and waist to hip ratio, neither the experimental nor the control group showed any significant change. Respective values for the waist to hip ratio and body mass index (pre and post) were as follows: 1 ± 0.1 vs 0.9 ± 0.1 (experimental) and 0.9 ± 0.1 versus 0.9 ± 0.1 (controls) while for BMI they were 29 ± 1.4 versus 29 ± 1.2 (experimental) and 26 ± 0.7 vs. 26 ± 0.7 (controls). CARDIORESPIRATORY FITNESS: In the experimental group, predicted values for absolute V02 Max increased by 10 ± 3% (i.e. 3.3 ± 0.1 to 3.6 ± 0.1 liters min -1 while that of control subjects did not change (3.4 ± 0.2 and 3.4 ± 0.2 liters min-I). In terms of relative values for V02 Max, the experimental group increased by 11 ± 2% (37 ± 1.4 to 41 ± 1.4 ml kg-l min-I) while that of control subjects did not change (41 ± 1.4 and 40 ± 1.4 ml kg-l min-I). BLOOD LIPIDS: Compared to pre-test values, post-test values for HDL were decreased by 14 ± 5 % in the experiment group (from 52.4 ± 4.4 to 45.2 ± 4.3 mg dl-l) while HDL data for the control group was unchanged (49.7 ± 3.6 and 48.3 ± 4.1 mg dl-l, respectively. On the other hand, LDL levels did not change for either the experimental or control group (110.2 ± 10.4 versus 112.3 ± 7.1 mg dl-1 and 106.1 ± 11.3 versus 127 ± 15.1 mg dl-1, respectively). Further, total cholesterol did not change in either the experimental or control group (181.3 ± 8.7 mg dl-1 versus 178.7± 4.9 mg dl-l) and 190.7 ± 12.2 versus 197.1 ± 16.1 mg dl-1, respectively). Similarly, the ratio of TC/HDL did not change for either the experimental or control group (3.8 ± 0.4 versus 4.5 ± 0.5 and 4 ± 0.4 versus 4.2 ± 0.4, respectively). Blood triglyceride levels were also not altered in either the experimental or control group (100.3 ± 19.6 versus 114.8 ± 15.3 mg dl-1 and 140 ± 23.5 versus 137.3 ± 17.9 mg dl-l, respectively). BLOOD GLUCOSE: Fasted blood glucose levels did not change in either the experimental or control group. Pre- and post-values for experimental and control groups were 92.5 ± 4.8 versus 93.3 ± 4.3 mg dl-l and 92.3 ± 11.3 versus 93.2 ± 2.6 mg dl-1 , respectively. BLOOD PRESSURE: No aspect of blood pressure was altered in either the experimental or control group. For example, pre- and post-test systolic blood pressures were 131 ± 2 versus 129 ± 2 mmHg (experimental) and 123 ± 2 and 125 ± 2 mmHg (controls), respectively. Pre- and post-test diastolic blood pressures were 84 ± 2 and 83 ± 2 mmHg (experimental) and 81 ± 1 versus 82 ± 1 mmHg, respectively. Similarly, calculated pulse pressure was not altered in the experimental or control as pre- and post-test values were 47 ± 1 versus 47 ± 2 mmlHg and 42 ± 2 versus 43 ± 2 mmHg, respectively. FRAMINGHAM POINT SCORE: The concerted changes reported above produced an increased risk in the Framingham Point Score for the subjects in the experimental group. For example, the pre- and post-test FPS increased from 1.4 ± 0.9 to 2.7 ± 0.7. On the other hand, pre- and post-test scores for the control group were 1.8 ± 1 versus 1.8 ± 0.9. Conclusions: Our data confirms previous studies showing that interval-type exercise is a useful intervention for increasing aerobic fitness. Moreover, the increase in V02 Max we found in response to limited participation in ball hockey (i.e. 16 games) suggests that recreational sport may help reduce this aspect of coronary risk in previously sedentary individual. On the other hand, our results showing little or no positive change in body composition, blood lipids or blood pressures suggest that one season of recreational sport in not in of itself a powerful enough stimulus to reduce the overall risk of coronary artery disease. In light of this, it is recommended that, in addition to participation in recreational sport, the performance of regular physical activity is used as an adjunct to provide a more powerful overall stimulus for decreasing coronary risk factors. LIMITATIONS: The increase in the FPS we found for the experimental group, indicative of an increased risk for coronary disease, was largely due to the large decrease in HDL we observed after compared to above one season of ball hockey. In light of the fact that cardiorespiratory fitness was increased and % body fat was decreased, as well as the fact that other parameters such as blood pressure showed positive (but non statistically significant) trends, the possibility that the decrease in HDL showed by our data was anomalous should be considered. FUTURE DIRECTIONS: The results of this study suggesting that recreational sport may be a potentially useful intervention in the reduction of CAD require to be corroborated by future studies specifically employing 1) more rigorous assessment of fitness and fitness change and 2) more prolonged or frequent participants.

Health-related quality of life among patients attending cardiovascular rehabilitation

Purpose: f i rst , an investigation of baseline differences in Health-Related Quality of l i fe (HRQOl) among adhere and non-adhere patients of Phase III cardiac rehabilitation (CR) was examined. Second, among patients who adhered to the program, effectiveness of t reatment based on HRQOl was evaluated. Methods: Data was collected by the Brock University Heart Institute. Participants completed a questionnaire battery at baseline and again at six months i f they were still a client. Results: The physical dimension of HRQOl differed at baseline between the adhere and non-adhere groups. for everyone point increase in physical HRQOl scores there was an associated 1.06 times greater likelihood that an individual would adhere to the program. Second, in those who adhered to the program for six months, physical HRQOl scores improved 3.18 points. Conclusions: Phase III CR significant improves HRQOl in patients suffering f rom cardiovascular disease.

Molybdenum (IV) imido silylamido and hydride complexes : stoichiometric and catalytic reactivity, mechanistic aspects of hydrosilation reactions

This thesis describes the synthesis, structural studies, and stoichiometric and catalytic reactivity of novel Mo(IV) imido silylamide (R'N)Mo(R2)(173_RIN-SiR32-H)(PMe3)n (1: Rl = tBu, Ar', Ar; R2 = Cl; R32 = Me2, MePh, MeCl, Ph2, HPh; n = 2; 2: R' = Ar, R2 = SiH2Ph, n = 1) and hydride complexes (ArN)Mo(H)(R)(PMe3)3 (R = Cl (3), SiH2Ph (4». Compounds of type 1 were generated from (R'N)Mo(PMe3)n(L) (5: R' = tBu, Ar', Ar; L = PMe3, r/- C2H4) and chlorohydrosilanes by the imido/silane coupling approach, recently discovered in our group. The mechanism of the reaction of 5 with HSiCh to give (ArN)MoClz(PMe3)3 (8) was studied by VT NMR, which revealed the intermediacy of (ArN)MCh(172 -ArN=SiHCl)(PMe3)z (9). The imido/silyl coupling methodology was transferred to the reactions of 5 with chlorine-free hydrosilanes. This approach allowed for the isolation of a novel ,B-agostic compound (ArN)Mo(SiHzPh)(173 -NAr-SiHPhH)(PMe3) (10). The latter was found to be active in a variety of hydrosilation processes, including the rare monoaddition of PhSiH3 to benzonitrile. Stoichiometric reactions of 11 with unsaturated compounds appear to proceed via the silanimine intermediate (ArN)M(17z-ArN=SiHPh)(PMe3) (12) and, in the case of olefins and nitriles, give products of Si-C coupling, such as (ArN)Mo(R)(173 -NAr-SiHPh-CH=CHR')(PMe3) (13: R = Et, R' = H; 14: R = H, R' = Ph) and (ArN)Mo(172-NAr-SiHPh-CHR=N)(PMe3) (15). Compound 13 was also subjected to catalysis showing much improved activity in the hydrosilation of carbonyls and alkenes. Hydride complexes 3 and 4 were prepared starting from (ArN)MoCh(PMe3)3 (8). Both hydride species catalyze a diversity of hydrosilation processes that proceed via initial substrate activation but not silane addition. The proposed mechanism is supported by stoichiometric reactions of 3 and 4, kinetic NMR studies, and DFf calculations for the hydrosilation of benzaldehyde and acetone mediated by 4.

Synthesis, Catalysis and Stoichiometric Reactivity of Mo Imido Complexes

The syntheses, catalytic reactivity and mechanistic investigations of novel Mo(IV) and Mo(VI) imido systems is presented. Attempts at preparing mixed bis(imido) Mo(IV) complexes of the type (RN)(R′N)Mo(PMe3)n (n = 2 or 3) derived from the mono(imido) complexes (RN)Mo(PMe3)3(X)2 (R = tBu (1) or Ar (2); X = Cl2 or HCl, Ar=2,6-iPr2C6H3) are also described. The addition of lithiated silylamides to 1 or 2 results in the unexpected formation of the C-H activated cyclometallated complexes (RN)Mo(PMe3)2(η2-CH2PMe2)(X) (R = Ar, X = H (3); R = tBu, X = Cl (4)). Complexes 3 and 4 were used in the activation of R′E-H bonds (E = Si, B, C, O, P; R′ = alkyl or aryl), which typically give products of addition across the M-C bond of the type (RN)Mo(PMe3)3(ER′)(X) (4). In the case of 2,6-dimethylphenol, subsequent heating of 4 (R = Ar, R′ = 2,6-Me2C6H3, E = O) to 50 °C results in C-H activation to give the cyclometallated complex (ArN)Mo(PMe3)3(κ2-O,C-OPh(Me)CH2) (5). An alternative approach was developed in synthesizing the mixed imido complex (ArN)(tBuN)Mo(PMe3)(η2-C2H4) (6) through EtMgBr reduction of (ArN)(tBuN)MoCl2(DME) in the presence of PMe3. Complex 6 reacts with various hydro- and chlorosilanes to give β-agostic silylamido complexes and in one case, when Me2SiHCl is the silane, leads to the silanimine complex (tBuN)Mo(η2-SiMe2-NAr)(Et)(η2-C2H4) (7). Mechanistic studies on the formation of the Mo(VI) tris(silyl) complex (tBuN)Mo(SiHPh)(H){(μ-NtBu)(SiHPh)}(PMe3)2 (8) were done from the addition of three equivalents of PhSiH3 to (tBuN)Mo(PMe3)(η2-C2H4), resulting in identification of β- and γ-agostic SiH…Mo intermediates. The reactivity of complex 8 towards ethylene and nitriles was studied. In both cases coupling of unsaturated substrates with the Mo-Si bond of the metalacycle was observed. In the case of nitriles, insertion into the 4-membered disilaazamolybdacycle results in complexes of the type (tBuN)Mo{(κ2-Si,C-SiHPh-NtBu-SiHPh-N=C(R)}(PMe3)2. Catalytic hydrosilylation of carbonyls mediated by the β-agostic silylamido complex (ArN)2Mo(η3-NtBu-SiMe2-H)(H) (9) was investigated. Stoichiometric reactions with organic substrates showed that catalysis with 9 does not proceed via the conventional insertion of substrate into the Mo-H bond.

Autonomic Cardiovascular Control in Children and Adolescents

This thesis investigated the impact of pubertal maturation and sex on cardiovagal baroreflex sensitivity (BRS) and arterial properties of the common carotid artery (CCA), and the relationship between CCA arterial properties and BRS. This thesis also investigated the effect of orthostatic stress on arterial properties of the CCA and carotid sinus (CS), as well as their impact on BRS in response to orthostatic stress. Children and adolescents between the ages of 8-18 years were examined. To assess pubertal maturation participants were organized into five pubertal groups based on the criteria of Tanner. BRS was assessed by transfer function analysis in the low frequency range (0.05 – 0.15Hz). Pulse pressure (PP) was measured at the CCA (PPCCA) and CS (PPCS) using applanation tonometry, and at the finger (PPFinger) using photoplethysmography. Ultrasound sonography and applanation tonometry were used to determine the distensibility coefficient (DC) at the CCA (DCCCA) and CS (DCCS). A moderate posture stimulus was implemented by passively moving participants into a 50° seated-recumbent (SR) position. The results demonstrated a sex-by-maturation interaction on BRS (p= 0.019). BRS decreased from early- to post-puberty in males (p<0.01), and remained unchanged in females. Females demonstrated greater BRS compared to males post-puberty (p<0.05). CCA distensibility was not affected by sex or maturation and was not related to BRS. PPCS was greater than PPCCA (p<0.001), while PPFinger was greater than both PPCCA (p<0.001) and PPCS (p<0.001). In response to SR, the relative change in PPFinger was significantly different than the relative change in PPCCA (p<0.001) and PPCS (p<0.001), while the relative change between PPCCA and PPCS were not different. Finally, in response to SR there was a significant decrease in DCCS (p=0.001), but not DCCCA. The relative change in BRS in response to SR was significantly correlated to the relative change in DCCS (p=0.004), but not DCCCA. The findings demonstrated an important sex-dependent maturation effect on BRS in children and adolescents that was not explained by CCA distensibility. Also, the CS and CCA responded differently to orthostatic stress. The CS was more suitable to evaluate the effect of arterial distensibility on BRS in response to posture change.

Mirroring Enzymes: The Role of H-Bonding In HQuin-BAM Catalyzed Asymmetric Aza-Henry Reactions: A DFT Study into the Reactivity, Mechanism, and Origins of Selectivity

The exact mechanistic understanding of various organocatalytic systems in asymmetric reactions such as Henry and aza-Henry transformations is important for developing and designing new synthetic organocatalysts. The focus of this dissertation will be on the use of density functional theory (DFT) for studying the asymmetric aza-Henry reaction. The first part of the thesis is a detailed mechanistic investigation of a poorly understood chiral bis(amidine) (BAM) Brønsted acid catalyzed aza-Henry reaction between nitromethane and N-Boc phenylaldimine. The catalyst, in addition to acting as a Brønsted base, serves to simultaneously activate both the electrophile and the nucleophile through dual H-bonding during C-C bond formation and is thus essential for both reaction rate and selectivity. Analysis of the H-bonding interactions revealed that there was a strong preference for the formation of a homonuclear positive charge-assisted H-bond, which in turn governed the relative orientation of substrate binding. Attracted by this well-defined mechanistic investigation, the other important aspect of my PhD research addressed a detailed theoretical analysis accounting for the observed selectivity in diastereoselective versions of this reaction. A detailed inspection of the stereodetermining C-C bond forming transition states for monoalkylated nitronate addition to a range of electronically different aldimines, revealed that the origins of stereoselectivity were controlled by a delicate balance of different factors such as steric, orbital interactions, and the extent of distortion in the catalyst and substrates. The structural analysis of different substituted transition states established an interesting dependency on matching the shape and size of the catalyst (host molecule) and substrates (guest molecules) upon binding, both being key factors governing selectivity, in essence, offering an analogy to positive cooperative binding effect of catalytic enzymes and substrates in Nature. In addition, both intra-molecular (intra-host) and inter-molecular (host-guest, guest-guest) stabilizing interactions play a key role to the high π-facial selectivity. The application of dispersion-corrected functionals (i.e., ωB97X-D and B3LYP-D3) was essential for accurately modeling these stabilizing interactions, indicating the importance of dispersion effects in enantioselectivity. As a brief prelude to more extensive future studies, the influence of a triflate counterion on both reactivity and selectivity in this reaction was also addressed.