999 resultados para Thermal-injury
Resumo:
Kinetics and product studies of the decompositions of allyl-t-butyl peroxide and 3-hydroperoxy- l-propene (allyl hydroperoxide ) in tolune were investigated. Decompositions of allyl-t-butyl peroxide in toluene at 130-1600 followed first order kinetics with an activation energy of 32.8 K.cals/mol and a log A factor of 13.65. The rates of decomposition were lowered in presence of the radical trap~methyl styrene. By the radical trap method, the induced decomposition at 1300 is shown to be 12.5%. From the yield of 4-phenyl-l,2- epoxy butane the major path of induced decomposition is shown to be via an addition mechanism. On the other hand, di-t-butYl peroxyoxalate induced decomposition of this peroxide at 600 proceeded by an abstraction mechanism. Induced decomposition of peroxides and hydroperoxides containing the allyl system is proposed to occur mainly through an addition mechanism at these higher temperatures. Allyl hydroperoxide in toluene at 165-1850 decomposes following 3/2 order kinetics with an Ea of 30.2 K.cals per mole and log A of 10.6. Enormous production of radicals through chain branching may explain these relatively low values of E and log A. The complexity of the reaction is indicated a by the formation of various products of the decomposition. A study of the radical attack of the hydro peroxide at lower temperatures is suggested as a further work to throw more light on the nature of decomposition of this hydroperoxide.
Resumo:
The purpose of this qualitative study was to understand the client and occupational therapist experiences of a mental health group. A secondary aim was to explore the extent to which this group seemed to have reflected a client-centred approach. The topic emerged from personal and professional issues related to the therapist as teacher and to inconsistencies in practice with the profession's client-centred philosophy. This philosophy, the study's frame of reference, was established in terms of themes related to the client-therapist relationship and to client values. Typical practice was illustrated through an extensive literature review. Structured didacticexperiential methods aiming toward skill development were predominant. The interpretive sciences and, to a lesser extent, the critical sciences directed the methodology. An ongoing support group at a community mental health clinic was selected as the focus of the study; the occupational therapist leader and three members became the key participants. A series of conversational interviews, the . core method of data collection, was supplemented by observation, document review, further interviews, and fieldnotes. Transcriptions of conversations were returned to participants for verification and for further reflection Analysis primarily consisted of coding and organizing data according to emerging themes. The participants' experiences of group, presented as narrative stories within a group session vignette, were also returned to participants. There was a common understanding of the group's structure and the importance of having "air time" within the group; however, differences in perceptions of such things as the importance of the group in members' lives were noted. All members valued the therapeutic aspects of group, the role of group as weekly activity and, to a lesser extent, the learning that came from group. The researcher's perspective provided a critique of the group experience from a client-centred perspective. Some areas of consistency with client-centred practice were noted (e.g., therapist attitudes); however the group seemed to function far from a client-centred ideal. Members held little authority in a -relationship dominated by the leaders, and leader agendas rather than member values controlled the session. Possible reasons for this discrepancy ranging from past health care encounters through to co-leader discord emerged. The actual and potential significance of this study was discussed according to many areas of implications: to OT practice, especially client-centred group practice, to theory development, to further areas of research and methodology considerations, to people involved in the group and to my personal growth and development.
Resumo:
:ofiedian lethal temperatures ( LT50' s ) were determined for rainbow trout, Salmo gairdnerii, acclimated for a minimum of 21 days at 5 c onstant temperatures between 4 and 20 0 C. and 2 diel temperature fluctuations ( sinewave curves of amplitudes ± 4 and ± 7 0 C. about a mean temperature of 12 0 C. ) . Twenty-four-, 48-, and 96-hour LT50 estimates were c alculated f ollowing standard flow-through aquatic bioassay techniques and probi t transformation of mortality data. The phenomenon of delayed thermal mortality was also investigated. Shifts in upper incipient lethal temperature occurred as a result of previous thermal conditioning. It was shown that increases in constant acclimation temperature result in proportional l inear increases in thermal tolerances. The increase i n estimated 96-hour LT50's was approximately 0.13 0 c. X 1 0 C:1 between 8 and 20 0 C. The effect of acclimation to both cyclic temperature regimes was an increase in LT50 to values between the mean and maximum constant equivalent daily temperatures of the cycles. Twenty-four-, 48-, and 96-hour LT50 estimates of both cycles corresponded approximately to the LT50 values of the 16 0 C. c onstant temperature equivalent . This increase i n thermal tolerance was further demonstrated by the delayed thermal mortality experiments . Cycle amplitudes appeared to i nfluence thermal resistance through alterations in initi al mortality since mortality patterns characteristic of base temperature acclimations re-appeared after approximately 68 hours exposure to test temperatures for the 12 + 4 0 C. group, whereas mortality patterns stabilized and remained constant for a period greater than 192 hours with the larger therma l cycle ( 12 + 7 0 C. ). NO s ignificant corre lations between s pecimen weight and time-to-death was apparent. Data are discussed in relation to the establishment of thermal criteria for important commercial and sport fishes , such as the salmonids , as is the question whether previously reported values on lethal temperature s may have been under estimated.
Resumo:
Re~tes artd pJ~oducts of tllerma]. d,ecom.position of sec-butyl peroxide at 110 - 150°C i.n four solvents h,ave been determined. The d,ecompos i tion vJas sb.o\'\Tn to be tlnlmolecl.llar wi tho energies of activation in toluene, benzene, and cyclohexane of 36 .7-+ 1.0, 33.2 +- 1..0, 33.t~) +.. 1.0 I'(:cal/mol respectively. The activation energy of thermal decomposition for the d,et.1terated peroxide was found to be 37.2 4:- 1.0 KC8:1/1TIol in toluene. A.bo1J.t 70 - 80/~ ol~ tJJ.e' pl~od.1..1CtS could, be explained by kn01rJ11 reactions of free allcoxy raclicals J and very littJ...e, i.f allY, disPl"Opox~tiol'lation of tll10 sec-butoxy radica.ls in t116 solvent cage could be detected. The oth,er 20 - 30% of the peroxide yielded H2 and metb.:'ll etb..yl 1{etol1e. Tl1.e yield. o:f H2 "'lIas unafJ:'ected by the nature or the viscosity of the solvent, but H2 was not formed when s-t1U202 lrJaS phctolyzed. in tolttene at 35°C nor 'tl!Jrl.en the peroxide 1;'JaS tl1.ermally o..ecoJnposed. in the gas p11ase. ~pC-Dideutero-~-butYlperoxide was prepared and decomposed in toluene at 110 - 150°C. The yield of D2 was about ·•e1ne same 248 the yield. of I{2 from s-Bu202, bU.t th.e rate of decomposition (at 135°C) 1iJas only 1/1.55 as fast. Ivlecl1.anisms fOl') J:1ydrogen produ.ction are discussed, but none satisfactorily explains all the evidence.
Resumo:
Rates and products have been determined for the thermal decomposition of bis diphenyl methyl peroxide and diphenyl methyl tert* butyl peroxide at 110@~145@C* The decomposition was uniformly unimolecular with activation energies for the bis diphenyl methyl peroxide in tetrachloroethylene* toluene and nitrobenzene 26,6* 28*3f and 27 Kcals/mole respectively. Diphenyl methyl tert* butyl peroxide showed an activation energy of 38*6 Kcals/mole* About 80-90% of the products in the case of diphenyl methyl peroxide could be explained by the concerted process, this coupled with the negative entropies of activation obtained is a conclusive evidence for the reaction adopting a major concerted path* All the products in the case of diphenyl methyl peroxide could be explained by known reactions of alkoxy radicals* About 80-85% of tert butanol and benzophenone formed suggested far greater cage disproportionation than diffusing apart* Rates of bis triphenyl methyl peroxide have been determined in tetrachloroethylene at 100-120@C* The activation energy was found to be 31 Kcals/mole*
Resumo:
A large variety of social signals, such as facial expression and body language, are conveyed in everyday interactions and an accurate perception and interpretation of these social cues is necessary in order for reciprocal social interactions to take place successfully and efficiently. The present study was conducted to determine whether impairments in social functioning that are commonly observed following a closed head injury, could at least be partially attributable to disruption in the ability to appreciate social cues. More specifically, an attempt was made to determine whether face processing deficits following a closed head injury (CHI) coincide with changes in electrophysiological responsivity to the presentation of facial stimuli. A number of event-related potentials (ERPs) that have been linked specifically to various aspects of visual processing were examined. These included the N170, an index of structural encoding ability, the N400, an index of the ability to detect differences in serially presented stimuli, and the Late Positivity (LP), an index of the sensitivity to affective content in visually-presented stimuli. Electrophysiological responses were recorded while participants with and without a closed head injury were presented with pairs of faces delivered in a rapid sequence and asked to compare them on the basis of whether they matched with respect to identity or emotion. Other behavioural measures of identity and emotion recognition were also employed, along with a small battery of standard neuropsychological tests used to determine general levels of cognitive impairment. Participants in the CHI group were impaired in a number of cognitive domains that are commonly affected following a brain injury. These impairments included reduced efficiency in various aspects of encoding verbal information into memory, general slower rate of information processing, decreased sensitivity to smell, and greater difficulty in the regulation of emotion and a limited awareness of this impairment. Impairments in face and emotion processing were clearly evident in the CHI group. However, despite these impairments in face processing, there were no significant differences between groups in the electrophysiological components examined. The only exception was a trend indicating delayed N170 peak latencies in the CHI group (p = .09), which may reflect inefficient structural encoding processes. In addition, group differences were noted in the region of the N100, thought to reflect very early selective attention. It is possible, then, that facial expression and identity processing deficits following CHI are secondary to (or exacerbated by) an underlying disruption of very early attentional processes. Alternately the difficulty may arise in the later cognitive stages involved in the interpretation of the relevant visual information. However, the present data do not allow these alternatives to be distinguished. Nonetheless, it was clearly evident that individuals with CHI are more likely than controls to make face processing errors, particularly for the more difficult to discriminate negative emotions. Those working with individuals who have sustained a head injury should be alerted to this potential source of social monitoring difficulties which is often observed as part of the sequelae following a CHI.
The kinetics and solvent effects on the thermal decomposition of isopropyl peroxide and 1, 2-dioxane
Resumo:
Rates of H2 formation have been determined for the thermal decomposition of isopropyl peroxide at l30o-l50oC in toluene and methanol and at l400C in isopropyl alcohol and water. Product studies have been carried out at l400C in these solvents. The decomposition of isopropyl peroxide was shown to be unimolecular with energies of activation in toluene, and methanol of 39.1, 23.08 Kcal/mole respectively. It has been shown that the rates of H2 formation in decomposition of isopropyl peroxide are solvent dependent and that the ~ vs "'2';' values (parameters for solvent polarity) givesastraight line. Mechanisms for hydrogen production are discussed which satisfactorily explain the stabilization of the six-centered transition state by the solvent. One possibility is that of conformation stabilization by solvent and the other, a transition state with sufficient ionic character to be stabilized by a polar solvent. Rates of thermal decomposition of 1,2-dioxane in tert-butylbenzene at l40o-l70oC have been determined. The activation energy was found to be 33.4 Kcal/mole. This lower activation energy, compared to that for the decomposition of isopropyl peroxide in toluene (39.1 Kcal/mole) has been explained in terms of ring strain. Decomposition of 1,2 dioxane in MeOH does not follow a first order reaction. Several mechanisms have been suggested for the products observed for decomposition of 1;2-dioxane in toluene and methanol.
Resumo:
We examined the cognitive and emotional sequelae following mild head injury (MHI; e.g., concussion) in high-functioning individuals and whether persons with MHI pre~ent, both physiologically and via self-report, in a manner different from (i.e., underaroused) that of persons who have no history of head injury. We also investigated the effect arousal state ~as on the cognitive performance of this population. Using a quasiexperimental research design (N = 91), we examined changes in attention, working memory, and cognitive flexibility (subtests ofthe WAIS-III, 1997,WMS-III, 1997, & DKEFS, 2002) as a function of manipulated arousal (i.e., induced psychosocial stress/activation; reduced activation/relaxation). In addition to self-reported arousal and state anxiety (State-Trait Anxiety Inventory; Speilberger, 1983a) measures, physiological indices of arousal state (i.e., electrodermal responsivity, heart rate, and respiration activity) were recorded (via Polygraph Professional Suite, 2008) across a 2.5 hour interval while completing various cognitive tasks. Students also completed the Post-concussive Symptom Checklist (Gouvier et aI., 1992). The results demonstrate that university students who report a history ofMHI (i.e., "altered state of consciousness") experience significantly lower levels of anxiety, were physiologically underaroused, and were less responsive to stressors in their environment, compared to their non-~HI cohorts. As expected, cognitive flexibility (but not other neuropsychological measures of cognition) was advantaged with increased stress, and disadvantaged with reduced stress, in persons with reported MHI, but not for those without reported MHI which provided limited support for our hypothesis. Further, university students who had no complaints related to their previous MHI endorsed a greater number of traditional post-concussive symptoms in terms of intensity, duration and frequency as compared to students who did not report a MHI. The underarousal in traumatic brain injury has been associated with (ventromedial prefrontal cortex) VMPFC disruption and may be implicated in MHI generally. Students who report sustaining a previous MHI may be less able to physiologically respond and/or cognitively appraise, stressful experiences as compared to their no-MHI cohort and experience persistent, long-lasting consequences despite the subtle nature of a history of head injury.
Resumo:
Individuals who have sustained a traumatic brain injury (TBI) often complain of t roubl e sleeping and daytime fatigue but little is known about the neurophysiological underpinnings of the s e sleep difficulties. The fragile sleep of thos e with a TBI was predicted to be characterized by impairments in gating, hyperarousal and a breakdown in sleep homeostatic mechanisms. To test these hypotheses, 20 individuals with a TBI (18- 64 years old, 10 men) and 20 age-matched controls (18-61 years old, 9 men) took part in a comprehensive investigation of their sleep. While TBI participants were not recruited based on sleep complaint, the fmal sample was comprised of individuals with a variety of sleep complaints, across a range of injury severities. Rigorous screening procedures were used to reduce potential confounds (e.g., medication). Sleep and waking data were recorded with a 20-channel montage on three consecutive nights. Results showed dysregulation in sleep/wake mechanisms. The sleep of individuals with a TBI was less efficient than that of controls, as measured by sleep architecture variables. There was a clear breakdown in both spontaneous and evoked K-complexes in those with a TBI. Greater injury severities were associated with reductions in spindle density, though sleep spindles in slow wave sleep were longer for individuals with TBI than controls. Quantitative EEG revealed an impairment in sleep homeostatic mechanisms during sleep in the TBI group. As well, results showed the presence of hyper arousal based on quantitative EEG during sleep. In wakefulness, quantitative EEG showed a clear dissociation in arousal level between TBls with complaints of insomnia and TBls with daytime fatigue. In addition, ERPs indicated that the experience of hyper arousal in persons with a TBI was supported by neural evidence, particularly in wakefulness and Stage 2 sleep, and especially for those with insomnia symptoms. ERPs during sleep suggested that individuals with a TBI experienced impairments in information processing and sensory gating. Whereas neuropsychological testing and subjective data confirmed predicted deficits in the waking function of those with a TBI, particularly for those with more severe injuries, there were few group differences on laboratory computer-based tasks. Finally, the use of correlation analyses confirmed distinct sleep-wake relationships for each group. In sum, the mechanisms contributing to sleep disruption in TBI are particular to this condition, and unique neurobiological mechanisms predict the experience of insomnia versus daytime fatigue following a TBI. An understanding of how sleep becomes disrupted after a TBI is important to directing future research and neurorehabilitation.
Resumo:
Type 1 Diabetes Mellitus (T1DM) is an autoimmune disease that destroys pancreatic beta cells, affecting glucose homeostasis. In T1DM, glucoregulation and carbohydrate oxidation may be altered in different ambient temperatures; however, current literature has yet to explore these mechanisms. This study examines the effects of 30 minutes of exercise at 65% VO2max in 5ºC, 20ºC and 35ºC in individuals with T1DM. No significant differences were observed for blood glucose across the 3 conditions (p = 0.442), but significance was found for core temperature, heat storage, and sweat rate (p < 0.01). Blood glucose was also shown to vary greatly between individuals among conditions. The mechanisms behind the differences in blood glucose may be due to the lack of significant glucagon production among conditions. These findings suggest that T1DM individuals may exercise submaximally for 30 minutes in different ambient temperatures without significant differences in glucoregulation.
Resumo:
Lead chromium oxide is a photoconductive dielectric material tha t has great potential of being used as a room temperature photodetector. In this research, we made ceramic pellets of this compound as well as potassium doped compound Pb2-xKxCr05, where x=O, 0.05, 0.125. We also investigate the properties of the lanthanum doped sample whose chemical formula is Pb1.85Lao.15Cr05' The electronic, magnetic and thermal properties of these materials have been studied. Magnetization measurements of the Pb2Cr05 sample indicate a transition at about 310 K, while for the lanthanum doped sample the transition temperature is at about 295 K indicating a paramagnetic behavior. However, the potassium doped samples are showing the transition from paramagnetic state to diamagnetic state at different temperatures for different amounts of potassium atoms present in the sample. We have studied resistivity as a function of temperature in different gas environments from 300 K to 900 K. The resistivity measurement of the parent sample indicates a conducting to insulating transition at about 300 K and upon increasing the temperature further, above 450 K the sample becomes an ionic conductor. As temperature increases a decrease in resistance is observed in the lanthanum/potassium doped samples. Using Differential Scanning Calorimetry experiment an endothermic peak is observed for the Pb2Cr05 and lanthanum/potassium doped samples at about 285 K.
Resumo:
Acquired brain injury (ABI) is the leading cause of death and disability amongst children and adolescents andpresents itself with challenges associated in cognitive, social, emotional, and behavioural domains. These changes may interfere with academic performance and social inclusion, influencing self-esteem and personal success. The current study examined a subset of data to capture the sense of academic and social belonging for students with ABI as a function of the classroom teachers’ subjective perception of ability, their ABI knowledge, and student identification. Overall, a discrepancy was found between educators’ subjective ratings of student performance and students’ neurocognitive capacity. Educator knowledge and identification of ABI influenced student success in academic and social domains independent of teaching approach. This research has implications for the identification of ABI in the classroom and related challenges students experience. Educators are underprepared for the reintegration of students returning to school and lack appropriate knowledge and strategies to accommodate individual needs.
Resumo:
The purpose of this study was to investigate the effects of a 12-week FES-ambulation program on locomotor function and quality of life after incomplete spinal cord injury. Six individuals with incomplete SCI participated in the study. Over-ground walking endurance (6MWT), speed (10MWT), independence (WISCI II) and body-weight support were assessed. Quality of life was assessed via the SF-36, WHOQOL-BREF, Perceived Stress Scale, Center of Epidemiological Studies for Depression scale, and task self-efficacy. Participants experienced significant improvements in walking endurance (223.6±141.5m to 297.3±164.5m; p=0.03), body-weight support (55.3±12.6% to 14.7±23.2%; p= 0.005) and four of the six participants showed improvements on the WISCI II scale (1-4 points). In addition, there was a significant reduction in reported bodily pain (6.5±1.2 to 5.0±1.7; p=0.04). Therefore, FES-ambulation is an effective means for enhancing over-ground locomotor function in individuals with incomplete SCI. It may also be an effective method for reducing pain in individuals with SCI.
Resumo:
Sexuality after spinal cord injury (SCI) is a complex issue that is influenced by a number of social, psychological and physiological factors, one of which is urinary incontinence (UI). Using a phenomenological approach, seven mixed methods interviews combining both the interview guide and standardized open-ended approaches were conducted to examine the experience of sexuality for women who are concerned about UI following SCI. Sexual function was one of the top priorities for the women after SCI, and UI was one of the main concerns the women had regarding sexuality. The findings of this study demonstrate that various dimensions of intimacy and the sexual experience as a whole were affected by UI, and the women discussed both physical and psychological concerns. The main issues regarding sexuality included concerns related to relationships, frustrations with limited sexual activities and the difficulty of being sexually satisfied, the number of unanswered questions and concerns, and a fear of being hurt or injured while participating in sexual activities. The main concerns regarding UI were embarrassment, the work and inconvenience involved with the clean-up of UI, bladder infections, the lack of accessible washrooms, and the negative effects of UI medications. When examining sexuality and UI together, the major issues were the constant comparison to the way things were before SCI, as well as the new concerns that the women did not have to worry about previously, worrying about how their partner would react if UI were to occur during sexual activity, and the impact of their own feelings toward UI on sexuality, a connection between pleasurable sexual sensations and UI as well as difficulty differentiating between the sensation of UI with the sensation of UI, dealing with infected urine during sexual activity, having to discuss UI with a new potential sexual partner, and a fear of rejection. Other identified issues included those related to body image, a lack of resources, Doctors who were inadequately educated regarding SCI, and issues related to both having and raising children. There is a significant shortage of information available for women with SCI to use as a resource regarding sexual function in general, and sexual function as it relates to UI. It is necessary that future work focus on creating resources to assist in this area, and that the dissemination of those resources becomes both appropriate and effective. Addressing sexual function and UI which are among the top concerns for this population has the opportunity to greatly improve quality of life (QOL) for these individuals.
Resumo:
Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.