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Polybrominated dibenzo-p-dioxins : Natural formation mechanisms and biota retention, maternal transfer, and effectsArnoldsson, Kristina January 2012 (has links)
Polybrominated dibenzo-p-dioxins (PBDD) and dibenzofurans (PBDF) are a group of compounds of emerging interest as potential environmental stressors. Their structures as well as toxic responses are similar to the highly characterized toxicants polychlorinated dibenzo-p-dioxins. High levels of PBDDs have been found in algae, shellfish, and fish, also from remote areas in theBaltic Sea. This thesis presents studies on PBDD behavior in fish and offspring, and natural formation of PBDDs from naturally abundant phenolic precursors. The uptake, elimination, and maternal transfer of mono- to tetraBDD/Fs were investigated in an exposure study reported in Paper I. The effects of PBDDs in fish were examined in a dose-response study (Paper II). It was shown that fish can assimilate PBDD/Fs from their feed, although non-laterally substituted congeners were rapidly eliminated. Laterally substituted congeners were retained as was congeners without vicinal hydrogens to some extent. PBDD/Fs were transferred to eggs, and congeners that were rapidly eliminated in fish showed a higher transfer ratio to eggs. Exposure to the laterally substituted 2,3,7,8-TeBDD had significant effects on the health, gene expression and several reproduction end-points of zebrafish, even at the lowest dose applied. The geographical and temporal variations of PBDD in biota samples from the Baltic Seasuggest biogenic rather than anthropogenic origin. In Paper III, bromoperoxidase-mediated coupling of 2,4,6-tribromophenol yielded several PBDD congeners, some formed after rearrangement. The overall yield was low, but significantly higher at low temperature, and the product profile obtained was similar to congener profiles found in biota from the Swedish West Coast. In Paper IV, photochemically induced cyclization of hydroxylated polybrominated diphenyl ethers under natural conditions produced PBDDs at percentage yield. Rearranged products were not detected, and some abundant congeners do not seem to be formed this way. However, the product profile obtained was similar to congener profiles found in biota from the Baltic Proper. Since the PBDD congeners found in biota have a high turn-over in fish, the exposure must be high and continuous to yield the PBDD levels measured in wild fish. Thus, PBDDs must presumably be formed by common precursors in general processes, such as via enzymatic oxidations, UV-initiated reactions or a combination of both. The presented pathways for formation of PBDDs are both likely sensitive to changes in climatic conditions.
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Impact de la chimie des poussières minérales sur la photochimie atmosphérique / Impact of mineral dust photochemistry on the atmosphereDupart, Yoan 19 December 2012 (has links)
Les travaux de cette thèse reposent sur l’étude des processus hétérogènes à la surface desparticules minérales en présence d’irradiation UV-A. Nous savons que les poussièresminérales contiennent des oxydes métalliques pouvant absorber la radiation solaire et ainsiactiver une chimie très différente de celle observée à l’obscurité. Un réacteur à écoulementd’aérosols a été utilisé pour étudier les interactions des gaz (SO2, NO2 et O3) avec devéritables poussières minérales, évitant ainsi les artéfacts de mesure liés à la naturemacroscopique des films comme dans les études précédentes.La mise en suspension des poussières minérales a permis d’observer une formation inattenduede nouvelles particules ultrafines en présence de SO2. Le mécanisme proposé pour expliquerce phénomène de nucléation suggère une désorption de radicaux OH photoproduits à lasurface des minéraux vers la phase gazeuse. Ce mécanisme a pu être corroboré par descampagnes de mesure en atmosphère réelle. Nous avons étudié la chimie des échantillons de réelles cendres volcaniques issus de la dernière éruption du volcan Eyjafjallajökull en Islande (2010). Ceci nous a permis d’élaborerdes cinétiques de capture du SO2 sur des films macroscopiques de cendres aboutissant à descoefficients de capture de l’ordre de 10-7. Ces cinétiques couplées à des analyses chimiquesont permis de proposer un mécanisme réactionnel expliquant la formation de sulfate de fer àla surface des cendres. Finalement, nous avons étudié les interactions photochimiques de O3 et NO2 sur les poussièresminérales dans le réacteur à écoulement mettant en évidence un bon accord avec des étudesantérieures sur des surfaces macroscopiques / The objective of this work is to study the heterogeneous processes of mineral dust surfacesunder UV-A radiation. It is know that mineral dust containing metal oxides which can absorbsolar radiation and therefore activate a different chemistry compared to that observed in thedark. In order to avoid measurement artifacts related to the nature of macroscopic films, anaerosol flow tube was developed during this work and applied to study the interactions ofSO2, NO2 and O3 with real mineral dust.An unexpected formation of new particles in the presence of SO2 was observed. In order toexplain this phenomenon, we suggest the desorption of OH radicals from the mineral dustsurface to the gas phase. This mechanism has also been supported by field campaigns.Using real samples of volcanic ash from the last eruption of Eyjafjallajökull in Iceland (2010)allowed us study capture of SO2 on macroscopic ashes films with uptake coefficient around10-7. Associated kinetic experiments combined with chemical analysis allowed us to propose areaction mechanism explaining the formation of iron sulfate on the surface of ashes.Finally, we investigated the photochemical interactions of O3 and NO2 with minerals dustaerosols in the flow tube reactor showing a good agreement with previous data obtained onmacroscopic surfaces.
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Spéciation, transfert vers les végétaux et approche toxicologique des émissions atmosphériques d'une usine de recyclage de plomb / Speciation, plant transfer and toxicological approach for atmospheric fallout from a lead-recyvling plantUzu, Gaëlle 30 October 2009 (has links)
Depuis la révolution industrielle en Europe (XIXe siècle), les nombreuses activités anthropiques ont provoqué des changements environnementaux globaux considérables. La composition de l'atmosphère terrestre en particulier, a été fortement modifiée par l'émission de polluants gazeux et particulaires. Actuellement, l'industrie métallurgique de seconde fusion contribue de façon significative aux émissions atmosphériques de métaux. C'est pourquoi ce travail de thèse s'est focalisé sur l'étude des transferts et impacts sur les sols, les végétaux et l'homme, des particules émises par le procédé de recyclage du plomb en relation avec leurs propriétés physico-chimiques. Trois sources principales d'émissions de particules ont été identifiées dans le procédé du recyclage du plomb et caractérisées en vue d'étudier les impacts potentiels sur les cibles végétales et humaines. Les particules échantillonnées (postes de travail et émissions canalisées) et ségréguées en fonction de leur taille (PMtot, PM10 et PM2,5) sont principalement composées de métaux (jusqu'à 50% en masse de la composition totale en métaux de transition, alcalins et alcalino-terreux), avec une majeur partie de plomb (25-45 %). Les spéciations majoritaires du plomb sont la galène (PbS), le sulfate du plomb (PbSO4) ou dérivés (xPbO.PbSO4 x=1,2 ou 3). L'étude du transfert des particules dans le sytème sol-plante a montré que, lorsque la taille des particules de process présentes dans le sol diminue (de 10µm à 2.5µm), le tranfert du plomb vers les parties aériennes des salades augmente de 20%. Le transfert foliaire de plomb issu des particules de process a été mis en évidence et des mécanismes d'absorption.ont été proposés. Enfin, l'étude exploratoire des particules riches en plomb sur la santé humaine a permis de montrer que la diminition de la taille des particules ingérées augmentait la bioaccessibilité gastrique du plomb. Dans le cas de l'inhalation, il a été démontré que les particules n'induisaient pas de cytotoxicité jusqu'à 50µg/cm2, mais provoquaient une réponse inflammatoire dose-dépendante des cellules épithéliales pulmonaires. / Since the Industrial Revolution in Europe (XIXe century), human activities have caused significant global environmental changes. The composition of the atmosphere in particular, has been extensively modified by the emission of gaseous and particulate pollutants. Currently, the secondary (or recycling) metallurgical industry contributes significantly to air emissions of metals. Therefore, this thesis focused on the study of transfers and impacts on soils, plants and humans, of particles from the recycling process of lead in relation to their physicochemical properties. Three main sources of particulate emissions have been identified in the process of recycling lead and characterized, to study the potential impacts on plant and human targets. The particles sampled (workstations and channelled emissions), and segregated according to their size (PMtot, PM10 and PM2, 5), are mainly composed of metals (up to 50% by weight of the total composition in transition metals alkaline and alkaline), with a major part of lead (25-45%). The major speciations of lead are galena (PbS), lead sulfate (PbSO4) or derivatives (xPbO.PbSO4 x = 1,2 or 3). The study of transfer of particles in the soil-plant system has shown that when the particle size of processes in the soil decreases (from 2.5µm to 10µm), the transfer of lead into the aerial parts of lettuce growing at 20 %. The uptake of lead from particles process by leaves has been demonstrated and mechanisms of absorption have been proposed. Finally, exploratory study of lead-rich particles on human health has shown that diminution of the size of particles ingested increased gastric bioaccessibility of lead. In the case of inhalation, it was shown that the particles did not induce cytotoxicity up 50µg/cm2, but caused a dose-dependent inflammatory response of lung epithelial cells
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An exploration of barriers associated with low voluntary counselling and testing uptake by adult tuberculosis patients attending primary health care clinics, buffalo city municipality, Eastern CapeJafta, Zukiswa January 2008 (has links)
Magister Public Health - MPH / The aim of the study is to explore the barriers associated with low VCT uptake by the TB patients attending primary health care clinics within the Buffalo City municipality. The study population was drawn from TB patients attending the primary health care facilities in Buffalo city municipality in the Eastern Cape Province. Eight participants were purposively selected to include those who had accepted VCT as well as those who did not.
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New poly(hydroxyalkanoate)-based copolymers : from synthesis to tunable self-assembled systems / Copolymères originaux dérivés de poly(hydroxyalkanoate)s : Synthèse et formulation de systèmes auto-assemblés modulablesBarouti, Ghislaine 27 September 2016 (has links)
Les copolymères à blocs amphiphiles s’auto-assemblent en solution aqueuse grâce à l’association de leurs segments hydrophobes. Les nanoparticules formées à partir de copolymères biocompatibles et biodégradables tels que les poly(hydroxyalkanoates) (PHAs) sont particulièrement attractives pour la conception de systèmes à libération prolongée de principes actifs. La relation entre la composition/structure chimique du copolymère, ses propriétés d’auto-assemblage et ses effets sur les cellules in-vitro doit être étudiée. Des copolymères à blocs poly(acide malique)-b-poly(3-hydroxybutyrate) (PMLA-b-PHB), PMLA-b-PHB-b-PMLA et poly(triméthylène carbonate)-b-poly(acide-malique) (PTMC-b-PMLA) ont été synthétisés par polymérisation par ouverture cycle (ROP) des monomères correspondants, suivie d’une hydrogénolyse. Une gamme de copolymères bien définis, caractérisés par spectroscopie RMN 1H, 13C{1H}, HSQC, HMBC, et DOSY, par analyses SEC, DSC, TGA, et mesure des angles de contact, présentant des balances hydrophile/hydrophobe modulables, a été obtenue grâce au control précis de la fraction hydrophile f (11-82%). Des auto-assemblages modulables ont été formés par nanoprécipitation des copolymères en l’absence d’agent tensio-actif. De larges agrégats ainsi que des micelles cœur-couronne (Rh = 16-335 nm) ont été obtenus en fonction du copolymère utilisé (dibloc vs. tribloc). Des micelles stables pendant 10 jours à 37 °C en solution aqueuse ont été obtenues pour les copolymères avec f allant jusqu’à 50%. Les copolymères PMLA-b-PHB et PTMC-b-PMLA n’ont pas révélé de toxicité aigüe in-vitro. De plus, l’utilisation du PHB a avantageusement permis de diminuer la captation des nano-objets par les macrophages et d’augmenter la captation par les cellules hépatiques. / Amphiphilic block copolymers are able to form self-assembled systems in aqueous solution by association of their hydrophobic segments. Nanoparticles formed from biodegradable and biocompatible polymers such as poly(hydroxyalkanoate) copolymers are particularly attractive for drug delivery applications. The relationship between the chemical structure/composition of the macromolecule, its self-assembly properties and its effect on cells in-vitro has to be studied.The synthesis of poly(-malic acid)-b-poly(3-hydroxybutyrate) (PMLA-b-PHB), PMLA-b-PHB-b-PMLA, and poly(trimethylene carbonate)-b-poly(-malic acid) (PTMC-b-PMLA) was established through the ring-opening polymerization (ROP) of the corresponding monomers followed by hydrogenolysis. A range of well-defined copolymers characterized by 1H, 13C{1H}, HSQC, HMBC, DOSY NMR spectroscopy, SEC, DSC, TGA, contact angle analyses, with tunable hydrophilic/hydrophobic balance were thus obtained through the precise control of the hydrophilic weight fraction f (11-82%). Tunable self-assembled systems were obtained by nanoprecipitation of the amphiphilic PHA-based copolymers without the use of a surfactant. Large aggregates and core-shell micelles (Rh = 16-335nm) were obtained depending on the polymer topology. PHB-based copolymers with f up to 50% formed highly stable micelles at 37 °C over a period of 10 days in aqueous solution. PMLA-b-PHB as well as PTMC-b-PMLA copolymers revealed no acute in-vitro cytotoxicity. The use of PHB as hydrophobic segment enabled to minimize the non-specific scavenging by macrophages cells while the cellular uptake by hepatocytes was favored.
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Modulation de l’absorption intestinale postprandiale du glucose apès Roux-en-Y Gastric Bypass chez le miniporc / Modulation of intestinal glucose absorption by Roux-en-Y Gastric Bypass in the minipigBaud, Grégory 09 December 2016 (has links)
Le DT2 est caractérise par un défaut combiné de la sécrétion et de l’action de l’insuline. Depuis près d’un demi siècle la chirurgie bariatrique et notamment le Roux-en-Y Gastric Bypass (RYGB) ont montré des effets spectaculaires sur le contrôle glycémique remettant en question le paradigme de la prise en charge médicale du DT2. L’exclusion gastro duodénale induite par le RYGB améliore le métabolisme glucidique indépendemment de la perte de poids. Ainsi les modifications du flux biliaire semblent jouer un rôle, cependant les mécanismes sous-jacents ne sont pas clairs. Nous avons réalisés des RYGB chez le miniporc et nous avons montré que l'absorption intestinale du glucose est diminuée dans l’anse alimentaire (AL) dépourvue de bile. L'absorption du glucose dans l’AL était restaurée par l'ajout de la bile, et cet effet était inhibé lorsque le co transport actif sodium glucose 1 (SGLT1) était bloquée par la phlorizine. SGLT1 restait exprimée dans la AL, cependant la teneur dans la lumière de l’intestin en sodium était nettement diminuée. L’ajout de sodium dans l'AL provoquait le même effet que la bile sur l'absorption du glucose et augmentait également l’excursion glycémique post prandiale chez le miniporc au cours d’un repas test vigil. La diminution de l'absorption intestinale du glucose après RYGB a ensuite été confirmée chez l'homme. Nos résultats démontrent que la l’exclusion biliaire affecte le métabolisme post prandiale du glucose par modulation des co transporteurs intestinaux sodium-glucose. / Type 2 diabetes (T2D) is characterized primarily as a combined defect of insulin secretion and insulin action. For nearly a decade, the somewhat mysterious but spectacular benefit of metabolic surgery, and more specifically of Roux-en-Y gastric bypass (RYGB), on glucose control has been caused a questioning the current paradigm of T2D management. Gastro-intestinal exclusion by RYGB improves glucose metabolism, independent of weight loss. Although changes in intestinal bile trafficking have been shown to play a role, the underlying mechanisms are unclear. We performed RYGB in minipigs and showed that the intestinal uptake of ingested glucose is blunted in the bile deprived alimentary limb (AL). Glucose uptake in the AL was restored by the addition of bile, and this effect was abolished when active glucose intestinal transport was blocked with phlorizin. Sodium-glucose cotransporter 1 remained expressed in the AL, while intraluminal sodium content was markedly decreased. Adding sodium to the AL had the same effect as bile on glucose uptake. It also increased postprandial blood glucose response in conscious minipigs following RYGB. The decrease in intestinal uptake of glucose after RYGB was confirmed in humans. Our results demonstrate that bile diversion affects postprandial glucose metabolism by modulating sodium-glucose intestinal cotransport.
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Efeitos do treinamento físico por natação sobre o sistema cardiovascular e marcadores moleculares de hipertrofia cardíaca em ratas wistar / Swimming training effects on cardiovascular system and hypertrofic cardiac molecular markesrs in wistar femalesNara Yumi Hashimoto 20 September 2007 (has links)
O treinamento por natação leva a uma sobrecarga de volume no coração, que induz a hipertrofia cardíaca (HC) excêntrica, com aumento da massa e do diâmetro cardíaco. Neste trabalho foram investigadas as adaptações no sistema cardiovascular e na expressão de genes relacionados à HC patológica, na gênese da HC por treinamento de natação. 42 ratas wistar foram divididas em grupos: sedentário controle (SC) treinado protocolo 1 (P1) e treinado protocolo 2 (P2). O treinamento de P1 foi de 1x60min/dia, 5x/semana, por 10 semanas. O de P2 foi igual ao P1 até a 8ª semana. Na 9ª semana 2x/dia e na 10ª semana 3x/dia. Os grupos treinados, em relação ao SC, apresentaram bradicardia de repouso, melhora no desempenho físico do teste máximo e do consumo máximo de oxigênio e HC, sem alterar a pressão arterial média e a expressão dos genes do fator natriurético atrial e da alfa actina esquelética. O grupo P2 apresentou aumento no diâmetro cardíaco e redução da expressão do gene da beta miosina de cadeia pesada. Este último resultado é contrário à literatura para a HC patológica, que mostra o aumento não só da expressão deste gene como a dos outros genes estudados. Os resultados de HC de P2 assemelham-se aos encontrados em estudos recentes com atletas de modalidades de maior componente aeróbio, sendo este um bom modelo para investigação dos mecanismos envolvidos na HC destes atleta / Swimming training leads to a cardiac volume overload that induces excentric cardiac hypertrophy (CH) with an increase in cardiac mass and diameter. Cardiovascular system adaptations and expression of genes relatated with pathological CH were investigated in swimming training CH. We studied 42 wistar females, divided in sedentary control (SC) group, protocol 1 trained group (P1) and protocol 2 trained group (P2). The P1 training program was once a day for 5 times/week for 10 weeks. P2 was the same as P1 until 8th week. In 9th week it was twice a day and in 10th week 3 times a day. Trained groups, in contrast with SC, showed rest bradycardia, improvement in physical performance, maximum oxygen uptake and CH, with no alteration in the medium arterial pressure and in the expression of atrial natriuretic factor and skeletal alpha actin genes. Moreover, P2 showed an increase in cardiac diameter and decrease in the expression of beta myosin heavy chain gene. This expression result is different of patological CH literature wich shows an increase of this gene expression and also in the others genes we had investigated. P2 CH results were similar to those recently found in endurance-type athletes, sugesting this is a good model to investigate mechanisms involved in endurance-type athletes CH
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Determinação das zonas de transição metabólica durante a corrida mediante os limiares de variabilidade da frequência cardíaca / Determination of transition metabolic zones during running using hert rate variability thresholdsEduardo Marcel Fernandes Nascimento 17 January 2011 (has links)
O propósito do presente estudo foi obter evidências de validade e reprodutibilidade dos limiares de variabilidade da frequência cardíaca (VFC) durante a corrida. Dezenove sujeitos homens, saudáveis e praticantes de corrida (30,4 ± 4,1 anos; 175,9 ± 6,4 cm; 74,3 ± 8,5 kg) foram submetidos a um teste progressivo máximo em esteira rolante com velocidade inicial 5 km.h-1 e incrementos de 1 km.h-1 a cada 3 minutos (1% de inclinação constante) até exaustão voluntária. Todos os indivíduos realizaram o reteste em um intervalo de tempo entre 48 horas e uma semana. Foram realizadas as medidas das trocas gasosas, do lactato sanguíneo e da VFC (plotagem de Poincaré). Os limiares aeróbio (LAe) e anaeróbio (LAn) foram determinados pelos limares de lactato, ventilatórios e da VFC. Para a comparação entre os métodos foi uitlizada ANOVA para medidas repetidas, acompanhada de teste de post hoc de Bonferroni. A reprodutibilidade das variáveis analisadas foram verificadas pela plotagem de Bland-Altman e pelo coeficiente de correlação intraclasse (CCI). Os resultados do presente estudo demonstraram que a velocidade correspondente ao segundo e terceiro modelos utilizados para se determinar o LA pela VFC não eram significativamente diferentes (p > 0,05) do primeiro limiar de lactato e ventilatório. Em relação ao LAn, não foram observadas diferenças significativas nas velocidades correspondentes ao LAn detectado pelos diferentes métodos (p > 0,05). Os valores do CCI estavam entre 0,69 a 0,80 (p < 0,001). Conclui-se que o LAe e o LAn podem ser identificados pela análise da VFC, desde que se utilize os procedimentos empregados na presente investigação / The aim of the present study was to obtain evidences of validity and reliability of the thresholds of heart rate variability (HRV). Nineteen male subjects, healthy and runners (30,4 ± 4,1 years; 175,9 ± 6,4 cm; 74,3 ± 8,5 kg) performed a progressive maximal test on a treadmill with initial velocity 5 km.h-1 e increases of 1 km.h-1 every 3 minutes (1% slope) until voluntary exhaustion. All subjects performed the retest at an interval of time between 48 hours and one week. It was measured gas exchange, blood lactate and heart rate variability (Poincaré plot). The aerobic threshold (AT) and anaerobic (AnT) were determined by lactate, ventilatory and heart rate variability. ANOVA for repeated measures and post-hoc test of Bonferroni was used to compare the methods. To analyze the reproducibility of the variables were used the Bland- Altman plots and intraclass correlation coefficient (ICC). The results of this study show that the velocity at the second and third models employed to determine the AT by HRV were not significantly different (p > 0.05) of the first lactate threshold and ventilatory. Similarly, there were no significant differences in the velocities corresponding to AnT detected by different methods (p> 0.05). The ICC values were between 0.69 to 0.80 (p < 0.001). We conclude that the AT and the AnT can be estimated by HRV analysis, since it utilizes the procedures employed in this study
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Understanding the role of e-skills in the utilisation of electronic small business development support servicesKatunga, Natasha January 2013 (has links)
Magister Commercii - MCom / The Internet is now facilitating the provision of an increasing number of
services. Thus, technology has become a more integrated part of people‟s
daily routine. Some of these technologies include electronic communication,
online banking, and shopping as well as electronic learning - to name but a
few. However, for various reasons, such as limited formal education (which is
a key promoter of reading and writing skills), access and skills, not everyone
has an equal opportunity to benefit from the use of these technologies. The
unequal distribution of opportunities of such nature is often broadly referred to
as the digital divide. That is the gap between those who have access to
Information and Communication Technology (ICT) and those who do not.
One noted challenge that influences the use of ICT consists of socioeconomic conditions, which together elicit high levels of poverty. An identified
strategy for uplifting these areas was (and still is) entrepreneurship, notably
small businesses. These small businesses however, generally have very
short and mostly unsuccessful lives. As a result the government at all levels
(national, provincial and local) has endeavoured to provide support to these
businesses. Some of this support is provided through mediums, such as the
Internet (here named “electronic support”) to assist these small businesses.
This support, which comes from government, is however, not being fully
utilised by the intended beneficiaries. Thus, the small businesses are not
benefiting from the support provided. Consequently, many are still
experiencing a short and unsuccessful existence. This research thus analyses
the small businesses in areas of the greater Cape Town, which are
characterised by high levels of poverty and unemployment.
Previous studies in these areas have reported the lack of ICT related skills,
also known as electronic skills (e-skills), as one of the reasons for the low
uptake of electronic support (e-support). This e-support is provided by various
levels of government through selected agencies (service providers).
In essence, this study is aimed at investigating the influence of e-skills in the
access and use of the provided e-support by owners of small businesses.
Considering that the lack of adequate e-skills has been identified as
influencing the use of e-support, the study also aims to identify the e-skills
needed to fully utilise the provided e-support.
The approach to this investigation included a review of pertinent literature and
devising a conceptual model. This model was then tested in the empirical
setting of this study. This setting included: (i) Providers of e-support (various
specialised government agencies) and (ii) the intended beneficiaries of this esupport, i.e. small businesses in the previously disadvantaged areas (PDAs)
of the greater Cape Town.
Through the use of case study methodology and face to face interviews, it
was found that many small business owners were not able to appropriately
use the provided e-support. This was due to their lack of e-skills, which
resulted in their inability to use ICT. Additionally, some were unaware of the
existence of the e-support or the service providers.
During the review of pertinent literature done as part of the study, an e-skills
framework was designed. The framework identified the e-skills considered
necessary in order for small business owners to effectively utilise the provided
e-support and other technologies. The e-skills framework suggested by this
study could be used as a tool to assist: (i) The providers of e-support to
understand the usage of their services and enable (ii) a more informed
understanding of the need for appropriate e-skills among small business
owners, in relation to their use of the provided e-support. Additionally, (iii)
small business owners should be in a better position to recognise the benefits
of using technology, especially the Internet.
The contribution of this study is seen as twofold. Firstly, it should assist the
providers and users of e-support. This is done by addressing the practical
side of the provision and usage of these services. Secondly, the study
contributes an informative e-skills framework related to the effective use of esupport. This study also furthers academic knowledge in the area of the
investigation, and suggests further directions for research.
Considering, the limited small business sample (only participants from three
PDAs), the generalisation of this study is limited. This limitation does not
however, influence the validity of this research, or the credibility of the
findings.
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Contribution à la compréhension des mécanismes de vieillissement hydrothermique de matériaux composites unidirectionnels polyester insaturé/fibre de lin / Understanding the hydrothermal aging mechanisms of unsaturated polyester-reinforced flax fiber unidirectional compositesRouch, Matthias 19 April 2018 (has links)
De nombreux exemples de matériaux composites obtenus par l’association de fibres végétales et de polymères ont permis des allègements conséquents de structures dans divers domaines d’application. Cependant, la question demeure quant de la durabilité de ces pièces en service, essentiellement par manque de connaissances sur le vieillissement des fibres végétales, sur leurs interactions avec la matrice polymère et sur le comportement hydrothermique des composites biosourcés au cours du temps. Dans cette étude, nous avons étudié les cinétiques et mécanismes de sorption du matériau composite afin d’appréhender son comportement hydrique lors des vieillissements hydrothermiques par immersion dans l’eau à 23°C et 70°C. Cette étude a mis en évidence l’influence des fibres végétales sur les grandeurs caractéristiques de l’absorption en eau du matériau composite : forte prise en eau, gonflement anisotrope. Elle a également permis l’identification des mécanismes de dégradation des fibres de lin ; le rôle très nocif des résidus d’écorce rappelle l’importance du rouissage et du défibrage sur les performances de ces fibres. L’étude du comportement des constituants et du composite confrontés à des vieillissements hydrothermiques a ensuite été entreprise afin d’identifier et quantifier l’influence de chacun des matériaux constitutifs, ainsi que leur synergie. Il en ressort que la détérioration des fibres de lin est la principale cause de l’abattement des propriétés mécaniques du matériau composite. Si une immersion à 23°C pendant 70 jours n’a que peu d’effet sur les propriétés mécaniques, l’élévation de la température à 70°C induit des endommagements importants dès 14 jours d’immersion. La destruction des parois cellulaires et la dégradation des interfaces fibre/matrice sous l’effet de la présence d’eau détériorent le transfert de charge matrice/fibre. La corrélation entre les vieillissements accélérés et naturel a fait ressortir une similitude entre le maintien pendant 70 jours dans l’eau à 23°C et l’exposition aux conditions naturelles pendant 24 mois ; l’immersion à 70°C s’avère trop sévère. Une solution d’amélioration serait d’accentuer le rouissage des fibres afin de supprimer davantage les composés pectiques de la lamelle mitoyenne et de la paroi primaire. L’élimination de ces composés facilement hydrolysables par l’eau permettrait de prétendre à une meilleure qualité de l’interface fibres/matrice tout au long du vieillissement. / A great number of plant fiber – reinforced polymer composites allowed substantial lightening of structures in various fields of application. However, the question remains about the durability of these parts in service, mainly for lack of knowledge about the aging of plant fibers, their interactions with the polymer matrix and the hydrothermal behavior of biosourced composites over time. In this work, water absorption mechanisms and kinetics by the composite material are studied in order to understand the hydric behavior during hydrothermal aging by immersion in deionized water at 23°C or 70°C. The results show that water absorption by the composite is characterized by a high water uptake and an anisotropic swelling. It also allowed the identification of the degradation mechanisms of flax fibers; the very harmful role of bark residues recalls the importance of retting and decortication on the performance of these fibers.The investigation of the behaviors of the constituents and the composite under hydrothermal aging was then undertaken with the aim to identify and quantify the influence of each on the constituent materials, as well as their synergy. It shows that the deterioration of the flax fibers is the main cause of the reduction of the mechanical properties of the composite. If immersion at 23 ° C for 70 days has little effect on the mechanical properties, raising the temperature to 70 ° C induces significant damage from 14 days of immersion. The destruction of the cell walls and the degradation of the fiber/matrix interfaces due to water deteriorate the load transfer efficiency by the fiber/matrix interface. The correlation between accelerated and natural aging showed a similarity between holding for 70 days in water at 23 ° C and exposure to natural conditions for 24 months; immersion at 70 ° C is too severe. An improvement solution would be to increase the retting of the fibers in order to further remove the pectic compounds from the middle lamella and the primary wall. The elimination of these compounds easily hydrolysable by water would claim to a better quality of the fiber / matrix interface throughout aging.
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