No description available.

In the first part of these studies, we have performed standard microsurgical procedures provide a solution for long standing bone and soft tissue defects, even in cases of longstanding osteomyelitis of long bones. When long bony segments are missing, the microvascular bone transfer provides a reliable method. In smaller soft tissue and bone defects, the application of a descending genicular osteomyocutaneous flap provides an option with low donor site morbidity. In the second part, we have focussed on reducing the donor site morbidity and expanded on the application of tissue engineering methods. MSCs derived from bone marrow can be injected percutaneous or be combined with an autologous bony scaffold for treatment of delayed union and nonunion. The outcome of our studies, however, limited in number of patients, clearly showed the possibilities and advantages of this new approach. A multimodality approach is essential, but it can provide promising solutions. Well-established microvascular and modern biotechnology methods will improve patient satisfaction and functional recovery in severe limb trauma, often the result of high-energy motorcycle accidents. / Doctorat en Sciences médicales (Médecine) / info:eu-repo/semantics/nonPublished

Underground excavations break the balance of the initial stress field and cause stress redistributions in the surrounding rock masses. Problems normally arise as the stress exceeds the rock mass strength. In addition, the rock mass contains preexisting defects, such as the fissures, fractures, joints, faults, shear zones, dikes, etc., which could significantly weaken the rock mass strength and make the rock mass behavior complicated. The stability of underground excavations is of great importance to an operating mine project since it ensures the safety of the working environment and the successful ore exploration. Due to the complex geological conditions and engineering disturbances, the assessment of rock mass stability for a practical engineering problem is extremely challenging and difficult, which needs to be solved by the modern numerical methods. In this dissertation, the rock mass stability around tunnels in an underground mine in the USA was investigated by performing three-dimensional modeling using the 3DEC 3-Dimensional Distinct Element Code. Comprehensive stress analyses were respectively carried out on a preliminary model and a more advanced model. In the preliminary study, the built model contains the inclined lithologies, a non-persistent fault, and a convoluted tunnel system. The geomechanical property values used for the rock masses and discontinuities in the numerical model were estimated using the available geotechnical information and the experience of the research group. The Mohr-Coulomb and strain softening constitutive relations were prescribed for the rock masses; the coulomb slip joint model was assigned for the discontinuities. The influence of the boundary conditions, block constitutive models, horizontal in situ stress and rock support system on the tunnel stability was investigated. The rock mass behavior was quantified using the results of stress, displacement, and yielded zones around the tunnels. It showed that the roller boundary conditions resulted in slightly different but comparable results with the combined boundary conditions (roller and stress combined) where K0 equals to 0.4 or 0.5. Whereas the in-situ stress field for a complex geological system can only be obtained by applying proper boundary stresses and then by performing stress analysis. The softening behavior of the rock masses caused more deformations and yielded zones around the tunnels; the rock masses around the tunnels were observed to reach the residual strength values, which can be treated as failed areas. In addition, the M-C and s-s rock masses reacted differently as the K0 value changed. At K0=1.0, the tunnels seemed to be the most stable; K0=1.5, however, provided the worst scenario with roof and floor problems. With respect to the effectiveness of the support system, a large amount of the bonds of the supports was failing, thus, the deformations and yielded zones around the tunnels were slightly improved. Finally, comparisons between the numerical modeling results and the field measurements implied the applicability of strain softening behavior and a K0 value between 0.5 and 1.0 for the mine. Based on the specific geological, geotechnical, and construction information, a numerical model incorporating accurate features was developed. It includes a non-planar, weak interlayer, the persistent and non-persistent faults, and the open and backfilled excavations. The mechanical property values used for the rock masses and faults were estimated based on the laboratory test results of the intact rock and smooth joints. The strain softening behavior was specified for the rock masses belonging to the average quality, and the rock masses that reached residual strengths were assumed to be failing. The linear relations between the fault stiffnesses and normal stress were described using the continuously yielding joint model. To simulate the mine construction process in the field, the sequential excavation, backfilling, and supporting procedures were numerically implemented; additionally, a novel routine was applied to account for the delayed installation of the supports. Results showed that the tunnels close to the fault and the backfilled area were less stable. Most of the displacements around the tunnels occurred within a distance of zero to 2 or 3 m from the tunnel surface. The varying K0 value caused great changes in the rock mass behavior and the shear behavior of the major fault; significant instability of the tunnels was triggered by the high horizontal in situ stress. Parametric studies on the rock mass condition, rock mass residual strengths, and fault property values showed that the tunnel stability was more sensitive to the former two factors than the last one. A systematic investigation was conducted to evaluate the current rock supports installed at the mine where the increasing stress relaxation was incorporated. The deformations and of the failure zone thicknesses around the tunnels were reduced up to 8% and 20% after applying the supports instantaneously, and the reductions were improved by the delayed installation of supports. Additionally, the safety of supports was evaluated by the bond shear and bolt tensile failures, which was also improved with incorporation of delayed supporting. It was found that the current rock supports are insufficient in length, bond and tensile strengths. Therefore, a stronger support system was suggested. The stronger supports worked better in stabilizing the tunnels. Based on the deformations and failures of the rock masses, the length of the bolts on walls was suggested to be 4-5 m. At the end, the horizontal convergence strain predicted by the numerical simulations were calculated at two locations where the tape extensometers were installed. Good agreements with the field measurements were obtained for the cases that have the average rock mass properties and K0 values in the range 0.5-1.25.

Magister Public Health - MPH / The aim of this study was to identify factors associated with reporting incidents of sexual violence after seventy-two hours at the sexual assault service centre in Newcastle, KwaZulu-Natal. This descriptive study was based on retrospective analysis of 534 medical records of victims of sexual violence at the Newcastle hospital between 2005 and 2009. A data collection sheet was designed to extract information from three sources namely: the victims' hospital files, J88 forms and specific hospital forms that were completed for sexual assault victims. The collected data were entered into and processed for analysis using EPI INFO statistical package. Frequencies, means and standard deviations were calculated for the data set. Test of significance was also done using the Chi-square test and presented using odds ratios with 95% CI and p-value of <0.05. The victims' age range was 2-81years (mean= 18.84, σ=13.25). Approximately 87% were female and 59.4% of the victims were aged 0-17 years. One in five victims (19.7%) was HIV positive, and most (74.4%) reported rape with vaginal penetration. Fifty-nine percent reported within 72 hours of being assaulted. The most common reason for delayed reporting (21.5%) was fear of the perpetrator. Most of the sexual assaults were committed by male (96%) and single perpetrator (90%). Nearly a third (32.4%) of the sexual violence occurred within intimate relationships and more than two-thirds (68%) knew the perpetrators. In all, 35% sustained injuries during the assault and a third (34.5%) reported the use of weapons during the assault. Nearly half of the victims (48.7%) were referred to hospital by their relatives who also accompanied them to the facility (42.1%). Of the 198 victims that were offered post-exposure prophylaxis (PEP), 87% collected the full 28-day course. / South Africa

No description available.

Cette thèse porte sur la conception, la synthèse et la caractérisation de nouveaux dérivés accepteurs d'électrons. Elle se concentre sur l’étude des dérivés de la 1,2,4,5-tétrazine, mais contient également l’étude de dérivés du benzonitrile, précurseurs typiques de la préparation des 1,2,4,5-tétrazines et de dérivés de la pyridazine, les produits dérivés de la réaction de Diels – Alder à Demande Inverse (IEDDA) des dérivés de la tétrazine. De plus, les dérivés de 1,2,3,4-thiatriazole, en tant que produits imprévus de la synthèse de Pinner modifiée, sont également étudiés de manière approfondie. En raison des états de transfert de charge (CT) introduits dans le système donneur-accepteur, les dérivés préparés accepteur d'électrons présentent en général des propriétés photophysiques et électrochimiques intéressantes, et ont donc un intérêt particulier pour l'électronique organique.Le point culminant de cette thèse est le développement de méthodologies synthétiques dans chaque chapitre. En résumé, le chapitre 2 met en évidence une nouvelle approche synthétique sans métal pour les 1,2,4,5-tétrazines 3-monosubstituées, qui sont très utiles pour la chimie du click bioorthogonal. Le chapitre 3 décrit une stratégie de synthèse élaborée pour de nouveaux dérivés de benzonitrile donneur-accepteur qui présentent de la TADF, de l’ AIE et du mécanochromisme. Le chapitre 4 présente une étude détaillée de la réaction de couplage croisé Buchwald – Hartwig en tant que méthodologie de synthèse importante dans la synthèse de molécules de tétrazine. Le chapitre 5 décrit l'étude de la réaction à l'IEDDA comme un outil synthétique utile pour préparer des dérivés de pyridazine. Le chapitre 6 présente une nouvelle synthèse pratique de 1,2,3,4-thiatriazoles à partir de composés nitriles. / This PhD thesis deals with the design, synthesis and characterization of novel electron-acceptor derivatives. It is focused on the study of 1,2,4,5-tetrazine derivatives, but also involves the study of benzonitrile derivatives which are the typical precursors for the preparation of 1,2,4,5-tetrazines, and pyridazine derivatives which are the products derived from Inverse Electron Demand Diels–Alder (IEDDA) reaction of tetrazine derivatives. Moreover, 1,2,3,4-thiatriazole derivatives, as unpredicted products from modified Pinner synthesis, are also elaborately investigated. Due to the charge-transfer (CT) states introduced in the donor-acceptor system, the prepared electron-acceptor derivatives exhibit interesting photophysical and electrochemical properties, and therefore are of particular interest in organic electronics.The highlight of this thesis is the development of synthetic methodologies in each chapter. To sum up, Chapter 2 demonstrates a novel metal-free synthetic approach to 3-monosubstituted 1,2,4,5-tetrazines, which are highly useful for bioorthogonal click chemistry. Chapter 3 describes an elaborative synthetic strategy for novel donor-acceptor benzonitrile derivatives which exhibit TADF, AIE and mechanochromism. Chapter 4 presents a detailed study of Buchwald–Hartwig cross-coupling reaction as an important synthetic methodology in the synthesis of tetrazine molecules. Chapter 5 described the study of IEDDA reaction as a useful synthetic tool to prepare pyridazine derivatves. Chapter 6 presented a novel convenient one-pot synthesis of 1,2,3,4-thiatriazoles directly from nitrile compounds.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23495号 / 工博第4907号 / 新制||工||1767(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 米田 稔, 教授 清水 芳久, 教授 高岡 昌輝 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Iron deficiency (ID) is especially common in pregnant women and may even persist following childbirth. This is of concern in light of reports demonstrating that ID may be sufficient to produce homeostatic dysregulation of other metals, including manganese (Mn). These results are particularly important considering the potential introduction of the Mn-containing gas additive, methyl cyclopentadienyl manganese tricarbonyl (MMT), in various countries around the world. In order to model this potentially vulnerable population, we fed female rats fed either control (35 mg Fe/kg chow; 10 mg Mn/kg chow) or low iron/high-manganese (IDMn; 3.5 mg Fe/kg chow; 100 mg Mn/kg chow) diet, and examined whether these changes had any long-term behavioral effects on the animals' spatial abilities, as tested by the Morris water maze (MWM). We also analyzed behavioral performance on auditory sensorimotor gating utilizing prepulse inhibition (PPI), which may be related to overall cognitive performance. Furthermore, brain and blood metal levels were assessed, as well as regional brain isoprostane production. We found that treated animals were slightly ID, with statistically significant increases in both iron (Fe) and Mn in the hippocampus, but statistically significantly less Fe in the cerebellum. Additionally, isoprostane levels, markers of oxidative stress, were increased in the brain stem of IDMn animals. Although treated animals were indistinguishable from controls in the PPI experiments, they performed less well than controls in the MWM. Taken together, our data suggest that vulnerable ID populations exposed to high levels of Mn may indeed be at risk of potentially dangerous alterations in brain metal levels which could also lead to behavioral deficits.

This Ph.D. dissertation focuses on a comprehensive study of seismic waveform similarity aiming at two themes: (1) reliable identification of repeating earthquakes (repeaters) and (2) investigation of the detailed source process of induced seismicity through the three-dimensional spatiotemporal evolution of mainly neighbouring earthquakes. Theme 1: Reliable identification of repeaters. Repeaters, occurring repeatedly on the same fault patch with nearly identical waveforms, are usually identified with the match-filtering (MF) method which essentially measures the degree of waveform similarity between an earthquake pair through the corresponding cross-correlation coefficient (CC). However, the performance of the MF method can be severely affected by the length of the cross‐correlation window, the frequency band of the applied digital filter, and the presence of a large‐amplitude wave train. To optimize the performance of MF, I first examine the effects of different operational parameters and determine generic rules for selecting the window length and the optimal frequency passband. To minimize the impact of a large‐amplitude wave train, I then develop a new method, named the match-filtering with multisegment cross-correlation (MFMC) method. By equally incorporating the contributions from various segments of the waveforms, the new method is much more effective in capturing the minor waveform discrepancy between an event pair due to location difference and hence is more reliable in detecting potential repeaters and discriminating non-repeaters with large inter-event separation. With both synthetic and borehole array waveform data, I further reveal that waveform similarity is controlled by not only the inter-event separation but also many other factors, including station azimuth, epicentral distance, velocity structure, etc. Therefore, in contrast to the traditional view, the results indicate that waveform similarity alone is insufficient to unambiguously identify true repeaters. For reliable repeater identification, we should rely on a physics-based approach considering both the overlapped source area and magnitude difference. Specifically, I define an event pair to be true repeaters if their inter-event separation is smaller than the rupture radius of the larger event and their magnitude difference is no more than 1. For the precise estimation of inter-event distance in cases of limited data, I develop the differential traveltime double-difference (DTDD) method which relies on the relative S-P differential traveltime. The findings of this study imply that previously identified repeaters and their interpretations/hypotheses potentially can be biased and hence may need a systematic reexamination. Theme 2: Investigation of the detailed source process of induced seismicity. Earthquakes induced by hydraulic fracturing (HF), especially those with large magnitudes, are often observed to have occurred near/after well completion. The delayed triggering of induced seismicity with respect to injection commencement poses serious challenges for risk mitigation and hazard assessment. By performing waveform cross-correlation and hierarchical clustering analysis, I reveal a high-resolution three-dimensional source migration process with mainshock delayed triggering that is probably controlled by local hydrogeological conditions. The results suggest that poroelastic effects might contribute to induced seismicity but are likely insufficient to activate a non-critically stressed fault of sufficient size. My analysis shows that the rapid pore-pressure build-up from HF can be very localized and capable of producing large, felt earthquakes on non-critically stressed fault segments. I further infer that the number of critically stressed, large intraplate faults should be very limited, and that reactivation of such faults may require sufficient pore-pressure accumulation. The findings of this study may also explain why so few fluid injections are seismogenic. / Graduate

Thermally activated delayed fluorescence (TADF) has been proposed as a pathway to achieve high efficiency organic light-emitting diodes (OLEDs) without the use of heavy metal atoms in molecular structures. Many different factors can be decisive for efficient light emission from TADF emitters. However, a complete picture of the working mechanisms behind TADF is still missing and further research exploring novel material and device ideas is required. This thesis aims to extend the understanding of TADF emitter and OLED design considerations by investigating photophysical properties of novel materials as well as fabricating, optimizing and characterizing devices. TADF emitters have great potential of being used in OLEDs because they allow for high quantum efficiencies by utilizing triplet states via reverse intersystem crossing (RISC). In small molecules this is done by spatially separating the frontier orbitals, forming an intramolecular charge-transfer state (iCT) and leading to a small energy difference between lowest excited singlet and triplet states (Δ𝐸ST). In polymer emitters, sufficient frontier orbital separation is harder to achieve, and typical strategies usually include adding known TADF units as sidechains onto a polymer backbone. In this thesis, a novel pathway of TADF polymer design is explored. A shift from a non-TADF monomer to TADF oligomers is explored. The monomer shows non-TADF emission and the delayed emission is shown to be of triplet-triplet annihilation (TTA) origin. An iCT state is formed already in the dimer, leading to a much more efficient TADF emission. This is confirmed by an almost two-fold increase of photoluminescence quantum yield (PLQY), a decrease in the delayed luminescence lifetime and the respective spectral line shapes of the molecules. Recently, intermolecular effects between small-molecule TADF emitters have been given more attention, revealing strong solid-state solvation or aggregation induced changes of sample performance. Implications of this on device performance are not yet fully covered. A thorough investigation of a novel TADF emitter 5CzCO2Me is conducted. Steady-state emission spectra reveal a luminescence redshift with increasing emitter concentration in a small molecule host. In all investigated concentrations, the emission profile remains the same, thus the redshift is attributed to the solid-state solvation effect. The highest photoluminescence quantum yield (PLQY) is achieved in the 20 wt% sample, reaching 66 %. The best OLED in terms of current-voltage-luminance and external quantum efficiency parameters is the device with 60 wt% emitter concentration, reaching maximal EQE values of 7.5 %. It is shown that the emitter transports holes and that charge carrier recombination does not take place on the bandgap of the host, but rather, a mixed host-guest concentration dependent recombination is seen. The hole transporting properties of 5CzCO2Me allows for a new dimension in tuning the device performance by controlling the emitter concentration.