Die vorliegende Arbeit beschäftigt sich mit der Tätigkeit konsiliarpsychiatrischer Dienste am Allgemeinkrankenhaus. In einem historischen Abriß wird zunächst die Integration des psychiatrischen Fachgebiets in die Allgemeinkrankenhäuser als wesentliche Bedingung für die Entwicklung der Konsiliarpsychiatrie am Beispiel der USA dargestellt, gefolgt von europäischen Perspektiven und der Entwicklung in Deutschland, unter besonderer Berücksichtigung der Psychiatrie-Enquête. Anschließend werden Aspekte somatopsychischer Komorbidät als Grundlage der Konsiliarpsychiatrie und ihre Implikationen für Diagnostik und Therapie skizziert. Vorschläge zur Bestimmung des Bedarfs der konsiliarpsychiatrischen Versorgung werden diskutiert. Das Spektrum konsiliar-liaisonpsych-iatrischer Versorgungsmöglichkeiten wird dargestellt, Interventionsmöglichkeiten mit ihren differentia specifica im Setting des Allgemeinkrankenhauses am Beispiel von supportiver Psychotherapie und Psychopharmakatherapie bei körperlich kranken Patienten werden verdeutlicht. Im empirischen Teil wird auf Grundlage einer Längsschnittstudie über einen 10jährigen Be-obachtungszeitraum eines amerikanischen, sowie einer Vergleichsstudie der Tätigkeit eines deutschen und eines amerikanischen Konsildienstes über einen einjährigen Beobachtungszeitraum versucht, einen Kernbereich konsiliarpsychiatrischer Tätigkeit am Allgemeinkrankenhaus zu definieren. In der Längsschnittuntersuchung wurde ein zeitüberdauernder Bereich konsiliarpsychiatrischer Tätigkeit identifiziert, der im Vergleich mit ähnlichen, allerdings weniger detaillierten Studien (Lipowski & Wolston 1981, Paddison et al. 1989) ebenfalls überwiegend Gemeinsamkeiten deutlich werden läßt. Auch die vergleichende Querschnittsuntersuchung zeigte, daß psychiatrische Konsiliartätigkeit über nationale Grenzen hinweg eine Reihe von Gemeinsamkeiten aufweist. Auch dies konnte im Vergleich mit anderen Studien bestätigt werden (vgl. Übersichten bei Hengeveld et al. 1984, Diefenbacher 1999, Huyse et al. 1997). Anschließend werden Veränderungen im Gefolge der Tätigkeit eines neu beginnenden psychiatrischen Konsiliars über einen einjährigen Beobachtungszeitraum untersucht und im Hinblick auf die Implementation eines Konsildiensten auf für die konsiliarpsychiatrische Praxis bzw. Interventionsforschung wichtige Parameter wie z.B. Zusammenarbeit mit den Stationsteams und Beeinflussung von Krankenhausverweildauer und Zeitintervall zwischen stationärer Aufnahme und Konsilanforderung diskutiert. Zusammenfassend wird ein Kernbereich konsiliarpsychiatrischer Tätigkeit beschrieben, von dem erwartet wird, daß er für die nahe Zukunft konstant bleibt und somit als Orientierungshilfe für administrative und evaluative Zwecke dienen kann. Abschließend werden Perspektiven weiterer Forschung in der Konsiliarpsychiatrie diskutiert und auf Aspekte der Fort- und Weiterbildung im psychiatrischen Konsiliar-Liaisondienst in der psychiatrischen Facharztweiterbildung, sowie auf Schnittstellen für eine mögliche Zusammenarbeit mit dem hausärztlichen Bereich eingegangen. / Psychiatric consultation-liaison (c-l) service delivery in the general hospital is the topic of this study. In the first part, an historical outline of the development of psychiatric c-l-services in the USA is presented, followed by recent developments in Europe and Germany, with special emphasis - for the latter - of the impact of the so-called "Psychiatrie-Enquête" (1975) on the implementation of psychiatric departments in general hospitals since the 1980s. The issue of somato-psychic comorbidity of general hospital inpatients, the very reason of existence of c-l-psychiatry, is discussed, as are its implications for diagnosis and treatment. Proposals for the evaluation of need for such services are presented, as is the scope of c-l-psychiatric interventions and their special nature with the example of supportive psychotherapy and psychopharmaco-therapy in the medically and psychiatrically ill inpatient. The second empirical part consists of a 10-year-longitudinal study of a c-l-psychiatric service in New York City, and a comparative cross-sectional study (over a 1-year-period) of a German and an American c-l-psychiatric service in order to delineate a common core of psychiatric c-l-service delivery in the general hospital. In both studies, a cross-national common core and a time stable course over time, respectively, are identified and then discussed in comparison to other less detailed studies (e.g. Lipowski & Wolston 1981, Hengeveld et al. 1984, Huyse et al. 1997). In addition, the implementation phase of a newly started psychiatric c-l-service is studied over a 1-year-period with regard to variables important for c-l-psychiatric intervention studies, such as influence on length of stay in hospital, lagtime between admission to hospital and day of consultation request, and cooperation with staff. In conclusion, a core field of psychiatric c-l-service delivery in the general hospital is identified, that is expected to remain stable in years to come and thus might help as an orientation for administrative and evaluative purposes. Finally, perspectives for further research in the field, for training and education, and for the cooperation with primary care doctors are discussed.

Die These fasst die ersten Untersuchungen zum Pawlowsch`-Instrumentellen Transfer in alkoholabhängigen (AA) Patienten zusammen. Es ist bekannt, dass kontextuelle Umgebungsreize Verhalten beeinflussen. Tier- und Humanstudien haben gezeigt, dass positive Pawlowsche Reize instrumentelles Antwortverhalten verstärken und negative Pawlowsche Reize dieses reduzieren (PIT-Effekt). Bei Abhängigkeit wird angenommen, dass dieser Mechanismus relevant für Rückfall ist, da z.B. drogenassoziierte Reize bei Patienten im Vergleich zu Kontrollen erhöhtes Verlagen und funktionelle Aktivität in Belohnungsarealen auslösen. In Tier- und Humanstudien wurden stärkere PIT-Effekte vor allem mit funktioneller Aktivierung im Nucleus Accumbens (NAcc) beobachtet. Weiterhin zeigten sich bei Probanden mit stärkerem PIT-Effekt und bei AA Patienten erhöhte Impulsivitätswerte. Die PIT-Aufgabe besteht aus 3 Hauptteilen: i) Instrumentelle Konditionierung, ii) Pawlowsche Konditionierung, iii) Transfer mit Pawlowschen oder alkoholassoziierten Kontextstimuli. Impulsives Auswahlverhalten wurde durch die delay discounting Aufgabe erhoben. Es zeigten sich signifikant stärkere PIT-Effekte mit Pawlowschen Kontextreizen in AA Patienten im Vergleich zu Kontrollen mit funktioneller Aktivierung im NAcc, die zur Rückfallvorhersage beitrug. Der Transfer mit alkoholassoziierten Kontextreizen bewirkte eine signifikante Reduktion des instrumentellen Antwortverhaltens mit neuronalem Korrelat im NAcc nur bei abstinenten Patienten. Impulsives Auswahlverhalten und PIT hingen nur bei Patienten positiv zusammen. Die Studien lassen darauf schließen, dass PIT ein für Rückfall wichtiger Mechanismus ist mit funktionellem Korrelat im NAcc, der sich für motivationale Prozesse als auch als Salienzsignal relevant gezeigt hat. Die Subgruppe von hoch impulsiven Patienten ist im Besonderen durch Kontextreize im instrumentellen Antwortverhalten beeinflussbar, daher sollte ihr besondere Aufmerksamkeit bei Interventionen zukommen. / This thesis summarizes the first Pavlovian-to-instrumental transfer (PIT) studies in alcohol-dependent (AD) patients. Contextual stimuli are known to influence our behavior. Animal and human studies showed that positive Pavlovian stimuli enhance and negative Pavlovian stimuli reduce instrumental behavior (PIT effect). This mechanism might be relevant for relapse risk, as drug-associated stimuli have shown to enhance e.g. craving and functional activation in reward-related brain areas in patients compared to controls. In animal and human studies enhanced PIT effects were associated with activation particularly in the nucleus accumbens (NAcc). Moreover, control subjects with stronger PIT effects and AD patients were more impulsive on different facets of impulsivity. The PIT task consists of three main parts: i) instrumental conditioning, ii) Pavlovian conditioning, iii) transfer with Pavlovian background stimuli and instrumental task in the foreground (nondrug-related PIT: Pavlovian contextual cues; drug-related PIT: alcohol-related contextual cues). Choice impulsivity was measured by delay discounting task. We observed significantly enhanced nondrug-related PIT effects in AD patients compared to controls with a functional activation in the NAcc being predictive for relapse. Regarding drug-related PIT effects, we observed significantly reduced instrumental behavior during alcohol-related backgrounds with neural correlates in the NAcc in abstainers only. Choice impulsivity was positively related to PIT in AD patients only. Our data suggest that PIT is a mechanism contributing to relapse in AD patients with functional correlations within the NAcc, which based on our data is involved in motivation and attribution of salience. The subgroup of high impulsive patients is particularly susceptible for PIT effects, thus should be main target for intervention programs.

Die vorliegende kumulative Promotion umfasst drei veröffentlichte Publikationen, die im Rahmen der Berliner Borderline Versorgungsstudie (BBV-Studie) durchgeführt wurden. In Studie 1 wurde die effectiveness der ambulanten Dialektisch-Behavioralen Therapie (DBT) an N = 47 Patienten mit einer Borderline Persönlichkeitsstörung (BPS), die das DBT-Behandlungsjahr vollständig durchlaufen haben, untersucht. Im Prä-Post-Vergleich zeigten sich für die untersuchten Symptombereiche signifikante Veränderungen und die Effektstärken lagen überwiegend im mittleren Bereich. 77% der Patienten erfüllten nach einem Jahr DBT nicht mehr die diagnostischen Kriterien für eine BPS. In Studie 2 wurden die Krankheitskosten von N = 55 BPS-Patienten in dem Jahr vor der ambulanten DBT umfassend aus einer gesellschaftlichen Perspektive erhoben. Die durchschnittlichen Kosten lagen bei €26.882 (SD = €32.275). Davon gingen mit €17.976 (SD = €23.867) etwa 66% auf die direkten, mit €8.906 (SD = €15.518) knapp 34% auf die indirekten Kosten zurück. In Studie 3 wurden für die N = 47 DBT- compleater die Krankheitskosten im Jahr vor der Therapie mit denen während des DBT-Behandlungsjahres und mit denen während des ersten Katamnesejahres (N = 33) verglichen. Die durchschnittlichen Krankheitskosten lagen im Jahr vor der DBT bei €28.026 (SD = €33.081), während des DBT-Jahres bei €18.758 (SD = €19.450) und sanken innerhalb des Katamnesejahres weiter auf €14.750 (SD = €18.592). Die deutlichsten Kostenreduktionen zeigten sich im stationären Bereich. Hingegen konnten die indirekten Kosten kaum gesenkt werden. Insgesamt weist die vorliegende Promotion darauf hin, dass die ambulante DBT auch unter Versorgungsbedingungen in Berlin wirksam ist. Zudem besitzt die BPS auch in Deutschland eine hohe gesellschaftliche Relevanz. Die Krankheitskosten können deutlich gesenkt werden, wenn BPS-Patienten in einem DBT-Netzwerk behandelt werden. Hieraus ergeben sich erste Hinweise auf die Effizienz der ambulanten DBT. / This thesis includes three publications that were conducted as part of a Berlin wide treatment study (“Berliner Borderline Versorgungsstudie“). In study 1, we examined the effectiveness of dialectical behavior therapy (DBT) for borderline personality disorder (BPD) under the routine health care situation in Berlin. N = 47 patients completed the one-year treatment and provided data. Our findings demonstrate significant improvements on all measures with medium effect sizes. Moreover, at the end of the first treatment year, 77% of the patients no longer met the criteria for a BPD diagnosis. In Study 2, BPD-related cost-of-illness 12 months prior to outpatient DBT was assessed in a sample of N = 55 BPD-patients from a societal perspective. Total cost-of-illness was €26882 (SD = €32275) per patient. €17976 (SD = €23867; 66%) were direct costs and €8906 (SD = €15518; 34%) were calculated as indirect costs. In study 3, societal cost-of-illness of the N = 47 DBT completers was calculated for 12 months prior to DBT and further investigated during DBT-treatment year and during the following year. Total mean annual cost-of-illness was €28026 (SD = €33081) during pre-treatment, €18758 (SD = €19450) during the DBT treatment year and €14750 (SD = €18592) during the follow-up year for the N = 33 patients who participated in the final assessment. Cost savings were mainly due to marked reductions of inpatient treatment costs, while indirect costs barely decreased. In sum, the present thesis shows that outpatient DBT under routine mental health care conditions in Berlin leads to positive results. Furthermore, mean annual cost-of-illness of German BPD-patients exceed those of many other mental disorders meaning that BPD poses a high economic burden. Importantly, treatment of BPD patients with an outpatient DBT program is associated with substantial overall cost savings. Correspondingly, outpatient DBT has the potential to be an efficient treatment.

Trotz zahlreicher Untersuchungen lässt sich bei der Zwangsstörung noch kein einheitliches, alle Befunde integrierendes Krankheitsmodell formulieren. Die Verarbeitung von emotionalen Reizen könnte bei Personen mit Zwangsstörungen verändert sein. Dies trägt möglicherweise zur Entwicklung und Aufrechterhaltung der Störung bei. Das Ziel der vorliegenden Arbeit war es, spezifische Komponenten dieser Verarbeitung zu untersuchen. Zuerst wurde in zwei unterschiedlichen Studien überprüft, ob die Orientierung der Aufmerksamkeit zu neuen Reizen bei Patienten mit Zwangsstörungen verstärkt ist. Zu diesem Zweck wurden durch neue Reize evozierte Potentiale im Elektroenzephalogramms (EEG) gemessen. Anschließend wurde in einer Studie überprüft, ob das Verhältnis der Aktivierungen von dem Vermeidungs- zum Annäherungssystem bei den Betroffenen verändert ist. Dies lässt sich an Hand der Ermittlung der hemisphärischen Verteilung von Alpha-Wellen in frontalen Hirnregionen feststellen. Die Ergebnisse der ersten beiden Studien ergaben, dass Patienten unabhängig vom emotionalen Kontext eine stärkere Aufmerksamkeitshinwendung zu neuen Reizen zeigen (Studie 1), was allerdings nicht beobachtet wurde, wenn die neuen Reize innerhalb des Aufmerksamkeitsfokus lagen (Studie 2). Dieses Ergebnis wurde als überaktives Gefahrenerkennungssystem bei Patienten interpretiert. Weiterhin ließ sich feststellen, dass Patienten im Vergleich zu gesunden Kontrollen in frontalen Hirnregionen eine Verlagerung der Alpha Asymmetrie zur linken Gehirnhemisphäre aufwiesen (Studie 3). Dieser Befund wurde unabhängig von einer Stimulierung durch emotionale Reize gemacht. Er lässt sich als stärkere Aktivierung des Vermeidungs- im Verhältnis zum Annäherungssystem deuten. Zusammengefasst zeigte sich bei Patienten mit Zwangsstörungen eine veränderte Verarbeitung von emotionalen Reizen. Aus diesen Befunden können spezifische Empfehlungen für die Behandlung der Störung abgeleitet werden. / It is so not possible to formulate a disease model of obsessive-compulsive disorder (OCD) that integrates all the results of the many studies carried out. The neural processing of emotional stimuli might be altered in people with OCD. This might play an important role in the development and maintenance of OCD. The present work aimed to investigate specific components of the neural processing of emotional stimuli. The first two studies examined if the orienting of attention towards novel stimuli is enhanced in patients with OCD. For this purpose the event-related brain potentials evocated by novel stimuli in the electroencephalogram were recorded. The third study tested if the relationship between the withdrawal-avoidance mode and the approach mode of the motivational brain system is altered in OCD patients. This can be assessed by the hemispheric distribution of alpha power in frontal brain regions. The results of the first two studies showed that the orienting of attention towards novel stimuli is enhanced in patients with OCD independently of the emotional context condition (study 1), which could not be observed if the novel stimuli were listened to in active attentional mode (study 2). This was interpreted as a hypersensitive threat detection system. Further, it was found that patients showed a shift of frontal alpha activity to the left hemisphere compared to healthy control subjects (study 3). This result was independent of the viewing of emotional stimuli. It can be concluded that the avoidance mode is relatively increased in patients with OCD. Taken together, patients showed an altered neural processing of emotional stimuli. Specific recommendations for he treatment of the disorder can be drawn out of them.

Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2017-10-26T16:09:28Z No. of bitstreams: 1 Tese Eng. Piedade.pdf: 6225051 bytes, checksum: c7f77823a538300959734acada65a861 (MD5) / Rejected by Caroline Xavier (caroline.xavier@pucrs.br), reason: Devolvido devido a 1) Arquivo PDF sem capa institucional. 2) Na primeira e segunda folha do arquivo PDF, o nome do autor est? incompleto. Na ficha catalogr?fica e publica??o enviada est? completo. 3) Nome e descri??o do arquivo na publica??o est?o em desacordo com o manual enviado. on 2017-11-07T13:03:14Z (GMT) / Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2017-11-08T17:01:40Z No. of bitstreams: 1 final para entrega com capa.pdf: 6291908 bytes, checksum: a447082574d55fe4709b55f1c2da38fb (MD5) / Approved for entry into archive by Caroline Xavier (caroline.xavier@pucrs.br) on 2017-11-17T12:16:13Z (GMT) No. of bitstreams: 1 final para entrega com capa.pdf: 6291908 bytes, checksum: a447082574d55fe4709b55f1c2da38fb (MD5) / Made available in DSpace on 2017-11-17T12:20:52Z (GMT). No. of bitstreams: 1 final para entrega com capa.pdf: 6291908 bytes, checksum: a447082574d55fe4709b55f1c2da38fb (MD5) Previous issue date: 2017-08-18 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Quasicrystals are materials that have unusual characteristics, they can not be described as crystalline, for not having long-range order, or as amorphous, have medium-range structure. Some Al-Cu-Fe family alloys presents quasicrystalline phases when have rapidly solidification. In order to obtain this alloy, ingots of the Al65Cu35-xFex family were casted with x=6 (atomic), initially in a standard mold with solidification equilibrium. To provide samples with different cooling rates, the alloy was cast in a stepped mold, containing six different steps, resulting in samples out of equilibrium state (rapidly solidification). For the analysis of the cooling curves, the CACC-TA technique was used, with cooling rates varying from170 to 540?C / s, which were obtained by dT/dt. Analyzes by optical microscopy, scanning electron microscopy (SEM), dispersive energy spectrometry (EDS), show microstructure with faceted dendrites, lamellar interdendritic formations and pentagonal precipitates (IQC). The Vickers microhardness ranged from 4.09 to 7.22 GPa and the X-ray diffraction (XRD) proved by characteristic diffractograms the icosahedral quasicrystalline phase formation. / Os quasicristais s?o materiais que apresentam caracter?sticas incomuns, pois n?o podem ser descritos como cristalinos, por n?o apresentarem ordem de longo alcance, nem como amorfos, apresentam estrutura de m?dio alcance. Algumas ligas da fam?lia Al-Cu-Fe apresentam fases quasicristalinas quando rapidamente solidificadas. Para obter-se esta liga, foram fundidos lingotes da fam?lia Al65Cu35-xFex com x=6 (at?mico), inicialmente em um molde padr?o com solidifica??o em estado de equil?brio. Para proporcionar amostras com taxas de resfriamento variadas, a liga foi vazada em um molde escalonado, contendo seis cavidades diferentes, resultando em amostras solidificadas fora do estado de equil?brio (solidifica??o r?pida). Para an?lise das curvas de resfriamento utilizou- se a t?cnica CACC-TA, com taxas de resfriamento variando entre 170 e 540?C/s, que foram obtidas por meio de dT/dt. An?lises por microscopia ?ptica, microscopia eletr?nica de varredura (MEV), espectrometria por energia dispersiva (EDS), mostram microestrutura com dendritas facetadas, forma??es interdendr?ticas lamelares e precipitados pentagonais (IQC). A microdureza Vickers variou entre 417 HV e 736 HV (4,09 e 7,22 GPa) e a difra??o de raios X (DRX) comprovou por meio de difratogramas caracter?sticos a forma??o de fase quasicristalina icosa?drica.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / The structural and thermal decomposition properties of Mg-Fe and Co-Cu-Fe hy- drotalcites (HT) have been studied through thermogravimetric analysis, X ray powder difraction (XRD), Fourier transform infrared spectroscopy and 57Fe MÃssbauer spec- troscopy. In the Mg-Fe system, the destruction of the layered structure took place at about 300 oC. The broad peaks observed in the X ray difractograms suggests that the resultant oxides constitute a solid solution. For samples treated at temperatures higher than 500 oC the formation of the MgO and MgFe2O4 formation of the MgO and MgFe2O4 spinel phases is observed. 57Fe MÃssbauer spectroscopy was employed to monitor the Fe chemical environment for the samples annealed at diferent temperatures (100-900 oC). In situ XRD experiments revealed that the HTs start an interlayer contraction at about 180 oC. This phenomenon is identified as being due to a grafting process for which the interlamellar anions attach to the layers through a covalent bond. The reconstruction of the Mg-Fe HTs was also investigated and its eficiency depends on the thermal anneal- ing temperature and on the Mg/Fe ratio. The structure of the reconstructed samples was found to be exactly the same as the parent structure. The in situ 57Fe MÃssbauer experiments were performed in the 100-500 oC temperature range confirm an increasing structural disorder in this temperature range. The quadrupolar splitting indicates that the maximum disorder occurs at 300 oC. Regarding the Co-Cu-Fe ternary system we have observed that due to the strong Jahn-Teller effect the Cu-Fe layered system is stabilized only in the presence of Co2+. At low Co2+ contents, additional phases are segregated in the solids. X ray patterns diffraction show the presence of Cu(OH)2 and CuO. The decomposition process was investigated by in situ X ray, in situ MÃssbauer and FTIR experiments. By increasing the temperature from 25 oC up to 180 oC we observed that the structural disorder increases. This effect has been likely attributed to the Co2+ to Co3+ oxidation since thermal decomposition was carried out under static air atmosphere. Part of the Co3+ cations could migrate to the interlayer region, thus forming a metastable compound that still has a layered structure. Collapse of the layered structure was ob- served at about 200 oC. By further increasing the temperature the system becomes more crystalline and the formation of Co3O4 is observed in the X ray patterns. In Cu-rich HT, some of the carbonate anions are released at temperatures higher than 550 oC and this phenomenon is attributed to the formation of a carbonate-rich phase. The specific surface area data present its highest values in the temperature range where the collapse of the layered structure takes place. / As propriedades estruturais e de decomposiÃÃo tÃrmica das hidrotalcitas Mg-Fe e Co-Cu-Fe foram estudadas atravÃs de espectroscopia MÃssbauer de 57Fe, anÃlise termo- gravimÃtrica, difraÃÃo de raios X, e espectroscopia de absorÃÃo no infravermelho (FTIR). No sistema Mg-Fe a destruiÃÃo da estrutura lamelar ocorre em torno de 300 oC. O alargamento dos picos de difraÃÃo de raios X observados nos difratogramas sugerem que os Ãxidos resultantes constituem uma soluÃÃo sÃlida. Para as amostras tratadas em temperaturas maiores do que 500 oC a formaÃÃo de fases do tipo MgO e MgFe2O4 à observada. A espectroscopia MÃssbauer de 57Fe foi empregada para monitorar o ambiente quÃmico do Fe na faixa 100-900 oC de temperatura. As medidas in situ de difraÃÃo de raios X revelam que em 180 oC inicia-se uma contraÃÃo interlamelar. Este fenÃmeno à atribuÃdo ao processo de âgrafting" no qual os Ãnions interlamelares ligam-se nas camadas atravÃs de uma ligaÃÃo covalente. A reconstruÃÃo estrutural da hidrotalcita Mg-Fe tambÃm foi investigada. A eficiÃncia da reconstruÃÃo estrutural depende da temperatura de tratamento e da razÃo molar Mg/Fe. A estrutura das amostras reconstruÃdas sÃo as mesmas da amostra inicial. As medidas in situ de espectroscopia MÃssbauer de 57Fe foram realizadas na faixa 100-500 oC confirmaram uma desordem estrutural crescente nesta regiÃo de temperaturas. Os valores do desdobramento quadrupolar indicam que o mÃximo de desordem ocorre em 300 oC. Com relaÃÃo ao sistema ternÃrio Co-Cu-Fe observamos que devido ao efeito Jahn-Teller o sistema Cu-Fe somente à estabilizado na presenÃa de Co2+. Para baixas concentraÃÃes Co2+ fases adicionais segregadas sÃo observadas nos sÃlidos. Os padrÃes de difraÃÃo de raios X indicam a presenÃa de Cu(OH)2 e CuO. O processo de decomposiÃÃo tÃrmica foi investigado atravÃs de difraÃÃo de raios X, espectroscopia MÃssbauer de 57Fe in situ e de espectroscopia de absorÃÃo no infravermelho (FTIR). Aumentando a temperatura de tratamento tÃrmico das amostras de 25 oC a 180 oC observamos um aumento da desordem estrutural. Este efeito tem sido atribuÃdo a oxidaÃÃo Co2+ para Co3+ uma vez que a decomposiÃÃo foi realizada ao ar. Parte dos cÃtions Co3+ migram para a regiÃo interlamelar formando um composto metastÃvel que ainda possui uma estrutura lamelar. O colapso da estrutura lamelar à observado a 300 oC. Com o aumento posterior da temperatura o sistema torna-se mais cristalino e a formaÃÃo de Co3O4 à observada atravÃs do ensaio de raios X. Nas hidrotalcitas com maior teor de Cu, alguns dos Ãnions carbonato sÃo liberados somente acima de 550 oC sendo este fenÃmeno atribuÃdo a formaÃÃo de uma fase rica em carbonato. Os valores de Ãrea superficial especÃfica apresentam um mÃximo na faixa de temperatura onde ocorre o colapso da estrutura lamelar.

Dans l'ouest de l'Europe, une grande importance est accordée à la composante sol dans l'élaboration des vins. La nutrition minérale est la principale voie par laquelle le sol peut avoir une influence sur la vigne et par conséquent sur le vin qui en est issu. Dès lors, ce travail de thèse appréhende la question plus large des transferts élémentaires entre le sol et la plante à travers de l'utilisation d'outils géochimiques en milieu viticole. Une combinaison de techniques impliquant des indicateurs classiques tels que les rapports élémentaires ou des bilans de masses ainsi que des traceurs plus innovants comme les rapports isotopiques du Cu et la résonance paramagnétique électronique (RPE) est utilisée. Dans un premier temps, l'influence du sol sur la composition élémentaire du vin a été étudiée dans plus que 200 vins provenant d'Allemagne, d'Espagne, de France, et d'Italie. A cette échelle, le type de sol (classé comme calcaire ou non-calcaire) et les conditions météorologiques apparaissent comme des critères discriminants. Par la suite, deux parcelles viticoles de Soave (Italie) aux sols contrastés ont été étudiées afin de d´déterminer l'influence du type du sol sur les vignes. Même si les sols présentent des propriétés pédologiques différentes, une pédogénèse complexe a induit des propriétés géochimiques similaires. Dans les vignes, les traceurs élémentaires et biochimiques montrent que la variabilité inter-annuelle et inter-individuelle est plus grande que la différence liée au sol lui-même. Néanmoins, il est possible de déterminer quel est le sol considéré par l'étude des rapports isotopiques du Sr. Parmi tous les nutriments et éléments toxiques généralement étudiés pour leur mobilité dans les sols, le cuivre a été suivi dans la dernière partie de cette thèse, essentiellement du fait de son épandage toujours massif comme fongicide en viticulture. En effet, les pesticides cupriques comme la bouillie bordelaise sont utilisés depuis environ 150 ans en viticulture. Le Cu s'accumule d`es lors dans les sols et les conséquences ´ecotoxicologiques en font un sujet de plus en plus sensible. Parmi les pesticides analysés dans notre étude, les rapports isotopiques du Cu varient autant entre les différents fongicides que dans les sols étudiés dans la littérature, rendant ainsi impossible l'utilisation de ces isotopes comme traceurs d'origine du Cu dans les sols. [...] / In western Europe, soil is of primordial importance for wine making. Soil qualities are often discussed and an influence on wine flavor is frequently inferred. However, evidence for a role of soil chemistry on wine composition and taste is scarce, but mineral nutrition of grapevine plants is one possible way of influence. This thesis approaches the complex question of elemental cycling between soil and plant through the use of geochemical tracers in vineyard environments. A combination of traditional tracers such as elemental ratios and mass balances as well as innovative tools such as Cu isotope analysis and electron paramagnetic resonance (EPR) are used on different observation scales. The influence of soil type on wine elemental composition was investigated using over 200 wine samples from France, Germany, Italy and Spain. Results of chemical analysis were then statistically linked to environmental conditions. At this scale, elemental contents of wine vary depending on soil type (calcareous or not), meteorological conditions, and wine making practice. To determine which soil properties can influence the chemical composition of grapevine plants, two vineyard plots on contrasted soils in Soave (Italy) were examined. Soil forming mechanisms were studied along two catenas and subsequently linked to elemental composition of grapevine plants and biochemical markers of plant health. Even though soil morphology was different, complex soil forming processes led to similar geochemical properties of soils. Differences in plant chemical compositions between soil types are small compared to inter-individual and inter-annual variability. However the use of Sr isotopic ratios allows the determination of the pedological origin of plants. In a next step, the fate of Cu pesticides in vineyard soils was studied. Cu-based pesticides have been used for almost 150 years in European vineyards and Cu accumulates in soils, so that the fate of Cu and its ecotoxicological implications are of growing importance. Therefore, Cu mobility in vineyard soils and transfer to grapevine plants were investigated using stable Cu-isotope ratios and EPR-measurements. Isotope ratios of Cu-based fungicides vary largely between products, covering Cu isotope ratios in soils reported in literature and thus making source tracing impossible. However, Cu isotope ratios are useful for tracing biogeochemical mechanisms of Cu transport in soils. The vertical transport of Cu in different soil types was investigated in the Soave vineyard using a combination of mass balance calculations, kinetic extractions and δ65Cu-isotope ratios. Results suggest that Cu can be transported to depth even in carbonated environments. Besides it is shown that heavy organic-bound Cu is lost from carbonated soil columns likely caused by dissolution of Cu carbonates by organic matter. [...]

AA6061 Al alloys modified with addition of Mn, Cr and Cu were homogenized at temperatures between 350 ºC and 550 ºC after casting. STEM experiments revealed that the formation of α-Al(MnFeCr)Si dispersoids during homogenization were strongly affected by various factors such as heating rate, concentration of Mn, low temperature pre-nucleation treatment and homogenization temperature. Through analysis of the STEM results using an image software Image-Pro, the size distributions and number densities of the dispersoids formed during different annealing treatments were quantitatively measured. It was revealed that increasing the heating rate or homogenization temperature led to a reduction of the number density and an increase in size of the dispersoids. The number density of dispersoids could be markedly increased through a low temperature pre-nucleation treatment. A higher Mn level resulted in the larger number density, equivalent size and length/width ratio of the dispersoids in the alloy. Upsetting tests on two of these Mn and Cr-containing AA6061 (Al-Mg-Si-Cu) Al alloys with distinctive Mn contents were carried out at a speed of 15 mm s-1 under upsetting temperature of 450 ºC after casting and subsequent homogenization heat treatment using a 300-Tone hydraulic press. STEM experiments revealed that the finely distributed α-Al(MnFeCr)Si dispersoids formed during homogenization showed a strong pinning effect on dislocations and grain boundaries, which could effectively inhibit recovery and recrystallization during hot deformation in the two alloys. The fractions of recrystallization after hot deformation and following solution heat treatment were measured in the two alloys with EBSD. It was found that the recrystallization fractions of the two alloys were less than 30%. This implied that the finely distributed α-dispersoids were rather stable against coarsening and they stabilized the microstructure by inhibiting recovery and recrystallization by pinning dislocations during deformation and annealing at elevated temperatures. By increasing the content of Mn, the effect of retardation on recrystallization were further enhanced due to the formation of higher number density of the dispersoids. STEM and 3-D atom probe tomography experiments revealed that α-Al(MnFeCr)Si dispersoids were formed upon dissolution of lathe-shaped Q-AlMgSiCu phase during homogenization of the modified AA6061 Al alloy. It was, for the first time, observed that Mn segregated at the Q-phase/matrix interfaces in Mn-rich regions in the early stage of homogenization, triggering the transformation of Q-phase into strings of Mn-rich dispersoids afterwards. Meanwhile, in Mn-depleted regions the Q-phase remained unchanged without segregation of Mn at the Q-phase/matrix interfaces. Upon completion of α-phase transformation, the atomic ratio of Mn and Si was found to be 1:1 in the α-phase. The strengthening mechanisms in the alloy were also quantitatively interpreted, based on the measurements of chemical compositions, dispersoids density and size, alloy hardness and resistivity as a function of the annealing temperature. This study clarified the previous confusion about the formation mechanism of α-dispersoids in 6xxx series Al alloys. Four-point bend fatigue tests on two modified AA6061 Al alloys with different Si contents (0.80 and 1.24 wt%, respectively) were carried out at room temperature, f = 20 Hz, R = 0.1, and in ambient air. The stress-number of cycles to failure (S-N) curves of the two alloys were characterized. The alloys were solution heat treated, quenched in water, and peak aged. Optical microscopy and scanning electron microscopy were employed to capture a detailed view of the fatigue crack initiation behaviors of the alloys. Fatigue limits of the two alloys with the Si contents of 0.80 and 1.24 wt% were measured to be approximately 224 and 283.5 MPa, respectively. The number of cracks found on surface was very small (1~3) and barely increased with the applied stress, when the applied stress was below the yield strength. However, it was increased sharply with increase of the applied stress to approximately the ultimate tensile strength. Fatigue crack initiation was predominantly associated with the micro-pores in the alloys. SEM examination of the fracture surfaces of the fatigued samples showed that the crack initiation pores were always aspheric in shape with the larger dimension in depth from the sample surface. These tunnel-shaped pores might be formed along grain boundaries during solidification or due to overheating of the Si-containing particles during homogenization. A quantitative model, which took into account the 3-D effects of pores on the local stress/strain fields in surface, was applied to quantification of the fatigue crack population in a modified AA6061 Al alloy under cyclic loading. The pores used in the model were spherical in shape, for simplicity, with the same size of 7 μm in diameter. The total volume fraction of the pores in the model were same as the area fraction of the pores measured experimentally in the alloy. The stress and strain fields around each pore near the randomly selected surface in a reconstructed digital pore structure of the alloy were quantified as a function of pore position in depth from the surface using a 3-D finite element model under different stress levels. A micro-scale Manson-Coffin equation was used to estimate the fatigue crack incubation life at each of the pores in the surface and subsurface. The population of fatigue cracks initiated at an applied cyclic loading could be subsequently quantified. The simulated results were consistent with those experimentally measured, when the applied maximum cyclic stress was below the yield strength, but the model could not capture the sudden increase in crack population at UTS, as observed in the alloy. This discrepancy in crack population was likely to be due to the use of the spherical pores in the model, as these simplified pores could not show the effects of pore shape and their orientations on crack initiation at the pores near surface. Although it is presently very time-consuming to calculate the crack population as a function of pore size and shape in the alloy with the current model, it would still be desirable to incorporate the effects of shape and orientation of the tunnel-shaped pores into the model, in the future, in order to simulate the fatigue crack initiation more accurately in the alloy.

Cette thèse porte sur la synthèse de composés d'Au(III) et de Cu(III) ainsi que sur l'étude de leur stabilité et de leur réactivité vis-à-vis de substrats p. Une approche conjointe expérimentale et théorique a été exploitée afin d'accéder à des complexes capables d'induire des processus d'insertion migratoire. Le premier chapitre aborde de manière globale la chimie organométallique de l'or et du cuivre sur le plan bibliographique. L'importance du degré d'oxydation +III est mis en évidence par la description des principaux exemples ayant contribué à la compréhension des processus associés à l'accès et la réactivité des complexes d'Au(III) et de Cu(III). Le second chapitre traite de la synthèse de deux complexes p-arènes d'Au(III) par insertion migratoire d'oléfines dans la liaison Au-C(sp)2 d'un composé (P,C) cyclométallé. Les interactions entre les systèmes aromatiques et l'or ont été mises en évidence par RMN, DFT et DRX pour un des complexes. Sur la base de cette réactivité, un processus d'arylation directe de l'éthylène a été mis en évidence. Le chapitre trois a pour objet la mise au point d'une réaction d'hydroarylation intermoléculaire d'alcynes catalysée par des complexes de type [(P,C)Au(III)(OAcF)2]. Ces derniers se sont avérés très actifs et robustes en présence d'acide trifluoroacétique. La réaction a pu être généralisée à un large panel de substrats et une étude comparative, notamment avec des complexes (N,C) cyclométallés, a mis en évidence la supériorité des complexes (P,C) pour l'hydroarylation des alcynes. Le quatrième chapitre expose la stratégie envisagée pour le développer d'un processus d'oligomérisation de l'éthylène catalysé par le cuivre. Une approche prédictive basée sur les calculs DFT a permis de mettre en évidence des insertions migratoires plus aisées dans les liaisons Cu(III)-C que dans les Cu(I)-C. Deux stratégies d'accès aux complexes de Cu(III) par addition oxydante de liaisons C-I sur des précurseurs de Cu(I) ont été évaluées théoriquement. Les calculs les plus favorables ont orienté le choix des modèles de ligands envisagés dans les chapitres cinq et six. Le cinquième chapitre aborde l'étude expérimentale associée à la première stratégie d'accès au Cu(III) : l'addition oxydante intramoléculaire dirigée par des ligands naphthylphosphine et naphthylamine peri-iodées. [...] / The present work deals with the synthesis of Au(III) and Cu(III) compounds and the study of their stability and reactivity toward p substrates. An experimental and theoretical approach has been used in order to access complexes capable of undergoing migratory insertion processes. The first chapter delivers a bibliographic overview of the organometallic chemistry of gold and copper. The importance of the high oxidation state +III is highlighted by the description of important examples having contributed to the understanding of processes associated to the access and reactivity of Au(III) and Cu(III) complexes. The second chapter describes the synthesis of two p-arene Au(III) complexes by migratory insertion of olefins in the Au-C(sp)2 bond of a (P,C) cyclometallated complex. Interactions between the metallic center and the aromatic systems have been characterized by NMR, DFT and XRD for one of the complexes. Based on this insertion reactivity, a process of direct arylation of ethylene has been evidenced. The third chapter concerns the development of an intermolecular hydroarylation of alkynes process, catalyzed by [(P,C)Au(III)(OAcF)2] complexes. These have shown great activity and robustness in presence of trifluoroacetic acid. The reaction has been generalized to a broad substrate scope and a comparative study has been carried on, especially with (N,C) cyclometallated complexes, showing the superiority of (P,C) complexes for the hydroarylation of alkynes. The fourth chapter presents the envisioned strategy to develop a copper-catalyzed oligomerization of ethylene process. A predictive approach based on DFT calculations permitted to evidence easier migratory insertions in the Cu(III)-C bond than in the Cu(I)-C bond. Two strategies for the access to Cu(III) species have been theoretically evaluated. The most favourable calculations have oriented the choice of ligand models used in chapters five and six. The fifth chapter deals with the experimental study related to the first strategy of access to Cu(III) species: the directed intramolecular oxidative addition by peri-iodo napthylphosphine and naphthylamine ligands. [...]

alpha-Interferon (alpha IFN) ist derzeit die Grundlage jeder Behandlung der chronischen Hepatitis C. Zu den unerwünschten Effekten von alpha-IFN gehört die Entwicklung psychiatrischer Nebenwirkungen, die sich häufig als Depressivität äussern. Deren Häufigkeit, Schweregrad und Behandlungsbedarf wurden jedoch bisher nur unzureichend erforscht. 66 Patienten mit chronischer Hepatitis C wurden in einer Pilotstudie mit alpha-IFN als Monotherapie (3x3 MU/ Woche) oder in Kombination mit Ribavirin (1000-1200 mg/ Woche) behandelt. Sämtliche Patienten wurden vor, während und nach der Therapie hinsichtlich ihrer Depressivität beurteilt. Dies geschah sowohl im persönlichen Gespräch als auch mit Hilfe der Selbstbeurteilungsinstrumente ADS (Allgemeine Depressions Skala) und BDI (Beck Depressions Inventar). Die Ausgangsdepressivität der Hepatitispatienten entsprach dem gesunden Eichkollektiv. Im Gesamtdurchschnitt stieg die Depressivität innerhalb der ersten drei Behandlungsmonate um 5,15 (+/-8,94) Punkte auf der ADS und um 3,85 (+/-6,94) Punkte im BDI an. Weniger als ein Drittel der Patienten erlebte keine Zunahme der Depressivität. Patienten, die vor Therapiebeginn eine geringe Depressivität aufwiesen, beschrieben eine stärkere Zunahme depressiver Symptome als Patienten, die initial als depressiv beurteilt wurden. Letztere blieben während des Therapieverlaufs jedoch weiterhin depressiver als die anfangs nicht-depressiven Patienten. Vier Patienten wurden wegen schwerster depressiver Nebenwirkungen stationär psychiatrisch behandelt. Es wurde kein signifikanter Zusammenhang zwischen Ausgangsdepressivität und Behandlungserfolg festgestellt. Um stark gefährdete Patienten frühzeitig zu erkennen, wird vorgeschlagen, sowohl ADS als auch BDI vor und während der Therapie zu verwenden. Anhand eines ADS-Grenzwertes von > 17 vor und >= 30 während der Behandlung konnten 75% derjenigen Patienten, die im Verlauf der Therapie mit alpha-IFN schwerste depressive Symptome entwickelten, identifiziert werden. / Interferon-alpha (alpha-IFN) is presently the mainstay of the treatment of chronic hepatitis C. Side effects include a range of psychiatric symptoms, most frequently the development of depressive symptoms. Their incidence, severity and necessity for therapeutic intervention has not yet been sufficiently studied. 66 patients with chronic hepatitis C were enrolled in a pilot study and treated with either alpha-IFN alone (3x3 MU/ week) or in combination with Ribavirin (1000-1200 mg/ week). All patients went through repeated evaluations concerning their depressive symptoms before, during, and after treatment. Apart from individual interviews with the psychosomatic staff, the psychometric instruments used were the ADS (Allgemeine Depressions Skala, the German version of the Center for Epidemiological Studies Depression Scale, CES-D) and the BDI (Beck Depression Inventory). The initial depression score of the hepatitis C patients was comparable to that of a healthy population. On average, depression scores increased by 5,15 points (+/-8,94) on the ADS and 3,85 points (+/-6,94) on the BDI during the first 3 months of treatment. Less than a third of all patients did not show an increase of depressive symptoms. Patients with an initially low depression score experienced a greater increase of depressive symptoms than patients initially diagnosed as depressive. Nevertheless, the latter patients remained more depressive throughout the study period. Four patients developed severe depressions that necessitated admission to a psychiatric clinic. There was no significant correlation between the initial depression score and the treatment response. In order to recognize those patients at high risk for the development of severe depressions at an early stage, the author proposes the use of ADS and BDI both before and during treatment with alpha-IFN. Using a cut-off score of more than 17 points on the ADS before, and >=30 points during treatment, 75% of all patients developing severe depressions during treatment with alpha-IFN could be identified.