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[EN] In case of a severe accident in a NPP fission products are released from the degraded fuel and may reach the environment if their confinement is lost and/or bypassed. Given the high radio-toxic nature of nuclear aerosols for environment and population, their unrestricted release should be absolutely avoided. One particular situation is the core meltdown sequence with steam generator tube rupture (SGTR). The containment bypass turns this sequence into an indispensable scenario to model when assessing PWR risk. As a result, a significant database on the aerosol behavior in the secondary side of the steam generator (SG) has been developed within the international projects EU-SGTR, ARTIST and ARTIST-2. The role played by the break stage is particularly significant since it might be responsible for a good fraction of the total mass retained and for the shift of the particle size distribution towards smaller diameters. This awoke the interest in the effect of variables such as the particle nature, the breach type (size and shape) and the tubes vibration on the particle retention within the breach stage of a dry steam generator. Those aspects have been experimentally investigated in the first part of this thesis. Two experimental campaigns, CAAT2 and SET, were conducted in order to explore the potential influence of the particle nature on their retention. Moreover, the effect of the breach size and shape has been investigated in the CAAT2 campaign while the SET experiments were devoted to the tube vibration characterization and the effect of the vibration on the particle retention. The tests conducted highlighted several key insights: the strong effect of particle nature in the secondary side capability to scrub the particle-laden gas; the confirmation of the high retention efficiency when using compact particles and the significant one when using agglomerates; the similarities between guillotine and fish-mouth breaches in terms of efficiency, but their noticeable different deposition patterns; and the secondary effect of the breach size. Finally, the tube vibration is not as significant as the particle nature effect on the net deposition. The second part of the thesis is focused on the fraction of particles susceptible of leaving the containment in case of a severe accident regardless of the SGTR sequence. Accidents like Fukushima highlighted the importance of relying on efficient mitigation systems capable of reducing any release to the environment as much as possible. Although many reactors worldwide had installed filtered containment venting systems (FCVS) the interest in FCVS and even other mitigation systems has become of outstanding importance in nuclear safety. This is the frame of the PASSAM project in which an experimental sound database is being built to explore potential enhancement of existing source term mitigation devices and demonstrate the ability of innovative systems to achieve even larger source term attenuation. As a matter of fact, particle agglomeration processes via the propagation of acoustic vibrations through a gas could be applied for a better decontamination. High-intensity acoustic fields applied to an aerosol induce interaction effects among suspended particles, giving rise to successive collisions and agglomerations, resulting in larger particles that can be more easily removed or precipitated. The mitigative system acoustic agglomerator was built-up and tested in the AAA experimental campaign. The tests were conducted under a constant ultrasonic field with aerosols of different nature and size with different gas mass flow rates. The results pointed out two main insights: the small acoustic-agglomeration effect and the key effect of the gas mass flow rate and the aggregation state of the former particles in the agglomeration process. This research is the first approximation on the application of the ultrasonic chamber as an innovative system for the source term mitigation. / [ES] Durante un accidente severo en una central nuclear los productos de fisión liberados como consecuencia de la degradación del combustible podrían llegar a la atmósfera si se pierde la hermeticidad de la contención o si encuentran vías alternativas (bypass) para salir. Dada la radio-toxicidad del término fuente, las centrales nucleares deben contar con medios y medidas técnicas de seguridad para contener estos productos. En un reactor PWR, un caso particular de secuencia accidental donde los productos de fisión tienen acceso directo a la atmósfera, es aquella en el que además de la fusión de núcleo existe rotura de tubos del generador de vapor (secuencia SGTR). En este caso, es de vital importancia la evaluación del riesgo del suceso, objetivo de los proyectos internacionales EU-SGTR, ARTIST y ARTIST-2. Particularmente significativa es la "etapa de rotura" (break stage) del generador de vapor (SG), que es responsable de la retención de una fracción importante de partículas y de la evolución de su distribución a tamaños más pequeños. Estos motivos despertaron el interés hacia la propia retención de las partículas sobre los tubos y el efecto de variables como la naturaleza de la partícula, el tipo de rotura y la vibración de tubos sobre la retención en la etapa de rotura en condiciones secas; aspectos en los que se centra la primera parte de esta tesis. Con el objetivo de estudiar las cuestiones señaladas se han llevado a cabo dos campañas experimentales, CAAT2 y SET, con materiales enmarcados en el posible espectro de los aerosoles nucleares. La primera de ellas se centró en explorar la influencia potencial de la naturaleza de la partícula y el efecto del tipo de rotura de los tubos (forma y tamaño) sobre la retención de aerosoles. La segunda concierne la caracterización de la vibración de los tubos y el estudio de su efecto en la eficiencia de retención de partículas. Las pruebas realizadas resaltan varias ideas clave: el fuerte efecto de la naturaleza de la partícula sobre la retención en el lado secundario del SG; la alta eficiencia de retención cuando las partículas son compactas y la significativa retención cuando están aglomeradas; las pequeñas diferencias en eficiencia neta entre distintos tipos de rotura (guillotina vs. boca de pez) que resultan notables sobre los patrones de deposición, y el efecto secundario del tamaño de la rotura. Finalmente los resultados revelaron que frente a la naturaleza de la partícula, la vibración de tubos juega un papel secundario en la eficiencia de la retención. La segunda parte de este trabajo se centra en la fracción de partículas que es susceptible de alcanzar la contención en caso de accidente severo. Accidentes como el de Fukushima ponen de manifiesto la necesidad de tecnologías capaces de evitar las indeseadas consecuencias de la emisión de material radiactivo al medio ambiente. Esta es la dirección de investigación del proyecto PASSAM (7º Programa Marco de EURATOM) que está construyendo una base de datos experimental para el desarrollo de sistemas innovadores y la mejora de los sistemas de venteo filtrado de la contención que ya existen. Entre estos sistemas se encuentran las cámaras de ultrasonidos donde las ondas acústicas facilitan la aglomeración y el crecimiento de partículas, resultando sistemas potenciales para su mitigación. La campaña experimental AAA ha constituido una primera aproximación para la aplicación de las cámaras de ultrasonidos como sistemas innovadores para la mitigación del término fuente en la contención. El sistema de mitigación de aglomeración acústica (MSAA) se construyó y ha sido probado durante los experimentos AAA. Los resultados obtenidos ponen de manifiesto el leve efecto del campo acústico sobre el crecimiento de las partículas. Además, tanto el flujo másico de gas portador como la naturaleza de la partícula son claves en el proceso de aglomeración. / [CA] En cas d'accident sever d'una central nuclear els productes de fissió resultants del combustible degradat podrien assolir l'atmosfera si es perd la hermeticitat de la contenció o si troben un camí alternatiu que l'evitin. Donada la naturalesa radio-tòxica dels aerosols nuclears ha d'evitar-se per tots els mitjans que surtin a l'exterior. En un reactor PWR, un cas particular d'accident és en el qual a més de la fusió de nucli existeix trencament de tubs del generador de vapor. En aquest cas, l'alliberament de material radioactiu cap al medi ambient fa que l'escenari sigui indispensable de modelar en l'avaluació del risc d'aquest reactor. Aquesta és la raó dels projectes internacionals EU-SGTR, ARTIST i ARTIST-2, gràcies als quals s'ha construït una extensa base de dades sobre el comportament dels aerosols en el circuit secundari del generador de vapor (Steam Generator, SG). Particularment significativa és l'etapa de trencament, que és responsable de la retenció d'una fracció important de partícules i de modificar la seva distribució cap a les mides més petites. Aquests motius van despertar l'interès vers l'efecte de variables com la naturalesa de la partícula, el tipus de trencament i la vibració de tubs sobre la retenció de partícules sobre els tubs en condicions seques a l'etapa de trencament del SG. Aquests són els aspectes en els quals es centra la primera part d'aquesta tesi. Dues campanyes experimentals, CAAT2 i SET, s'han dut a terme amb diferents materials, tots ells emmarcats dins del possible rang dels aerosols nuclears. La primera d'elles es va centrar a explorar la influència potencial de la naturalesa de la partícula i l'efecte del tipus de trencament (forma i grandària) sobre la retenció d'aerosols en els tubs. La segona va seguir per la caracterització en termes de vibració dels tubs i el seu efecte en l'eficiència de retenció de partícules. Les proves realitzades ressalten diverses idees clau: el fort efecte de la naturalesa de la partícula sobre la retenció en el costat secundari del SG; l'alta eficiència de retenció quan les partícules són compactes i la també significativa retenció quan són aglomerats; les petites diferències en eficiència entre diferents tipus de trencament (guillotina vs. boca de peix), però notables sobre els patrons de deposició, i l'efecte secundari de la grandària de trencament. Finalment van revelar que enfront de la naturalesa de la partícula, la vibració de tubs juga un paper secundari en l'eficiència de retenció del feix de tubs. La segona part d'aquesta tesi es centra en la fracció de partícules que en cas d'accident sever, amb o sense seqüència SGTR, és susceptible d'aconseguir la contenció. Accidents com Fukushima posen de manifest la necessitat de tecnologia capaç de cobrir les indesitjades conseqüències de l'emissió de material radioactiu al medi. Aquesta és la raó del projecte PASSAM (7é Programa Marc d'EURATOM) que està construint una base de dades experimental per al desenvolupament de sistemes innovadors i millorar els sistemes de venteig filtrat que ja existeixen de la contenció. Les ones d'ultrasons faciliten l'aglomeració de partícules i resulten sistemes potencials per a la seva mitigació. S'ha realitzat una primera aproximació per a l'aplicació de les càmeres d'ultrasons com a sistemes innovadors per a la mitigació del terme font en la contenció. El sistema de mitigació d'aglomeració acústica (MSAA) es va construir i ha estat provat durant la campanya experimental AAA. Els experiments duts a terme en la planta PECA-MSAA del LASS. Els resultats obtinguts posen de manifest dues idees: el sistema MSAA és efectiu en la reducció de la massa de partícules i tant el flux màssic de gas portador com la naturalesa de la partícula són claus en l'eficiència de retenció del sistema. / Delgado Tardáguila, R. (2016). Experimental investigations on nuclear aerosols in a severe accident [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/63243

Printed circuit board manufacturing involves subtractive copper (Cu) etching where fine features are developed with a specific spatial resolution and etch profile of the Cu interconnects. A UV-Vis ATR metrology, to characterize the chemical transitions, has been developed to monitor the state of the bath by an in-situ measurement. This method provides a direct correlation of the Cu etch bath and was able to predict a 35% lower etch rate that was not predicted by the three current monitoring methods (ORP, specific gravity, and conductivity). Application of this UV-Vis ATR probe confirmed that two industrial etch baths, in identical working conditions, confirmed a difference in Cu2+ concentration by the difference of the near IR 860nm peak. The scope of this probe allowed chemically specific monitoring of the Cu etch bath to achieve a successful regeneration for repeated use. Interlayer dielectrics (ILDs) provide mechanical and electrical stability to the 3D electrical interconnects found in IC devices. It is particularly important that the structural support is created properly in the multilayered architecture to prevent the electrical cross signaling in short range distances. A combined multiple internal reflection and transmission FTIR has been employed for the characterization of silicon oxycarbonitride (SiOCN) films. These dielectric low-k films incorporate various functional groups bonded to silicon and require chemical bonding insight in the transformation and curing process. Distinct SiOx bonding patterns were differentiated, and the structure of the films can be predicted based on the amount of Si network and caged species. Further optimization of the FTIR analysis must minimize interference from moisture that can impact the judgement of peak heights. To accommodate this, a high-quality glove box was designed for dry air feedthrough to achieve a 95% moisture reduction during analysis, where less than 0.1 mAbs of moisture is detected in the spectra (without additional correction). The glove box allows for the rapid analysis of multiple sample throughput to outpace alternative characterization methods while retaining low spectral noise and a dry environment for 24/7 analysis. There is a great need to identify new catalysts that are suitable for tackling current economic demands, one of which is the nitrogen reduction reaction (NRR). The development of the surface enhanced infrared absorption spectroscopy (SEIRAS) has been applied to characterize the NRR mechanisms on the vanadium oxynitride electrocatalyst. Electrochemical measurements demonstrate NRR activity that is up to three times greater in the presence of N2 than the control Ar. FTIR operando suggests that a considerable number of intermediates were formed and continued to increase in absorbing value under an applied potential of -0.8 V vs Ag/AgCl. XPS results of the post-NRR film suggest a restricting of the film where vanadium oxynitride films are prone to instabilities under the possible MvK mechanism. After 90 minutes of NRR, the NH3 generated was approximately 0.01 ppm was calculated for through the salicylate colorimetric method. On-going efforts are focusing on optimizing the vanadium oxynitride film by the tuning of the oxynitride ratios and crystalline properties to promote the formation of V≡N: during the nitrogen reduction reaction.

Das Krankheitsbild der Adipositas hat sich weltweit zu einem relevanten Gesundheitsproblem entwickelt. Die bariatrische Chirurgie wird zunehmend als wirkungsvolle Behandlung bei schwer ausgeprägter Adipositas eingesetzt. Jedoch ist über die Rolle psychologischer Variablen im bariatrischen Behandlungsverlauf noch wenig bekannt. Die vorliegende Dissertation untersucht Einfluss und Veränderung patientenberichteter Gesundheitsmerkmale in der chirurgischen Adipositastherapie. Dazu werden in einer naturalistischen Beobachtungsstudie Patienten mit schwerer Adipositas vor und im Durchschnitt zwei Jahre nach einer bariatrischen Operation (OP) befragt. Ziele der Arbeit sind 1) die Charakterisierung adipöser Patienten vor OP hinsichtlich bio-psycho-sozialer Variablen; 2) die Identifikation möglicher Einflussvariablen auf den gewichtsbezogenen Behandlungserfolg nach OP; 3) die Untersuchung von Auswirkungen der OP auf das Essverhalten; und 4) die Analyse von Veränderungen in der essstörungsbezogenen Psychopathologie und in der gesundheitsbezogenen Lebensqualität nach OP. Die Ergebnisse der bariatrischen Patienten werden im Vergleich zu denen konservativ behandelter Patienten betrachtet. Die Ergebnisse zeigen, dass Patienten mit bariatrischem Behandlungswunsch eine somatisch und psychisch belastete Patientengruppe darstellen. Die bariatrische OP führt im zweiten postoperativen Jahr zu einer nachhaltigen und klinisch bedeutsamen Gewichtsreduktion. Der präoperative Body-Maß-Index, das Bildungsniveau und aktives Problembewältigungsverhalten sind mit dem Gewichtsverlust nach OP assoziiert. Im Vergleich zur konservativen Behandlung berichten die Patienten, die sich der OP unterziehen, über stärker ausgeprägte Verbesserungen in ihrem Essverhalten und eine Steigerung ihrer Lebensqualität. Auf Basis der Befunde wird ein routinemäßiges Monitoring der somatischen und psychischen Situation der Patienten nach bariatrischer OP empfohlen, um die gezeigten Behandlungserfolge optimal zu sichern. / Obesity has become a relevant global health problem. Bariatric surgery is an effective treatment for severe obesity. However, while the number of operations performed continues to increase, the role of psychological variables throughout the bariatric surgery pathway remains uncertain. The present dissertation investigates the patient-reported health status as it impacts and results from bariatric surgery. In a naturalistic observational study, patients with severe obesity are assessed before and, on average, two years after the surgical treatment. Main aims are 1) to characterize obese patients prior to bariatric surgery in terms of biological, psychological and socio-demographic variables; 2) to identify possible predictors for the postoperative weight-related treatment success after bariatric surgery; 3) to examine changes in eating behaviors; and 4) to analyze changes in eating-related psychopathology and in health-related quality of life (HRQoL). The outcomes of surgical patients are compared with those of conservatively treated patients for the same follow-up period. The findings show that bariatric surgery candidates represent a vulnerable patient group with high physical and psychological burden. In the second postoperative year after bariatric surgery, a sustainable and clinically meaningful weight reduction is achieved. The preoperative body mass index, education level and active coping behavior are associated with weight loss after surgery. Compared with conservative treatment, patients who undergo bariatric surgery report not only greater improvements in their eating behavior and eating-related psychopathology but also an increase in their HRQoL. Based on the results, the provision of a routine monitoring of the somatic and psychological situation of patients following bariatric surgery is recommended to secure longer-term treatment success.

In den Jahren 1992-1995 kamen ca. 35 Tausend bosnische Kriegsflüchtlinge nach Berlin und wurden vorübergehend geduldet. Nach Kriegsende 1995 sollten sie schnellstmöglich wieder zurückkehren. Traumatisierte und Ältere ohne Angehörige im Heimatland wurden weiterhin geduldet bis Bosnien-Herzegowina wieder aufgebaut ist. Doch der Wiederaufbau verlief schleppend. Mit dem Friedensvertrag von Dayton begannen nicht Frieden und Wiederaufbau, sondern die Konsolidierung der ethnischen Grenzen in demokratischen Strukturen. Deshalb sahen viele Flüchtlinge keine Möglichkeit in ihre Heimatorte zurückzukehren und versuchten ihre Rückkehr hinauszuschieben. Möglich war dies mithilfe der Attestierung einer kriegsbedingten Posttraumatischen Belastungsstörung und ihre psychotherapeutische Behandlung, die den Inhabenden und ihren Familienmitgliedern eine Aufenthaltsverlängerung ermöglichte und ab dem Jahr 2000 den Erhalt eines dauerhaften Aufenthaltstitels. Die Verbindung einer psychischen Krankheit und ihrer Psychotherapie mit einem Aufenthaltsrecht ist neu in der Geschichte des deutschen Ausländerrechts und obwohl Berliner Psychiater, Psychiaterinnen, Psychologinnen und Psychologen maßgeblich an der Schaffung der „Traumatisiertenregelung“ beteiligt waren, wurden ihre Atteste von der Berliner Verwaltung in Frage gestellt. In der Dissertation werden die Standpunkte der Flüchtlinge, Behandelnden und der Verwaltung dargelegt und ihre Interaktionen beschrieben.Die Rolle des Krankheitskonzeptes der Posttraumatischen Belastungsstörung wird als "boundary object" (Star/Griesemer 1989) untersucht. Der Schwerpunkt liegt auf den Lebenswelten und Taktiken der Flüchtlinge, sich in Berlin zurechtzufinden und Anerkennung und Verständnis für ihre Situation zu finden. Ihre Bedürfnisse wurden in einen psychotherapeutischen Bedarf übersetzt und damit den Berliner Psychotherapeutinnen und -therapeuten ein neues Betätigungs- und Professionalisierungfeld geboten, was kritisch hinterfragt wird. / From 1992 until 1995 about 35 thousand Bosnian war refugees fled to Berlin and were allowed to stay temporarily. After the end of the war in 1995 they were expected to leave as soon as possible. Traumatized persons and elderly without relatives in Bosnia had the possibility to prolong their visa until Bosnia is reconstructed. But the rebuilding process progressed only slowly. With the end of the war did not start the expected peace time and rebuilding but the consolidation of ethnic borders inside democratic structures. Therefore many refugees did not see a possibility to return to their property and tried to delay their return. This was possible with an medical statement certifying a war related posttraumatic stress disorder and their psychotherapeutic treatment. These medical statements ensured the extension of the visa for the concerned person and its family members. From 2000 onwards they could receive a permanent residence title. The connection of a mental illness and psychotherapy with residence entitlements is a novelty in the German aliens law. And despite the fact that psychiatrists and psychologists from Berlin were leading actors in the establishment of the „regularization of the traumatized“ their medical/psychological statements were impeached by the authorities. The dissertation describes the viewpoints of refugees, treating physicians and psychologists and the authorities and how they interact with each other. Additionally is the concept of posttraumatic stress disorder examined and discussed as „boundary object“ (Star/Griesemer 1989). An important aspect is the description of life worlds and tactics of the refugees to get along in Berlin, to gain respect and appreciation for their situation. Their needs were translated into a psychotherapeutic demand and this led to the invention of a new field of work and professionalization for psychotherapists in Berlin. This development is critically reflected.

Desenvolveu-se um método espectrofotométrico para determinação de íons Cu(II), Fe(II) e Fe(III) com o reagente cromogênico di-2-piridil cetona benzoilhidrazona (DPKBH), em condições estacionárias e em fluxo. Fez-se a caracterização estrutural e estequiométrica do complexo de Cu(II) com DPKBH usando-se técnicas espectroscópicas de infravermelho e massas, além de análise térmica e elementar. Estudou-se, ainda, a estequiometria dos complexos de Fe(II) e Fe(III) com DPKBH utilizando espectrometria de massas com ionização por electrospray. Desenvolveu-se, preliminarmente, um método espectrofotométrico para a determinação de íons Cu(II) com DPKBH e aplicou-se em amostras de aguardente. Posteriormente, adaptou-se para análise por injeção em fluxo, utilizando-se injetor comutador manual. Em seguida, desenvolveu-se em condições estacionárias um método espectrofotométrico para determinação de Fe(II) e Fe(III) e Cu(II) em uma mesma amostra, com o uso de agentes mascarantes. Fez-se também a adaptação do método para análise em fluxo empregando multicomutação e amostragem binária. Finalmente, determinou-se a concentração de íons Cu(II), Fe(II) e Fe(III) em amostras sintéticas e Cu(II) e ferro total em amostras de sedimento coletadas no reservatório de Guarapiranga. Os resultados obtidos foram comparados com o método de referência de ICP-OES, apresentando concordância para um nível de confiança de 95% da média. / A spectrophotometric method was developed to the determination of Cu(II), Fe(II) and Fe(III) with the chromogenic reagent di-2pyridyl ketone benzoylhydrazone (DPKBH) in stationary conditions as a flow injection process. The structural characterization and the stoichiometry of Cu(II)/DPKBH complex were achieved using infrared spectrometry, mass spectrometry, thermal and elementar analysis. Toe stoichiometry of the Fe(II) and Fe(III) complexes with DPKBH was studied by electrospray ionization mass spectrometry. The spectrophotometric method for the determination of Cu(II) with DPKBH was developed in stationary conditions and, after this, it was adapted to flow injection analysis, using a manual commutator. Subsequently, a spectrophotometric method was developed to determine Fe(II), Fe(III) and Cu(II) in the same sample, in stationary conditions, using masking reagents. This method was also adapted to flow injection analysis, using multicommutation and binary sampling. Finally, Cu(II), Fe(II) and Fe(III) were determined in sediments from Guarapiranga reservoir. The obtained results were compared with the ICP-OES standard methods, showing a good agreement into a 95% confidence level (t-test).

Desenvolveu-se um método espectrofotométrico para determinação de íons Cu(II), Fe(II) e Fe(III) com o reagente cromogênico di-2-piridil cetona benzoilhidrazona (DPKBH), em condições estacionárias e em fluxo. Fez-se a caracterização estrutural e estequiométrica do complexo de Cu(II) com DPKBH usando-se técnicas espectroscópicas de infravermelho e massas, além de análise térmica e elementar. Estudou-se, ainda, a estequiometria dos complexos de Fe(II) e Fe(III) com DPKBH utilizando espectrometria de massas com ionização por electrospray. Desenvolveu-se, preliminarmente, um método espectrofotométrico para a determinação de íons Cu(II) com DPKBH e aplicou-se em amostras de aguardente. Posteriormente, adaptou-se para análise por injeção em fluxo, utilizando-se injetor comutador manual. Em seguida, desenvolveu-se em condições estacionárias um método espectrofotométrico para determinação de Fe(II) e Fe(III) e Cu(II) em uma mesma amostra, com o uso de agentes mascarantes. Fez-se também a adaptação do método para análise em fluxo empregando multicomutação e amostragem binária. Finalmente, determinou-se a concentração de íons Cu(II), Fe(II) e Fe(III) em amostras sintéticas e Cu(II) e ferro total em amostras de sedimento coletadas no reservatório de Guarapiranga. Os resultados obtidos foram comparados com o método de referência de ICP-OES, apresentando concordância para um nível de confiança de 95% da média. / A spectrophotometric method was developed to the determination of Cu(II), Fe(II) and Fe(III) with the chromogenic reagent di-2pyridyl ketone benzoylhydrazone (DPKBH) in stationary conditions as a flow injection process. The structural characterization and the stoichiometry of Cu(II)/DPKBH complex were achieved using infrared spectrometry, mass spectrometry, thermal and elementar analysis. Toe stoichiometry of the Fe(II) and Fe(III) complexes with DPKBH was studied by electrospray ionization mass spectrometry. The spectrophotometric method for the determination of Cu(II) with DPKBH was developed in stationary conditions and, after this, it was adapted to flow injection analysis, using a manual commutator. Subsequently, a spectrophotometric method was developed to determine Fe(II), Fe(III) and Cu(II) in the same sample, in stationary conditions, using masking reagents. This method was also adapted to flow injection analysis, using multicommutation and binary sampling. Finally, Cu(II), Fe(II) and Fe(III) were determined in sediments from Guarapiranga reservoir. The obtained results were compared with the ICP-OES standard methods, showing a good agreement into a 95% confidence level (t-test).

Zahlreiche Studien belegen, dass Maillard-Reaktionsprodukte (MRP) in vivo einen Einfluss auf den physiologischen Metallionenhaushalt haben können. Da bisher noch keine Korrelation zwischen dem Entstehen von definierten MRP und einem erhöhten Metallionenbindungsvermögen ermittelt werden konnte, war es das Ziel dieser Arbeit, die Komplexbildungseigenschaften der ausgewählten MRP Nε-Carboxymethyllysin, Isomaltol und Maltosin sowie deren Strukturanaloga Maltol, Deferipron, Mimosin und Pyridosin mit den physiologisch relevanten Metallionen Cu(II), Zn(II), Fe(III), Al(III) und Mn(II) zu untersuchen. Dazu wurden die MRP Nε-Carboxymethyllysin und Maltosin sowie die parallel untersuchten Substanzen Pyridosin, Maltosin-3-benzylether, Nα-Hippuryl- und Nα-Acetylmaltosin in ausreichender Menge und Reinheit synthetisiert. Dabei gelang es, für Maltosin und Pyridosin neue und effiziente Synthesewege zu entwickeln, bei welchen zum ersten Mal beide Substanzen gezielt aufgebaut wurden. Die Komplexbildungskonstanten der Liganden mit den Metallionen wurden pH-potentiometrisch bestimmt (I[KNO3] = 0,15 M; θ = 25 °C). Durch die Auswertung der Protonierungskonstanten der gebildeten Komplexe und das Vermessen geeigneter Derivate konnten für die untersuchten Komplexe zusätzlich die Koordinationsstellen der Liganden aufgeklärt werden. Die Untersuchungen zu den Komplexbildungseigenschaften bestätigten erstmals die Vermutung, dass MRP in der Lage sind, Metallionen zu binden. Dabei wurde weiterhin ermittelt, dass die Bindung von Cu(II) durch Nε-Carboxymethyllysin und von Fe(III), Al(III) und Cu(II) durch Maltosin durchaus von physiologischer Relevanz sind. Die Bedeutung der Ergebnisse wurde qualitativ durch Versuche mit Maltosin-derivatisiertem Rinderserumalbumin unterstrichen. Als besonderes Ergebnis der Arbeit ist herauszustellen, dass das MRP Maltosin und die Verbindung Pyridosin deutlich stabilere Komplexe mit Fe(III) bilden als das zur Fe(III)-Chelattherapie eingesetzte Medikament Deferipron. Diese festgestellte Eigenschaft bietet interessante Perspektiven für zukünftige Studien zur möglichen Anwendung von z. B. Maltosin als Pharmakon. / Several studies show that Maillard reaction products (MRP) may influence the physiological metal ion balance. But none of these studies prove a correlation between the formation of defined MRP and an enhanced metal ion binding. Therefore it was the aim of this work to investigate the complex formation characteristics of the selected MRP Nε-carboxymethyllysine, isomaltol and maltosine as well as the structural analogues maltol, deferiprone, mimosine and pyridosine with the physiological relevant metal ions Cu(II), Zn(II), Fe(III), Al(III) and Mn(II). For that purpose the MRP Nε-carboxymethyllysine and maltosine plus the parallel analysed substances pyridosine, maltosine-3-benzylether, Nα-hippuryl- and Nα-acetylmaltosine were synthesised. Thereby new and efficient syntheses for maltosine and pyridosine were developed. The stability constants of the ligands with the metal ions were determined by pH-potentiometry (I(KNO3) = 0,15 M; θ = 25 °C). Furthermore the donor atoms within the formed complexes were determined by the evaluation of the protonation constants of the formed complexes and by the analysis of adequate derivatives. The studies to the complex formation characteristics confirm for the first time the assumption, that MRP are able to form stable complexes with metal ions. Withal it was ascertained that the coordination of Cu(II) by Nε-carboxymethyllysine and of Fe(III), Al(III) and Cu(II) by maltosine may be of physiological relevance. The significance of the results was pointed out by experiments with maltosine derivatised bovine serum albumine. The fact that the MRP maltosine and the compound pyridosine form more stable complexes with Fe(III) as the medicament for the Fe(III) chelate therapy deferiprone is a particular result of this work. This property affords interesting perspectives for future studies about a possible appliance of e.g. maltosine as pharmaceutical.