Im Wasser-oxidierenden Cluster („oxygen-evolving complex“, OEC) des Photosystem II findet sich die primäre Quelle der Sauerstoffproduktion der Erde. Der OEC katalysiert in grünen Pflanzen unter Absorption von Sonnenlicht die Vierelektronen-Oxidation von Wasser zu Sauerstoff in einer zyklischen Sequenz von Oxidationszuständen (Kok-Zyklus). In dieser Arbeit wurden Strukturen, Spindichteverteilungen sowie EPR-Parameter ein-, zwei- und vierkerniger Mangankomplexe, die in Bezug auf den OEC modelliert wurden, mit Hilfe der Dichtefunktionaltheorie (DFT) berechnet. Hauptziel war das Verständnis der molekularen und elektronischen Struktur des vierkernigen Manganclusters des OEC durch direkten Vergleich mit experimentellen EPR-Daten. / Photosynthesis is the most fundamental process of life on earth. The biological production of oxygen in plant photosynthesis occurs in photosystem II (PSII). Here two water molecules are coupled in a four-electron oxidation to one O2 molecule, catalyzed by a tetranuclear manganese complex, known as the oxygen-evolving complex (OEC). In this thesis, density-functional theory (DFT) methods were validated and subsequently employed to study structures, spin-density distributions and EPR parameters of mono-, di-, and tetranuclear complexes with regard to the OEC. The goal was to draw conclusions on the molecular and electronic structure of the OEC.

Reactive oxygen species (ROS) are continuously generated in cells and are involved in physiological processes including signal transduction but also their damaging effects on biological molecules have been well described. A number of reports in the literature implicate excessive oxidative stress and/or inadequate antioxidant defense in the pathogenesis of cancer, atherosclerosis, chronic and age related disorders. Several studies have indicated that activation of the renin-angiotensin-aldosterone-system can lead to the formation of ROS. Epidemiological studies have revealed higher renal cell cancer incidences and also higher cancer mortalities in hypertensive individuals. Recently, our group has shown that perfusion of the isolated mouse kidney with Ang II or treatment of several cell lines with Ang II leads to formation of DNA damage and oxidative base modifications. Here, we tried to scrutinize the pathway involved in genotoxicity of Ang II. We confirmed the genotoxicity of Ang II in two kidney cell lines of human origin. Ang II treatment led to the production of superoxide anions which we could hinder when we used the membrane permeable superoxide dismutase (SOD) mimetic TEMPOL. One of the enzymes which is activated in the cells after Ang II treatment and is able to produce ROS is NADPH oxidase. We demonstrated the activation of NADPH oxidase in response to Ang II by upregulation of its p47 subunit using RT-PCR. Also, pPhosphorylation of p47 subunit of NADPH oxidase after Ang II treatment was enhanced. Using two inhibitors we showed that NADPH oxidase inhibition completely prevents DNA damage by Ang II treatment. To differentiate between Nox2 and Nox4 isoforms of NADPH oxidase subunits in the genotoxicity of Ang II, we performed siRNA inhibition and found a role only for Nox4, while Nox2 was not involved. Next, we investigated PKC as a potential activator of NADPH oxidase. We showed that PKC becomes phosphorylated after Ang II treatment and also that inhibition of PKC hinders Ang II from damaging the cells. Our results from using several inhibitors of different parts of the pathway revealed that PKC activation in this pathway is dependent on the action of PLC on membrane phospholipids and production of IP3. IP3 binds to its receptor at endoplasmic reticulum (ER), opening a channel which allows calcium efflux into the cytoplasm. In this manner, both ER calcium stores and extracellular calcium cooperate so that Ang II can exert its genotoxic effect. PLC is activated by AT1R stimulation. We could also show that the genotoxicity of Ang II is mediated via AT1R signaling using the AT1R antagonist candesartan. In conclusion, here we have shown that Ang II is able to damage genomic damage in cell lines of kidney origin. The observed damage is associated with production of ROS. A decrease in Ang II-induced DNA damage was observed after inhibition of G-proteins, PLC, PKC and NADPH oxidase and interfering with intra- as well as extracellular calcium signaling. This leads to the following preliminary model of signaling in Ang II-induced DNA damage: binding of Ang II to the AT1 receptor activates PLC via stimulation of G-proteins, resulting in the activation of PKC in a calcium dependent manner which in turn, activates NADPH oxidase. NADPH oxidase with involvement of its Nox4 subunit then produces reactive oxygen species which cause DNA damage. Dopamine content and metabolism in the peripheral lymphocytes of PD patients are influenced by L-Dopa administration. The PD patients receiving a high dose of L-Dopa show a significantly higher content of dopamine in their lymphocytes compared to PD patients who received a low dose of L-Dopa or the healthy control. Central to many of the processes involved in oxidative stress and oxidative damage in PD are the actions of monoamine oxidase (MAO), the enzyme which is responsible for the enzymatic oxidation of dopamine which leadsing to production of H2O2 as a by-product. We investigated whether dopamine oxidation can cause genotoxicity in lymphocytes of PD patents who were under high dose L-Dopa therapy and afterward questioned the occurrence of DNA damage after dopamine treatment in vitro and tried to reveal the mechanism by which dopamine exerts its genotoxic effect. The frequency of micronuclei in peripheral blood lymphocytes of the PD patients was not elevated compared to healthy age-matched individuals, although the formation of micronuclei revealed a positive correlation with the daily dose of L-Dopa administration in patients who received L-Dopa therapy together with dopamine receptor agonists. In vitro, we describe an induction of genomic damage detected as micronucleus formation by low micromolar concentrations in cell lines with of different tissue origins. The genotoxic effect of dopamine was reduced by addition of the antioxidants TEMPOL and dimethylthiourea which proved the involvement of ROS production in dopamine-induced DNA damage. To determine whether oxidation of dopamine by MAO is relevant in its genotoxicity, we inhibited MAO with two inhibitors, trans-2-phenylcyclopropylamine hydrochloride (PCPA) and Ro 16-6491 which both reduced the formation of micronuclei in PC-12 cells. We also studied the role of the dopamine transporter (DAT) and dopamine type 2 receptor (D2R) signaling in the genotoxicity of dopamine. Inhibitors of the DAT, GBR-12909 and nomifensine, hindered dopamine-induced genotoxicity. These results were confirmed by treatment of MDCK and MDCK-DAT cells, the latter containing the human DAT gene, with dopamine. Only MDCK-DAT cells showed elevated chromosomal damage and dopamine uptake. Although stimulation of D2R with quinpirole in the absence of dopamine did not induce genotoxicity in PC-12 cells, interference with D2R signaling using D2R antagonist and inhibition of G-proteins, phosphoinositide 3 kinase and extracellular signal-regulated kinases reduced dopamine-induced genotoxicity and affected the ability of DAT to take up dopamine. Furthermore, the D2R antagonist sulpiride inhibited the dopamine-induced migration of DAT from cytosol to cell membrane. Overall, the neurotransmitter dopamine causes DNA damage and oxidative stress in vitro. There are also indications that high dose L-Dopa therapy might lead to oxidative stress. Dopamine exerts its genotoxicity in vitro upon transport into the cells and oxidization oxidation by MAO. Transport of dopamine by DAT has the central role in this process. D2R signaling is involved in the genotoxicity of dopamine by affecting activation and cell surface expression of DAT and hence modulating dopamine uptake. We provided evidences for receptor-mediated genotoxicity of two compounds with different mechanism of actions. The involvement of these receptors in many human complications urges more investigations to reveal whether abnormalities in the endogenous compounds-mediated signaling can play a role in the initiation of new conditions like carcinogenesis. / Reaktive Sauerstoffspezies (ROS) werden kontinuierlich in Zellen generiert und sind an physiologischen Prozessen wie der Signaltransduktion beteiligt. Aber auch ihre schädigenden Auswirkungen auf biologische Moleküle sind seit langem bekannt. Eine Reihe von Literaturberichten sieht einen Zusammenhang zwischen übermäßigem oxidativen Stress oder einer unzureichenden antioxidativen Verteidigung und Krebs, Atherosklerose und chronischen bzw. altersbedingten Erkrankungen. Mehrere Studien haben belegt, dass die Aktivierung des Renin-Angiotensin-Aldosteron-Systems zur Bildung von ROS führen kann. Epidemiologische Studien haben gezeigt, dass Nierenkarzinom-Inzidenzen und -Mortalitäten bei Hypertonikern erhöht sind. Vor kurzem konnte unsere Gruppe zeigen, dass die Perfusion von isolierten Maäusen-Nieren und dieoder Behandlung mehrerer Zelllinien mit Angiotensin II (Ang II) zur Bildung von DNA-Schäden und oxidativen Basenmodifikationen führt. Ziel der vorliegenden Arbeit war es, die Signalwege der Genotoxizität von Ang II zu bestimmen. Wir bestätigten dDie Genotoxiziät von Ang II in zwei Nieren-Zelllinien humaner Herkunft konnte bestätigt werden. Wir zeigten, dass Ang II-Behandlung zur Produktion von Superoxid-Anionen führt, die durch das membrangängige Superoxid-Dismutase-Mimetikum TEMPOL verhindert werden kann. Eines der Enzyme, das in den Zellen nach Ang II-Behandlung aktiviert wird und ROS produzieren kann, ist die NADPH-Oxidase. Die mittels RT-PCR gemessene Hochregulierung von p47 beweist die Aktivierung der NADPH-Oxidase nach Ang II-Behandlung. Auch die Phosphorylierung von p47 nach Ang II-Behandlung wurde gesteigert. Mittels zweier Inhibitoren zeigten wir, dass NADPH-Oxidase-Hemmung DNA-Schäden durch Ang II-Behandlung vollständig verhindert. Wir versuchten, die Rolle der Nox2- und Nox4-Isoformen der NADPH-Oxidase-Untereinheiten bei der Genotoxizität von Ang II zu differenzieren. Hemmung mittels siRNA bestätigte nur eine Beteiligung der Nox4. Anschließend überprüften wir die Rolle der PKC als potentiellem Aktivator der NADPH-Oxidase. Wir zeigten, dass die PKC nach Ang II-Behandlung PKC phosphoryliert wird und durch die Hemmung der PKC Ang II-induzierten Schäden verhindert werdenird. Die Verwendung mehrerer Inhibitoren der verschiedenen Teile des Signalweges zeigte, dass die PKC-Aktivierung von der Reaktion der PLC mit Membranphospholipiden und der Produktion von IP3 und DAG abhängig ist. IP3 bindet an seinen Rezeptor am Endoplasmatischen Retikulum (ER)., dDie in der Folge auftretende Öffnung eines Kanals ermöglicht einen Calcium-Ausstrom in das Cytoplasma. Auf diese Weise sind sowohl ER-Calcium als auch extrazelluläres Calcium an der Ang II-induzierten genotoxische Wirkung beteiligt. PLC wird durch AT1R-Stimulation aktiviert. Wir konnten mit Hilfe des AT1R-Antagonisten Candesartan auch zeigen, dass die Genotoxizität von Ang II über AT1R-Signaltransduktion vermittelt wird. Zusammenfassend haben wir gezeigt, dass Ang II genomische Schäden in humanen Nieren-Zelllinien verursacht. Die Schäden sind mit der Produktion von ROS verbunden. Eine Reduktion der Ang II-induzierten DNA-Schäden wurde nach Hemmung vonder G-Proteinen, der PLC, PKC und NADPH-Oxidase und Beeinflussung intra- sowie extrazellulärer Calium-Signalgebung gezeigt. Dies führt zu folgendem vorläufigen Modell der Signaltransduktion der von Ang II-induzierten DNA-Schäden: Die Bindung von Ang II an den AT1-Rezeptor aktiviert die PLC durch Stimulationerung der G-Proteine und die PKC in Calcium-abhängiger Weise, dies wiederum aktiviert die NADPH-Oxidase. Die NADPH Oxidase unter Beteiligung ihrerseiner Nox4-Untereinheit erzeugt dann reaktive Sauerstoffspezies, die DNA-Schäden verursachen. Dopamingehalt und -stoffwechsel in peripheren Lymphozyten von Parkinson-Patienten werden durch L-Dopa-Gabe beeinflusst. Die Patienten, die eine hohe Dosis L-Dopa erhalten, zeigen einen signifikant höheren Gehalt an Dopamin in den Lymphozyten im Vergleich zu Patienten, die eine niedrige Dosis L-Dopa erhalten oder der gesunden Kontrollgruppe. Im Mittelpunkt vieler Prozesse bei der Entstehung von oxidativem Stress und oxidativer Schäden bei Parkinson-Patienten steht die Monoaminoxidase (MAO), die für die enzymatische Oxidation von Dopamin und in der Folge für die Entstehung von H2O2 verantwortlich ist. Wir untersuchten, ob die Oxidation von Dopamin genotoxische Wirkung in Lymphozyten von Parkinson-Patienten mit hochdosierter L-Dopa-Therapie induzieren kann. Danach überprüftenfragten wir, ob die Behandlung mit Dopamin in vitro DNA-Schäden induzieren kann und versuchten aufzuzeigen, durch welchen Mechanismus Dopamin seine genotoxische Wirkung entfaltet. Die Häufigkeit von Mikrokernen in peripheren Lymphozyten der Parkinson-Patienten war nicht erhöht im Vergleich zur gesunden Kontrollgruppe, allerdings zeigte die Mikrokernfrequenz eine positive Korrelation mit der täglichen L-Dopa-Dosis bei Patienten, die eine L-Dopa-Therapie zusammen mit einem Dopamin-Rezeptor-Agonisten erhielten. In vitro beobachteten wir bei niedrigen mikromolaren Konzentrationen eine Induktion des genomischen Schadens in Zelllinien, die aus verschiedenen Geweben stammten. Die genotoxische Wirkung von Dopamin wurde durch Zugabe der Antioxidantien TEMPOL und DMTU reduziert, wodurch die Beteiligung von ROS gezeigt werden konnte. Um festzustellen, ob die Oxidation von Dopamin durch MAO für die Genotoxizität relevant ist, hemmten wir MAO mit zwei Inhibitoren, trans-2-Phenylcyclopropylamin-Hydrochlorid (PCPA) und Ro 16-6491, die beide die Bildung von Mikrokernen in PC-12-Zellen reduzieren konnten. Wir untersuchten auch die Rolle des Dopamin-Transporters (DAT) und Dopamin-Typ-2-Rezeptor (D2R)-assoziierter Signalwege in der Genotoxizität von Dopamin. Die Inhibitoren des DAT, GBR-12909 und Nomifensin verhinderten die Dopamin-induzierte Genotoxizität. Diese Ergebnisse wurden durch Behandlung von MDCK- und MDCK-DAT- Zellen (die das humane DAT-Gen besitzen) mit Dopamin bestätigt. Nur MDCK-DAT-Zellen zeigten erhöhte chromosomale Schäden und Dopaminaufnahme. Obwohl die Stimulation mit dem D2R-Rezeptor-Agonisten Quinpirol in Abwesenheit von Dopamin keine Genotoxizität in PC-12-Zellen induzierte, reduzierten sowohl ein D2R-Antagonist, wie auch Inhibitoren des in der Signalkaskade involvierten G-Proteins, der Phosphoinositol-3-Kinase und der extrazellulären signalregulierten Kinasen die Aufnahme von Dopamin mittels DAT und die Dopamin-vermittelte Genotoxizität. Der D2R-Antagonist Sulpirid hemmte die Dopamin-induzierte Migration von DAT aus dem Cytosol zur Zellmembran. Insgesamt verursacht der Neurotransmitter Dopamin DNA-Schäden und oxidativen Stress in vitro. Es gibt Hinweise, dass eine hochdosierte L-Dopa-Therapie zu oxidativem Stress führt. In vitro führt Dopamin zu Genotoxizität durch den Transport in die Zellen und Oxidation durch MAO. Der Transport von Dopamin durch DAT spielt eine zentrale Rolle in diesem Prozess. Die D2R-Signalwege sind an der Genotoxizität von Dopamin durch Auswirkung auf die Aktivierung und Membranexpression von DAT und damit der Dopaminaufnahme beteiligt.

Thesis advisor: John F. Baldovin / This dissertation is about three key moments in the developing theology of the Church's holiness and sinfulness in the twentieth century: the ressourcement movement of the 1930's-50's, Vatican II, and the pontificate of John Paul II. Chapter One discusses the contributions of these six early-twentieth century theologians: (a) Emile Mersch ---Church as Mystical Body of Christ (b) Henri de Lubac ---the paradoxes in understanding the Church as in time and beyond time (c) Hans urs Von Balthasar ---the Church as covenant (d) Yves Congar ---the scandal of division in the Church and the image of the Church as the People of God (e) Karl Rahner---the Church as sacrament for the World (f) Charles Journet ---the Holy Spirit as the formal cause of the Church Chapter Two discusses the influence of the theologians examined in Chapter One on specific passages in Vatican II's document on the Church, Dogmatic Constitution on the Church, Lumen Gentium (1964). Chapter Three shows how Pope John Paul II further advanced the understanding of the Church's holiness and sinfulness in his millennial program which included two documents, Tertio Millennio Adveniente (1994) and Novo Millennio Ineunte (2001) and a public apology on March 12, 2000 for the sins of the members of the Church. The Conclusion argues that John Paul II's apology was the fruit of a century of theological reflection on the nature and mission of the Church that began with ressourcement theology and was advanced by the convocation of Vatican II and its subsequent documents, particularly Lumen Gentium. Additionally, there is a discussion of the agenda for further theological investigation in the twenty-first century that these three twentieth-century moments suggest. / Thesis (STD) — Boston College, 2012. / Submitted to: Boston College. School of Theology and Ministry. / Discipline: Sacred Theology.

ABSTRACT All members registered on the managed care database for the chronic condition Rheumatoid Arthritis (RA), for the period 01 January 2003 to 30 June 2003, were evaluated to determine the prescribing pattern of the cyclo-oxygenase (COX) II inhibitors and non-selective non-steroidal anti-inflammatory (NSAIDs). A total of 2818 members were registered on the managed care database of the chronic condition RA and 1372 members were identified as using COX II inhibitors and 827 members were using nonsteroidal anti-inflammatory (NSAIDs). The prescribing frequency determined for the COX II inhibitors were 48.60% and 29.35% for the NSAIDs. The members identified as either using a COX II inhibitor or a NSAIDs were divided into two groups. The prescribing patterns of each group such as age, gender, co-morbid conditions, concomitant medication use and frequency were analysed and compared to the national institute of clinical excellence (NICE) and the South African Rheumatism and Arthritis Association (SARAA) guidelines for the appropriate prescribing of the COX II inhibitors. Celecoxib was the most frequently prescribed COX II inhibitor accounting for 46% of all the COX II inhibitors identified and diclofenac was the most frequently prescribed NSAID accounting for 34% of all the NSAIDs prescriptions. COX II inhibitors were prescribed more frequently to females with a mean age of 55 years than males. A similar prescribing trend was found with the NSAIDs. The COX II inhibitors were frequently prescribed to patients over the age of 56 with co morbid gastro-oesophageal disease and concomitant warfarin and steroid use. The prescribing patterns found in the managed care environment were similar to those recommended by the NICE and SARAA guidelines. The managed care data showed that the COX II inhibitors, which are supposed to have less gastric adverse side effects, were frequently used in combination with gastroprotective agents (GPA’s). This study indicates that even though COX II inhibitors were prescribed more frequently than NSAIDs in the managed care environment the recommended clinical guidelines and protocols employed by the managed care environment were adhered to. However, there v is a need to closely monitor patients on concomitant GPA’s treatment and COX II inhibitors. This study helped to evaluate the current prescribing patterns of COX II inhibitors in the managed health care environment. This study confirmed that guidelines and protocols were adhered to. These are excellent tools to be used in the managed health care environment to ensure effective and appropriate prescribing.

Nesta pesquisa foram avaliados 30 pacientes, sendo 15 para cada gênero, idade iniciais entre 10,83 e 16,24 anos, sendo a média de idade inicial 13,32 anos; leucodermas, brasileiros, naturais da cidade de Bauru, caracterizados por má oclusão de Classe II 1ª e 2ª divisão de Angle, na presença ou não dos segundos molares superiores e sem comprometimento esquelético. Os jovens pertencentes a essa amostra receberam o aparelho Jones jig a fim de distalizar os molares superiores a uma relação molar de ?super Classe I?; sendo que em média esse dispositivo permaneceu por 0,86 anos, ou seja, 10 meses e 10 dias. Ao final da sobrecorreção, os molares distalizados receberam um botão de Nance e como ancoragem extrabucal, o AEB com tração média-alta (capacete jeans); com o intuito de verticalizar e corrigir a angulação radicular dos molares distalizados. Foram realizadas tomadas radiográficas em dois diferentes tempos; ou seja, telerradiografias em normal lateral inicial (T1) e pós-distalização (T2) a fim de avaliar as alterações dentárias e esqueléticas decorrentes do aparelho Jones jig. As medidas cefalométricas foram submetidas ao teste t dependente de Student para avaliar as alterações de T1 para T2 e o teste t independente para avaliar o dimorfismo entre os gêneros e os efeitos provocados pela presença dos segundos molares superiores. Com base nos resultados obtidos e a partir da metodologia empregada observou-se alterações dentárias significantes como movimentação distal linear e angular dos segundos e primeiros molares superiores, assim como intrusão no sentido vertical; sendo que a taxa de distalização mensal foi de 0,26mm. Também se confirmou efeitos indesejáveis como a perda de ancoragem refletida em mesialização, extrusão e angulação mesial dos segundos pré-molares, protrusão dos incisivos superiores, aumento do overbite e overjet. Pode-se confirmar que certas movimentações dentárias promovem significantes alterações esqueléticas de estruturas localizadas à distância, ou seja, observou-se extrusão significante dos segundos pré-molares superiores, o que resultou em rotação mandibular, aumento significante da altura facial ântero-inferior e protrusão do lábio inferior. Observou-se que a presença dos segundos molares superiores interfere significantemente apenas no resultado final da angulação distal dos primeiros molares superiores e que as maiorias das variáveis se correlacionam significantemente entre si. / Thirty patients were evaluated in this study, 15 males and 15 females, leukoderm, Brazilian, natural from Bauru city, with initial ages ranging from 10.83 years to 16.24 years, being the average age 13.32 years old. They were characterized by Angle Class II division I and II malocclusion, with or without the second maxillary molars, and, no skeletal compromising. The patients were treated with the appliance Jones jig. The treatment last for 0.86 years. It´s purpose was the distalization of the first maxillary molars to normal molar relationship. After this movement, the maxillary molars were anchored with Nance button, and extraoral headgear was used to correct tipping of the distalized molars. Lateral cephalograms were obtained at two observation stages: before treatment, and after distalization to evaluate dental and skeletal changes of appliance Jones jig. Cephalometric values were submitted to: dependent sample Student t test to identify changes between T1 and T2, and, independent sample Student t test to evaluate generic dimorphism and the effects from the presence of the second maxillary molars. On the basis of obtained results and applied methodology, significant dental changes were observed, such as distalization, distal tipping, and, intrusion of first maxillary molars, with the monthly rate of distal movement being 0.26mm. Anchorage loss was also observed, characterized by significant extrusion; mesial movement and tipping of the maxillary second premolar; protrusion of the maxillary incisors; and, increase of the overbite and overjet. It can be said that some dental movements promote significant skeletal changes, such as, significant extrusion of the second maxillary premolars resulted in clockwise mandibular rotation, increase of the lower anterior face height, and, protrusion of the lower lip. Another fact also observed was that the presence of second maxillary molars interfere significantly on the first maxillary molars?s distal tipping results, and, that the variables correlate significantly amongst themselves.

Thesis advisor: Franziska Seraphim / This thesis primarily focuses on jazz in Japan and the role it played in the American occupation after World war II. The trajectory jazz took in Japan changed a multitude of times: in the 1920s it was immensely popular with the rise of consumerism and internationalism, and was emblematic of the carefree attitude of that time period. After Pearl Harbor occurred, enemy music, clearly being American jazz, was formally forbidden in Japan but periodically still played for the entertainment of the troops. Thus jazz went from being incredibly popular to practically banned. As the occupation took place, jazz yet again was popular but became more associated with connotations of homogeneity and representative of America. The Japanese reacted in various and differing ways, which I demonstrate in this thesis by examining the work of Japanese director Kurosawa Akira and the widely popular Japanese singer Kasagi Shizuko. Therefore, jazz was not only a form of entertainment but a tool of manipulation by many throughout the 1920s, 1930s, and, most importantly, the American occupation in Japan. / Thesis (BA) — Boston College, 2015. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: Departmental Honors. / Discipline: History.

A estabilidade dos resultados obtidos pelo tratamento ortodôntico apresenta-se atualmente como um dos aspectos mais preocupantes e pouco compreendidos na literatura, sem respostas conclusivas. A sobremordida, ou trespasse vertical, define-se como o trespasse entre os incisivos superiores e inferiores, apresentando-se como um aspecto necessário para a correção das más oclusões e importante na avaliação dos resultados dos tratamentos e sua estabilidade. Este estudo se propôs a avaliar, cefalometricamente e em modelos de estudo, a recidiva da sobremordida e sua relação com as curvas de Spee e ocluso-incisal, e suas respectivas recidivas. A amostra (grupo experimental) constituiu-se das telerradiografias em norma lateral e modelos de estudo de 29 pacientes, de ambos os gêneros, que apresentavam inicialmente má oclusão de Classe II, 1 divisão e sobremordida profunda de no mínimo 3,5 mm, tratados com extração dos 4 primeiros pré-molares e aparelho ortodôntico fixo, utilizando-se a técnica Edgewise simplificada. Este grupo experimental foi comparado a um grupo controle, com oclusão normal, constituído também de 29 indivíduos. Ambos os grupos utilizados fazem parte do arquivo de documentação da Disciplina de Ortodontia da FOB-USP. Foram avaliadas, para o grupo experimental, as telerradiografias em norma lateral e os modelos de estudo do início, final e 5 anos pós-tratamento, e, para o grupo controle, as telerradiografias de dois tempos de avaliação, compatível com o tempo de tratamento do grupo experimental. Para a comparação intergrupos, utilizou-se o teste t não pareado, e para a comparação intragrupo, o teste ANOVA, e na presença de resultados significantes, aplicou-se também o teste de Tukey. Para verificar a relação da recidiva da sobremordida com as curvas de Spee e ocluso-incisal, utilizou-se o teste de correlação de Pearson. Pela análise dos resultados obtidos, observou-se que a sobremordida apresentou uma correlação significante com a curva de Spee na fase pós-contenção / The long-term stability of the treatment outcomes presents as one of the main points in orthodontic literature, without conclusive answers. The overbite is defined as the vertical distance between upper and lower incisors, and it is important for malocclusions correction and for evaluation of treatment and its stability. This study aimed to evaluate, in cephalograms and study casts, the overbite relapse and its relation with the curve of Spee. The sample (experimental group) comprised 29 patients of both genders, presenting Class II, division 1 malocclusion and an overbite of at least 3.5 mm, treated by Edgewise mechanics. This experimental group was compared to a control group of normal occlusion, comprising 29 subjects. Both groups are part of the records from Orthodontic Department at Bauru Dental School, University of São Paulo. For the experimental group, cephalograms and study casts of the pretreatment, posttreatment and 5 years postretention were studied, and for the control group, cephalograms in two times of evaluation, compatible with the treatment time of the experimental group. The independent t test was used for the intergroup comparison, and the one way ANOVA, for intragroup comparison. In order to verify the relation between the overbite relapse and the curve of Spee, a Pearson's correlation test was performed. The results showed that the overbite was significantly corrected by the orthodontic treatment, when compared to the control group, and presented a significant relapse in the postretention phase. The overbite relapse presents a significant correlation with the curve of Spee in the postretention stage

O tratamento ortodôntico possui diversos objetivos, sendo que um dos mais importantes é a estabilidade das correções alcançadas, entretanto, após várias décadas de estudos, evidenciou-se que a estabilidade do alinhamento dos dentes é altamente variável e amplamente imprevisível. Considerando que é de grande valia para os ortodontistas a possibilidade de previsão das prováveis alterações no período pós-tratamento, decidiu-se investigar, neste estudo, a recidiva do apinhamento ântero-inferior. A amostra utilizada consistiu-se de 40 pacientes leucodermas, de ambos os gêneros, com más oclusões de Classe I ou II, tratados com mecânica Edgewise e sem extrações no arco inferior. Avaliaram-se os modelos de estudo e as telerradiografias laterais dos pacientes nas fases inicial e final de tratamento e póscontenção (em média 5 anos pós-tratamento). Avaliou-se, então, a presença de associações entre a recidiva do apinhamento ântero-inferior e os seguintes fatores: o aumento das distâncias intercaninos e intermolares, o aumento do comprimento do arco, o gênero dos pacientes, a realização de extrações no arco superior, a realização de desgastes interproximais no segmento ântero-inferior, o tipo de má oclusão inicial, o padrão de crescimento craniofacial predominante, o grau de apinhamento inicial, o aumento ou não da protrusão dos incisivos inferiores devido ao tratamento, a posição final dos incisivos inferiores, os tempos de tratamento e de contenção. Os dados foram comparados pelo teste estatístico de Mann-Whitney209, e mediu-se o apinhamento ântero-inferior pelo índice de irregularidade de Little. Como resultados, encontrou-se que a recidiva do apinhamento ânteroinferior ocorreu na maioria dos pacientes, porém a porcentagem média desta recidiva foi relativamente pequena (26,54%). O gênero masculino apresentou, em média, maior apinhamento nas fases inicial e póscontenção do que o gênero feminino. A porcentagem média de recidiva foi maior no gênero masculino do que no feminino, mas não estatisticamente significante. O grupo com má oclusão de Classe II e o grupo com padrão de crescimento craniofacial redominantemente vertical apresentaram maior recidiva, porém não significantes estatisticamente. O grupo com apinhamento inicial suave apresentou maior recidiva que o grupo com apinhamento inicial severo, com valores estatisticamente significantes, portanto, pode-se concluir que o grau de apinhamento inicial influenciou e se mostrou associado à recidiva do apinhamento ântero-inferior. O grupo com maiores tempos de contenção apresentou menor recidiva, porém, não significante estatisticamente. Com relação aos demais fatores estudados, aumento das distâncias intercaninos e intermolares, aumento do comprimento do arco, realização de extrações no arco superior, realização de desgastes interproximais, aumento da protrusão dos incisivos inferiores devido ao tratamento, posição final dos incisivos inferiores e tempo de tratamento, nenhum deles se mostrou significantemente associado à recidiva do apinhamento ântero-inferior. / One of the most important objectives of Orthodontics is treatment stability. However, after many decades of research there is a consensus that stability of the aligned teeth is variable and largely unpredictable. Considering the great importance that clinical orthodontists place on the ability to predict when posttreatment changes are prone to occur, it was decided to evaluate the relapse of mandibular anterior crowding. The experimental sample consisted of 40 patients, of both gender, presenting with either Class I or II malocclusions, treated without extractions in the mandibular arch with Edgewise mechanics. The lateral cephalogram and dental casts of each patient were evaluated at three different stages: pretreament, posttreatment and after a mean postretention period of 5 years. The relapse of mandibular anterior crowding was assessed and associations between this relapse and the following factors were investigated: increase in intercanine and intermolar distances, increase in arch length, gender, extractions in the upper arch, interproximal stripping, type of malocclusion, craniofacial growth pattern, degree of initial mandibular anterior crowding, protrusion of the lower incisors consequent to treatment, final position of the lower incisors, treatment time and retention time. The data were evaluated by the Mann-Whitney test, and the mandibular anterior crowding was measured by the Little irregularity index. Results demonstrated that the relapse of mandibular anterior crowding occurred in most of the patients. However, the mean relapse amount was relatively small (26,54%). The male patients showed more mandibular anterior crowding in the pretreatment and postretention periods. The mean relapse amount was greater in the male patients, but not statistically significant. The group with Class II malocclusion and the group with vertical craniofacial growth pattern presented more relapse than the other groups, but not statistically significant. The group with the smaller amount of initial crowding demonstrated a statistically significant greater relapse than the other groups. Therefore, it was concluded that the degree of initial crowding was associated with the relapse of mandibular anterior crowding. The group with greater retention time presented less relapse, but not statistically significant. The other evaluated factors did not present any association with the relapse of mandibular anterior crowding.

Desenvolveu-se sistemática de trabalho para coletar valores da função ñ vs. concentração de ligante e processos de cálculo de constantes de equilíbrio. Os sistemas Co(II)/N-3 e Ni(II)/N-3 foram analisados com o objetivo de identificar os complexos formados e determinar as respectivas constantes de estabilidade. O estudo desses sistemas foi realizado a (25,0 ± 0,l) °C e em força iônica 2,0 M ajustada com NaClO4. Com base na formação de soluções tampão N-3/ HN3 e na variação de pH provocada pela adição do íon metálico Co(II) ou Ni(II), realizou-se um estudo potenciométrico para cada um dos sistemas acima indicados. Estes estudos foram realizados numa ampla faixa de concentração analítica de azoteto (0 a 2,000 M) e para diversas concentrações do íon metálico, para possibilitar uma análise mais detalhada sobre a formação dos complexos. Em relação ao sistema Co(II)/N-3 foi possível determinar a formação de cinco espécies mononucleares. As respectivas constantes de estabilidade foram calculadas por três métodos diferentes. A comparação dos desvios calculados para os valores de ñ obtidos a partir de cada um dos três conjuntos de constantes permitiu decidir pelo seguinte conjunto de constantes: β1 = 5,67 ± 0,20 M-1 β2 = 19,5 ± 2,1 M-2 β3 = 6,52 ± 4,66 M-3 β4 = 15,8 ± 2,0 M-4 β5 = 4,83 ± 0,31 M-5 Num comportamento diverso ao dos íons Co (II) o niquel levou à formação de complexos polinucleares. Realizou-se então um estudo monográfico envolvendo aspectos estruturais, qualitativos e quantitativos sobre a formação de complexos polinucleares. O sistema Ni(II)/-3 foi então analisado através do método potenciométrico citado mas em condições que permitiram a obtenção de um número maior de dados experimentais em relação ao sistema Co(II)/N-3, para tornar possível a determinação da composição assim como o cálculo das constantes de estabilidade das espécies existentes em equilíbrio. Dois métodos de cálculo foram utilizados, adotando-se o seguinte conjunto de constantes de equilibrio: mononucleares Ni(N3)+ β11 = 5,80 Ni(N3)2 β12 = 9,69 Ni(N3)-3 β13 = 7,54 Ni(N3)=4 β14 = 534 binucleares Ni2(N3)3+ β21 = 4,06 Ni2(N3)2+2 β22 = 31,8 Ni2(N3)+3 β23 = 175 Ni2(N3)4 β24 = 2,06x104 Ni2(N3)-5 β25 = 2,30x105 Ni2(N3)=6 β26 = 7,15x105 trinucleares Ni3(N3)2+4 β34 = 2,28x104 Ni3(N3)+5 β35 = 3,51x106 Ni3(N3)6 β36 = 1,17x108 Três estudos complementares foram realizados para o sistema Ni(II)/N-3. A utilização de métodos espectrofotométrico e potenciométrico em condições de excesso de metal em relação ao ligante permitiu determinar as contantes de estabilidade das espécies mono e binucleares mais simples: NiN+3 e Ni2N3+3. O método espectrofotométrico forneceu um valor de β11 = 6,90 M-1, enquanto que o segundo método forneceu β11 = 7,53 ± 0,10 M-1 e β21 = 4,29 ± 0,15 M-2. Medidas espectrofotométricas realizadas nas condições do segundo método permitiram calcular as absortividades molares das duas espécies, em cinco comprimentos de onda na faixa do ultravioleta. No comprimento de onda de absorção máxima dos complexos (293 nm) os valores de ε encontrados foram os seguintes: ε11 = 362 e ε21 = 475 cm-1mol-11. Finalmente, um estudo condutométrico feito em alta concentração de Ni(II) (0,4 M) e para concentrações variáveis de azoteto permitiu identificar a formação da espécie Ni2(N3)-5. Fez-se uma série de diagramas de distribuiçao, os quais mostraram as contribuições de cada espécie em função do ligante e, eventualmente, da concentração total do íon metálico (sistemas polinucleares). / A systematic approach in order to obtain ñ data vs. free ligand concentration was developed as well as calculation procedures for treatment of the data to obtain stability constants. The Co(II)/N-3 and Ni(II)/N-3 systems were analysed with the purpose to identify the formed complexes and to compute its stability constants. The equilibria studies were performed at 25.0 ± 0.1° C and 2.0 M ionic strength maintained with NaClO4. The pH change in azide/hydrazoic acid buffers caused by the metal cation addition was the basis of the potentiometric method to study the complex formation. A wide range of azide concentration was used at several metal cation (cobalt or nickel) concentration in order to provide reliable results. With regard to the Co(II)/N-3 system the formation of five stepwise complexes was detected. The stability constants were computed from three different calculation procedures. The best set of formation constants is: β1 = 5,67 ± 0,20 M-1 β2 = 19,5 ± 2,1 M-2 β3 = 6,52 ± 4,66 M-3 β4 = 15,8 ± 2,0 M-4 β5 = 4,83 ± 0,31 M-5 The nickel(II)/azide system presented a quite different behaviour as compared with the cobalt(ll) one, as extensive polynuclear complex formation is attained. A monographic study about this kind of complex formation seemed interesting to be included in this thesis. An extensive study of the nickel(II)/azide system was performed at conditions wich provide enough experimental data to be treated on basis of polynuclear complex formation. Two different calculation procedures lead to the following set of equilibrium constant: mononuclear Ni(N3)+ β11 = 5,80 Ni(N3)2 β12 = 9,69 Ni(N3)-3 β13 = 7,54 Ni(N3)=4 β14 = 534 binuclears Ni2(N3)3+ β21 = 4,06 Ni2(N3)2+2 β22 = 31,8 Ni2(N3)+3 β23 = 175 Ni2(N3)4 β24 = 2,06x104 Ni2(N3)-5 β25 = 2,30x105 Ni2(N3)=6 β26 = 7,15x105 trinuclears Ni3(N3)2+4 β34 = 2,28x104 Ni3(N3)+5 β35 = 3,51x106 Ni3(N3)6 β36 = 1,17x108 Two complementary studies, potentiometric and spectrophotometric, were performed at high metal cation/1igand ratio in order to create conditions for the existence of on1y a few species as Ni(N3)+ and Ni2(N3)3+. β11 from spectrophotometric method is 6.90 M-1; from potentiometric method β11 is 7.53 ± 0.10 M-1 and β21 is 4.29 ± 0.15 M-2. The molar absorptivities at λmax, 293 nm, was calcu1ated as ε11 = 362 cm-1. mol-1.1 and ε21 = 475 cm-1. mol-1.1. Finally a conductometric titration of 0.4 M niekel(II) with 3.9 M sodium azide showed a high contribution of Ni2(N3) -5 in agreement with the potentiometric study. A series of distribution diagrarns were plotted in order to have the percent contribution of each species vs. the ligand concentration and, eventually, vs. the metal concentration when polynuclear complexes are formed.

Esta pesquisa objetivou estudar cefalometricamente as estruturas dentoesqueléticas em pacientes de Classe II, 1ª divisão, por meio de tratamentos realizados com um protocolo; ancoragem extrabucal e aparelho fixo inferior até a obtenção da relação molar normal e o nivelamento dos dentes e da curva de Spee, e para a finalização o aparelho fixo superior. A amostra (grupo experimental) para a realização deste estudo consistiu de 50 telerradiografias, 25 ao início e 25 ao final do tratamento, de 25 pacientes tratados ortodonticamente, apresentando má oclusão inicial de Classe II, 1ª divisão, de ambos os gêneros, com idade média de 10 anos e 2 meses. Para comparação, utilizou-se um grupo controle, composto de 14 indivíduos não tratados, com má oclusão de Classe II, 1ª divisão, de ambos os gêneros, com idade média de 9 anos e 6 meses. As telerradiografias desses indivíduos não tratados foram tomadas em dois tempos, compatíveis com o tempo de tratamento de 31,9 meses do grupo experimental. Após a análise estatística das medidas obtidas, no início e no final das avaliações, em ambos os grupos, concluiu-se que, quanto à influência do tratamento (protocolo): não ocorreram alterações no padrão de crescimento; a maxila apresentou uma restrição no seu deslocamento para anterior, evidenciado pelo ponto A; ocorreu uma estabilidade dos planos oclusal e mandibular em relação à base do crânio; não ocorreu alteração estatisticamente significante nos componentes mandibulares; nos molares e nos incisivos superiores e inferiores, não ocorreram alterações estatisticamente significantes nos sentidos horizontal, vertical e nas medidas angulares. A correção da Classe II ocorreu mais devido a alterações dentoalveolares mandibulares pela mesialização dos molares inferiores e manutenção do plano oclusal, associado à restrição dos molares superiores, sem alterações esqueléticas estatisticamente significantes. / This cephalometric study aimed to evaluate the dentoskeletal structures in Class II, division 1 subjects, treated with a different treatment protocol; Klöehn Head Gear (KHG) which is used in the upper arch and fixed appliance in the lower arch, to correct the dental and skeletal discrepancies, and to obtain the leveling of the curve of Spee, and then finalizing with the fixed appliance in the upper arch. The sample (experimental group) comprised 50 lateral cephalograms, 25 pretreatment and 25 posttreatment, from patients of both genders, presenting initially Class II division 1 malocclusion, with a mean age of 10 years. This sample was compared to a control group of 14 nontreated subjects of both genders, with the same malocclusion and the same mean age of the experimental group. The groups were compared by the t test. The results showed that, for the experimental group: no change in the craniofacial growth pattern was observed; the forward displacement of the maxilla was restraint; the occlusal and mandibular planes in relation to the cranial base presented stable; no significant alteration in mandibular components was noted; the upper and lower incisors did not change in the vertical, horizontal and sagital senses; and the correction of the Class II was due more to dentoalveolar changes than to skeletal changes.