Die Diphthalocyanine der Seltenerdmetalle werden durch Reaktion von Seltenerdmetallacetat mit o-Phthalsaeuredinitril hergestellt. Die Diphthalocyanine existieren in zwei Formen, die sich in der Existenz eines delokalisierten freien Elektrons (Radikalform) oder eines ¨zusaetzlichen¨ Wasserstoffatoms unterscheiden. Die Charakterisierung der beiden Diphthalocyaninformen erfolgt mittels der IR-Spektroskopie und UV/VIS/NIR-Spektroskopie. Detailliert wird das spektroskopische Verhalten der Diphthalocyanine in unterschiedlichen Loesungsmitteln untersucht. ESR-spektroskopisch ist das freie Elektron der Radikalform nachweisbar. Zur Untersuchung des elektrochromen Verhaltens der Diphthalocyanine werden Schichten durch Sublimationsverfahren oder durch LB-Technik hergestellt. Die Analyse der Schichtstruktur erfolgt mittels HRTEM. Das elektrochrome Verhalten wird unter Beruecksichtigung des Schichtherstellungsverfahrens, der Diphthalocyaninform und der Art des verwendeten Elektrolyten untersucht. Die beobachteten Farbaenderungen reichen von violett, blau, gruen, blass-gelb, orange nach rot. Die entsprechenden UV/VIS-Spektren werden im Zusammenhang mit den ablaufenden Oxidations- und Reduktionsreaktionen diskutiert.

ABSTRACT ELECTROCHEMICAL SYNTHESIS OF CROWNED CONDUCTING POLYMERS: NATURE OF RADICAL CATIONS IN POLYMERIZATION AND MECHANISM OF CONDUCTIVITY Cihaner, Atilla Ph. D., Department of Chemistry Supervisor: Prof. Dr. Ahmet M. &Ouml / nal June 2004, 96 Pages Poly(dibenzo-18-crown-6) (Poly(DB18C6)) was synthesized by electrochemical oxidation of dibenzo-18-crown-6 (DB18C6) using a mixture of acetonitrile and dichloromethane as solvent and tetrabutylammonium tetrafluoroborate (TBABF4) or tetrabutylammonium hexafluorophosphate (TBAPF6) as supporting electrolyte. The anodic polymerization of DB18C6 was investigated using in-situ ESR and in-situ UV-VIS spectroscopic techniques. Spectroelectrochemical (SPEL) properties and thermal analysis of the resulting polymers have been investigated using UV-VIS, Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA). Furthermore, new compounds consisting of bis(2-thienyl) methyl (I and II) and bis(2-thienyl) ethyl (III) units linked by polyether bridges have been synthesized and their electrochemical polymerization was performed via constant potential electrolysis (CPE) in an electrolytic solution containing 0.1 M TBAPF6 dissolved in CH3CN. Also, I and II were polymerized via chemical oxidation which yielded broken &amp / #61552 / -conjugated polymers except for III. The polymers were characterized using 1H-NMR and FT-IR spectroscopic techniques. In addition, copolymers of III with thiophene (Th) and pyrrole (Py) were studied with cyclic voltammetry (CV). SPEL behaviors of the products were investigated using UV-VIS spectroscopic technique.

Submitted by Natalia de Souza Gonçalves (natalia.goncalves@ufpe.br) on 2016-09-23T11:47:49Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE RLA_Número 128 do PROTEN (1).pdf: 33719595 bytes, checksum: b30f5b4c6bf01a2a0e411971586424f3 (MD5) / Made available in DSpace on 2016-09-23T11:47:50Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE RLA_Número 128 do PROTEN (1).pdf: 33719595 bytes, checksum: b30f5b4c6bf01a2a0e411971586424f3 (MD5) Previous issue date: 2016-02-25 / CAPES / FACEPE / O sítio arqueológico Lagoa Uri de Cima é uma lagoa intermitente, hoje seca, localizada no município de Salgueiro, estado de Pernambuco, Brasil. Durante as escavações realizadas no local entre os anos de 2010 e 2013, ossadas de mamíferos de grande porte, atualmente extintos, conhecidos como animais da megafauna, típicos do período quaternário,foram encontradas nas camadas mais profundas da lagoa. Este trabalho apresenta os resultados das datações por espectroscopia por ressonância paramagnética eletrônica (RPE) realizadas em amostras de dentes, provenientes das ossadas da megafauna encontradas na Lagoa Uri de Cima: 1 dente da espécie Hippidion bonaerensis, 2 dentes da família Toxodontidae, e 2 dentes de espécie Haplomastodon waring. Sedimentos em diferentes níveis estratigráficos da lagoa também foram analisados e datados pela técnica de luminescência opticamente estimulada (LOE). As doses acumuladas nas amostras de dentes e sedimentos foram determinadas, respectivamente, através dos métodos de doses aditavas e doses regenerativas. A taxa de dose anual foi estimada através da determinação dos teores de urânio, tório e potássio presentes nas amostras de dentes analisadas, bem como nos sedimentos do local. Para as amostras de dentes, as taxas de dose anual e idades foram estimadas através dos programas ROSY e DATA, que levam em consideração fatores como umidade e forma como o urânio foi incorporado pelos tecidos dentários, através dos modelos de captação: precoce (CP), linear (CL) e combinado (CC). Para as amostras de sedimentos, foi utilizado o programa AGE. Em relação a datação dos dentes, valores semelhantes de taxas de dose anual e idades para cada amostra foram obtidos através dos dois programas. As maiores e menores idades estimadas foram, respectivamente, para a espécie Hippidion bonaerensis: 20 ± 0,90mil anos (CP), 22 ± 0,70mil anos (CL),20± 0,80 mil anos (CC); e Haplomastodon waring: 13 ± 0,70mil anos (CP), 15 ± 0,80mil anos (CL),13 ± 0,80 kanos (CC). Em relação à datação dos sedimentos, os resultados obtidos estão dentro das perspectivas dos arqueólogos que estudam a formação geológica do sítio Lagoa do Uri de Cima, tendo sido estimado para o nível mais superficial da lagoa a idade de 3,6 ± 0,60mil anos e para o nível mais profundo 152 ± 16mil anos. Levandose em consideração os níveis estratigráficos em que os dentes da megafauna foram coletados, as idades estimadas para os dentes mostram uma coerência com as idades estimadas para os sedimentos coletados nos diferentes níveis estratigráficos da lagoa através da técnica de datação por LOE, permitindo uma maior confiabilidade para a datação dos sedimentos. Além disso, este trabalho contribuiu para a implantação da técnica de datação de dentes por espectroscopia RPE no laboratório do Grupo de Metrologia Arqueológica e Patrimonial (MAP) da Universidade Federal de Pernambuco (UFPE), o que permitirá auxiliar outras pesquisas arqueológicas e geológicas realizadas em outros sítios, além das realizadas no sítio Lagoa Uri de Cima. / the municipality of Salgueiro, in Pernambuco state, Brazil. During the excavations at this site, between the years 2010 and 2013, fossils of large mammal, presently extinct, also known as megafauna animals, typical of the quaternary period, were found in the lower layers on bottom of this lake. This study presents the results of electron spin resonance (ESR) spectroscopy dating performed on samples of teeth from megafauna fossils found in "Lagoa Uri de Cima" site: a Hippidion bonaerensis tooth, two Toxodontidae teeth, and two Haplomastodon waring teeth. Sediments from different stratigraphic levels of the lake were also analyzed and dated by optically stimulated luminescence (OSL). Cumulative doses from the teeth and sediments samples were determined, respectively, by additive doses and regenerative doses methods. The annual dose rate was estimated by the determination of the levels of uranium, thorium and potassium present in the teeth samples as well in the surrounding sediments. For the teeth samples, annual dose rates and ages were estimated via ROSY and DATA softwares, which take into account factors such as humidity and how uranium was incorporated by dental tissues through the uptake models: early (EU), linear (LU) and combined (CU). For sediments, the AGE software was used. Concerning the teeth dating, similar values from annual dose rates and ages were obtained from both programs. The highest and lowest estimated ages were, respectively, for the species Hippidion bonaerensis: 20 ± 0,90 thousand years (EU), 22 ± 0,70 thousand years (LU), 20 ± 0,80 thousand years (CU); and Haplomastodon waring: 13 ± 0,70 thousand years (EU), 15 ± 0,80 thousand years (LU), 13 ± 0,80thousand years (CU).. Regarding the dating of the sediments, the results are within the perspectives of the archaeologists that study the geological formation of the “Lagoa Uri de Cima” site, having been estimated for the most superficial level of the lagoon an age of3,6 ± 0,60 thousand years and for the most deeper level an age of 152 ± 16 thousand years. Taking into account the stratigraphic levels in which the megafauna teeth were collected, the estimated ages for these teeth show a consistency with the estimated ages for the sediment collected at different stratigraphic levels of the lagoon, through the LOE dating method, allowing a greater reliability for the dating of the sediments. Furthermore, this work contributed to the implementation of the RPE dating for teeth by the group of “Metrologia Arqueológica e Patrimonial” (MAP) at the “Universidade Federal de Pernambuco” (UFPE), which will support other archaeological and geological researches, in other sites, beyond the researches performed at "Lagoa Uri de Cima" site.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16876号 / 工博第3597号 / 新制||工||1543(附属図書館) / 29551 / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 白川 昌宏, 教授 佐藤 啓文, 教授 梶 弘典 / 学位規則第4条第1項該当

Die Elektronen-Spin-Resonanz (ESR) Spektroskopie hat sich in Verbindung mit der Spinsondentechnik (SDSL) bereits seit einigen Jahren zur Struktur- und Dynamikanalyse von Biomakromolekülen etabliert. Diese Dissertation beschäftigt sich mit dem Aufbau eines Hochfeld-/Hochfrequenz-ESR-Spektrometers bei 3,4T/95GHz (W-Band) und drei attraktiven Anwendungen auf spinmarkierte Proteine. Als eine Anwendung wird die Bestimmung von Polaritäten und Protizitäten spinmarkierter Positionen des sensorischen Rhodopsin-Transducer-Komplexes (SRII/HtrII) aus Natronomonas pharaonis mit Hilfe von cw-Messungen bei Temperaturen <190 K präsentiert. Es werden Rückschlüsse auf die Struktur der HAMP-Domäne des Proteinkomplexes durchgeführt. Positionsabhängige Unterschiede der Protizität werden auf verschiedene Anteile mit null bis zwei Wasserstoffbrücken zum Nitroxid zurückgeführt. Als nächste Anwendung wird die Gewinnung von Reorientierungspotentialen der Spinträgerseitenkette mit dem SRLS-Model und in Kombination mit X- und Q-Bandmessungen bei Raumtemperatur demonstriert. Für die spinmarkierte Position einer Konformation des SRII/HTrII ergibt sich ein Potential, dass mit Ergebnissen von Molekulardynamiksimulationen eines helikalen Polypeptids gut übereinstimmt. Ebenfalls durchgeführt wurde die Bestimmung des Potentials an Position 166 der Kanal bildenden Domäne des Colicin A aus E. coli. Schließlich werden im Temperaturbereich von 120 bis 220 K die Einflüsse verschiedener (Isotopen-)Derivate des Spinlabels und der Einfluss der Wasserprotonen auf den Hahn-Echozerfall zur Bestimmung orientierungsabhängiger Librationsamplituden an einer weiteren SRII/HtrII-Probe und der gleichen Colicin A-Probe wie oben vorgestellt. Es werden Folgerungen für die Struktur der Proteine gezogen und, im Fall der Colicin A-Probe, ein Bezug zur Kristallstruktur hergestellt.

The cytoskeletal protein vinculin plays a key role in the control of cell-cell or cell-matrix adhesions. It is involved in the assembly and disassembly of focal adhesions and affects their mechanical stability. While many facts highlight the importance and significance of vinculin for vital processes, its precise role in the regulation of cell adhesions is still only partially understood. Various EPR methods are used in this work in order to study the vinculin tail (Vt) domain in an aqueous buffer solution and its structural changes induced by F-actin and acidic phospholipids. EPR results in combination with a rotamer library approach (RLA), MD simulation and other computational methods allowed the construction of molecular models of Vt and dimeric Vt in the presence and absence of its binding partners. Furthermore, X-band orientation selective DEER measurements were applied on a Vt double mutant. It could be shown that the determination of the mutual orientation of protein bound spin labels is possible at X-band frequencies, if the orientation correlation of the spin label pair is strong. The method established here can be used to determine valuable information about proteins and nucleic acids, expanding the virtue of DEER spectroscopy as a tool for structure determination.

No description available.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / This study concerns the phenomenon of environmental stress cracking resistance (ESCR) in three impact polypropylene copolymers (IPPCs). The main purpose was to correlate the ESCR with their properties such as microstructure, molecular weight (MW), molecular weight distribution (MWD), crystallinity and morphology. Initially the selection of a suitable test method and an active stress cracking agent (SCA) were the preliminary concerns. The Bell telephone test was used to evaluate SCAs, while a published procedure for determining ESCR of ethylene based plastics was adapted for the purpose of this study. Isopropanol was selected as SCA. Polymers were fully characterized by FTIR, 13C NMR, DSC and high temperature GPC. Optical microscopy was used to investigate craze formation and crack growth, and scanning electron microscopy (SEM) was used to study the morphology of the polymers. Since IPPCs are known to have multi-fraction copolymeric structures and each of these fractions has significantly different average properties, fractions were selectively removed from the materials, either by solvent extraction at room temperature, or by TREF fractionation. The effect of removing these fractions on the ESCR was determined. The effect of the molecular composition of the three IPPCs on the ESCR of these materials, as well as the effect of the removal of the selected molecular fractions on the ESCR, morphology and molecular characteristics are discussed and compared. Conclusions are drawn as to the factors controlling ESCR in these materials.

Background: Renal cell carcinoma (RCC) is most lethal of the urological cancers, with more than 40% dying of the disease. About 30% of the patients have metastases at initial diagnosis and up to 40% undergoing nephrectomy for localized RCC develop metastasis. A follow-up protocol based on accurate prognostic variables allows identification of low and high risk patients and selection of those most likely to benefit from adjuvant therapy. I have studied a number of prognostic patient-related factors, including tumour stage and grade, angiogenetic factors and tumour markers, in order to improve follow-up guideline as well as to try to predict prognosis and clinical outcome for individual patients. Material and Methods: The studies are based on patients treated for RCC between 1982 and 2002. All patients eligible for surgery with or without metastasis were treated with nephrectomy and were followed according to a scheduled follow-up programme. Serum samples were collected after obtained informed consent. Multiple clinicopathological, laboratory variables and preoperative radiological examinations were analyzed. Results: Study I- After nephrectomy in 187 patients with non-metastatic RCC, 30% developed metastases during the follow-up. The risk for metastases was greater for more advanced stage and was adjusted by size and DNA ploidy. The median time to the diagnosis of metastases was 14.5 months. Metastases occurred in 43% of the patients within one year, within 2 years in 70% and 80% in 3 years. Patients with tumours less than 5 cm and diploid pT1&gt;5cm and pT2 tumours survived longer than those with larger and aneuploid tumours. The 5-years survival rate for pT1, pT2, pT3 tumours were 95%, 87%, and 37% respectively. In pT3 tumours DNA ploidy had no relation to survival time. Study II and IV- The median survival time for patients with metastatic RCC was 7 months. Cytoreductive nephrectomy was associated with longer survival time. Factors including performance status (PS), number of metastatic sites, erythrocyte sedimentation rate (ESR), calcium in serum, vein invasion, capsule invasion had independent prognostic value with Cox multivariate analysis. Study III- The incidence of adrenal tumour involvement was 5.3 %, unaffected of RCC type, tumour location or side. Gender (male) and locally advanced tumours (pT3 &gt; 5cm) were factors predicting adrenal involvement. The presence of adrenal involvement was a significant adverse prognostic variable, indicating a significantly shorter survival in patients both with and without distant metastases. Conclusion: Optimal follow-up guidelines are important from both medical and economic perspectives. The risk for progression depends mainly on stage, which in combination with other prognostic factors may allow more individualized and cost effective follow-up, in some cases by avoiding unnecessary examinations in a third of the patients. Cytoreductive nephrectomy in patients with good PS, metastases limited to one organ, low ESR, normal calcium and no vein invasion were factors associated to long survival time. Soluble angiogenic factors in serum gave no prognostic information. Ipsilateral adrenalectomy in conjunction with radical nephrectomy should be performed if an adrenal lesion cannot be cleared of suspicion during preoperative work up. Ipsilateral adrenal involvement is a highly adverse prognostic factor and should be staged as M1a in the TNM staging system.

The epilepsies are a heterogenous group of symptom complexes, whose common features is the recurrence of seizures. There is no certain therapy for epilepsy. In order to promote new advances for the prevention of epilepsy the molecular mechanism of epileptic activities should be clarified. In the present study the goal is to obtain information for molecular mechanism of epilepsy. To achieve this, molecular alterations from pentylenetetrazol (PTZ)-induced epileptic activities on rat brain tissue and cell membranes were investigated by Fourier Transform Infrared (FTIR) spectroscopy, Fourier Transform Infrared Microscopy and Atomic Force Microscopy (AFM). Moreover, the therapeutic role of an antiepileptic agent vigabatrin (VGB) on epileptic rat brain membranes were examined at molecular level. For better understanding of the action mechanism of PTZ and an antiepileptic drug VGB in cell membranes we firstly studied at model level using multilamellar liposomes (MLVs). We investigated PTZ-DPPC MLVs interactions in terms of lipid phase behavior, order and dynamics and nature of hydrogen bonding around its polar part, using Fourier Transform Infrared (FTIR) spectroscopy, Differential Scanning Calorimetry (DSC), Electronspin Resonans Spectroscopy (ESR) and Steady State Fluorescence Spectroscopy. According to our data, PTZ has no ability to interact with membrane lipids. On the other hand, the results of VGB-DPPC interactions showed that VGB strongly interact with the head group and/or the region near the head of membrane phospholipids. The molecular investigation of PTZ-induced epileptic activities revealed that PTZ-induced seizures cause a decrease in the lipid and protein content, membrane fluidity and glycogen level. They stimulate alterations in membrane packing and the secondary structure of proteins as well as lipid peroxidation. In addition, our results show the transcription of early genes following high dose PTZ administration. All these molecular alterations variatins are only resulted from the consequences of epileptic activities not from convulsant agent PTZ itself. The important finding is that, VGB restored some of the alterations by PTZ-induced epileptic activities on brain cell membrane. For instance, it restored membrane fluidity, lipid peroxidation, phospholipid degradation and changes in membrane organization. However, it was found that VGB has no significant effects on the changes in protein secondary structure.