Thesis (doctoral)--Freie Universität Berlin, 1980.

Düsseldorf, Universiẗat, Diss., 2003.

Over the past decade, the occurrence and removal of emerging contaminants in the environment has received much attention. Both natural and synthetic progestogens, which are hormones, and also benzotriazoles are two examples of such emerging contaminants. Sewage treatment works are recognised as one of the main routes of these compounds to the environment. Low concentrations (nanograms per litre) of biologically active chemicals may exhibit an impact on aquatic organisms and human health. This study was undertaken to determine the occurrence and removal of these two classes of chemicals at sewage treatment works, along with an evaluation of the performance of advanced treatment and also to investigate their fate in the aquatic environment. Therefore, field-based sampling campaigns were undertaken at a sewage treatment works, rivers and potable water to achieve these aims. Solid phase extraction and LC/MS/MS were used in order to analyse the samples from these different locations, along with catchment modelling and assessment of how the use of benzotriazoles may contribute to their presence in the environment. The results have demonstrated that progestogens and benzotriazoles are in the sewage system; the natural hormone (progesterone) was the most predominant compound entering the sewage treatment work (46.9 ng/l) among the progestogens while concentrations of the benzotriazoles were two orders of magnitude higher than the progestogens. The conventional sewage treatment works were, to some extent, able to remove these compounds from wastewaters. However, this may not be adequate to afford protection to the environment. The investigation of advanced treatments, ozone, granular activated carbon and chlorine dioxide, indicated no further significant removal of progestogens, probably as a result of concentrations being close to method detection limits. However, there were indications that benzotriazoles were removed. A degradation study demonstrated that the natural hormone (progesterone) was degraded rapidly while benzotriazoles were not degraded. Catchment modelling indicated that high (up to 2,000 ng/l) concentrations of benzotriazoles would be present in surface waters used for potable supply, and consequently benzotriazoles were found in the tap water with mean concentrations of 30.9 ng/l (benzotriazole) and 15.1 ng/l for tolyltriazole. It is therefore apparent that although conventional treatment may be seen as effective, achieving over 90% removal, this may not be good enough. However, before investing in tertiary treatment, a number of factors, such as the effectiveness at different sites, the presence of degradation products and costs, both financial and in relation to energy use, need to be considered.

Zugl.: Berlin, Techn. Univ., Diss., 2007

No description available.

No description available.

Les amines homoallyliques sont des synthons clés pour la construction de nombreuses molécules d'intérêt biologique. Du fait de la double liaison carbone-carbone du fragment allylique, facilement fonctionnalisable, elles sont également très utilisées en synthèse organique. Ce travail de recherche s'oriente sur la synthèse d'amines homoallyliques grâce à des complexes de titane. En effet, le couplage réducteur d'imines et de diènes promu par du titane permet la formation d'amines homoallyliques diastéréoisomères syn et anti. La diastéréosélectivité de la réaction est directement affectée par le substituant porté par l'atome d'azote. Selon qu'il s'agit d'un groupement benzyle ou phényle, la sélectivité sera marquée en faveur de l'amine syn ou anti respectivement. De plus, l'ajout de l'acide de Lewis BF3.OEt2 permet de diminuer considérablement le temps de réaction mais également d'inverser la diastéréosélectivité obtenue avec la réaction sans acide de Lewis.L'instabilité des amines homoallyliques durant le processus de purification a permis d'autre part de mettre en lumière un réarrangement cationique 2-Aza-Cope. Ce réarrangement a été appliqué à la synthèse catalytique d'homocrotylamines et d'un acide aminé , insaturé. Ce manuscrit rapporte également la synthèse d'amines homoallyliques par couplage entre des diènes et des dérivés benzotriazole. Ces dérivés génèrent des iminiums qui réagissent plus efficacement que les imines pour former les amines souhaitées. De plus, la réaction effectuée avec des dérivés de type bis(benzotriazole) conduit sélectivement à des homoallyl-(E)- homocrotylamines. Cette réactivité est expliquée par une triple réaction en cascade à savoir : allyltitanation - réarrangement cationique 2-Aza-Cope - allyltitanation.D'autre part, une partie de ce manuscrit s'intéresse à la réaction entre le complexe Ti(NMe2)4 et des dioxocyclames qui forment de nouvelles diamidines macrocyliques. Les propriétés chimiques de ces amidines présentent de nombreux intérêts pour la formation de complexes avec des métaux tels que le Cu, le Ni et le Pd. Les analyses des complexes méritent d'être approfondies afin de déterminer sans ambigüité leur structure et de mieux comprendre le mode de coordination de ces nouveaux macrocycles azotés.

O comportamento eletroquímico do aço-carbono 1005, do aço galvanizado e do zinco foi estudado em meios aerados de ácido sulfúrico 0,5 mol.L-1 (aço-carbono) e cloreto de sódio 0,01 mol.L-1 na ausência e presença do inibidor de corrosão benzotriazol (BTAH), a 25 ºC. Foram empregadas como técnicas ensaios gravimétricos, medidas de transitórios de potencial de circuito aberto, voltametria linear, espectroscopia de impedância eletroquímica (EIE), varredura com eletrodo vibratório (SVET), microscopia eletrônica de varredura (MEV), espectroscopia por dispersão de energia (EDS), espectroscopia eletrônica de raio X (XPS), espectroscopia Raman. O BTAH se mostrou inibidor para os três materiais metálicos nos meios estudados, comportando-se como inibidor misto. A sua ação inibidora decresce na ordem Zn>aço carbono>aço galvanizado em meio de cloreto de sódio. Para o aço-carbono em meio de ácido sulfúrico a adição de íons Cu(II) eleva a eficiência do BTAH, mas em tempos mais elevados de imersão há formação de cobre metálico que promove corrosão galvânica. Em meio de cloreto de sódio os filmes formados sobre aço e sobre zinco correspondem aos respectivos complexos Fe(III) e Fe(II) e de Zn(II) com BTAH. A ação sobre o zinco do BTAH, no caso do aço galvanizado reduz a eficiência na proteção catódica conferida pelo zinco ao aço. A eficiência inibidora sobre aço-carbono depende da composição da liga e da natureza das inclusões presentes no material. Estudos sobre a secção transversal do aço galvanizado em meio de cloreto de sódio mostraram que o BTAH inibe a oxidação do zinco, com formação do complexo, e a redução do oxigênio sobre o aço, com adsorção da molécula de BTAH. O filme formado sobre zinco, ensaiado separadamente, obedece à isoterma de Langmuir, com valores de energia livre padrão de adsorção que evidenciam a natureza química da adsorção, apontando para um complexo com BTAH. / The electrochemical behavior of carbon steel, galvanized steel and zinc has been studied in aerated 0.5 mol.L-1 sulfuric acid and 0.01 mol.L-1 sodium chloride solutions in the absence and presence of benzotriazole (BTAH) at 25ºC. Weight loss experiments, open circuit potential, transient measurements, linear voltammetry, electrochemical impedance spectroscopy (EIS), scanning electronic microscopy (SEM), energy dispersive spectroscopy (EDS), canning vibrating electrode technique (SVET), X-ray photoelectron spectroscopy and Raman spectroscopy used as techniques. BTAH has shown inhibition for the three materials in the media studied and acted as a mixed inhibitor. Its inhibitive effect decreases in the sequence Zn>carbon steel>galvanized steel in chloride medium. In sulfuric medium the BTAH efficiency is improved with the presence of Cu(II) ions but this effect is suppressed at long times immersion when metallic copper is formed promoting galvanic corrosion. The films formed on zinc and carbon steel in chloride medium correspond, respectively to a Fe(II), Fe(III) mixed complex and to Zn(II) complex with BTAH. Studies on the cross section of galvanized steel (cut edge) have shown that the high effect of BTAH as inhibitor for zinc tends to decrease the efficiency of cathodic protection of this metal on carbon steel. For carbon steel in sulfuric medium the composition and the nature of inclusions have an important role on the inhibitor efficiency. On the cut edge the inhibitor promotes the formation of a zinc complex on this metal and it is adsorbed on carbon steel as a molecule inhibiting the oxygen reduction. The film formed on zinc when separately studied obeys to a Langmuir isotherm with standard adsorption free energy values denoting the presence of chemical adsorption as an indicative of the presence of a complex

The synthesis and optoelectronic properties of biphenyl based conjugated copolymers with varying acceptor units in the polymer backbone were investigated. The well known Donor-Acceptor Theory was used to establish the synthetic pathway for the structural modifications. Solubility issues regarding biphenyl polymer was solved by copolymerizing with soluble units. For this purpose / poly 4-(biphenyl-4-yl)- 4&rsquo / -tert butylspiro[benzo[d]imidazole-2,1&rsquo / -cyclohexane] (P1), poly 4-(biphenyl-4-yl)- 2- dodecyl-2H-benzo[d][1,2,3]triazole (P2) and poly(4-(5-(biphenyl-4-yl)-4-hexylthiophen- 2-yl)-2-dodecyl-7-(4-hexylthiophen-2-yl)-2H-benzo[d][1,2,3]triazole (P3) were synthetized using Suzuki coupling process. Electrochemical properties of these polymers were examined by cyclic voltammetry, spectroelectrochemistry and kinetic studies. Polymers P2 and P3 showed both p- and n-doping behaviors and multicolored electrochromic states. Optical studies revealed that emission color of biphenyl is tuned from blue to orange and the polymers are good candidates for light emitting diode applications. OLED application of P3 was established and outputs of the device were increased by energy transfer studies. The preliminary investigation indicated that P3 possesses promising efficiencies.

Benzimidazole and benzotriazole derivatives, 4-(2,3-Dihydrothieno[3,4-b][1,4] dioxin-5-yl)-7-(2,3-dihydrothieno[3,4b][1,4]dioxin-7-yl)-2-benzyl-1H-benzo[d] imidazole (BIm-Ed), 2-benzyl-4,7-di(thiophen-2-yl)-2H-benzo[d] [1,2,3] triazole (BBTS), and 2-benzyl-4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2Hbenzo[ d] [1,2,3] triazole (BBTES) were employed as photosensitizers for diaryliodonium salt photoinitiators in cationic photopolymerization of various epoxide and vinyl ether monomers. Diphenyliodonium hexafluorophosphate (Ph2I+PF6&macr / ) salt was used as the photoinitiator in this study. Extended conjugation and electron-rich moieties of the photosensitizers enabled the use of long wavelength UV and visible light emitting light sources in cationic photopolymerizations. Polymerizations were achieved at room temperature and monitored by optical pyrometry. Photopolymerization of a diepoxide monomer with ambient solar irradiation was examined.