Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-08-09T22:44:45Z No. of bitstreams: 1 AntonioMarcosUrbanoDeAraujo_TESE.pdf: 3225313 bytes, checksum: e25ff75db18347413666f8caf426a50e (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-08-10T22:25:30Z (GMT) No. of bitstreams: 1 AntonioMarcosUrbanoDeAraujo_TESE.pdf: 3225313 bytes, checksum: e25ff75db18347413666f8caf426a50e (MD5) / Made available in DSpace on 2016-08-10T22:25:30Z (GMT). No. of bitstreams: 1 AntonioMarcosUrbanoDeAraujo_TESE.pdf: 3225313 bytes, checksum: e25ff75db18347413666f8caf426a50e (MD5) Previous issue date: 2016-01-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Foram sintetizados neste trabalho em solu??o aquosa os seguintes compostos de coordena??o: [Ni(LDP)(H2O)2Cl2].2H2O, [Co(LDP)Cl2].3H2O, [Ni(CDP)Cl2].4H2O, [Co(CDP)Cl2].4H2O, [Ni(BDZ)2Cl2].4H2O e [Co(BDZ)2Cl2].(H2O). Esses complexos foram sintetizados por adi??o estequiom?trica do ligante nas respectivas solu??es de cloretos do metal. A precipita??o ocorreu ap?s a secagem dos solventes sob temperatura ambiente. A caracteriza??o e proposta das estruturas foram realizadas utilizando-se de m?todos convencionais de an?lise tais como: an?lise elementar (CHN), espectroscopia de absor??o na regi?o do infravermelho com transformada de Fourier (FTIR), difratometria de raios X pelo m?todo do p? e as t?cnicas termoanal?ticas TG/DTG (termogravimetria/termogravimetria derivada) e DSC (calorimetria explorat?ria diferencial). Estas t?cnicas forneceram informa??es sobre desidrata??o, modos de coordena??o, comportamento t?rmico, composi??o e estrutura dos compostos sintetizados. Com os resultados das curvas TG, p?de-se estabelecer a f?rmula geral de cada composto sintetizado. Pela an?lise dos difratogramas de raios X foi observado que quatro dos complexos sintetizados apresentam estrutura n?o cristalina que foram os complexos obtidos a partir da L-dopa e Carbidopa e para os complexos obtidos a partir do benzimidazol obteve-se estruturas cristalinas. As observa??es dos espectros na regi?o do infravermelho sugeriram uma coordena??o monodentada do ligante aos respectivos centros met?licos atrav?s do grupo amina para todos os complexos. As curvas TG-DTG e DSC forneceram informa??es e importantes sobre o comportamento e a decomposi??o t?rmica dos compostos sintetizados. Os dados de condutividade molar apontaram que as solu??es dos complexos formados se comportam como um n?o-eletr?lito, o que implica dizer que o cloro est? coordenado ao ?tomo central nos complexos. / Were synthesized in this work in the following aqueous solution coordination compounds: [Ni(LDP)(H2O)2Cl2].2H2O, [Co(LDP)Cl2].3H2O, [Ni(CDP)Cl2].4H2O, [Co(CDP)Cl2].4H2O, [Ni(BDZ)2Cl2].4H2O and [Co(BDZ)2Cl2(H2O)2]. These complexes were synthesized by stoichiometric addition of the binder in the respective metal chloride solutions. Precipitation occurred after drying the solvent at room temperature. The characterization and proposed structures were made using conventional analysis methods such as elemental analysis (CHN), absorption spectroscopy in the infrared Fourier transform spectroscopy (FTIR), X-ray diffraction by the powder method and Technical thermoanalytical TG / DTG (thermogravimetry / derivative thermogravimetry) and DSC (differential scanning calorimetry). These techniques provided information on dehydration, coordination modes, thermal performance, composition and structure of the synthesized compounds. The results of the TG curve, it was possible to establish the general formula of each compound synthesized. The analysis of X-ray diffraction was observed that four of the synthesized complex crystal structure which does not exhibit the complex was obtained from Ldopa and carbidopa and the complex obtained from benzimidazole was obtained crystal structures. The observations of the spectra in the infrared region suggested a monodentate ligand coordination to metal centers through its amine group for all complexes. The TG-DTG and DSC curves provide important information and on the behavior and thermal decomposition of the synthesized compounds. The molar conductivity data indicated that the solutions of the complexes formed behave as a nonelectrolyte, which implies that chlorine is coordinated to the central atom in the complex.

Die Verpackung und Spaltung konkatemerer DNA ist ein essentieller Prozeß bei der Reifung von Virionen. Die an diesem Prozess maßgeblich beteiligten Proteine werden als Terminase bezeichnet. Die Inhibition der HCMV Terminase bietet einen attraktiven alternativen Ansatzpunkt für die antivirale Therapie. Zur Inhibition der Terminase Aktivität wurden die neuen Benzimidazol D-Ribonukleosid Derivate BTCRB und Cl4RB auf ihre antivirale Wirkung analysiert. Die neuen Benzimidazol D-Ribonukleosid Derivate BTCRB und Cl4RB zeigten sowohl gegen den HCMV Laborstamm AD169 als auch gegen klinische HCMV-Isolaten eine Wirkung. Weiterhin wurde die Wirksamkeit der Substanzen auf anderen Herpesviren getestet. Interessanterweise zeigten BTCRB und Cl4RB sowohl einen Effekt gegen Varicella-Zoster-Virus (VZV) als auch Ratten-Cytomegalovirus (RCMV), wohingegen der Effekt gegen Herpes-simplex-Virus Typ-1 (HSV-1) und Maus-Cytomegalovirus (MCMV) gering war. Infolgedessen eignen sich beide Substanzen BTCRB und Cl4RB als attraktive alternative Inhibitoren für die weitere Entwicklung einer antiviralen Therapie. / DNA packaging is the key step in viral maturation and involves binding and cleavage of viral DNA containing specific DNA-packaging motifs. This process is mediated by a group of specific enzymes called terminase. The development for an inhibitor of HCMV terminase would be of great value, because it would act subsequent to DNA synthesis and block the first steps in viral maturation. Therefore we characterized two inhibitors targeting the HCMV terminase, 2-bromo-4,5,6-trichloro-1-(2,3,5-tri-O-acetly-ß-D-ribofuranosyl) benzimidazole (BTCRB) and 2,4,5,6-tetrachloro-1-(2,3,5-tri-O-acetly-ß-D-ribofuranosyl) benzimidazole (Cl4RB). By using viral plaque formation, viral yield, viral growth kinetics and electron microscopy, we demonstrated that two compounds BTCRB und Cl4RB are highly active against HCMV AD 169 and HCMV clinical isolates. In addition, the antiviral effect on other herpesviruses was determined. Interestingly BTCRB was active all tested herpesviruses. The best effects were observed on VZV-and RCMV-infected cells. Therefore new compounds might be promising attractive compounds for antiviral therapy in the future.

The aim of this thesis is to modify and improve the n-type semiconducting polymer PNDIT2 for thermoelectric generators (TEGs) applications. Although the PNDIT2 is considered a prime n-type material due to its high electron mobility, low air-stability of radical anions after doping and the low doping efficiency with molecular dopants are severe drawbacks and lead to limited application in TEGs. To this end, the backbone structure of PNDIT2 is modified by polymer analogous thionation and the branched aliphatic side chains are replaced by branched, fully oligoethylene glycol-based side chains. PNDIT2 was prepared by DAP and subjected to various conditions of thionation. The polymer analogous thionation of PNDIT2 was done by using Lawesson´s reagent (LR). The O/S conversion was controlled by solvent, T and amount of LR. For an excess of LR, only two carbonyls out of four present in the NDI repeating unit are converted to thiocarbonyls with regioselective trans-conformation (2S-trans-PNDIT2). Chlorobenzene (CB) is an excellent solvent in which the highest O/S conversion was achieved and the best reproducibility. Tri- or tetra- substitution in one NDI repeat unit did not take place due to steric hinderance of T2 comonomer. Thionation affected all properties. The lower thermal stability, UV-vis spectra were bathochromically shifted and a new band of the thionated NDI unit appeared. Chain aggregation was stronger as probed by UV-vis and NMR spectroscopy. The LUMO energy level of 2S-trans-PNDIT2 was lowered by 0.2 eV, giving -4.0 eV. This is at the border of what is needed for air stability of radical anions. The scattering on thin films indicated lower order and less crystalline textures of 2S-trans-PNDIT2 compared to PNDIT2. Likewise, electron mobility decreased with increasing conversion. While chapter 2 focused on the synthesis, opto-electronic and thermal properties of 2S-trans-PNDIT2, chapter 3 was concerned with details on morphology and electrical properties. To this end, 2S-trans-PNDIT2 was doped by N-DPBI in toluene at various concentrations and conductivities were determined. Undoped 2S-trans-PNDIT2 exhibited one order of magnitude higher conductivity than pristine PNDIT2. After doping with 5 wt.-% N-DPBI, the conductivity of 2S-trans-PNDIT2 increased by two orders of magnitude and reached a maximum conductivity of 6*10-3 S/cm at 15 wt.-% doping. This value was approx.5 times higher than the conductivity of PNDIT2 at the same doping level. Furthermore, the stability of conductivity of doped 2S-trans-PNDIT2 under ambient conditions was investigated and compared to PNDIT2. Upon exposure air (50 % humidity), conductivity of PNDIT2 rapidly decreased to the pristine film level, while the conductivity of 2S-trans-PNDIT2 was reduced by a factor of less than two after 16 h. While the initially higher conductivity of 2S-trans-PNDIT2 is ascribed to its less crystalline structure and thus higher doping efficacy, its better stability can be ascribed to the lower LUMO energy level. The topic of chapter 4 is on the synthesis of fully ether-based, polar and branched side chains (EO) and introduction into PNDIT2. The advantages of polar side chains over aliphatic side chains have been reported. However, previously reported PNDIT2 with linear polar side chains is limited in MW due to solubility. The EO side chain with amine functionality was synthesized in three steps and used for monomer synthesis (EO-NDIBr2). Initial efforts to use DAP to prepare P(EO-NDIT2) from EO-NDIBr2 and pristine bithiophene gave only oligomeric products. Stille polycondensation was therefore used, giving high MW. As extreme aggregation occurred in solvents used for GPC, absolute MW were determined by 1H NMR spectroscopy. To enable reliable end group analysis, model compounds with methyl end groups were prepared. In P(EO-NDIT2), methyl end groups are dominating as a result of incorrect transmetalation from the stannylated monomer. The end groups seen by 1H NMR spectroscopy were further confirmed by MALDI-ToF. Absolute MW were between Mn,NMR= 11 kg/mol to 116 kg/mol depending on reaction conditions. Aggregation was further probed by UV-vis and NMR spectroscopy as a function of the solvent and temperature, shining light into the degree of aggregation, which is important for thin film preparation. Solvent quality decreased with the following order: CHCl3, 1-Chloronaphthalene (CN), 1,2-Dichlorobenzene (o-DCB), DMF, 1,4-Dioxane, CB and Anisole (AN). According to these results, three doping protocols based on CB and o-DCB, as well as temperature variations, were used to prepare films for conductivity measurements. The best results were obtained for processing from chlorobenzene at 80 °C, which aggregates are dissolved. Strikingly, maximum conductivity values were achieved already for 5 wt.-% dopant concentration. The PF reached a maximum even for 1 wt.-% doping level. This unusually low value is promising and suggests a high doping efficacy.