Th.--Sci. phys.--Toulouse 3, 1978. N°: 827.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1968. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1968. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliography.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1955. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 137-139).

Thesis (Ph. D.)--University of Wisconsin, 1966. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1967. / Vita. Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thèse de doctorat : Électrochimie : Strasbourg : 2009. / Titre provenant de l'écran-titre. Bibliogr. 10 p.

The near ultraviolet absorption spectra of cyclohexanone, cyclohexanone α, α, α', α'd₄ and cyclohexanone d₁₀ have been recorded and analysed under low and high resolution. The vibrational and rotational structure accompanying the electronic singlet-singlet ṉ→π* transition have been analysed. Some complementary information has been obtained from the infrared vapour spectrum of cyclohexanones. The geometries of the ground and first excited state have been determined. In the excited state configuration, the oxygen atom was bent out of the plane of the three adjacent carbon atoms by about 30º, and the carbon oxygen bond increases by 0.08 Å between the ground state and the excited state. Some ring modes are strongly active in the electronic spectra of the three isomers. This may indicate some coupling between the carbonyl group and the ring. The results obtained by band contour analysis are consistent with those obtained by calculation of a double minimum potential function, as well as those obtained in previous work on related molecules. / Thesis / Master of Science (MSc)

A crescente demanda energética mundial vem estimulando pesquisas em novas fontes de energia limpa e renovável e de baixo custo. Nesse contexto, as células solares orgânicas (fotovoltaicos orgânicos – OPVs) destacam-se como uma alternativa promissora no campo dos fotovoltaicos. Por serem fabricadas a partir de soluções eletrônicas, sua fabricação se dá deposição sobre substratos rígidos ou flexíveis, e com isso, também por técnicas de impressão. Muitas moléculas poliméricas têm mostrados excelentes resultados, porém o desempenho das células dependem também da morfologia do filme ultrafino da camada ativa, a qual depende do processamento e sobretudo da atividade dos solventes orgânicos. Até o momento, a maioria dos solventes usados para a fabricação das OPVs de alto desempenho é da classe dos halogenados, como por exemplo, o clorobenzeno e o 1,2-diclorobenzeno. Esses solventes, além de exibirem alto custo de produção, apresentam toxicidade relativamente alta, com impactos adversos à saúde humana e ao meio ambiente. Visto que a tecnologia dos OPVs está próxima de sua comercialização, a procura por solventes alternativos de baixa toxicidade coloca-se como um desafio a essa área. Neste trabalho, identificou-se por meio dos parâmetros de solubilidade de Hansen, um solvente da classe dos não halogenados e não aromáticos com baixa toxicidade ao ser humano e ambientalmente amigável para ser aplicado como solvente de processamento de células solares orgânicas do tipo heterojunção de volume (BHJ). Para isso, os possíveis solventes foram avaliados segundo os parâmetros de solubilidade de Hansen para os polímeros, P3HT e PTB7-Th, e para as moléculas PC61BM e PC71BM, levando em consideração os critérios de riscos com base na ficha de segurança de produtos químicos. Desse modo, a ciclohexanona foi selecionada por conter as características desejadas para o estudo proposto no presente trabalho. As soluções de P3HT e de PTB7- Th em ciclohexanona foram avaliadas quanto à influência da temperatura das soluções na conformação dos polímeros, a partir da técnica de termocromismo. Os resultados revelam necessidade de aquecimento para que haja uma conformação menos agregada tanto do P3HT quanto do PTB7-Th em solução de ciclohexanona. Os filmes de P3HT:PC61BM e PTB7-Th:PC71BM foram depositados pela técnica de spin-coating sobre substratos de vidro e estudos sobre sua morfologia foram realizados por técnicas de imagens de microscopia óptica, AFM e medidas de absorção pela técnica UV-vis, e correlacionadas ao desempenho das células fabricadas. Os resultados obtidos foram promissores uma vez que nesse trabalho conseguimos células de até 5,5 % de eficiência. / The growing global demand for energy has been stimulating research into new sources of clean and renewable energy and low cost. In this context, organic solar cells (organic photovoltaic - OPVs) stand out as a promising alternative in the field of photovoltaics. Because they are manufactured from electronic solutions, it can be deposited on rigid or flexible substrates, facilitating their production by printing techniques. Many polymer molecules have shown excellent results, but the performance of the cells also depends on the morphology of the ultrathin film of the active layer, which depends on the processing and above all the activity of the organic solvents. To date, most of the solvents used in the manufacture of high-performance OPVs belong to the halogen class, for example chlorobenzene and 1,2-dichlorobenzene. These solvents, in addition to exhibiting high cost of production, have relatively high toxicity, with adverse impacts on human health and the environment. Since the technology of OPVs is close to commercialization, the search for low-toxicity alternative solvents poses a challenge in this area. In this work, Hansen\'s solubility parameters were used to identify solvents of non-halogenated and non-aromatic class with low toxicity to humans and environmentally friendly, as substitutes of traditional solvents used to process organic solar cells (BHJ). For this, several solvents were evaluated according to the Hansen solubility parameters for the polymers, P3HT and PTB7-Th, and for the molecules PC61BM and PC71BM, taking into account the risk criteria based on the chemical safety data sheet. The solutions of P3HT and PTB7-Th in cyclohexanone were evaluated taking into account the influence of the temperature of the solutions on the conformation of the polymers, using the thermochromic technique. The solutions of P3HT and PTB7-Th in cyclohexanone were evaluated taking into account the influence of the temperature of the solutions on the conformation of the polymers, using the thermochromic technique. The resulted morphology was then correlated with the devices performance. The results obtained were promising since in this work we obtained cells of up to 5.5% efficiency.

There is an important need to immobilise enzymes for use in industry, to do this I have the promising idea that by conjugating the enzyme to a hydrogel network, thus fabricating a stable biocatalytic network would be a potential method for immobilising enzymes for the manufacture of fine chemicals, this has not been done before for octapeptide systems. Hydrogels have been previously shown as a viable way of immobilising and stabilising enzymes. In this thesis the octapeptide VKVKVEVK (V is valine, K is lysine and E is glutamic acid) is used to immobilise enzymes tagged with VKVKVEVK. This peptide sequence is chosen as it forms stable hydrogels at enzyme appropriate conditions (pH 7). The enzymes chosen are; PETNR as it is well understood and is therefore a good starting point, CDH and CHMO were also chosen as they could combine with PETNR to form a cascade reaction. PETNR was both chemically conjugated to VKVKVEVK (SpepPETNR) and also genetically modified to express the peptide tag (CpepPETNR), whilst CDH and CHMO were genetically modified to express the tag (NpepCDH and CpepCHMO respectively). For S/CpepPETNR retention within the hydrogels was superior to retention for untagged PETNR. NpepCDH was found to not precipitate within the hydrogel whilst untagged was found to do so. CpepCHMO functionalised hydrogels were found to be heterogeneous. Characterisation of CpepPETNR functionalised hydrogels was undertaken using micro differential scanning calorimetry (µDSC), rheology, small angle neutron scattering (SANS) and atomic force microscopy (AFM). From the µDSC evidence of 'protective immobilisation' was observed by the increase in denaturation energy (+253 kJ mol-1) in the hydrogel in comparison to in solution (+18 kJ mol-1). The ability of S/CpepPETNR functionalised hydrogels to perform the ketoisophorone to levodione biotransformation reaction was explored with yields of 86%. S/CpepPETNR within VKVKVEVK hydrogels was found to retain ~90% conversion for at least 9 months at room temperature. Incubation overnight at 90°C resulted in a yield of 84% of levodione. These two results added more evidence for 'protective immobilisation'. Hydrogels functionalised with NpepCDH or CpepCHMO were characterised using rheology and atomic force microscopy. The biotransformation ability of NpepCDH was elucidated; the overall yield of carvone was a maximum of 54% from the hydrogel phase. NpepCDH was used alongside CpepPETNR for the cascade reaction producing dihydrocarvone in low yields; however, an improvement from 2% to 13% in yield is presented. The yield of lactone products from CpepCHMO functionalised hydrogel was low at 15%. The CpepPETNR/ CpepPETNR cascade reaction proceeded with a yield of 36%. The initial activities of CpepPETNR, NpepCDH and CpepCHMO were assayed in both solution and in gel phase using a modified method. The activities were assessed with varying conditions; temperature, pH, quantity of ethanol and incubation at high and low temperatures. Generally, it was found that immobilisation within the hydrogel phase resulted in 'protective immobilisation' against non-optimal conditions. This work will be of benefit to those who are interesting immobilising enzymes within hydrogels in the future.