O extrato pirolenhoso é uma substância orgânica resultante da condensação da fumaça gerada durante a carbonização da madeira ou de outras fontes de matéria-prima vegetal, sendo constituído por, pelo menos, 80% de água e dezenas de compostos, dentre os quais se incluem substâncias fenólicas, aldeídos e ácidos orgânicos. Portanto, não seria utópico supor-se que nessa gama de compostos possam estar incluídas substâncias que apresentem propriedades conservantes para aplicações na área cosmética e de saneantes. É nessa direção que se avaliou o potencial de utilização do extrato pirolenhoso da madeira de eucalipto. Especificamente, houve a intenção de se estudar as características e propriedades do extrato pirolenhoso obtido dessa madeira levando-se em conta duas fontes distintas; avaliar em particular suas propriedades antifúngicas, e as possibilidades do uso do extrato pirolenhoso como conservante, na substituição de ingredientes como, por exemplo, o formaldeído, ainda hoje utilizado na indústria em formulações de produtos cosméticos e atualmente proibido em produtos saneantes, segundo nova resolução RDC 35/08 da ANVISA. Os compostos químicos presentes am ambos os extratos foram identificados mediante análises em cromatógrafo acoplado a espectrômetro de massa (GC/MS). De forma geral, as análises dos extratos demonstraram a presença de uma gama de compostos oxigenados, tais como ácidos carboxílicos, ésteres, éteres e cetonas. Além disso, foram detectados fenol, guaicol e derivados fenólicos. O produto que apresentou o melhor potencial antifúngico foi o extrato pirolenhoso de uma das fontes estudadas. / Pyroligneous extract is an organic substance resulting from the condensation of the smoke generated during the carbonization of wood or other vegetable raw material, consisting of at least 80% of water and many compounds including: phenolic substances, aldehydes and organic acids. It would not be utopian, therefore, to assume that, in this gamma of compounds there could be substances having preservative properties for cosmetic and sanitizing products. This study evaluates the potential of the pyroligneous extract of eucalyptus wood. Specifically, the characteristics and properties of the pyroligneous extract from eucalyptus wood from two distinct sources; to evaluate in particular its antifungal proprieties and the possibility of using the pyroligneous extract as a preservative. This would substitute, for example, the formaldehyde currently used in the cosmetic industry. In fact formaldehyde has now been forbidden in sanitizing products; resolution RDC 35/08 of ANVISA. The chemical compounds of both extracts were identified by analyses of a gaseous chromatograph connected to the mass spectrometer (GC/MS). In general, the analysis of extracts demonstrated the presence of oxygenated components gamma such as carboxylic acids, esters, ethers and ketenes. Moreover, phenol, guaicol and phenol derivatives were detected. The product that showed better potential antifungal results was the pyroligneous extract from one of the studied sources.

A comparison of the composition and structure of carbon films deposited by ns and fs laser ablation of graphite is the subject of this thesis. In addition, the effect of irradiation on the surface of graphite has been investigated in detail. Laser-induced phase transitions from graphite to sp-bonded carbon and trans-polyacetylene chains as well as the formation of nano-diamond have been observed after irradiation with fs pulses. An optical orientation mechanism involving both electric and magnetic interactions is proposed to understand the formation of nano-stripes and other structures on irradiated graphite surfaces. These phenomena are not observed after nanosecond laser irradiation. Tetrahedral carbon (ta-C) films deposited at cryogenic temperatures using ns laser radiation consist of sub-micron graphitized grains embedded in a matrix of sp3-hybridized bonded carbon. Nano-buckling is evident in ta-C films deposited by fs ablation where the composition is found to consist of mixed sp, sp2, and sp3 – hybridized carbons species. It is found that the concentration of sp-bonded chains is negligible in ns-C films. Surface enhanced Raman spectroscopy has been used to characterize molecular species in ns and fs carbon films. Time of flight mass spectroscopy has been used to study plume species produced by laser ablation. It is also found that polyyne molecules can be formed by fs laser dissociation of small molecules in organic solvents. This process is accompanied by the deposition of hexagonal nano-diamond films on substrates placed near the laser focus during irradiation. This opens a new path in the synthesis of 1D conducting molecules and nano-diamond materials for nano-science applications. Quantum chemical calculations involving density functional theory (Gaussian '03) have been carried out in support of this work and have been used to study Raman and IR vibrational modes of several novel carbon molecules synthesized in ta-C films and in the liquid phase. These studies have been extended to assist in the identification of astronomical spectra.

A comparison of the composition and structure of carbon films deposited by ns and fs laser ablation of graphite is the subject of this thesis. In addition, the effect of irradiation on the surface of graphite has been investigated in detail. Laser-induced phase transitions from graphite to sp-bonded carbon and trans-polyacetylene chains as well as the formation of nano-diamond have been observed after irradiation with fs pulses. An optical orientation mechanism involving both electric and magnetic interactions is proposed to understand the formation of nano-stripes and other structures on irradiated graphite surfaces. These phenomena are not observed after nanosecond laser irradiation. Tetrahedral carbon (ta-C) films deposited at cryogenic temperatures using ns laser radiation consist of sub-micron graphitized grains embedded in a matrix of sp3-hybridized bonded carbon. Nano-buckling is evident in ta-C films deposited by fs ablation where the composition is found to consist of mixed sp, sp2, and sp3 – hybridized carbons species. It is found that the concentration of sp-bonded chains is negligible in ns-C films. Surface enhanced Raman spectroscopy has been used to characterize molecular species in ns and fs carbon films. Time of flight mass spectroscopy has been used to study plume species produced by laser ablation. It is also found that polyyne molecules can be formed by fs laser dissociation of small molecules in organic solvents. This process is accompanied by the deposition of hexagonal nano-diamond films on substrates placed near the laser focus during irradiation. This opens a new path in the synthesis of 1D conducting molecules and nano-diamond materials for nano-science applications. Quantum chemical calculations involving density functional theory (Gaussian '03) have been carried out in support of this work and have been used to study Raman and IR vibrational modes of several novel carbon molecules synthesized in ta-C films and in the liquid phase. These studies have been extended to assist in the identification of astronomical spectra.

Allyl methacrylate, AMA was polymerized by chemical initiator and by &amp / #947 / -radiation under different conditions. The polymer obtained is mostly gel type with some soluble fractions at lower conversions. Arrhenius activation energy is 82.3 kJ/mol for chemical initiated polymerization. The polymer was characterized by FT-IR, NMR, DSC, TGA, XPS, XRD, DLS, and MS methods. It was found that about 98-99% of allyl side groups retained as pendant even after completion of the polymerization, while 1-2% may give crosslinking and/or cyclization that yields lactones and anhydrides. The spectroscopic and thermal results of the work showed that the reaction is not cyclopolymerization, but may have end group cyclization. Molecular weight of 1.1x106 was measured by DLS. Therefore, insolubility is due to the high molecular weight of polymer, even in the early stage of polymerization rather than crosslinking. The Tg of PAMA was observed as 94&ordm / C before curing, upon curing at 150-200&ordm / C, Tg increased to 211&ordm / C as measured by DSC. The thermal treatment of polymer at about 350&ordm / C gave anhydride by linkage type degradation, following side group cyclization. The XPS analysis showed the presence of radical fragments of AIBN and CCl4 associated with oligomers. The MS and TGA thermograms showed two or three stage degradations depending on solubility. The first stage was mostly linkage type degradation for the fragmentation of pendant allyl groups at 225-350&ordm / C. In the second stage, at 395-515&ordm / C, the degradation is random scission and depolymerization.

The ultimate objective of this research was to develop a low cost, reliable system that would lead to early detection of lung cancer. Tests involved the quantitation of gaseous metabolic emissions from immortalized lung cancer cell lines in order to correlate the chemical markers to be of cancerous origin. The specific aims of the project were the study of gas emissions in selected cancer cell lines and identification of volatile organic compounds (VOCs) in them. Disadvantages of earlier studies were that the measurements were not real time or state specific so that molecular identification was often inconclusive. Furthermore the methods of study used in the past were not quantitative, which limited their practicality for medical applications. We felt the need to prove or disprove these earlier results using a new technique. The method we proposed is different and unique when compared to previous methods because cell lines have not been studied extensively for cancer markers. We have studied cancer cell lines which are adherent, immortalized cultures originating from primary tumors obtained from patients with no prior treatment for lung cancer. We have used an alternative method for the spectrometric analysis and quantitation of the selected chemical markers. The pre-concentration method involved a Purge and Trap unit with a thermal desorber where the vapor concentration was enhanced. The concentrated head space gases were analyzed using a Gas Chromatograph ?? Mass Spectrometer setup. This setup eliminated the bulky apparatus used in earlier studies. It is simpler in design and more comprehensive so that external factors such as patient??s diet, habitat and lifestyle do not contribute to our study of recognition of cancer markers. Based on the results obtained in the above experiments, a more comprehensive, inexpensive study of lung cancer related markers could be made. The first section, after giving an introduction to lung cancer, goes on to explain the background work done by other researchers on cancer. The third section gives a detailed explanation of the experimental setup. This is followed by all the tests conducted with corresponding results. The final section deals with the conclusions drawn from all experiments.

A new instrument using a time-of-flight (TOF) mass filter (MF) for resonance enhanced multiphoton ionization (REMPI) studies of gas phase molecules was developed. This instrument was designed to make use of the selectivity of the REMPI process and the sensitivity of a TOF-MF with a microchannel plate detector. A pulsed valve inlet system was tested to determine its effectiveness in “cooling” molecules but it was not used for the bulk of the studies performed. The instrument was tested using molecular and atomic bromine, atomic carbon, and atomic iodine. The atomic bromine, carbon, and iodine, were generated by the photodissociation of molecular bromine, hydrocarbons, and methyl iodide respectively. Nitrogen gas in air was used to test the pulsed valve system. The instrument was then used to conduct REMPI studies of five dichlorotoluene (DCT) isomers (2,4-DCT; 2,5-DCT; 3,4-DCT; 2,6-DCT; and 2,3-DCT). REMPI studies of six dichloroaniline (DCA) isomers, including 2,5-DCA; 3,4-DCA; 3,5-DCA; 2,6-DCA; 2,4-DCA; and 2,3-DCA were conducted. Six isomers of dichlorophenol (DCP) were studied (2,5-DCP; 3,4-DCP; 3,5-DCP; 2,3-DCP; 2,4-DCP; and 2,6-DCP). It was determined that the 2,3-DCP; 2,4-DCP; and 2,6-DCP isomers photodissociated to form CCl, which itself could be observed through a REMPI process. The results from the REMPI studies of the dichloroaromatics and data from previous ultraviolet, infrared, and RAMAN studies of these molecules was used in order to assign the observed peaks. The observed 0,0 π→π* transition energies of the dichloroaromatics studied were used along with ultraviolet 0,0 π→π* transition energies from previous works in order to discuss substituent effects. A qualitative method of predicting the relative location of 0,0 π→π* transition energies of dichloroaromatics was developed.

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