Orientador: Marcos Nogueira Eberlin / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T09:34:26Z (GMT). No. of bitstreams: 1 Lima_MairaFasciottiPinto_M.pdf: 3076235 bytes, checksum: bc4b63f365634b0b6e2e36e84cb49537 (MD5) Previous issue date: 2012 / Resumo: Esta dissertação apresenta uma breve introdução sobre a técnica de mobilidade iônica acoplada a espectrometria de massas (Capítulo 1) e a discussão de resultados aplicados a três subprojetos distintos. A técnica de TWIM-MS é uma técnica de separação na qual a separação em dos íons ocorre em uma cela de mobilidade iônica e é baseada em parâmetros como a seção de choque, carga, polarizabilidade, que é a capacidade de um íon ter sua densidade eletrônica distorcida pela interação com o gás de mobilidade, além de, obviamente, da estrutura tridimensional dos íons em fase gasosa. Sobre o Capitulo 2, objetivo do trabalho em petroleômica foi desenvolver e otimizar um método para a identificação de compostos polares presentes em amostras de petróleo e seus derivados como diesel e gasolina, que fosse capaz de diferenciar amostras distintas com relação essas composições, verificando quais respostas esta técnica pode fornecer nos estudos petroleômicos. Puderam ser identificadas as classes N, O2 e NO, com excelente resolução com a técnica de TWIM-MS. Entretanto, acredita-se que algumas outras classes ainda podem ser elucidadas. O CO2 se mostrou ser o melhor gás de mobilidade a ser utilizado para a resolução destas classes. A técnica de TWIM-MS também se mostrou adequada para a caracterização de gasolina e seus aditivos, entretanto mais amostras de diesel aditivado devem ser investigadas, para se descobrir porque os aditivos não puderam ser detectados através da técnica de ESI-TWIM-MS. Com relação ao estudo das estruturas em fase gasosa dos isômeros do Corrol (Capítulo 3), podese observar que o corrorin tem a estrutura tridimensional mais compacta entre todos os isômeros, enquanto NCC4 e corrol são os isômeros com maiores seções de choque e maiores drift times. Mesmo que o norrole tenha os maiores valores previstos de CCS, seu menor momento de dipolo resulta em interações mais fracas com o gás de mobilidade, e um drift time menor do que o esperado é obtido. Uma melhor resolução entre os isômeros de corrol foi alcançada usando CO2 como gás de mobilidade. Além disso, estes isômeros podem ser diferenciados monitorando íons característicos resultantes de suas fragmentações. Em conclusão, mostrou-se que a diferenciação por TWIM-MS destas estruturas pode ser conseguida através do monitoramento das diferenças entre as suas mobilidades relativas e também pelos espectros distintos de MS/MS obtidos para cada isômero. Já o Capítulo 4, visou avaliar a separação de 4 dissacarídeos isoméricos, em que se observou que a utilização de mais gases polarizáveis, tais como o CO2 na análise realizada com o Synapt G2 permite uma resolução quase na linha de base, o que não foi possível utilizando N2 como gás de mobilidade e nem na primeira geração do equipamento comercial Synapt, mesmo usando CO2 como gás de mobilidade / Abstract: This dissertation presents a brief introduction of the technique of Ion Mobility Mass Spectrometry (Chapter 1) and also the discussion of results applied to three distinct subprojects. The technique of Traveling Wave Ion Mobility Mass Spectrometry, is a separation technique in which the separation of the ions occurs in a mobility cell and is based on parameters such as collision cross-section, charge, polarizability (the capacity of an ion to have its electronic density distorted by interaction with the drift gas) and the three dimensional structure (shape) of ions in the gaseous phase. The main goal of the work performed in petroleomics (Chapter 2), was to develop and optimize a method for the identification of polar compounds present in oil samples and its derivatives, such as diesel and gasoline. The applied method was able to differentiate oil samples based on some polar components. Classes N, O2 and NO could be identified with proper resolution with TWIM-MS technique. However, it is believed that some other classes may be elucidated. CO2 was shown to be the best drift gas to be used for the separation of these classes. The technique of TWIM-MS also proved to be suitable for the characterization of gasoline and its additives, however, more samples of additive diesel must be investigated to find out why the additives could not be detected by the technique of ESI-TWIM-MS. During the study of tridimensional structures in the gaseous phase of five Corrole isomers (Chapter 3), it was observed that significant differences in shape and charge distributions for the protonated molecules lead to contrasting gas phase mobilities, most particularly for corroin, the most "confused¿ isomer. Accordingly, corroin was predicted by DFT and collisional cross section calculations to display the most compact tridimensional structure. NCC4 and corrole, on the other hand were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas and contrasting labilities towards CID, allowed the prompt differentiation of some isomers. Chapter 4 aimed to evaluate the separation of four isomeric disaccharides, where it was observed that the use of more polarizable gases, such as CO2, in the analysis performed with a Synapt G2 allows almost a baseline resolution for some isomeric pairs. This was not possible using N2 as drift gas with the Synapt G2, and not with the Synapt G1 using either N2 or CO2 / Mestrado / Quimica Analitica / Mestra em Química

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Potato tubers can be used as food or seed. Potatoes are mostly sold for tablestock and processing consumptions. Each destination has its own requirements to attend consumers exigencies. The aim of this work was to evaluate the processing quality and physiological aging of potato tubers produced during spring and autumn growing conditions in Rio Grande do Sul (RS). Tubers of 15 potato clones were evaluated for processing quality during spring 2003 and autumn 2004. The best performance of chips color, dry matter, and reduced sugar was obtained with potatoes of the clones SMIJ461-1, SMIJ319-1, SMIJ456-4Y, SMIC148-A, SMIDO40-4RY and SMIH095-1. Among these clones, SMIDO40-4RY and SMIH095-1 were less affected by temperature and sunlight conditions of the RS growing seasons. The clones SMIJ461-1 and SMIJ456-4Y cultivated during spring showed the highest dry matter and the lightest chip color. The physiological aging was studied in potato tubers of the Asterix, SNINIA793101-3 and SMIJ461-1 clones produced during spring and autumn 2004 and stored at 4, 8, 12 and 25°C for 180 days. The physiological aging of the three evaluated clones was affected by the growing conditions. Potato tubers cultivated in autumn and stored at 4 and 8°C remained dormant for 180 days. When tubers were produced during spring, only the clones SMINI793101-3 and SMIJ461-1 stored at 4°C remained dormant for 180 days. The growing conditions and genetic differences influence both processing quality and physiological aging of potato tubers. The storage at low temperature is efficient to delay physiological aging only during the dormant period of the potato tubers. / Os tubérculos de batata podem ser destinados para o consumo ou semente. Para o consumo, estes podem ser utilizados para mesa ou para processamento. Ambas as finalidades exigem tubérculos com qualidades distintas, as quais são essenciais para atender as necessidades do consumidor. O objetivo deste trabalho foi avaliar a qualidade de processamento e o envelhecimento fisiológico de tubérculos produzidos durante a primavera e o outono na região central do Rio Grande do Sul. A qualidade de processamento foi avaliada em 15 clones produzidos durante a primavera de 2003 e o outono de 2004. O envelhecimento fisiológico foi estudado em tubérculos dos clones Asterix, SNINIA793101-3 e SMIJ461-1 produzidos durante o outono e primavera de 2004 e armazenados a 4, 8, 12 e 25°C por um período de 180 dias. Para qualidade de processamento, os clones SMIJ461-1, SMIJ319-1, SMIJ456-4Y, SMIC148-A, SMIDO40-4RY e SMIH095-1 foram os que apresentaram o melhor desempenho em coloração dos chips e teores de massa seca e açúcares redutores. Dentre esses clones, SMIDO40-4RY e SMIH095-1 foram os menos influenciados pelas épocas de cultivo de outono e primavera na região central do RS. Os clones SMIJ461-1 e SMIJ456-4Y apresentaram maior teor de massa seca e coloração mais clara dos chips no cultivo da primavera. De acordo com a avaliação do envelhecimento fisiológico, os três clones sofreram influência das condições de cultivo. O cultivo de outono combinado com o armazenamento a 4 e 8°C manteve os tubérculos dos diferentes clones em estádio de dormência por 180 dias. Quando os tubérculos foram produzidos na primavera, somente os clones SMINI793101-3 e SMIJ461-1 submetidos a temperatura de 4°C mantiveram a dormência durante os 180 dias de armazenamento. As condições de cultivo e as diferenças genéticas alteram tanto a qualidade de processamento quanto o envelhecimento fisiológico dos tubérculos. O armazenamento dos tubérculos a baixa temperatura é eficaz para retardar o envelhecimento fisiológico somente durante o período de dormência.

Quorum sensing (QS) is a population-dependent signaling process bacteria use to control multiple processes including virulence, critical for establishing infection. There are two major pathways of QS systems. Type 1 is species specific or intra-species communication in which N-acylhomoserine lactones (Gram-negative bacteria) or oligopeptides (Gram-positive bacteria) are employed as signaling molecules (autoinducer one). Type 2 is inter-species communication in which S-4,5-dihydroxy-2,3-pentanedione (DPD) or its borate esters are used as signaling molecules. The DPD is biosynthesized by LuxS enzyme from S-ribosylhomocysteine (SRH). Recent increase in prevalence of bacterial strains resistant to antibiotics emphasizes the need for the development of new generation of antibacterial agents. Interruption of QS by small molecules is one of the viable options as it does not affect bacterial growth but only virulence, leading to less incidence of microbial resistance. Thus, in this work, inhibitors of both N-acylhomoserine lactone (AHL) mediated intra-species and LuxS enzyme, involved in inter-species QS are targeted. The γ-lactam and their reduced cyclic azahemiacetal analogs, bearing the additional alkylthiomethyl substituent, were designed and synthesized targeting AHL mediated QS systems in P. aeruginosa and Vibrio harveyi. The γ-lactams with nonylthio or dodecylthio chains acted as inhibitors of las signaling in P. aeruginosa with moderate potency. The cyclic azahemiacetal with shorter propylthio or hexylthio substituent were found to strongly inhibit both las and rhl signaling in P. aeruginosa at higher concentrations. However, lactam and their azahemiacetal analogs were found to be inactive in V. harveyi QS systems. The 4-aza-S-ribosyl-L-homocysteine (4-aza-SRH) analogs and 2-deoxy-2-substituted-S-ribosyl-L-homocysteine analogs were designed and synthesized targeting Bacillus subtilis LuxS enzyme. The 4-aza-SRH analogs in which oxygen in ribose ring is replaced by nitrogen were further modified at anomeric position to produce pyrrolidine, lactam, nitrone, imine and hemiaminal analogs. Pyrrolidine and lactam analogs which lack anomeric hydroxyl, acted as competitive inhibitors of LuxS enzyme with KI value of 49 and 37 µM respectively. The 2,3-dideoxy lactam analogs were devoid of activity. Such findings attested the significance of hydroxyl groups for LuxS binding and activity. Hemiaminal analog of SRH was found to be a time-dependent inhibitor with IC50 value of 60 µM.

Heparin glycosaminoglycans mediate a range of biological events, including anticoagulation as well as a diversity of cell proliferation and differentiation processes. Heparin saccharides have been shown to act as inhibitors against angiogenesis and metastasis of tumour cells. This thesis describes work developing chemistry towards varying length oligosaccharide sequences with potential to offer variable sulfation patterns. The main synthetic components to this work were contribution to developing scalable syntheses of an orthogonally protected L-Iduronic acid unit and a differentially protected D-glucosamine unit. The synthetic work also evaluated a recently reported diazo transfer reagent, which allowed for earlier placement of azide protection over that of previously developed routes within the group. This provided a cheaper, more atom efficient route towards protected D-glucosamine building blocks. Glycosylation of the developed D-GlcN donor units with the L-Ido acceptor allowed the production of key disaccharides which facilitated an efficient iterative glycosylation strategy towards longer oligosaccharides, ultimately providing a differentially protected pentasaccharide. The project evaluated methods towards generating various dimeric heparin type systems through forming new O4 ether linkages between GlcN residues across various short linker fragments. The most successful of these dimerisations used a methallyl dichloride core which allowed for further derivatisation towards dihydroxylated species, the analysis of which highlighted some interesting proton NMR data. The final aspect of this project began development of chemistry towards non-reducing end-labelled oligosaccharide sequences by implementation of a masked aldehyde unit on the C4 hydroxyl of GlcN synthesised from the allylated GlcN precursor via dihydroxylation chemistry. Incorporation of this moiety (protected as a 1,2-dibenzyl glycol) within both a trisaccharide and a pentasaccharide was achieved. Further development of this chemistry should allow for late step oxidative cleavage to reveal the reactive aldehyde, potentially allowing for attachment of various amine functionalised fluorophores via reductive amination. Radiolabelling of such a species should also be possible through sodium borotritide reduction for example.

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Atmospheric aerosols play an important role in various atmospheric issues (effect to the radiation budget of the atmosphere, visibility reduction, smog production, destruction of stratospheric ozone, …). Epidemiological studies proved a correlation between increased mortality and high concentration of ambient particulate matter. Over the past decade, a growing attention has been focused on the organic compounds that are constituents of aerosol particles. Although organic compounds comprise often up to 60% of the total aerosol mass, their composition, concentration and formation mechanisms are not well understood. Diploma thesis will deal with the study of chemical composition of organic compounds bound to atmospheric aerosols with focus on polyaromatic hydrocarbons and sugars. Atmospheric aerosols will be sampled on filters and filter extracts will be analysed for content of studied organic compounds by means of GC, GC-MS or LC, respectively. Development and optimalization of extraction methods (PSE, …) and detection of compounds of interest. Concentration of studied organic compounds in aerosol size fractions PM 10, PM 2.5 and PM 1 will be compared.

There are many changes in fruit quality during its ripening and storage. The following four apple varieties were studied: Champion, Glostr, Golden Delicious and Idaret. Amount of reducing sugars, total amount of sugars, quantities of acids, refractive solids and loss of starch were monitored. The changes of parameters, the differences between the varieties and differences in storage were compared. Parameters were monitored from mid-August 2008, when the apples ripened. After the harvest, apples were stored in a cool box at 2 - 3 ° C and at room temperature 20 - 23 ° C. Apples stored in the cool box were analyzed till the end of March 2009, and apples stored at room temperature until the beginning of January 2009. Total quantity of sugars in all varieties increases before harvest, while it decreases after picking the apples. The quantity of reducing sugars in apples rises gradually and after their picking it falls significantly in apples stored at 20 - 23 ° C. In apples stored in the cool box it continues rising until the end of November, and then it also decreases. Losses of starch are considerable and they are accelerated after the harvest. The quantity of acids also decreases throughout and amounts of refractive solids increases. For all varieties there are significant changes in storage at 20 - 23 ° C. Temperature, therefore, significantly affects processing of sugars and acids in fruit respiration.

The aim of this diploma thesis is the assay of total alkaloids in different tobacco types. To measure the content of total alkaloids are utilized types of tobacco used for preparation of tobacco blends and consecutive production of cigarettes. The samples of analyzed tobacco include various countries of cultivation and different crop years. There is described tobacco as a plant, in it contained alkaloids and the utilization of tobacco in the theoretical part. In more detail it deals with the production and construction of cigarettes which is closely related to the content monitoring of total alkaloids in tobacco. The contents of total alkaloids are determined by the continuous flow analyzer- SKALAR. On this spectrophotometer are set the contens of reducing sugars as well. The comparison of total alkaloids contents and reducing sugars from the perspective of single tobacco types, countries of cultivation and crop years is clearly summarized in the experimental part of the thesis that was performed in the company Philip Morris ČR, a.s.

Origin of life is a still-enduring gap in human knowledge. This work is focused on revealing of several pieces of this puzzle. State of the art scenarios of biomolecules synthesis under prebiotic conditions are presented and discussed. This thesis presents our recent experiments suggesting a novel idea that neutral planetary atmosphere containing a mixture of neutral volcanic-type gasses (CO2, N2, H2O) can be converted over acidic mineral catalysts upon irradiation by a soft UV-radiation into a relatively reactive mixture of reducing gases (CH4, CO), which can be further reprocessed by high-energy chemistry. The resulting mixture (CH4, CO + N2) represents a common reducing atmosphere related e.g. to the chemistry of Titan, the largest moon of Saturn, as well as a possible representation of the secondary atmosphere of our planet. Also, photocatalytic reduction of CO2-rich atmosphere can explain the abiotic origin of methane on current Mars or other terrestrial planets. In our subsequent experiments, corresponding equimolar model mixture of CH4 : CO : N2 in presence of water vapour was subjected to reprocessing by high-power laser plasma simulating an asteroid impact - one of a series of impact events which the young Earth experienced during the first 600 million years of her history. Upon delivery...

This diploma thesis studies the utilization of whey using thermophilic bacteria of the genus Thermus and Geobacillus. The whey stripped off proteins was used as a cultivation medium during experiments. The cultivation took place in the Erlenmeyer flasks, to assess the optimal conditions for microrganism’s growth. During the cultivation in the bioreactor, growth curves were established. The amount of whey utilization was assessed by analytical methods that determine the concentration of reducing saccharides (lactose) and chemical oxygen demand (COD) while studying the optimal conditions and a method determining the concentration of reducing saccharides during growth curves analysis.