Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-09-28T18:08:52Z No. of bitstreams: 1 2017 - V?ctor de Carvalho Martins.pdf: 5700751 bytes, checksum: 07961d0468442fc22ade82dc8b861206 (MD5) / Made available in DSpace on 2017-09-28T18:08:52Z (GMT). No. of bitstreams: 1 2017 - V?ctor de Carvalho Martins.pdf: 5700751 bytes, checksum: 07961d0468442fc22ade82dc8b861206 (MD5) Previous issue date: 2017-02-14 / CAPES / Coffee is one of the most appreciated beverages in the world, due to its sensorial and functional characteristics. Currently, as the main producer and exporter in the world, it is estimated that in Brazil there will be growth in the domestic market in the coming years, in which roasted and ground coffee predominates. This type of product is impaired mainly by adulteration with other plant materials. The implementation of more sensitive and selective methods is necessary to ensure higher quality products. The objective of this dissertation was to develop a method to detect adulterants (rice, barley, corn and soybeans) in commercial samples of coffee, through the oligosaccharides profile and the techniques of Ultra Performance Liquid Chromatography coupled to Tandem Mass Spectrometry (UPLC-MS-MS). From standard solutions of five possible chemical markers (maltose, raffinose, stachyose, 1-kestose and nystose) in aqueous solution of 0.1% formic acid and acetonitrile (1:1) and in Milli-Q grade water, the operational parameters of the mass spectrometer and the chromatographic conditions were tested. The adopted chromatographic method consisted of chromatography by hydrophilic interaction and gradient elution of acetonitrile and aqueous solution of formic acid 0.1%, with injector temperature 20?C; injection volume 1.0 ?L; flow rate 0.5 mL/min; column temperature 35?C; and run time 10 min. For the spectrometric method, electrospray ionization was used in positive mode, with capillary, sampling and extraction cones voltages of, respectively, 3.0 kV, 50 V, 2.0 V; sample temperature 80?C; cone gas flow 40 L/h; temperature and flow of desolvation gas 300?C and 500 L/h; and collision energies of at least 15.0 V. The results indicated a good repeatability among analysis of standard solution, with selectivity by the real-time monitoring of the sequential mass spectra. Extracts from the previously roasted samples of adulterants were analyzed. It was confirmed the effect of temperature as an interfering factor for the detection of oligosaccharides. Only soybean presented as potential chemical markers raffinose and stachyose. For the grains of rice, barley and corn, another precursor ion of the same mass/charge ratio (m/z) of raffinose and 1-kestose was observed. It has been identified as maltotriose, in which isomeric differentiation can be ensured by different fragmentation profiles. The study of the mass spectra still ratified these results by the observation of a greater susceptibility of the rupture of ?, ? (1?2) bonds and the formation of ions fragments with saturated cyclic chain. However, through the use of the methodology, the chemical markers were not detected in the commercial samples of coffee, even with the samples previously disapproved for the presence of barley. The optimization of the extraction method or the inclusion of sodiated solvents may be necessary and, therefore, new experiments should still be performed, ensuring the applicability of the method by UPLC-MS-MS. / O caf? consiste em uma das bebidas mais apreciadas em todo o mundo, devido a suas caracter?sticas sensoriais e funcionais. Atualmente como principal produtor e exportador no mundo, estima-se que no Brasil haja crescimento no mercado interno para os pr?ximos anos, em que se predomina o caf? torrado e mo?do. Este tipo de produto ? prejudicado principalmente pela pr?tica de adultera??o com outras mat?rias-primas vegetais. A implementa??o de m?todos de maior sensibilidade e seletividade ? necess?ria para a garantia de produtos de maior qualidade. O objetivo desta disserta??o foi desenvolver um m?todo de detec??o de adulterantes (arroz, cevada, milho e soja) em amostras comerciais de caf?, atrav?s do perfil de oligossacar?deos e das t?cnicas de Cromatografia L?quida de Ultra Efici?ncia acoplada a Espectrometria de Massas Sequencial (CLUE-EM-EM). A partir de solu??es padr?o de cinco poss?veis marcadores qu?micos (maltose, rafinose, estaquiose, 1-kestose e nistose) em solvente solu??o aquosa de ?cido f?rmico a 0,1% e acetonitrila (1:1) e em ?gua grau Milli-Q, foram testados os par?metros operacionais do espectr?metro de massas e as condi??es cromatogr?ficas. O m?todo cromatogr?fico adotado consistiu no uso da cromatografia por intera??o hidrof?lica e elui??o em gradiente de acetonitrila e solu??o aquosa de ?cido f?rmico, com as condi??es de temperatura do injetor de 20?C; volume de inje??o de 1,0 ?L; fluxo de 0,5 mL/min; temperatura da coluna de 35?C; e tempo de corrida de 10 min. Para o m?todo espectrom?trico, empregou-se a ioniza??o por eletrospray em modo positivo, com voltagem no capilar, nos cones de amostragem e de extra??o de, respectivamente, 3,0 kV, 50 V, 2,0 V; temperatura da amostra de 80?C; fluxo do g?s do cone de 40 L/h; temperatura e fluxo do g?s de dessolvata??o de 300?C e 500 L/h; e energias de colis?o de, no m?nimo, 15,0 V. Os resultados indicaram uma boa repetitividade entre as an?lises das solu??es padr?o, com a seletividade sendo garantida pelo monitoramento em tempo real dos espectros de massas sequencial. Extratos das amostras previamente torradas dos adulterantes foram analisados, sendo confirmado o efeito da temperatura como um fator interferente para a detec??o dos oligossacar?deos. Apenas a soja apresentou como potenciais marcadores qu?micos rafinose e estaquiose. Para os gr?os de arroz, cevada e milho, foi observado outro ?on precursor de mesma rela??o massa/carga (m/z) da rafinose e da 1-kestose. Este foi identificado como a maltotriose, em que a diferencia??o isom?rica pode ser garantida pelos diferentes perfis de fragmenta??o. O estudo dos espectros de massas ainda ratificou estes resultados pela observa??o de uma maior facilidade da ruptura das liga??es ?,? (1?2) e de forma??o de ?ons fragmentos de cadeia c?clica saturada. Por?m, atrav?s do emprego da metodologia, n?o foram detectados os marcadores qu?micos nas amostras comerciais de caf? analisadas, mesmo com as amostras previamente reprovadas pela presen?a de cevada. A otimiza??o do m?todo de extra??o ou a inclus?o de solventes sodiados podem ser necess?rios e, por tal raz?o, novos experimentos ainda devem ser realizados, garantindo a aplicabilidade do m?todo por CLUE-EM-EM.

Made available in DSpace on 2014-12-17T14:27:29Z (GMT). No. of bitstreams: 1 LuizFPN_DISSERT.pdf: 1155478 bytes, checksum: 9e8987b9d6b2c6260ed4b50e8325c276 (MD5) Previous issue date: 2014-03-19 / The neoconstitutionalism led to a process of ethical revaluation of the normative systems and the process of constitutionalization of the many fields of law. This study examines the consequences of this process in criminal law, so important a Law field for the protection of the most valuable assets by the society, including the fundamental guarantees, thus emphasizing the necessity of protection of the collective and individual rights, which are guided by the observance of the defendants individual rights in the course of criminal proceedings and the search for the best efficiency of penal protection, according to the corollaries of defense against the state (prohibition of the excess or ?bermassverbot) and the provision of rights by the state (prohibition of insufficient protection or Untermassverbot). The offense of fuel adulteration is taken as an object of study, since it is a vital market to a nation dependent of people and good s movement for their living, driven by fossil and biofuels. Such a crime affects essential legal interests to the development of society, interests such as the environment, consumer relations and economic order, particularly the principle of free competition. This paper seeks to analyze the need of a greater efficiency of this particular criminal protection, once concluded the conduct harm and social fear as a consequence by it as growing, and therefore having its former crime type, engraved in Article 1 of Law No. 8.176/1991, rewritten in compliance with the criminal law s principle of legality. Thus, the reformation proposals and legislative creation involving this crime were observed, with emphasis on the bill No. 2498/2003, which keeps it as blank heterogeneous criminal norm, kind of penal normative whose constitutionality is raised, including the forethought of criminal responsibility in the perpetrating of the offense as culpable and subsequently increasing the applicable minimum penalty, as well as the inclusion of new activities in the typical nucleus / O neoconstitucionalismo levou a um processo de revaloriza??o ?tica dos sistemas normativos e o processo de Constitucionaliza??o dos v?rios ramos do Direito. O presente estudo analisa as conseq??ncias deste processo no Direito Penal, ramo ?ltimo de prote??o dos bens mais valorados pela sociedade, incluindo as garantias fundamentais, destacando a necessidade de prote??o da coletividade e do indiv?duo, o que passa pela observ?ncia das garantias individuais dos acusados no curso do processo penal e pela busca de melhor efici?ncia da prote??o penal, conforme os corol?rios da defesa contra o Estado (proibi??o de excesso ou ?bermassverbot) e a presta??o pelo Estado (proibi??o de infraprote??o ou Untermassverbot). Toma-se por objeto de estudo o delito de adultera??o de combust?veis, os quais comp?em mercado vital para uma na??o dependente do deslocamento de pessoas e mercadorias para sua viv?ncia, impulsionada por combust?veis f?sseis e biocombust?veis. Tal crime atinge bens jur?dicos vitais ao desenvolvimento da sociedade, como o meio ambiente, as rela??es de consumo e a ordem econ?mica, destacando-se o princ?pio da livre concorr?ncia. Busca o presente trabalho analisar a necessidade da maior efici?ncia desta espec?fica prote??o penal, verificada a danosidade da conduta e o temor social por ela despertado, o que passa por uma reformula??o da reda??o do tipo penal insculpido no artigo 1? da Lei n? 8.176/1991, em observ?ncia ao princ?pio da legalidade no Direito Penal. Observam-se assim as propostas de reforma e cria??o legislativa envolvendo este crime, com destaque para o Projeto de Lei n? 2498/2003, que o mant?m como norma penal em branco heterog?nea, esp?cie normativa cuja constitucionalidade ? abordada, e incluindo a previs?o de responsabiliza??o criminal no cometimento do delito na modalidade culposa e majorando a pena m?nima aplic?vel, al?m da inclus?o de novas atividades no n?cleo t?pico