Submitted by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2015-02-19T13:34:46Z No. of bitstreams: 5 edu.pdf: 1793374 bytes, checksum: 659bf4622f25b099b1d7c3bd613d8f8a (MD5) license_url: 52 bytes, checksum: 3d480ae6c91e310daba2020f8787d6f9 (MD5) license_text: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) license.txt: 2110 bytes, checksum: b4c884761e4c6c296ab2179d378436d4 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2015-02-20T11:06:41Z (GMT) No. of bitstreams: 5 edu.pdf: 1793374 bytes, checksum: 659bf4622f25b099b1d7c3bd613d8f8a (MD5) license_url: 52 bytes, checksum: 3d480ae6c91e310daba2020f8787d6f9 (MD5) license_text: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) license.txt: 2110 bytes, checksum: b4c884761e4c6c296ab2179d378436d4 (MD5) / Made available in DSpace on 2015-02-20T11:06:41Z (GMT). No. of bitstreams: 5 edu.pdf: 1793374 bytes, checksum: 659bf4622f25b099b1d7c3bd613d8f8a (MD5) license_url: 52 bytes, checksum: 3d480ae6c91e310daba2020f8787d6f9 (MD5) license_text: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) license.txt: 2110 bytes, checksum: b4c884761e4c6c296ab2179d378436d4 (MD5) Previous issue date: 2013-02-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (Capes) / Neste trabalho est? descrito uma nova metodologia para a produ??o de biodiesel (?steres met?licos ou et?licos de ?cidos graxos) a partir do emprego de diversos ?leos vegetais na sua forma ?bruta?, assim como ?leos residuais oriundos de processo de fritura e tamb?m gordura animal (sebo) como material de partida. Al?m deste desafio, procurou-se realizar as rea??es de transesterifica??es em um processo acelerado por irradia??o das micro-ondas obtidas a partir de um forno de micro-ondas dom?stico, o qual n?o sofreu adapta??es, tais como: inser??o de um sistema de agita??o e tamb?m de refluxo, para ser utilizado em rea??es qu?micas. O primeiro passo do trabalho incluiu a utiliza??o dos diferentes ?leos vegetais brutos, isto ?, desprovidos de processo de refino e de degomagem, para a produ??o de biodiesel. Para tanto foi necess?rio o desenvolvimento de uma metodologia que permitisse a purifica??o desses ?leos vegetais brutos, pois estes podem conter subst?ncias, como a ?gua, os ?cidos graxos livres (AGL) e os ?steres de f?sforos (fosfat?dicos) que s?o inibidoras do processo de transesterifica??o. Na busca por uma t?cnica que permitisse a pr?via purifica??o desses ?leos vegetais, foram testados e obtidos excelentes resultados, quando foi realizada a sua filtra??o em s?lica gel 60 Mesh. A polaridade dessa s?lica oriunda dos grupos silan?is permitiu com grande ?xito a reten??o de AGL e dos ?steres de f?sforo, al?m do seu alto poder de adsor??o, reduzindo de maneira significativa o teor de ?gua presente nesses ?leos vegetais. O fator limitante para o emprego da s?lica gel comercial nos processos de purifica??o das diversas oleaginosas foi o seu alto custo, o que tornava invi?vel o processo de purifica??o. Ap?s diversos estudos e tentativas de encontrar um processo que substitu?sse a s?lica gel comercial anteriormente empregada, foi realizado a s?ntese de uma nova s?lica gel a partir do emprego de areia de constru??o e de carbonatos, sendo um processo simples e de baixo custo. Os resultados obtidos no processo de purifica??o dos ?leos vegetais brutos empregando s?lica gel ?sint?tica? foram similares aos da s?lica gel ?comercial?, o que levou o emprego desse processo de purifica??o de maneira sistem?tica no preparo de mat?ria-prima (reagentes) para posterior transesterifica??o. Os bons resultados permitiram testes dessa nova metodologia de purifica??o em ?leos e gorduras residuais (OGR) oriundos de processos de fritura. Nesses ?leos foram encontrados um n?mero bem maior de subprodutos (impurezas) que podem inibiriooooooo65t\azs NM de maneira parcial ou total o processo de transesterifica??o. Dessa forma, a purifica??o dos OGR tornou-se um grande desafio para a s?lica gel ?sint?tica?. Entre as impurezas contidas nesses ?leos residuais, podemos destacar os AGL, ?gua e os produtos oriundos da degrada??o oxidativa e t?rmica (per?xidos, alde?dos, cetonas, furanos, mon?meros c?clicos e n?o c?clicos) dos ?leos vegetais. Os OGR foram purificados com excelentes resultados por filtra??o sob s?lica gel ?sint?tica? em um processo realizado a temperatura ambiente. Al?m dos ?leos residuais puros, nesse processo foi obtida a gordura animal, a qual ficou retida sobre a s?lica sint?tica dentro do funil de filtra??o. Essa gordura animal foi posteriormente purificada por filtra??o a 60 ?C tamb?m em s?lica gel sint?tica e assim como o ?leo residual utilizada como material de partida na s?ntese de biodiesel. Vale ressaltar que os bons resultados alcan?ados no processo de purifica??o sob s?lica gel sint?tica e a necessidade crescente de mat?ria-prima (?leos vegetais), incentivou a amplia??o do programa de coleta de ?leo e gorduras residuais (OGR) na cidade de Diamantina/MG, intitulado como ?Doe Energia? e implantado em 2006. Tanto os ?leos vegetais brutos, como os ?leos residuais e a gordura animal purificados em s?lica gel sint?tica foram transesterificados a biodiesel (met?lico ou et?lico) em alcoolatos (metanolatos e etanolatos) previamente preparados ?in situ? a partir da solubiliza??o de NaOH ou KOH em metanol ou etanol. Neste processo ocorreu a adi??o do alcoolato sobre o material de partida, sendo a rea??o conduzida sob irradia??o de micro-ondas dom?stica a 240 W durante dez minutos e acompanhada por cromatografia em camada delgada (CCD). Os produtos da rea??o (biodiesel e glicerina) foram separados por decanta??o em funil de separa??o, sendo o biodiesel (et?lico ou met?lico) posteriormente lavado at? pH neutro, seco em Na2SO4 e purificados por destila??o a press?o reduzida. A caracteriza??o do biodiesel produzido foi realizada por m?todos espectrom?tricos como a RMN1H e 13C, al?m disso, o controle de qualidade do biodiesel produzido foi realizado empregando t?cnicas anal?ticas seguindo as normas preconizadas pela Ag?ncia Nacional de Petr?leo, G?s Natural e Biocombust?veis (ANP). A glicerina foi purificada, atrav?s de um pr?vio tratamento com adi??o de ?cido sulf?rico ou clor?drico, gerando o AGL, biodiesel e sulfatos ou cloretos de metais alcalinos como co-produtos. Alguns desses sais como o sulfato de s?dio foi posteriormente purificados por recristaliza??o e utilizados como dessecantes para o pr?prio biodiesel. A efici?ncia da metodologia empregando irradia??o de micro-ondas dom?stica, levou ao estudo do seu uso em rea??es in situ, ou seja, transesterifica??o direta das sementes e dos frutos de oleaginosas, tais como a soja e a mamona. Esse processo consiste em uma desidrata??o pr?via dos frutos ou sementes a uma temperatura de 80 ?C durante 8 horas. O alcoolato preparado foi adicionado sobre os frutos ou sementes triturados e secos e a mistura foi agitada com o aux?lio de um agitador mec?nico a 7500 rpm durante 10 minutos a temperatura ambiente, a fim de homogeneizar a mistura reacional. Essa mistura foi levada a um forno de micro-ondas dom?stico e irradiada a 240 W durante 10 minutos em um processo acompanhado por CCD. Ap?s esse per?odo a massa reacional foi filtrada sob v?cuo, a fim de eliminar o res?duo vegetal s?lido (torta). A solu??o resultante foi transferida para um funil de separa??o, onde ocorreu ap?s poucos minutos, a separa??o do biodiesel (fase superior) da glicerina (fase inferior) por simples decanta??o. Os produtos foram separados por decanta??o e tanto a glicerina como o biodiesel (et?lico ou met?lico) foram purificados e caracterizados. O rendimento em biodiesel foi de aproximadamente 96% no emprego de sementes de soja e de 97% empregando sementes de mamona. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2011. / ABSTRACT This work described a new methodology for the production of biodiesel (methyl or ethyl esters of fatty acids) from the use of various vegetable oils in its "raw" as well as waste oil from the frying process and also animal fat (tallow) as starting material. In addition to this challenge, we tried to carry out the reactions transesterification in a process accelerated by microwave irradiation obtained from a domestic microwave oven, which has not undergone changes, such as insertion of an agitation system and also reflux for used in chemical reactions. The first step of the work included the use of different crude oils, this is, devoid of the process of refining and degumming, for the production of biodiesel. For this purpose it was necessary to develop a methodology that allows the purification of crude vegetable oils, as they may contain different substances such as water, free fatty acids (FFA) and esters of phosphorus (Phosphatidic) which are inhibitors of the transesterification process. In the search for a technique that allowed the prior purification of vegetable oils have been tested and achieved excellent results when your filtration was performed on silica gel 60 Mesh. The polarity of this coming from the silica silanol groups with great success allowed the retention of FFA and phosphorus esters, in addition to its high adsorption, significantly reducing the water content present in these oils. The limiting factor for the commercial use of silica gel in the purification processes of other crops was the high cost, which made impossible the purification process. After several studies and attempts to find a process to replace the previously used commercial silica gel was carried out the synthesis of a new silica gel from the use of construction sand and carbonates, with a simple and low cost. The results obtained in the purification process of crude vegetable oils using silica gel "synthetic" were similar to those of silica gel "commercial", which led to the use of this purification process in a systematic manner in the preparation of raw materials (reagents) for subsequent transesterification. The good results allowed testing of this new method of purification of waste oils and fats (WOF) from the frying process. These oils have been found a much larger number of products (impurities) in a manner that can inhibit the partial or total transesterification process. Thus, the purification of WOF has become a major challenge for the silica gel "synthetic". Among the residual impurities contained in these oils, we can highlight the FFA, water and products from thermal and oxidative degradation (peroxides, aldehydes, ketones, furans, cyclic and non cyclic monomers) of vegetable oils. The WOF with excellent results were purified by filtration on silica gel "synthetic" in a process performed at room temperature. Besides the pure residual oils, this process was obtained animal fat, which was held on the synthetic silica into the filter funnel. This fat was then purified by filtration at 60 ?C also on silica gel and synthetic as well as the residual oil is also used as starting material in the synthesis of biodiesel. It is noteworthy that the good results achieved in the purification process in synthetic silica gel and the increasing need of raw material (vegetable oils) has encouraged the expansion of the program to collect waste oil and fats (WOF) in the Diamantina / MG city, titled as "Energy Donate" and implemented in 2006. Both crude vegetable oils, such as waste oils and animal fat purified on silica gel synthesis was transesterified biodiesel (methyl or ethyl) in alcoholates (metanolatos and ethanolate) previously prepared "in situ" from the solubilization of NaOH or KOH in methanol or ethanol. This process was the addition of alcoholates on the starting material, and the reaction was conducted under microwave irradiation of a 240 W home for ten minutes and accompanied by thin layer chromatography (TLC). The reaction products (biodiesel and glycerol) were separated by decanting funnel separation, and biodiesel (methyl or ethyl) subsequently washed until neutral, dried on Na2SO4 and purified by distillation at reduced pressure. The characterization of the biodiesel produced was performed by spectrometric methods such as RMN 1H and 13C, in addition, the quality control of biodiesel was carried out using analytical techniques following the standards recommended by the National Petroleum, Natural Gas and Biofuels Agency (ANP). The glycerin was purified through a previous treatment with sulfuric acid or hydrochloric acid, generating the FFA, biodiesel or chlorides and sulfates of alkali metals as co-product. Some of these salts such as sodium sulfate was further purified by recrystallization and used as desiccants for their own biodiesel. The efficiency of the methodology using a household microwave irradiation, led to the study of their use in reactions in situ, that is, direct transesterification of seeds and fruits of oilseeds such as soybeans and castor beans. This process consists of a prior dehydration of fruits or seeds at a temperature of 80 ?C for 8 hours. The alcoholates prepared was added on the fruits or seeds crushed and dried mixture was stirred with the aid of a mechanical stirrer at 7500 rpm for 10 minutes at room temperature in order to homogenize the reaction mixture. This mixture was brought to a domestic microwave oven and irradiated at 240 W for 10 minutes in a process monitored by TLC. After this time the reaction mass was filtered under vacuum to remove the solid waste plant (cake). The resulting solution was transferred to a separatory funnel, which occurred a few minutes, after the separation of biodiesel (upper phase) of glycerin (lower phase) by simple decantation. The products were separated by decantation and glycerin as much biodiesel (methyl or ethyl) have been purified and characterized. The yield of biodiesel was approximately 96% in the use of soybean and 97% employing castor beans.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-04-03T19:41:30Z No. of bitstreams: 1 SarahPollyanaDiasDosSantos_DISSERT.pdf: 10111393 bytes, checksum: 44cc6b08e8b21238733661e330e1b811 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-04-05T19:31:53Z (GMT) No. of bitstreams: 1 SarahPollyanaDiasDosSantos_DISSERT.pdf: 10111393 bytes, checksum: 44cc6b08e8b21238733661e330e1b811 (MD5) / Made available in DSpace on 2017-04-05T19:31:53Z (GMT). No. of bitstreams: 1 SarahPollyanaDiasDosSantos_DISSERT.pdf: 10111393 bytes, checksum: 44cc6b08e8b21238733661e330e1b811 (MD5) Previous issue date: 2016-07-14 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / Aspidosperma pyrifolium Mart., esp?cie nativa da caatinga com grande ocorr?ncia no nordeste, conhecida popularmente como pereiro, utilizada na medicina popular no tratamento de doen?as e enfermidades. Consta na literatura diversos trabalhos realizados, relatando a presen?a de classes de compostos org?nicos como alcaloides, entre outras, que seriam respons?veis por propriedades terap?uticas existentes nessa esp?cie. O estudo fitoqu?mico de A. pyrifolium, das fra??es da semente e cascas do fruto, utilizando m?todos cromatogr?ficos cl?ssicos e purifica??o por CLAE, nos permitiu o isolamento de tr?s compostos. A partir da fra??o hex?nica das cascas do fruto (APCF-H) foi isolado o triterpeno ?cido betul?nico, n?o relatado anteriormente na esp?cie A. pyrifolium. Das fra??es diclorometano (APSE/DCM) e acetato de etila 50% dicloromentano (APSEA/50% DCM) das sementes foi poss?vel o isolamento do alcaloide plumerano pentac?clico aspidospermina, do alcaloide ?-carbolina glicosilado Cordifolina, n?o descrito anteriormente na esp?cie e outro composto do tipo ?-carbolina que n?o possui uma estrutura elucidada at? o momento. O extrato das sementes fra??o diclorometano (APSE/DCM) foi analisado por CG/EM (cromatografia gasosa acoplada a espectrometria de massa) e seus dados foram comparados com dados na literatura em banco de dados (NIST08.LIB), foi identificada a presen?a dos alcaloides 1-acetil-aspidospermidina, aspidospermina e pirifolina, dentre outros compostos minorit?rios. A avalia??o da atividade antioxidante, pelo m?todo sequestrador de radical livre de DPPH (2,2-difenil-1picril-hidrazila), da fra??o APSE/DCM apresentou um percentual de atividade antioxidande m?ximo (AA% m?ximo) de 83,68%, com concentra??o inibit?ria 50% (IC50) 133,4867 ? 2,22. A fra??o das sementes fra??o diclorometano (APSE/DCM) foi avaliada em rela??o ? toxicidade contra Artemia salina, tendo em vista que j? existiam relatos da toxicidade nas folhas de A. pyrifolium, comprovamos a toxicidade aguda nas fra??o das sementes diclorometano com concentra??o letal m?dia (CL50) em 24 horas de 1,1524 ?g.ml-1, sendo consideradas t?xicas as esp?cies que apresentam CL50 inferior a 1000 ?g.ml-1. Na segunda parte do trabalho foi realizado um levantamento bibliogr?fico de alcaloides do tipo ?-carbolina de ocorr?ncia natural, com suas estruturas, atividades relatadas e um banco de dados com seus deslocamentos qu?micos em RMN 1H e 13C, totalizando 169 alcaloides descritos na literatura, do per?odo de 1992 a 2016, agrupados em quatro principais grupos, denominados ?-carbolina, dihidro-?-carbolina, tetrahidro-?-carbolina e os ?-carbolinas divergentes, este levantamento auxiliar? na elucida??o estrutural de novas mol?culas. / Aspidosperma pyrifolium Mart., a native species of the caatinga with great occurrence in the northeast, known perpularmente as pereiro, used in popular medicine in the treatment of diseases and diseases. There are several studies carried out in the literature, reporting the presence of classes of organic compounds such as alkaloids, among others, that would be responsible for the therapeutic properties of this species. The phytochemical study of A. pyrifolium, seed fractions and fruit peels using classical chromatographic methods and purification by HPLC allowed us to isolate three compounds. From the hexanic fraction of fruit peels (APCF-H) was isolated the betulinic acid triterpene, not previously reported in the A. pyrifolium species. From the dichloromethane (APSE/DCM) and ethyl acetate 50% dichloromethane (APSEA / 50% DCM) fractions of the seeds, it was possible to isolate the pentacyclic pentameric aspidospermine alkaloid from the glycosylated ?-carboline alkaloid Cordifolina, not previously described in the species and another compound of the ?-carboline type that does not have a structure elucidated until the moment. The extract of the seeds dichloromethane fraction (APSE/DCM) was analyzed by GC/MS (gas chromatography coupled to mass spectrometry) and its data were compared with data in the literature in database (NIST08.LIB), the presence of the alkaloids 1-acetyl-aspidospermidine, aspidospermine and pyrifoline, among other minor compounds. The antioxidant activity evaluation of the APSE/DCM fraction showed a percentage of maximum antioxidant activity (AA% maximum) of 83.68%, with the free radical sequestration method of DPPH (2,2-diphenyl-1-picryl-hydrazila). Inhibitory concentration 50% (IC50) 133.4867 ? 2.22. The fraction of the seeds dichloromethane fraction (APSE/DCM) was evaluated in relation to the toxicity against Artemia salina, considering that there were already reports of the toxicity in the leaves of A. pyrifolium, we verified the acute toxicity in the seed dichloromethane fraction with average lethal concentration (CL50) in 24 hours of 1.1524 ?g.ml-1, species with CL50 less than 1000 ?g.ml-1 being considered toxic. In the second part of the work a bibliographic survey of naturally occurring ?-carboline alkaloids with their structures, reported activities and a database with their chemical displacements in 1H and 13C NMR were carried out, totaling 169 alkaloids described in the literature. From 1992 to 2016, grouped into four main groups, named ?-carboline, dihydro-?-carboline, tetrahydro-?-carboline and the divergent ?-carbolines, this survey will aid in the structural elucidation of new molecules.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-05-18T19:21:27Z No. of bitstreams: 1 2010 - Luiza D'Oliveira Sant'Ana.pdf: 2146437 bytes, checksum: 5d8a20463f01fc73a88b5b0c2e56d28c (MD5) / Made available in DSpace on 2017-05-18T19:21:27Z (GMT). No. of bitstreams: 1 2010 - Luiza D'Oliveira Sant'Ana.pdf: 2146437 bytes, checksum: 5d8a20463f01fc73a88b5b0c2e56d28c (MD5) Previous issue date: 2010-07-05 / This work aimed at the evaluation of the total phenolic and flavonoid contents of sixty Apis mellifera honey samples, commercialized in different regions of the state of Rio de Janeiro (Metropolis, Southern, Central, Northwestern and Seaside). For each sample, the total phenolic and the total flavonoid contents were analyzed by the Folin-Denis and aluminum chloride (AlCl3) methods, respectively. Also, the antioxidant activity (%AA and EC50) for all the honey samples was evaluated, as well as for some phenolic acids and flavonoids, used as standards. The determination of the antioxidant capacity was carried out by the method of trapping the 2,2-diphenyl-1-picryl-hydrazyl organic radical (DPPH) by antioxidant compounds, resulting in an absorbance decrease at 520 nm. The analyzed honeys were classified as monofloral or heterofloral. For the monofloral samples, it was observed that Anadenanthera honeys showed the highest average value for total phenolics (112,60 mgEAG/100g) and also for the antioxidant capacity (59,93 (AA)mgEQC/500g or 18,92 mg/mL if expressed as EC50), while the Eucalyptus honeys showed the highest mean for total flavonoids (9,17 mgEQC/100g). With these results, a comparative study was carried out with diverse honey samples of different regions, in terms of total phenolic and flavonoid content, antioxidant capacity and some physico-chemistry parameters (HMF, acidity, pH, humidity, water activity and color intensity). Comparison of these results allowed to observe that darker honeys showed both higher antioxidant activity and the highest values for total phenolic and flavonoid contents, as well as for all the other physico-chemical parameters. / O objetivo deste trabalho foi avaliar os teores de fen?licos e flavon?ides totais de sessenta amostras de mel de Apis mellifera comercializadas em diferentes mesorregi?es do estado do Rio do Janeiro (Metropolitana, Sul, Centro, Noroeste Fluminense e Baixada Litor?nea). Para cada amostra foram analisados os totais de fen?licos e flavon?ides, atrav?s dos m?todos de Folin-Denis e cloreto de alum?nio (AlCl3), respectivamente. Foi determinado, tamb?m, o potencial da atividade antioxidante (%AA e CE50) para todas as amostras de mel, bem como para alguns padr?es de ?cidos fen?licos e flavon?ides. O m?todo utilizado para determinar a capacidade antioxidante foi o de captura do radical org?nico 2,2-difenil-1-picril-hidrazil (DPPH) por antioxidantes, produzindo um decr?scimo da absorb?ncia a 520 nm. Os m?is avaliados foram classificados de monoflorais e heteroflorais. Para os monoflorais foi observado que os m?is de Anadenanthera apresentaram a maior m?dia em totais de fen?licos (112,60 mgEAG/100g), e tamb?m a maior atividade antioxidante (59,93 (AA)mgEQC/500g ou 18,92 mg/mL em termos de CE50), enquanto os m?is de Eucalyptus apresentaram, em m?dia, o maior conte?do de flavon?ides totais (9,17 mgEEC/100g). A partir dos resultados obtidos foi feito um estudo comparativo entre as v?rias amostras de m?is de diferentes regi?es quanto ao teor de fen?licos e flavon?ides totais, a atividade antioxidante e algumas propriedades f?sico-qu?micas (HMF, acidez, pH, umidade, atividade de ?gua e intensidade de colora??o). Ao comparar esses resultados, foi poss?vel observar que os m?is mais escuros apresentaram uma maior atividade antioxidante e uma maior quantidade de fen?licos e flavon?ides totais, bem como valores mais altos para todos os outros par?metros f?sico-qu?micos comparados.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2018-08-29T19:26:49Z No. of bitstreams: 1 2017 - Cristiane Frauches dos Santos.pdf: 7660831 bytes, checksum: d9f6418f111957d4be1789ee9411cc8f (MD5) / Made available in DSpace on 2018-08-29T19:26:49Z (GMT). No. of bitstreams: 1 2017 - Cristiane Frauches dos Santos.pdf: 7660831 bytes, checksum: d9f6418f111957d4be1789ee9411cc8f (MD5) Previous issue date: 2017-09-25 / CAPES / CNPq / FAPERJ / Petrobr?s / Corrosion is one of the serious problems faced in industrial processes, generating enormous financial losses. Several techniques are used to prevent or remedy corrosion in the different materials it affects. Among them, the use of organic or inorganic inhibitors has been widely used. Thus, in this thesis were synthesized 34 heterocyclic compounds, 18 chlorides of 1,3,4-thiadiazolium-2-phenylamines, (11 unpublished), and the other 16 compounds belonging to the class of mesoionic 1,3,4-triazolium -2-thiolate, (15 unpublished), with the objective of evaluating its efficiency as inhibitors of corrosion in acidic corrosion. Derivatives of the class 1,3,4-thiadiazolium-2-phenylamines were obtained with satisfactory purity and yields in the range of 42-96% and, in the class of 1,3,4-triazolium-2-thiolates in 20 -97%. All compounds were characterized by IR, 1H and 13C NMR spectroscopies. The theoretical study was conducted using the SPARTAN-PRO program in the semi-empirical method with the Hamiltonian AM1, to determine its structural and electronic properties of 1,3,4-thiadiazolium-2-phenylamines that could contribute to the efficiency of inhibition of corrosion. The compounds of 1,3,4-thiadiazolium-2-phenylamine class were tested against corrosion of AISI 1020 carbon steel in 0.5 mol L-1HCl and in 0.5 mol L-1 H2SO4. For this evaluation, the electrochemical techniques of Potenciodynamic Polarization (PP), Resistance to Linear Polarization (RPL) and Electrochemical Impedance Spectroscopy (EIS) were used. The results showed significant percentages of corrosion inhibition in both acidic solutions, reaching the rate of up to 95% efficiency for the compound 4-phenyl-5-(3'-methoxy-phenyl)-1,3,4-thiadiazolium-2-phenylamine chloride in the concentration of 3.5x10-4 mol L-1 for the HCl solution, and 99% efficiency for the 2'-chloro and 2'-fluorosubstituted compounds in the concentration of3.5x10-4 mol L-1 for the H2SO4 solution. In addition to the electrochemical techniques, the gravimetric technique was used, which presented 99% of anticorrosive efficiency for the 2'-trifluoromethyl-substituted 1,3,4-thiadiazolium-2-phenylamine derivative, showed the best inhibitory effect in HCl solution. However, the 2'-trifluoromethyl-substituted 1,3,4-triazolium-2-thiol derivative showed less corrosion efficiency than its corresponding isomer. The methodologies used to evaluate the corrosion activity (PP, RPL and EIE), including the theoretical evaluation by molecular modeling, indicated the mesoionic chloridrates as efficient mixed corrosion inhibitors. / S?ntese e avalia??o da atividade anticorrosiva de cloretos de 1,3,4-tiadiaz?lio-2-fenilaminas e 1,3,4-triaz?lio-2-tiolatos em meio ?cido. 2017. 251p Tese (Doutorado em Qu?mica, Ci?ncia exatas, s?ntese org?nica). Departamento de qu?mica, Universidade Federal Rural do Rio de Janeiro, Serop?dica, RJ, 2017. A corros?o ? um dos s?rios problemas enfrentados nos processos industriais, gerando enormes preju?zos financeiros. Diversas t?cnicas s?o utilizadas para evitar ou remediar a corros?o nos diferentes materiais que ela afeta. Dentre elas o uso de agentes inibidores org?nicos ou inorg?nicos tem sido muito utilizado. Assim, neste trabalho de tese foram sintetizados 34 compostos heteroc?clicos, sendo 18 cloretos de 1,3,4-tiadiaz?lio-2-fenilaminas (11 in?ditos) e os outros 16 compostos pertencentes ? classe dos mesoi?nicos 1,3,4-triaz?lio-2-tiolato (15 in?ditos), com o objetivo de avaliar sua efici?ncia como inibidores de corros?o em meio ?cido. Os derivados sintetizados da classe 1,3,4-tiadiaz?lio-2-fenilaminas foram obtidos com grau de pureza e rendimentos satisfat?rios na faixa de 42-96% e, da classe dos 1,3,4-triaz?lio-2-tiolatos em 20-97%. Todos os compostos foram caracterizados por espectroscopia de IV, RMN de 1H e13C. Foi realizado o estudo de modelagem molecular, utilizando o programa SPARTAN-PRO com o m?todo semi-emp?rico, hamiltoniano AM1, para determina??o das propriedades estruturais e eletr?nicas dos 1,3,4-tiadiaz?lio-2-fenilaminas que pudessem contribuir para a efici?ncia de inibi??o da corros?o. Os cloridratos mesoi?nicos da classe 1,3,4-tiadiaz?lio-2-fenilaminas foram testados frente ? corros?o de a?o carbono AISI 1020 em solu??o de HCl 0,5 mol L-1 e em H2SO4 0,5 mol L-1. Para tal avalia??o foram utilizadas as t?cnicas eletroqu?micas de Polariza??o potenciodin?mica (PP), Resist?ncia ? polariza??o linear (RPL) e Espectroscopia de imped?ncia eletroqu?mica (EIE). Os resultados mostraram percentuais significativos de inibi??o da corros?o em ambas solu??es ?cidas, alcan?ando o ?ndice de at? 95% de efici?ncia para o composto cloreto de 4-fenil-5-(3?-met?xi-fenil)-1,3,4-tiadiaz?lio-2-fenilamina na concentra??o de 3,5x10-4 mol L-1 para a solu??o de HCl e, 99% de efici?ncia para os compostos 2?-cloro e 2?-fluor-substitu?dos na concentra??o de 3,5x10-4 mol L-1 para a solu??o de H2SO4. Al?m das t?cnicas eletroqu?micas, foi utilizada a t?cnica gravim?trica que apresentou 99% de efici?ncia anticorrosiva para o derivado 2?-trifluormetil-substitu?do da classe 1,3,4-tiadiaz?lio-2-fenilamina que mostrou o melhor efeito inibidor em solu??o HCl. No entanto, o derivado 2?-trifluormetil-substitu?do da classe 1,3,4-triaz?lio-2-tiol apresentou menor efici?ncia anticorrosiva do que seu is?mero correspondente. As metodologias utilizadas para avalia??o da atividade anticorrosiva (PP, RPL e EIE), incluindo a avalia??o te?rica por modelagem molecular, indicaram os cloridratos mesoi?nicos como eficientes inibidores de corros?o mistos.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-11-09T17:58:22Z No. of bitstreams: 1 2017 - Mariana de Albuquerque Almeida.pdf: 2619920 bytes, checksum: 48c00262629bac9a7779fc4ea9ec94a6 (MD5) / Made available in DSpace on 2017-11-09T17:58:22Z (GMT). No. of bitstreams: 1 2017 - Mariana de Albuquerque Almeida.pdf: 2619920 bytes, checksum: 48c00262629bac9a7779fc4ea9ec94a6 (MD5) Previous issue date: 2017-05-10 / CAPES / This dissertation presents the evaluation of four thiosemicarbazones, from extracts of species of vegetables Talinum triangulare, Physalis angulata e Theobroma cacao L. besides formulation obtained from the combination extract of thiosemicarbazones vegetables as corrosion inhibitor in the presence of carbon steel AISI 1020. Thiosemicarbazones were obtained with good level of purity, satisfactory throughput and identified by NMR of 1H and 13C. The watery extract of Talinum triangulare was obtained using ultrasound device. The extracts of Physalis angulata species were obtained by maceration in water and the other one in ethyl acetate. The watery extracts of Theobroma cacao L. species were obtained using ultrasound device and decoction and hydroalcoholic extract was obtained by maceration in ethanol:water (80:20). The thiosemicarbazones, the vegetable extracts and their formulation were tested in the presence of corrosion of carbon steel AISI 1020 in solution 1 mol. L-1 of HCl. For this evaluation it was used the gravimetric techinique of weight loss and electrochemical techiniques of potentiodynamic polarization and electrochemical impedance spectroscopy. The results showed that the presence of thiosemicarbazones, as well as, the formulation increased significantly the resistence of carbon steel AISI 1020 in acidic medium. The results obtained in different used essays (weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy) show that these techniques are complementary in relation to the evaluation of corrosion inhibition. The best anti-corrosion efficiency was observed for thiosemicarbazone chloro and hydroxy-substituted and its formulations with the extract of T. triangulare achieving 88% and 87% of efficiency, by electrochemical impedance spectroscopy, respectively. / Nesta Tese ? apresentada a avalia??o de quatro tiossemicarbazonas, dos extratos das esp?cies vegetais Talinum triangulare, Physalis angulata e Theobroma cacao L., al?m de formula??es obtidas pela combina??o extrato vegetal:tiossemicarbazonas, como inibidores de corros?o frente ao a?o carbono AISI 1020 em meio de ?cido cloridr?co. As tiossemicarbazonas foram obtidas com bom grau de pureza, em rendimentos satisfat?rios e, caracterizadas por IV, RMN de ^1H e ^13C. O extrato aquoso de Talinum triangulare foi obtido em aparelho de ultrassom, os extratos da esp?cie Physalis angulata, foram obtidos sob macera??o em ?gua e o outro em acetato de etila; j? os extratos aquosos da esp?cie Theobroma cacao L. foram obtidos em aparelho de ultrassom e decoc??o e, finalmente, o extrato hidroalco?lico foi obtido por macera??o em etanol:?gua (80:20). As tiossemicarbazonas, os extratos vegetais e suas formula??es foram testadas frente ? corros?o de a?o carbono AISI 1020 em solu??o 1mol.L-1 de HCl. Para tal avalia??o foi utilizada a t?cnica gravim?trica de Perda de Massa e as t?cnicas eletroqu?micas de Polariza??o Potenciodin?mica e Espectroscopia de Imped?ncia Eletroqu?mica. Os resultados mostraram que a presen?a de tiossemicarbazonas, bem como, das formula??es aumentam significativamente a resist?ncia do a?o carbono AISI 1020 em ?cido. Os resultados obtidos nos diferentes ensaios utilizados (Perda de Massa, Polariza??o Potenciodin?mica e Espectroscopia de Imped?ncia Eletroqu?mica) mostraram que estas t?cnicas s?o complementares quanto a avalia??o da inibi??o da corros?o. A melhor efici?ncia anticorrosiva foi observada para as tiossemicarbazonas cloro e hidroxi-substitu?das e, para suas formula??es com o extrato da T. triangulare obtendo-se 88% e 87% de efici?ncia por espectroscopia de imped?ncia eletroqu?mica, respectivamente.