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Orientador : Chhiu-Tsu Lin Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica Doutorado

Orientador : Chhiu-Tsu Lin Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica Mestrado

Submitted by Noam Silva (prof.dr.noam@gmail.com) on 2022-02-09T23:43:30Z No. of bitstreams: 4 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) TESE_Noam_Doutorado_V2022.001.pdf: 20784397 bytes, checksum: 00b718dd4f574f83276fd033a7a1eac2 (MD5) CartaEncaminhamentoTCC-TESE-DISSERTA????O Noam Gadelha.pdf: 165217 bytes, checksum: 6034d80f10667f439d3e681aad942b16 (MD5) FOLHA _APROVA????O_NOAM_GADELHA_assinado.pdf: 232902 bytes, checksum: 43cab885ddb71493f05d47a5db7d2876 (MD5) Approved for entry into archive by PPGQ Qu??mica (ppgqsecretaria@gmail.com) on 2022-02-10T12:33:10Z (GMT) No. of bitstreams: 4 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) TESE_Noam_Doutorado_V2022.001.pdf: 20784397 bytes, checksum: 00b718dd4f574f83276fd033a7a1eac2 (MD5) CartaEncaminhamentoTCC-TESE-DISSERTA????O Noam Gadelha.pdf: 165217 bytes, checksum: 6034d80f10667f439d3e681aad942b16 (MD5) FOLHA _APROVA????O_NOAM_GADELHA_assinado.pdf: 232902 bytes, checksum: 43cab885ddb71493f05d47a5db7d2876 (MD5) Rejected by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br), reason: Na Ficha catalogr??fica, Inserir as palavras-chave com a primeira letra mai??scula e as demais min??sculas, exceto quando forem nomes pr??prios. Em caso de siglas, tudo em mai??scula, seguida de h??fen e seu significado. on 2022-02-10T20:42:54Z (GMT) Submitted by Noam Silva (prof.dr.noam@gmail.com) on 2022-03-09T18:52:52Z No. of bitstreams: 4 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) CartaEncaminhamentoTCC-TESE-DISSERTA????O Noam Gadelha.pdf: 165217 bytes, checksum: 6034d80f10667f439d3e681aad942b16 (MD5) FOLHA _APROVA????O_NOAM_GADELHA_assinado.pdf: 232902 bytes, checksum: 43cab885ddb71493f05d47a5db7d2876 (MD5) TESE_Noam_Doutorado_V2022.001.pdf: 20790403 bytes, checksum: 61609d8a9babc5e4decc97e2a94b5593 (MD5) Approved for entry into archive by PPGQ Qu??mica (ppgqsecretaria@gmail.com) on 2022-03-09T19:04:03Z (GMT) No. of bitstreams: 4 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) CartaEncaminhamentoTCC-TESE-DISSERTA????O Noam Gadelha.pdf: 165217 bytes, checksum: 6034d80f10667f439d3e681aad942b16 (MD5) FOLHA _APROVA????O_NOAM_GADELHA_assinado.pdf: 232902 bytes, checksum: 43cab885ddb71493f05d47a5db7d2876 (MD5) TESE_Noam_Doutorado_V2022.001.pdf: 20790403 bytes, checksum: 61609d8a9babc5e4decc97e2a94b5593 (MD5) Approved for entry into archive by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br) on 2022-03-09T20:19:02Z (GMT) No. of bitstreams: 4 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) CartaEncaminhamentoTCC-TESE-DISSERTA????O Noam Gadelha.pdf: 165217 bytes, checksum: 6034d80f10667f439d3e681aad942b16 (MD5) FOLHA _APROVA????O_NOAM_GADELHA_assinado.pdf: 232902 bytes, checksum: 43cab885ddb71493f05d47a5db7d2876 (MD5) TESE_Noam_Doutorado_V2022.001.pdf: 20790403 bytes, checksum: 61609d8a9babc5e4decc97e2a94b5593 (MD5) Made available in DSpace on 2022-03-09T20:19:02Z (GMT). No. of bitstreams: 4 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) CartaEncaminhamentoTCC-TESE-DISSERTA????O Noam Gadelha.pdf: 165217 bytes, checksum: 6034d80f10667f439d3e681aad942b16 (MD5) FOLHA _APROVA????O_NOAM_GADELHA_assinado.pdf: 232902 bytes, checksum: 43cab885ddb71493f05d47a5db7d2876 (MD5) TESE_Noam_Doutorado_V2022.001.pdf: 20790403 bytes, checksum: 61609d8a9babc5e4decc97e2a94b5593 (MD5) Previous issue date: 2021-02-23 Currently, many studies exemplify the advantages of using combined theoretical and experimental methods. However, many researchers assume that the simulations are very superficial, far from the experimental reality, and this generates resistance in the use of these theoretical tools. This thesis exemplifies how Computational Theoretical Chemistry contributes to the understanding of experimental observations, bringing the researcher closer to the atomic and molecular level, which can be associated with statistical thermodynamics (a branch of science that explores the relationships between properties at both levels). For the development of this thesis, three separate and independent case studies were carried out. Methods based on quantum mechanics (AM1, PM3, PM6 and DFT / B3LYP) and molecular mechanics (molecular docking and molecular dynamics) were used. The first case study compared four similar compounds and derivatives, and the results, some already published, confirm the proximity of most properties. With molecular dynamics studies, the possibility of formation of molecular clusters proved to be an interesting approach for investigating biomolecular activities. The second case study reproduced the interactive effects of the polyaniline/silica nano-composite, explaining how the molecular vibrations combine and intensify in order to superimpose and ???hide??? silica signals. In addition, molecular aspects of polyaniline and interactions with silica allowed a better understanding of the formation of the nano-composite. The third case study validates the possibility of the existence of two conformations for an alkaloid skeleton, in addition to predicting the energy trends in the formation of derivatives and suggesting a way to "follow" the reactions in an energetic and geometric perspective. Adapted optimizations converge reagents for products, validating the description of interactions between nucleophiles and electrophiles in the gas phase. Atualmente, muitos estudos exemplificam as vantagens do uso de m??todos te??ricos e experimentais combinados. No entanto, muitos pesquisadores assumem a ideia de que as simula????es s??o muito superficiais, distantes da realidade experimental, e isso gera resist??ncia no uso dessas ferramentas te??ricas. A presente tese exemplifica como a Qu??mica Te??rica Computacional contribui para o entendimento de observa????es experimentais, aproximando o pesquisador do n??vel at??mico e molecular, o que pode ser associado ?? termodin??mica estat??stica (ramo da ci??ncia que explora as rela????es entre as propriedades nos dois n??veis). Para o desenvolvimento dessa tese, realizou-se tr??s estudos de caso separados e independentes. Utilizou-se m??todos baseados na mec??nica qu??ntica (AM1, PM3, PM6 e DFT/B3LYP) e na mec??nica molecular (acoplamento molecular e din??mica molecular). O primeiro estudo de caso comparou quatro compostos similares e derivados, e os resultados, alguns j?? publicados, confirmam a proximidade da maioria das propriedades. Com estudos de din??mica molecular, a possibilidade de forma????o de aglomerados moleculares se mostrou uma interessante abordagem para investiga????o de atividades biomoleculares. O segundo estudo de caso reproduziu os efeitos interativos de nano-comp??sito Polianilina/S??lica, explicando como as vibra????es moleculares se combinam e se intensificam de forma a sobrepor e ???esconder??? sinais da s??lica. Al??m disso, aspectos moleculares da polianilina e das intera????es com a s??lica permitiram um melhor entendimento da forma????o do nano-comp??sito. O terceiro estudo de caso valida a possibilidade da exist??ncia de duas conforma????es para esqueleto de alcaloide, al??m de predizer as tend??ncias energ??ticas de forma????o de derivados e sugerir uma maneira de ???acompanhar??? as rea????es em perspectiva energ??tica e geom??trica. Otimiza????es adaptadas convergem reagentes para produtos, validando a descri????o de intera????es entre nucle??filos e eletr??filos em fase gasosa.

Submitted by Gisele Franco (francogisele@hotmail.com) on 2020-12-04T22:18:47Z No. of bitstreams: 4 Tese 2020 Gisele Franco de Castro-Biblioteca UFAM.pdf: 5690539 bytes, checksum: 1539c5e2ebe139de1e3bc71ac75c8d92 (MD5) CartaEncaminhamentoAutodep??sitoTESE Gisele Franco (3).pdf: 60231 bytes, checksum: 7f903239a5a04ed44dedb38ab325b5b5 (MD5) ATA Gisele (2) (4).pdf: 417669 bytes, checksum: c924bdc982689baacc3d534e981ebfad (MD5) Folha de assinatura enviar esse (2).pdf: 143327 bytes, checksum: ca3677bfa125f83b22b86331ccd9a32b (MD5) Approved for entry into archive by PPGQ Qu??mica (ppgqsecretaria@gmail.com) on 2020-12-07T17:49:09Z (GMT) No. of bitstreams: 4 Tese 2020 Gisele Franco de Castro-Biblioteca UFAM.pdf: 5690539 bytes, checksum: 1539c5e2ebe139de1e3bc71ac75c8d92 (MD5) CartaEncaminhamentoAutodep??sitoTESE Gisele Franco (3).pdf: 60231 bytes, checksum: 7f903239a5a04ed44dedb38ab325b5b5 (MD5) ATA Gisele (2) (4).pdf: 417669 bytes, checksum: c924bdc982689baacc3d534e981ebfad (MD5) Folha de assinatura enviar esse (2).pdf: 143327 bytes, checksum: ca3677bfa125f83b22b86331ccd9a32b (MD5) Approved for entry into archive by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br) on 2020-12-08T20:56:53Z (GMT) No. of bitstreams: 4 Tese 2020 Gisele Franco de Castro-Biblioteca UFAM.pdf: 5690539 bytes, checksum: 1539c5e2ebe139de1e3bc71ac75c8d92 (MD5) CartaEncaminhamentoAutodep??sitoTESE Gisele Franco (3).pdf: 60231 bytes, checksum: 7f903239a5a04ed44dedb38ab325b5b5 (MD5) ATA Gisele (2) (4).pdf: 417669 bytes, checksum: c924bdc982689baacc3d534e981ebfad (MD5) Folha de assinatura enviar esse (2).pdf: 143327 bytes, checksum: ca3677bfa125f83b22b86331ccd9a32b (MD5) Made available in DSpace on 2020-12-08T20:56:53Z (GMT). No. of bitstreams: 4 Tese 2020 Gisele Franco de Castro-Biblioteca UFAM.pdf: 5690539 bytes, checksum: 1539c5e2ebe139de1e3bc71ac75c8d92 (MD5) CartaEncaminhamentoAutodep??sitoTESE Gisele Franco (3).pdf: 60231 bytes, checksum: 7f903239a5a04ed44dedb38ab325b5b5 (MD5) ATA Gisele (2) (4).pdf: 417669 bytes, checksum: c924bdc982689baacc3d534e981ebfad (MD5) Folha de assinatura enviar esse (2).pdf: 143327 bytes, checksum: ca3677bfa125f83b22b86331ccd9a32b (MD5) Previous issue date: 2020-07-27 The bioactive organic molecules (MOB) have their application extended both in physics and in medicine due to their photophysical properties. The study of the interaction of these molecules with the biological environment is a way to enhance these effects, especially pharmacological effects. This type of study often because they are indirect measures leave some unknowns regarding: active species; transport mechanism in the biological membrane; type of interaction and associative site. Emission spectroscopy using pseudomembranes (micelles) makes it possible to answer or elucidate these questions. We sought to analyze three MOBs: DHMC, Harmina and APNH. All with aromatic ring in their structures and distinct biological properties: antifungal, hallucinogenic and carcinogenic, respectively. DFT calculations based on 6-31 + G * and functional B3LYP were used with the Spartan16 ?? and Origin ?? program simulating hydrophilic and hydrophobic environments. Subsequently, spectroscopic measurements of UV-VIS absorption and emission (??exc = 313nm) were performed in hydrophobic, hydrophilic solvent and in micelles (neutral, anionic and cationic). The DHMC action species is DHMC-H. DHMC + deprotones and enters the micelle and remains anchored in its hydrophilic region. The Harmina molecule behaved differently according to the micelle charge. When the micelle is neutral, the deprotoned monocation and within the micelle two species coexist: HR anchored in the hydrophobic region and the HR-H species anchored in the hydrophilic region. Now when the micellar load is negative, Harmina has HR-forte as its active species. This species is anchored in the aqueous region, forming a hydrogen bonding complex between the nitrogen of the HR species pyridine. The micellar charge also provided a distinct photophysical behavior for the APNH molecule. The neutral micelle emission was similar to the photophysical behavior in hydrophilic medium. The APNH entered the micelle and stayed in the region close to the surface. APHH in anionic micelle had its photophysical properties canceled and in cationic micelle APNH was in the hydrophobic region (in the micelle nucleus). This photophysical behavior helps to clarify the understanding of the mechanism of transport of APNH into a micelle. It also helps to understand the carcinogenicity of this molecule in front of cells. The emission systems along with the other methodologies were effective in studying the photophysical properties of these molecules, demonstrating that this methodology is also a way of helping to understand the drug / pseudomembrane interaction, providing an idea of the pharmacological action. As mol??culas org??nicas bioativas (MOB) t??m sua aplica????o estendida tanto na f??sica quanto na medicina devido as suas propriedades fotof??sicas. O estudo da intera????o dessas mol??culas com o meio biol??gico ?? um caminho para potencializar esses efeitos, principalmente os farmacol??gicos. Esse tipo de estudo muitas vezes por serem medidas indiretas deixam algumas inc??gnitas com rela????o a: esp??cie ativa; mecanismo de transporte na membrana biol??gica; tipo de intera????o e s??tio associativo. A espectroscopia de emiss??o com o uso de pseudomembranas (micelas) possibilita responder ou elucidar estas quest??es. Buscou-se analisar tr??s MOB: o DHMC, a Harmina e o APNH, todas com anel arom??tico em suas estruturas e propriedades biol??gicas distintas: antif??ngico, alucin??geno e um carcinog??nico, respectivamente. Foram utilizados c??lculos da DFT com base 6-31 + G* e funcional B3LYP com o programa Spartan16 ?? e Origin ?? simulando ambientes hidrof??lico e hidrof??bicos. Posteriormente foram realizadas medidas espectrosc??picas de absor????o UV-VIS e emiss??o (??exc= 313nm) em solvente hidrof??bico, hidrof??lico e em micelas (neutra, ani??nica e cati??nica). A esp??cie a????o do DHMC ?? o DHMC-H. O DHMC + desprotona e entra na micela e permanece acorado em sua regi??o hidrof??lica. A mol??cula Harmina comportou-se de forma diferente conforme a carga da micela. Quando a micela ?? neutra o monoc??tion desprotona e dentro da micela coexistem duas esp??cies: HR ancorada na regi??o hidrof??bica e a esp??cie HR-H ancorada na regi??o hidrof??lica. Agora quando a carga micelar ?? negativa a Harmina tem como esp??cie ativa o HR-forte. Essa esp??cie fica ancorada na regi??o aquosa formando um complexo de liga????o de hidrog??nio entre o nitrog??nio da piridina da esp??cie HR. A carga micelar tamb??m propiciou um comportamento fotof??sico distinto para a mol??cula APNH. A emiss??o em micela neutra foi semelhante ao comportamento fotof??sico em meio hidrof??lico. O APNH entrou na micela e ficou na regi??o pr??xima ?? superf??cie. O APNH em micela ani??nica teve suas propriedades fotof??sicas anuladas e em micela cati??nica o APNH ficou na regi??o hidrof??bica (no n??cleo da micela). Esse comportamento fotof??sico ajuda a esclarecer o entendimento do mecanismo de transporte do APNH para o interior de uma micela. Tamb??m auxilia a compreens??o da carcinogenicidade dessa mol??cula frente as c??lulas. Os sistemas de emiss??o juntamente com as outras metodologias foram eficazes no estudo das propriedades fotof??sicas destas mol??culas, demonstrando que essa metodologia tamb??m ?? uma forma de aux??lio ao entendimento da intera????o droga/pseudomembrana fornecendo uma ideia da a????o farmacol??gica.

Submitted by Renyer Costa (renyer.costa@gmail.com) on 2019-02-22T21:40:27Z No. of bitstreams: 4 Tese doutorado Revis??o final.pdf: 18731681 bytes, checksum: c1284967d443b97028e3e732827dd3d1 (MD5) ATA DA DEFESA.pdf: 702115 bytes, checksum: 7ed1540cc7f0948a810f5cb607a4da96 (MD5) Doc Feb 22 2019.pdf: 397611 bytes, checksum: 894a698a4682a63c085e6a533107b08a (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Approved for entry into archive by PPGQ Qu??mica (ppgqsecretaria@gmail.com) on 2019-02-25T18:10:36Z (GMT) No. of bitstreams: 4 Tese doutorado Revis??o final.pdf: 18731681 bytes, checksum: c1284967d443b97028e3e732827dd3d1 (MD5) ATA DA DEFESA.pdf: 702115 bytes, checksum: 7ed1540cc7f0948a810f5cb607a4da96 (MD5) Doc Feb 22 2019.pdf: 397611 bytes, checksum: 894a698a4682a63c085e6a533107b08a (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Rejected by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br), reason: Incluir ficha catalogr??fica na Tese, ap??s a folha de rosto. Voc?? pode elaborar a ficha catalogr??fica por meio do sistema dispon??vel em: http://fichacatalografica.ufam.edu.br/fichacatalografica/ficha/create on 2019-02-25T18:33:33Z (GMT) Submitted by Renyer Costa (renyer.costa@gmail.com) on 2019-02-25T19:54:13Z No. of bitstreams: 4 ATA DA DEFESA.pdf: 702115 bytes, checksum: 7ed1540cc7f0948a810f5cb607a4da96 (MD5) Doc Feb 22 2019.pdf: 397611 bytes, checksum: 894a698a4682a63c085e6a533107b08a (MD5) Tese doutorado Revis??o final.pdf: 18786429 bytes, checksum: 5a893f30e072862ef90dc633b5ace460 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Approved for entry into archive by PPGQ Qu??mica (ppgqsecretaria@gmail.com) on 2019-02-25T19:57:07Z (GMT) No. of bitstreams: 4 ATA DA DEFESA.pdf: 702115 bytes, checksum: 7ed1540cc7f0948a810f5cb607a4da96 (MD5) Doc Feb 22 2019.pdf: 397611 bytes, checksum: 894a698a4682a63c085e6a533107b08a (MD5) Tese doutorado Revis??o final.pdf: 18786429 bytes, checksum: 5a893f30e072862ef90dc633b5ace460 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Approved for entry into archive by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br) on 2019-02-26T15:42:24Z (GMT) No. of bitstreams: 4 ATA DA DEFESA.pdf: 702115 bytes, checksum: 7ed1540cc7f0948a810f5cb607a4da96 (MD5) Doc Feb 22 2019.pdf: 397611 bytes, checksum: 894a698a4682a63c085e6a533107b08a (MD5) Tese doutorado Revis??o final.pdf: 18786429 bytes, checksum: 5a893f30e072862ef90dc633b5ace460 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Made available in DSpace on 2019-02-26T15:42:24Z (GMT). No. of bitstreams: 4 ATA DA DEFESA.pdf: 702115 bytes, checksum: 7ed1540cc7f0948a810f5cb607a4da96 (MD5) Doc Feb 22 2019.pdf: 397611 bytes, checksum: 894a698a4682a63c085e6a533107b08a (MD5) Tese doutorado Revis??o final.pdf: 18786429 bytes, checksum: 5a893f30e072862ef90dc633b5ace460 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-05-11 CNPq 993550932 The alkaloids constitute a class of metabolites with great biological activity and o great importance in human history. Among the several classes, the idole and oxoaporphine type alkaloids are worth mentioning. About 1000 of these types alkaloids have already been isolated from plants, however theoretical studies that justify their activities providing new data about their structural, spectroscopic and quantum properties lack in the literature. Based on this premise, the present study investigated the alkaloids strictosidine, stricnobrasiline, 12-hydroxy-10,11-dimethoxystricnobrasiline, liriodenine, cantinone and 7-methoxy-cantinone through a theoretical approach by DFT calculations using the hybrid electronic correlation function B3LYP and the 6-31 G (d), 6-311G (2d, p) and 6-311G ++ (2d, p) basis set. Theoretical geometric optimization data were compared with X-ray spectroscopy data of similar structures in the literature presenting similar values. In addition calculations of Natural Bond Orbitals (NBOs), HOMO and LUMO orbitals and electrostatic potential maps were performed. Theoretical spectra of UV-Vis revealed to be quite similar to the experimental spectra being possible to signal the electronic transitions. Based on the maps of electrostatic potential and the theoretical spectra of IV (by stretches N-H and O-H) it was possible to predict the formation of hydrogen bonds that influences de physic-chemical properties. Molecular docking calculations against human DNA-Topoisomerase II enzyme complexes and Candida albicans dihydropholate reductase were carried out in order to perform the described activities in literature. Os alcaloides constituem uma classe de metab??litos com grande atividade biol??gica e de grande import??ncia na hist??ria humana. Dentre as diversas classes merecem destaque os alcaloides ind??licos e aporf??nicos. Cerca de 1000 tipos de alcaloides dessas classes j?? foram isolados, entretanto estudos te??ricos que justifiquem as suas atividades e forne??am novos dados acerca das suas propriedades estruturais, espectrosc??picas e qu??nticas s??o escassos na literatura. Partindo desta premissa o presente estudo investigou os alcaloides strictosidina, stricnobrasilina, 12-hidroxi-10,11-dimetoxiestricnobrasilina, liriodenina, cantinona e 7-metoxi-cantinona atrav??s de uma abordagem te??rica por c??lculos DFT usando o funcional h??brido de correla????o eletr??nica B3LYP e as bases 6-31 G(d), 6-311G(2d,p) e 6-311G++(2d,p). Dados te??ricos de otimiza????o geom??trica foram comparados com dados de espectroscopia de raio-X de estruturas similares existentes na literatura apresentando valores similares. Em adi????o c??lculos de Orbitais Naturais de liga????o (Natural Bond Orbitals-NBOs), orbitais HOMO e LUMO e mapas de potencial eletrost??tico foram realizados. Espectros te??ricos de UV-Vis revelaram-se bastante similares aos espectros experimentais sendo poss??vel o assinalamento das transi????es eletr??nicas. Baseados nos mapas de potencial eletrost??tico e nos espectros te??ricos de IV (por estiramentos N-H e O-H) foi poss??vel prever a forma????o de liga????es de hidrog??nio. C??lculos de docking molecular frente os complexos enzim??ticos DNA-Topoisomerase II humana e com Diidrofalato redutase de C??ndida albicans foram realizados no intuito de justificar as atividades previamente descritas na literatura. Foi a primeira defesa com artigos publicados no PPGQ. Ao todo foram quatro artigos com estudos in??ditos.

Submitted by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br) on 2017-03-22T13:24:29Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Disserta????o - Douglas S. Gon??alves.pdf: 4488285 bytes, checksum: cae59ce04883e29f0ff34bfb5aac8fc3 (MD5) Approved for entry into archive by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br) on 2017-03-22T13:26:36Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Disserta????o - Douglas S. Gon??alves.pdf: 4488285 bytes, checksum: cae59ce04883e29f0ff34bfb5aac8fc3 (MD5) Approved for entry into archive by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br) on 2017-03-22T13:26:47Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Disserta????o - Douglas S. Gon??alves.pdf: 4488285 bytes, checksum: cae59ce04883e29f0ff34bfb5aac8fc3 (MD5) Made available in DSpace on 2017-03-22T13:26:47Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Disserta????o - Douglas S. Gon??alves.pdf: 4488285 bytes, checksum: cae59ce04883e29f0ff34bfb5aac8fc3 (MD5) Previous issue date: 2017-01-05 CNPq - Conselho Nacional de Desenvolvimento Cient??fico e Tecnol??gico The study of aerosol particles has become quite relevant in recent years as they are found to influence directly or indirectly the climate, resulting in serious consequences for ecosystems, affecting the natural cycles of rain and drought, among others. Aerosols may scatter or absorb solar radiation, altering the eenergetic balance os the atmosphere. In the present work we dedicate our efforts to study the interaction of well-known atmospheric nucleation precursors (NH3 and H2SO4) with atmospheric molecules containing sulfur, such as methanesulfonic acid (CH3SO3H) or MSA and methanesulfinic acid (CH3SO2H) or MSIA. to analyze if these molecules can contribute in the process of aerosol formation in the atmosphere. Our calculations using Density Functional Theory (DFT) and B3LYP/6 - 31 + +G(d,p) model, reveal the presence of strong hydrogen bonding in the binary MSAIMSIA- NH3/H2SO4 and ternary MSAIMSIA- (NH3 - H2SO4) clusters in the gas phase. Analysing some of the quantum-chemical molecular properties like electronic structure, binding energy and vibrational spectroscopy we conclude that among NH3 and H2SO4, MSA forms stronger binary cluster with NH3 while MSIA pre-fers H2SO4. However, among the ternary clusters, MSA- (NH3 - H2SO4) is clearly the most stabilized structure which may be helpful in aerossol formation. O estudo das part??culas de aerossol tem se tornado mais relevante nos ??ltimos anos por influenciarem direta e indiretamente o clima, implicando em s??rias consequ??ncias aos ecossistemas, ciclos naturais de chuvas e secas, dentre outros, atingindo a sociedade como um todo. Os aeross??is atuam espalhando e absorvendo a radia????o solar, afetando o balan??o energ??tico da atmosfera. No presente trabalho, dedicamos nossos esfor??os ao estudo da intera????o de precursores atmosf??ricos de nuclea????o (NH3 e H2SO4) com mol??culas de interesse atmosf??rico contendo enxofre, tais como ??cido metanosulf??nico (CH3SO3H) ou MSA e ??cido metanosulf??nico (CH3SO2H) ou MSIA para analisar se essas mol??culas contribuem para o processo de forma????o de aeross??is na atmosfera. Os c??lculos usando teoria do funci-onal da densidade (DFT), com modelo B3LY P16-31-1-+G(d,p) nos mostrou o surgimento de fortes liga????es de hidrog??nio nos sistemas bin??rios MSAIMSI A ??? NH31112,904 e tern??rios MSA/MSIA ??? (NH3 ??? H2SO4). A an??lise das propriedades qu??mico-qu??nticas, tais como estrutura eletr??nica, energia de liga????o e espectroscopia vibracional, conclu??mos que, entre NH3 e H2SO4, MSA forma aglomerados bin??rios mais fortes com NH3, enquanto que MSIA prefere H2SO4. Entretanto, nos aglomerados tern??rios, claramente a estrutura mais est??vel ?? MSA ??? (NH3 ??? H2SO4), podendo ser mais favor??vel para a forma????o dos aeross??is.

Submitted by L??cia Brand??o (lucia.elaine@live.com) on 2015-07-15T15:41:32Z No. of bitstreams: 1 Disserta????o - Julio Rodolfo Pessoa Iank.pdf: 1520296 bytes, checksum: 1a18bad919bdfcbc7a82826ae5107cc5 (MD5) Approved for entry into archive by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-07-20T15:18:56Z (GMT) No. of bitstreams: 1 Disserta????o - Julio Rodolfo Pessoa Iank.pdf: 1520296 bytes, checksum: 1a18bad919bdfcbc7a82826ae5107cc5 (MD5) Approved for entry into archive by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-07-20T15:16:48Z (GMT) No. of bitstreams: 1 Disserta????o - Julio Rodolfo Pessoa Iank.pdf: 1520296 bytes, checksum: 1a18bad919bdfcbc7a82826ae5107cc5 (MD5) Approved for entry into archive by Divis??o de Documenta????o/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-07-20T15:21:32Z (GMT) No. of bitstreams: 1 Disserta????o - Julio Rodolfo Pessoa Iank.pdf: 1520296 bytes, checksum: 1a18bad919bdfcbc7a82826ae5107cc5 (MD5) Made available in DSpace on 2015-07-20T15:21:32Z (GMT). No. of bitstreams: 1 Disserta????o - Julio Rodolfo Pessoa Iank.pdf: 1520296 bytes, checksum: 1a18bad919bdfcbc7a82826ae5107cc5 (MD5) Previous issue date: 2014-01-29 CAPES - Coordena????o de Aperfei??oamento de Pessoal de N??vel Superior CAPES - Coordena????o de Aperfei??oamento de Pessoal de N??vel Superior The current study of carbon nanostructures, among which we can cite the buckyballs and carbon nanotubes, have generated a great interest in theoretical and experimental researchers due to the application of chemical and physical properties of these structures. Among these is the ability to encapsulate different chemicals inside, especially gases under specific conditions of reaction temperature, pressure and speed rating. This work analyzed the stability of carbon nanostructures like buckyballs, as the storage of gases. We used a theoretical-computational level PM3 (Parametric Method 3). For that we used a set of Quad Core processors with computational package GAUSSIAN existing at the Laboratory of Theoretical and Computational Chemistry in UFAM. The structures of buckyballs analyzed with gas molecules inserted (H2O, CO2, O2 and N2) showed different stabilities against the maximum storage of gases: C60@9H2O, C60@4CO2, C60@5O2 and C60@4N2; C70@6H2O, C70@3CO2, C70@6O2 and C70@7N2; C78@10H2O, C78@6CO2, C78@8O2 and C78@7N2; C80@14H2O, C80@5CO2, C80@8O2 and C80@10N2; C82@9H2O, C82@5CO2, C82@7O2 and C82@9N2. These results show the maximum storage of buckyballs analyzed in relation to the gases mentioned and these may be used as models for possible gas storage systems. O estudo atual de nanoestruturas de carbono, dentre as quais se podem citar as buckyballs e os nanotubos de carbono, tem gerado um grande interesse em pesquisadores te??ricos e experimentais devido ?? aplica????o das propriedades qu??micas e f??sicas destas estruturas. Entre estas se encontra a capacidade de encapsulamento de diferentes subst??ncias qu??micas em seu interior, especialmente gases, sob condi????es espec??ficas de rea????o, temperatura, press??o e taxa de velocidade. Neste trabalho se analisou a estabilidade das nanoestruturas de carbono do tipo buckyballs, como meio de armazenagem de gases. Foi utilizada uma abordagem te??rico-computacional, em n??vel PM3 (Parametric Method 3). Para tanto se utilizou um conjunto de processadores Quad Core com o pacote computacional GAUSSIAN, existente no Laborat??rio de Qu??mica Te??rica e Computacional na UFAM. As estruturas das buckyballs analisadas com mol??culas de gases inseridas (H2O, CO2, O2 e N2) apresentaram diferentes estabilidades frente ao limite m??ximo de armazenamento de gases: C60@9H2O, C60@4CO2, C60@5O2 e C60@4N2; C70@6H2O, C70@3CO2, C70@6O2 e C70@7N2; C78@10H2O, C78@6CO2, C78@8O2 e C78@7N2; C80@14H2O, C80@5CO2, C80@8O2 e C80@10N2; C82@9H2O, C82@5CO2, C82@7O2 e C82@9N2. Estes resultados mostram o limite m??ximo de armazenamento das buckyballs analisadas em rela????o aos gases mencionados e os mesmos poder??o ser utilizados como modelos para poss??veis sistemas de armazenamento de gases.