Impressos e bio-híbridos luminescentes baseados em Ln- MOFs
| Autor(a) principal: | |
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| Data de Publicação: | 2018 |
| Tipo de documento: | Tese |
| Idioma: | por |
| Título da fonte: | Repositório Institucional da UFPE |
| dARK ID: | ark:/64986/00130000138bz |
| Texto Completo: | https://repositorio.ufpe.br/handle/123456789/33091 |
Resumo: | SANTOS, Marcos Malta dos, também é conhecido(a) em citações bibliográficas por: MALTA, Marcos |
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LUZ, Leonis Lourenço dahttp://lattes.cnpq.br/8952196044903176http://lattes.cnpq.br/9563158536061549ALVES JUNIOR, SeverinoRODRIGUES, Marcelo OliveiraSANTOS, Marcos Malta dos2019-09-17T20:37:44Z2019-09-17T20:37:44Z2018-04-05https://repositorio.ufpe.br/handle/123456789/33091ark:/64986/00130000138bzSANTOS, Marcos Malta dos, também é conhecido(a) em citações bibliográficas por: MALTA, MarcosEste trabalho visa explorar o processo de síntese de redes metal-orgânicas com íons lantanídeos (Ln-MOFs), tais como, [Ln₂(C₁₂O₁₂)(H₂O) ₈] 2H₂O (Ln = Eu³⁺, Tb³⁺, Nd³⁺ e Gd³⁺) acelerado por agente precipitante, determinar suas estabilidades química e física, e suas propriedades ópticas no desenvolvimento de impressos e bio-hibridos luminescentes. Utilizando solvente de precipitação (metanol, etanol ou i-propanol), conseguiu-se reduzir o tempo de síntese destas Ln-MOFs de 15-20 dias para poucos minutos. Estas MOFs isoestruturais foram caracterizadas por raios X de pó e de monocristal, espectroscopias no infravermelho com transformada de Fourier (FTIR) e de fotoluminescência, análise termogravimétrica (TGA) e microscopia eletrônica de varredura (MEV). As Eu-MOF (R-MOF), Tb-MOF (G-MOF), Gd-MOF (B-MOF) e Nd-MOF (BIR-MOF) apresentam fotoluminescência no vermelho (⁵D₀ → ⁷FJ, J = 0, 1, 2, 3 e 4), verde (⁵D₄ → ⁷FJ, J = 0, 1, 2, 3, 4, 5 e 6), azul (π* → π) e azul/infravermelho (π* → π/⁴F₃/₂ → ⁴IJ, J = 11/2 e 13/2), respectivamente. O processo de precipitação das Ln-MOF mediado por solvente de cristalização possibilitou a deposição destas MOFs sobre substratos flexíveis empregando impressoras jato-de-tinta comum. Com esta metodologia, realizou-se a deposição de R-MOF, G-MOF, BIR-MOF e padrões combinados destas. As propriedades ópticas das Ln-MOFs permitiram a previsibilidade de cor, viabilizou a geração de códigos de barra luminescentes e, consequentemente, a codificação de informações. Dentre os impressos, os em papel vegetal apresentaram as melhores propriedades mecânicas e térmicas, com a possibilidade de impressão de textos sobre as MOFs depositadas sem alteração das propriedades luminescentes do material. Esta propriedade habilita a inclusão destas MOFs como dispositivo de segurança em impressos em geral. As estabilidades químicas e físicas das Ln-MOFs foram utilizadas como critério para sua escolha no desenvolvimento de bio-híbridos luminescentes, Fungo/Ln-MOF (Ln = Eu e Tb), a partir do cultivo dos fungos filamentosos Aspergillus Niger, Phialomyces Macrosporos ou Trichoderma, em solução de glicose 0,2% e cristais de Eu-MOF e Tb-MOF suspensos. Os bio-híbridos foram caracterizados por raios X de pó, TGA, microscopias de fluorescência, microscopia confocal, MEV e espectroscopia de luminescência. Em conjunto, estas técnicas mostraram que os cristais das Ln-MOFs foram incorporados pelos fungos e não sofreram nenhum processo de decomposição. Além disso, as microscopias mostraram que as hifas fúngicas foram completamente revestidas com MOF. As imagens de microscopia de fluorescência revelam ainda o preenchimento dos vacúolos das espécies Phialomyces macrosporos e Trichoderma, e a cor de fotoluminescência adquiridas pelas hifas fúngicas após a incorporação das Ln-MOF. Esta abordagem experimental para a obtenção de bio-híbridos Fungo/Ln-MOF abre precedentes para a exploração de sistemas desta natureza, por exemplo, em catálise heterogênea e tratamento de doenças infecciosas e parasitárias.FACEPEThis work aims at exploring the process of synthesis of the metal-organic frameworks based on lanthanide ions (Ln-MOFs), such as [Ln₂(C₁₂O₁₂)(H₂O) ₈] 2H₂O (Ln = Eu³⁺, Tb³⁺, Nd³⁺ e Gd³⁺) accelerated by precipitating agent, ascertain their chemical and physical stabilities, and their optical properties in the development of luminescent printed and bio-hybrids materials. Using a precipitation solvent (methanol, ethanol or i-propanol), the time of synthesis of the Ln-MOFs was reduced from 15-20 days to a few minutes. These isostructural MOFs were characterized by powder and single crystal X-ray diffraction, Fourier-transform infrared (FTIR) and photoluminescence spectroscopies, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The Eu-MOF (R-MOF), Tb-MOF (G-MOF), Gd-MOF (B-MOF) e Nd-MOF (BIR-MOF) have shown photoluminescence in the red (⁵D₀ → ⁷FJ, J = 0, 1, 2, 3 and 4) , green (⁵D₄ → ⁷FJ, J = 0, 1, 2, 3, 4, 5 and 6), blue (π* → π) e blue/NIR (π* → π/⁴F₃/₂ → ⁴IJ, J = 11/2 and 13/2), respectively. The solvent-mediated crystallization process of Ln-MOFs has allowed the deposition of these MOFs on flexible substrates employing common inkjet printers. With this methodology, we perform the deposition of R-MOF, G-MOF, BIR-MOF and combined patterns of these. The optical properties of the Ln-MOFs allowed the predictability of color, enabled the generation of luminescent bar codes and, consequently, encoding information. Among the printed materials, the vegetal paper sheet printed material exhibits the best mechanical and thermal properties, with the possibility of printing texts on the luminescent printed material without changing its luminescent properties. This property enables the inclusion of these MOFs as a printed security device. The most chemically and physically stable of Ln-MOFs were used in the development of luminescent bio-hybrids, Fungus/Ln-MOF (Ln = Eu and Tb), by cultivating filamentous fungi Aspergillus Niger, Phialomyces Macrosporos or Trichoderma, in a 0.2% glucose solution with suspended Eu-MOF and Tb-MOF crystals. The bio-hybrids were characterized by powder X-rays diffraction, TGA, fluorescence microscopy, confocal microscopy, SEM and luminescence spectroscopy. Together, these techniques showed that the Ln-MOFs crystals were incorporated by the fungi and did not undergo any decomposition processes. In addition, microscopies showed that the fungal hyphae were completely coated by MOF. The fluorescence microscopy images also showed the filling of the vacuoles of the Phialomyces macrosporos and Trichoderma, and the color of photoluminescence acquired by the fungal hyphae after the incorporation of the Ln-MOF. This experimental approach for obtaining fungus/Ln-MOF bio-hybrids opens up perspective for the exploration of theses systems in heterogeneous catalysis, treatment of infectious and parasitic diseases, for example.porUniversidade Federal de PernambucoPrograma de Pos Graduacao em QuimicaUFPEBrasilAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessQuímica InorgânicaMetal-organic FrameworkLantanídeosBio-híbridosImpressos e bio-híbridos luminescentes baseados em Ln- MOFsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisdoutoradoreponame:Repositório Institucional da UFPEinstname:Universidade Federal de Pernambuco (UFPE)instacron:UFPETHUMBNAILTESE Leonis Lourenço da Luz.pdf.jpgTESE Leonis Lourenço da Luz.pdf.jpgGenerated Thumbnailimage/jpeg1295https://repositorio.ufpe.br/bitstream/123456789/33091/5/TESE%20Leonis%20Louren%c3%a7o%20da%20Luz.pdf.jpgb0a3f24641cef0a8c249eff1d941653cMD55ORIGINALTESE Leonis Lourenço da Luz.pdfTESE Leonis Lourenço da Luz.pdfapplication/pdf16345456https://repositorio.ufpe.br/bitstream/123456789/33091/1/TESE%20Leonis%20Louren%c3%a7o%20da%20Luz.pdf7042d70a86618011b307c447eac358a0MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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Impressos e bio-híbridos luminescentes baseados em Ln- MOFs |
| title |
Impressos e bio-híbridos luminescentes baseados em Ln- MOFs |
| spellingShingle |
Impressos e bio-híbridos luminescentes baseados em Ln- MOFs LUZ, Leonis Lourenço da Química Inorgânica Metal-organic Framework Lantanídeos Bio-híbridos |
| title_short |
Impressos e bio-híbridos luminescentes baseados em Ln- MOFs |
| title_full |
Impressos e bio-híbridos luminescentes baseados em Ln- MOFs |
| title_fullStr |
Impressos e bio-híbridos luminescentes baseados em Ln- MOFs |
| title_full_unstemmed |
Impressos e bio-híbridos luminescentes baseados em Ln- MOFs |
| title_sort |
Impressos e bio-híbridos luminescentes baseados em Ln- MOFs |
| author |
LUZ, Leonis Lourenço da |
| author_facet |
LUZ, Leonis Lourenço da |
| author_role |
author |
| dc.contributor.authorLattes.pt_BR.fl_str_mv |
http://lattes.cnpq.br/8952196044903176 |
| dc.contributor.advisorLattes.pt_BR.fl_str_mv |
http://lattes.cnpq.br/9563158536061549 |
| dc.contributor.author.fl_str_mv |
LUZ, Leonis Lourenço da |
| dc.contributor.advisor1.fl_str_mv |
ALVES JUNIOR, Severino |
| dc.contributor.advisor-co1.fl_str_mv |
RODRIGUES, Marcelo Oliveira SANTOS, Marcos Malta dos |
| contributor_str_mv |
ALVES JUNIOR, Severino RODRIGUES, Marcelo Oliveira SANTOS, Marcos Malta dos |
| dc.subject.por.fl_str_mv |
Química Inorgânica Metal-organic Framework Lantanídeos Bio-híbridos |
| topic |
Química Inorgânica Metal-organic Framework Lantanídeos Bio-híbridos |
| description |
SANTOS, Marcos Malta dos, também é conhecido(a) em citações bibliográficas por: MALTA, Marcos |
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2018 |
| dc.date.issued.fl_str_mv |
2018-04-05 |
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2019-09-17T20:37:44Z |
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2019-09-17T20:37:44Z |
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info:eu-repo/semantics/publishedVersion |
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info:eu-repo/semantics/doctoralThesis |
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https://repositorio.ufpe.br/handle/123456789/33091 |
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ark:/64986/00130000138bz |
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por |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ |
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openAccess |
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Universidade Federal de Pernambuco |
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Programa de Pos Graduacao em Quimica |
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UFPE |
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Brasil |
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Universidade Federal de Pernambuco |
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