Síntese de nanopartículas de ouro para amplificação do espalhamento Raman (SERS) e da fluorescência (SEF) visando aplicações sensoriais
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Data
2018-01-24
Autores
Camacho, Sabrina Aléssio
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Editor
Universidade Estadual Paulista (Unesp)
Resumo
O presente trabalho abrange a síntese de nanopartículas metálicas com propriedades plasmônicas específicas incorporadas a filmes finos nanoestruturados de moléculas de interesse, como metaloporfirinas e outras. Nanopartículas de ouro (AuNPs 16 nm) foram incorporadas a filmes Langmuir-Blodgett (LB) de metaloporfirina visando o efeito SERS (espalhamento Raman amplificado em superfície). A incorporação das AuNPs se deu por codeposição, a partir das interações entre as AuNPs (presentes na subfase do filme de Langmuir) e as moléculas de metaloporfirina (espalhadas na interface ar/água). Nanopartículas de ouro recobertas com sílica (Au-SHINs), com tamanhos diferentes (40 e 100 nm) e mesma espessura de recobrimento (10 nm), também foram incorporadas em filmes LB e em solução aquosa visando o efeito SEF (fluorescência amplificada em superfície). Três variáveis foram aplicadas para aumentar a fluorescência: tamanho de nanopartícula, agregação e temperatura da amostra. Resultados teóricos e experimentais mostraram que as Au-SHINs 100 nm apresentam uma intensidade de amplificação cerca de 3 vezes maior e um espalhamento 2 ordens de grandeza maior que as Au-SHINs 40 nm, levando a maiores fatores de amplificação (EF). Além disso, a agregação das Au-SHINs com eletrólito e a diminuição da temperatura da amostra também resultou em maiores EF. Visando uma aplicação ambiental, AuNPs 100 nm e Au-SHINs 100 nm recobertas com 4 nm de sílica foram aplicadas na detecção do herbicida ametrina. Soluções etanólicas com concentração de 10-5 mol/L em coloides de AuNPs e Au-SHINs foram detectadas via SERS. Já em cana-de-açúcar, a detecção foi possível somente com AuNPs, porém, com concentrações no intervalo de 10-4 a 10-8 mol/L, sendo 5,3 x 10-8 mol/L o limite máximo de resíduos de ametrina permitido em produtos agrícolas. Visando uma aplicação biológica, Au-SHINs 100 nm recobertas com 10 e 4 nm de sílica foram utilizadas na fabricação de SEF e SERS tags, respectivamente, para detecção dos antígenos IgM e do vírus da Zika em plataformas de imunoensaio. Os limites de detecção alcançados foram de 5,0 e 12,5 ng/mL para os antígenos IgM e Zika, respectivamente. Neste último caso foi possível a distinção com antígenos da Dengue, evitando a reatividade cruzada, um entrave freqüentemente encontrado em ensaios de diagnóstico da Zika.
The present work covers the synthesis of metallic nanoparticles with specific plasmonic properties incorporated into nanostructured thin films of target molecules, as metalloporphyrins and others. Gold nanoparticles (AuNPs 16 nm) were incorporated into Langmuir-Blodgett (LB) films of metalloporphyrin aiming the SERS effect (surface-enhanced Raman spectroscopy). AuNPs were incorporated by co-deposition, taking advantage of the interaction between the AuNPs (in the Langmuir film subphase) and the metalloporphyrin molecules (sprayed at the air/water interface). Gold shell-isolated nanoparticles (Au-SHINs), with different sizes (40 and 100 nm) and same silica shell thickness (10 nm), were also incorporated into LB films and in aqueous solution targeting the SEF effect (surface-enhanced fluorescence). Three variables were applied to increase the fluorescence: size of nanoparticle, aggregation and sample temperature. Theoretical and experimental results showed that the Au-SHINs 100 nm have an enhancement intensity about 3 times higher and a scattering 2 orders of magnitude higher than the Au-SHINs 40 nm, leading to higher enhancement factors (EF). Besides, the aggregation of Au-SHINs with electrolyte and the sample temperature decreased also resulted to higher EF. Aiming an environmental application, AuNPs 100 nm and Au-SHINs 100 nm coated with 4 nm of silica were applied to detect the herbicide ametryn. Ethanolic solution with concentration of 10-5 mol/L in AuNPs and Au-SHINs colloids were detected via SERS. While in sugar cane, the detection was only possible with AuNPs, however, with concentrations at the range from 10-4 to 10-8 mol/L, being 5.3 x 10-8 mol/L the maximum residual limit of ametryn allowed in agricultural products. Aiming a biological application, Au-SHINs 100 nm coated with 10 and 4 nm of silica were used in the development of SEF and SERS tags, respectively, for detecting IgM and Zika virus antigens on immunoassay platforms. The limits of detection were 5.0 and 12.5 ng/mL for IgM and Zika antigens, respectively. In the latter, it was possible the distinction with Dengue antigens, preventing the cross-reactivity, an obstacle frequently found in diagnostic assays of Zika.
The present work covers the synthesis of metallic nanoparticles with specific plasmonic properties incorporated into nanostructured thin films of target molecules, as metalloporphyrins and others. Gold nanoparticles (AuNPs 16 nm) were incorporated into Langmuir-Blodgett (LB) films of metalloporphyrin aiming the SERS effect (surface-enhanced Raman spectroscopy). AuNPs were incorporated by co-deposition, taking advantage of the interaction between the AuNPs (in the Langmuir film subphase) and the metalloporphyrin molecules (sprayed at the air/water interface). Gold shell-isolated nanoparticles (Au-SHINs), with different sizes (40 and 100 nm) and same silica shell thickness (10 nm), were also incorporated into LB films and in aqueous solution targeting the SEF effect (surface-enhanced fluorescence). Three variables were applied to increase the fluorescence: size of nanoparticle, aggregation and sample temperature. Theoretical and experimental results showed that the Au-SHINs 100 nm have an enhancement intensity about 3 times higher and a scattering 2 orders of magnitude higher than the Au-SHINs 40 nm, leading to higher enhancement factors (EF). Besides, the aggregation of Au-SHINs with electrolyte and the sample temperature decreased also resulted to higher EF. Aiming an environmental application, AuNPs 100 nm and Au-SHINs 100 nm coated with 4 nm of silica were applied to detect the herbicide ametryn. Ethanolic solution with concentration of 10-5 mol/L in AuNPs and Au-SHINs colloids were detected via SERS. While in sugar cane, the detection was only possible with AuNPs, however, with concentrations at the range from 10-4 to 10-8 mol/L, being 5.3 x 10-8 mol/L the maximum residual limit of ametryn allowed in agricultural products. Aiming a biological application, Au-SHINs 100 nm coated with 10 and 4 nm of silica were used in the development of SEF and SERS tags, respectively, for detecting IgM and Zika virus antigens on immunoassay platforms. The limits of detection were 5.0 and 12.5 ng/mL for IgM and Zika antigens, respectively. In the latter, it was possible the distinction with Dengue antigens, preventing the cross-reactivity, an obstacle frequently found in diagnostic assays of Zika.
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Palavras-chave
Nanopartículas de ouro, SERS, SEF