Filmes finos de complexos metálicos: efeito da arquitetura supramolecular na aplicação de eletrodos modificados como sensores para catecolaminas
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Data
2017-08-25
Autores
Sonvesso, Cibely da Silva Martin [UNESP]
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Universidade Estadual Paulista (Unesp)
Resumo
Esse trabalho explora a modificação de substratos condutores em aplicações sensoriais a partir da deposição de filmes finos pelas técnicas de Langmuir-Schaefer (LS) e eletropolimerização utilizando dois complexos metálicos (Ni-Salpn e FePc) visando correlacionar propriedades estruturais e eletroquímicas destes filmes. Os filmes de Langmuir de Ni-Salpn apresentaram baixa estabilidade na interface água/ar, o que impossibilitou a deposição destes filmes sobre substratos sólidos via técnica LS. No entanto, foram facilmente depositados por eletrodeposição. Em termos estruturais, o filme de Ni-Salpn apresenta a formação de “colunas moleculares”, sendo as moléculas de Ni-Salpn orientadas preferencialmente com um dos macrociclos do complexo perpendicular ao plano do substrato. Os filmes de FePc foram obtidos por ambas técnicas de deposição (LS e eletrodeposição). Em termos estruturais os filmes de FePc eletrodepositados apresentaram-se mais homogêneos (morfologia superficial), menos rugosos e mais compactos em relação aos filmes LS, estando as moléculas de FePc organizadas preferencialmente flat-on em relação a superfície do substrato para ambos os filmes. O maior diferencial entre os filmes LS e eletrodepositados de FePc é o estado de oxidação do centro metálico, sendo de FeII para o filme LS e FeI para o eletrodepositado. As caracterizações eletroquímicas em eletrólito suporte e na presença de dopamina em solução revelaram diferentes efeitos dos filmes de Ni-Salpn e FePc, sendo os filmes de FePc mais estáveis e com potencial para aplicação sensorial. Os filmes de FePc foram avaliados eletroquimicamente em solução de diferentes catecolaminas (L-tirosina, L-Dopa, dopamina, noroepinefrina e epinefrina) e também aplicados como sensor para a detecção de L-Dopa em amostra farmacêutica. De maneira geral, o arranjo supramolecular (que depende do complexo metálico e da técnica de deposição) dos filmes finos influencia diretamente no comportamento eletroquímico em solução padrão de catecolaminas, bem como nas respostas sensoriais.
This work reports the modification of conductor substrates in sensorial application from the deposition of thin films of two metallic complexes (Ni-Salpn and FePc) using the Langmuir-Schaefer (LS) and electrodeposition techniques, aiming to correlate the structural and electrochemical properties of these films. The Langmuir films of Ni-Salpn exhibited low stability on the interface water/air, which made it impossible the deposition of these films on solid substrates using the LS technique. However, were easy deposited by electrodeposition. In structural terms, the Ni-Salpn electrodeposited film showed a formation of “molecular columns”, being the Ni-Salpn molecules preferentially oriented with one of the complex macrocycles perpendicular to the substrate plane. The FePc films were formed by both deposition techniques (LS and electrodeposition). In structural terms, the FePc electrodeposited films were more homogeneous (surface morphology), less rough and more compact than the LS films. The FePc molecules are preferentially oriented in a flat-on position in relation to the substrate plane to both FePc films. The largest difference between FePc LS and FePc electrodeposited films is the oxidation state of the metal center, being the FeII to LS films and FeI to electrodeposited films. The electrochemical characterizations in supporting electrolyte and in presence of dopamine showed different behavior for Ni-Salpn and FePc films. The FePc films were more stable and with great potential to sensorial applications. The FePc films were electrochemically evaluated in catecholamines solutions (L-tyrosine, L-Dopa, dopamine, norepinephrine, and epinephrine) and also applied as a sensor to L-Dopa detection in real samples. In general, the supramolecular arrangement (which depends on metallic complexes and deposition technique) of the thin films have an influence on electrochemical behavior in catecholamines standard solutions as well as in sensorial responses.
This work reports the modification of conductor substrates in sensorial application from the deposition of thin films of two metallic complexes (Ni-Salpn and FePc) using the Langmuir-Schaefer (LS) and electrodeposition techniques, aiming to correlate the structural and electrochemical properties of these films. The Langmuir films of Ni-Salpn exhibited low stability on the interface water/air, which made it impossible the deposition of these films on solid substrates using the LS technique. However, were easy deposited by electrodeposition. In structural terms, the Ni-Salpn electrodeposited film showed a formation of “molecular columns”, being the Ni-Salpn molecules preferentially oriented with one of the complex macrocycles perpendicular to the substrate plane. The FePc films were formed by both deposition techniques (LS and electrodeposition). In structural terms, the FePc electrodeposited films were more homogeneous (surface morphology), less rough and more compact than the LS films. The FePc molecules are preferentially oriented in a flat-on position in relation to the substrate plane to both FePc films. The largest difference between FePc LS and FePc electrodeposited films is the oxidation state of the metal center, being the FeII to LS films and FeI to electrodeposited films. The electrochemical characterizations in supporting electrolyte and in presence of dopamine showed different behavior for Ni-Salpn and FePc films. The FePc films were more stable and with great potential to sensorial applications. The FePc films were electrochemically evaluated in catecholamines solutions (L-tyrosine, L-Dopa, dopamine, norepinephrine, and epinephrine) and also applied as a sensor to L-Dopa detection in real samples. In general, the supramolecular arrangement (which depends on metallic complexes and deposition technique) of the thin films have an influence on electrochemical behavior in catecholamines standard solutions as well as in sensorial responses.
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Palavras-chave
Arquitetura supramolecular, Filmes finos, Sensores