Estudo teórico da reatividade de compostos orgânicos: sensores poliméricos e fotopolimerização de quinolinas
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Data
2023-04-27
Autores
Barboza, Bruno Hori
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Universidade Estadual Paulista (Unesp)
Resumo
Recentemente nota-se um número crescente de trabalhos dedicados ao design e processamento de materiais para variadas aplicações tecnológicas. Neste cenário, compostos orgânicos configuram-se como relevantes materiais, os quais são amplamente utilizados em diversificadas áreas. Neste trabalho são conduzidos estudos teóricos de reatividade relativos a dois temas de interesse associados a estes materiais: i) mecanismo de resposta de polímeros em sensores químicos, e ii) processo de fotopolimerização de derivados de quinolinas para a formação de resinas. Os polímeros têm se mostrado materiais promissores na confecção de sensores químicos, no entanto, dada a complexidade dos mecanismos envolvidos, detalhes acerca da interação destes compostos com espécies químicas externas são de difícil descrição. Neste contexto, a fim de melhor compreender as propriedades sensoriais destes materiais e propor possíveis derivados otimizados, cálculos de estrutura eletrônica (CEE) e simulações via dinâmica molecular (DM) foram conduzidos em conjunto para a identificação de sítios ativos e avaliação de processos de adsorção. No que tange o segundo tema, foram avaliados os mecanismos de fotopolimerização de quinolinas sintéticas, recentemente reportados como possíveis materiais fotoiniciadores biocompatíveis. A fim de melhor compreender os processos envolvidos e identificar características desejáveis para aplicação destes compostos como fotoiniciadores de resinas, foram avaliadas as suas propriedades estruturais, optoeletrônicas e de reatividade. Os resultados obtidos no primeiro tema evidenciam a eficácia dos descritores de reatividade em prever as interações polímero/analitos, sugerindo que sistemas mais promissores devem apresentar cargas líquidas apropriadas em regiões com alto índice de reatividade. Relativo ao segundo tema, os resultados obtidos indicam a plausibilidade do uso de índices de reatividade local na previsão da posição de sítios de maior reatividade dos fotoiniciadores e materiais fotopolimerizáveis durante o processo de formação das resinas. Em especial, os resultados sugerem derivados quinolínicos contendo grupos de nitro como fotoiniciadores eficazes enquanto que aminoquinolinas metacriladas tendem a atuar como eficientes agentes fotopolimerizáveis.
In recent years there is an increasing number of studies dedicated to the design and processing of materials for a wide range of technological applications. In this scenario, organic compounds are relevant materials, which are widely explored in different research areas. In this research, theoretical reactivity studies are performed on two subjects of interest associated with such materials: i) response mechanism of organic polymers as chemical sensors, and ii) photopolymerization process of quinoline derivatives for acrylic resin formations. Organic polymers are promising materials for chemical sensors, however, given the complexity of the mechanisms involved, the details regarding the interaction of these compounds with external chemical species are difficult to describe. In this context, to better understand the sensory properties of these materials and propose optimized derivatives, electronic structure calculations and molecular dynamics simulations were conducted to identify reactive sites and evaluate adsorption processes. Regarding the second subject, it was evaluated the photopolymerisation mechanisms of synthetic quinolines, recently reported as possible biocompatible photoinitiator materials. To better understand the processes and identify desirable properties of quinoline derivatives as photoinitiators, this study evaluates the structural, optoelectronic and reactivity properties of functionalized compounds via electronic structure calculations. For the first topic, the results show the effectiveness of evaluating reactivity descriptors for the prediction of polymer/analyte interactions, so that promising systems should present appropriate net charges on regions with high reactivity indexes. Regarding the second topic, the results indicate the plausibility of using local reactivity descriptors to predict regions of greater reactivity of photoinitiators and light curing agents of synthetic resins. In particular, it is noticed that nitroquinolines can act as effective photoinitiators while methacrylated aminoquinolines can act as photopolymerizers.
In recent years there is an increasing number of studies dedicated to the design and processing of materials for a wide range of technological applications. In this scenario, organic compounds are relevant materials, which are widely explored in different research areas. In this research, theoretical reactivity studies are performed on two subjects of interest associated with such materials: i) response mechanism of organic polymers as chemical sensors, and ii) photopolymerization process of quinoline derivatives for acrylic resin formations. Organic polymers are promising materials for chemical sensors, however, given the complexity of the mechanisms involved, the details regarding the interaction of these compounds with external chemical species are difficult to describe. In this context, to better understand the sensory properties of these materials and propose optimized derivatives, electronic structure calculations and molecular dynamics simulations were conducted to identify reactive sites and evaluate adsorption processes. Regarding the second subject, it was evaluated the photopolymerisation mechanisms of synthetic quinolines, recently reported as possible biocompatible photoinitiator materials. To better understand the processes and identify desirable properties of quinoline derivatives as photoinitiators, this study evaluates the structural, optoelectronic and reactivity properties of functionalized compounds via electronic structure calculations. For the first topic, the results show the effectiveness of evaluating reactivity descriptors for the prediction of polymer/analyte interactions, so that promising systems should present appropriate net charges on regions with high reactivity indexes. Regarding the second topic, the results indicate the plausibility of using local reactivity descriptors to predict regions of greater reactivity of photoinitiators and light curing agents of synthetic resins. In particular, it is noticed that nitroquinolines can act as effective photoinitiators while methacrylated aminoquinolines can act as photopolymerizers.
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Palavras-chave
Cálculos de estrutura eletrônica, Polímeros conjugados, Derivados quinolínicos, Teoria do funcional densidade, Dinâmica molecular de campos reativos, Electronic structure calculations, Conjugated polymers, Quinolines derivatives, Density functional theory, Molecular dynamics