Publicação
Sustainable affinity materials for sensing, catalysis ad biopurification
| Resumo: | The global market for bioseparation and biopurification systems is rapidly growing, driven by an increasing demand for biopharmaceuticals. However, conventional biopurification techniques typically rely on protein–based technologies, which have cost limitations and lack of stability. This thesis explored the green development of high–affinity materials, specifically molecularly imprinted polymers (MIPs) and dendrimers for bio–industry applications, using supercritical CO2 (scCO2) technology and mechanochemistry (ball milling). Herein, MIPs towards small biomolecules, such as amino acids, were developed for use as solid–phase extraction devices and as biosensors for monitoring downstream processes. Innovative strategies were followed, such as dual–templating, photochromism, and the use of beryllium–based functional monomers for thermal sensing. Rational design methods, including quantum mechanics and molecular dynamics simulations, were used to predict the best MIP systems. Acrylamide was identified as the best functional monomer for L–leucine (LEU) using ball milling, while 2–vinylpyridine was better when using scCO2 technology. A dual–templating MIP achieved an imprinting factor (IF) of 7 in solution with target amino acids and BSA protein. Photochromic MIPs towards L–isoleucine demonstrated UV–induced color change and reversible optical sensing. Beryllium–based monomers, known for their coordination chemistry, enhanced LEU–MIP properties, achieving an IF of 12 with binding capacity of 173 mg LEU g–1 BeMIP using scCO2 technology, and an IF of 5 with a binding capacity of 130 mg LEU g–1 BeMIPM using ball milling. Thermal sensors based on these MIPs displayed strong LEU sensing performance within a range of 0.3 – 3.8 mM. Additionally, a novel surface imprinting method on aluminium sensor chips was developed, combining plasma activation with scCO2 technology. Beryllium–based dendrimers were also evaluated for catalytic applications. This thesis underscores the importance of green methodologies in the synthesis of affinity materials with potential for industrial biopurification processes. |
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| Autores principais: | Furtado, Ana Isabel Carreiro |
| Assunto: | Supercritical carbon dioxide Mechanochemistry Molecularly imprinted polymers Dendrimers Beryllium Biorecognition |
| Ano: | 2024 |
| País: | Portugal |
| Tipo de documento: | tese de doutoramento |
| Tipo de acesso: | acesso aberto |
| Instituição associada: | Universidade Nova de Lisboa |
| Idioma: | inglês |
| Origem: | Repositório Institucional da UNL |
| Resumo: | The global market for bioseparation and biopurification systems is rapidly growing, driven by an increasing demand for biopharmaceuticals. However, conventional biopurification techniques typically rely on protein–based technologies, which have cost limitations and lack of stability. This thesis explored the green development of high–affinity materials, specifically molecularly imprinted polymers (MIPs) and dendrimers for bio–industry applications, using supercritical CO2 (scCO2) technology and mechanochemistry (ball milling). Herein, MIPs towards small biomolecules, such as amino acids, were developed for use as solid–phase extraction devices and as biosensors for monitoring downstream processes. Innovative strategies were followed, such as dual–templating, photochromism, and the use of beryllium–based functional monomers for thermal sensing. Rational design methods, including quantum mechanics and molecular dynamics simulations, were used to predict the best MIP systems. Acrylamide was identified as the best functional monomer for L–leucine (LEU) using ball milling, while 2–vinylpyridine was better when using scCO2 technology. A dual–templating MIP achieved an imprinting factor (IF) of 7 in solution with target amino acids and BSA protein. Photochromic MIPs towards L–isoleucine demonstrated UV–induced color change and reversible optical sensing. Beryllium–based monomers, known for their coordination chemistry, enhanced LEU–MIP properties, achieving an IF of 12 with binding capacity of 173 mg LEU g–1 BeMIP using scCO2 technology, and an IF of 5 with a binding capacity of 130 mg LEU g–1 BeMIPM using ball milling. Thermal sensors based on these MIPs displayed strong LEU sensing performance within a range of 0.3 – 3.8 mM. Additionally, a novel surface imprinting method on aluminium sensor chips was developed, combining plasma activation with scCO2 technology. Beryllium–based dendrimers were also evaluated for catalytic applications. This thesis underscores the importance of green methodologies in the synthesis of affinity materials with potential for industrial biopurification processes. |
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