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Enhanced biosensing by green, switchable photochromic molecularly imprinted polymers
Publication . Furtado, Ana I.; Lobato, Diogo; Gago, Sandra; Bonifácio, Vasco D. B.; Viveiros, Raquel; Casimiro, Teresa; DQ - Departamento de Química; LAQV@REQUIMTE; Elsevier
Photochromic Molecularly Imprinted Polymers (PC–MIPs) synthesized using supercritical carbon dioxide (scCO2) represent a key approach to produce green stimuli–responsive polymers. In this work, methacryloyloxyethyl)–3’,3’–dimethyl–6–nitrospiro(2H–1benzopyran–2,2’–indoline (SPMA) was incorporated as the functional photochromic monomer (M), L–isoleucine (IsoLEU) as the template (T) molecule, and ethylene glycol dimethacrylate (EGDMA) as the crosslinker (C). Two different PC–MIP systems were explored by changing the crosslinker degree, T:M:C (1:12:50 and 1:12:100). Moreover, enantiomeric separation was evaluated by static binding tests using L–leucine (LEU) and IsoLEU from aqueous solutions. The PC–MIP with high crosslinker degree (PC–MIP1) exhibited the highest affinity and selectivity in template solutions, with a maximum binding capacity of 127 mg IsoLEU/g polymer and an imprinting factor of 1.6. The experiments performed under UV–light (365 nm), both PC–MIPs (PC–MIP1 and PC–MIP2), ranged from white to bluish purple, with reversible color changes upon exposure to visible light. Additionally, both PC–MIPs demonstrated delayed optical responses upon incorporation of the target molecule into the polymeric matrix, enabling real–time detection. This study underscores the potential of PC–MIPs as green and cost–effective optical sensors for bioprocess monitoring, offering high sensitivity and selectivity for IsoLEU detection in aqueous media.
Mechanosynthesis and thermal bio–sensing of beryllium–based molecularly imprinted polymers
Publication . Furtado, Ana I.; Lowdon, Joseph W.; Eersels, Kasper; Grinsven, Bart van; Cruz, Adriana; Serpa, Jacinta; Bonifácio, Vasco D. B.; Viveiros, Raquel; Casimiro, Teresa; DQ - Departamento de Química; LAQV@REQUIMTE; Centro de Estudos de Doenças Crónicas (CEDOC); Elsevier
The adsorption of amino acids on electrode surfaces is pertinent to understanding the interfacial behaviours of biological molecules and addressing industrial challenges associated with their purification and monitoring in downstream processes. Molecularly imprinted polymers (MIPs) are ideal candidates for targeted molecular recognition. Metals offer significant potential for enhancing biological molecule recognition by enabling the creation of selective binding sites within polymeric matrices through molecular imprinting. The metal mediated coordination between the monomer and the biomolecule used as template greatly enhances both the affinity and selectivity of molecular recognition. Herein, beryllium–based natural monomers (curcumin and lawsone) were synthesized and applied as functional monomers in the synthesis of MIPs using the amino acid L–leucine (LEU) as template. Mechanochemistry (ball milling) was chosen as key methodology for the synthesis of both the beryllium–based monomers and MIP (BeMIPMs) fabrication. Subsequently, supercritical CO2 (scCO2) technology was used for efficiently desorb of the template, yielding vacant receptors. These two green technologies allowed the preparation of BeMIPMs as ready–to–use and stable dry polymeric powders. The prepared BeMIPM particles were then incorporated into a thermally conductive layer via micro–contact deposition. Their response towards LEU and analogues molecules was analysed using the heat–transfer method (HTM), and their performance was compared to the non–imprinted polymer (BeNIPMs) reference. The generated biosensor was found to have an optimal linear range of 0.30–0.93 mM and LoD of 0.16 mM (obtained by the 3σ method), while also being selective when comparing the thermal response to other analogues molecules (IFeffect-LEU = 1.6–1.8 vs. IFanalogues-molecule = 0.5–1.5). BeMIPM shows a promising performance for the monitoring of LEU in purification processes due to its thermal response, inclusive in real samples, offering a low–cost thermal platform for monitoring specific amino acids in complex industrial matrices.
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Entidade financiadora
Fundação para a Ciência e a Tecnologia
Programa de financiamento
Concurso para Financiamento de Projetos de Investigação Científica e Desenvolvimento Tecnológico em Todos os Domínios Científicos - 2017
Número da atribuição
PTDC/EQU-EQU/32473/2017