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Projeto de investigação
Desenvolvimento sustentável de nanomateriais híbridos para catálise e biopurificação.
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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.
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.
Biomolecular Fishing
Publication . Furtado, Ana I.; Viveiros, R.; Bonifácio, Vasco D. B.; Melo, André; Casimiro, T.; DQ - Departamento de Química; LAQV@REQUIMTE; ACS - American Chemical Society
Biopurification is a challenging and growing market. Despite great efforts in the past years, current purification strategies still lack specificity, efficiency, and cost-effectiveness. The development of more sustainable functional materials and processes needs to address pressing environmental goals, efficiency, scale-up, and cost. Herein, l-leucine (LEU)-molecularly imprinted polymers (MIPs), LEU-MIPs, are presented as novel biomolecular fishing polymers for affinity sustainable biopurification. Rational design was performed using quantum mechanics calculations and molecular modeling for selecting the most appropriate monomers. LEU-MIPs were synthesized for the first time by two different green approaches, supercritical carbon dioxide (scCO2) technology and mechanochemistry. A significant imprinting factor of 12 and a binding capacity of 27 mg LEU/g polymer were obtained for the LEU-MIP synthesized in scCO2 using 2-vinylpyridine as a functional monomer, while the LEU-MIP using acrylamide as a functional monomer synthesized by mechanochemistry showed an imprinting factor of 1.4 and a binding capacity of 18 mg LEU/g polymer, both systems operating at a low binding concentration (0.5 mg LEU/mL) under physiological conditions. As expected, at a higher concentration (1.5 mg LEU/mL), the binding capacity was considerably increased. Both green technologies show high potential in obtaining ready-to-use, stable, and low-cost polymers with a molecular recognition ability for target biomolecules, being promising materials for biopurification processes.
Sustainable development of dual–templating molecularly imprinted polymers for biopurification
Publication . Furtado, Ana I.; Lobato, Diogo; Bonifácio, Vasco D. B.; Viveiros, Raquel; Casimiro, Teresa; DQ - Departamento de Química; LAQV@REQUIMTE; Elsevier
The demand for bio–based products is increasing, but the development of efficient purification processes is lagging. However, typically these processes are expensive, non–specific and/or lack of efficiency. Molecularly imprinted polymers (MIPs) are synthetic affinity materials able to mimic the molecular recognition ability of natural molecules, offering a cost–effective alternative to replace the commercial affinity–driven materials based on proteins and antibodies. In this work, MIPs were developed using supercritical carbon dioxide (scCO2) technology using two approaches: i) one–templating (O–MIPs), using L–leucine (LEU) as template, and ii) a dual–templating (D–MIPs), using LEU and L–lysine (LYS) as templates, to evaluate their potential in the molecular recognition of amino acids in simple and complex aqueous solutions. MIPs produced in scCO2 have already shown good performances in organic and aqueous solutions, for small and non–polar template molecules. Herein, their applicability is extended to amino acids but also proteins. MIPs were produced using 2–vinylpyridine (VP) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as crosslinker under scCO2 conditions. Polymers were obtained as white, ready–to–use dry powders. Their affinity performance was assessed by Static Binding Tests (SBTs) and Solid Phase Extraction (SPE) assays using different amino acids and proteins. The best SBT results was obtained by D–MIP with Qmax = 216 mg LEU + LYS/g D–MIP, and IFmax = 8.3. D–MIP also presented higher binding capacities to adsorb their templated–molecules by a dynamic process (SPE) (Qmax = 79 mg LEU + LYS/g D–MIP), and selectively bind their templates in a solution containing a protein (IFmax = 6.8). The green D–MIP provides a robust, tailor–made and sustainable alternative for biopurification processes.
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Fundação para a Ciência e a Tecnologia
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OE
Número da atribuição
SFRH/BD/150696/2020