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Mechanosynthesis and thermal bio–sensing of beryllium–based molecularly imprinted polymers

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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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Funding Information: The authors would like to acknowledge financial support from Fundação para a Ciência e a Tecnologia, Ministério da Ciência, Tecnologia e Ensino Superior (FCT/MCTES, Portugal) through projects PTDC/EQU–EQU/32473/2017, and PTDC/MEC–ONC/29327/2017. A.I.F. acknowledges her PhD grant (SFRH/BD/150696/2020) in the aim of the International Year of the Periodic Table – a Protocol established between the Portuguese Chemical Society (SPQ) and the FCT/MCTES, the Young European Research Universities Network (YERUN) Research Mobility Award 2022 and the Short–term Scientific Mission (STSM) grant founded by COST under project action CA21101 (E–COST–GRANT–CA21101–04013b56) to financial support the work developed in the Maastricht University. R.V. would like to acknowledge for her Individual Support from Scientific Employment Stimulus (CEEC–IND, reference 2020.00377.CEECIND) from the FCT/MCTES, Portugal. The Associate Laboratory Research Unit for Green Chemistry – Clean Technologies and Processes – LAQV–REQUIMTE is financed by national funds from FCT/MCTES (10.54499/LA/P/0008/2020, 10.54499/UIDP/50006/2020, 10.54499/UIDB/50006/2020) and co–financed by the ERDF under the PT2020 Partnership Agreement (POCI–01–0145–FEDER – 007265). Publisher Copyright: © 2025 The Author(s)

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Beryllium complexes Green chemistry Heat–transfer method sensors Mechanochemistry Supercritical fluid extraction Synthetic affinity materials Biotechnology Biophysics Biomedical Engineering Electrochemistry

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