Molecular Imprinting and Sensing Technologies: a happy marriage based on established and innovative strategies

Molecular Imprinting and Sensing Technologies: a happy marriage based on established and innovative strategies Elisabetta Mazzotta, Tiziano Di Giulio, Cosimino Malitesta Università del Salento, Lecce Analitica 2023 XXX Congresso Divisione Chimica Analitica Vasto, 17-21 settembre 2023 Outline Molecular Imprinting Technology: A rapid review Design a MIP suitable for sensing applications: A «challeng-easy» approach Our contribution to the field light-mediated MIP polymerization vapor-phase MIP polymerization Molecular Imprinting Technology: Molecular Imprinting Technology: A rapid review Molecular imprinting technology Sensing technology Molecular imprinting Sensing technology Molecular imprinting Papers about «MIP+sensor» from 1 to 4158 from 1993 to 2023, with 535 only in 2022 (Scopus, september 2023) Wide range of templates from metal ions, small molecules to macromolecules as proteins and peptides Different MIP formats as thin films to nanoparticles Sensing technology Molecular imprinting NO GENERAL RULES MIP synthesis conditions depending on target molecule and monomer Key role of transducer type The last word belongs to the final application Molecular Imprinting Technology: Design a MIP suitable for sensing applications: A «challeng-easy» approach MIP for sensing applications: A «challeng-easy» approach Target and monomer(s) molecule Types of occurring interactions Computational approaches Molecular docking Machine Learning-based predictions Small VS large (bio)molecules Specific imprinting approaches for large molecules (epitope imprinting, surface imprinting) Biologic nature of the template Light-mediated polymerization: Photo-iniferter polymerization mediated by green light Monitoring functionalization steps of nPSiO2 toward MIP synthesis by UV-VIS reflectance spectroscopy 5 10 15 20 25 30 500 550 600 650 700 Reflectance (%) Wavelength (nm) APTES PolyMAA Washing procedure 0 100 200 300 400 500 600 700 1) pSiO2 silanization (with APTES) 2) CDTPA functionalization 3) Polymer deposition (5 hs) 4)Template removal (2 hs) EOT-EOTPSiO2(nm) 0 100 200 300 400 500 600 1) pSiO2 silanization (with APTES) 2) CDTPA functionalization 3) Polymer deposition (5 hs) 4) Washing procedure (MetOH/AA) EOT-EOTPSiO2(nm) NIPs MIPs Calibration curves: LOD 3.4 M Imprinting Factor (IF): 19 Propranolol optical detection tests 0 20 40 60 80 100 120 10 20 60 80 100 EOT-EOT0(nm) concentration (M) propranolol atenolol metoprolol timolol y = 1.1672x + 0.1764 R² = 0.9972 y = 0.0557x + 5.7594 0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 EOT-EOT0(nm) [propranolol] (M) MIPs NIPs Vapor-phase polymerization Not only a highly suitable approach for MIP deposition on complex geometry transducer nanosurfaces but also a highly versatile strategy for the imprinting of any target molecule producing biocompatible MIPs Mazzotta et al., Small, 2023. DOI:10.1002/smll.202302274 Vapor phase polymerization: Polypyrrole (PPy) imprinted for human hemoglobin (HHb) HHb (yellow crosses) preliminarily anchored to nanaoporous silicon/oxidizing agent (FeCl3) Pyrrole (Py) as functional monomer vapor form at RT The vapor phase synthesis leverages a >1000-fold increase in the diffusion coefficient of monomers compared to liquid phase, overcoming diffusion-limited transport and enabling the controlled and reliable polymerization also in nanostructured materials with high aspect ratio Well known PPy biocompatibility, in-vivo applications and large use for the imprinting of wide range of molecules Vapor phase polymerization: Polypyrrole (PPy) imprinted for human hemoglobin (HHb) 2. APTES linking 1. PSiO2 scaffold 5. PPy vapor deposition c) 3. Glutaraldehyde binding 6. HHb removal 4. HHb binding Monitoring functionalization steps of nPSiO2 toward MIP synthesis by UV-VIS reflectance spectroscopy Example of SURFACE IMPRINTING APPROACH 0 1 10 20 30 0 20 40 60 80 100 120 140 EOT - EOT0 (nm) Time (days) MIP analytical characterization Imprinting Factor (IF): 13.1 LOD: 0.024 mg mL− Suitability for the imprinting of biomolecules On-Demand Bioresorbable OptoElectronic System for In-Vivo and In-Situ Monitoring of Chemotherapeutic Drugs Horizon-EIC-2021-Pathfinder Open-01 www.resorb-project.eu