A novel integration of Molecularly Imprinted Polymers with nanoporous silicon for selective and sensitive optical detection of proteins

A NOVEL INTEGRATION OF MOLECULARLY IMPRINTED POLYMERS WITH NANOPOROUS SILICON FOR SELECTIVE AND SENSITIVE OPTICAL DETECTION OF PROTEINS ELISABETTA MAZZOTTA1, TIZIANO DI GIULIO1, MARTINA CORSI2, STEFANO MARIANI2, COSIMINO MALITESTA1, GIUSEPPE BARILLARO2 1Dipartimento di Scienze e Tecnologie Biologiche e Ambientali (Di.S.Te.B.A.), Università del Salento, Lecce, Italy 2Dipartimento di Ingegneria dell’Informazione, Università di Pisa, Pisa, Italy Analitica 2022 XXIX Congresso della Divisione di Chimica Analitica Milazzo, 11-15 settembre 2022 OBJECT OF THE RESEARCH Development of optical sensing devices for protein detection by a novel, effective route enabling the preparation of artificial receptors on nanostructured materials: room temperature vapor-phase synthesis of molecularly imprinted polymers (MIPs) OBJECT OF THE RESEARCH MIPs Imprinted polypyrrole Nanostructured material Nanoporous silicon Target protein Human hemoglobin Development of optical sensing devices for protein detection by developing novel, effective route enabling the preparation of artificial receptors on nanostructured materials: room temperature vapor-phase synthesis of molecularly imprinted polymers (MIPs) MIPs Imprinted polypyrrole Target (=template) removal imprinted cavities MIP MOLECULAR MEMORY Target selective rebinding MIPs Imprinted polypyrrole Target (=template) removal imprinted cavities MIP MOLECULAR MEMORY Target selective rebinding Integration of MIPs on the transducer surface remains a key issue for sensing applications, especially with nanostructured materials MIPs Imprinted polypyrrole Target (=template) removal imprinted cavities MIP MOLECULAR MEMORY Target selective rebinding Integration of MIPs on the transducer surface remains a key issue for sensing applications, especially with nanostructured materials One-step electropolymerization Pre-formed polymer Chemical polymerization MIP nanoparticles MIP nanofilaments on nanoporous alumina oxide MIPs Imprinted polypyrrole Target (=template) removal imprinted cavities MIP MOLECULAR MEMORY Target selective rebinding Integration of MIPs on the transducer surface remains a key issue for sensing applications, especially with nanostructured materials One-step electropolymerization Pre-formed polymer Chemical polymerization MIP nanoparticles MIP nanofilaments on nanoporous alumina oxide MIPs Imprinted polypyrrole OUR APPROACH: MIP VAPOR-PHASE POLYMERIZATION MIPs Imprinted polypyrrole Chem Eng J 381 (2020) 122700 ACS Appl Polym Mater 2 (2020) 1933 Biosens Bioelectron 63 (2015) 240 Analytical and Bioanalytical Chemistry 414 (2022) 5165 ECS Sens Plus 1 (2022) 010603 OUR APPROACH: MIP VAPOR-PHASE POLYMERIZATION Nanostructured material Nanoporous silicon POROUS SILICON (PSi) as optical transducer x=2nL FOURIER TRANSFORM Effective Optical Thickness (EOT) Nanostructured material Nanoporous silicon POROUS SILICON (PSi) as optical transducer x=2nL FOURIER TRANSFORM Effective Optical Thickness (EOT) red-shift of Fabry-Perot fringe pattern 12900 13000 13100 13200 EOT [nm] increase of EOT value = Target protein Human hemoglobin Clinical relevance of human haemoglobin (HHb) detection for several diseases, including anemia, cardiovascular risk, and coronary artery disease PPy VAPOR-PHASE DEPOSITION ON PSi 1. as-made PSi 2. oxidation to PSiO23. exposure to FeCl34. PPy vapor deposition PPy VAPOR-PHASE DEPOSITION ON PSi 1. as-made PSi 2. oxidation to PSiO23. exposure to FeCl34. PPy vapor deposition PPy VAPOR-PHASE DEPOSITION ON PSi as-made PSi PPy vapor phase 8h PPy liquid phase 5h scale bar 200 nm PPy VAPOR-PHASE DEPOSITION ON PSi as-made PSi PPy vapor phase 8h PPy liquid phase 5h scale bar 200 nm PPy VAPOR-PHASE DEPOSITION ON PSi 1234 0.4 0.6 0.8 1.0 1.2 PPy liquid phase 5h PPy vapor phase 8h Normalized PeakN/PeakO(%) Pore depth (m) Higher diffusion coefficient of species in vapor phase (about 10-5 vs10-2 cm2 s-1) can facilitate the diffusion of monomer vapors within the nanostructure (as widely reported for gas diffusion through nanoporous membranes). PPy VAPOR-PHASE DEPOSITION ON PSi FeCl3PSiO2 nanopore Pyrrole (v) PSiO2PSiO2 PPy Higher diffusion coefficient of species in vapor phase (about 10-5 vs10-2 cm2 s-1) can facilitate the diffusion of monomer vapors within the nanostructure (as widely reported for gas diffusion through nanoporous membranes). PPy VAPOR-PHASE DEPOSITION ON PSi FeCl3PSiO2 nanopore Pyrrole (l) PSiO2PSiO2 PPy