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Enantioselective SERS sensing of pseudoephedrine in blood plasma biomatrix by hierarchical mesoporous Au films coated with a homochiral MOF

O. Guselnikova, H. Lim, J. Na, M. Eguchi, HJ. Kim, R. Elashnikov, P. Postnikov, V. Svorcik, O. Semyonov, E. Miliutina, O. Lyutakov, Y. Yamauchi

. 2021 ; 180 (-) : 113109. [pub] 20210224

Language English Country Great Britain

Document type Journal Article

Persistent link   https://www.medvik.cz/link/bmc21018602

Here, we present a new family of hierarchical porous hybrid materials as an innovative tool for ultrasensitive and selective sensing of enantiomeric drugs in complex biosamples via chiral surface-enhanced Raman spectroscopy (SERS). Hierarchical porous hybrid films were prepared by the combination of mesoporous plasmonic Au films and microporous homochiral metal-organic frameworks (HMOFs). The proposed hierarchical porous substrates enable extremely low limit of detection values (10-12 M) for pseudoephedrine in undiluted blood plasma due to dual enhancement mechanisms (physical enhancement by the mesoporous Au nanostructures and chemical enhancement by HMOF), chemical recognition by HMOF, and a discriminant function for bio-samples containing large biomolecules, such as blood components. We demonstrate the effect of each component (mesoporous Au and microporous AlaZnCl (HMOF)) on the analytical performance for sensing. The growth of AlaZnCl leads to an increase in the SERS signal (by around 17 times), while the use of mesoporous Au leads to an increase in the signal (by up to 40%). In the presence of a complex biomatrix (blood serum or plasma), the hybrid hierarchical porous substrate provides control over the transport of the molecules inside the pores and prevents blood protein infiltration, provoking competition with existing plasmonic materials at the limit of detection and enantioselectivity in the presence of a multicomponent biomatrix.

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$a Guselnikova, Olga $u Department of Solid State Engineering, University of Chemistry and Technology, 16628, Prague, Czech Republic; Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, 634049, Tomsk, Russian Federation. Electronic address: guselnikovaoa@tpu.ru
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$a Here, we present a new family of hierarchical porous hybrid materials as an innovative tool for ultrasensitive and selective sensing of enantiomeric drugs in complex biosamples via chiral surface-enhanced Raman spectroscopy (SERS). Hierarchical porous hybrid films were prepared by the combination of mesoporous plasmonic Au films and microporous homochiral metal-organic frameworks (HMOFs). The proposed hierarchical porous substrates enable extremely low limit of detection values (10-12 M) for pseudoephedrine in undiluted blood plasma due to dual enhancement mechanisms (physical enhancement by the mesoporous Au nanostructures and chemical enhancement by HMOF), chemical recognition by HMOF, and a discriminant function for bio-samples containing large biomolecules, such as blood components. We demonstrate the effect of each component (mesoporous Au and microporous AlaZnCl (HMOF)) on the analytical performance for sensing. The growth of AlaZnCl leads to an increase in the SERS signal (by around 17 times), while the use of mesoporous Au leads to an increase in the signal (by up to 40%). In the presence of a complex biomatrix (blood serum or plasma), the hybrid hierarchical porous substrate provides control over the transport of the molecules inside the pores and prevents blood protein infiltration, provoking competition with existing plasmonic materials at the limit of detection and enantioselectivity in the presence of a multicomponent biomatrix.
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$a Lim, Hyunsoo $u Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, QLD, 4072, Australia; New & Renewable Energy Research Center, Korea Electronics Technology Institute (KETI), 25, Saenari-ro, Bundang-gu, Seongnam-si, Gyeonggi-do, 13509, Republic of Korea
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$a Na, Jongbeom $u Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, QLD, 4072, Australia
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$a Eguchi, Miharu $u Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, QLD, 4072, Australia; JST-ERATO Yamauchi Materials Space-Tectonics Project and International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan
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$a Kim, Hyun-Jong $u Surface Technology Group, Korea Institute of Industrial Technology (KITECH), Incheon, 21999, Republic of Korea
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$a Elashnikov, Roman $u Department of Solid State Engineering, University of Chemistry and Technology, 16628, Prague, Czech Republic
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$a Postnikov, Pavel $u Department of Solid State Engineering, University of Chemistry and Technology, 16628, Prague, Czech Republic; Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, 634049, Tomsk, Russian Federation
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$a Svorcik, Vaclav $u Department of Solid State Engineering, University of Chemistry and Technology, 16628, Prague, Czech Republic
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$a Semyonov, Oleg $u Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, 634049, Tomsk, Russian Federation
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$a Miliutina, Elena $u Department of Solid State Engineering, University of Chemistry and Technology, 16628, Prague, Czech Republic; Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, 634049, Tomsk, Russian Federation
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$a Lyutakov, Oleksiy $u Department of Solid State Engineering, University of Chemistry and Technology, 16628, Prague, Czech Republic; Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, 634049, Tomsk, Russian Federation
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$a Yamauchi, Yusuke $u Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, QLD, 4072, Australia; JST-ERATO Yamauchi Materials Space-Tectonics Project and International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan. Electronic address: y.yamauchi@uq.edu.au
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