Real Time SPR Assessment of the Structural Changes of Adaptive Dynamic Constitutional Frameworks as a New Route for Sensing

Cross linked gold-dynamic constitutional frameworks (DCFs) are functional materials of potential relevance for biosensing applications, given their adaptivity and high responsivity against various external stimuli (such as pH, temperature) or specific interactions with biomolecules (enzymes or DNA)...

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Main Authors: Sorin David, Mihaela Gheorghiu, Sanaa Daakour, Raluca-Elena Munteanu, Cristina Polonschii, Szilveszter Gáspár, Mihail Barboiu, Eugen Gheorghiu
Format: Article
Language:English
Published: MDPI AG 2022-01-01
Series:Materials
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Online Access:https://www.mdpi.com/1996-1944/15/2/483
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author Sorin David
Mihaela Gheorghiu
Sanaa Daakour
Raluca-Elena Munteanu
Cristina Polonschii
Szilveszter Gáspár
Mihail Barboiu
Eugen Gheorghiu
author_facet Sorin David
Mihaela Gheorghiu
Sanaa Daakour
Raluca-Elena Munteanu
Cristina Polonschii
Szilveszter Gáspár
Mihail Barboiu
Eugen Gheorghiu
author_sort Sorin David
collection DOAJ
description Cross linked gold-dynamic constitutional frameworks (DCFs) are functional materials of potential relevance for biosensing applications, given their adaptivity and high responsivity against various external stimuli (such as pH, temperature) or specific interactions with biomolecules (enzymes or DNA) via internal constitutional dynamics. However, characterization and assessment of their dynamic conformational changes in response to external stimuli has never been reported. This study proves the capability of Surface Plasmon Resonance (SPR) assays to analyse the adaptive structural modulation of a functional matrix encompassing 3D gold-dynamic constitutional frameworks (Au-DCFs) when exposed to pH variations, as external stimuli. We analyse Au-DCFs formed from Au nanoparticles, (AuNP) connected through constitutionally dynamic polymers, dynamers, with multiple functionalities. For increased generality of this proof-of-concept assay, Au-DCFs, involving DCFs designed from 1,3,5-benzene-tricarbaldehyde (BTA) connecting centres and polyethylene glycol (PEG) connectors, are covalently attached to standard SPR sensing chips (Au nanolayers, carboxyl terminated or with carboxymethyl dextran, CMD top-layer) and analysed using state-of-the art SPR instrumentation. The SPR effects of the distance from the Au-DCFs matrix to the Au nanolayer of the sensing chip, as well as of Au-DCFs thickness were investigated. This study reveals the SPR response, augmented by the AuNP, to the conformational change, i.e., shrinkage, of the dynamer and AuNP matrix when decreasing the pH, and provides an unexplored insight into the sensing applicability of SPR real-time analysis of adaptive functional materials.
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spelling doaj.art-881a5d7f9b804e60988100b1f94d7fbd2023-11-23T14:29:52ZengMDPI AGMaterials1996-19442022-01-0115248310.3390/ma15020483Real Time SPR Assessment of the Structural Changes of Adaptive Dynamic Constitutional Frameworks as a New Route for SensingSorin David0Mihaela Gheorghiu1Sanaa Daakour2Raluca-Elena Munteanu3Cristina Polonschii4Szilveszter Gáspár5Mihail Barboiu6Eugen Gheorghiu7International Centre of Biodynamics, 060101 Bucharest, RomaniaInternational Centre of Biodynamics, 060101 Bucharest, RomaniaAdaptive Supramolecular Nanosystems Group, Institut Europeen des Membranes, University of Montpellier, ENSCM-CNRS, 34095 Montpellier, FranceInternational Centre of Biodynamics, 060101 Bucharest, RomaniaInternational Centre of Biodynamics, 060101 Bucharest, RomaniaInternational Centre of Biodynamics, 060101 Bucharest, RomaniaAdaptive Supramolecular Nanosystems Group, Institut Europeen des Membranes, University of Montpellier, ENSCM-CNRS, 34095 Montpellier, FranceInternational Centre of Biodynamics, 060101 Bucharest, RomaniaCross linked gold-dynamic constitutional frameworks (DCFs) are functional materials of potential relevance for biosensing applications, given their adaptivity and high responsivity against various external stimuli (such as pH, temperature) or specific interactions with biomolecules (enzymes or DNA) via internal constitutional dynamics. However, characterization and assessment of their dynamic conformational changes in response to external stimuli has never been reported. This study proves the capability of Surface Plasmon Resonance (SPR) assays to analyse the adaptive structural modulation of a functional matrix encompassing 3D gold-dynamic constitutional frameworks (Au-DCFs) when exposed to pH variations, as external stimuli. We analyse Au-DCFs formed from Au nanoparticles, (AuNP) connected through constitutionally dynamic polymers, dynamers, with multiple functionalities. For increased generality of this proof-of-concept assay, Au-DCFs, involving DCFs designed from 1,3,5-benzene-tricarbaldehyde (BTA) connecting centres and polyethylene glycol (PEG) connectors, are covalently attached to standard SPR sensing chips (Au nanolayers, carboxyl terminated or with carboxymethyl dextran, CMD top-layer) and analysed using state-of-the art SPR instrumentation. The SPR effects of the distance from the Au-DCFs matrix to the Au nanolayer of the sensing chip, as well as of Au-DCFs thickness were investigated. This study reveals the SPR response, augmented by the AuNP, to the conformational change, i.e., shrinkage, of the dynamer and AuNP matrix when decreasing the pH, and provides an unexplored insight into the sensing applicability of SPR real-time analysis of adaptive functional materials.https://www.mdpi.com/1996-1944/15/2/483dynamic constitutional frameworkssignal amplification by gold nanoparticlesconformational dynamicssurface plasmon resonance analysispH sensing
spellingShingle Sorin David
Mihaela Gheorghiu
Sanaa Daakour
Raluca-Elena Munteanu
Cristina Polonschii
Szilveszter Gáspár
Mihail Barboiu
Eugen Gheorghiu
Real Time SPR Assessment of the Structural Changes of Adaptive Dynamic Constitutional Frameworks as a New Route for Sensing
Materials
dynamic constitutional frameworks
signal amplification by gold nanoparticles
conformational dynamics
surface plasmon resonance analysis
pH sensing
title Real Time SPR Assessment of the Structural Changes of Adaptive Dynamic Constitutional Frameworks as a New Route for Sensing
title_full Real Time SPR Assessment of the Structural Changes of Adaptive Dynamic Constitutional Frameworks as a New Route for Sensing
title_fullStr Real Time SPR Assessment of the Structural Changes of Adaptive Dynamic Constitutional Frameworks as a New Route for Sensing
title_full_unstemmed Real Time SPR Assessment of the Structural Changes of Adaptive Dynamic Constitutional Frameworks as a New Route for Sensing
title_short Real Time SPR Assessment of the Structural Changes of Adaptive Dynamic Constitutional Frameworks as a New Route for Sensing
title_sort real time spr assessment of the structural changes of adaptive dynamic constitutional frameworks as a new route for sensing
topic dynamic constitutional frameworks
signal amplification by gold nanoparticles
conformational dynamics
surface plasmon resonance analysis
pH sensing
url https://www.mdpi.com/1996-1944/15/2/483
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