Biofunctionalization of Metal–Organic Framework Nanoparticles via Combined Nitroxide‐Mediated Polymerization and Nitroxide Exchange Reaction

Abstract Surface engineering of metal–organic framework nanoparticles (MOF NPs), and enabling their post‐synthetic modulation that facilitates the formation of bio‐interfaces has tremendous potential for diverse applications including therapeutics, imaging, biosensing, and drug‐delivery systems. Des...

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Main Authors: Ilona Wagner, Simon Spiegel, Julian Brückel, Matthias Schwotzer, Alexander Welle, Martina H. Stenzel, Stefan Bräse, Salma Begum, Manuel Tsotsalas
Format: Article
Language:English
Published: Wiley-VCH 2023-09-01
Series:Macromolecular Materials and Engineering
Subjects:
Online Access:https://doi.org/10.1002/mame.202300048
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author Ilona Wagner
Simon Spiegel
Julian Brückel
Matthias Schwotzer
Alexander Welle
Martina H. Stenzel
Stefan Bräse
Salma Begum
Manuel Tsotsalas
author_facet Ilona Wagner
Simon Spiegel
Julian Brückel
Matthias Schwotzer
Alexander Welle
Martina H. Stenzel
Stefan Bräse
Salma Begum
Manuel Tsotsalas
author_sort Ilona Wagner
collection DOAJ
description Abstract Surface engineering of metal–organic framework nanoparticles (MOF NPs), and enabling their post‐synthetic modulation that facilitates the formation of bio‐interfaces has tremendous potential for diverse applications including therapeutics, imaging, biosensing, and drug‐delivery systems. Despite the progress in MOF NPs synthesis, colloidal stability and homogeneous dispersity—a desirable property for biotechnological applications, stands as a critical obstacle and remains a challenging task. In this report, dynamic surfaces modification of MOF NPs with polyethylene glycol (PEG) polymer is described using grafting‐from PEGylation by employing nitroxide‐mediated polymerization (NMP) and inserting arginylglycylaspartic acid (RGD) peptides on the surface via a nitroxide exchange reaction (NER). The dynamic modification strategy enables tailoring PEG‐grafted MOF NPs of the type UiO‐66‐NH2 with improved colloidal stability, and high dispersity, while the morphology and lattice crystallinity are strictly preserved. The interaction of PEG‐grafted MOF NPs with human serum albumin (HSA) protein under physiological conditions is studied. The PEG‐grafted colloidal MOF NPs adsorb less HSA protein than the uncoated ones. Therefore, the described approach increases the scope of bio‐relevant applications of colloidal MOF NPs by reducing nonspecific interactions using NMP based PEGylation, while preserving the possibility to introduce targeting moieties via NER for specific interactions.
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spelling doaj.art-93045e41d54b414d8040d20cd03751612023-09-15T09:14:11ZengWiley-VCHMacromolecular Materials and Engineering1438-74921439-20542023-09-013089n/an/a10.1002/mame.202300048Biofunctionalization of Metal–Organic Framework Nanoparticles via Combined Nitroxide‐Mediated Polymerization and Nitroxide Exchange ReactionIlona Wagner0Simon Spiegel1Julian Brückel2Matthias Schwotzer3Alexander Welle4Martina H. Stenzel5Stefan Bräse6Salma Begum7Manuel Tsotsalas8Institute of Functional Interfaces (IFG) Karlsruhe Institute of Technology (KIT) Hermann‐von Helmholtz‐Platz 1 76344 Eggenstein‐Leopoldshafen GermanyInstitute of Functional Interfaces (IFG) Karlsruhe Institute of Technology (KIT) Hermann‐von Helmholtz‐Platz 1 76344 Eggenstein‐Leopoldshafen GermanyInstitute for Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT) Fritz‐Haber‐Weg 6 76131 Karlsruhe GermanyInstitute of Functional Interfaces (IFG) Karlsruhe Institute of Technology (KIT) Hermann‐von Helmholtz‐Platz 1 76344 Eggenstein‐Leopoldshafen GermanyInstitute of Functional Interfaces (IFG) Karlsruhe Institute of Technology (KIT) Hermann‐von Helmholtz‐Platz 1 76344 Eggenstein‐Leopoldshafen GermanyCenter for Advanced Macromolecular Design, School of Chemistry University of New South Wales Sydney NSW 2052 AustraliaInstitute for Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT) Fritz‐Haber‐Weg 6 76131 Karlsruhe GermanyInstitute of Functional Interfaces (IFG) Karlsruhe Institute of Technology (KIT) Hermann‐von Helmholtz‐Platz 1 76344 Eggenstein‐Leopoldshafen GermanyInstitute of Functional Interfaces (IFG) Karlsruhe Institute of Technology (KIT) Hermann‐von Helmholtz‐Platz 1 76344 Eggenstein‐Leopoldshafen GermanyAbstract Surface engineering of metal–organic framework nanoparticles (MOF NPs), and enabling their post‐synthetic modulation that facilitates the formation of bio‐interfaces has tremendous potential for diverse applications including therapeutics, imaging, biosensing, and drug‐delivery systems. Despite the progress in MOF NPs synthesis, colloidal stability and homogeneous dispersity—a desirable property for biotechnological applications, stands as a critical obstacle and remains a challenging task. In this report, dynamic surfaces modification of MOF NPs with polyethylene glycol (PEG) polymer is described using grafting‐from PEGylation by employing nitroxide‐mediated polymerization (NMP) and inserting arginylglycylaspartic acid (RGD) peptides on the surface via a nitroxide exchange reaction (NER). The dynamic modification strategy enables tailoring PEG‐grafted MOF NPs of the type UiO‐66‐NH2 with improved colloidal stability, and high dispersity, while the morphology and lattice crystallinity are strictly preserved. The interaction of PEG‐grafted MOF NPs with human serum albumin (HSA) protein under physiological conditions is studied. The PEG‐grafted colloidal MOF NPs adsorb less HSA protein than the uncoated ones. Therefore, the described approach increases the scope of bio‐relevant applications of colloidal MOF NPs by reducing nonspecific interactions using NMP based PEGylation, while preserving the possibility to introduce targeting moieties via NER for specific interactions.https://doi.org/10.1002/mame.202300048MOF nanoparticlesnitroxide exchange reactionnitroxide‐mediated polymerizationpost‐synthetic modificationsurface functionalization
spellingShingle Ilona Wagner
Simon Spiegel
Julian Brückel
Matthias Schwotzer
Alexander Welle
Martina H. Stenzel
Stefan Bräse
Salma Begum
Manuel Tsotsalas
Biofunctionalization of Metal–Organic Framework Nanoparticles via Combined Nitroxide‐Mediated Polymerization and Nitroxide Exchange Reaction
Macromolecular Materials and Engineering
MOF nanoparticles
nitroxide exchange reaction
nitroxide‐mediated polymerization
post‐synthetic modification
surface functionalization
title Biofunctionalization of Metal–Organic Framework Nanoparticles via Combined Nitroxide‐Mediated Polymerization and Nitroxide Exchange Reaction
title_full Biofunctionalization of Metal–Organic Framework Nanoparticles via Combined Nitroxide‐Mediated Polymerization and Nitroxide Exchange Reaction
title_fullStr Biofunctionalization of Metal–Organic Framework Nanoparticles via Combined Nitroxide‐Mediated Polymerization and Nitroxide Exchange Reaction
title_full_unstemmed Biofunctionalization of Metal–Organic Framework Nanoparticles via Combined Nitroxide‐Mediated Polymerization and Nitroxide Exchange Reaction
title_short Biofunctionalization of Metal–Organic Framework Nanoparticles via Combined Nitroxide‐Mediated Polymerization and Nitroxide Exchange Reaction
title_sort biofunctionalization of metal organic framework nanoparticles via combined nitroxide mediated polymerization and nitroxide exchange reaction
topic MOF nanoparticles
nitroxide exchange reaction
nitroxide‐mediated polymerization
post‐synthetic modification
surface functionalization
url https://doi.org/10.1002/mame.202300048
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