19F NMR Relaxometry and Diffusometry for Measuring Cargo Molecule Dynamics in GelMA Hydrogels

Abstract Understanding payload diffusion is an important topic in hydrogel drug delivery. While proton nuclear magnetic resonance (NMR) spectroscopy allows for direct examination of water dynamics in hydrogels, it is challenging to study the dynamics of payloads due to spectral crowding and distorti...

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Main Authors: Chun‐Wei Chang, Bronwin L. Dargaville, Konstantin I. Momot, Dietmar W. Hutmacher
Format: Article
Language:English
Published: Wiley-VCH 2025-08-01
Series:Macromolecular Materials and Engineering
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Online Access:https://doi.org/10.1002/mame.202400348
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author Chun‐Wei Chang
Bronwin L. Dargaville
Konstantin I. Momot
Dietmar W. Hutmacher
author_facet Chun‐Wei Chang
Bronwin L. Dargaville
Konstantin I. Momot
Dietmar W. Hutmacher
author_sort Chun‐Wei Chang
collection DOAJ
description Abstract Understanding payload diffusion is an important topic in hydrogel drug delivery. While proton nuclear magnetic resonance (NMR) spectroscopy allows for direct examination of water dynamics in hydrogels, it is challenging to study the dynamics of payloads due to spectral crowding and distortions. Fluorine‐19, not biologically endogenous in humans and having high NMR receptivity, can be easily incorporated into molecules of interest and therefore used as an alternative probe for dynamics of payload molecules in hydrogels. In this study, the dynamics of fluorine‐containing compounds trifluoroethylamine (TFEA, a small molecule), ciprofloxacin (CF, a medium‐size molecule), and fluorinated lysozyme (FL, a ≈15 kDa protein) are measured both in solution and gelatin methacrylate (GelMA) hydrogels. For each payload molecule, the rotational correlation time and translational diffusion coefficient, as well as the effective microviscosity of the media, are measured. Spin‐spin relaxation (T2) is also used to probe chemical exchange as an indicator of payload–polymer interactions. The in situ interaction between payload and polymer network and precise characterization of payload dynamics within hydrogels show that fluorine‐19 nuclear magnetic resonance (19F NMR) relaxometry and diffusometry are important techniques in hydrogel drug delivery and, more generally, in biomaterial science, tissue engineering, and regenerative medicine.
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institution Kabale University
issn 1438-7492
1439-2054
language English
publishDate 2025-08-01
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series Macromolecular Materials and Engineering
spelling doaj-art-340d7644618a42e2bbf38cc4bfbb965b2025-08-20T08:39:24ZengWiley-VCHMacromolecular Materials and Engineering1438-74921439-20542025-08-013108n/an/a10.1002/mame.20240034819F NMR Relaxometry and Diffusometry for Measuring Cargo Molecule Dynamics in GelMA HydrogelsChun‐Wei Chang0Bronwin L. Dargaville1Konstantin I. Momot2Dietmar W. Hutmacher3Max Planck Queensland Centre on the Materials Science for Extracellular Matrices Queensland University of Technology (QUT) Brisbane QLD 4059 AustraliaMax Planck Queensland Centre on the Materials Science for Extracellular Matrices Queensland University of Technology (QUT) Brisbane QLD 4059 AustraliaSchool of Chemistry and Physics Queensland University of Technology (QUT) Brisbane QLD 4001 AustraliaMax Planck Queensland Centre on the Materials Science for Extracellular Matrices Queensland University of Technology (QUT) Brisbane QLD 4059 AustraliaAbstract Understanding payload diffusion is an important topic in hydrogel drug delivery. While proton nuclear magnetic resonance (NMR) spectroscopy allows for direct examination of water dynamics in hydrogels, it is challenging to study the dynamics of payloads due to spectral crowding and distortions. Fluorine‐19, not biologically endogenous in humans and having high NMR receptivity, can be easily incorporated into molecules of interest and therefore used as an alternative probe for dynamics of payload molecules in hydrogels. In this study, the dynamics of fluorine‐containing compounds trifluoroethylamine (TFEA, a small molecule), ciprofloxacin (CF, a medium‐size molecule), and fluorinated lysozyme (FL, a ≈15 kDa protein) are measured both in solution and gelatin methacrylate (GelMA) hydrogels. For each payload molecule, the rotational correlation time and translational diffusion coefficient, as well as the effective microviscosity of the media, are measured. Spin‐spin relaxation (T2) is also used to probe chemical exchange as an indicator of payload–polymer interactions. The in situ interaction between payload and polymer network and precise characterization of payload dynamics within hydrogels show that fluorine‐19 nuclear magnetic resonance (19F NMR) relaxometry and diffusometry are important techniques in hydrogel drug delivery and, more generally, in biomaterial science, tissue engineering, and regenerative medicine.https://doi.org/10.1002/mame.202400348fluorine‐19 nuclear magnetic resonance (NMR) spectroscopygelatin methacrylatehydrogel drug delivery system (DDS)relaxometry
spellingShingle Chun‐Wei Chang
Bronwin L. Dargaville
Konstantin I. Momot
Dietmar W. Hutmacher
19F NMR Relaxometry and Diffusometry for Measuring Cargo Molecule Dynamics in GelMA Hydrogels
Macromolecular Materials and Engineering
fluorine‐19 nuclear magnetic resonance (NMR) spectroscopy
gelatin methacrylate
hydrogel drug delivery system (DDS)
relaxometry
title 19F NMR Relaxometry and Diffusometry for Measuring Cargo Molecule Dynamics in GelMA Hydrogels
title_full 19F NMR Relaxometry and Diffusometry for Measuring Cargo Molecule Dynamics in GelMA Hydrogels
title_fullStr 19F NMR Relaxometry and Diffusometry for Measuring Cargo Molecule Dynamics in GelMA Hydrogels
title_full_unstemmed 19F NMR Relaxometry and Diffusometry for Measuring Cargo Molecule Dynamics in GelMA Hydrogels
title_short 19F NMR Relaxometry and Diffusometry for Measuring Cargo Molecule Dynamics in GelMA Hydrogels
title_sort 19f nmr relaxometry and diffusometry for measuring cargo molecule dynamics in gelma hydrogels
topic fluorine‐19 nuclear magnetic resonance (NMR) spectroscopy
gelatin methacrylate
hydrogel drug delivery system (DDS)
relaxometry
url https://doi.org/10.1002/mame.202400348
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AT bronwinldargaville 19fnmrrelaxometryanddiffusometryformeasuringcargomoleculedynamicsingelmahydrogels
AT konstantinimomot 19fnmrrelaxometryanddiffusometryformeasuringcargomoleculedynamicsingelmahydrogels
AT dietmarwhutmacher 19fnmrrelaxometryanddiffusometryformeasuringcargomoleculedynamicsingelmahydrogels