Abstract
Polymerization-induced self-assembly (PISA) is an easily applied synthetic technique for the preparation of polymer nanoparticles with various shapes and at high concentrations. Although PISA has been applied to prepare nanoparticles for a variety of different applications, to date there have been no attempts to employ nanoparticles prepared via PISA as a novel platform from which to prepare positive contrast agents for magnetic resonance imaging (MRI). To this end, here we report an efficient synthesis of surface-functional polymer-based nanoparticles with tunable size and morphology (micelles, filomicelles and vesicles) via PISA, their post-synthetic functionalisation and an initial investigation into their use as a positive MRI contrast agent. A short functional block of poly(glycidyl methacrylate) was prepared using reversible addition-fragmentation chain transfer (RAFT) polymerization, and this was chain extended with oligo(ethylene glycol) methyl ether methacrylate to create a novel macromolecular chain transfer agent for PISA. A library of surface-functional self-assembled nanoparticles with different shapes was then synthesized, and the versatility of the glycidyl methacrylate units for post-synthetic surface functionalization was demonstrated by ring opening the epoxide with a primary thiol, a primary amine and sodium azide. The resulting azide functional materials could be further modified via copper-catalysed azide-alkyne cycloaddition. The epoxide groups were also exploited to conjugate Gd-DOTA to the polymeric nanoparticles and the application of the diverse polymeric nanoparticles for T1-weighted MRI was investigated, with the filomicelle emerging as a promising candidate due to both a good gadolinium-labelling efficiency and a high T1 relaxivity. Given that filomicelles typically exhibit enhanced blood circulation times, the gadolinium-labelled filomicelles could have potential applications as a blood pool agent for magnetic resonance angiography, and in cancer diagnostics/theranostics.
| Original language | English |
|---|---|
| Pages (from-to) | 7325-7337 |
| Number of pages | 13 |
| Journal | Polymer Chemistry |
| Volume | 7 |
| Issue number | 47 |
| DOIs | |
| Publication status | Published - 21 Dec 2016 |
Cite this
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Gadolinium-functionalized nanoparticles for application as magnetic resonance imaging contrast agents : via polymerization-induced self-assembly. / Esser, Lars; Truong, Nghia P.; Karagoz, Bunyamin; Moffat, Bradford A.; Boyer, Cyrille; Quinn, John F.; Whittaker, Michael R.; Davis, Thomas P.
In: Polymer Chemistry, Vol. 7, No. 47, 21.12.2016, p. 7325-7337.Research output: Contribution to journal › Article › Research › peer-review
TY - JOUR
T1 - Gadolinium-functionalized nanoparticles for application as magnetic resonance imaging contrast agents
T2 - via polymerization-induced self-assembly
AU - Esser, Lars
AU - Truong, Nghia P.
AU - Karagoz, Bunyamin
AU - Moffat, Bradford A.
AU - Boyer, Cyrille
AU - Quinn, John F.
AU - Whittaker, Michael R.
AU - Davis, Thomas P.
PY - 2016/12/21
Y1 - 2016/12/21
N2 - Polymerization-induced self-assembly (PISA) is an easily applied synthetic technique for the preparation of polymer nanoparticles with various shapes and at high concentrations. Although PISA has been applied to prepare nanoparticles for a variety of different applications, to date there have been no attempts to employ nanoparticles prepared via PISA as a novel platform from which to prepare positive contrast agents for magnetic resonance imaging (MRI). To this end, here we report an efficient synthesis of surface-functional polymer-based nanoparticles with tunable size and morphology (micelles, filomicelles and vesicles) via PISA, their post-synthetic functionalisation and an initial investigation into their use as a positive MRI contrast agent. A short functional block of poly(glycidyl methacrylate) was prepared using reversible addition-fragmentation chain transfer (RAFT) polymerization, and this was chain extended with oligo(ethylene glycol) methyl ether methacrylate to create a novel macromolecular chain transfer agent for PISA. A library of surface-functional self-assembled nanoparticles with different shapes was then synthesized, and the versatility of the glycidyl methacrylate units for post-synthetic surface functionalization was demonstrated by ring opening the epoxide with a primary thiol, a primary amine and sodium azide. The resulting azide functional materials could be further modified via copper-catalysed azide-alkyne cycloaddition. The epoxide groups were also exploited to conjugate Gd-DOTA to the polymeric nanoparticles and the application of the diverse polymeric nanoparticles for T1-weighted MRI was investigated, with the filomicelle emerging as a promising candidate due to both a good gadolinium-labelling efficiency and a high T1 relaxivity. Given that filomicelles typically exhibit enhanced blood circulation times, the gadolinium-labelled filomicelles could have potential applications as a blood pool agent for magnetic resonance angiography, and in cancer diagnostics/theranostics.
AB - Polymerization-induced self-assembly (PISA) is an easily applied synthetic technique for the preparation of polymer nanoparticles with various shapes and at high concentrations. Although PISA has been applied to prepare nanoparticles for a variety of different applications, to date there have been no attempts to employ nanoparticles prepared via PISA as a novel platform from which to prepare positive contrast agents for magnetic resonance imaging (MRI). To this end, here we report an efficient synthesis of surface-functional polymer-based nanoparticles with tunable size and morphology (micelles, filomicelles and vesicles) via PISA, their post-synthetic functionalisation and an initial investigation into their use as a positive MRI contrast agent. A short functional block of poly(glycidyl methacrylate) was prepared using reversible addition-fragmentation chain transfer (RAFT) polymerization, and this was chain extended with oligo(ethylene glycol) methyl ether methacrylate to create a novel macromolecular chain transfer agent for PISA. A library of surface-functional self-assembled nanoparticles with different shapes was then synthesized, and the versatility of the glycidyl methacrylate units for post-synthetic surface functionalization was demonstrated by ring opening the epoxide with a primary thiol, a primary amine and sodium azide. The resulting azide functional materials could be further modified via copper-catalysed azide-alkyne cycloaddition. The epoxide groups were also exploited to conjugate Gd-DOTA to the polymeric nanoparticles and the application of the diverse polymeric nanoparticles for T1-weighted MRI was investigated, with the filomicelle emerging as a promising candidate due to both a good gadolinium-labelling efficiency and a high T1 relaxivity. Given that filomicelles typically exhibit enhanced blood circulation times, the gadolinium-labelled filomicelles could have potential applications as a blood pool agent for magnetic resonance angiography, and in cancer diagnostics/theranostics.
UR - http://www.scopus.com/inward/record.url?scp=85000995838&partnerID=8YFLogxK
U2 - 10.1039/c6py01797e
DO - 10.1039/c6py01797e
M3 - Article
VL - 7
SP - 7325
EP - 7337
JO - Polymer Chemistry
JF - Polymer Chemistry
SN - 1759-9954
IS - 47
ER -