Internal Structure of Thermoresponsive Physically Crosslinked Nanogel of Poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>Block</i>-Poly[<i>N</i>-(2,2-difluoroethyl)acrylamide], Prominent <sup>19</sup>F MRI Tracer

Fluorine-19 MRI is a promising noninvasive diagnostic method. However, the absence of a nontoxic fluorine-19 MRI tracer that does not suffer from poor biodistribution as a result of its strong fluorophilicity is a constant hurdle in the widespread applicability of this otherwise versatile diagnostic...

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Main Authors: David Babuka, Kristyna Kolouchova, Ondrej Groborz, Zdenek Tosner, Alexander Zhigunov, Petr Stepanek, Martin Hruby
Format: Article
Language:English
Published: MDPI AG 2020-11-01
Series:Nanomaterials
Subjects:
Online Access:https://www.mdpi.com/2079-4991/10/11/2231
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author David Babuka
Kristyna Kolouchova
Ondrej Groborz
Zdenek Tosner
Alexander Zhigunov
Petr Stepanek
Martin Hruby
author_facet David Babuka
Kristyna Kolouchova
Ondrej Groborz
Zdenek Tosner
Alexander Zhigunov
Petr Stepanek
Martin Hruby
author_sort David Babuka
collection DOAJ
description Fluorine-19 MRI is a promising noninvasive diagnostic method. However, the absence of a nontoxic fluorine-19 MRI tracer that does not suffer from poor biodistribution as a result of its strong fluorophilicity is a constant hurdle in the widespread applicability of this otherwise versatile diagnostic technique. The poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>block</i>-poly[<i>N</i>-(2,2-difluoroethyl)acrylamide] thermoresponsive copolymer was proposed as an alternative fluorine-19 MRI tracer capable of overcoming such shortcomings. In this paper, the internal structure of self-assembled particles of this copolymer was investigated by various methods including 1D and 2D NMR, dynamic light scattering (DLS), small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS). The elucidated structure appears to be that of a nanogel with greatly swollen hydrophilic chains and tightly packed thermoresponsive chains forming a network within the nanogel particles, which become more hydrophobic with increasing temperature. Its capacity to provide a measurable fluorine-19 NMR signal in its aggregated state at human body temperature was also investigated and confirmed. This capacity stems from the different fluorine-19 nuclei relaxation properties compared to those of hydrogen-1 nuclei.
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spelling doaj.art-9a8e315d56804e3183fb68359d26a1072023-11-20T20:26:36ZengMDPI AGNanomaterials2079-49912020-11-011011223110.3390/nano10112231Internal Structure of Thermoresponsive Physically Crosslinked Nanogel of Poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>Block</i>-Poly[<i>N</i>-(2,2-difluoroethyl)acrylamide], Prominent <sup>19</sup>F MRI TracerDavid Babuka0Kristyna Kolouchova1Ondrej Groborz2Zdenek Tosner3Alexander Zhigunov4Petr Stepanek5Martin Hruby6Institute of Macromolecular Chemistry, Czech Academy of Sciences, Heyrovského náměstí 2, 162 06 Prague 6, Czech RepublicInstitute of Macromolecular Chemistry, Czech Academy of Sciences, Heyrovského náměstí 2, 162 06 Prague 6, Czech RepublicInstitute of Macromolecular Chemistry, Czech Academy of Sciences, Heyrovského náměstí 2, 162 06 Prague 6, Czech RepublicDepartment of NMR Spectroscopy, Faculty of Science, Charles University, Hlavova 8, 128 43 Prague 2, Czech RepublicInstitute of Macromolecular Chemistry, Czech Academy of Sciences, Heyrovského náměstí 2, 162 06 Prague 6, Czech RepublicInstitute of Macromolecular Chemistry, Czech Academy of Sciences, Heyrovského náměstí 2, 162 06 Prague 6, Czech RepublicInstitute of Macromolecular Chemistry, Czech Academy of Sciences, Heyrovského náměstí 2, 162 06 Prague 6, Czech RepublicFluorine-19 MRI is a promising noninvasive diagnostic method. However, the absence of a nontoxic fluorine-19 MRI tracer that does not suffer from poor biodistribution as a result of its strong fluorophilicity is a constant hurdle in the widespread applicability of this otherwise versatile diagnostic technique. The poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>block</i>-poly[<i>N</i>-(2,2-difluoroethyl)acrylamide] thermoresponsive copolymer was proposed as an alternative fluorine-19 MRI tracer capable of overcoming such shortcomings. In this paper, the internal structure of self-assembled particles of this copolymer was investigated by various methods including 1D and 2D NMR, dynamic light scattering (DLS), small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS). The elucidated structure appears to be that of a nanogel with greatly swollen hydrophilic chains and tightly packed thermoresponsive chains forming a network within the nanogel particles, which become more hydrophobic with increasing temperature. Its capacity to provide a measurable fluorine-19 NMR signal in its aggregated state at human body temperature was also investigated and confirmed. This capacity stems from the different fluorine-19 nuclei relaxation properties compared to those of hydrogen-1 nuclei.https://www.mdpi.com/2079-4991/10/11/2231fluorine-19magnetic resonance imagingself-assemblydiblock copolymerPHPMAPDFEA
spellingShingle David Babuka
Kristyna Kolouchova
Ondrej Groborz
Zdenek Tosner
Alexander Zhigunov
Petr Stepanek
Martin Hruby
Internal Structure of Thermoresponsive Physically Crosslinked Nanogel of Poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>Block</i>-Poly[<i>N</i>-(2,2-difluoroethyl)acrylamide], Prominent <sup>19</sup>F MRI Tracer
Nanomaterials
fluorine-19
magnetic resonance imaging
self-assembly
diblock copolymer
PHPMA
PDFEA
title Internal Structure of Thermoresponsive Physically Crosslinked Nanogel of Poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>Block</i>-Poly[<i>N</i>-(2,2-difluoroethyl)acrylamide], Prominent <sup>19</sup>F MRI Tracer
title_full Internal Structure of Thermoresponsive Physically Crosslinked Nanogel of Poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>Block</i>-Poly[<i>N</i>-(2,2-difluoroethyl)acrylamide], Prominent <sup>19</sup>F MRI Tracer
title_fullStr Internal Structure of Thermoresponsive Physically Crosslinked Nanogel of Poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>Block</i>-Poly[<i>N</i>-(2,2-difluoroethyl)acrylamide], Prominent <sup>19</sup>F MRI Tracer
title_full_unstemmed Internal Structure of Thermoresponsive Physically Crosslinked Nanogel of Poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>Block</i>-Poly[<i>N</i>-(2,2-difluoroethyl)acrylamide], Prominent <sup>19</sup>F MRI Tracer
title_short Internal Structure of Thermoresponsive Physically Crosslinked Nanogel of Poly[<i>N</i>-(2-hydroxypropyl)methacrylamide]-<i>Block</i>-Poly[<i>N</i>-(2,2-difluoroethyl)acrylamide], Prominent <sup>19</sup>F MRI Tracer
title_sort internal structure of thermoresponsive physically crosslinked nanogel of poly i n i 2 hydroxypropyl methacrylamide i block i poly i n i 2 2 difluoroethyl acrylamide prominent sup 19 sup f mri tracer
topic fluorine-19
magnetic resonance imaging
self-assembly
diblock copolymer
PHPMA
PDFEA
url https://www.mdpi.com/2079-4991/10/11/2231
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