Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer
In this work, the synthesis, selective chemical modifications, and self-assembly behavior in aqueous media of a novel poly(2-(dimethylamino)ethyl acrylate)<sub>20</sub>-b-poly(N-isopropylacrylamide)<sub>11</sub>-b-poly(oligo ethylene glycol methyl ether acrylate)<sub>18...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-06-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/12/6/1382 |
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| author | Despoina Giaouzi Stergios Pispas |
| author_facet | Despoina Giaouzi Stergios Pispas |
| author_sort | Despoina Giaouzi |
| collection | DOAJ |
| description | In this work, the synthesis, selective chemical modifications, and self-assembly behavior in aqueous media of a novel poly(2-(dimethylamino)ethyl acrylate)<sub>20</sub>-b-poly(N-isopropylacrylamide)<sub>11</sub>-b-poly(oligo ethylene glycol methyl ether acrylate)<sub>18</sub> (PDMAEA<sub>20</sub>-b-PNIPAM<sub>11</sub>-b-POEGA<sub>18</sub>) dual-responsive (pH and temperature) and triply hydrophilic amino-based triblock terpolymer are reported. The amine functional triblock terpolymer was synthesized by sequential reversible addition fragmentation chain transfer polymerization (RAFT) polymerization and molecularly characterized by size exclusion chromatography (SEC) and <sup>1</sup>H-NMR spectroscopy that evidenced the success of the three-step polymerization scheme. The tertiary amine pendant groups of the PDMAEA block were chemically modified in order to produce the Q<sub>1</sub>PDMAEA<sub>20</sub>-b-PNIPAM<sub>11</sub>-b-POEGA<sub>18</sub> as well as the Q<sub>6</sub>PDMAEA<sub>20</sub>-b-PNIPAM<sub>11</sub>-b-POEGA<sub>18</sub> quaternized triblock terpolymers (Q<sub>1</sub> and Q<sub>6</sub> prefixes show the number of carbon atoms (C1 and C6) attached on the PDMAEA groups) using methyl iodide (CH<sub>3</sub>I) and 1-iodohexane (C<sub>6</sub>H<sub>13</sub>I) as the quaternizing agents and the SPDMAEA<sub>20</sub>-b-PNIPAM<sub>11</sub>-b-POEGA<sub>18</sub> sulfobetainized triblock terpolymer using 1,3 propanesultone (C<sub>3</sub>H<sub>6</sub>O<sub>3</sub>S) as the sulfobetainization agent. The self-assembly properties of the triblock terpolymers in aqueous solutions upon varying temperature and solution pH were studied by light scattering and fluorescence spectroscopy experiments. The novel triblock terpolymers self-assemble into nanosized aggregates upon solution temperature rise above the nominal lower critical solution temperature (LCST) of the temperature-responsive PNIPAM block. The remarkable stimuli-responsive self-assembly behavior of the novel triblock terpolymers in aqueous media make them interesting candidates for biomedical applications in the fields of drug and gene delivery. |
| first_indexed | 2024-03-10T19:01:19Z |
| format | Article |
| id | doaj.art-82e752153df24ea4a87805d80d55863f |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T19:01:19Z |
| publishDate | 2020-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-82e752153df24ea4a87805d80d55863f2023-11-20T04:24:02ZengMDPI AGPolymers2073-43602020-06-01126138210.3390/polym12061382Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock TerpolymerDespoina Giaouzi0Stergios Pispas1Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, 11635 Athens, GreeceTheoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, 11635 Athens, GreeceIn this work, the synthesis, selective chemical modifications, and self-assembly behavior in aqueous media of a novel poly(2-(dimethylamino)ethyl acrylate)<sub>20</sub>-b-poly(N-isopropylacrylamide)<sub>11</sub>-b-poly(oligo ethylene glycol methyl ether acrylate)<sub>18</sub> (PDMAEA<sub>20</sub>-b-PNIPAM<sub>11</sub>-b-POEGA<sub>18</sub>) dual-responsive (pH and temperature) and triply hydrophilic amino-based triblock terpolymer are reported. The amine functional triblock terpolymer was synthesized by sequential reversible addition fragmentation chain transfer polymerization (RAFT) polymerization and molecularly characterized by size exclusion chromatography (SEC) and <sup>1</sup>H-NMR spectroscopy that evidenced the success of the three-step polymerization scheme. The tertiary amine pendant groups of the PDMAEA block were chemically modified in order to produce the Q<sub>1</sub>PDMAEA<sub>20</sub>-b-PNIPAM<sub>11</sub>-b-POEGA<sub>18</sub> as well as the Q<sub>6</sub>PDMAEA<sub>20</sub>-b-PNIPAM<sub>11</sub>-b-POEGA<sub>18</sub> quaternized triblock terpolymers (Q<sub>1</sub> and Q<sub>6</sub> prefixes show the number of carbon atoms (C1 and C6) attached on the PDMAEA groups) using methyl iodide (CH<sub>3</sub>I) and 1-iodohexane (C<sub>6</sub>H<sub>13</sub>I) as the quaternizing agents and the SPDMAEA<sub>20</sub>-b-PNIPAM<sub>11</sub>-b-POEGA<sub>18</sub> sulfobetainized triblock terpolymer using 1,3 propanesultone (C<sub>3</sub>H<sub>6</sub>O<sub>3</sub>S) as the sulfobetainization agent. The self-assembly properties of the triblock terpolymers in aqueous solutions upon varying temperature and solution pH were studied by light scattering and fluorescence spectroscopy experiments. The novel triblock terpolymers self-assemble into nanosized aggregates upon solution temperature rise above the nominal lower critical solution temperature (LCST) of the temperature-responsive PNIPAM block. The remarkable stimuli-responsive self-assembly behavior of the novel triblock terpolymers in aqueous media make them interesting candidates for biomedical applications in the fields of drug and gene delivery.https://www.mdpi.com/2073-4360/12/6/1382triblock terpolymerthermoresponsiveRAFT polymerizationchemical modificationstimuli responsiveself-assembly |
| spellingShingle | Despoina Giaouzi Stergios Pispas Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer Polymers triblock terpolymer thermoresponsive RAFT polymerization chemical modification stimuli responsive self-assembly |
| title | Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer |
| title_full | Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer |
| title_fullStr | Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer |
| title_full_unstemmed | Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer |
| title_short | Effects of Chemical Modifications on the Thermoresponsive Behavior of a PDMAEA-b-PNIPAM-b-POEGA Triblock Terpolymer |
| title_sort | effects of chemical modifications on the thermoresponsive behavior of a pdmaea b pnipam b poega triblock terpolymer |
| topic | triblock terpolymer thermoresponsive RAFT polymerization chemical modification stimuli responsive self-assembly |
| url | https://www.mdpi.com/2073-4360/12/6/1382 |
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