Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents
The synthesis of functional poly(2-alkyl-2-oxazoline) (PAOx) copolymers with complex nanoarchitectures using a graft-through ring-opening metathesis polymerization (ROMP) approach is described. First, well-defined norbornene-terminated poly(2-ethyl-2-oxazoline) (PEtOx) macromonomers (MM) were prepar...
| Main Authors: | , , , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
American Chemical Society (ACS)
2020
|
| Online Access: | https://hdl.handle.net/1721.1/125832 |
| _version_ | 1826202392071241728 |
|---|---|
| author | Alvaradejo, Gabriela Gil Nguyen, Hung VanThanh Harvey, Peter Gallagher, Nolan Le, Dao Ottaviani, M. Francesca Jasanoff, Alan Pradip Delaittre, Guillaume Johnson, Jeremiah A. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Alvaradejo, Gabriela Gil Nguyen, Hung VanThanh Harvey, Peter Gallagher, Nolan Le, Dao Ottaviani, M. Francesca Jasanoff, Alan Pradip Delaittre, Guillaume Johnson, Jeremiah A. |
| author_sort | Alvaradejo, Gabriela Gil |
| collection | MIT |
| description | The synthesis of functional poly(2-alkyl-2-oxazoline) (PAOx) copolymers with complex nanoarchitectures using a graft-through ring-opening metathesis polymerization (ROMP) approach is described. First, well-defined norbornene-terminated poly(2-ethyl-2-oxazoline) (PEtOx) macromonomers (MM) were prepared by cationic ring-opening polymerization. ROMP of these MMs produced bottlebrush copolymers with PEtOx side chains. In addition, PEtOx-based branched MMs bearing a terminal alkyne group were prepared and conjugated to an azide-containing bis-spirocyclohexyl nitroxide via Cu-catalyzed azide-alkyne cycloaddition (CuAAC). ROMP of this branched MM, followed by in situ cross-linking, provided PEtOx-based brush-arm star polymers (BASPs) with nitroxide radicals localized at the core-shell interface. These PEtOx-based nitroxide-containing BASPs displayed relaxivity values on par with state-of-the-art polyethylene glycol (PEG)-based nitroxide materials, making them promising as organic radical contrast agents for metal-free magnetic resonance imaging (MRI). |
| first_indexed | 2024-09-23T12:06:43Z |
| format | Article |
| id | mit-1721.1/125832 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T12:06:43Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1258322022-09-28T00:14:36Z Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents Alvaradejo, Gabriela Gil Nguyen, Hung VanThanh Harvey, Peter Gallagher, Nolan Le, Dao Ottaviani, M. Francesca Jasanoff, Alan Pradip Delaittre, Guillaume Johnson, Jeremiah A. Massachusetts Institute of Technology. Department of Chemistry Massachusetts Institute of Technology. Department of Biological Engineering Massachusetts Institute of Technology. Department of Brain and Cognitive Sciences Massachusetts Institute of Technology. Department of Nuclear Science and Engineering The synthesis of functional poly(2-alkyl-2-oxazoline) (PAOx) copolymers with complex nanoarchitectures using a graft-through ring-opening metathesis polymerization (ROMP) approach is described. First, well-defined norbornene-terminated poly(2-ethyl-2-oxazoline) (PEtOx) macromonomers (MM) were prepared by cationic ring-opening polymerization. ROMP of these MMs produced bottlebrush copolymers with PEtOx side chains. In addition, PEtOx-based branched MMs bearing a terminal alkyne group were prepared and conjugated to an azide-containing bis-spirocyclohexyl nitroxide via Cu-catalyzed azide-alkyne cycloaddition (CuAAC). ROMP of this branched MM, followed by in situ cross-linking, provided PEtOx-based brush-arm star polymers (BASPs) with nitroxide radicals localized at the core-shell interface. These PEtOx-based nitroxide-containing BASPs displayed relaxivity values on par with state-of-the-art polyethylene glycol (PEG)-based nitroxide materials, making them promising as organic radical contrast agents for metal-free magnetic resonance imaging (MRI). 2020-06-17T14:00:43Z 2020-06-17T14:00:43Z 2019-04 2019-01 2019-12-23T14:40:09Z Article http://purl.org/eprint/type/JournalArticle 2161-1653 2161-1653 https://hdl.handle.net/1721.1/125832 Alvaradejo, Gabriela Gil et al. "Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents." ACS Macro Letters 8, 4 (April 2019): 473–478 © 2019 American Chemical Society en http://dx.doi.org/10.1021/acsmacrolett.9b00016 ACS Macro Letters Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) PMC |
| spellingShingle | Alvaradejo, Gabriela Gil Nguyen, Hung VanThanh Harvey, Peter Gallagher, Nolan Le, Dao Ottaviani, M. Francesca Jasanoff, Alan Pradip Delaittre, Guillaume Johnson, Jeremiah A. Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents |
| title | Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents |
| title_full | Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents |
| title_fullStr | Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents |
| title_full_unstemmed | Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents |
| title_short | Polyoxazoline-Based Bottlebrush and Brush-Arm Star Polymers via ROMP: Syntheses and Applications as Organic Radical Contrast Agents |
| title_sort | polyoxazoline based bottlebrush and brush arm star polymers via romp syntheses and applications as organic radical contrast agents |
| url | https://hdl.handle.net/1721.1/125832 |
| work_keys_str_mv | AT alvaradejogabrielagil polyoxazolinebasedbottlebrushandbrusharmstarpolymersviarompsynthesesandapplicationsasorganicradicalcontrastagents AT nguyenhungvanthanh polyoxazolinebasedbottlebrushandbrusharmstarpolymersviarompsynthesesandapplicationsasorganicradicalcontrastagents AT harveypeter polyoxazolinebasedbottlebrushandbrusharmstarpolymersviarompsynthesesandapplicationsasorganicradicalcontrastagents AT gallaghernolan polyoxazolinebasedbottlebrushandbrusharmstarpolymersviarompsynthesesandapplicationsasorganicradicalcontrastagents AT ledao polyoxazolinebasedbottlebrushandbrusharmstarpolymersviarompsynthesesandapplicationsasorganicradicalcontrastagents AT ottavianimfrancesca polyoxazolinebasedbottlebrushandbrusharmstarpolymersviarompsynthesesandapplicationsasorganicradicalcontrastagents AT jasanoffalanpradip polyoxazolinebasedbottlebrushandbrusharmstarpolymersviarompsynthesesandapplicationsasorganicradicalcontrastagents AT delaittreguillaume polyoxazolinebasedbottlebrushandbrusharmstarpolymersviarompsynthesesandapplicationsasorganicradicalcontrastagents AT johnsonjeremiaha polyoxazolinebasedbottlebrushandbrusharmstarpolymersviarompsynthesesandapplicationsasorganicradicalcontrastagents |