Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand
We present a new class of polymeric ligands for quantum dot (QD) water solubilization to yield biocompatible and derivatizable QDs with compact size (10−12 nm diameter), high quantum yields (>50%), excellent stability across a large pH range (pH 5−10.5), and low nonspecific binding. To address th...
| Main Authors: | , , , , , , , , , , , , |
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| Format: | Article |
| Language: | en_US |
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American Chemical Society
2012
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| Online Access: | http://hdl.handle.net/1721.1/73650 https://orcid.org/0000-0003-2220-4365 https://orcid.org/0000-0002-8277-5226 https://orcid.org/0000-0002-4507-1115 https://orcid.org/0000-0001-9769-2418 |
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| author | Liu, Wenhao Greytak, Thomas J. Lee, Jungmin Wong, Cliff Park, Jongnam Marshall, Lisa Faye Jiang, Wen Curtin, Peter N. Ting, Alice Y. Nocera, Daniel G. Fukumura, Dai Jain, Rakesh K. Bawendi, Moungi G. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Liu, Wenhao Greytak, Thomas J. Lee, Jungmin Wong, Cliff Park, Jongnam Marshall, Lisa Faye Jiang, Wen Curtin, Peter N. Ting, Alice Y. Nocera, Daniel G. Fukumura, Dai Jain, Rakesh K. Bawendi, Moungi G. |
| author_sort | Liu, Wenhao |
| collection | MIT |
| description | We present a new class of polymeric ligands for quantum dot (QD) water solubilization to yield biocompatible and derivatizable QDs with compact size (10−12 nm diameter), high quantum yields (>50%), excellent stability across a large pH range (pH 5−10.5), and low nonspecific binding. To address the fundamental problem of thiol instability in traditional ligand exchange systems, the polymers here employ a stable multidentate imidazole binding motif to the QD surface. The polymers are synthesized via reversible addition−fragmentation chain transfer-mediated polymerization to produce molecular weight controlled monodisperse random copolymers from three types of monomers that feature imidazole groups for QD binding, polyethylene glycol (PEG) groups for water solubilization, and either primary amines or biotin groups for derivatization. The polymer architecture can be tuned by the monomer ratios to yield aqueous QDs with targeted surface functionalities. By incorporating amino-PEG monomers, we demonstrate covalent conjugation of a dye to form a highly efficient QD-dye energy transfer pair as well as covalent conjugation to streptavidin for high-affinity single molecule imaging of biotinylated receptors on live cells with minimal nonspecific binding. The small size and low serum binding of these polymer-coated QDs also allow us to demonstrate their utility for in vivo imaging of the tumor microenvironment in live mice. |
| first_indexed | 2024-09-23T14:02:04Z |
| format | Article |
| id | mit-1721.1/73650 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T14:02:04Z |
| publishDate | 2012 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/736502022-10-01T18:42:19Z Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand Liu, Wenhao Greytak, Thomas J. Lee, Jungmin Wong, Cliff Park, Jongnam Marshall, Lisa Faye Jiang, Wen Curtin, Peter N. Ting, Alice Y. Nocera, Daniel G. Fukumura, Dai Jain, Rakesh K. Bawendi, Moungi G. Massachusetts Institute of Technology. Department of Chemistry Massachusetts Institute of Technology. Department of Physics Bawendi, Moungi G. Bawendi, Moungi G. Liu, Wenhao Greytak, Thomas J. Lee, Jungmin Wong, Cliff Park, Jongnam Marshall, Lisa Faye Curtin, Peter N. Ting, Alice Y. Nocera, Daniel G. We present a new class of polymeric ligands for quantum dot (QD) water solubilization to yield biocompatible and derivatizable QDs with compact size (10−12 nm diameter), high quantum yields (>50%), excellent stability across a large pH range (pH 5−10.5), and low nonspecific binding. To address the fundamental problem of thiol instability in traditional ligand exchange systems, the polymers here employ a stable multidentate imidazole binding motif to the QD surface. The polymers are synthesized via reversible addition−fragmentation chain transfer-mediated polymerization to produce molecular weight controlled monodisperse random copolymers from three types of monomers that feature imidazole groups for QD binding, polyethylene glycol (PEG) groups for water solubilization, and either primary amines or biotin groups for derivatization. The polymer architecture can be tuned by the monomer ratios to yield aqueous QDs with targeted surface functionalities. By incorporating amino-PEG monomers, we demonstrate covalent conjugation of a dye to form a highly efficient QD-dye energy transfer pair as well as covalent conjugation to streptavidin for high-affinity single molecule imaging of biotinylated receptors on live cells with minimal nonspecific binding. The small size and low serum binding of these polymer-coated QDs also allow us to demonstrate their utility for in vivo imaging of the tumor microenvironment in live mice. National Cancer Institute (U.S.) (Grant no. R01-CA126642) National Cancer Institute (U.S.) (Grant no. R01-CA085140) National Cancer Institute (U.S.) (Grant no. R01-CA115767) National Cancer Institute (U.S.) (Grant no. P01-CA080124) National Cancer Institute (U.S.) (Grant no. R01-CA096915) National Institutes of Health (U.S.) (MIT-Harvard NIH Center for Cancer Nanotechnology Excellence (1U54-CA119349)) Massachusetts Institute of Technology. Dept. of Chemistry Instrumentation Facility (CHE-980806) Massachusetts Institute of Technology. Dept. of Chemistry Instrumentation Facility (DBI-9729592) Massachusetts Institute of Technology. Institute for Soldier Nanotechnologies (W911NF-07-D-0004) National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (DMR-0117795) United States. Army Research Office (W911NF-06-1-0101) National Science Foundation (U.S.) (Graduate Research Fellowship) Life Sciences Research Foundation (Novartis Fellow) 2012-10-05T15:14:01Z 2012-10-05T15:14:01Z 2009-12 2009-09 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/73650 Liu, Wenhao et al. “Compact Biocompatible Quantum Dots via RAFT-Mediated Synthesis of Imidazole-Based Random Copolymer Ligand.” Journal of the American Chemical Society 132.2 (2010): 472–483. Web. https://orcid.org/0000-0003-2220-4365 https://orcid.org/0000-0002-8277-5226 https://orcid.org/0000-0002-4507-1115 https://orcid.org/0000-0001-9769-2418 en_US http://dx.doi.org/10.1021/ja908137d Journal of the American Chemical Society 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 PMC |
| spellingShingle | Liu, Wenhao Greytak, Thomas J. Lee, Jungmin Wong, Cliff Park, Jongnam Marshall, Lisa Faye Jiang, Wen Curtin, Peter N. Ting, Alice Y. Nocera, Daniel G. Fukumura, Dai Jain, Rakesh K. Bawendi, Moungi G. Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand |
| title | Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand |
| title_full | Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand |
| title_fullStr | Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand |
| title_full_unstemmed | Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand |
| title_short | Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand |
| title_sort | compact biocompatible quantum dots via raft mediated synthesis of imidazole based random copolymer ligand |
| url | http://hdl.handle.net/1721.1/73650 https://orcid.org/0000-0003-2220-4365 https://orcid.org/0000-0002-8277-5226 https://orcid.org/0000-0002-4507-1115 https://orcid.org/0000-0001-9769-2418 |
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