Harnessing Cytosine for Tunable Nanoparticle Self-Assembly Behavior Using Orthogonal Stimuli

Abstract

Nucleobases control the assembly of DNA, RNA, etc. due to hydrogen bond complementarity. By combining these unique molecules with state-of-the-art synthetic polymers, it is possible to form nanoparticles whose self-assembly behavior could be altered under orthogonal stimuli (pH and temperature). Herein, we report the synthesis of cytosine-containing nanoparticles via aqueous reversible addition-fragmentation chain transfer polymerization-induced self-assembly. A poly(N-acryloylmorpholine) macromolecular chain transfer agent (mCTA) was chain-extended with cytosine acrylamide, and a morphological phase diagram was constructed. By exploiting the ability of cytosine to form dimers via hydrogen bonding, the self-assembly behavior of cytosine-containing polymers was altered when performed under acidic conditions. Under these conditions, stable nanoparticles could be formed at longer polymer chain lengths. Furthermore, the resulting nanoparticles displayed different morphologies compared to those at pH 7. Additionally, particle stability post-assembly could be controlled by varying pH and temperature. Finally, small-angle X-ray scattering was performed to probe their dynamic behavior under thermal cycling.

Publication DOI: https://doi.org/10.1021/acs.biomac.4c00352
Divisions: College of Engineering & Physical Sciences > Aston Institute of Materials Research (AIMR)
College of Engineering & Physical Sciences > Aston Polymer Research Group
College of Engineering & Physical Sciences > Aston Advanced Materials
College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
Funding Information: This work was carried out with the support of Diamond Light Source, Instrument I22 (proposal sm33098), and the authors would like to acknowledge Dr. Andy Smith and all the I22 beamline staff for the support we received during the experiment. S.D.P.F. than
Additional Information: Copyright © 2024 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/).
Uncontrolled Keywords: Cytosine/chemistry,Hydrogen Bonding,Hydrogen-Ion Concentration,Nanoparticles/chemistry,Polymerization,Polymers/chemistry,Temperature
Publication ISSN: 1526-4602
Data Access Statement: The Supporting Information is available free of charge at<br/>https://pubs.acs.org/doi/10.1021/acs.biomac.4c00352.<br/><br/>'GPC and DLS characterization for PNAM-b-PCAm polymerizations at pH 7, DLS characterization for PNAM-PCAm polymerizations at pH 2, and temperature-responsive small-angle X-ray scattering analysis of PNAM-b-PCAm polymers' (PDF)
Last Modified: 07 Oct 2024 07:59
Date Deposited: 25 Jul 2024 07:27
Full Text Link:
Related URLs: https://pubs.ac ... .biomac.4c00352 (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2024-08-12
Published Online Date: 2024-07-15
Accepted Date: 2024-07-12
Authors: Parkinson, Sam J.
Fielden, Stephen D. P.
Thomas, Marjolaine
Miller, Alisha J.
Topham, Paul D. (ORCID Profile 0000-0003-4152-6976)
Derry, Matthew J. (ORCID Profile 0000-0001-5010-6725)
O’Reilly, Rachel K.

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