Chemical specificity in REDOX-responsive materials:the diverse effects of different Reactive Oxygen Species (ROS) on polysulfide nanoparticles


REDOX responsive (nano)materials typically exhibit chemical changes in response to the presence and concentration of oxidants/reductants. Due to the complexity of biological environments, it is critical to ascertain whether the chemical response may depend on the chemical details of the stimulus, in addition to its REDOX potential, and whether chemically different responses can determine a different overall performance of the material. Here, we have used oxidation-sensitive materials, although these considerations can be extended also to reducible ones. In particular, we have used poly(propylene sulfide) (PPS) nanoparticles coated with a PEGylated emulsifier (Pluronic F127); inter alia, we here present also an improved preparative method. The nanoparticles were exposed to two Reactive Oxygen Species (ROS) typically encountered in inflammatory reactions, hydrogen peroxide (H2O2) and hypochlorite (ClO−); their response was evaluated with a variety of techniques, including diffusion NMR spectroscopy that allowed to separately characterize the chemically different colloidal species produced. The two oxidants triggered a different chemical response: H2O2 converted sulfides to sulfoxides, while ClO− partially oxidized them further to sulfones. The different chemistry correlated to a different material response: H2O2 increased the polarity of the nanoparticles, causing them to swell in water and to release the surface PEGylated emulsifier; the uncoated oxidized particles still exhibited very low toxicity. On the contrary, ClO− rapidly converted the nanoparticles into water-soluble, depolymerized fragments with a significantly higher toxicity. The take-home message is that it is more correct to discuss ‘smart’ materials in terms of an environmentally specific response to (REDOX) stimuli. Far from being a problem, this could open the way to more sophisticated and precisely targeted applications.

Publication DOI:
Divisions: College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
Additional Information: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Funding: Financial support from EPSRC (grant no. EP/C543564/1)
Uncontrolled Keywords: Polymers and Plastics,Organic Chemistry,Biochemistry,Biomedical Engineering,Bioengineering
Publication ISSN: 1759-9962
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Related URLs: http://www.scop ... tnerID=8YFLogxK (Scopus URL)
http://pubs.rsc ... 5d#!divAbstract (Publisher URL)
PURE Output Type: Article
Published Date: 2014-02-21
Published Online Date: 2013-11-19
Authors: Jeanmaire, Damien
Laliturai, Jureerat
Almalik, Abdulaziz
Carampin, Paolo
D'Arcy, Richard
Lallana, Enrique
Evans, Robert (ORCID Profile 0000-0003-1471-201X)
Winpenny, Richard E P
Tirelli, Nicola



Version: Published Version

License: Creative Commons Attribution

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