Polystyrene and Poly(ethylene glycol)-b-Poly(epsilon-caprolactone) Nanoparticles with Porphyrins: Structure, Size, and Photooxidation Properties

0532310 - ÚFCH JH 2021 RIV US eng J - Journal Article
Kubát, Pavel - Henke, P. - Raya, R.K. - Štěpánek, M. - Mosinger, Jiří
Polystyrene and Poly(ethylene glycol)-b-Poly(epsilon-caprolactone) Nanoparticles with Porphyrins: Structure, Size, and Photooxidation Properties.
Langmuir. Roč. 36, č. 1 (2020), s. 302-310. ISSN 0743-7463
R&D Projects: GA ČR(CZ) GA19-09721S
Grant - others:GA MŠk(CZ) CZ.02.1.01/0.0/0.0/15_003/0000417
Institutional support: RVO:61388955 ; RVO:61388980
Keywords : singlet oxygen * photodynamic therapy * polymeric nanoparticles * nanofiber materials * protein corona * temperature * photosensitizers * delivery * nanofabrics * particles
OECD category: Physical chemistry; Inorganic and nuclear chemistry (UACH-T)
Impact factor: 3.882, year: 2020
Method of publishing: Open access with time embargo

The transport of a photosensitizer to target biological structures followed by the release of singlet oxygen is a critical step in photodynamic therapy. We compared the (photo)physical properties of polystyrene nanoparticles (TPP@PS) of different sizes and self-assembled poly(ethylene glycol)-b-poly(epsilon-caprolactone) core/shell nanoparticles (TPP@PEG-PCL) with different lengths of copolymer blocks, both suitable for the transport of the tetraphenylporphyrin (TPP) photosensitizer. The singlet oxygen was formed inside both nanoparticles after irradiation with visible light. Its kinetics was controlled by the size of TPP@PS, its lifetime (tau(Delta)) increased with increasing nanoparticle size (from 6.5 to 16 mu s) because of hindered diffusion into the external aqueous environment, where it was quickly deactivated. Accordingly, the prolongation of the singlet oxygen-sensitized delayed fluorescence kinetics was found for TPP@PS of high size. The TPP@PEG-PCL self-assemblies allowed for enhanced oxygen diffusion, and the estimated low values of tau(Delta) approximate to 3.7 mu s were independent of the size of building blocks. The delayed fluorescence in oxygen-free conditions originating from triplet-triplet annihilation indicated a high mobility of TPP in the PCL core in comparison with fixed molecules in the PS matrix. Photooxidation of uric acid revealed the highest efficacy for TPP@PS of small sizes, whereas the largest TPP@PS exhibited the lowest activity, and the efficacy of TPP@PEG-PCL remained independent of the sizes of the building blocks.
Permanent Link: http://hdl.handle.net/11104/0310832