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Multi-stimuli responsive block copolymers as a smart release platform for a polypyridyl ruthenium complex

Appold, M. ; Mari, C. ; Lederle, C. ; Elbert, J. ; Schmidt, C. ; Ott, I. ; Stühn, B. ; Gasser, G. ; Gallei, M. (2017)
Multi-stimuli responsive block copolymers as a smart release platform for a polypyridyl ruthenium complex.
In: Polymer Chemistry, 8
doi: 10.1039/C6PY02026G
Article

Abstract

A variety of applications of amphiphilic block copolymers result from the control of their self-assembled structures. Herein, the synthesis and structure formation of block copolymers (BCPs) consisting of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) as one segment and poly(methyl methacrylate) (PMMA) or a statistical copolymer (PDMAEMA-co-PMMA) as a second segment, is described. The BCPs provide molar masses between 8.9 kg mol-1 and 35.6 kg mol-1 with low polydispersity index values, D = 1.05-1.13. BCPs are synthesized via sequential anionic polymerization strategies while structure formation in water is investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The PDMAEMA-containing micelles in water are loaded with a Ru(ii) polypyridyl complex, i.e. Ru(bipy)2-dppz-7-hydroxymethylPF62 (bipy = 2{,}2prime or minute-bipyridine; dppz = dipyridophenazine){,} which was previously shown to act as a potential photosensitizer in photodynamic therapy (PDT). Successful loading of the BCP micelles is evidenced by TEM measurements after dialysis in water. Stimulus-responsive release of the Ru(ii) complex from the BCP micelles is shown using ultrasound{,} change of pH or temperature as external triggers. The quantification and release profiles for the Ru(ii) complex are obtained by atomic absorption spectrometry (AAS). As a result{,} PDMAEMA-b-PMMA is not capable of releasing the Ru(ii) complex in a controlled manner after application of{,} for instance{,} ultrasound or temperature change as external triggers due to the shielding (stealth effect) of the BCP. On the contrary{,} micelles made of BCPs featuring PDMAEMA and PDMAEMA-co-PMMA segments reveal excellent Ru(ii) complex release profiles due to the tailored molecular composition of the underlying block segments as evidenced by temperature-dependent DLS and AAS measurements. Thus{,} these smart PDMAEMA-containing BCPs pave the way to a variety of applications for selective triggered release of small molecules.

Item Type: Article
Erschienen: 2017
Creators: Appold, M. ; Mari, C. ; Lederle, C. ; Elbert, J. ; Schmidt, C. ; Ott, I. ; Stühn, B. ; Gasser, G. ; Gallei, M.
Type of entry: Bibliographie
Title: Multi-stimuli responsive block copolymers as a smart release platform for a polypyridyl ruthenium complex
Language: English
Date: 2017
Publisher: The Royal Society of Chemistry
Journal or Publication Title: Polymer Chemistry
Volume of the journal: 8
DOI: 10.1039/C6PY02026G
URL / URN: http://dx.doi.org/10.1039/C6PY02026G
Abstract:

A variety of applications of amphiphilic block copolymers result from the control of their self-assembled structures. Herein, the synthesis and structure formation of block copolymers (BCPs) consisting of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) as one segment and poly(methyl methacrylate) (PMMA) or a statistical copolymer (PDMAEMA-co-PMMA) as a second segment, is described. The BCPs provide molar masses between 8.9 kg mol-1 and 35.6 kg mol-1 with low polydispersity index values, D = 1.05-1.13. BCPs are synthesized via sequential anionic polymerization strategies while structure formation in water is investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The PDMAEMA-containing micelles in water are loaded with a Ru(ii) polypyridyl complex, i.e. Ru(bipy)2-dppz-7-hydroxymethylPF62 (bipy = 2{,}2prime or minute-bipyridine; dppz = dipyridophenazine){,} which was previously shown to act as a potential photosensitizer in photodynamic therapy (PDT). Successful loading of the BCP micelles is evidenced by TEM measurements after dialysis in water. Stimulus-responsive release of the Ru(ii) complex from the BCP micelles is shown using ultrasound{,} change of pH or temperature as external triggers. The quantification and release profiles for the Ru(ii) complex are obtained by atomic absorption spectrometry (AAS). As a result{,} PDMAEMA-b-PMMA is not capable of releasing the Ru(ii) complex in a controlled manner after application of{,} for instance{,} ultrasound or temperature change as external triggers due to the shielding (stealth effect) of the BCP. On the contrary{,} micelles made of BCPs featuring PDMAEMA and PDMAEMA-co-PMMA segments reveal excellent Ru(ii) complex release profiles due to the tailored molecular composition of the underlying block segments as evidenced by temperature-dependent DLS and AAS measurements. Thus{,} these smart PDMAEMA-containing BCPs pave the way to a variety of applications for selective triggered release of small molecules.

Divisions: 05 Department of Physics > Institute for condensed matter physics (2021 merged in Institute for Condensed Matter Physics) > Experimental Condensed Matter Physics
05 Department of Physics > Institute for condensed matter physics (2021 merged in Institute for Condensed Matter Physics)
05 Department of Physics
Date Deposited: 21 Nov 2017 09:03
Last Modified: 21 Nov 2017 09:03
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