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Aggregation Behavior of Doubly Thermoresponsive Polysulfobetaine-b-poly(N-isopropylacrylamide) Diblock Copolymers

  • A 2-fold thermoresponsive diblock copolymer PSPP430-b-PNIPAM(200) consisting of a zwitterionic polysulfobetaine (PSPP) block and a nonionic poly(N-isopropylacrylamide) (PNIPAM) block is prepared by successive RAFT polymerizations. In aqueous solution, the corresponding homopolymers PSPP and PNIPAM feature both upper and lower critical solution temperature (UCST and LCST) behavior, respectively. The diblock copolymer exhibits thermally induced "schizophrenic" aggregation behavior in aqueous solutions. Moreover, the ion sensitivity of the, cloud point of the zwitterionic PSPP block to both the ionic strength and the nature of the salt offers the possibility to create switchable systems which respond sensitively to changes of the temperature and of the electrolyte type and concentration. The diblock copolymer solutions in D2O are investigated by means of turbidimetry and small-angle neutron scattering (SANS) with respect to the phase behavior and the self-assembled structures in dependence on temperature and electrolyte content. Marked,A 2-fold thermoresponsive diblock copolymer PSPP430-b-PNIPAM(200) consisting of a zwitterionic polysulfobetaine (PSPP) block and a nonionic poly(N-isopropylacrylamide) (PNIPAM) block is prepared by successive RAFT polymerizations. In aqueous solution, the corresponding homopolymers PSPP and PNIPAM feature both upper and lower critical solution temperature (UCST and LCST) behavior, respectively. The diblock copolymer exhibits thermally induced "schizophrenic" aggregation behavior in aqueous solutions. Moreover, the ion sensitivity of the, cloud point of the zwitterionic PSPP block to both the ionic strength and the nature of the salt offers the possibility to create switchable systems which respond sensitively to changes of the temperature and of the electrolyte type and concentration. The diblock copolymer solutions in D2O are investigated by means of turbidimetry and small-angle neutron scattering (SANS) with respect to the phase behavior and the self-assembled structures in dependence on temperature and electrolyte content. Marked, differences of the aggregation below the UCST-type and above the LCST-type transition are observed. The addition of a small amount of NaBr (0.004 M) does not affect the overall behavior, and only the UCST-type transition and aggregate structures are slightly altered, reflecting the well-known ion sensitivity of the zwitterionic PSPP block.show moreshow less

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Author details:Natalya S. Vishnevetskaya, Viet HildebrandGND, Bart-Jan Niebuur, Isabelle Grillo, Sergey K. Filippov, Andre LaschewskyORCiDGND, Peter Müller-Buschbaum, Christine M. PapadakisORCiDGND
DOI:https://doi.org/10.1021/acs.macromol.6b01186
ISSN:0024-9297
ISSN:1520-5835
Title of parent work (English):Macromolecules : a publication of the American Chemical Society
Publisher:American Chemical Society
Place of publishing:Washington
Publication type:Article
Language:English
Year of first publication:2016
Publication year:2016
Release date:2020/03/22
Volume:49
Number of pages:14
First page:6655
Last Page:6668
Funding institution:Deutsche Forschungsgemeinschaft (DFG) [Pa771/14-1, Mu1487/17-1, La611/11-1]
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer review:Referiert
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