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Phase Separation and pH-Dependent Behavior of Four-Arm Star-Shaped Porphyrin-PNIPAM4 Conjugates

Velychkivska, Nadiia, Sedláček, Ondřej, Shatan, Anastasiia B., Spasovová, Monika, Filippov, Sergey K., Chahal, Mandeep Kaur, Janisova, Larisa, Brus, Jiří, Hanyková, Lenka, Hill, Jonathan P., and others. (2022) Phase Separation and pH-Dependent Behavior of Four-Arm Star-Shaped Porphyrin-PNIPAM4 Conjugates. Macromolecules, 55 (6). pp. 2109-2122. ISSN 0024-9297. E-ISSN 1520-5835. (doi:10.1021/acs.macromol.1c02188) (Access to this publication is currently restricted. You may be able to access a copy if URLs are provided) (KAR id:103658)

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Star-shaped porphyrin-PNIPAM4 (PP) conjugates having four PNIPAM arms connected to a central tetraphenylporphyrin unit were synthesized using reversible addition–fragmentation chain-transfer polymerization. Temperature-induced phase-separation behavior of the conjugates was investigated, and the lower critical solution temperature (type II)–composition phase diagram was constructed using Flory–Huggins theory. Interestingly, in contrast to PNIPAM homopolymers, the shorter PNIPAM arms of PP conjugates lead to a lower phase-separation temperature (Tp). The concentration dependency of the size of the cooperative domain was also determined. Below Tp, experimental data indicate that PP behaves as a 1D supramolecular polymer with a concentration-dependent length, while above Tp, PP globules adopt a larger spherical shape. Various temperature–pH reversible and irreversible interdependencies (“cross-effects”) between phase separation and protonation were observed. The PP conjugates represent a dual temperature–pH-responsive model system possessing various aggregated states, making them candidates for visual indicators, pH or temperature sensors, or singlet oxygen generators for biomedical applications.

Item Type: Article
DOI/Identification number: 10.1021/acs.macromol.1c02188
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
Depositing User: Mandeep Kaur Chahal
Date Deposited: 09 Nov 2023 12:00 UTC
Last Modified: 12 Mar 2024 14:23 UTC
Resource URI: (The current URI for this page, for reference purposes)

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Chahal, Mandeep Kaur.

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