Phosphates Induced H-Type or J-Type Aggregation of Cationic Porphyrins with Varied Side Chains

Date
2023-05-16
Authors
Li, Zhiliang
Zeman, Charles J.
Valandro, Silvano
Bantang, Jose Paolo O.
Schanze, Kirk S.
Journal Title
Journal ISSN
Volume Title
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Abstract

Non-covalent interactions have been extensively used to fabricate nanoscale architectures in supramolecular chemistry. However, the biomimetic self-assembly of diverse nanostructures in aqueous solution with reversibility induced by different important biomolecules remains a challenge. Here, we report the synthesis and aqueous self-assembly of two chiral cationic porphyrins substituted with different types of side chains (branched or linear). Helical H-aggregates are induced by pyrophosphate (PPi) as indicated by circular dichroism (CD) measurement, while J-aggregates are formed with adenosine triphosphate (ATP) for the two porphyrins. By modifying the peripheral side chains from linear to a branched structure, more pronounced H- or J-type aggregation was promoted through the interactions between cationic porphyrins and the biological phosphate ions. Moreover, the phosphate-induced self-assembly of the cationic porphyrins is reversible in the presence of the enzyme alkaline phosphatase (ALP) and repeated addition of phosphates.

Description
Keywords
aggregation hydrolysis, phosphates, porphyrins, self-assembly
Citation
Molecules 28 (10): 4115 (2023)
Department
Chemistry