Thiophene α-Chain-End-Functionalized Oligo(2-methyl-2-oxazoline) as Precursor Amphiphilic Macromonomer for Grafted Conjugated Oligomers/Polymers and as a Multifunctional Material with Relevant Properties for Biomedical Applications


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Bendrea A., Cianga L., Ailiesei G., Çolak D., Popescu I., Cianga I.

International Journal of Molecular Sciences, vol.23, no.14, 2022 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 23 Issue: 14
  • Publication Date: 2022
  • Doi Number: 10.3390/ijms23147495
  • Journal Name: International Journal of Molecular Sciences
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, CAB Abstracts, EMBASE, Food Science & Technology Abstracts, MEDLINE, Veterinary Science Database, Directory of Open Access Journals
  • Keywords: electroactive macromonomers, oligo(2-methyl-2-oxazoline), amphiphiles, clusteroluminescence, polythiophenes, WELL-DEFINED POLY(EPSILON-CAPROLACTONE), SOLID-STATE POLYMERIZATION, SELF-ASSEMBLY BEHAVIOR, SIDE-CHAINS, CONDUCTING POLYMERS, POLY(METHYL METHACRYLATE), BLOCK-COPOLYMERS, POLYSTYRENE, POLYTHIOPHENE, WATER
  • Istanbul Technical University Affiliated: Yes

Abstract

© 2022 by the authors. Licensee MDPI, Basel, Switzerland.Because the combination of π-conjugated polymers with biocompatible synthetic counterparts leads to the development of bio-relevant functional materials, this paper reports a new oligo(2methyl-2-oxazoline) (OMeOx)-containing thiophene macromonomer, denoted Th-OMeOx. It can be used as a reactive precursor for synthesis of a polymerizable 2,2’-3-OMeOx-substituted bithiophene by Suzuki coupling. Also a grafted polythiophene amphiphile with OMeOx side chains was synthesized by its self-acid-assisted polymerization (SAAP) in bulk. The results showed that Th-OMeOx is not only a reactive intermediate but also a versatile functional material in itself. This is due to the presence of 2-bromo-substituted thiophene and ω-hydroxyl functional end-groups, and due to the multiple functionalities encoded in its structure (photosensitivity, water self-dispersibility, self-assembling capacity). Thus, analysis of its behavior in solvents of different selectivities revealed that Th-OMeOx forms self-assembled structures (micelles or vesicles) by “direct dissolution”.Unexpectedly, by exciting the Th-OMeOx micelles formed in water with λabs of the OMeOx repeating units, the intensity of fluorescence emission varied in a concentration-dependent manner.These self-assembled structures showed excitation-dependent luminescence as well. Attributed to the clusteroluminescence phenomenon due to the aggregation and through space interactions of electron-rich groups in nonconjugated, non-aromatic OMeOx, this behavior certifies that polypeptides mimic the character of Th-OMeOx as a non-conventional intrinsic luminescent material.