Well‐defined diblock copolymers possessing fluorescent and metal chelating functionalities as novel macromolecular sensors for amines and metal ions

Abstract

The amino‐ and metal‐ion sensing capability of a novel type of well‐defined block copolymers based on 9‐anthrylmethyl methacrylate (AnMMA; hydrophobic, fluorescent) and 2‐(acetoacetoxy)ethyl methacrylate (AEMA; hydrophobic, metal chelating) has been investigated in organic media. AEMAx‐b‐AnMMAy diblock copolymers were prepared for the first time using reversible addition‐fragmentation chain transfer (RAFT) polymerization. All polymers were characterized in terms of molecular weights, polydispersity indices and compositions by size exclusion chromatography and 1H NMR spectroscopy, respectively. The glass transition (Tg) temperatures of the AEMAx and AnMMAx homopolymers and the AEMAx‐b‐AnMMAy diblock copolymers were determined using differential scanning calorimetry. These systems were evaluated toward their ability to act as effective dual chemosensors (i.e., amino‐ and metal‐ion sensors) in an organic solvent (chloroform). More precisely, the fluorescence intensity of both the AnMMAx homopolymers and the AnMMAx‐b‐AEMAy diblock copolymers in solution exhibited a significant decrease in the presence of triethylamine. Moreover, the presence of iron (III) cations were also found to significantly affect the fluorescence signal of the anthracene moieties when those were combined in a block copolymer structure with the AEMA units, due to complex formation occurring between the β‐ketoester groups of the AEMAx segment and the cations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Controlled radical polymerization of anthracene-containing methacrylate copolymers for stimuli-responsive materials

“…Well‐defined PAMMA homopolymers were successfully synthesized following typical RAFT methodologies (Scheme ), and RAFT polymerization of AMMA was previously reported by Krasia‐Christoforou et al However, detailed kinetic studies of the polymerization were not reported, although the resulting polymer had relatively narrow PDI. Table summarizes the conditions and the results of conventional free radical polymerization and RAFT polymerization of AMMA.…”

Cost‐Effective Polymethacrylate‐Based Electrospun Fluorescent Fibers toward Ammonia Sensing

“…The PMMA homopolymer ( M w ≈ 350 000) was purchased from Sigma‐Aldrich and used as received from the manufacturer. The poly(9‐anthrylmethyl methacrylate) ( M n = 27 900 g mol −1 , where M n is the number average molecular weight determined by size exclusion chromatography using PMMA calibration standards) was in house synthesized by RAFT controlled radical polymerization according to our previous publication . Tetrahydrofuran (THF, extra pure), that was the solvent of choice for the preparation of the polymer solutions to be electrospun, was purchased from Scharlau.…”

“…We have previously reported on the synthesis of well‐defined methacrylate‐based homopolymers and block copolymers containing anthracene side‐chains functionalities. These materials were prepared by reversible addition–fragmentation chain transfer (RAFT) controlled radical polymerization and they were evaluated as dual fluorescent chemosensors for amines and transmission metal ions in solution …”

Vesicular and micellar self‐assembly of stimuli‐responsive poly(N‐isopropyl acrylamide‐b‐9‐anthracene methyl methacrylate) amphiphilic diblock copolymers

“…Along with this, anthracene's functionality is of great interest when it is used as a substrate material for crosslinking in reversible network polymeric materials because of its thermally reversible Diels–Alder [4 + 2] cycloadditions and reversible photodimerization, depending on the irradiated λ . Poly(anthracene methyl methacrylate) is a polycyclic hydrocarbon; because of its properties and interactions with other polymers and drug materials, various research teams have synthesized its polymers with conventional and controlled or living radical polymerization techniques and studied their properties for photoluminescent films, photoresists, and chemiluminescent fluorophores …”

“…To date, a limited number of reports have been published on well‐defined (co)polymer synthesis based on 9‐anthracene methyl methacrylate (AnMMA) and their photoresponsiveness . To the best of our knowledge, no report has been published on the synthesis of poly( N ‐isopropyl acrylamide‐ b ‐9‐anthracene methyl methacrylate) [poly(NIPAAm‐ b ‐AnMMA)] SRABCs with various hydrophobic poly(9‐anthracene methyl methacrylate) [poly(AnMMA)] block lengths through RAFT polymerization with poly(NIPAAm) as a macro‐RAFT agent and their self‐assembly in solution.…”