Multi-stimuli-responsive copolymers based on 1-pyrenol polyphotoacids

Kaberov, Leonid I.; Sittig, Maria; Chettri, Avinash; Ibrahim, Abdelrahman; Dietzek‐Ivanšić, Benjamin; Schacher, Felix H.

doi:10.1039/d3py00537b

Cited by 1 publication

(5 citation statements)

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“…The steady-state absorption and emission spectrum of HPSAPMA are taken from a previous publication. [1] band centered at 475 nm. Similarly, at pH 11, the absorption and emission spectra of I(a-d) show broad bands with a maximum at 455 and 525 nm, respectively.…”

Section: Steady-state Absorption and Emission Spectroscopy Of Hpsapma...mentioning

confidence: 99%

“…Light as a trigger to introduce amphiphilicity changes in a polymer by integrating photoacids into the polymer side chains was introduced recently. [1] The ability of these polymeric photoacids to respond to light -and, in addition, to other external stimuli such as, pH and temperature -renders them a promising platform to design environmentally responsive materials. [1] While preliminary studies report excited-state pro-ton transfer (ESPT) in these polymers, [1] the effect of the local environment on the intermolecular proton transfer reaction involving the polymers is yet to be explored.…”

Section: Introductionmentioning

confidence: 99%

“…In a polymeric photoacid (see Scheme 1 for a schematic depiction), the light-triggered release of a proton in the immediate environment of the photoacidic side chain induces changes in the polymer amphiphilicity which in-turn changes its chain folding. [1] Thus, there is an intricate interplay between the local protonation state of the photoacid side chains, their local environment and their proton transfer ability. [2] It is plausible to assume an interdependence of the polymer morphology, controlled by the amphiphilicity, and the ability of the polymer to undergo further proton transfer.…”

Section: Introductionmentioning

confidence: 99%

“…II(a-c) contains chemically similar monomeric units and a comparable degree of polymerization. Adding to our previous study, which focused on polyethylene glycol (PEG) systems, [1] this contribution targets the properties of poly(2-oxazoline)s as they can be obtained in higher yields and are frequently used in biomedical applications. [4] By investigating polyoxazoline-based macromolecular photoacids with different degrees of amphiphilicity we show that proton transfer is restricted in the polymers with the highest hydrophobicity, likely due to a reduced accessibility of the photoacid units to water molecules.…”

Section: Introductionmentioning

confidence: 99%

“…All experiments are performed in non-inert condition. The steady-state absorption and emission spectrum of HPSAPMA are taken from a previous publication [1].…”

mentioning

confidence: 99%

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Poly(2‐Oxazoline) Amphiphilicity Tunes the Excited‐State Proton Transfer of Pyrenol‐Based Polyphotoacids

Chettri,

Kaberov,

Klosterhalfen

et al. 2024

Chemistry A European J

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The ability of light to change the properties of light‐responsive polymers opens avenues for targeted release of cargo with a high degree of spatial and temporal control. Recently, we established photoacid polymers as light‐switchable macromolecular amphiphiles. In these systems, light‐induced excited‐state proton transfer (ESPT) causes changes in amphilicity. However, as the intermolecular process itself critically depends on the local environment of the photoacid unit within the polymer, the overall amphiphilicity directly influences ESPT. Thus, understanding the impact of the local environment on the photophysics of photoacidic side chains is key to material design. In this contribution we address both thermodynamic and kinetic aspects of ESPT in oxazoline‐based amphiphilic polymers with pyrenol‐based photoacid side chains. We will compare the effect of polymer design, i.e. statistical and block arrangements, i.e. in poly[(2‐ethyl‐2‐oxazoline)‐co‐(1‐(6/8‐hydroxyperene)sulphonylaziridine)] and poly(2‐ethyl‐2‐oxazoline)‐block‐poly[(2‐ethyl‐2‐oxazoline)‐co‐(2‐(3‐(6‐hydroxypyrene)sulphona mide)propyl‐2‐oxazoline), on the intermolecular proton transfer reaction by combining steady‐state and time‐resolved absorption and emission spectroscopy. ESPT appears more prominent in the statistical copolymer compared to a block copolymer with overall similar pyrenol loading. We hypothesize that the difference is due to different local chain arrangements adopted by the polymers in the two cases.

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Section: Steady-state Absorption and Emission Spectroscopy Of Hpsapma...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…All experiments are performed in non-inert condition. The steady-state absorption and emission spectrum of HPSAPMA are taken from a previous publication [1].…”

mentioning

confidence: 99%

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