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Peer-reviewedCC BY 4.0Langmuir

Hydrogel-Controlled Electropolymerization of Polynorepinephrine through Confined Noncovalent Self-Assembly

5 affiliations
  1. 1Department of Analytical Chemistry, University of Gdańsk, Wita Stwosza 63, Gdańsk 80-308, Poland
  2. 2Photophysics Department, Institute of Fluid−Flow Machinery, Polish Academy of Sciences, Fiszera 14, Gdańsk 80-231, Poland
  3. 3Department of Corrosion and Electrochemistry, Faculty of Chemistry, Gdansk University of Technology, Narutowicza 11/12, Gdansk 80-233, Poland
  4. 4Faculty of Applied Physics and Mathematics, Institute of Nanotechnology and Materials Engineering, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland
  5. 5Department of Optoelectronics, Faculty of Electronics, Telecommunications and Electronics, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland

Abstract

Polymerization of monomers confined within hydrated polymer networks represents a promising strategy for engineering multifunctional, bioinspired interfaces. However, the role of the hydrogel environment in directing polymer growth and the resulting physicochemical properties remains poorly understood. Here, we demonstrate that chitosan hydrogels act as chemically programmed confined reaction environments that govern the electropolymerization of polynorepinephrine (PNOR). The polymer growth inside the matrix leads to hydrogel restructuring and hierarchical noncovalent self-assembly with only minor changes in the chemical composition of both components. The resulting composite exhibits permanently immobilized catechol/quinone redox centers, enhanced broadband optical absorption, and pronounced fluorescence quenching, demonstrating coupled electrochemical and photophysical functionality. Density functional theory reveals that electrostatic interactions are the main factor driving the composite formation with the supportive role of π–cation and hydrogen bonds. Moreover, oxidation of PNOR from the catechol to quinone state substantially modifies the electronic structure responsible for the observed optical response. The results establish hydrogel-controlled, confinement-driven electropolymerization as a general strategy for programming the electrochemical and optical properties of hydrogel interfaces through controlled molecular organization rather than extensive covalent modification.

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BibTeX
@article{smulka2026hydrogelcontrolled,
  title = {{Hydrogel-Controlled Electropolymerization of Polynorepinephrine through Confined Noncovalent Self-Assembly}},
  author = {Agata Smułka and Mirosław Sawczak and Łukasz Gaweł and Piotr Okoczuk and Tadeusz Ossowski and Adrian Olejnik},
  journal = {Langmuir},
  year = {2026},
  month = oct,
  doi = {10.1021/acs.langmuir.6c04478},
  url = {https://doi.org/10.1021/acs.langmuir.6c04478},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Hydrogel-Controlled Electropolymerization of Polynorepinephrine through Confined Noncovalent Self-Assembly
AU  - Agata Smułka
AU  - Mirosław Sawczak
AU  - Łukasz Gaweł
AU  - Piotr Okoczuk
AU  - Tadeusz Ossowski
AU  - Adrian Olejnik
PY  - 2026
DA  - 2026/10/19
JO  - Langmuir
DO  - 10.1021/acs.langmuir.6c04478
UR  - https://doi.org/10.1021/acs.langmuir.6c04478
AB  - Polymerization of monomers confined within hydrated polymer networks represents a promising strategy for engineering multifunctional, bioinspired interfaces. However, the role of the hydrogel environment in directing polymer growth and the resulting physicochemical properties remains poorly understood. Here, we demonstrate that chitosan hydrogels act as chemically programmed confined reaction environments that govern the electropolymerization of polynorepinephrine (PNOR). The polymer growth inside the matrix leads to hydrogel restructuring and hierarchical noncovalent self-assembly with only minor changes in the chemical composition of both components. The resulting composite exhibits permanently immobilized catechol/quinone redox centers, enhanced broadband optical absorption, and pronounced fluorescence quenching, demonstrating coupled electrochemical and photophysical functionality. Density functional theory reveals that electrostatic interactions are the main factor driving the composite formation with the supportive role of π–cation and hydrogen bonds. Moreover, oxidation of PNOR from the catechol to quinone state substantially modifies the electronic structure responsible for the observed optical response. The results establish hydrogel-controlled, confinement-driven electropolymerization as a general strategy for programming the electrochemical and optical properties of hydrogel interfaces through controlled molecular organization rather than extensive covalent modification.
SN  - 0743-7463
SN  - 1520-5827
ER  -