TY - JOUR

T1 - A polyacrylamide–chitosan semi-interpenetrating self-healing network with embedded Keplerate {Mo132} for pH-controlled release of Eu-fluorescent tags

AU - Grzhegorzhevskii, Kirill

AU - Rudakova, Ekaterina

AU - Krinochkin, Alexey

AU - Kopchuk, Dmitry

AU - Shtaitz, Yaroslav

AU - Adamova, Lidia

AU - Kim, Grigory

AU - Rusinova, Elena

AU - Shmidt, Alisa

N1 - Текст о финансировании This work was supported by the Russian Science Foundation: project No. 21-73-00311 in the part of the study of Keplerate interaction with polyacrylamide (chaotropic effect) and the Ministry of Science and the Higher Education of RF: Ref. # 075-15-2022-1118, dated 29 June 2022 in the part of the hydrogel preparation and synthesis of the fluorescent tag. Analytical studies were carried out using equipment of the Center for Joint Use “Spectroscopy and Analysis of Organic Compounds” at the Postovsky Institute of Organic Synthesis of the Russian Academy of Sciences (Ural Branch).

PY - 2023

Y1 - 2023

N2 - Delivery systems with pH-controlled release of drugs and fluorescent tags meets the challenge of rational design of functional hydrogel structures. Here, we report on a simple and versatile approach to fabrication of biocompatible hydrogels with a pH-dependent release of loaded molecules by harnessing properties of the nontoxic polyoxometalate (POM) Keplerate {Mo132}. Due to the template effect of the nanoscale POM, molecular complementarity between photo-polymerized polyacrylamide (PAAm) and low molecular weight chitosan (Chit) is realized through forming a homogeneous, self-healing, semi-interpenetrating polymer network (semi-IPN). We characterize the composition of the semi-IPN with IR and Raman spectroscopy, while also affirming POM's structural integrity within the system. Swelling kinetic experiments suggest that varying both cross-linking frequency via imine bonds and the molecular weight of PAAm (0.67-11.4 MDa) significantly alters the hydrogel's structure and its swelling behavior: mechanical properties and pH-sensitive response. The latter one is governed through electrostatic linkages between Chit and negatively charged {Mo132}. The optimized hydrogel formulation - PAAm@Chit@Mo132 - was chosen to evaluate parameters needed for the controlled release of the fluorescent tag (EuIIIL complex, L= 4-(2-fluorophenyl)-[2,2′-bipyridin] derivative) into a series of aqueous solutions (water, 0.97% NaCl, and PBS) at 25 °C and 37 °C. We found a cumulative release of the loaded EuIIIL tag (serving as the model drug) from the PAAm@Chit@Mo132 hydrogel to be as high as 75% and assessed how the hydrogel composition and the nature of the chemical environment affect that number. These results make this hydrogel system a promising platform for the rational design of injectable hydrogel-based drug-delivery systems. © 2023 The Royal Society of Chemistry.

AB - Delivery systems with pH-controlled release of drugs and fluorescent tags meets the challenge of rational design of functional hydrogel structures. Here, we report on a simple and versatile approach to fabrication of biocompatible hydrogels with a pH-dependent release of loaded molecules by harnessing properties of the nontoxic polyoxometalate (POM) Keplerate {Mo132}. Due to the template effect of the nanoscale POM, molecular complementarity between photo-polymerized polyacrylamide (PAAm) and low molecular weight chitosan (Chit) is realized through forming a homogeneous, self-healing, semi-interpenetrating polymer network (semi-IPN). We characterize the composition of the semi-IPN with IR and Raman spectroscopy, while also affirming POM's structural integrity within the system. Swelling kinetic experiments suggest that varying both cross-linking frequency via imine bonds and the molecular weight of PAAm (0.67-11.4 MDa) significantly alters the hydrogel's structure and its swelling behavior: mechanical properties and pH-sensitive response. The latter one is governed through electrostatic linkages between Chit and negatively charged {Mo132}. The optimized hydrogel formulation - PAAm@Chit@Mo132 - was chosen to evaluate parameters needed for the controlled release of the fluorescent tag (EuIIIL complex, L= 4-(2-fluorophenyl)-[2,2′-bipyridin] derivative) into a series of aqueous solutions (water, 0.97% NaCl, and PBS) at 25 °C and 37 °C. We found a cumulative release of the loaded EuIIIL tag (serving as the model drug) from the PAAm@Chit@Mo132 hydrogel to be as high as 75% and assessed how the hydrogel composition and the nature of the chemical environment affect that number. These results make this hydrogel system a promising platform for the rational design of injectable hydrogel-based drug-delivery systems. © 2023 The Royal Society of Chemistry.

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U2 - 10.1039/D3NJ03041E

DO - 10.1039/D3NJ03041E

M3 - Article

VL - 47

SP - 17007

EP - 17019

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 36

ER -