Redox-sensitive ferrocene functionalised double cross-linked supramolecular hydrogels

Liubimtsev, Nikolai; Kösterke, Tom; Che, Yunjiao; Appelhans, Dietmar; Gaitzsch, Jens; Voit, Brigitte

doi:10.1039/d1py01211h

Cited by 11 publications

(20 citation statements)

References 38 publications

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“…Furthermore, ferrocene units have been proven to be very useful for host–guest interactions with cyclodextrins for drug delivery . Cyclodextrin is a relatively low cost, biocompatible, biodegradable, and highly explored material for drug delivery, medical devices, biosensor, tissue engineering, and bioimaging. , …”

Section: Introductionmentioning

confidence: 99%

Redox- and pH-Responsive Polymersomes with Ferrocene Moieties Exhibiting Peroxidase-like, Chemoenzymatic Activity and H₂O₂-Responsive Release Behavior

et al. 2022

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The development of compartments for the design of cascade reactions in a local space requires a selective spatiotemporal control. The combination of enzyme-loaded polymersomes with enzymelike units shows a great potential in further refining the diffusion barrier and the type of reactions in nanoreactors. Herein, pH-responsive and ferrocene-containing block copolymers were synthesized to realize pH-stable and multiresponsive polymersomes. Permeable membrane, peroxidase-like behavior induced by the redox-responsive ferrocene moieties and release properties were validated using cyclovoltammetry, dye TMB assay, and rupture of host–guest interactions with β-cyclodextrin, respectively. Due to the incorporation of different block copolymers, the membrane permeability of glucose oxidase-loaded polymersomes was changed by increasing extracellular glucose concentration and in TMB assay, allowing for the chemoenzymatic cascade reaction. This study presents a potent synthetic, multiresponsive nanoreactor platform with tunable (e.g., redox-responsive) membrane properties for potential application in therapeutics.

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Section: Introductionmentioning

confidence: 99%

Redox- and pH-Responsive Polymersomes with Ferrocene Moieties Exhibiting Peroxidase-like, Chemoenzymatic Activity and H₂O₂-Responsive Release Behavior

et al. 2022

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“…Similar synthesis steps of PMOXA macromonomers have been described in detail in our previous studies. [33,36] Here, two different routes were chosen. CD-PMOXA was obtained from PMOXA chains from an initiator bearing an alkyne (Alk) group and VBP as a polymerizable end group.…”

Section: Synthesis and Analysis Of Polymersmentioning

confidence: 99%

“…Especially the latter can also be transferred back to our previously published systems based on 𝛽-CD/adamantane and 𝛽-CD/ferrocene. [33,36] The double crosslinked supramolecular 𝛼-CD/Azo hydrogel network hence showcases significant, reproducible and reversible changes in its properties through non-invasive changes induced by irradiation with UV and VIS light.…”

Section: Hydrogel Synthesis and Characterisationmentioning

confidence: 99%

“…They differed in amount of covalent crosslinker (0.75 mol% "a" or 1 mol% "b") and in the PMOXA chain length (CD-33+Azo-31 or CD-43+Azo-40) (Table 2), as the mechanical properties of hydrogels were expected to depend on their composition. [33,36] For example, GH-40a was a grafted hydrogel with functional PMOXA macromonomers of ≈40 (i.e., DP ≈ 83 for CD-43 and Azo-40) and 0.75 mol% of permanent cross-linker. The amount of covalent cross-linking points was increased for GH-40b (1 mol%) and the length of the PMOXA chain was reduced from DP ≈ 83 to DP ≈ 64 for GH-31a (CD-33 and Azo-31).…”

Section: Hydrogel Synthesis and Characterisationmentioning

confidence: 99%

“…Until now, such double cross-linked supramolecular hydrogels were either not suitable for several switching cycles like the 𝛽-CD/adamantane system or relied on an invasive chemical change like the 𝛽-CD/ferrocene supramolecular complex. [36,37] Supramolecular hydrogels based on 𝛼-CD/Azo complex; however, would circumvent both issues. The system only forms a complex with 𝛼-CD in the trans-from of azobenzene and not in the cis-form, thus, a reversible cleavage and formation of the host-guest complex is possible.…”

Section: Introductionmentioning

confidence: 99%

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Photoresponsive Double Cross‐Linked Supramolecular Hydrogels Based on A‐Cyclodextrin/Azobenzene Host–Guest Complex

Liubimtsev

Zagradska-Paromova

Appelhans

et al. 2022

Macro Chemistry & Physics

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Smart hydrogels are interesting materials as they can change their dimensions upon an external trigger. Herein, a photoresponsive double cross-linked hydrogel system based on polyacrylamide (AAm) with grafted poly(2-methyl-2-oxazoline) (PMOXA) chains with a 𝜶-cyclodextrin/azobenzene host-guest complex is present. Switching azobenzene from the trans to the cis-conformation through irradiation with UV light breaks the complex reversibly. Well-defined PMOXA macromonomers have been synthesized and functionalized with the respective host and guest functionalities as well as double bonds for the incorporation into the polymer network as grafted side chains. The chemical structure of the macromonomers and the complex is confirmed by 1 H NMR, 2D NOESY NMR, GPC, and UV-VIS measurements. Hydrogels with different ratios of permanent and photoresponsive cross-linkers as well as different chain lengths of the PMOXA macromonomers are analyzed toward differences in their swelling/deswelling and elastic properties. Successive irradiation of supramolecular hydrogels with UV and VIS light allowed for a repeated swelling and de-swelling of the hydrogels. This system is studied at both macro and micro scales, showing similar swelling tendencies. The tuned properties of photoresponsive double cross-linked hydrogel makes this system a promising tool for various applications, for example, as in situ controllable valves in microfluidic flow cells.

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Supramolecular nanomedicines based on host–guest interactions of cyclodextrins

Tong

Zhou

et al. 2023

Exploration

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In the biomedical and pharmaceutical fields, cyclodextrin (CD) is undoubtedly one of the most frequently used macrocyclic compounds as the host molecule because it has good biocompatibility and can increase the solubility, bioavailability, and stability of hydrophobic drug guests. In this review, we generalized the unique properties of CDs, CD‐related supramolecular nanocarriers, supramolecular controlled release systems, and targeting systems based on CDs, and introduced the paradigms of these nanomedicines. In addition, we also discussed the prospects and challenges of CD‐based supramolecular nanomedicines to facilitate the development and clinical translation of these nanomedicines.

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Redox-sensitive ferrocene functionalised double cross-linked supramolecular hydrogels

Abstract: Responsive double cross-linked hydrogels have proven to be a powerful approach to create smart polymer networks, but unfold an even greater potential if combined with supramolecular chemistry. A novel redox-sensitive...

Cited by 11 publications

References 38 publications

Redox- and pH-Responsive Polymersomes with Ferrocene Moieties Exhibiting Peroxidase-like, Chemoenzymatic Activity and H₂O₂-Responsive Release Behavior

Redox- and pH-Responsive Polymersomes with Ferrocene Moieties Exhibiting Peroxidase-like, Chemoenzymatic Activity and H₂O₂-Responsive Release Behavior

Photoresponsive Double Cross‐Linked Supramolecular Hydrogels Based on A‐Cyclodextrin/Azobenzene Host–Guest Complex

Supramolecular nanomedicines based on host–guest interactions of cyclodextrins

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Redox-sensitive ferrocene functionalised double cross-linked supramolecular hydrogels

Abstract: Responsive double cross-linked hydrogels have proven to be a powerful approach to create smart polymer networks, but unfold an even greater potential if combined with supramolecular chemistry. A novel redox-sensitive...

Cited by 11 publications

References 38 publications

Redox- and pH-Responsive Polymersomes with Ferrocene Moieties Exhibiting Peroxidase-like, Chemoenzymatic Activity and H2O2-Responsive Release Behavior

Redox- and pH-Responsive Polymersomes with Ferrocene Moieties Exhibiting Peroxidase-like, Chemoenzymatic Activity and H2O2-Responsive Release Behavior

Photoresponsive Double Cross‐Linked Supramolecular Hydrogels Based on A‐Cyclodextrin/Azobenzene Host–Guest Complex

Supramolecular nanomedicines based on host–guest interactions of cyclodextrins

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Product

Resources

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Redox- and pH-Responsive Polymersomes with Ferrocene Moieties Exhibiting Peroxidase-like, Chemoenzymatic Activity and H₂O₂-Responsive Release Behavior

Redox- and pH-Responsive Polymersomes with Ferrocene Moieties Exhibiting Peroxidase-like, Chemoenzymatic Activity and H₂O₂-Responsive Release Behavior