Mechanoresponsive Metal-Organic Cage-Crosslinked Polymer Hydrogels

被引：10
作者：
Kueng, Robin [1 ]
Germann, Anne [1 ]
Kruesmann, Marcel [2 ]
Niggemann, Louisa P. [3 ,4 ]
Meisner, Jan [5 ]
Karg, Matthias [2 ]
Goestl, Robert [3 ]
Schmidt, Bernd M. [1 ]
机构：
[1] Heinrich Heine Univ Dusseldorf, Inst Organ Chem & Macromol Chem, Univ Str 1, D-40225 Dusseldorf, Germany
[2] Heinrich Heine Univ Dusseldorf, Inst Phys Chem Colloids & Nanoopt 1, Univ Str 1, D-40225 Dusseldorf, Germany
[3] Leibniz Inst Interact Mat, DWI, Forckenbeckstr 50, D-52056 Aachen, Germany
[4] Rhein Westfal TH Aachen, Inst Tech & Macromol Chem, Worringerweg 1, D-52074 Aachen, Germany
[5] Heinrich Heine Univ Dusseldorf, Inst Phys Chem, Univ Str 1, D-40225 Dusseldorf, Germany
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2023年 / 29卷 / 18期
关键词：
host-guest systems; hydrogels; mechanochemistry; palladium; supramolecular chemistry; MECHANOCHEMICAL ACTIVATION; COMPLEXES; DYNAMICS; STATE; GELS;
D O I：
10.1002/chem.202300079
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report the formation of metal-organic cage-crosslinked polymer hydrogels. To enable crosslinking of the cages and subsequent network formation, we used homodifunctionalized poly(ethylene glycol) (PEG) chains terminally substituted with bipyridines as ligands for the Pd6L4 corners. The encapsulation of guest molecules into supramolecular self-assembled metal-organic cage-crosslinked hydrogels, as well as ultrasound-induced disassembly of the cages with release of their cargo, is presented in addition to their characterization by nuclear magnetic resonance (NMR) techniques, rheology, and comprehensive small-angle X-ray scattering (SAXS) experiments. The constrained geometries simulating external force (CoGEF) method and barriers using a force-modified potential energy surface (FMPES) suggest that the cage-opening mechanism starts with the dissociation of one pyridine ligand at around 0.5 nN. We show the efficient sonochemical activation of the hydrogels HG(3)(-6), increasing the non-covalent guest-loading of completely unmodified drugs available for release by a factor of ten in comparison to non-crosslinked, star-shaped assemblies in solution.
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页数：7
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