Fantoni Antonella, Salvadori Alice, Ovsianikov Aleksandr, Liska Robert, Baudis Stefan
Institute of Applied Synthetic Chemistry, Technische Universität Wien, Getreidemarkt 9, 1060 Vienna, Austria.
Austrian Cluster for Tissue Regeneration, 1200 Vienna, Austria.
Biomacromolecules. 2025 Jul 14;26(7):4084-4094. doi: 10.1021/acs.biomac.5c00062. Epub 2025 May 8.
Photolabile hydrogels have gained tremendous interest for a wide range of applications in materials and life sciences. Usually, photodegradability is introduced via chromophores and labile bonds, making such materials intrinsically light sensitive. In recent years, disulfide bonds have emerged as an innovative alternative, as they can be selectively cleaved in the presence of (photo)generated radicals. However, such materials suffer from limited network stability and high swelling as a result of thiol-disulfide metathesis reactions. Herein, we present two strategies to counteract such phenomena by network stabilization either via physical or chemical incorporation of (un)modified gelatin macromers to norbornene-modified poly(vinyl alcohol) networks. Photolabile behavior was introduced by a simple disulfide-containing dithiol cross-linker. Tunable material properties were investigated by means of in situ photorheology, in vitro swelling, and degradation experiments. Finally, we demonstrate an innovative method for localized disulfide cleavage via two-photon micropatterning.
光不稳定水凝胶在材料科学和生命科学的广泛应用中引起了极大的关注。通常，光降解性是通过发色团和不稳定键引入的，这使得此类材料本质上对光敏感。近年来，二硫键作为一种创新的替代方案出现了，因为它们可以在（光）产生的自由基存在下被选择性地裂解。然而，由于硫醇-二硫键复分解反应，此类材料存在网络稳定性有限和高溶胀的问题。在此，我们提出了两种策略来对抗这些现象，即通过将（未）改性的明胶大分子单体物理或化学掺入降冰片烯改性的聚乙烯醇网络中来实现网络稳定。通过一种简单的含二硫键的二硫醇交联剂引入光不稳定行为。通过原位光流变学、体外溶胀和降解实验研究了可调的材料性能。最后，我们展示了一种通过双光子微图案化进行局部二硫键裂解的创新方法。
