Loch Alex S, Mikhail Ibram, Bianco Simona, Ghosh Dipankar, Sonani Ravi R, Chechik Victor, Vassalli Massimo, Egelman Edward H, Smith Andrew J, Adams Dave J
School of Chemistry, University of Glasgow, Glasgow G12 8QQ, U.K.
Department of Biochemistry and Molecular Genetics, University of Virginia, Charlottesville, Virginia 22903, United States.
ACS Appl Mater Interfaces. 2025 May 21;17(20):30297-30305. doi: 10.1021/acsami.5c03506. Epub 2025 May 12.
Benzophenone-based materials remain widely used as photoinitiators for ultraviolet light-induced free radical polymerizations. Traditionally, polymerization is spatially controlled using top-down techniques such as photomasks, which produce well-defined polymeric films. In contrast, we present an alternative method for controlling polymerization by employing supramolecular materials to localize the photoinitiator. This approach uses benzophenone-functionalized dipeptides that are specifically tuned to enable supramolecular gel noodle formation, which act as structural templates. We show that polymerization of acrylate monomers around the gel noodles can increase the Young's modulus by up to 2 orders of magnitude and produce mechanically robust structures that can be handled. The self-assembly of the supramolecular photoinitiators is also explored using viscosity and SAXS measurements, providing an understanding of why only successfully forms gel noodles. Our method offers a simple yet effective technique for localizing polymerization, enabling fine-tuning of mechanical properties and the fabrication of intricate designs such as hollow-core structures.
基于二苯甲酮的材料仍然广泛用作紫外线诱导自由基聚合的光引发剂。传统上，聚合反应是通过光掩模等自上而下的技术进行空间控制的，这些技术可以制备出定义明确的聚合物薄膜。相比之下，我们提出了一种通过使用超分子材料来定位光引发剂从而控制聚合反应的替代方法。这种方法使用了经过特殊调整的二苯甲酮功能化二肽，以形成超分子凝胶面条，这些凝胶面条充当结构模板。我们表明，围绕凝胶面条的丙烯酸酯单体聚合可以使杨氏模量提高多达2个数量级，并产生可处理的机械坚固结构。还使用粘度和小角X射线散射测量来探索超分子光引发剂的自组装，从而理解为什么只有 成功形成凝胶面条。我们的方法提供了一种简单而有效的定位聚合技术，能够微调机械性能并制造复杂的设计，如中空结构。
