Gillhuber Sebastian, Holloway Joshua O, Mundsinger Kai, Kammerer Jochen A, Harmer Jeffrey R, Frisch Hendrik, Barner-Kowollik Christopher, Roesky Peter W
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT) Engesserstraße 15 76131 Karlsruhe Germany
School of Chemistry and Physics, Queensland University of Technology (QUT) 2 George Street 4000 Brisbane QLD Australia
Chem Sci. 2024 Aug 29;15(37):15280-90. doi: 10.1039/d4sc03079f.
We herein pioneer the visible light ( = 410 nm) mediated flow synthesis of catalytically active single-chain nanoparticles (SCNPs). Our design approach is based on a copolymer of poly(ethylene glycol) methyl ether methacrylate and a photocleavable 2-((((2-nitrobenzyl)oxy)carbonyl)amino)ethyl methacrylate monomer which can liberate amine groups upon visible light irradiation, allowing for single-chain collapse the complexation of Cu(ii) ions. We initially demonstrate the successful applicability of our design approach for the batch photochemical synthesis of Cu(ii) SCNPs and transfer the concept to photoflow conditions, enabling, for the first time, the continuous production of functional SCNPs. Critically, we explore their ability to function as a photocatalyst for the cleavage of carbon-carbon single and double bonds on the examples of xanthene-9-carboxylic acid and oleic acid, demonstrating the advantageous effect SCNPs can provide over analogous small molecule catalysts.
我们在此开创了可见光（ = 410纳米）介导的催化活性单链纳米颗粒（SCNP）的流动合成方法。我们的设计方法基于聚（乙二醇）甲基醚甲基丙烯酸酯与可光裂解的2-（（（（2-硝基苄基）氧基）羰基）氨基）乙基甲基丙烯酸酯单体的共聚物，该单体在可见光照射下可释放胺基，从而实现单链塌缩以及铜（II）离子的络合。我们首先证明了我们的设计方法在铜（II）SCNP的间歇式光化学合成中的成功适用性，并将该概念转移到光流条件下，首次实现了功能性SCNP的连续生产。至关重要的是，我们以呫吨-9-羧酸和油酸为例，探索了它们作为光催化剂裂解碳-碳单键和双键的能力，证明了SCNP相对于类似小分子催化剂可提供的有利效果。
