Sciortino Flavien, Rydzek Gaulthier, Grasset Fabien, Kahn Myrtil L, Hill Jonathan P, Chevance Soizic, Gauffre Fabienne, Ariga Katsuhiko
University of Rennes, Centre National de la Recherche Scientifique (CNRS, France), Institut des Sciences Chimiques de Rennes (ISCR), UMR 6226, F-35000 Rennes, France.
Phys Chem Chem Phys. 2018 Jan 24;20(4):2761-2770. doi: 10.1039/c7cp07506e.
Hollow nanocapsules (named Hybridosomes®) possessing a polymer/nanoparticle shell were used to covalently construct hybrid films in a one-pot fashion. The alkyne bearing organic/inorganic Hybridosomes® were reticulated with azide bearing homobifunctional polyethyleneglycol (PEG) linkers, by using an electro-click reaction on F-SnO (FTO) electrodes. The coatings were obtained by promoting the Cu(i)-catalyzed click reaction between alkyne and azide moieties in the vicinity of the electrode by the electrochemical generation of Cu(i) ions. The physicochemical properties of the covalently reticulated hybrid films obtained were studied by SEM, AFM, UV-vis and fluorescence spectroscopy. The one-pot covalent click reaction between the nanocapsules and the PEG linkers in the film did not affect the desirable features of the Hybridosomes® i.e. their hollow nanostructure their chemical versatility and their pH-sensitivity. Consequently, both the composition and the cargo-loading of the Hybridosomes® films could be tuned, demonstrating the versatility of these hybrid coatings. For example, the Hybridosome® films were used to encapsulate and release a bodipy fluorescent probe in response to either a pH drop or the application of an oxidative +1 V potential (vs. Ag/AgCl) at the substrate. By advancing the field of electro-synthesized films a step further toward the design of complex physicochemical interfaces, these results open perspectives for multifunctional coatings where chemical versatility, controllable stability and a hollow nanostructure are required.
具有聚合物/纳米颗粒壳的中空纳米胶囊（名为Hybridosomes®）被用于以一锅法共价构建杂化膜。通过在F-SnO（FTO）电极上进行电点击反应，使带有炔基的有机/无机Hybridosomes®与带有叠氮基的同双功能聚乙二醇（PEG）连接体交联。通过在电极附近通过电化学产生Cu(i)离子促进炔基和叠氮基部分之间的Cu(i)催化点击反应来获得涂层。通过扫描电子显微镜（SEM）、原子力显微镜（AFM）、紫外-可见光谱和荧光光谱研究了所得共价交联杂化膜的物理化学性质。膜中纳米胶囊与PEG连接体之间的一锅共价点击反应不会影响Hybridosomes®的理想特性，即它们的中空纳米结构、化学多功能性和pH敏感性。因此，Hybridosomes®膜的组成和载药量都可以调节，证明了这些杂化涂层的多功能性。例如，Hybridosome®膜被用于响应pH下降或在底物上施加+1 V氧化电位（相对于Ag/AgCl）来封装和释放硼二吡咯荧光探针。通过将电合成膜领域向前推进，朝着复杂物理化学界面的设计更进一步，这些结果为需要化学多功能性、可控稳定性和中空纳米结构的多功能涂层开辟了前景。
