Ferreira José, Michiels Jeroen, Herregraven Marty, Korevaar Peter A
Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, Nijmegen 6525 AJ, The Netherlands.
TechnoCentre, Faculty of Science, Radboud University, Heyendaalseweg 135, Nijmegen 6525 AJ, The Netherlands.
J Am Chem Soc. 2024 Jul 17;146(28):19205-19217. doi: 10.1021/jacs.4c04346. Epub 2024 Jul 3.
Self-organization of inorganic matter enables bottom-up construction of materials with target shapes suited to their function. Positioning the building blocks in the growth process involves a well-balanced interplay of the reaction and diffusion. Whereas (supra)molecular structures have been used to template such growth processes, we reasoned that molecular assemblies can be employed to actively create concentration gradients that guide the deposition of solid, wire-like structures. The core of our approach comprises the interaction between myelin assemblies that deliver copper(II) ions to the tips of copper dendrites, which in turn grow along the Cu gradient upon electrodeposition. First, we successfully include Cu ions among amphiphile bilayers in myelin filaments, which grow from tri(ethylene glycol) monododecyl ether (CE) source droplets over air-water interfaces. Second, we characterize the growth of dendritic copper structures upon electrodeposition from a negative electrode at the sub-mM Cu concentrations that are anticipated upon release from copper(II)-loaded myelins. Third, we assess the intricate growth of copper dendrites upon electrodeposition, when combined with copper(II)-loaded myelins. The myelins deliver Cu at a negative electrode, feeding copper dendrite growth upon electrodeposition. Intriguingly, the copper dendrites follow the Cu gradient toward the myelins and grow along them toward the source droplet. We demonstrate the growth of dynamic connections among electrodes and surfactant droplets in reconfigurable setups─featuring a unique interplay between molecular assemblies and inorganic, solid structures.
无机物质的自组织能够自下而上构建具有适合其功能的目标形状的材料。在生长过程中定位构建块涉及反应和扩散之间的良好平衡相互作用。虽然（超）分子结构已被用于模板化此类生长过程，但我们推断分子组装体可用于主动创建浓度梯度，以引导固体丝状结构的沉积。我们方法的核心包括髓磷脂组装体之间的相互作用，这些组装体将铜（II）离子输送到铜树枝状晶体的尖端，而铜树枝状晶体在电沉积时会沿着铜梯度生长。首先，我们成功地将铜离子纳入髓磷脂细丝中的两亲双层中，这些细丝从三（乙二醇）单十二烷基醚（CE）源液滴在空气 - 水界面上生长。其次，我们表征了在从负电极进行电沉积时，在从负载铜（II）的髓磷脂释放时预期的亚毫摩尔铜浓度下树枝状铜结构的生长。第三，我们评估了与负载铜（II）的髓磷脂结合时，电沉积时铜树枝状晶体的复杂生长。髓磷脂在负电极处输送铜，在电沉积时促进铜树枝状晶体的生长。有趣的是，铜树枝状晶体沿着铜梯度朝向髓磷脂生长，并沿着它们向源液滴生长。我们展示了在可重构设置中电极和表面活性剂液滴之间动态连接的生长——呈现出分子组装体与无机固体结构之间独特的相互作用。
