Shape-Controlled Synthesis of Luminescent Hemoglobin Capped Hollow Porous Platinum Nanoclusters and their Application to Catalytic Oxygen Reduction and Cancer Imaging.

Engineering hollow and porous platinum nanostructures using biomolecular templates is currently a significant focus for the enhancement of their facet-dependent optical, electronic, and electrocatalytic properties. However, remains a formidable challenge due to lack of appropriate biomolecules to have a structure-function relationship with nanocrystal facet development. Herein, human hemoglobin found to have facet-binding abilities that can control the morphology and optical properties of the platinum nanoclusters (Pt NCs) by regulation of the growth kinetics in alkaline media. Observations revealed the growth of unusual polyhedra by shape-directed nanocluster attachment along a certain orientation accompanied by Ostwald ripening and, in turn, yield well-dispersed hollow single-crystal nanotetrahedrons, which can easily self-aggregated and crystallized into porous and polycrystalline microspheres. The spontaneous, biobased organization of Pt NCs allow the intrinsic aggregation-induced emission (AIE) features in terms of the platinophilic interactions between Pt(II)-Hb complexes on the Pt(0) cores, thereby controlling the degree of aggregation and the luminescent intensity of Pt(0)@Pt(II)-Hb core-shell NCs. The Hb-Pt NCs exhibited high-performance electrocatalytic oxygen reduction providing a fundamental basis for outstanding catalytic enhancement of Hb-Pt catalysts based on morphology dependent and active site concentration for the four-electron reduction of oxygen. The as-prepared Hb-Pt NCs also exhibited high potential to use in cellular labeling and imaging thanks to the excellent photostability, chemical stability, and low cytotoxicity.