Compartmentalization and Unidirectional Cross-Domain Molecule Shuttling of Organometallic Single-Chain Nanoparticles

Abstract

Compartmentalization and unidirectional cross-domain molecule shuttling are omnipresent in proteins, and play key roles in molecular recognition, enzymatic reaction, and other living functions. Nanomachinery design emulating these biological functions is being considered as one of the most ambitious and challenging tasks in modern chemistry and nanoscience. Here, we present a biomimetic nanomachinery design using single-chain technology. Stepwise complex of the outer blocks of water-soluble linear ABC triblock terpolymer to copper ions yields dumbbell-shaped single-chain nanoparticle. A novel nanomachine capable of compartmentalization and unidirectional cross-domain molecule shuttling has been achieved upon ascorbic acid reduction, leading to synergistically donating/accepting copper centers between discrete double heads, overall dumbbell-to-tadpole configurational transition, and intake of oxidized ascorbic acid into reconstructed head. Subsequent air oxidation results in the inverse molecule shuttling and configurational transition processes. This is the first demonstration of biomimetic nanomachinery design that is capable of compartmentalization and unidirectional cross-domain molecule shuttling, exemplified simply using a new single-chain technology.

Advances in the Multi-Orthogonal Folding of Single Polymer Chains into Single-Chain Nanoparticles

“…The combination of hydrophobic interactions, metal complexation and electrostatic charges allowed Zimmerman and co-workers to develop a variety of dynamic SCNPs showing enzyme-like catalytic behavior ( Figure 5) [62,63] and, even, able to perform tandem reactions together with enzymes inside living cells [64]. Independently, the presence of compartmentalized ultra-fine nanoclusters in metal folded SCNPs and subdomains in their assemblies was reported by Cai et al [65], which used single chain technology to demonstrate unidirectional cross-domain molecule shutting of dumbbell-shaped SCNPs prepared by stepwise complexation of the outer blocks of an ABC-type linear triblock copolymer to copper ions [66].…”

“…Independently, the presence of compartmentalized ultra-fine nanoclusters in metal folded SCNPs and subdomains in their assemblies was reported by Cai et al [ 65 ], which used single chain technology to demonstrate unidirectional cross-domain molecule shutting of dumbbell-shaped SCNPs prepared by stepwise complexation of the outer blocks of an ABC-type linear triblock copolymer to copper ions [ 66 ].…”

100th Anniversary of Macromolecular Science Viewpoint: Re-examining Single-Chain Nanoparticles

“…Copyright 2019 American Chemical Society. (B) Schematic illustration of the formation of dumbbell-shaped SCNP1 and suggested molecular shuttling mechanism of SCNP . Reprinted with permission from ref .…”

“…(B) Schematic illustration of the formation of dumbbell-shaped SCNP1 and suggested molecular shuttling mechanism of SCNP . Reprinted with permission from ref . Copyright 2018 American Chemical Society.…”

One‐Shot Intrablock Cross‐Linking of Linear Diblock Copolymer to Realize Janus‐Shaped Single‐Chain Nanoparticles

“…One of the interesting compartmentalized configurations is the dumbbell‐shaped SCNP, where the chemically different intramolecularly cross‐linked blocks are tethered by a short spacer block (Figure 1 a). [40–42] Furthermore, Matsumoto et al., [43, 44] Jiang et al., [45] Ji et al., [46] and Lang et al [47] . recently succeeded in the distinct intramolecular cross‐linking of the two segments of BCPs without the spacer, yielding double‐core SCNPs (Figure 1 b).…”