Metal‐Coordinated Supramolecular Self‐Assemblies for Cancer Theranostics

Abstract

Metal‐coordinated supramolecular nanoassemblies have recently attracted extensive attention as materials for cancer theranostics. Owing to their unique physicochemical properties, metal‐coordinated supramolecular self‐assemblies can bridge the boundary between traditional inorganic and organic materials. By tailoring the structural components of the metal ions and binding ligands, numerous multifunctional theranostic nanomedicines can be constructed. Metal‐coordinated supramolecular nanoassemblies can modulate the tumor microenvironment (TME), thus facilitating the development of TME‐responsive nanomedicines. More importantly, TME‐responsive organic–inorganic hybrid nanomaterials can be constructed in vivo by exploiting the metal‐coordinated self‐assembly of a variety of functional ligands, which is a promising strategy for enhancing the tumor accumulation of theranostic molecules. In this review, recent advancements in the design and fabrication of metal‐coordinated supramolecular nanomedicines for cancer theranostics are highlighted. These supramolecular compounds are classified according to the order in which the coordinated metal ions appear in the periodic table. Furthermore, the prospects and challenges of metal‐coordinated supramolecular self‐assemblies for both technical advances and clinical translation are discussed. In particular, the superiority of TME‐responsive nanomedicines for in vivo coordinated self‐assembly is elaborated, with an emphasis on strategies that enhance the accumulation of functional components in tumors for an ideal theranostic outcome.

Highly-fluorescent BODIPY-functionalised metallacages as drug delivery systems: synthesis, characterisation and cellular accumulation studies

“…17,19 The four bidentate ligands L2 are coordinated in a square-planar fashion to two Pd 2+ ions each with a Pd-Pd distance of 11.874 Å. The coordination geometry of the Pd 2+ ions deviates slightly from squareplanarity with angles of 90.06 (15), 89.92(9), 90.09 (15) and 89.92 (11)°and Pd-N distances of 2.027(3) and 2.028(3) Å.…”

“…5–10 Thus, various metal-based precursors have been used to synthesise SCCs of different shapes, including triangles, squares, helicates, rectangles, prisms, cubes and cages among others. Interestingly, the possibility to modify the ligand structure both pre- and post-self-assembly, via the covalent linkage of different functionalities to the SCC's architecture, is crucial for the development of innovative cancer theranostics; 11 e.g. , enabling prolonged blood circulation, targeted drug release, accurate bioimaging, and superior anticancer performance.…”

Topical progress in medicinal applications of self‐assembled organoplatinum complexes using diverse Pt(II)‐ and N‐based tectons

“…[ 93 ] The library of organometallic molecules that have shown antiproliferative activities has seen substantial growth since the last decade with several reports of such organometallic compounds. [ 94 ]…”

Tuning the aqueous self-assembly of porphyrins by varying the number of cationic side chains

“…Supramolecular self-assembly, in which the molecules with specific properties have an order that is arranged through non-covalent interactions, is a powerful tool for building various functional nanomaterials. [1][2][3][4] The artificial assembling systems have succeeded in utilizing thermodynamic equilibrium to drive monomers into ordered aggregates that are the prerequisite to proceed with the self-assembly process. 5 The aggregation mode of the monomers plays a key role in determining the self-assembly pathways, as well as the structures and functions of the final obtained assemblies.…”