Bioinorganic supramolecular coordination complexes and their biomedical applications

Abstract

The field of Bioinorganic Supramolecular Chemistry is an emerging research area including metal‐based supramolecules resulting from coordination‐driven self‐assembly (CDSA), whereby metal ions and organic ligands can be easily linked by metal–ligand bonds via Lewis' acid/base interactions. The focus of this ‘In a Nutshell’ review will be on the family of supramolecular coordination complexes, discrete entities formed by CDSA, which have recently captured widespread attention as a new class of versatile multifunctional materials with broad biological applications including molecular recognition, biosensing, therapy, imaging and drug delivery. Herein, we provide a summary of the state‐of‐the‐art use of these systems in biomedicine, with some selected representative examples, as well as our visions of the challenges and possible directions in the field.

Inorganic Self‐assembly: Going Bio

“…Moreover, the use of intracellular coordination-driven self-assembly which could derive in important imaging or therapeutic applications is still unexplored. [38,[83][84][85] For instance, when compared to purely organic building blocks the possibilities of self-assembly of metal-organic entities are enriched by the extended toolbox of available non-covalent interactions, [86] for example, coordination bonds or metallophilic contacts, [87,88] which further generate aggregates with attractive properties. [59,89] The design of building blocks that self-assemble under these principles could render the assembly process selective in complex biological matrices.…”

“…Besides, the use of inorganic building blocks for the generation of supramolecular assemblies into the living milieu would undoubtfully uncover further applications in these areas. Moreover, the use of intracellular coordination‐driven self‐assembly which could derive in important imaging or therapeutic applications is still unexplored [38,83–85] . For instance, when compared to purely organic building blocks the possibilities of self‐assembly of metal‐organic entities are enriched by the extended toolbox of available non‐covalent interactions, [86] for example, coordination bonds or metallophilic contacts, [87,88] which further generate aggregates with attractive properties [59,89] .…”

“…[28][29][30][31] The advances and challenges in the different branches of this area have been recently summarized in different reviews and critical works. [32][33][34][35][36][37][38] Bioorthogonal chemistry -a term coined by Carolyn Bertozzi, that describes the use of living cells' milieu as a reaction flaskhas been one of the main achievements of the chemistry of this century, as recognized by the 2022 Nobel Prize in Chemistry. [39] Nowadays, it is possible to extend this concept and envision the emergence of other bioorthogonal processes, [40] for example bioorthogonal self-assembly: namely, the self-assembly of exogenous materials into the living environment (in-bio).…”

“…The so‐called biomimetic self‐assembly [27] has produced amazing examples, but still their complexity is far from that of living systems [28–31] . The advances and challenges in the different branches of this area have been recently summarized in different reviews and critical works [32–38] …”

Nobel symposium #168 Visions of bio‐inorganic chemistry: metals and the molecules of life

“…This encompasses distances we are unused to thinking about in the biochemical context, for example, cable bacteria that conduct electrons over cm-distances to connect electron donors and acceptors in aquatic sediments. Bren and Casini [17,18] provide examples of applications of bioinorganic and bioinspired systems. Bren considers the key current issue of energy storage by finding inspiration for proton and carbon dioxide reduction in nature.…”