Fullerene-Based Mimics of Biocatalysts Show Remarkable Activity and Modularity

Abstract

The design of catalysts with greater control over catalytic activity and stability is a major challenge with substantial impact on fundamental chemistry and industrial applications. Due to their unparalleled diversity, selectivity, and efficiency, enzymes are promising models for next-generation catalysts, and considerable efforts have been devoted to incorporating the principles of their mechanisms of action into artificial systems. We report a heretofore undocumented catalyst design that introduces fullerenes to the field of biocatalysis, which we refer to as f ullerene nanocatalysts, and that emulates enzymatic active sites through multifunctional self-assembled nanostructures. As a proof-ofconcept, we mimicked the reactivity of hydrolases using fullerene nanocatalysts functionalized with the basic components of the parent enzyme with remarkable activity. Owing to the versatile amino acid-based functionalization repertoire of fullerene nanocatalysts, these next-generation carbon/biomolecule hybrids have potential to mimic the activity of other families of enzymes and, therefore, offer new perspectives for the design of biocompatible, high-efficiency artificial nanocatalysts.

Nanoarchitectonics of Fullerene‐Based Enzyme Mimics for Osteogenic Induction of Stem Cells

“…The undeniable performance of fullerene enzyme mimics in phosphoester hydrolysis reactions, biomineralization, and osteoinduction is unique among the other artificial catalysts such that they simultaneously recapitulate the catalytic and metabolic activity of native enzymes. Furthermore, they have significantly higher catalytic efficiencies for the hydrolysis of pNPP than one of the most promising peptide‐based phosphatase mimics in literature, [ 24 ] taking advantage of the hydrophobic tuning by the nonfunctionalized fullerene parts [ 39 ] and a greater portion of active groups that synergistically interact with each other due to clustering spherical structures rather than the linear arrangement of active groups. Structural, chemical, and surface features of fullerene molecules distinguish them from the peptide‐based and organic molecule‐based artificial catalysts, which are far more stable than peptide‐based enzyme mimics and less toxic and soluble compared to organic molecule‐based enzyme mimics.…”

Unusual Mathematical Approaches Untangle Nervous Dynamics

“…The spontaneous occurrence of distinctive self-assembled artificial structures could be compared with the design of natural organic crystalline materials, such as the nervous structures. In particular, both artificial and natural quasicrystal structures can generate fullerenic-like self-assemblies grounded on simple, overarching geometric rules [ 45 , 137 , 138 , 139 , 140 , 141 , 142 , 143 , 144 , 145 ]. The same fullerenic structures have been recently proposed to explain the features of cortical microcolumns that can be flattened to form fullerene-like, two-dimensional lattices [ 146 , 147 ].…”

Carbon Nanomaterials (CNMs) and Enzymes: From Nanozymes to CNM-Enzyme Conjugates and Biodegradation

“…Finally, besides peroxidases, and, generally, redox-active enzymes, which represent the vast majority of nanozyme mimicry studies on CNMs, hydrolases have started to attract scientists’ attention. In a recent report, fullerene derivatives were applied to this end through the presentation of multiple functional groups inspired from the natural enzymes’ catalytic sites [ 344 ]. Analogously to the other CNMs, fullerenes could also act as peroxidase mimics at acidic pH, and were thus envisaged for the eradication of Helycobacter pylori in vivo [ 345 ].…”