Bioinspired Self‐Assembling Materials for Modulating Enzyme Functions

Abstract

Enzymes tend to malfunction when they work out of their natural cellular environments. Engineering a favorable microenvironment around enzymes has emerged as an effective strategy to finely tune the enzymatic functions and reshape the biocatalytic activities. Supramolecular self-assembly provides a bottom-up approach for spatial arrangement of functional groups and fabrication of materials with tailorable local properties. In this review, the progress in designing, creating, and tailoring the enzyme microenvironments is discussed, with the bioinspired self-assembling materials as the scaffolds built from molecular building blocks. The relationship between the physicochemical properties and the local environments (pH, substrates, or hydration) of the scaffolds, and the catalytic properties of the scaffolded enzymes are focused upon. The power of the self-assembly to regulate the catalytic systems dynamically is also highlighted. In the end, an outlook on the obstacles, possible solutions, and future directions on the microenvironment engineering of enzymes is provided.

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“…also proposed that the embedded external quartet was in favor of the enhanced affinity to hemin and activation of the iron atom in hemin ( Wang et al., 2020 ). Moreover, the addition of histidine-rich peptides can also contribute to enhanced enzymatic activity ( Liu et al., 2017b , 2020b ; Du et al., 2021 , 2022 ), as is shown in Figure 2 C. Van der Waals force drives histidine-rich peptides to assemble with G-rich Dzs for capturing hemin. The stacking state of hemin presented at the terminals of folded G-rich Dzs allows more hemins to be exposed to H 2 O 2 , resulting in the enhanced catalytic activity.…”

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“…Through EISA, nanostructures can be selectively formed in cancer cells and show the expected anti‐cancer effect. [ 33‐34 ] Combination of enzyme responsive molecular and therapeutic drugs can achieve precise drug delivery at specific lesion sites. [ 35‐36 ]…”