Heme-Dependent Supramolecular Nanocatalysts: A Review

Abstract

Enzymes fold into three-dimensional structures to distribute amino acid residues for catalysis, which inspired the supramolecular approach to construct enzyme-mimicking catalysts. A key concern in the development of supramolecular strategies is the ability to confine and orient functional groups to form enzyme-like active sites in artificial materials. This review introduces the design principles and construction of supramolecular nanomaterials exhibiting catalytic functions of heme-dependent enzymes, a large class of metalloproteins, which rely on a heme cofactor and spatially configured residues to catalyze diverse reactions via a complex multistep mechanism. We focus on the structure–activity relationship of the supramolecular catalysts and their applications in materials synthesis/degradation, biosensing, and therapeutics. The heme-free catalysts that catalyze reactions achieved by hemeproteins are also briefly discussed. Towards the end of the review, we discuss the outlook on the challenges related to catalyst design and future prospective, including the development of structure-resolving techniques and design concepts, with the aim of creating enzyme-mimicking materials that possess catalytic power rivaling that of natural enzymes..

Self-Assembly of Designed Peptides with DNA to Accelerate the DNA Strand Displacement Process for Dynamic Regulation of DNAzymes

“…To further evaluate the working principle of this system, we measured UV–vis spectra of Target-12/hemin, before and after strand displacement (Figure S26). Both spectra exhibited a peak at 398 nm along with a shoulder at 370 nm, indicating the coexistence of monomeric hemin and μ-oxo bihemin (the dimer of hemin). , Of note, after multiple cycles of the strand displacement reactions, the spectra remained similar. We then investigated the UV–vis spectra in the presence of K 10 , which also exhibited the peak at 398 nm and shoulder at 370 nm (Figure S27).…”

Dual-Mode Arginine Assay Based on the Conformation Switch of a Ferrocene-Grafted Polypeptide

“…The morphology of aggregate for self-assembled polypeptide is subject to its preparation conditions such as concentration and self-assembling time. , The peptide molecules with a sequence of lipoic acid-GSGS­FGHI­HEGY­EGGK-Fc (P 16 Fc) in aqueous solution at a low initial concentration of 0.1 μM are self-assembled into an irregular nanostructure as shown in Figure A. As the initial concentration of P 16 Fc is increased, the structural appearance is gradually changed from irregular to regular and nanosphere-like with increasing diameters, to be specific, at 1.0 μM with a diameter of approximately 70 nm (Figure B), and at 10.0 μM with a diameter of approximately 400 nm (Figure C).…”

Advancements in Biosensors Based on the Assembles of Small Organic Molecules and Peptides

“…Furthermore, the nanospheres were employed for the detection of various disease-related biomarkers through the cooperative coupling of enzymatic reactions. Metalloporphyrins, such as iron(III) protoporphyrin IX (heme), exhibiting enzyme-like catalytic properties, are involved in various biological catalytic processes [258]. Recently, self-assembled nanostructures based on porphyrin derivatives have gained attention due to their remarkable photonic, catalytic, electronic, and biochemical properties, finding applications in diverse fields ranging from catalysis to biosensing [259][260][261].…”

“…Chen et al demonstrated that nanoporphyrin could serve as a peroxidase-like catalyst for the colorimetric detection of glucose and H2O2 (Figure 15) [262]. In their study, dodecyl trimethyl ammonium bromide (DTAB) was employed as a surfactant to stabilize the suspension of self-assembled zinc tetrakis(4-pyridinyl) porphyrin (ZnTPyP) Metalloporphyrins, such as iron(III) protoporphyrin IX (heme), exhibiting enzyme-like catalytic properties, are involved in various biological catalytic processes [258]. Recently, self-assembled nanostructures based on porphyrin derivatives have gained attention due to their remarkable photonic, catalytic, electronic, and biochemical properties, finding applications in diverse fields ranging from catalysis to biosensing [259][260][261].…”