Al³⁺ Cofactor Evoking Iron Porphyrin-AuNP Hybrids as Oxidase-Mimicking Nanozymes with Prominent Catalytic Efficiency in a Broad pH Range

Abstract

Nanomaterial-based artificial enzymes (nanozymes) have great potential for boosting their intrinsic activities to narrow the gaps against natural enzymes. Different from natural enzymes, nanozymes usually cannot work efficiently under physiological pH, which limits their application in environmental and biological fields. Here, we proposed that the originally futile tetrakis (4carboxyphenyl) iron porphyrin (FeTCPP) compounds in the Fe II -TCPP-Au nanoparticle (Fe II -TCPP-AuNP) hybrid are functionalized to serve as critical active sites involved in cytochrome P450 to greatly boost the oxidase-mimicking activity by an Al 3+ cofactor at neutral pH. The microenvironment around FeTCPP can be chemically optimized to provoke the oxidase-mimicking activity with 3,3′,5,5′-tetramethylbenzidine (TMB) as a substrate with the help of Al 3+ . The activity-provoking ability of the system is tunable by changing the concentrations of Al 3+ , the strong ligand F − , and temperature. Based on this, the selective and sensitive colorimetric sensor of Al 3+ based on nanozymes was first developed. The novelty of the present work is not only a new means to develop iron porphyrin nanozymes with superior oxidase-mimicking activity at neutral pH but is also the first example that hard acid Al 3+ can serve as a robust and efficient cofactor to synergize the catalytic performance of nanozymes. Therefore, this study provides some enlightenment about the integration of artificial cofactors in biomimetic chemistry and expands the application of nanozymes in environmental fields.

Breaking the pH Limitation of Nanozymes: Mechanisms, Methods, and Applications

“…Therefore, a Fe II ‐TCPP‐AuNP nanozymes based Al 3+ colorimetric sensor was developed with a detection range of 5–100 µ m and LOD value of 100 n m . [ 218 ] Moreover, substrates with inhibition effect that weakens the combination of nanozymes with those promoting factors could reduce the activity of original nanozymes, thus becoming sensible. Based on this conception, Au‐NCs were prepared for the colorimetric sensing of protamine under physiological condition.…”

A Bioengineered Stable Protein 1‐Hemin Complex with Enhanced Peroxidase‐Like Catalytic Properties

“…[23][24][25][26][27][28] Recently, approaches to mimic the enzyme's active site have been developed. [29] These include, hemin-free fibrils, [30] coordinated hemin to organic or inorganic scaffolds, [31,32] DNA G-quadruplex formation, [33][34][35][36][37] proteins, [38][39][40][41][42] supramolecular and nano hydrogels, [43][44][45] copolymers, [46,47] carbon nanotubes, [48,49] and hybrids of the above. [50,51] However, the construction of a flexible active DOI: 10.1002/smsc.202400025…”