Fe-Porphyrin-Based Covalent Organic Framework As a Novel Peroxidase Mimic for a One-Pot Glucose Colorimetric Assay

Abstract

Covalent organic frameworks (COFs) have recently emerged as very fascinating porous polymers due to their attractive design synthesis and various applications. However, the catalytic application of COF materials as enzymatic mimics remains largely unexplored. In this work, the Fe-porphyrin-based covalent organic framework (Fe-COF) has been successfully synthesized through a facile postsynthetic strategy for the first time. In the presence of hydrogen peroxide (H 2 O 2 ), the Fe-COF can catalyze a chromogenic substrate (3,3′,5,5′-tetramethylbenzidine (TMB)) to produce color, and this just goes to show that it has an inner peroxidase-like activity. Moreover, the kinetic studies indicate that the Fe-COF nanomaterial has a higher affinity toward both the substrate H 2 O 2 and TMB than the natural enzyme, horseradish peroxidase (HRP). Under the optimized conditions, the Fe-COF nanomaterial was applied in a colorimetric sensor for the sensitive detection of H 2 O 2 . The detection range was from 7 to 500 μM, and the detection limit was 1.1 μM. Furthermore, the combination of the Fe-COF with glucose oxidase (GOx) can be implemented to measure glucose by a one-pot method, and the obtained detection range was from 5 to 350 μM; the detection limit was 1.0 μM. It was proved that the sensor can be successfully used to detect the concentration of glucose in human serum samples. As a peroxidase mimic, the Fe-COF exhibits the advantages of easy preparation, good stability, and ultrahigh catalytic efficiency. We believed that the proposed method in this work would facilitate the applications of COF-based composites as enzymatic mimics in biomedical fields.

Covalent Organic Frameworks: Chemical Approaches to Designer Structures and Built‐In Functions

“…COFs have been developed for biomimetic catalysis. An iron‐porphyrin Fe‐COF (Figure a) oxidizes 3,3′,5,5′‐tetramethylbenzidine to form a blue product in the presence of H 2 O 2 , thus mimicking horseradish peroxidase . Fe‐COF can be coupled with the glucose oxidase enzyme to develop a one‐pot colorimetric assay for glucose with a detection limit of 1.0 μM.…”

“…[218] COFs have been developed for biomimetic catalysis.A n iron-porphyrin Fe-COF (Figure 25 a) oxidizes 3,3',5,5'-tetramethylbenzidine to form ab lue product in the presence of H 2 O 2 ,t hus mimicking horseradish peroxidase. [219] Fe-COF can be coupled with the glucose oxidase enzyme to develop aone-pot colorimetric assay for glucose with adetection limit of 1.0 mM. Immobilization of amano lipase PS into the pores of TPB-DMTP-COF (Figure 17), driven by hydrogen-bonding interactions,v an der Waals forces,a nd hydrophobic interactions,can increase the stability and recyclability of the enzyme.T he composite catalyzes the reaction between racemic 1-phenylethanol with vinyl acetate to achieve 49 % conversion in 30 min, which is much higher than that of the enzyme itself (3 %c onversion in 30 min).…”

Kovalente organische Gerüstverbindungen: chemische Ansätze für Designerstrukturen und integrierte Funktionen

“…Es wurden auch COFs für die biomimetische Katalyse entwickelt. Ein Eisenporphyrin‐Fe‐COF (Abbildung a) oxidiert 3,3′,5,5′‐Tetramethylbenzidin in Gegenwart von H 2 O 2 zu einem blauen Produkt, wodurch Meerrettichperoxidase nachgeahmt wird . Fe‐COF kann mit dem Glucoseoxidaseenzym gekuppelt werden, um einen kolorimetrischen Eintopf‐Test zum Glucosenachweis mit einer Nachweisgrenze von 1.0 μ m zu ermöglichen.…”

“…Ein Eisenporphyrin-Fe-COF (Abbildung 25 a) oxidiert 3,3',5,5'-Tetramethylbenzidin in Gegenwart von H 2 O 2 zu einem blauen Produkt, wodurch Meerrettichperoxidase nachgeahmt wird. [219] Fe-COF kann mit dem Glucoseoxidaseenzym gekuppelt werden, um einen kolorimetrischen Eintopf-Test zum Glucosenachweis mit einer Nachweisgrenze von 1.0 mm zu ermçglichen. Die von Wasserstoffbrücken, Va n-der-Waals-Kräften und hydrophoben Wechselwirkungen getriebene Immobilisierung von Amanolipase PS in den Poren von TPB-DMTP-COF (Abbildung 17) kann die Stabilitätu nd Wiederverwertbarkeit des Enzyms erhçhen.…”

Improved Photoreduction of CO2 with Water by Tuning the Valence Band of Covalent Organic Frameworks

“…Porphyrins have also emerged in the field of photocatalysis, for example, as homogeneous catalysts, photosensitizers, and metal–organic framework (MOF) ligands . Therefore, it is feasible to design a porphyrin‐based COF catalyst for photocatalytic reduction of CO 2 …”