Short communicationDegradation of phenol using a peroxidase mimetic catalyst through conjugating deuterohemin-peptide onto metal-organic framework with enhanced catalytic activity
Graphical abstract
Introduction
Among various water pollutants, phenol and its derivatives are widely present in wastewater from industrial processes, such as petrochemical manufacture, steel smelting, and pharmaceutical industries [1]. As representative advanced oxidation processes (AOPs), heterogeneous Fenton processes with separable solid catalysts have been widely reported to removal phenol in mild conditions and produce few residual sludges [2,3]. However, most of these catalysts are related to weak catalytic activity, low dispersion and stability. It is highly necessary to construct efficient and stable heterogeneous catalysts for the Fenton process.
Recently, well-studied enzymes such as horseradish peroxidase (HRP), laccase, and nanozyme have been successfully utilized in the Fenton/Fenton-like process to remove the phenolic contaminants [[4], [5], [6], [7]]. However, natural enzyme catalysts revealed some disadvantages in aqueous-system catalysis, such as low stability and recovery, high environmental sensitivity, as well as time-consuming preparation and purification [[8], [9], [10]]. Deuterohemin-β-Ala-His-Thr-Val-Glu-Lys (DhHP-6) is a novel peptide mimetic of nature microperoxidase-11 (MP-11), which consists of a deuterohemin prosthetic group bonded to six amino acid residues [11]. As a unique type of peroxidase mimetic, which is easy to synthesize, DhHP-6 possesses well-defined structure, high stability, and most of all, vigorous peroxidase activity [12,13]. Currently, DhHP-6 has been widely applied in biology and chemistry, such as biocatalysis, biotherapy, and atom transfer radical polymerization (ATRP) catalysis [[14], [15], [16]]. Structure and characteristics of DhHP-6 suggest that it might be an efficient catalyst for the Fenton process; however, no relevant work has been reported as far as we know. Besides, immobilization of enzymes to appropriate substrate materials have been proved to enhance the catalytic activity and prevent aggregation. Therefore, a suitable substrate material is necessary for DhHP-6 to work as a heterogeneous Fenton catalyst effectively and efficiently.
Metal-organic frameworks (MOFs) are associated with a series of desirable properties such as high surface areas, adjustable pore sizes, and surface modifiability. Therefore, they showed considerable influences in numerous fields such as catalysis [17], gas adsorption [18], separation [19], drug delivery, and energy storage [20,21]. Significant efforts have been made to develop enzyme guest species (HRP, GOx, MP-11) encapsulated MOFs and progressed a long way [[22], [23], [24], [25]]. However, the catalytic activity, efficiency, and stability of modified enzyme composites are impeded by their metal leaching and remote catalytic sites. Further development is significant to optimize the overall performance of this unique type of hybrid material.
Herein, Zr-MOF (NH2-UiO-66) was selected as the support for DhHP-6 not only because of its excellent properties similar to other MOFs, but also the superior chemical stability in acid-base and oxidative environment, and the possibility of post-synthetic modification (Lewis-basic amine groups). Specifically, the peroxidase mimetic catalyst (DhHP-6-c-ZrMOF) was successfully synthesized by employing a strategy of precipitation and cross-linking strategy. Systematic analyses were carried on the DhHP-6-c-ZrMOF. The as-synthesized heterogeneous Fenton catalyst with outstanding recoverability exhibited excellent kinetics performance, peroxidase activity, pH stability, and phenol degradation capacity.
Section snippets
Materials
DhHP-6 was kindly provided by Dr. Liping Wang from School of Life Sciences, Jilin University (Changchun, China). All other chemicals were of the highest grade purchased from Energy Chemical and used as received.
Synthesis of ZrMOF and DhHP-6-c-ZrMOF
The synthesis of ZrMOF was performed according to a previous report [26]. Typically, DhHP-6-c-ZrMOF was prepared as follows, 25 mg of ZrMOF was mixed with 6 mg of DhHP-6 in 2 mL PBS buffer (10 mM, pH = 7.4) under sonication for 10 min, followed by adding 8 mL of saturated ammonium
Result and discussion
The immobilization of DhHP-6 onto ZrMOF is illustrated in Scheme 1. Firstly, saturated ammonium sulfate was used to precipitate DhHP-6 onto ZrMOF. Subsequently, glutaraldehyde (GA), a universal protein cross-linking agent, was added to form stabilized covalent bonds between DhHP-6 and ZrMOF. As shown in Fig. S1, DhHP-6-c-ZrMOF presented a colour of reddish brown which distinctly different from the yellow ZrMOF. Effects of experimental parameters on enzyme utilization and phenol oxidative
Conclusions
In summary, peroxidase mimetic (DhHP-6-c-ZrMOF) was synthesized by precipitation and cross-linking strategy. The immobilization of DhHP-6 onto the surface of ZrMOF was achieved through stable covalent bonds. The kinetics performance, peroxidase activity, and pH stability of DhHP-6-c-ZrMOF were systematic studied and exhibited remarkable improvements compared with free DhHP-6. Furthermore, the as-synthesized heterogeneous Fenton catalyst also delivered excellent phenol degradation capacity and
Acknowledgments
This work was supported by Science and Technology Development Project of Science and Technology Department of Jilin Province [NO. 20180201086G X].
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
References (27)
- et al.
Enhanced photocatalytic removal of phenol from aqueous solutions using ZnO modified with Ag
Appl. Catal. B Environ.
(2018) - et al.
Nano-sized magnetic iron oxides as catalysts for heterogeneous Fenton-like reactions-influence of Fe(II)/Fe(III) ratio on catalytic performance
J. Hazard. Mater.
(2012) - et al.
Degradation of phenolic compounds by laccase immobilized on carbon nanomaterials: diffusional limitation investigation
Talanta
(2015) - et al.
Recyclable ferromagnetic chitosan nanozyme for decomposing phenol
Carbohydr. Polym.
(2018) - et al.
A deuterohemin peptide protects a transgenic caenorhabditis elegans model of Alzheimer's disease by inhibiting Abeta1-42 aggregation
Bioorg. Chem.
(2019) - et al.
Enhancing CO2/N2 adsorption selectivity via post-synthetic modification of NH2-UiO-66(Zr)
Microporous Mesoporous Mater.
(2018) - et al.
Constructing magnetic catalysts with in-suit solid-liquid interfacial photo-Fenton-like reaction over Ag3PO4 @NiFe2O4 composites
Appl. Catal. B Environ.
(2017) - et al.
Horseradish peroxidase immobilized on graphene oxide: physical properties and applications in phenolic compound removal
J. Phys. Chem. C
(2010) - et al.
Eg occupancy as an effective descriptor for the catalytic activity of perovskite oxide-based peroxidase mimics
Nat. Commun.
(2019) - et al.
Nanozyme: new horizons for responsive biomedical applications
Chem. Soc. Rev.
(2019)
Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes
Chem. Soc. Rev.
Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes (II)
Chem. Soc. Rev.
A deuterohemin peptide extends lifespan and increases stress resistance in Caenorhabditis elegans
Free Radic. Res.
Cited by (10)
Mesoporous molecularly imprinted nanoparticles with peptide mimics for the detection of phenolic compounds
2023, Analytica Chimica ActaNanobioremediation: a sustainable approach for environmental monitoring with special reference to the restoration of heavy metal contaminated soil and wastewater treatment
2023, Role of Green Chemistry in Ecosystem Restoration to Achieve Environmental SustainabilityUiO-66 metal–organic frameworks in water treatment: A critical review
2022, Progress in Materials ScienceCitation Excerpt :Additionally, the scavenger experiment suggested that hydroxide and superoxide radicals are the main species responsible for the photodegradation of TCH. A great deal of research has focused on the development of UiO-66-based catalysts for other applications such as one-pot production of biodiesel from the low-cost acidic oil feedstocks [550,551], photo-oxidation coupling of amines [552], Sonogashira coupling reactions [553], hydrolyzing a methylparaoxon (MPO) nerve agent simulant [554], degradation of phenol [555,556], phenol hydrogenation in aqueous solution [555], degradation of chemical warfare agent simulants [557], aerobic oxidation of alkenes [558], H2 evolution and CO2 reduction [559,560], production of butyl butyrate [561], esterification [562], and water splitting [563], which other researchers performed in-depth investigations. Excessive discharge of phosphate, which is one of the most challenging pollutants in wastewater, could pose long-term environmental hazards like eutrophication, leading to depletion of dissolved oxygen, growth of harmful red tides and large-scale algae, and deterioration of water quality, and finally, ecosystem collapse [564–566].
Metal-organic frameworks functionalized with nucleic acids and amino acids for structure- and function-specific applications: A tutorial review
2022, Chemical Engineering JournalCitation Excerpt :Ascribing to this novel design of biocatalyst, the biomineralized iron catalyst in the synthesized DhHP-6@ZIF-8 avoided the aggregation of DhHP-6 and provided enhanced catalytic activity as well as easy separation of DhHP-6 form the polymer product, revealing their potential applications for highly effective production of polymerized materials. In a recent study, they synthesized a novel biocatalyst by conjugating DhHP-6 onto ZrMOF through the cross-linking strategy [111], and found that the formed DhHP-6-c-ZrMOF exhibited enhanced peroxidase-mimetic catalysis activity for the degradation of phenol (Fig. 9b). By the biodegradation test, it was found that up to 98% of phenol was degraded within 120 min by using the created DhHP-6-c-ZrMOF as heterogeneous Fenton catalyst.
Advances in organometallic/organic nanozymes and their applications
2021, Coordination Chemistry ReviewsCitation Excerpt :The catalytic sites of organometallic/organic nanozymes mainly come from organometallics/organics rather than nanomaterials. Organometallics (e.g. hemin [15–18], metalloporphyrin [19–22], 1,4,7-triazacyclonane-Zn2+ complex [23,24], DNA-Cu2+ complex [25], and peptide-Zn2+ fibril [26]) and organics (e.g. imidazole groups [27,28] and chitin-acetic acid [29]) mimic the cofactors of natural enzymes to maximize the density of catalytic sites and thus enhance the catalytic activity of nanozymes. In addition, organometallic/organic nanozymes have the advantages of tunable catalytic activity, high stability, and material variety.