Facile strategy to prepare a metalloporphyrin-based hydrophilic porous organic polymer with enhanced peroxidase-like activity and high stability for colorimetric detection of H2O2 and glucose
Graphical abstract
Introduction
Hydrogen peroxide (H2O2) is an important chemical substance in many fields such as food, medicine and so on. Apart from this, the role of H2O2 in the human body cannot be ignored. For example, H2O2 is a byproduct in the oxidation of glucose by glucose oxidase (GOD). Hence, many glucose sensors are based on the detection of H2O2 [1,2]. For these reason, it is important to detect H2O2 and glucose quickly and accurately. Over the last few decades, there have been many methods developed and applied for H2O2 and glucose detection, including fluorescence [3], colorimetric assay [4], electrochemistry [[5], [6], [7]] and so on. Among them, colorimetric assay is an efficient and simple approach due to its low cost and practicality. For colorimetric assay, the peroxidase is the crux.
Natural enzymes are extremely exquisite biocatalysts. They can catalyze a variety of biological reactions with high substrate specificity and activity [8,9]. However, the practical application of enzymes is often hampered by their intrinsic drawbacks, such as inherent intolerance to harsh conditions and easily denaturation, along with low temperature storage and poor operational stability [10,11]. To overcome these limitations, great efforts have been made to explore various materials including cyclodextrins, metal complexes and porphyrins for the purpose to mimic the structures and functions of naturally occurring enzymes [11,12].
Benefiting from tremendous progress in nano-research, nanozymes with unexpected enzyme-like activity, have received increasing attention recently due to their cost-effectivity, amenability to large-scale production, and high stability and robustness relative to natural enzymes [10,[13], [14], [15], [16]]. Meanwhile, nanozymes have also exhibited some unique characteristics superior to natural enzymes in terms of large surface areas, integrated multifunctionality besides catalysis and tunable catalytic activities. So far, lots of nanomaterials have been demonstrated to possess intrinsic activity similar to natural enzymes such as catalase [17,18] or peroxidase [19]. And applications of nanozymes have also been investigated vigorously due to their potential application in biosensors, nanomedicine and environmental protection. For example, peroxidase mimicking nanozymes can catalyze the oxidation of some peroxidase substrates to give color changes, which have been utilized to construct colorimetric biosensors [2,4,20]. By using nanozymes’ H2O2 scavenging ability, therapeutic applications of nanozymes have also emerged, including biofilm disruption, antioxidation and tissue regeneration [[21], [22], [23]]. Although significant progress has been made, it still remains several unknowns and challenges for the development of nanozymes because of their low activity, poor substrate selectivity and limited reaction types compared to natural enzymes. Thus, exploring new nanomaterials as high efficient nanozymes is greatly anticipated.
Currently, porphyrin-based nanozymes have attracted increasing attention due to their close biological relevance to nature enzymes such as hemoglobin and cytochrome P450 [24]. However, utilities of synthetic metalloporphyrins as catalysts in homogeneous oxidation reactions have been rather limited because of their rapid inactivity through either the oxidative degradation of porphyrin ring or formation of peroxo-bridged dimers [25]. To solve these problems, some general approaches have been developed, such as loading porphyrins in porous solids [26], modifying the porphyrin macrocycle with bulky functional groups to avoid dimerization [27], or immobilizing porphyrins into metal-organic frameworks (MOFs) [28]. These strategies really enhance the catalytic activity of porphyrin-based nanozymes. In addition to these, porphyrin-based porous organic polymers (POPs), namely PPOPs containing interlinked porphyrin units, have recently started to emerge as an outstanding subclass of nanozymes and received considerable interest [[29], [30], [31], [32], [33]]. PPOPs possess intrinsic advantages of POPs, such as large specific surface area, tunable pore structures and high thermal/chemical/water stability. These advantages provided the accessibility to substrates and simplification the diffusion of products. Integration metal porphyrins into PPOPs would endow the skeleton of POPs itself as catalysts and at the same time introduce high dense active sites onto skeleton. By incorporating the porphyrin units onto PPOPs, catalyst deactivation commonly associated with porphyrin aggregation could also be avoided. As a result, PPOPs have been intensive research in catalysis involving biomimetic catalysis. Despite these opportunities for the development of novel PPOPs-based high-efficiency peroxidase-mimicking nanozymes, the development of PPOPs is still hampered by hurdles and bottlenecks, such as reaction complexity and participation of precious metal for preparing PPOPs. In this regard, rational design of PPOPs materials would provide a highly promising strategy to fulfill the overall performance.
With this background in mind, in the present case we reported the construction of a high-efficiency peroxidase-mimicking nanozyme based on a functional PPOPs, namely FePPOPs-SO3H, Scheme 1a. FePPOPs-SO3H was a metalloporphyrin-based POPs with the framework itself can serve as a built-in catalyst, which could effectively avoid deactivation commonly associated with porphyrin aggregation. Unlike the PPOPs fabricated from monomeric metalloporphyrin via various coupling reaction, FePPOPs-SO3H was synthesized via an extensive aromatic electrophilic substitution between pyrrole and 2,6-dihydroxynaphthalene-1,5-dicarbaldehyde (DHNDA) and the following sulfonation reactions. This strategy was cost-efficient without the participation of precious metal catalysts. The covalent linkages between catalytic sites in the frameworks make FePPOPs-SO3H exhibit high long-term stability and reusability. Introduction of sulfonic acid side groups further improve the stability and water-dispersibility. These structural features together with the excellent catalytic performance make FePPOPs-SO3H exhibit a remarkably enhanced peroxidase-like activity over monomeric ferric porphyrin and normal Fe3O4 nanoparticles. Based on these findings, two super-sensitive and convenient colorimetric sensors have been constructed to detect H2O2 and glucose, respectively. The unique properties of synthesis strategy, structural features together with the excellent catalytic performance of FePPOPs-SO3H would highlight opportunities for the design of new metalloporphyrin-based porous organic polymers with built-in catalytic skeletons and inherently excellent peroxidase-mimicking performance.
Section snippets
Materials and regents
Pyrrole was purchased from Aladdin Bio-chem Technology Co. Ltd. (Shanghai, China). Hydrogen peroxide solution (H2O2, 30%), glucose, fructose, galactose and sucrose were obtained from Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China). 3,3′,5,5′-Tetramethylbenzidine (TMB) and glucose oxidase (GOD, 100–250 units/mg) were purchased from Shanghai Yuanye Bio-technology Co. Ltd. 2,6-Dihydroxynaphthalene was obtained from Energy Chemistry, Saen Chemical Technology Co. Ltd. Shanghai, China.
Synthesis and characterization of FePPOPs-OH
Previously, the preparation of PPOPs is mainly through various coupling reactions with the participation of precious metal catalysts, specific substituents (-Br, -I, -C≡C, etc.), pre-synthesized porphyrin units as well as high reaction temperatures and harsh reaction conditions [[36], [37], [38]]. It is known that the low synthesis yield of the monomer porphyrin, together with the precious metal catalysts, greatly increased the PPOPs’ synthetic cost. Furthermore, how to effectively remove the
Conclusion
In conclusion, we have developed a metalloporphyrin-based porous organic polymer, FePPOPs-SO3H, for the construction of a high-efficiency peroxidase-mimicking nanozyme. Relative to monomeric porphyrinato iron and normal Fe3O4 nanoparticles, FePPOPs-SO3H demonstrated enhanced peroxidase-like activity. The covalent linkages between catalytic sites in the frameworks make FePPOPs-SO3H exhibits high long-term stability and reusability. Introduction of sulfonic acid side groups further improve the
Notes
The authors declare no competing financial interest.
Acknowledgements
Financial support from the National Natural Science Foundation of China (21472117), the Fundamental Research Funds of Shandong University (2018JC036) and Open Project of State Key Laboratory of Infrared Physics (M201701) are gratefully acknowledged.
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