Iron-based mimetic enzyme sensor for NO photorelease from sodium nitroprusside
Graphical abstract
Introduction
Nitric oxide (NO) is a naturally occurring free radical in the human body which plays important roles in regulating a wide range of physiological processes, including cellular immunity, vascular tone and neurotransmission [1]. The introduction of exogenous NO donors to obtain the desired cellular biological effects and the real-time detection of the quantitative release of NO are of great significance for life sciences [2]. Enzyme electrochemical sensors for NO are widely used in modern biomedicine [3,4], which have the advantages of simple operation, high sensitivity, good selectivity, and in-situ detection. Some natural enzymes can be used for the catalysis and detection of NO [5,6]. However, these natural enzymes are expensive, which usually present in small amounts in the living body and are difficult to purify, transport and store [7,8]. As a substitute, artificial mimic enzymes have attracted widespread attention in the past few decades.
Mimetic enzyme is a kind of synthesized material by chemical ways, which has the same catalytic activity as the natural enzymes and has attracted significant research attention. Wang et al. reported an enzyme-mimicking electrochemical biosensor based on the Cu(II)-PLH (PLH = poly-L-histidine) functionalized carboxylated multi-walled carbon nanotubes (CMWCNTs) for sensitive electrochemical detection of salvianic acid A, which exhibited high catalytic performance [9]. Li et al. used high-activity Fe3O4 nanozyme as a signal amplifier to construct an ultrasensitive photoelectrochemical immunoassay platform [10]. Md. et al. embedded Ag nanoparticles within a cotton fabric to act as a free-standing peroxidase-mimic nanozyme for the rapid detection of glucose in urine [11].
Metal complex has been widely applied in the field of electrochemical sensors in recent years [[12], [13], [14]]. NO molecule can coordinate with numerous transition metals, especially iron metal center having biological relevance. Some iron complexes were reported to have ability to act as artificial mimic enzymes [15,16]. The ordered arrangement of iron and organic ligands provides a reliable catalytic site for NO [17]. For example, Brown et al. investigated the electrocatalytic properties of several metal phthalocyanines (Pc) for nitric oxide and found that FePc has good selectivity for NO [18]. Zhang et al. found that the iron(II) porphyrin complex as a model of heme protein could induce the conversion of nitrite to NO [19]. Liao et al. designed a biomimetic model of biological cells based on two types of iron porphyrins and demonstrated the stepwise electrocatalytic reduction of NO was depended on a cationic picket-fence porphyrin incorporated in an ultrathin phospholipid film, which provided a new insight for understanding the denitrification mechanism in a biological system [20]. Fe-1,3,5-benzenetricarboxylic acid (Fe-BTC) also exhibited high catalytic activity and may be exploited as a novel mimetic enzyme [21]. Zhao et al. prepared a bifunctional metal organic framework of Fe(III)-BTC, which could act as a peroxidase mimic and as a solid support for immobilization of glucose oxidase, and it could be applied to determine the glucose in serum [22].
In this work, an eletrochemical sensing strategy for sensitive detection of NO was designed based on an iron-based complex Fe(II)-BTC as mimetic enzyme. The Fe(II)-BTC film was prepared using a mild electrodeposition method and its morphology and composition were characterized. The electrochemical responses of NO on the mimetic enzyme interface were investigated and the electrocatalysis mechanism for NO was discussed. The mimic enzyme sensor was applied to determine the photorelease of NO from the donor sodium nitroprusside (SNP).
Section snippets
Materials
All analytical grade chemicals were used in this experiment, including trimesic acid (H3BTC), triethyl amine hydrochloride (Et3NHCl), iron(III) chloride hexahydrate (FeCl3·6H2O), sodium phosphate monobasic, sodium phosphate dibasic, and they were supplied by Macklin Biochemical Co. Ltd. (Shanghai, China). SNP was obtained from Sinopharm Chemical Reagent Co., Ltd. Nitrogen (N2) used was high-purity of 99.999%, and water was processed with an ultra-pure water system (Beijing Epoch Electronic
Characterizations of Fe(II)-BTC film
Cyclic voltammetry (CV) was employed to investigate the electrodeposition process of Fe(II)-BTC, Fig. 1 shows CV curves of the bare GCE in different precursor solution with DMF as the dissolvent of electrolyte. A pair of irreversible redox peaks (I/II) appeared at about −0.5 V and 0.25 V for the electrode deposited in FeCl3·6H2O solution, which was formed by the reaction of Fe(III) + e− ↔ Fe(II) (black curve). The addition of H3BTC slightly increased the oxidation peak current at 0.25 V (red
Conclusion
In this study, an iron-based complex Fe(II)-BTC modified electrode as a mimetic enzyme sensor was designed and fabricated for detecting the photorelease of NO in SNP. After the electrodeposition of Fe(II)-BTC on GCE, the obtained sensor exhibited good catalytic activity for electrochemical oxidation of NO. Under optimal operating conditions, the sensor had a broad linear range of 18 nmol L−1 to 9 μmol L−1 and a low detection limit of 7.2 nmol L−1. Furthermore, the mimetic enzyme sensor showed
CRediT authorship contribution statement
Pin Huang: Conceptualization, Methodology, Validation, Data curation, Writing - original draft. Birong Zhang: Formal analysis, Investigation. Xueping Dang: Writing - review & editing, Project administration. Huaixia Chen: Supervision. Dongyun Zheng: Funding acquisition.
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.
Acknowledgments
This research is supported by the National Natural Science Foundation of China (No. 61301048) and the Natural Science Fund for Creative Research Groups of Hubei Province of China (No. 2011CDA111).
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