Investigating the properties of nano core-shell CeO2@C as haloperoxidase mimicry catalyst for antifouling applications

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Highlights

  • The core-shell structure of CeO2@C using the carbon sphere as template by a simple coprecipitation method.

  • CeO2@C displays intrinsic haloperoxidase-like activity by catalyzing the bromination of organic signaling compounds, and has well stability and recyclability.

  • CeO2@C can catalyze the oxidation of Br with H2O2 to the corresponding hypobromous acid (HBrO).

  • The forming HBrO exerts a strong antifouling activity against Gram-negative (E. coli), Gram-positive (S. aureus) bacteria and typical marine (P. aeruginosa) bacteria.

Abstract

Developing environmental and cost-effective antifouling technologies is essential to solve serious biofouling problems. Recently, enzyme mimics and halogenating enzymes have caught progressively attention as valuable tools to combat biofilm formation. In this work, the core-shell structure of CeO2@C, as one effective haloperoxidase-like enzyme mimics, was successfully synthesized using the carbon sphere as template through a simple coprecipitation method. Through the UV–vis absorption spectra and kinetic measurements, the CeO2@C displays intrinsic haloperoxidase-like activity via catalyzing the bromination of organic signaling compounds. Meanwhile, the prepared CeO2@C catalyst process high catalytic stability and recyclability, corresponding to a well catalytic performance repeatability after refresh of raw substrates (at least 10 times). The antibactrial property of CeO2@C as haloperoxidase mimicry is evaluated by immersing titanium plate/CeO2@C modified titanium plates into bacterial suspensions with different conditions for 4 h at 37 °C. It can catalyze the oxidation of Br with H2O2 to the corresponding hypobromous acid (HBrO), which exhibits strong antibacterial activity against Gram-negative (Escherichia coli), Gram-positive (Staphylococcus aureus) bacteria and typical marine (Pseudomonas aeruginosa) bacteria. This study introduces a stable, non-poisonous and inexpensive biomimetic material for antibacterial, antifouling and disinfection applications based on novel sustainable and conservation methods.

Graphical abstract

The synthesized nano core-shell CeO2@C as haloperoxidase mimicry catalyst displays well potential application for antifouling.

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Introduction

Biofouling is regarded as the colonization of small marine micro-organisms, generally leading to the increased hydrodynamic drag [1]. In the case of severe biofouling, corrosion of marine facilities happen consequently, which may bring serious consequences including huge economic losses and personal safety [2]. Therefore, marine biofouling is an expensive problem with no environmental friendly industrial solution nowadays [3]. Although antifouling coatings with releasing biocides are considered as the best effective approach [4], the release of biocides will cause cancer and environmental pollution [5]. Therefore, it is necessary to develop novel environmental friendly and cost-effective antifouling technologies.

Marine algae provides chemical mechanisms against microbial fouling by disrupting the quorum sensing and regulating biofilm formation [6,7], which can secrete vanadium haloperoxidases (V-HPOs) for catalyzing the oxidation of halides with hydrogen peroxide to the corresponding hypohalous acids [8]. These hypohalous acids, such as hypochlorous acid and hypobromous acid, induce severe damage in many organisms by biocidal and oxidation action, and prevent the formation of biofilms. Inspired by how naturally occurring V-HPOs enzymes prevent bacteria from forming biofilms on the surface of certain seaweeds [9,10], V-HPOs and functional recombinant V-HPOs have been widely used as additives in antifouling paints [11]. However, their use raises the issues of production costs, long-term stability, and proper reaction conditions. In addition, their large-scale application remains highly questionable, since vanadium compounds are mutagenic, carcinogenic, and teratogenic [12]. They are classified as critical according to the REACH (registration, evaluation, authorization and restriction of chemicals) criteria, and even their utilization is banned in some countries [13,14]. Therefore, developing novel materials with analogue enzyme is an important issue for combating biofouling.

It has been reported that fluorite-type ceria has non-stoichiometric oxygen vacancies [15], providing unique redox and structural properties with oxygen diffusion and oxygen storage/release capacity. Meanwhile, fluorite-type ceria has high stability and environmental compatibility [16]. Therefore, it has been used successfully in chemical and electrochemical fields. Ceria nanoparticles exhibit peroxidase and superoxide dismutase catalytic activity [[17], [18], [19], [20], [21]]. For example, Wolfgang et al. [22,23] reported CeO2−x nanorods exhibit an intrinsic haloperoxidase-like activity for combating biofouling.

In addition, carbon-based materials have shown great promise as alternative mimic enzyme catalysts, due to their advantages of earth-abundant, highly tunable and stability [[24], [25], [26]]. Furthermore, the catalytic performance of materials is strong correlated to their refined structure, such as heteroatom doping and electronic structure regulation [27,28]. Therefore, improving the catalytic activity and reducing the use of rare metals through carbon doping is an effective strategy.

Herein, we have prepared the core-shell structure of CeO2@C using the prepared carbon spheres as template through a simple coprecipitation method. The morphology and structure of as-prepared CeO2@C is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction technique (XRD), and X-ray photoelectron spectroscopy (XPS). The intrinsic haloperoxidase-like activity of CeO2@C is measured by catalyzing the bromination of organic signaling compounds. The stability and recyclability of CeO2@C is proved by reutilization test. Moreover, the produced HBrO through the oxidation of Br with H2O2 by CeO2@C catalyst, shows a strong antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa) bacteria. This study provides a new sustainable method for application in antibacterial, antifouling and disinfection.

Section snippets

Materials

Reagents: Phenol red (PR), H2O2 (30 %) and other reagents were purchased from Sinopharm Chemical Reagent Co. Ltd (Shanghai, China). Cerium(III) nitrate hexahydrate (Ce(NO3)3·6H2O) was purchased from Aladdin Chemical Reagent Co., Ltd (Shanghai, China). All the reagents and chemicals were used without further purification. Solutions of 25 mM phosphate buffers were prepared according to their corresponding standard procedure, and by adjusting their pH (3.0–10.0) before use. All aqueous solutions

Characterization

The morphologies and elemental compositions of the prepared samples are firstly investigated by SEM, TEM and SEM-EDS mapping. Fig. 1A shows the SEM image of the as-synthesized CeO2@C. CeO2-covered Cs, namely CeO2@C, is synthesized using the prepared Cs as the core material. Fig. 1(B and C) shows the TEM images of CeO2@C, representing solid sphere, and the lattice-resolved HRTEM images depict the clear lattice fringes with the spacing of 0.312 nm and 0.191 nm (Fig. 1C inset) corresponding to the

Conclusion

In summary, the core-shell structure of CeO2@C is successfully synthesized by a simple coprecipitation method. The CeO2@C can significantly catalyze the oxidation of H2O2 with bromination of organic signaling compounds to produce a blue-color reaction and possess excellent intrinsic haloperoxidase mimicry activity. Although the catalytic activity of CeO2@C is negligibly affected by temperature, it is sensitive to variations of pH, catalyst amount, and substrate concentration. The CeO2@C

CRediT authorship contribution statement

Nan Wang: Conceptualization, Methodology, Validation, Formal analysis, Investigation, Data curation, Writing - original draft, Writing - review & editing, Visualization. Wangqiang Li: Validation. Yadong Ren: Validation. Jizhou Duan: Writing - review & editing, Resources, Data curation, Supervision, Project administration, Funding acquisition. Xiaofan Zhai: Writing - review & editing, Data curation, Supervision, Project administration. Fang Guan: Funding acquisition. Lifei Wang: Project

Declaration of Competing Interest

The authors declare that they have no conflict of interest.

Acknowledgements

The present work was supported by the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (ZDBS-LY-DQC025), National Natural Science Foundation of China (No. 41706080 and No. 41806090), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDA13040403) and National Natural Science Foundation of China for Exploring Key Scientific Instrument (No. 41827805).

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