Mussel-inspired synthesis of magnetic N-Halamine nanoparticles for antibacterial recycling

https://doi.org/10.1016/j.colcom.2020.100320Get rights and content

Highlights

  • A mussel-inspired synthesis for achieving N-halamine coatings is proposed.

  • The coating mechanism relies on the ligand exchange.

  • N-Halamine coatings endow good antibacterial activity and renewability.

Abstract

Antibacterial N-halamine coatings are successful in avoiding and eliminating bacterial infections caused by bacterial contamination and biofilms on the surfaces. However, the N-halamine coatings remain a long-standing challenge faced by our healthcare system. Herein we reported a new mussel-inspired surface modification strategy to achieve N-halamine copolymer coatings with adhesive effects. The phenolic hydroxyl groups from N-halamine copolymers are used for ligand exchange with oleic acid on the magnetic Fe3O4 nanoparticles for binding the N-halamine copolymer onto the surface of the nanoparticles. The as-synthesized N-halamine coatings endow the magnetic Fe3O4 nanoparticles antibacterial activity toward both Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus). Since the super-paramagnetism of Fe3O4 in core, the N-halamine coatings are separable magnetically and remain high inactivating efficiency toward bacteria even after five cycles. We believe that, with the advantage of mussel-inspired strategy, the N-halamine coatings should have great potential for use in antibacterial and biomedical fields.

Introduction

At present, microbial infections arising from pathogenic microorganisms and biofilm have become a major concern to global healthcare [1,2]. A variety of antibacterial agents and techniques have been developed to combat pathogens [3,4], such as NO-releasing agents [5], silver nanoparticles [[6], [7], [8], [9]], quaternary ammonium salts [10,11], povidone iodine [12], and N-halamines [13,14] etc. Due to the effectiveness against a broad spectrum of microorganisms, long-term physicochemical stability, high structural durability, and the rechargeablity of their functional groups and antibacterial properties [15,16], N-halamines have been successful in eliminating harmful pathogens and are becoming the most popular disinfectants [17]. Especially, N-halamine coatings on materials that endows materials' surfaces antibacterial functions have become the main topic of antibacterial- and antifouling-associated research [18]. According to previous reports [19], N-halamines could attached onto various materials via the chemical bindings, including stainless steel [20], nanoparticles [21], and so on, to kill bacteria and resist biofilm. However, the N-halamine coatings suffered from cumbersome coating reaction, low yield, low halogen loading, and poor stability, which restricts the use of N-halamine coatings in practical application. Therefore, it is urgent to find a simple and efficient approach to develop N-halamine coatings with strong antibacterial activity and high durability.

Inspired by the distinct adhesion capability of mussels on wet surfaces [22], it was found dopamine have a broad range of applications as a universal surface modification agent for various materials [[23], [24], [25]]. Dopamine can interact with metals or non-metals, including precious metal and natural oxide surfaces, without the sophisticated instruments and harsh conditions [26]. It also can form a layer and adhere to nanoparticles via self-polymerization [27], which can not only functionalize the nanoparticles but also prevent the nanoparticles from being further oxidized [28,29]. Thanks to the excellent adhesion capability, dopamine and its derivatives have widely been used in materials science and polymer chemistry, as ideal cross-linking agents instead of chemical bindings.

Herein, we present a mussel-inspired synthesis to achieve magnetic N-halamine nanoparticles (i.e., Fe3O4@pDAH-Cl) promising for antibacterial use and recycling [30], which was constructed simply by anchoring dopamine crosslinked N-halamine copolymer onto Fe3O4 nanoparticles [31]. The poly(DMA-co-ADMH-co-HEMA) copolymer (pDAH) was synthesized via radical copolymerization of dopamine methacrylamide (DMA), 3-allyl-5,5-dimethylhydantoin (ADMH), and hydroxyethyl methacrylate (HEMA) [32], and adhered onto the surface of the magnetic Fe3O4 nanoparticles via the mussel-inspired “Graft to” approach with high loadings [30]. After the chlorination treatment, the hydantoin groups of pDAH transform to N-halamine structure, and the final products Fe3O4@pDAH-Cl nanoparticles formed. As expected, the as-prepared Fe3O4@pDAH-Cl nanoparticles showed magnetic properties and inactivated both Gram-positive S. aureus and Gram-negative E. coli. More importantly, the magnetic performance of the as-prepared nanoparticles allow them easily separable from aqueous solution by external magnets and reusable in antibacterial applications.

Section snippets

Materials

Methacrylicanhydride (95%) was purchased from Energy Chemical. Magnesium sulfate anhydrous (99.99%) was obtained from Macklin. FeSO4·7H2O (≥99.0%), ammonium hydroxide (25%), FeCl3·6H2O (99%), oleic acid (85%), sodium bicarbonate (98%), 5,5-dimethylhydantoin (DMH, ≥98.0%), 2,2-azobis(2-methylpropionitrile) (AIBN, 99%), allylbromide (98%), and 2-hydroxyethyl methacrylate (HEMA, 99%) were all purchased from Aladdin Bio-Chem Technology Co. Ltd. (Shanghai, China). Sodium hydroxide (NaOH) and sodium

Results and discussion

As shown in Fig. 1, the synthesis of DMA, ADMH and pDAH was confirmed by 1H NMR spectrum on a Bruker 400 MHz spectrometer, using DMSO as solvent. The peaks corresponding to ADMH showed at 8.0 and 3.7 ppm, which belong respectively to Nsingle bondH (e) and -CH2 (b) adjacent to five-membered ring [36]. It can be observed that the resonance signals of the phenolic hydroxyl (a), phenyl (b and c), and Nsingle bondH (f) of DMA appear at 8.7–8.8 ppm, 6.4–6.7 ppm, and 7.6 ppm, respectively [37]. Two -CH2 (d and e) signal

Conclusion

In summary, a mussel-inspired synthetic strategy was introduced as a novel and efficient method for coating N-halamine copolymers onto magnetic Fe3O4 nanoparticles. Through constructing the copolymer of dopamine and N-halamine with an interpenetrating network structure, the dopamine makes N-halamine more easily fix on magnetic nanoparticles. And the ligands exchanging between catechol structure (copolymer) and metal oxide (magnetic Fe3O4 nanoparticles) further reinforced the coatings onto

Declaration of Competing Interest

This manuscript has been submitted exclusively to Colloid and Interface Science Communications. It has not been published nor is it under consideration for publication elsewhere. All authors have read and approved the submission of the manuscript. There is no conflict of interest.

Acknowledgements

This research was supported by the National Natural Science Foundation of China (21304044 and 51663019), the Natural Science Foundation of Inner Mongolia Autonomous Region (2015MS0520 and 2019JQ03), the State Key Laboratory of Medicinal Chemical Biology (201603006 and 2018051), the State Key Laboratory of Polymer Physics and Chemistry (2018-08), and the Program of Higher-Level Talents of Inner Mongolia University (30105-125136).

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      Citation Excerpt :

      The signal peaks corresponding to CC (d) of NDAM appear at δ = 2.83 ppm and δ = 2.99 ppm [51,52]. The NH (e) on the five-membered ring and the NH (e) signal peak of the condensation reaction to form an amide is shown at 4.30 ppm [53]. The appearance of these peaks confirm the successful synthesis of the N-halamine precursor NDAM.

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