Novel Magnetoelectric Catalytic Nanoparticles: RNS Release and Antibacterial Efficiency

doi:10.15541/jim20240152

Abstract

Abstract:

Compared with antibiotics and other drugs with poor functionalities and risk to induce bacterial resistance, inorganic functional nanomaterials with catalytic activity occupy an increasingly important position in the treatment of pathogenic infections by advantages of high response to the infected microenvironment (e.g. weak acid, high H₂O₂ concentration) or external physical stimuli (e.g. laser, ultrasound) and broad-spectrum sterilization. However, the acidic infection microenvironment is weak and unstable, and light or sound signals with high power density will cause damage to human cells. In addition, antimicrobial applications of alternative magnetic field (AMF), a non-invasive signal type with high tissue penetration, convenience to be remotely controlled, and effective magnetoelectric catalysis based on AMF have not been reported. In this study, an AMF-responsive nanocatalytic strategy based on the magnetostrictive-piezoelectric catalytic effect was applied to antibacterial research, and the surface of CoFe₂O₄-BiFeO₃ magnetoelectric nanoparticles (BCFO) was modified with the nitrogen-containing group L-arginine (LA) to achieve a magneto-electric responsive controlled release of powerful bactericide reactive nitrogen species (RNS). In AMF, BCFO simultaneously generates reactive oxygen species (ROS) hydroxyl radical (·OH) and superoxide anion (·O₂^-). The former reacts with LA to release nitric oxide (NO), and the latter combines with NO to produce peroxynitrite (ONOO^-), a typical RNS. As a highly active nitrification and oxidation agent, ONOO^- could exhibit stronger antibacterial activity than ROS under biofriendly AMF. Successful production of ONOO^- and achievement of stronger bactericidal efficiency were validated in this study. This work not only applies magnetoelectric nanocatalysis for antibacterial purposes, but also significantly improves the antibacterial ability through the conversion of ROS to RNS.

Key words: nanocatalytic medicine, magnetoelectric response, reactive nitrogen species, antibacterial

CLC Number:

TB34
R613

ZHANG Zhimin, GE Min, LIN Han, SHI Jianlin. Novel Magnetoelectric Catalytic Nanoparticles: RNS Release and Antibacterial Efficiency[J]. Journal of Inorganic Materials, 2024, 39(10): 1114-1124.

Figures/Tables 10

Fig. 1 Schematic diagram of the ONOO- generating and antibacterial mechanisms of BCFO-LA BCFO: CoFe2O4-BiFeO3 magnetoelectric nanoparticles; LA: L-arginine

Fig. 2 Morphology, component and construction characterizations of BCFO (a-c) TEM (a), HRTEM (b) and bright field (c) images of BCFO; (d) Element mappings of BCFO; (e) Molar percentages of metal elements in BCFO according to ICP-OES; (f) XRD pattern of BCFO; (g-i) Total (g),Fe2p (h) and O1s (i) XPS spectra of BCFO; Colorful figures are available on website

Fig. 3 Performance evaluation of BCFO (a) Hysteresis loops of CFO and BCFO in AMF (1 emu/g = 104 G/g, 1 Oe = 79.577472 A/m); (b) Piezoresponsive amplitude and phase curves of BCFO; (c) EPR patterns of DMPO solutions with different treatments; (d) UV-Vis absorption spectra of DPBF treated by BCFO under AMF at different time points

Fig. 4 Theoretical simulation of BCFO in AMF (a-e) COMSOL simulations of magnetization (a), von Mises stress (b), volumetric strain (c), displacement (d), and electric potential (e) produced by BCFO in AMF; (f-h) Relationships between AMF and volumetric strain (f), AMF and displacement (g) as well as volumetric strain and electric potential (h) in BCFO derived from COMSOL

Fig. 5 Preparation, characterization and ONOO--generation property of BCFO-LA (a) Preparing processes of PLGA-TK-LA (EDCl: 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; NHS: N-Hydroxysuccinimide; DMF: N,N-Dimethylformamide; DCC: N,N'-Dicylohexylcarbodiimide; DMAP: 4-Dimethylaminopyridine); (b) 1H NMR spectrum of PLGA-TK-LA; (c) Schematic diagram of BCFO-LA preparation (BCFO: CoFe2O4-BiFeO3, cobalt ferrite-bismuth ferrite); (d) TEM image of BCFO-LA with negative staining, where the shaded area circled by dotted line refers to PLGA-TK-LA; (e) Hydraulic diameter distributions of BCFO-LA; (f) Fluorescence emission spectra of L-tyrosine probe after co-incubated with BCFO-LA at different time points under AMF (B = 1.7 mT, λex = 265 nm)

Fig. 6 Antibacterial performance of BCFO-LA (a, b) Plate-spreading photos (a) and survival rates (b) of S. aureus treated by BCFO; (c, d) Plate-spreading photos (c) and survival rates (d) of S. aureus treated by BCFO-LA; (e, f) Flow cytometry results of DCFH-DA stained S. aureus (e) and relative DCF fluorescence intensities (f)

Fig. S1 Morphology and phase characterizations of CFO (a, b) TEM image (a) and XRD pattern (b) of CFO; (c, d) TEM image (c) and XRD pattern (d) of CFO coated with BFO precursor

Fig. S2 Morphology characterization of BCFO (a) SEM image of BCFO; (b) Dark field image of BCFO derived from HRTEM

Fig. S3 Size distributions of CFO and BCFO (a, b) Size distributions of CFO (a) and BCFO (b) according to TEM images

Fig. S4 Influence of AMF on bacterial survival rates Plate-spreading photos (a) and survival rates (b) of S. aureus treated by AMF

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