负载硫化铋纳米簇的硅基杂化胶束制备及其光热抗菌性能

doi:10.15541/jim20240530

摘要/Abstract

摘要： 铋基纳米材料作为一种新型的光热试剂,具有价格便宜、毒性低、环境友好、原料廉价易得等优势,在生物光热治疗方面展示出较大的应用潜力,但其光热转换效率和抗菌性能仍然较低。本研究首先基于课题组前期报道的限域凝胶化方法,以普朗尼克聚合物F127和3-巯基丙基-三甲氧硅烷为原料,制备了有机硅氧骨架稳定胶束内核的硅基杂化胶束前驱体,发展了简便的“受限还原/硫化”方法,即利用杂化胶束有机氧化硅网络内核中丰富的巯基基团作为受限吸附位点、硼氢化钠作为还原剂、硫化钠作为硫化剂,制备了超小、具有无定形结构的硫化铋簇负载的硅基杂化胶束体系。结果表明,该功能杂化胶束体系具有优异的光热性能,其光热转换效率高达86.9%,这可归功于具有缺陷结构的硫化铋团簇在硅氧骨架网络中的单分散稳定负载,进而增强了硫化铋纳米材料在近红外光波段的光吸收能力。体外抗菌实验结果表明,该体系在808 nm近红外光的辐照下展示出优异的光热抗菌性能且具有良好的生物相容性。

关键词: 氧化硅, 嵌段共聚物, 硫化铋, 光热性能, 抗菌剂

Abstract: As a new type of photothermal compound, bismuth-based nanomaterials have advantages of low price, low toxicity, environmental friendliness and cheap raw materials, showing great application potential in biological photothermal therapy, but its photothermal conversion efficiency and antibacterial property are still low. In this paper, based on the confined gelation method reported by our previous literature, a silica-based hybrid micellar precursor with organosilica-stabilized micellar cores was prepared using Pluronic polymer F127 and 3-mercaptopropyl-trimethoxy- silane as raw materials, and a facile "confined reduction/sulfuration " method was further developed, that is, the abundant thiols groups in the organosilica framework of the micelle core were used as restricted adsorption site, sodium borohydride was used as reducing agent, and sodium sulfide was used as the vulcanizing agent to prepare ultra-small and amorphous bismuth sulfide clusters-supported silica-based hybrid micellar system. The results show that the functional hybrid micellar system has excellent photothermal performance, and its photothermal conversion efficiency is up to 86.9%, which may be attributed to monodisperse and stable loading of bismuth sulfide clusters with defective structure in the organosilica framework of hybrid micellar system, which enhances tlight absorption capacity of bismuth sulfide nanomaterials in the near-infrared wavelength range. The in vitro antimicrobial experiments showed that this bismuth-containing system exhibited excellent photothermal antibacterial properties under irradiation of 808 nm near-infrared laser and good biocompatibility.

Key words: silica, block copolymer, bismuth sulfide, photothermal property, antibacterial agent

中图分类号:

TQ174

赵丽华, 王言帅, 尹昕妩, 毛叶琼, 牛德超. 负载硫化铋纳米簇的硅基杂化胶束制备及其光热抗菌性能[J]. 无机材料学报, DOI: 10.15541/jim20240530.

ZHAO Lihua, WANG Yanshuai, YIN Xinwu, MAO Yeqiong, NIU Dechao. Bismuth Sulfide Nanoclusters-loaded Silica-based Hybrid Micelles: Preparation and Photothermal Antibacterial Property[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20240530.

参考文献

[1] ZHI D F, YANG T, O’HAGAN J,et al. Photothermal therapy. Journal of Controlled Release, 2020, 325: 52.
[2] LI C W, CHENG Y, LI D W,et al. Antitumor applications of photothermal agents and photothermal synergistic therapies. International Journal of Molecular Sciences, 2022, 23(14): 7909.
[3] HE Z Y, BU P Z, XU K,et al. Remodeling of the pro-inflammatory microenvironment in osteoarthritis via hydrogel-based photothermal therapy. Advanced Composites and Hybrid Materials, 2024, 7(2): 36.
[4] LV H W, ZHOU X M, YANG G,et al. Bismuth@Bismuth sulfide Core@Shell structure for near infrared II light triggered photothermal therapy. ChemistrySelect, 2024, 9(12): e202304834.
[5] YE M L, SHI F, SHEN M,et al. Composite soft-template method synthesis and biosensing application of hedgehog-like bismuth sulfide micro-nanostructures. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 613: 126094.
[6] SUN B, FENG T T, DONG J,et al. Green synthesis of bismuth sulfide nanostructures with tunable morphologies and robust photoelectrochemical performance. CrystEngComm, 2019, 21(9): 1474.
[7] ANASANE N, AMETA R.Morphologies of nanostructured bismuth sulphide and Mn (II) doped bismuth sulphide nanoparticles: characterization and application.Materials Science-Poland, 2017, 35(1): 6.
[8] SHAHBAZI M A, FAGHFOURI L, FERREIRA M P A,et al. The versatile biomedical applications of bismuth-based nanoparticles and composites: therapeutic, diagnostic, biosensing, and regenerative properties. Chemical Society Reviews, 2020, 49(4): 1253.
[9] NIKODIMOS Y, HUANG C J, TAKLU B W,et al. Chemical stability of sulfide solid-state electrolytes: stability toward humid air and compatibility with solvents and binders. Energy & Environmental Science, 2022, 15(3): 991.
[10] LI Y H, TAN X X, WANG H,et al. Spectral computed tomography-guided photothermal therapy of osteosarcoma by bismuth sulfide nanorods. Nano Research, 2023, 16(7): 9885.
[11] FANG Q L, XU Y, LUO L J, ,et al. Controllable synthesis of layered black bismuth oxidechloride nanosheets. Controllable synthesis of layered black bismuth oxidechloride nanosheets and their applications in internal tumor ablation. Regenerative Biomaterials, 2022, 9: rbac036.
[12] SONG S L, LIAO L, LEI H,et al. Purification of iodine from high-temperature argon environment by bismuth sulfide-modified zeolite. Atomic Energy Science and Technology, 2025, 59(1): 57.
[13] DING F C, WANG Q J, ZHOU S F,et al. Synthesis of Bi₂S₃ thin films based on pulse-plating bismuth nanocrystallines and its photoelectrochemical properties. Royal Society Open Science, 2020, 7(8): 200479.
[14] CHENG J H, FENG W L, YANG X Z,et al. High-performance Bi₂S₃ photodetector based on oxygen-mediated defect engineering and its wafer-scale fast fabrication. Journal of Colloid and Interface Science, 2025, 679: 373.
[15] ZHAO Z W, CHI Z R, SUN Q Q,et al. Preparation and performance of palladium clusters-loaded silica-based hybrid micelles. Journal of East China University of Science and Technology, 2023, 49(4): 498.
[16] ZHANG X, QIAO X F, SHI W,et al. Phonon and Raman scattering of two-dimensional transition metal dichalcogenides from monolayer, multilayer to bulk material. Chemical Society Reviews, 2015, 44(9): 2757.
[17] YU N, LIU X L, LU Z W, ,et al. Polymorph control. Polymorph control, phase transitions and photocatalytic activity of bismuth oxide with emphasis on sodium-impurity effects. Ceramics International, 2025, in press.
[18] CHENG D Y, CHANG Y, FENG Y L,et al. Deep-level defect enhanced photothermal performance of bismuth sulfide-gold heterojunction nanorods for photothermal therapy of cancer guided by computed tomography imaging. Angewandte Chemie International Edition, 2018, 57(1): 246.
[19] ZHAO X S, LI S W, HUANG T D,et al. Synthesis of Au/Bi₂S₃ nanoflowers for efficient photothermal therapy. New Journal of Chemistry, 2020, 44(43): 18724.
[20] LUO K Y, ZHAO J L, JIA C Z,et al. Integration of Fe₃O₄ with Bi₂S₃ for multi-modality tumor theranostics. ACS Applied Materials & Interfaces, 2020, 12(20): 22650.
[21] LU X, LI Y, BAI X, et al. Multifunctional Cu_1.94S-Bi₂S₃@polymer nanocomposites for computed tomography imaging guided photothermal ablation. Science China Materials, 2017, 60(8): 777.
[22] WANG X, ZHANG C Y, DU J F,et al. Enhanced generation of non-oxygen dependent free radicals by Schottky-type heterostructures of Au-Bi₂S₃ nanoparticles via X-ray-induced catalytic reaction for radiosensitization. ACS Nano, 2019, 13(5): 5947.
[23] WANG W N, PEI P, CHU Z Y,et al. Bi₂S₃ coated Au nanorods for enhanced photodynamic and photothermal antibacterial activities under NIR light. Chemical Engineering Journal, 2020, 397: 125488.
[24] YU G D, LIU A L, JIN H L,et al. Urchin-shaped Bi₂S₃/Cu₂S/Cu₃BiS₃ composites with enhanced photothermal and CT imaging performance. The Journal of Physical Chemistry C, 2018, 122(7): 3794.