AgNPs@ZIF-67复合纳米粒子的合成及其抗菌性能研究※

doi:10.6023/A21110519

化学学报 ›› 2022, Vol. 80 ›› Issue (2): 110-115.DOI: 10.6023/A21110519 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究论文

AgNPs@ZIF-67复合纳米粒子的合成及其抗菌性能研究^※

陈敬煌^a^,^b, 孟天^a^,^b, 武烈^a, 石恒冲^b^,^c, 杨帆^a, 孙健^a^,^*(), 杨秀荣^a^,^b^,^*()

a 中国科学院长春应用化学研究所电分析化学国家重点实验室长春 130022
b 中国科学技术大学应用化学与工程学院合肥 230026
c 中国科学院长春应用化学研究所高分子物理与化学国家重点实验室长春 130022

投稿日期:2021-11-16 发布日期:2022-02-07
通讯作者: 孙健, 杨秀荣
作者简介:
^※庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家自然科学基金(22034006); 国家自然科学基金(21974132); 国家自然科学基金(21721003); 中国科学院青年创新促进会(2018258); 中国科学院青年创新促进会(2020233); 中国科学院青年创新促进会(2017269)

Study on Synthesis and Antibacterial Properties of AgNPs@ZIF-67 Composite Nanoparticles^※

Jinghuang Chen^a^,^b, Tian Meng^a^,^b, Lie Wu^a, Hengchong Shi^b^,^c, Fan Yang^a, Jian Sun^a(), Xiurong Yang^a^,^b()

a State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Changchun 130022
b School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026
c State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Changchun 130022

Received:2021-11-16 Published:2022-02-07
Contact: Jian Sun, Xiurong Yang
About author:
^※Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Natural Science Foundation of China(22034006); National Natural Science Foundation of China(21974132); National Natural Science Foundation of China(21721003); Youth Innovation Promotion Association, CAS(2018258); Youth Innovation Promotion Association, CAS(2020233); Youth Innovation Promotion Association, CAS(2017269)

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摘要/Abstract

细菌感染和因抗生素滥用而引发的细菌耐药性问题已经成为威胁公共健康的重大隐患, 开发新型、高效的抗菌剂势在必行. 金属有机框架材料(MOFs)是当今抗菌材料研究的热点之一. 多孔的碳骨架结构能够提供有限空间避免负载的金属纳米颗粒聚集以及有利于其稳定存在. 基于ZIF-67的载体作用, 发展了一种新颖、绿色、简便、低成本的银纳米颗粒-沸石咪唑骨架(AgNPs@ZIF-67)复合纳米粒子的制备方法. 利用透射电子显微镜、元素分布图谱、X射线衍射、X射线光电子能谱、N₂吸-脱附等温线和Zeta电位等表征手段证实了小尺寸AgNPs均匀、稳定地分散在ZIF-67上. 少量的AgNPs沉积大幅提升了ZIF-67的抗菌性能, 使AgNPs@ZIF-67成为一种很有前途的抗菌纳米材料.

关键词: 沸石咪唑骨架材料, 银纳米颗粒, AgNPs@ZIF-67, 均匀负载, 抗菌性能

Bacterial infection and resistance have threatened public health and it is necessary to develop a novel and efficient antibacterial agent. Metal-organic frameworks (MOFs) have been widely studied and applied in the antibacterial field. The porous carbon frameworks could provide intrinsic conditions to avoid the agglomeration and avail the stabilization of metal nanoparticles, which may be some synergies. Herein, a novel kind of AgNPs@ZIF-67 composite nanoparticles was prepared by a green, rapid, and cost-effective method, during which zeolitic imidazolate framework-67 (ZIF-67) acted as a template and small silver nanoparticles (AgNPs) could be facilely prepared in situ by the reduction of silver ions with fresh sodium borohydride (NaBH₄). Specifically, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images confirmed the existence of as-prepared AgNPs with average diameters of (7.05±0.09) nm and the introduction of AgNPs did not alter the size and rhombic dodecahedron-type morphology of ZIF-67. Energy-dispersive X-ray spectroscopy (EDS) elemental mapping revealed that AgNPs@ZIF-67 mainly contained uniformly dispersed C, N, O, Co and Ag elements. And the loading ratio of Ag weight content was 0.98% in it. The X-ray diffraction (XRD) pattern of the AgNPs@ZIF-67 sample showed a series of typical and sharp diffraction peaks in the (011), (002), (112), and (222) planes but no obvious peaks attributed to the AgNPs, which exhibited the formation of phase-pure ZIF-67 and well-dispersed of metallic Ag in ZIF-67. Zeta potentials showed a higher potential of ZIF-67 (+25.6 mV) than AgNPs@ZIF-67 (+17.7 mV), indicating the load of negative charged AgNPs and good stability of the as-obtained AgNPs@ZIF-67. Furthermore, Staphylococcus aureus (S. aureus) (ATCC 6538) was used in the antibacterial assay and the bacterial concentration was regarded as 1×10⁸ CFU• mL^–1 when the OD₆₀₀ value of the suspensions was 0.1. The in vitro minimum inhibitory concentration (MIC) of AgNPs@ZIF-67, ZIF-67 were 300, 350 µg•mL^–1, respectively. The antibacterial efficiency of AgNPs@ZIF-67, ZIF-67, and AgNPs at 24 h were 99.889%, 57.192%, and 26.433%, respectively. It was illustrated that the decoration of AgNPs could significantly improve the antibacterial ability of ZIF-67 nanomaterials. Moreover, SEM images of S. aureus showed that AgNPs@ZIF-67 did more serious damage to the cell membrane than ZIF-67. This work provided a facile method to fabricate the AgNPs@ZIF-67 composite nanoparticles, which was demonstrated as a promising antibacterial material based on the synergistic effect of AgNPs and ZIF-67.

Key words: zeolitic imidazolate framework, Ag nanoparticles, AgNPs@ZIF-67, uniformly load, antibacterial property

引用此文

陈敬煌, 孟天, 武烈, 石恒冲, 杨帆, 孙健, 杨秀荣. AgNPs@ZIF-67复合纳米粒子的合成及其抗菌性能研究^※[J]. 化学学报, 2022, 80(2): 110-115.

Jinghuang Chen, Tian Meng, Lie Wu, Hengchong Shi, Fan Yang, Jian Sun, Xiurong Yang. Study on Synthesis and Antibacterial Properties of AgNPs@ZIF-67 Composite Nanoparticles^※[J]. Acta Chimica Sinica, 2022, 80(2): 110-115.

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图/表 6

图1. 银纳米颗粒-沸石咪唑骨架(Ag nanoparticles-Zeolitic imidazolate framework-67, AgNPs@ZIF-67)复合纳米粒子制备示意图及抗菌应用

Figure 1. Schematic of the preparation and antibacterial application for Ag nanoparticles-Zeolitic imidazolate framework-67 (AgNPs@ZIF-67)

图2. 沸石咪唑框架材料-67 (ZIF-67)的扫描电镜(SEM)图像(a)和(b); (c)能量色散X射线谱(EDS)、粒径分布; (d)银纳米颗粒-沸石咪唑骨架纳米复合物(AgNPs@ZIF-67)的SEM图; (e)透射电子显微镜(TEM)图像; (f) EDS、粒径分布; (h) AgNPs@ZIF-67的高角环形暗场扫描透射(HAADF-STEM)图像和EDS映射图像

Figure 2. Scanning electron microscopy (SEM) of ZIF-67 (a) and (b); (c) energy-dispersive X-ray spectroscopy (EDS), particle size distribution of ZIF-67; (d) SEM of AgNPs@ZIF-67; (e) transmission electron microscopy (TEM) of AgNPs@ZIF-67; (f) energy-dispersive X-ray spectroscopy (EDS) and Particle size distribution of AgNPs@ZIF-67; (h) magnified HAADF-STEM images of AgNPs@ZIF-67 and EDS mapping images of AgNPs@ZIF-67

图3. ZIF-67和AgNPs@ZIF-67的(a) X射线衍射(XRD)图谱, (b)傅立叶变换红外(FTIR)图谱, (c) N2吸/脱附等温线, (d) Zeta电位

Figure 3. (a) X-ray diffraction (XRD) patterns, (b) Fourier transform infrared (FTIR) absorption spectra, (c) N2 adsorption-desorption isotherms and (d) zeta potential of ZIF-67 and AgNPs@ZIF-67

图4. (a) ZIF-67和AgNPs@ZIF-67的X射线光电子能谱(XPS); AgNPs@ZIF-67的高分辨XPS谱图Co 2p (b), Ag 3d (c), C 1s (d)

Figure 4. (a) X-ray photoelectron spectroscopy (XPS) survey spectra of ZIF-67 and AgNPs@ZIF-67; high-resolution XPS spectra of Co 2p (b), Ag 3d (c), C 1s (d) in AgNPs@ZIF-67

图5. (a)~(c)金黄色葡萄球菌暴露在不同浓度的AgNPs@ZIF-67, ZIF-67或AgNPs中的生长曲线; (d) AgNPs@ZIF-67, ZIF-67或AgNPs分别在4、12、24 h时对金黄色葡萄球菌的抗菌效率(*显著性, *p<0.05, **p<0.01, ***p<0.001)

Figure 5. (a)~(c) Growth curves of S. aureus exposed to different concentrations of AgNPs@ZIF-67, ZIF-67, or AgNPs; (d) antimicrobial efficiencies of AgNPs@ZIF-67, ZIF-67, or AgNPs after incubation with S. aureus for 4, 12, or 24 h, respectively (*significant, *p<0.05, **p<0.01, ***p<0.001)

图6. (a)在琼脂板上与AgNPs@ZIF-67, ZIF-67, AgNPs或PBS共培养4, 12, 24 h后的金黄色葡萄球菌菌落图像; (b)分别与AgNPs@ZIF-67, ZIF-67, AgNPs或PBS共培养24 h的金黄色葡萄球菌采用SEM拍摄的形态学图像

Figure 6. (a) Images of surviving S. aureus colonies on culture plates after incubation with AgNPs@ZIF-67, ZIF-67, AgNPs, or PBS for 4, 12, and 24 h, respectively; (b) morphologies of S. aureus after incubation with AgNPs@ZIF-67, ZIF-67, AgNPs, or PBS for 24 h imaged using a SEM

参考文献 41

[1]	Qi, Y.; Ren, S.; Che, Y.; Ye, J.; Ning, G. Acta Chim. Sinica 2020, 78, 613. (in Chinese) doi: 10.6023/A20040126
	( 齐野, 任双颂, 车颖, 叶俊伟, 宁桂玲, 化学学报, 2020, 78, 613.)
[2]	Han, Y.; Liu, Z.; Chen, T. Front. Microbiol. 2021, 12, 643422. doi: 10.3389/fmicb.2021.643422
[3]	Chen, H.; Xu, F.; Xue, D.; Yang, Y.; Zhang, Q. Acta Chim. Sinica 2012, 70, 1362. (in Chinese) doi: 10.6023/A1201143
	( 陈华军, 徐伏秋, 薛冬, 阳永福, 张秋芬, 化学学报, 2012, 70, 1362.)
[4]	Liao, C.; Li, Y.; Tjong, S. Int. J. Mol. Sci. 2019, 20, 449. doi: 10.3390/ijms20020449
[5]	Zhang, Y.; Zhang, X.; Song, J.; Jin, L.; Wang, X.; Quan, C. Nanomaterials 2019, 9, 1579. doi: 10.3390/nano9111579
[6]	Braakhuis, M.; Gosens, I.; Krystek, P.; Boere, J.; Cassee, F.; Fokkens, P.; Post, J.; Loveren, H.; Park, M. Part. Fibre Toxicol. 2014, 11, 49. doi: 10.1186/s12989-014-0049-1
[7]	Li, R.; Chen, T.; Pan, X. ACS Nano 2021, 15, 3808. doi: 10.1021/acsnano.0c09617
[8]	Zeng, J.; Wang, X.; Zhang, X.; Zhuo, R. Acta Chim. Sinica 2019, 77, 1156. (in Chinese) doi: 10.6023/A19070259
	( 曾锦跃, 王小双, 张先正, 卓仁禧, 化学学报, 2019, 77, 1156.)
[9]	Li, J.; Lv, F.; Li, J.; Li, Y.; Gao, J.; Luo, J.; Xue, F.; Ke, Q.; Xu, H. Nano Res. 2020, 13, 2268. doi: 10.1007/s12274-020-2846-1
[10]	Chen, J.; Bao, X.; Meng, T.; Sun, J.; Yang, X. Chem. Eng. J. 2022, 430, 133091. doi: 10.1016/j.cej.2021.133091
[11]	Aguado, S.; Quiros, J.; Canivet, J.; Farrusseng, D.; Boltes, K.; Rosal, R. Chemosphere 2014, 113, 188. doi: 10.1016/j.chemosphere.2014.05.029
[12]	Shi, Q.; Luo, X.; Huang, Z.; Midgley, A. C.; Wang, B.; Liu, R.; Zhi, D.; Wei, T.; Zhou, X.; Qiao, M.; Zhang, J.; Kong, D.; Wang, K. Acta Biomater. 2019, 86, 465. doi: 10.1016/j.actbio.2018.12.048
[13]	Abd El Salam, H. M.; Nassar, H. N.; Khidr, A. S. A.; Zaki, T. J. Inorg. Organomet. Polym. Mater. 2018, 28, 2791. doi: 10.1007/s10904-018-0950-4
[14]	Li, W.; Yang, F.; Fang, X.; Rui, Y.; Tang, B. Electrochim. Acta 2018, 282, 276. doi: 10.1016/j.electacta.2018.06.066
[15]	Sun, D.; Yang, D.; Wei, P.; Liu, B.; Chen, Z.; Zhang, L.; Lu, J. ACS Appl. Mater. Interfaces 2020, 12, 41960. doi: 10.1021/acsami.0c11269
[16]	Takashima, Y.; Sato, Y.; Tsuruoka, T.; Akamatsu, K. Dalton Trans. 2020, 49, 17169. doi: 10.1039/D0DT03259J
[17]	Zhao, Y.; Sun, X.; Zhang, G.; Trewyn, B.; Slowing, I.; Lin, V. ACS Nano 2011, 5, 1366. doi: 10.1021/nn103077k
[18]	Recordati, C.; De Maglie, M.; Bianchessi, S.; Argentiere, S.; Cella, C.; Mattiello, S.; Cubadda, F.; Aureli, F.; D'Amato, M.; Raggi, A.; Lenardi, C.; Milani, P.; Scanziani, E. Part. Fibre Toxicol. 2016, 13, 12. doi: 10.1186/s12989-016-0124-x
[19]	Yang, M.; Shao, Z.; Liao, X.; Xu, W.; Zhang, Y. Chin. J. Anal. Chem. 2020, 48, 1674. (in Chinese)
	( 杨梅, 邵泽宇, 廖晓玲, 徐文峰, 张园园, 分析化学, 2020, 48, 1674.)
[20]	Han, B.; Yan, Q.; Xin, Z.; Yan, Q.; Jiang, J. Chin. J. Anal. Chem. 2020, 48, 1025. (in Chinese)
	( 韩冰雁, 闫琴, 辛泽, 燕琪芳, 姜静美, 分析化学, 2020, 48, 1025.)
[21]	Sun, Y.; Qi, Y.; Shen, Y.; Jing, C.; Chen, X.; Wang, X. Acta Chim. Sinica 2020, 78, 147. (in Chinese) doi: 10.6023/A19090338
	( 孙延慧, 齐有啸, 申优, 井翠洁, 陈笑笑, 王新星, 化学学报, 2020, 78, 147.)
[22]	Huang, X.; Lin, Y.; Zhang, J.; Chen, X. Angew. Chem., Int. Ed. 2006, 45, 1557. doi: 10.1002/(ISSN)1521-3773
[23]	Ivanova, T.; Harizanova, A.; Koutzarova, T.; Vertruyen, B. Superlattices Microstruct. 2014, 70, 1. doi: 10.1016/j.spmi.2014.03.007
[24]	Yu, Z.; Qian, L.; Zhong, T.; Ran, Q.; Huang, J.; Hou, Y.; Li, F.; Li, M.; Sun, Q.; Zhang, H. Mol. Catal. 2020, 485, 110797.
[25]	Zhao, K.; Guo, J.; Wei, H.; Yang, Y. Eur. J. Inorg. Chem. 2019, 46, 4920.
[26]	Sang, Y.; Cao, F.; Li, W.; Zhang, L.; You, L.; Deng, Q.; Dong, K.; Ren, J.; Qu, X. J. Am. Chem. Soc. 2020, 142, 5177. doi: 10.1021/jacs.9b12873
[27]	Fan, L.; Meng, T.; Yan, M.; Wang, D.; Chen, Y.; Xing, Z.; Wang, E.; Yang, X. Small 2021, e2100998.
[28]	Saghir, S.; Xiao, Z. J. Mol. Liq. 2021, 328, 115323. doi: 10.1016/j.molliq.2021.115323
[29]	Huang, X.; Xu, X.; Li, C.; Wu, D.; Cheng, D.; Cao, D. Adv. Energy Mater. 2019, 9, 1803970. doi: 10.1002/aenm.v9.22
[30]	Shakya, S.; He, Y.; Ren, X.; Guo, T.; Maharjan, A.; Luo, T.; Wang, T.; Dhakhwa, R.; Regmi, B.; Li, H.; Gref, R.; Zhang, J. Small 2019, 15, e1901065.
[31]	Miao, X.; Yu, F.; Liu, K.; Lv, Z.; Deng, J.; Wu, T.; Cheng, X.; Zhang, W.; Cheng, X.; Wang, X. Bioact. Mater. 2022, 7, 181.
[32]	Zhao, J.; Bao, X.; Meng, T.; Wang, S.; Lu, S.; Liu, G.; Wang, J.; Sun, J.; Yang, X. Chem. Eng. J. 2021, 420, 129674. doi: 10.1016/j.cej.2021.129674
[33]	Qian, L.; Lei, D.; Duan, X.; Zhang, S.; Song, W.; Hou, C.; Tang, R. Carbohydr. Polym. 2018, 192, 44. doi: 10.1016/j.carbpol.2018.03.049
[34]	Huang, L.; Chen, J.; Wang, J.; Dong, S. Sci. Adv. 2019, 5, eaav5490. doi: 10.1126/sciadv.aav5490
[35]	Chao, D.; Dong, Q.; Chen, J.; Yu, Z.; Wu, W.; Fang, Y.; Liu, L.; Dong, S. Appl. Catal., B 2022, 304, 121017. doi: 10.1016/j.apcatb.2021.121017
[36]	Liu, L.; Luo, X.; Liu, J. Small 2020, 16, e2000011.
[37]	Karimi Alavijeh, R.; Beheshti, S.; Akhbari, K.; Morsali, A. Polyhedron 2018, 156, 257. doi: 10.1016/j.poly.2018.09.028
[38]	Shen, M.; Forghani, F.; Kong, X.; Liu, D.; Ye, X.; Chen, S.; Ding, T. Compr. Rev. Food Sci. Food Saf. 2020, 19, 1397. doi: 10.1111/crf3.v19.4
[39]	Fang, G.; Li, W.; Shen, X.; Perez-Aguilar, J. M.; Chong, Y.; Gao, X.; Chai, Z.; Chen, C.; Ge, C.; Zhou, R. Nat. Commun. 2018, 9, 129. doi: 10.1038/s41467-017-02502-3
[40]	Li, Z.; Gao, J.; Jian, M.; Wang, Z. Chin. J. Anal. Chem. 2018, 46, 1904. (in Chinese)
	( 李铸衡, 高晶清, 简明红, 王振新, 分析化学, 2018, 46, 1904.)
[41]	Liu, T.; Yan, S.; Zhou, R.; Zhang, X.; Yang, H.; Yan, Q.; Yang, R.; Luan, S. ACS Appl. Mater. Interfaces 2020, 12, 42576. doi: 10.1021/acsami.0c13413

AgNPs@ZIF-67复合纳米粒子的合成及其抗菌性能研究^※

Study on Synthesis and Antibacterial Properties of AgNPs@ZIF-67 Composite Nanoparticles^※

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AgNPs@ZIF-67复合纳米粒子的合成及其抗菌性能研究※

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AgNPs@ZIF-67复合纳米粒子的合成及其抗菌性能研究^※

Study on Synthesis and Antibacterial Properties of AgNPs@ZIF-67 Composite Nanoparticles^※