Ag量子点协同四环素的抑菌及其机制

郭少波; 陈惠惠; 刘轲; 胡瑞玲; 王嘉伟; 余凡; 刘智峰; 史娟; 郭婷; 季晓晖; 张田雷

doi:10.13801/j.cnki.fhclxb.20240008.002

Ag量子点协同四环素的抑菌及其机制

doi: 10.13801/j.cnki.fhclxb.20240008.002

郭少波^{1, 2, ,},
陈惠惠¹,
刘轲⁴,
胡瑞玲¹,
王嘉伟¹,
余凡³,
刘智峰^{1, 2},
史娟^{1, 2},
郭婷^{1, 2},
季晓晖^{1, 2},
张田雷^{1, 2}

1.
陕西理工大学　化学与环境科学学院，汉中 723000
2.
陕西省催化基础与应用重点实验室，汉中 723000
3.
城固县市场监督管理局，汉中 723000
4.
延安市食品质量安全检测检测中心，延安 716000

基金项目: 秦巴生物资源与生态环境国家重点实验室科研基金(SXS-2105)；陕西省教育厅项目(22JK-0317)；陕西省自然科学基金(2023-JC-QN-0162；2023-YBSF-334)；陕西理工大学基础研究基金(SLGKYXM2208)

详细信息

通讯作者:
郭少波，博士，副教授，硕士生导师，研究方向为抑菌材料　E-mail: 545366954@qq.com

中图分类号: X524；TB332
计量
- 文章访问数: 257
- HTML全文浏览量: 168
- PDF下载量: 12
- 被引次数: 0
出版历程
- 收稿日期: 2023-11-06
- 修回日期: 2023-12-10
- 录用日期: 2023-12-23
- 网络出版日期: 2024-01-09
- 刊出日期: 2024-10-15

Bacteriostatic performance and mechanism of Ag quantum dots synergistic tetracycline

GUO Shaobo^{1, 2
, ,},
CHEN Huihui¹,
LIU Ke⁴,
HU Ruiling¹,
WANG Jiawei¹,
YU Fan³,
LIU Zhifeng^{1, 2},
SHI Juan^{1, 2},
GUO Ting^{1, 2},
JI Xiaohui^{1, 2},
ZHANG Tianlei^{1, 2}

1.
School of Chemistry and Environmental Science, Shaanxi University of Technology, Hanzhong 723000, China
2.
Shaanxi Province Key Laboratory of Catalytic Foundation and Application, Hanzhong 723000, China
3.
Chenggu County Market Authority, Hanzhong 723000, China
4.
Yan'an Food Quality and Safety Inspection and Testing Centre, Yan'an 716000, China

Funds: Scientific Research Fund of the State Key Laboratory of Biological Resources and Ecological Environment of Qinba (SXS-2105); Project of Shaanxi Provincial Department of Education (22JK-0317); Shaanxi Provincial Natural Science Foundation (2023-JC-QN-0162; 2023-YBSF-334); Fundamental Research Fund of Shaanxi University of Science and Technology (SLGKYXM2208)

摘要

摘要: 四环素类抗生素因具有高效、低毒、广谱抑菌性等优点而被广泛使用，但随着抗生素的滥用致使大量的耐药菌出现，使四环素类抗生素的药用价值逐渐降低。超小粒径的纳米Ag虽可使细菌甚至耐药菌失活，但单独使用毒性较强，且易团聚。为此，本文利用Ag的d轨道为满电子结构，可与供电子基团配位的原理，设计了核壳型介孔Fe₃O₄@SiO₂@mTiO₂@Ag-四环素(FSmTA-T)复合材料用以解决抗生素耐药和纳米Ag团聚、强毒性问题。研究结果显示，制备的复合材料中纳米Ag量子点的粒径约为2.84 nm，可与四环素环3中的羰基键合，同时，相比四环素，复合材料对大肠杆菌、金黄色葡萄球菌、耐四环素沙门氏菌和白色念珠菌均具有较高的抑菌活性，并可有效破坏细菌细胞壁而使其死亡，且对哺乳细胞的毒性降低为原来的1/3。因此，其优越的抑菌活性可应用于污水处理领域。
- 抑菌 /
- 纳米复合材料 /
- 抑菌机制 /
- 四环素 /
- 耐药 /
- Ag量子点
Abstract: Tetracycline antibiotics are widely used because of their high efficiency, low toxicity and broad-spectrum bacteriostasis, but with the abuse of antibiotics leading to the emergence of a large number of resistant bacteria, the medicinal value of tetracycline antibiotics gradually decreases. Although the ultra-small particle size of Ag can inactivate bacteria and even drug-resistant bacteria, it is highly toxic and easy to agglomerate when used alone. Therefore, in this study, the core-shell mesoporous Fe₃O₄@SiO₂@mTiO₂@Ag-tetracycline (FSmTA-T) composite was designed to solve the problems of antibiotic resistance, Ag nanoparticles agglomeration and strong toxicity by using the principle that the d orbital of Ag is a full electron structure and can be coordinated with the electron donor group. The results show that the particle size of the Ag quantum dots in the prepared composite is 2.84 nm, which could be bonded with the carbonyl group in tetracycline ring 3, and compared with tetracycline, the composite material has high bacteriostatic activity against Escherichia coli, Staphylococcus aureus, tetracycline-resistant Salmonella and Candida albicans, and could effectively destroy the bacterial cell wall and make it die, while the toxicity is reduced to 1/3 of the original. Therefore, its superior bacteriostatic activity can be applied to sewage treatment.
- bacteriostasis /
- nanocomposite material /
- antibacterial mechanism /
- tetracycline /
- drug resistance /
- Ag quantum dots

HTML全文

图 1 Fe₃O₄@SiO₂@mTiO₂@Ag-四环素(FSmTA-T)的制备原理示意图

Figure 1. Schematic diagram of the preparation principle of the Fe₃O₄@SiO₂@mTiO₂@Ag-tetracycline (FSmTA-T)

APTES—3-aminopropyl(diethoxy)methylsilane; Ag NPs—Silver nanoparticles

下载: 全尺寸图片幻灯片

图 2 F (a)、FS (b)、FST (c)、FSmT (d)、FSmTA-T (e)和Ag (f)的TEM图像

Figure 2. TEM images of F (a), FS (b), FST (c), FSmT (d), FSmTA-T (e) and Ag (f)

下载: 全尺寸图片幻灯片

图 3 (a) Ag量子点的粒径分布；(b) FSmTA-T的EDX图谱；((c), (d)) 不同样品的XRD和VSM图谱；(e)不同样品的紫外吸收图谱；(f) FSmTA-T的XPS全谱

Figure 3. (a) Particle size distribution of Ag quantum dots; (b) EDX spectrum of FSmTA-T; ((c), (d)) XRD and VSM patterns of different samples; (e) UV absorption spectra of different samples; (f) XPS spectrum of the FSmTA-T

d—Particle size

下载: 全尺寸图片幻灯片

图 4 C1s (a)、Fe2p (b)、N1s (c)、O1s (d)、Si2p (e)和Ti2p (f)的XPS图谱

Figure 4. XPS spectra of C1s (a), Fe2p (b), N1s (c), O1s (d), Si2p (e) and Ti2p (f)

下载: 全尺寸图片幻灯片

图 5 (a) Ag3d的XPS图谱；((b), (c))各材料的Zeta和FTIR图谱；((d), (e)) Ag量子点结合T的MS计算和对应的数据分析

Figure 5. (a) XPS spectrum of Ag3d; ((b), (c)) Zeta and FTIR spectra of different materials; ((d), (e)) MS theoretical calculation results of the Ag quantum dot bonding T and corresponding data

下载: 全尺寸图片幻灯片

图 6 (a) MIC抑菌数据结果；((b)~(e)) 各材料对E. coli、S. aureus、T-Salm和C. albicans滤纸片扩散分析结果数据；(f) FSmTA-T对菌的菌落计数分析结果

Figure 6. (a) Antibacterial data results of MIC; ((b)-(e)) Results of filter paper diffusion analysis of E. coli, S. aureus, T-Salm and C. albicans by different materials; (f) FSmTA-T on bacterial colony count analysis data results

r—Antibacterial zone radius

下载: 全尺寸图片幻灯片

图 7 FSmTA-T对E. coli ((a1), (b1))、S. aureus ((a2), (b2))、T-Salm ((a3), (b3))和C. albicans ((a4), (b4))的碘化丙啶(PI)染色结果；(c) Zeta电势分析结果；(d) GDC-0941、T、Ag和FSmTA-T对人乳腺上皮细胞(MCF-7)活力的影响

Figure 7. Propidium iodide (PI) staining analysis of FSmTA-T on E. coli ((a1), (b1)), S. aureus ((a2), (b2)), T-Salm ((a3), (b3)) and C. albican ((a4), (b4)); (c) Zeta potential analysis results; (d) Viability of human breast cancer cell line (MCF-7) cells exposed to GDC-0941, T, Ag and FSmTA-T

IC₅₀—Half maximal inhibitory concentration

下载: 全尺寸图片幻灯片

图 8 FSmTA-T的抑菌机制

Figure 8. Bacterial inhibition mechanism of the FSmTA-T

ROS—Reactive oxygen species

下载: 全尺寸图片幻灯片

图 9 FSmTA-T对E. coli、S. aureus、T-Salm和C. albicans的核酸泄露分析结果

Figure 9. DNA leakage analysis of FSmTA-T on E. coli, S. aureus, T-Salm and C. albicans

下载: 全尺寸图片幻灯片

图 10 FSmTA-T对E. coli、S. aureus、T-Salm和C. albicans的微量热分析

Figure 10. Microcalorimetric analysis of E. coli, S. aureus, T-Salm and C. albicans

下载: 全尺寸图片幻灯片

图 S1 FSmTA-T对大肠杆菌(E. coli)、金黄色葡萄球菌(S. aureus)、耐四环素沙门氏菌(T-Salm)和白色念珠菌(C. albicans)的最小抑菌浓度(MIC)测试照片

Figure S1. Minimal inhibit concentration (MIC) test photos of FSmTA-T on E. coli, S. aureus, T-Salm and C. albicans

下载: 全尺寸图片幻灯片

图 S2 不同材料对E. coli、S. aureus、T-Salm和C. albicans的滤纸片扩散照片(O为对照；A、B、C和D依次为Ag、T、FSmTA和FSmTA-T)

Figure S2. Paper diffusion photos of of different samples on E. coli, S. aureus, T-Salm and C. albicans (O is the control, A, B, C and D are Ag, T, FSmTA and FSmTA-T, respectively)

((a1)-(e1)) 25 μg/mL; ((a2)-(e2)) 50 μg/mL; ((a3)-(e3)) 100 μg/mL; ((a4)-(e4)) 150 μg/mL; ((a5)-(e5)) 200 μg/mL

下载: 全尺寸图片幻灯片

图 S3 FSmTA-T对E. coli、S. aureus、T-Salm和C. albicans的菌落计数实验结果(O为对照；A、B、C和D依次为10、20、30和40 min)

Figure S3. Photographs of the results of colony counting experiments of FSmTA-T on E. coli, S. aureus, T-Salm and C. albicans (O is the control; A, B, C and D are 10, 20, 30 and 40 min)

下载: 全尺寸图片幻灯片

参考文献(29)

[1]	WANG Y F, WANG C H, YAN S, et al. The removal of antibiotic, antibiotic resistant bacteria and genes in persulfate oxidation system via activating by antibiotic fermentation dregs derived biochar[J]. Journal of Cleaner Production, 2023, 394: 136328. doi: 10.1016/j.jclepro.2023.136328
[2]	WANG J Q, XU S Q, ZHAO K, et al. Risk control of antibiotics, antibiotic resistance genes (ARGs) and antibiotic resistant bacteria (ARB) during sewage sludge treatment and disposal: A review[J]. Science of The Total Environment, 2023, 877: 162772. doi: 10.1016/j.scitotenv.2023.162772
[3]	FANG H, LIU Y H, QIU P X, et al. Simultaneous removal of antibiotic resistant bacteria and antibiotic resistance genes by molybdenum carbide assisted electrochemical disinfection[J]. Journal of Hazardous Materials, 2022, 432: 128733. doi: 10.1016/j.jhazmat.2022.128733
[4]	ZHANG Z Q, XU Z N, WANG X G. The greenhouse effect of antibiotics: The influence pathways of antibiotics on methane release from freshwater sediment[J]. Environment International, 2023, 176: 107964. doi: 10.1016/j.envint.2023.107964
[5]	WANG S, HE L, ZHANG M Y, et al. Effects of antibiotic resistance genes and antibiotics on the transport and deposition behaviors of bacteria in porous media[J]. Environmental Science & Technology, 2023, 57(28): 10426-10437.
[6]	YA H B, ZHANG T, XING Y, et al. Co-existence of polyethylene microplastics and tetracycline on soil microbial community and ARGs[J]. Chemosphere, 2023, 335: 139082. doi: 10.1016/j.chemosphere.2023.139082
[7]	WANG Q D, XU Q Y, ZHAI S Y, et al. Understanding the coordination behavior of antibiotics: Take tetracycline as an example[J]. Journal of Hazardous Materials, 2023, 460: 132375. doi: 10.1016/j.jhazmat.2023.132375
[8]	WU X W, ZHAO X L, WANG X, et al. Bioaccessibility of polypropylene microfiber-associated tetracycline and ciprofloxacin in simulated human gastrointestinal fluids[J]. Environment International, 2023, 179: 108193. doi: 10.1016/j.envint.2023.108193
[9]	OSORIO V, MEZQUITA A S, BALCAZAR J L. Comparative metagenomics reveals poultry and swine farming are hotspots for multidrug and tetracycline resistance[J]. Environmental Pollution, 2023, 322: 121239. doi: 10.1016/j.envpol.2023.121239
[10]	MA X Q, WEN X, YANG D Q, et al. Collateral sensitivity between tetracyclines and aminoglycosides constrains resistance evolution in carbapenem-resistant Klebsiella pneumoniae[J]. Drug Resistance Updates, 2023, 68: 100961. doi: 10.1016/j.drup.2023.100961
[11]	LI H B, FAN Y F, SUN Z L, et al. Abrading-induced breakdown of Ag nanoparticles into atomically dispersed Ag for enhancing antimicrobial performance[J]. Environmental Science & Technology, 2023, 57(15): 6150-6158.
[12]	WANG C Y, ZHU S L, LIANG Y Q, et al. Flexible free-standing antibacterial nanoporous Ag ribbon[J]. Journal of Colloid and Interface Science, 2023, 645: 287-296. doi: 10.1016/j.jcis.2023.04.153
[13]	SUN X D, PAN W H, WANG G, et al. Ag nanoparticle and Ti-MOF cooperativity for efficient inactivation of E. coli in water[J]. ACS Applied Materials & Interfaces, 2023, 15(37): 43712-43723.
[14]	ZHANG J, SINGH P, CAO Z J, et al. Polydopamine/graphene oxide coatings loaded with tetracycline and green Ag nanoparticles for effective prevention of biofilms[J]. Applied Surface Science, 2023, 626: 157221. doi: 10.1016/j.apsusc.2023.157221
[15]	YAN J H, WANG Q F, YANG J L, et al. Chemical synthesis of innovative silver nanohybrids with synergistically improved antimicrobial properties[J]. International Journal of Nanomedicine, 2023, 18: 2295-2305. doi: 10.2147/IJN.S405255
[16]	SHI J, ZHENG J L, LIANG B, et al. Silver-decorated amino-modified Fe₃O₄@SiO₂@mTiO₂ core-shell nanocomposites with catalytic and antimicrobial bifunctional activity[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 668: 131402. doi: 10.1016/j.colsurfa.2023.131402
[17]	JI X H, WU Y H, HAN Y Y, et al. Synergistic antibacterial study of nano-Cu₂O/CuO@Ag-tetracycline composites[J]. Materials Chemistry and Physics, 2023, 306: 127904. doi: 10.1016/j.matchemphys.2023.127904
[18]	ZHOU Z B, XIAO J W, HUANG S, et al. A wet-adhesive carboxymethylated yeast β-glucan sponge with radical scavenging, bacteriostasis and anti-inflammatory functions for rapid hemostasis[J]. International Journal of Biological Macromolecules, 2023, 230: 123158. doi: 10.1016/j.ijbiomac.2023.123158
[19]	JIN Y Y, WANG C, XIA Z Y, et al. Photodynamic chitosan sponges with dual instant and enduring bactericidal potency for treating skin abscesses[J]. Carbohydrate Polymers, 2023, 306: 120589. doi: 10.1016/j.carbpol.2023.120589
[20]	CUI J Y, WAN M H, WANG Z H, et al. Preparation of PAN/SiO₂/CTAB electrospun nanofibrous membranes for highly efficient air filtration and sterilization[J]. Separation and Purification Technology, 2023, 321: 124270. doi: 10.1016/j.seppur.2023.124270
[21]	ONG T H D, YU N, MEENASHISUNDARAM G K, et al. Insight into cytotoxicity of Mg nanocomposites using MTT assay technique[J]. Materials Science and Engineering: C, 2017, 78: 647-652. doi: 10.1016/j.msec.2017.04.129
[22]	LU J, ZHOU Y, ZHOU Y B. Efficiently activate peroxymonosulfate by Fe₃O₄@MoS₂ for rapid degradation of sulfonamides[J]. Chemical Engineering Journal, 2021, 422: 130126. doi: 10.1016/j.cej.2021.130126
[23]	WANG L, SAGAGUCHI T, OKUHATA T, et al. Electron and phonon dynamics in hexagonal Pd nanosheets and Ag/Pd/Ag sandwich nanoplates[J]. ACS Nano, 2017, 11(2): 1180-1188. doi: 10.1021/acsnano.6b07082
[24]	WOOLSTON B M, STEPHANOPOULOS G. Engineering E. coli to grow on methanol[J]. Joule, 2020, 4(10): 2070-2072. doi: 10.1016/j.joule.2020.09.019
[25]	GREENHILL C. Role for S. aureus in insulin resistance[J]. Nature Reviews Endocrinology, 2018, 14: 381.
[26]	CHIN V, LEE T, RUSLIZA B, et al. Dissecting Candida albicans infection from the perspective of C. albicans virulence and omics approaches on host-pathogen interaction: A review[J]. International Journal of Molecular Sciences, 2016, 17(10): 1643. doi: 10.3390/ijms17101643
[27]	QIAN L W, LEI D, DUAN X, et al. Design and preparation of metal-organic framework papers with enhanced mechanical properties and good antibacterial capacity[J]. Carbohydrate Polymers, 2018, 192: 44-51. doi: 10.1016/j.carbpol.2018.03.049
[28]	XU X, LI Y L, WANG L X, et al. Triple-functional polyetheretherketone surface with enhanced bacteriostasis and anti-inflammatory and osseointegrative properties for implant application[J]. Biomaterials, 2019, 212: 98-114. doi: 10.1016/j.biomaterials.2019.05.014
[29]	MALGORZATA O R, WALDEMAR P, AGNIESZKA O S. Tetracyclines-an important therapeutic tool for dermatologists[J]. International Journal of Environmental Research and Public Health, 2022, 19(12): 7246. doi: 10.3390/ijerph19127246