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化学进展 2020, Vol. 32 Issue (5): 656-664 DOI: 10.7536/PC190929 前一篇   后一篇

• 综述 •

ZIF-8纳米颗粒的粒径调控及生物医学应用

胡强强1, 郭和泽1, 窦红静1,**()   

  1. 上海交通大学金属基复合材料国家重点实验室 材料科学与工程学院 上海 200240
  • 收稿日期:2019-09-23 修回日期:2019-11-26 出版日期:2020-05-15 发布日期:2020-02-20
  • 通讯作者: 窦红静
  • 基金资助:
    国家自然科学基金项目(21871180); 上海市“科技创新行动计划”基础研究领域项目(18JC1413500); 上海高校特聘教授(东方学者)计划(SHDP201802); 上海市教委“曙光计划”(12SG12)
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Size Control and Biomedical Applications of ZIF-8 Nanoparticles

Qiangqiang Hu1, Heze Guo1, Hongjing Dou1,**()   

  1. School of Materials Science and Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China
  • Received:2019-09-23 Revised:2019-11-26 Online:2020-05-15 Published:2020-02-20
  • Contact: Hongjing Dou
  • About author:
    ** e-mail:
  • Supported by:
    National Natural Science Foundation of China(21871180); Shanghai Science and Technology Innovation Action Plan Basic Research Area Project(18JC1413500); Shanghai University Distinguished Professor(Oriental Scholar) Program(SHDP201802); Shanghai Municipal Education Commission “Dawning Plan”(12SG12)

沸石咪唑酯骨架材料(Zeolitic Imidazolate Framework-8, ZIF-8)是由锌离子与2-甲基咪唑配位自组装成的多孔结晶材料,其比表面积大、孔隙率高、合成便捷、尺寸可控,在功能物质的包封与输运中具有突出的优势。与此同时,这类材料更具备优异的生物相容性,且其结构在生理条件下具有良好的稳定性,而在酸性条件下解体,对于与恶性肿瘤等多种疾病相关的弱酸性环境具有响应性,是控制药物运输与释放的理想载体,因而在生物医学上有很大的应用潜力。事实上,ZIF-8不但能高效负载阿霉素、5-氟尿嘧啶等小分子化疗药物,而且可以充当抗体、核酸等生物大分子的保护层。ZIF-8的粒径等性能对于相应的生物医学应用非常关键,而如何实现ZIF-8功能性的精准调控将是实现其生物医学应用的重要挑战,基于此,本文就ZIF-8的制备机理、性能调控及其生物医学应用进行综述和展望。

关键词： ZIF-8, 合成机理, 粒径调控, 弱酸性环境敏感, 生物医学应用

Zeolitic imidazolate framework-8(ZIF-8) is a class of porous crystalline materials formed by the self-assembly of zinc ions and 2-methylimidazole. It shows potential advantages in encapsulation and transportation of functional materials owing to its high porosity, large specific surface,convenient synthesis and controllable size. More importantly, ZIF-8 is an ideal carrier for drug delivery and release due to its excellent biocompatibility, stability under physiological conditions and responsiveness to the weak acidic environment associated with malignant tumors and other diseases. In fact, the small molecular drugs(doxorubicin, 5-fluorouracil) and biological macromolecules(antibody, nuclein) have all been loaded into ZIF-8 for chemotherapy, photothermal therapy, photodynamic therapy and biosensing. The particle size of ZIF-8 is very important for biomedical applications, and accurate functional regulation of ZIF-8 is agreat challenge for its biomedical application. Herein, we review the synthesis methods, size-control and biomedicalapplications of ZIF-8.

Contents

1 Introduction

2 Synthesis of ZIF-8 nanoparticles

2.1 Solvothermal process

2.2 Microwave-assist

2.3 Microfluidic

3 Size control of ZIF-8

3.1 Formation mechanism

3.2 Size control

4 Biomedical applications

4.1 Application in tumor treatment

4.2 Application in bioimagings

4.3 Protective coating for biomacromolecule

5 Conclusion and outlook

Key words: ZIF-8, synthetic mechanism, size control, acidic environmental responsivity, biomedical application
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图1 溶剂热法合成纳米金属有机框架[41]
Fig. 1 Surfactant-free synthesis by simply mixing precursors in appropriate solvents either at room temperature or at elevatedtemperature[41]. Copyright 2015, American Chemical Society
图2 纳米晶的尺寸对增强材料比表面积的重要性示意图[5]
Fig. 2 Schematic illustration of the importance of nanosized PCP crystals with the enhanced contribution of crystal interfaces[5]. Copyright 2010, American Chemical Society
图3 扩散理论下ZIF-8的结晶模型[19]
Fig. 3 Theoretical basis of the reaction-diffusion framework(RDF). (A) Diffusion profiles of HmIm(outer) and Zn2+/Co2+(inner) are depicted at a given time. Evolution of the reaction zone is also shown and exhibits a decrease of its amplitude and broadening of its width. Xf denotes thelocation of the peak which also corresponds to the location of the precipitation front.(B) Nucleation of pure ZIF-8 leading to nanosperoids takesplace within the reaction zone[19]. Copyright 2018, American Chemical Society
图4 三乙胺浓度对ZIF-8形成影响的示意图[27]
Fig. 4 A schematic illustration showing the influence of TEA concentration on ZIF-8 formation[27]. Copyright 2014, The Royal Society of Chemistry
图5 一步法构建纳米金属有机框架载药体系[29]
Fig. 5 The pH-induced one-pot synthesis of MOFs with encapsulated target molecules[29]. Copyright 2015, American Chemical Society
图6 CuS@ZIF-8在光照下解体的机理探究[37]
Fig. 6 Possible mechanism for the dissociation of CuS@ZIF-8 NPs underthe laser irradiation (a). Cell viability of MCF-7 cells after 24 h incubation inthe presence of different concentrations of DOX or DOX loaded CuS@ZIF-8NPs(b). Cell viability of MCF-7 cells treated with PBS solution as a control,CuS@ZIF-8(25 mg·mL-1), DOX(1 mg·mL-1) or DOX loaded CuS@ZIF-8 NPs(1 mg·mL-1 of DOX, 4% DOX/NPs, w/w) for 12 h and then exposed to the NIR laser for 1, 2, 4, and 6 min(c). Photothermal images of mice, saline(control, group Ⅰ), DOX(group Ⅱ) and DOX loaded CuS@ZIF-8(group Ⅲ) under NIR laser irradiation for 3 min(d)[37]. Copyright 2016, The Royal Society of Chemistry
图7 Fe3O4@PAA/AuNCs/ZIF-8用于三重显影及化疗的示意图[55]
Fig. 7 Schematic illustration of Fe3O4@PAA/AuNCs/ZIF-8 composite NPs for simultaneous tri-modal cancer imagingand chemotherapy[55]. Copyright 2015, The Royal Society of Chemistry
图8 ZIF-8仿生矿化复合材料形成示意图[60]
Fig. 8 Characterization of biomimetically mineralized biocomposite. (a) SEM image showing the crystals obtained using BSA as a growth agentfor biomimetic mineralization(scale bar, 1 μm).(b) Photograph and(c) confocal laser scanning microscopy image of the biomomimetically mineralized ZIF-8 composite obtained using BSA labelled with FITC. This biocomposite(ZIF-8/FITC-BSA) was prepared at 37 ℃, washed and exposed to ultraviolet light of wavelength 365 and 495 nm, respectively(scale bar, 10 μm).(d) PXRD of the MOF-BSA biocomposite.(e) FTIR spectra of BSA(red), ZIF-8/BSA(orange), standard ZIF-8 post incubated with BSA after washing(blue), and standard ZIF-8(black).(f) SAXS data of the ZIF-8/BSA biocompositeand a schematic showing the relative size of BSA to the mesopore.(g) Schematic proposing the biomimetically mineralized growthof ZIF-8. Each BSA molecule attracts 31 2-methylimidazole(HmIm) ligands and 22 Zn2+ ions, facilitating the nucleation of ZIF-8 crystals[60]. Copyright 2015, Springer Nature
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