金属-多酚网络的制备及在药物递送与诊疗中应用的研究进展

doi:10.19894/j.issn.1000-0518.250123

摘要/Abstract

摘要：

金属-多酚网络（Metal-phenolic networks， MPNs）是一类由金属离子与多酚类化合物通过配位作用自组装形成的多功能纳米材料，近年来因其独特的理化性质（如pH响应性、高载药效率、良好的生物相容性）在纳米药物领域备受关注。本综述系统总结了MPNs的制备以及在药物递送、联合治疗和诊疗一体化中的应用进展，重点总结了不同种类多酚与金属离子组成的性质独特的MPNs在不同领域的应用，为新型纳米药物的设计与优化提供理论参考。

关键词: 金属-多酚网络, 纳米药物, 制备与应用

Abstract:

Metal-phenolic networks （MPNs） are a class of multifunctional nanomaterials formed by the self-assembly of metal ions and polyphenolic compounds through coordination interactions. In recent years， they have attracted considerable attention in the field of nanomedicine due to their unique physicochemical properties， such as pH responsiveness， high drug loading efficiency， and good biocompatibility. This review systematically summarizes the preparation of MPNs and their application progress in drug delivery， combination therapy， and theranostics， with a particular focus on the unique properties and applications of MPNs composed of different types of polyphenols and metal ions in various fields. This provides theoretical references for the design and optimization of novel nanomedicines.

Key words: Metal-phenolic networks, Nanomedicine, Preparation and application

中图分类号:

O629.9

常鹏宇, 陈翠萍, 徐凯, 汪河滨. 金属-多酚网络的制备及在药物递送与诊疗中应用的研究进展[J]. 应用化学, 2025, 42(11): 1445-1460.

Peng-Yu CHANG, Cui-Ping CHEN, Kai XU, He-Bin WANG. Research Progress on the Preparation of Metal-Polyphenol Networks and Their Applications in Drug Delivery and Diagnosis and Treatment[J]. Chinese Journal of Applied Chemistry, 2025, 42(11): 1445-1460.

图/表 9

图1 MPNs的基本结构、常用金属离子以及3种常见制备方法：纳米涂层［7］、直接自组装［8］和逐层法［9］的过程示意图

Fig.1 The basic structure of MPNs， common metal ions， and the schematic diagram of three common preparation methods： nanocoating［7］， direct self-assembly［8］ and layer-by-layer［9］

图2 MPNs在抗肿瘤、抗氧化、抗菌以及抗炎过程中的作用机制

Fig.2 The mechanism of action of MPNs in anti-tumor， anti-oxidation， anti-bacterial and anti-inflammatory processes

图3 MPN/CpG纳米颗粒通过先天性免疫和获得性免疫来抑制肿瘤［25］

Fig.3 MPN/CpG NPs defends against tumors by activating innate and adaptive immune responses［25］

图4 （A）基于Fe3+和多酚之间的配位制备PPFH的示意图，以及由DFO触发的这些纳米颗粒的动态解组过程；（B）通过尾静脉顺序注射PPFH和DFO来调节TECM的示意图［31］

Fig.4 （A） Schematic diagram of the preparation of PPFH based on the coordination between Fe3+ and polyphenols， and the dynamic disassembly process of these nanoparticles triggered by DFO；（B） Schematic diagram of the modulation of TECM by sequential injection of PPFH and DFO into the tail vein［31］

图5 Cu-Pic/HA纳米颗粒通过全面消耗多胺诱导增强的细胞焦亡铜凋亡进行抗肿瘤过程的示意图［35］

Fig.5 Schematic diagram of the anti-tumor process of Cu-Pic/HA nanoparticles by inducing enhanced pyroptosis and cuproptosis via global depletion of polyamines processes［35］

表1 用于抗肿瘤的MPNs

Table 1 Structure types of MPNs that be used to antitumor

Metal ions	Poly-phenol	Material composition	Mechanism/Anti-tumor rate	Ref.
Fe³⁺	EGCG	Fe-Len/Adr@EGCG	CT/IMT/pH respond Hepa1-6：91.5%	［36］
Fe³⁺	EGCG	Cab@MPNs/CS	CT/CDT/pH respond B16F10：63.1%	［37］
Fe³⁺	EGCG	EArgFe@Ce6	PTT/PDT/pH respond 4T1：81.0%	［38］
Cu²⁺	TA	CacCO₃@DSF-TA-Cu	CT/CDT/pH respond 4T1：86.6%	［39］
Fe³⁺	TA	BSO/ZIF-8-Au@TA-Fe@HA	RT/CDT/pH respond/HA targeted 4T1：87.1%	［40］
Cu²⁺	TA	TCPP-Fe@DSF-TA-Cu	CT/CDT/PDT/pH，GSH respond MDA-MB-231：87.9%	［41］
Fe³⁺，Mn²⁺	PDA	FM-PDA-PE	CDT/PTT/pH respond 4T1：90.5%	［42］
Fe³⁺	EGCG	Cur@EGCG-Fe	CT/CDT/pH respond MCF-7：78.3%	［43］
Fe³⁺	TA	Hb-Ce6-TA-Fe	CDT/PDT/pH respond 4T1：89.4%	［8］
Fe³⁺	GA	Au/Fe-GA-Sorafenib@PEG	CT/CDT/PTT/pH respond 4T1：72.7%	［44］
Fe³⁺	TA	Cus_MPDA-DOX-TA-Fe	CT/PTT/pH respond HCT-116：65.3%	［45］
Cu²⁺	EA	DOX-EA-Cu-CS	CT/CDT/pH respond 4T1：79.6% MCF-7Adr：67.8% MCF-7：77.9%	［46］
Cu²⁺	TA	HOS@IR820@TA-Cu	CDT/PTT/pH，GSH respond 4T1：86.7%	［47］
Fe²⁺	GA	Fe-GA@BSA-SRF	CDT/PTT/pH respond 4T1：97.5%	［48］
Zn²⁺	TA	ZIF8-Hb/Gox-TA-Zn	ST/CDT/pH respond 4T1：92.6%	［49］

图6 PH/CuS/TM微针的合成及促进伤口愈合示意图。（A） TM NPs和PH/CuS/TM微针的制备；（B） PH/CuS/TM微针具有抗菌、清除ROS、免疫调节和促进血管生成等作用，从而实现糖尿病伤口的程序化治疗［34］

Fig.6 Schematic diagram of the synthesis of PH/CuS/TM MNs and the promotion of wound healing. （A） Preparation of TM NPs and PH/CuS/TM MNs；（B） PH/CuS/TM MNs could eradicate bacteria， scavenging ROS and immunomodulation while promoting angiogenesis， enabling programmed treatment of diabetic wounds［34］

表2 用于抗菌的MPNs结构

Table 2 Structure types of MPNs that be used to antibacterial

Metal ions	Poly-phenol	Material composition	Mechanism/Anti-bacterial rate	Ref.
Fe³⁺	TA	DHA@HA-TA-Fe	PTT/CDT/pH respond E.coil/S.aureus：＞99%	［50］
Cu²⁺	EGCG	Borax@EGCG-Cu@PVA	Cu²⁺/CDT/PTT/pH respond E.coil：97.3% S.aureus：83.9% P.aeruginosa：69.1% C.albican：72.2%	［51］
Ga³⁺	TA	TA-Ga	Ga³⁺/PTT/pH respond E.coil/S.aureus：＞99%	［52］
Ce⁴⁺	TA	HAP-HA@TA-Ce	PTT/CDT/pH respond S.aureus：＞99%	［53］
Fe³⁺	EGCG	Au@EGCG-Fe	PTT/PDT/pH respond S.aureus：98.2% E.coil：＞99%	［54］
Fe³⁺	TA	Ti₃C₂@TA-Fe@Ag	Ag⁺/PTT/pH respond E.coil/S.aureus：＞99%	［55］
Fe³⁺	TA	TA-Fe-SA	CDT/PTT/pH respond S.aureus：97.4% E.coil：93.9%	［56］
Fe³⁺	TA	Ce6/TA-Fe	CDT/PDT/pH respond S.aureus：97.8%	［57］
Fe³⁺	TA	TA-Fe-SA	CDT/PTT/pH respond E.coil/S.aureus：＞99%	［58］
Fe³⁺	PC	AuAg@PC-Fe	Ag⁺/PTT/pH respond P.Gingivalis：87.3% F.nucleatum：76.5%	［59］
Fe³⁺	EGCG	BSA@EGCG-Fe	CDT/PTT/pH respond E.coil/S.aureus：＞99%	［60］

图7 （A） GelMA/CMCSMAP-GACo水凝胶的合成和（B）在糖尿病伤口愈合中的潜在应用机制的示意图［61］

Fig.7 Schematic illustration of （A） synthesis of GelMA/CMCSMAP-GACo hydrogel and （B） potential application mechanism in diabetic wound healing［61］

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