MXenes的制备、性质及其在肿瘤诊疗中的研究进展

doi:10.15541/jim20210299

无机材料学报 ›› 2022, Vol. 37 ›› Issue (4): 361-375.DOI: 10.15541/jim20210299

所属专题：【生物材料】肿瘤治疗；【信息功能】Max层状材料、MXene及其他二维材料

• 综述 • 下一篇

MXenes的制备、性质及其在肿瘤诊疗中的研究进展

白志强¹^,²(), 赵璐², 白云峰²(), 冯锋¹^,²()

1.山西师范大学化学与材料科学学院, 临汾 041004
2.山西大同大学化学与化工学院, 化学生物传感山西省重点实验室, 大同 037009

收稿日期:2020-05-10 修回日期:2021-06-27 出版日期:2022-04-20 网络出版日期:2021-11-08
通讯作者: 白云峰, 教授. E-mail: baiyunfeng1130@126.com;
冯锋, 教授. E-mail: feng-feng64@263.net
作者简介:白志强(1987-), 男, 博士研究生. E-mail: baizq1987@126.com
基金资助:
国家自然科学基金(21975146);山西省高等学校科学研究优秀成果培育项目(2020KJ023);山西省省筹资金资助回国留学人员科研项目(2020-133);山西省高等学校科技创新项目(2021L368);山西师范大学研究生科技创新项目(2021XBY005)

Research Progress on MXenes: Preparation, Property and Application in Tumor Theranostics

BAI Zhiqiang¹^,²(), ZHAO Lu², BAI Yunfeng²(), FENG Feng¹^,²()

1. School of Chemistry and Material Science, Shanxi Normal University, Linfen 041004, China
2. Shanxi Provincial Key Laboratory of Chemical Biosensing, College of Chemistry and Chemical Engineering, Shanxi Datong University, Datong 037009, China

Received:2020-05-10 Revised:2021-06-27 Published:2022-04-20 Online:2021-11-08
Contact: BAI Yunfeng, professor. E-mail: baiyunfeng1130@126.com;
FENG Feng, professor. E-mail: feng-feng64@263.net
About author:BAI Zhiqiang (1987-), male, PhD candidate. E-mail: baizq1987@126.com
Supported by:
National Natural Science Foundation of China(21975146);Cultivate Scientific Research Excellence Programs of Higher Education Institutions in Shanxi(2020KJ023);Shanxi Scholarship Council of China(2020-133);Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2021L368);Postgraduate Science and Technology Innovation Project of Shanxi Normal University(2021XBY005)

摘要/Abstract

摘要：

二维过渡金属碳化物、氮化物或碳氮化物(MXenes)已成为二维材料中一个新兴的热点领域。MXenes材料具有优异的电子传递性能、出色的光热转换性能、较高的比表面积、良好的生物相容性和低毒性等特点, 在肿瘤诊疗中显示出良好的应用前景。本文简要总结了MXenes的制备方法, 包括氢氟酸法、氟盐法、熔融盐法、碱辅助水热法和化学气相沉积法, 及其稳定性、机械性质、光学性质和电学性质。重点综述了MXenes在肿瘤诊疗中的应用, 包括光热治疗、多模式联合治疗、构建MXenes表面介孔材料的联合治疗和MXenes主动靶向联合治疗, 以及建立MXenes诊断-治疗一体化平台。最后简要介绍了MXenes可能辅助肿瘤诊疗的其他特性及其应用, 并阐述了MXenes在肿瘤诊疗中存在的挑战以及未来发展前景。

关键词: MXenes, 制备方法, 肿瘤诊疗, 联合治疗, 综述

Abstract:

Two-dimensional (2D) materials have brought about significant technological advancements in the field of biomaterials. Transition metal carbides and/or nitrides (MXenes) have a planar structure educed from their corresponding parent MAX phase by selective etching of ‘A’ and further delamination. Since the first MXene was reported in 2011, MXenes now comprise a rapidly growing family of 2D materials, having attracted extensive attention from researchers. Owing to their excellent electronic properties, outstanding photothermal conversion performance, high specific surface area, good biocompatibility, and low toxicity, MXenes have shown a good application prospect in tumor theranostics. This paper reviews substantive findings of the original researches focused on the preparation, property and application in tumor theranotics, including recent advances, challenges and future perspectives of MXenes. Firstly, we briefly summarize the preparation methods and property of MXenes, including HF acid method, fluoride salt method, molten salt method, alkali-assisted hydrothermal method, and chemical vapor deposition method, as well as stability, mechanical, optical, and electrical properties. Secondly, we focus on the application of MXenes in photothermal therapy and combined therapy. The usual method is to combine photothermal therapy, photodynamic therapy and chemotherapy to carry out multi-modal combined treatment of tumors. The combined therapy can also be improved by constructing surface nanopores of MXenes and loading chemotherapy drugs in them. Furthermore, enhanced MXenes synergistic therapeutic effect on tumor and reduced toxic side effects on normal tissue can be endued by active targeting technology. In addition, the preparation of multifunctional MXenes composite nanomaterials to obtain radiation treatment and imaging capabilities such as computed tomography scans and magnetic resonance imaging, can establish an integrated platform for MXenes theranostics. Finally, we briefly introduced other applications of MXenes in biomedicine which are beneficial to tumor theranostics, and elaborate the current challenges and future development prospects of MXenes in cancer theranostics.

Key words: MXenes, preparation method, tumor theranostics, combined therapy, review

中图分类号:

TQ174

白志强, 赵璐, 白云峰, 冯锋. MXenes的制备、性质及其在肿瘤诊疗中的研究进展[J]. 无机材料学报, 2022, 37(4): 361-375.

BAI Zhiqiang, ZHAO Lu, BAI Yunfeng, FENG Feng. Research Progress on MXenes: Preparation, Property and Application in Tumor Theranostics[J]. Journal of Inorganic Materials, 2022, 37(4): 361-375.

图/表 10

图1 MXenes组成示意图[14]

Fig. 1 MXenes schematic composition[14] The first row shows structures of mono-transition metal (M) MXenes; The second row shows double-M solid solutions (SS), both of which contain two M molecules in the M layer being marked in green; The third row shows ordered double-M Mxenes, with one metal filling the outer M layer, and the other metal occupying the center M layer being marked in red; The fourth row shows an ordered divacancy structure, marked in pink. The schematic does not show the surface terminal Colorful figures are available on website

图2 MXenes制备方法示意图及化学气相沉积法制备的产物

Fig. 2 Schematic preparation methods for MXenes and products prepared by chemical vapor deposition (a) HF acid etching method[11]; (b) Molten salt method[19]; (c) Alkali assisted hydrothermal method[39]; (d) Optical images of ultra-thin α-Mo2C crystal ((d1): irregular shape, (d2): hexagonal shape)[41]

表1 MXenes的制备方法总结

Table 1 Summary of preparation methods of MXenes

Preparation method	Advantages	Disadvantages	Ref.
HF acid etching	Simple	Using highly corrosive and harmful HF	[11]
Fluoride salt	Milder reaction conditions; Safer than that of HF acid etching	Difficult to prepare nitride MXenes	[36-37]
Molten salt	Preparing nitride MXenes and preparing MXenes through non-MAX materials	Requiring inert protective gas, under high temperature condition	[19,38]
Alkali assisted hydrothermal	Preparing MXenes without fluorine functional groups	High concentration of NaOH, requiring inert protective gas, under high temperature condition	[39]
Chemical vapor deposition	Precise controlling element composition, size and surface groups	Difficult to prepare large-sized MXenes	[41]

图3 (a)Ti3C2纳米片对4T1肿瘤模型的荷瘤裸鼠PTT的示意图[30]和(b)Nb2C纳米片在NIR-I和NIR-II下进行体内PTT的示意图[28]

Fig. 3 (a) Schematic diagrams of Ti3C2 nanoparticles on PTT in 4T1 tumor bearing nude mice[30] and (b) Nb2C nanosheets for PTT in vivo under NIR-I and NIR-II[28]

表2 MXenes首次应用于肿瘤PTT的结果总结

Table 2 First application of MXenes in PTT on tumor

MXenes material	First report time	NIR range	Wavelength /nm	Extinction coefficient/(L·g^-1·cm^-1)	Photothermal conversion efficiency/%	NIR power /(W·cm^-2)	Irradiation time /min	Temperature range/℃	Ref.
Ti₃C₂	2016/10	NIR-I	808	25.2	-	0.8	5	23.5-60.0	54
Nb₂C	2017/10	NIR-I	808	37.6	36.5	1.5	5	25.0-60.0	28
Nb₂C	2017/10	NIR-II	1064	35.4	46.65	1.5	5	25.0-60.0	28
Ta₄C₃	2017/11	NIR-I	808	8.67	34.9	2.0	5	32.5-65.0	[27]
Ti₂C	2019/01	NIR-I	808	7.39	87.1	2.0	2	25.5-93.8	[48]
Mo₂C	2019/04	NIR-I	808	18.0	24.5	1.0	10	25.0-57.8	[49]
Mo₂C	2019/04	NIR-II	1064	12.3	43.3	1.0	10	25.0-62.3	[49]
V₂C	2020/01	NIR-I	808	38.3	48.5	0.48	10	24.0-57.9	[50]
Ti₂N	2020/11	NIR-I	808	41.25	48.62	1.0	5	25.0-60.0	[51]
Ti₂N	2020/11	NIR-II	1064	34.92	45.51	1.0	5	25.0-60.0	[51]

图4 (a)Ti3C2纳米材料负载DOX用于肿瘤PTT/PDT/CHEMO联合治疗[29]、(b)DOX@Ti3C2-SP纳米材料用于肿瘤PTT/CHEMO联合治疗[32]和(c)Ti3C2@Met@CP纳米材料用于肿瘤PTT/PDT/CHEMO联合治疗[57]示意图

Fig. 4 Schematic diagrams of (a) Ti3C2 nanomaterials loaded with DOX for tumor PTT/PDT/CHEMO combined therapy[29], (b) DOX@Ti3C2-SP nanomaterials for tumor PTT/CHEMO combined therapy[32], and (c) Ti3C2@Met@CP nanomaterials for tumor PTT/PDT/CHEMO combined therapy[57] SP: Soybean phospholipid

图5 (a)DOX@Ti3C2@mMSNs-RGD复合纳米材料[58]、(b)CTAC@Nb2C-MSN-PEG-RGD复合纳米材料在PTT下释放CTAC对肿瘤的联合治疗[59]、(c)A@Nb2C@Si复合纳米材料在PTT下产生自由基[60]和(d)Nb2C-MSNs-SNO复合纳米材料在PTT下释放NO对肿瘤联合治疗[61]的示意图

Fig. 5 Schematic illustrations for (a) combined therapy on HCC cells as assisted by DOX@Ti3C2@mMSNs-RGD at the cell level[58], (b) CTAC@Nb2C-MSN-PEG-RGD composite nanomaterials releaseing CTAC under the action of PTT for combined treatment of tumor[59], (c) AIPH@Nb2C@Si composite nanomaterials generating free radicals under the action of PTT[60], and (d) Nb2C-MSNs-SNO composite nanomaterials releasing NO under the action of PTT for combined treatment of tumor[61]

图6 用于肿瘤诊疗的多功能MXenes复合纳米材料(a)MnOx/Ti3C2[64]、(b)Ta4C3-IONP[62]、(c)MIG[65]、(d)GdW10@Ti3C2[66]和(e)Ti3C2@Au[67]的模式图

Fig. 6 Schematic diagrams of (a) MnOx/Ti3C2[64], (b) Ta4C3-IONP[62], (c) MIG[65], (d) GdW10@Ti3C2[66], and (e) Ti3C2@Au[67] composite nanomaterials in tumor theranostics

表3 应用于肿瘤诊疗的MXenes

Table 3 MXenes for application in tumor theranostics

MXenes	Report time	Cell lines	Treatment strategy	Diagnosis strategy	Molecule for targeting	Ref.
Ti₃C₂	2016/10	4T1	PTT	-	-	[54]
Ti₃C₂-SP	2016/12	4T1	PTT	-	-	[30]
MnO_x/Ti₃C₂-SP	2017/08	4T1	PTT	PA/MR	-	[64]
Nb₂C-PVP	2017/10	4T1	PTT	PA	-	[28]
Ti₃C₂	2017/10	HeLa/MCF-7/U251/HEK293	PTT	PA	-	[68]
Ti₃C₂-DOX	2017/11	HCT-116	PTT/PDT/CHEMO	-	HA	[29]
MnO_x/Ta₄C₃-SP	2017/11	4T1	PTT	MR/CT/PA	-	[27]
Ta₄C₃-SP	2017/12	4T1	PTT	PA/CT	-	[69]
GdW₁₀@Ti₃C₂	2018/01	4T1	PTT	CT/MR	-	[66]
DOX@Ti₃C₂-SP	2018/02	4T1	PTT/CHEMO	PA	-	[32]
Ta₄C₃-IONP-SP	2018/02	4T1	PTT	CT/MR	-	[62]
DOX@Ti₃C₂@mMSNs- RGD	2018/04	SMMC-7721	PTT/CHEMO	-	RGD	[58]
CTAC@Nb₂C-MSN-PEG-RGD	2018/08	U87	PTT/CHEMO	PA	RGD	[59]
Ti₃C₂@Au	2018/12	4T1	PTT/RT	PA/CT	-	[67]
A@Nb₂C@Si	2019/01	4T1	PTT/CHEMO	PA	-	[60]
Ti₂C	2019/01	A375/HaCaT/MCF-7/MCF-10A	PTT	-	-	[48]
Mo₂C	2019/04	4T1	PTT	-	-	[49]
Mo₂C@C	2019/04	HepG2/HUVEC/IOSE80	PTT/PDT	PA/CT	-	[70]
Au/Ti₃C₂	2019/06	MCF-7	PTT	-	-	[71]
Au/Fe₃O₄/Ti₃C₂	2019/06	MCF-7	PTT	-	-	[71]
MIG(Ti₃C₂-IONP@PEG-GOD)	2019/10	4T1	PTT/CHEMO	MR	-	[65]
Nb₂C-MSNs-SNO	2019/11	4T1	PTT/CHEMO	PA	-	[61]
Ti₂N	2019/11	MCF-7/A365/MCF-10A/HaCaT	PDT	-	-	[72]
V₂C	2020/01	MCF-7	PTT	-	-	[50]
TO-MX(Ti₃C₂/Ti₂O₃)	2020/02	A375/HaCaT/MCF-7/MCF-10A	PDT	-	-	[73]
PVP/Nb₂C	2020/04	4T1	PTT	-	-	[74]
Nb₂C/zein	2020/04	4T1	PTT	-	-	[75]
NMQDs-Ti₃C₂T_x	2020/04	ADSCs/HeLa/MCF-7	PDT/CHEMO	-	-	[76]
Nb₂C/PLL	2020/05	A375/HaCaT	PDT	-	-	[77]
Nb₄C₃/PLL	2020/05	A375/HaCaT	PDT	-	-	[77]
Ti₃C₂@Met@CP	2020/06	MDA-MB-231	PTT/PDT/CHEMO	-	-	[57]
DOX@Ti₃C₂-CoNWs	2020/06	4T1	PTT/CHEMO	-	-	[78]
Ti₃C₂/CA4@PLEL	2020/06	4T1/HUVECs	PTT/CHEMO	-	-	[79]
Ti₂N	2020/11	4T1/U87/293T	PTT	PA	-	[51]
MXene(Ti₃C₂)-DOX	2021/01	HeLa	PTT/PDT/CHEMO	-	-	[80]

图7 MXenes纳米材料在(a)生物传感[81]和(b)骨组织工程中的应用示意图[82]

Fig. 7 Schematic diagrams of the application of MXenes nanomaterials in (a) biosensing[81] and (b) bone tissue engineering[82]

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MXenes的制备、性质及其在肿瘤诊疗中的研究进展

Research Progress on MXenes: Preparation, Property and Application in Tumor Theranostics

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