无机材料学报 ›› 2022, Vol. 37 ›› Issue (4): 361-375.DOI: 10.15541/jim20210299 CSTR: 32189.14.10.15541/jim20210299
所属专题: 【生物材料】肿瘤治疗(202409); 【信息功能】MAX层状材料、MXene及其他二维材料(202409)
• 综述 • 下一篇
白志强1,2(), 赵璐2, 白云峰2(), 冯锋1,2()
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;作者简介:
白志强(1987-), 男, 博士研究生. E-mail: baizq1987@126.com
基金资助:
BAI Zhiqiang1,2(), ZHAO Lu2, BAI Yunfeng2(), FENG Feng1,2()
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;About author:
BAI Zhiqiang (1987-), male, PhD candidate. E-mail: baizq1987@126.com
Supported by:
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。
中图分类号:
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]
Preparation method | Advantages | Disadvantages | Ref. |
---|---|---|---|
HF acid etching | Simple | Using highly corrosive and harmful HF | [ |
Fluoride salt | Milder reaction conditions; Safer than that of HF acid etching | Difficult to prepare nitride MXenes | [ |
Molten salt | Preparing nitride MXenes and preparing MXenes through non-MAX materials | Requiring inert protective gas, under high temperature condition | [ |
Alkali assisted hydrothermal | Preparing MXenes without fluorine functional groups | High concentration of NaOH, requiring inert protective gas, under high temperature condition | [ |
Chemical vapor deposition | Precise controlling element composition, size and surface groups | Difficult to prepare large-sized MXenes | [ |
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 | [ |
Fluoride salt | Milder reaction conditions; Safer than that of HF acid etching | Difficult to prepare nitride MXenes | [ |
Molten salt | Preparing nitride MXenes and preparing MXenes through non-MAX materials | Requiring inert protective gas, under high temperature condition | [ |
Alkali assisted hydrothermal | Preparing MXenes without fluorine functional groups | High concentration of NaOH, requiring inert protective gas, under high temperature condition | [ |
Chemical vapor deposition | Precise controlling element composition, size and surface groups | Difficult to prepare large-sized MXenes | [ |
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]
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 | |
Nb2C | 2017/10 | NIR-I | 808 | 37.6 | 36.5 | 1.5 | 5 | 25.0-60.0 | |
NIR-II | 1064 | 35.4 | 46.65 | 1.5 | 5 | 25.0-60.0 | |||
Ta4C3 | 2017/11 | NIR-I | 808 | 8.67 | 34.9 | 2.0 | 5 | 32.5-65.0 | [ |
Ti2C | 2019/01 | NIR-I | 808 | 7.39 | 87.1 | 2.0 | 2 | 25.5-93.8 | [ |
Mo2C | 2019/04 | NIR-I | 808 | 18.0 | 24.5 | 1.0 | 10 | 25.0-57.8 | [ |
NIR-II | 1064 | 12.3 | 43.3 | 1.0 | 10 | 25.0-62.3 | |||
V2C | 2020/01 | NIR-I | 808 | 38.3 | 48.5 | 0.48 | 10 | 24.0-57.9 | [ |
Ti2N | 2020/11 | NIR-I | 808 | 41.25 | 48.62 | 1.0 | 5 | 25.0-60.0 | [ |
NIR-II | 1064 | 34.92 | 45.51 | 1.0 | 5 | 25.0-60.0 |
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 | |
Nb2C | 2017/10 | NIR-I | 808 | 37.6 | 36.5 | 1.5 | 5 | 25.0-60.0 | |
NIR-II | 1064 | 35.4 | 46.65 | 1.5 | 5 | 25.0-60.0 | |||
Ta4C3 | 2017/11 | NIR-I | 808 | 8.67 | 34.9 | 2.0 | 5 | 32.5-65.0 | [ |
Ti2C | 2019/01 | NIR-I | 808 | 7.39 | 87.1 | 2.0 | 2 | 25.5-93.8 | [ |
Mo2C | 2019/04 | NIR-I | 808 | 18.0 | 24.5 | 1.0 | 10 | 25.0-57.8 | [ |
NIR-II | 1064 | 12.3 | 43.3 | 1.0 | 10 | 25.0-62.3 | |||
V2C | 2020/01 | NIR-I | 808 | 38.3 | 48.5 | 0.48 | 10 | 24.0-57.9 | [ |
Ti2N | 2020/11 | NIR-I | 808 | 41.25 | 48.62 | 1.0 | 5 | 25.0-60.0 | [ |
NIR-II | 1064 | 34.92 | 45.51 | 1.0 | 5 | 25.0-60.0 |
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
MXenes | Report time | Cell lines | Treatment strategy | Diagnosis strategy | Molecule for targeting | Ref. |
---|---|---|---|---|---|---|
Ti3C2 | 2016/10 | 4T1 | PTT | - | - | [ |
Ti3C2-SP | 2016/12 | 4T1 | PTT | - | - | [ |
MnOx/Ti3C2-SP | 2017/08 | 4T1 | PTT | PA/MR | - | [ |
Nb2C-PVP | 2017/10 | 4T1 | PTT | PA | - | [ |
Ti3C2 | 2017/10 | HeLa/MCF-7/U251/HEK293 | PTT | PA | - | [ |
Ti3C2-DOX | 2017/11 | HCT-116 | PTT/PDT/CHEMO | - | HA | [ |
MnOx/Ta4C3-SP | 2017/11 | 4T1 | PTT | MR/CT/PA | - | [ |
Ta4C3-SP | 2017/12 | 4T1 | PTT | PA/CT | - | [ |
GdW10@Ti3C2 | 2018/01 | 4T1 | PTT | CT/MR | - | [ |
DOX@Ti3C2-SP | 2018/02 | 4T1 | PTT/CHEMO | PA | - | [ |
Ta4C3-IONP-SP | 2018/02 | 4T1 | PTT | CT/MR | - | [ |
DOX@Ti3C2@mMSNs- RGD | 2018/04 | SMMC-7721 | PTT/CHEMO | - | RGD | [ |
CTAC@Nb2C-MSN-PEG-RGD | 2018/08 | U87 | PTT/CHEMO | PA | RGD | [ |
Ti3C2@Au | 2018/12 | 4T1 | PTT/RT | PA/CT | - | [ |
A@Nb2C@Si | 2019/01 | 4T1 | PTT/CHEMO | PA | - | [ |
Ti2C | 2019/01 | A375/HaCaT/MCF-7/MCF-10A | PTT | - | - | [ |
Mo2C | 2019/04 | 4T1 | PTT | - | - | [ |
Mo2C@C | 2019/04 | HepG2/HUVEC/IOSE80 | PTT/PDT | PA/CT | - | [ |
Au/Ti3C2 | 2019/06 | MCF-7 | PTT | - | - | [ |
Au/Fe3O4/Ti3C2 | 2019/06 | MCF-7 | PTT | - | - | [ |
MIG(Ti3C2-IONP@PEG-GOD) | 2019/10 | 4T1 | PTT/CHEMO | MR | - | [ |
Nb2C-MSNs-SNO | 2019/11 | 4T1 | PTT/CHEMO | PA | - | [ |
Ti2N | 2019/11 | MCF-7/A365/MCF-10A/HaCaT | PDT | - | - | [ |
V2C | 2020/01 | MCF-7 | PTT | - | - | [ |
TO-MX(Ti3C2/Ti2O3) | 2020/02 | A375/HaCaT/MCF-7/MCF-10A | PDT | - | - | [ |
PVP/Nb2C | 2020/04 | 4T1 | PTT | - | - | [ |
Nb2C/zein | 2020/04 | 4T1 | PTT | - | - | [ |
NMQDs-Ti3C2Tx | 2020/04 | ADSCs/HeLa/MCF-7 | PDT/CHEMO | - | - | [ |
Nb2C/PLL | 2020/05 | A375/HaCaT | PDT | - | - | [ |
Nb4C3/PLL | 2020/05 | A375/HaCaT | PDT | - | - | [ |
Ti3C2@Met@CP | 2020/06 | MDA-MB-231 | PTT/PDT/CHEMO | - | - | [ |
DOX@Ti3C2-CoNWs | 2020/06 | 4T1 | PTT/CHEMO | - | - | [ |
Ti3C2/CA4@PLEL | 2020/06 | 4T1/HUVECs | PTT/CHEMO | - | - | [ |
Ti2N | 2020/11 | 4T1/U87/293T | PTT | PA | - | [ |
MXene(Ti3C2)-DOX | 2021/01 | HeLa | PTT/PDT/CHEMO | - | - | [ |
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 | - | - | [ |
Ti3C2-SP | 2016/12 | 4T1 | PTT | - | - | [ |
MnOx/Ti3C2-SP | 2017/08 | 4T1 | PTT | PA/MR | - | [ |
Nb2C-PVP | 2017/10 | 4T1 | PTT | PA | - | [ |
Ti3C2 | 2017/10 | HeLa/MCF-7/U251/HEK293 | PTT | PA | - | [ |
Ti3C2-DOX | 2017/11 | HCT-116 | PTT/PDT/CHEMO | - | HA | [ |
MnOx/Ta4C3-SP | 2017/11 | 4T1 | PTT | MR/CT/PA | - | [ |
Ta4C3-SP | 2017/12 | 4T1 | PTT | PA/CT | - | [ |
GdW10@Ti3C2 | 2018/01 | 4T1 | PTT | CT/MR | - | [ |
DOX@Ti3C2-SP | 2018/02 | 4T1 | PTT/CHEMO | PA | - | [ |
Ta4C3-IONP-SP | 2018/02 | 4T1 | PTT | CT/MR | - | [ |
DOX@Ti3C2@mMSNs- RGD | 2018/04 | SMMC-7721 | PTT/CHEMO | - | RGD | [ |
CTAC@Nb2C-MSN-PEG-RGD | 2018/08 | U87 | PTT/CHEMO | PA | RGD | [ |
Ti3C2@Au | 2018/12 | 4T1 | PTT/RT | PA/CT | - | [ |
A@Nb2C@Si | 2019/01 | 4T1 | PTT/CHEMO | PA | - | [ |
Ti2C | 2019/01 | A375/HaCaT/MCF-7/MCF-10A | PTT | - | - | [ |
Mo2C | 2019/04 | 4T1 | PTT | - | - | [ |
Mo2C@C | 2019/04 | HepG2/HUVEC/IOSE80 | PTT/PDT | PA/CT | - | [ |
Au/Ti3C2 | 2019/06 | MCF-7 | PTT | - | - | [ |
Au/Fe3O4/Ti3C2 | 2019/06 | MCF-7 | PTT | - | - | [ |
MIG(Ti3C2-IONP@PEG-GOD) | 2019/10 | 4T1 | PTT/CHEMO | MR | - | [ |
Nb2C-MSNs-SNO | 2019/11 | 4T1 | PTT/CHEMO | PA | - | [ |
Ti2N | 2019/11 | MCF-7/A365/MCF-10A/HaCaT | PDT | - | - | [ |
V2C | 2020/01 | MCF-7 | PTT | - | - | [ |
TO-MX(Ti3C2/Ti2O3) | 2020/02 | A375/HaCaT/MCF-7/MCF-10A | PDT | - | - | [ |
PVP/Nb2C | 2020/04 | 4T1 | PTT | - | - | [ |
Nb2C/zein | 2020/04 | 4T1 | PTT | - | - | [ |
NMQDs-Ti3C2Tx | 2020/04 | ADSCs/HeLa/MCF-7 | PDT/CHEMO | - | - | [ |
Nb2C/PLL | 2020/05 | A375/HaCaT | PDT | - | - | [ |
Nb4C3/PLL | 2020/05 | A375/HaCaT | PDT | - | - | [ |
Ti3C2@Met@CP | 2020/06 | MDA-MB-231 | PTT/PDT/CHEMO | - | - | [ |
DOX@Ti3C2-CoNWs | 2020/06 | 4T1 | PTT/CHEMO | - | - | [ |
Ti3C2/CA4@PLEL | 2020/06 | 4T1/HUVECs | PTT/CHEMO | - | - | [ |
Ti2N | 2020/11 | 4T1/U87/293T | PTT | PA | - | [ |
MXene(Ti3C2)-DOX | 2021/01 | HeLa | PTT/PDT/CHEMO | - | - | [ |
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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