黑磷(Black Phosphorus, BP)是一种新型的二维材料,由于其独特、优异的性能,越来越受到研究者的关注。黑磷的能带间隙随层数的变化而变化,且具有高的比表面积、优良的生物相容性和生物可降解性。这些优异的性能使黑磷在生物应用领域具备了无限的潜力,如在光热治疗(photothermal therapy, PTT)、光动力治疗(photodynamic therapy, PDT)、药物载体等方面。相较于其他二维材料,黑磷全部由磷元素构成,当黑磷被应用于体内时可以有效避免人体内部发生免疫反应并有效减少诱发毒性的可能性。虽然黑磷具备广阔的应用前景,但是黑磷在空气中极度不稳定且容易被氧化而失效,该性能严重限制了黑磷的应用。本文不仅总结了黑磷纳米片层的制备方法及如何防止黑磷纳米片层氧化的方法,而且对黑磷在生物医学方面应用的研究进展和未来的发展前景进行了综述和展望。
Black Phosphorus (BP), a new 2D material that owns many unique and excellent properties, has gained increased attention in the past years. In particular, its layer-dependent bandgap, large surface-area-to-volume ratio, biodegradability and biocompatibility make it an ideal candidate for photothermal therapy, photodynamic therapy and drug delivery. Compared to other 2D materials, BP is constituted by Phosphorus (P), which is required by the human body and thus it is expected to be biocompatible after suitable engineering of its formulations. Although black phosphorus has many advantages, it’s surface instability due to chemical degradation, which hinders its application. This review not only provides a comprehensive summary on BP preparation and biomedical ap-plications but also looking forward the future possibilities.
黑磷,二维材料,光热治疗,光动力治疗,药物载体,生物医学应用, Black Phosphorus 2D Materials Photothermal Therapy Photodynamic Therapy Drug Delivery Biomedical Applications黑磷纳米片层的制备方法 及其在生物医学领域的应用
李景果,韩奉奇. 黑磷纳米片层的制备方法及其在生物医学领域的应用 Preparation of Black Phosphorus Nanosheets Layer and Its Application in Biomedical Field[J]. 材料科学, 2020, 10(08): 655-667. https://doi.org/10.12677/MS.2020.108080
参考文献ReferencesNovoselov, K.S., Geim, A.K., Morozov, S.V., Jiang, D., Zhang, Y., Dubonos, S.V., Grigorieva, I.V. and Firsov, A.A. (2004) Electric Field Effect in Atomically Thin Carbon Films. Science, 306, 666-669.
<br>https://doi.org/10.1126/science.1102896Novoselov, K.S., Falko, V.I., Colombo, L., Gellert, P.R., Schwab, M.G. and Kim, K. (2012) A Roadmap for Graphene. Nature, 490, 192-200. <br>https://doi.org/10.1038/nature11458Lee, C., Wei, X., Kysar, J.W. and Hone, J. (2008) Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene, Science, 321, 385-388. <br>https://doi.org/10.1126/science.1157996Xin, T.Z., Ananthanarayanan, A., Luo, K.Q. and Peng, C. (2014) Glowing Graphene Quantum Dots and Carbon Dots: Properties, Syntheses, and Biological Applications. Small, 11, 1620-1636. <br>https://doi.org/10.1002/smll.201402648Zheng, L., Ma, L., Gang, S., Wu, Z., Gong, Y.J., Lei, S.D., Yang, X.B., Zhang, J.G., Yu, J.J., Hackenberg, K.P., Babakhani, A., Idrobo, J.C., Vajtai, R., Lou, J. and Ajayan, P.M. (2013) In-Plane Heterostructures of Graphene and Hexagonal Boron Nitride with Controlled Domain Sizes. Nature Nanotechnology, 8, 119-124.
<br>https://doi.org/10.1038/nnano.2012.256Gunawan, P. and Xu, R. (2009) Direct Assembly of Anisotropic Layered Double Hydroxide (LDH) Nanocrystals on Spherical Template for Fabrication of Drug-LDH Hollow Nano-spheres. Chemistry of Materials, 21, 781-783.
<br>https://doi.org/10.1021/cm803203xMitra, S., Sasmal, H.S., Kundu, T., Kandambeth, S., Illath, K. and Día, D.D. (2017) Targeted Drug Delivery in Covalent Organic Nanosheets (CONs) via Sequential Postsynthetic Modification. Journal of the American Chemical Society, 139, 4513-4520. <br>https://doi.org/10.1021/jacs.7b00925Sun, Z., Tang, S., Yu, X.F., Guo, Z., Shao, J. and Chu, P.K. (2015) Ultrasmall Black Phosphorus Quantum Dots: Synthesis and Use as Photothermal Agents. Angewandte Chemie International Edition, 54, 11526-11530.
<br>https://doi.org/10.1002/anie.201506154Liu, H., Du, Y., Deng, Y. and Ye, P.D. (2015) Semiconducting Black Phosphorus: Synthesis, Transport Properties and Electronic Applications. Chemical Society Reviews, 4, 2732-2743. <br>https://doi.org/10.1039/C4CS00257ABridgman, W.P. (1914) Two New Modifications of Phosphorus. Journal of the American Chemical Society, 36, 1344-1363. <br>https://doi.org/10.1021/ja02184a002Kou, L., Chen, C. and Smith, S.C. (2015) Phosphorene: Fabrication, Properties, and Applications. Journal of Physical Chemistry Letters, 6, 2794-2805. <br>https://doi.org/10.1021/acs.jpclett.5b01094Sun, J., Zheng, G., Lee, H.W., Liu, N., Wang, H., Yao, H., Yang, W. and Cui, Y. (2014) Formation of Stable Phosphorus-Carbon Bond for Enhanced Performance in Black Phosphorus Nanoparticle-Graphite Composite Battery Anodes. Nano Letters, 14, 4573-4580. <br>https://doi.org/10.1021/nl501617jSun, J., Lee, H., Pasta, M., Yuan, H., Zheng, G., Sun, Y., Li, Y. and Cui, Y. (2015) A Phosphorene-Graphene Hybrid Material as a High-Capacity Anode for Sodium-Ion Batteries. Nature Nanotechnology, 10, 980-985.
<br>https://doi.org/10.1038/nnano.2015.194Liu, H., Neal, A.T., Zhu, Z., Luo, Z., Xu, X., Tománek, D. and Ye, P.D. (2014) Phosphorene: An Unexplored 2D Semiconductor with a High Hole Mobility. ACS Nano, 8, 4033-4041. <br>https://doi.org/10.1021/nn501226zLi, L., Yu, Y., Ye, G.J., Ge, Q., Ou, X., Wu, H., Feng, D., Chen, X.H. and Zhang, Y.B. (2014) Black Phosphorus Field-Effect Transistors. Nature Nanotechnology, 9, 372-377. <br>https://doi.org/10.1038/nnano.2014.35Luo, Z., Maassen, J., Deng, Y., Du, Y., Garrelts, R.P., Lundstrom, M.S., Ye, P.D. and Xu, X.F. (2015) Anisotropic In-Plane Thermal Conductivity Observed in Few-Layer Black Phos-phorus. Nature Communications, 6, 8572.
<br>https://doi.org/10.1038/ncomms9572Abbas, A.N., Liu, B., Chen, L., Ma, Y., Cong, S., Aroonyadet, N., Köpf, M., Nilges, T. and Zhou, C. (2015) Black Phosphorus Gas Sensors. ACS Nano, 9, 5618-5624. <br>https://doi.org/10.1021/acsnano.5b01961Qiu, M., Ren, W.X., Jeong, T., Won, M., Park, G.Y., Sang, D.K., Liu, L.P., Zhang, H. and Kim, J.S. (2018) Omnipotent Phosphorene: A Next-Generation, Two-Dimensional Nanoplat-form for Multidisciplinary Biomedical Applications. Chemical Society Reviews, 47, 5588-5601. <br>https://doi.org/10.1039/C8CS00342DBrent, J., Savjani, N., Lewis, E.A., Haigh, S.J., Lewis, D.J. and O’Brien, P. (2014) Production of Few-Layer Phosphorene by Liquid Exfoliation of Black Phosphorus. Chemical Communications, 50, 13338-13341.
<br>https://doi.org/10.1039/C4CC05752JWang, H., Yang, X., Shao, W., Chen, S., Xie, J., Zhang, X., Wang, J. and Xie, Y. (2015) Ultrathin Black Phosphorus Nanosheets for Efficient Singlet Oxygen Generation. Journal of the American Chemical Society, 137, 11376-11382.
<br>https://doi.org/10.1021/jacs.5b06025Yasaei, P., Kumar, B., Foroozan, T., Wang, C., Asadi, M., Tuschel, D., Indacochea, J.E., Klie, R.F. and Khojin, A.S. (2015) High-Quality Black Phosphorus Atomic Layers by Liquid-Phase Exfoliation. Advanced Materials, 27, 1887-1892. <br>https://doi.org/10.1002/adma.201405150Guo, Z., Han, Z., Lu, S.B., Wang, Z.T., Tang, S.Y., Shao, J.D., Sun, Z.B., Xie, H.H., Wang, H.Y., Yu, X.F. and Chu, P.K. (2015) From Black Phosphorus to Phosphorene: Basic Solvent Exfoliation, Evolution of Raman Scattering, and Applications to Ul-trafast Photonics. Advanced Functional Materials, 25, 6996-7002.
<br>https://doi.org/10.1002/adfm.201502902Tao, W., Zhu, X., Yu, X., Zeng, X., Xiao, Q., Zhang, X., Ji, X., Wang, X., Shi, J. and Zhang, H. (2016) Black Phosphorus Nanosheets as a Robust Delivery Platform for Cancer Theranostics. Advanced Materials, 29, Article ID: 1603276. <br>https://doi.org/10.1002/adma.201603276Sun, Z.X., Xie, H., Tang, S., Yu, X.F., Guo, Z., Shao, J., Zhang, H., Huang, H., Wang, H. and Chu, P.K. (2015) Ultrasmall Black Phosphorus Quantum Dots: Synthesis and Use as Photothermal Agents. Angewandte Chemie International Edition, 54, 11526-11530. <br>https://doi.org/10.1002/anie.201506154Lalmi, B., Oughaddou, H., Enriquez, H., Kara, A., Vizzini, S., Ealet, B. and Aufray, B. (2010) Epitaxial Growth of a Silicene Sheet. Applied Physics Letters, 97, Article ID: 223109. <br>https://doi.org/10.1063/1.3524215Xu, Y., Yuan, J., Fei, L., Wang, X., Bao, Q., Wang, Y., Zhang, K. and Zhang, Y. (2016) Selenium-Doped Black Phosphorus for High-Responsivity 2D Photodetectors. Small, 12, 5000-5007. <br>https://doi.org/10.1002/smll.201600692Zhang, Y., Rui, X., Tang, Y., Liu, Y., Wei, J., Chen, S., Leow, W.R., Li, W., Liu, Y., Deng, J., Ma, B., Yan, Q. and Chen, X. (2016) Wet-Chemical Processing of Phosphorus Composite Nanosheets for High-Rate and High-Capacity Lithium-Ion Batteries. Advanced Energy Materials, 6, Article ID: 1502409. <br>https://doi.org/10.1002/aenm.201502409Yang, X., Wang, D., Zhu, J., Xue, L., Ou, C., Wang, W., Lu, M., Song, X. and Dong, X. (2019) Functional Black Phosphorus Nanosheets for Mitochondria-Targeting Photothermal/Photodynamic Synergistic Cancer Therapy. Chemical Science, 10, 3779-3785. <br>https://doi.org/10.1039/C8SC04844DWang, H., Zhong, L., Liu, Y., Xu, X., Xing, C., Wang, M., Bai, S.M., Lu, C.H. and Yang, H.H. (2018) Functional Black Phosphorus Nanosheets for Mitochondria-Targeting Photother-mal/Photodynamic Synergistic Cancer Therapy. Chemical Communications, 54, 3142-3145. <br>https://doi.org/10.1039/C8CC00931GLee, H.U., Park, S.Y., Lee, S.C., Choi, S., Seo, S., Kim, H., Won, J., Choi, K., Kang, K.S., Park, H.G., Kim, H.S., An, H.R., Jeong, K.H., Lee, Y.C. and Lee, J. (2016) Black Phosphorus (BP) Nanodots for Potential Biomedical Applications. Small, 12, 214-219. <br>https://doi.org/10.1002/smll.201502756Lv, R., Yang, D., Yang, P., Xu, J., He, F., Gai, S., Li, C., Dai, Y., Yang, G. and Lin, J. (2016) Integration of Upconversion Nanoparticles and Ultrathin Black Phosphorus for Efficient Photodynamic Theranostics under 808 nm Near-Infrared Light Irradiation. Chemistry of Materials, 28, 4724-4734.
<br>https://doi.org/10.1021/acs.chemmater.6b01720Chen, W., Ouyang, J., Liu, H., Chen, M., Zeng, K., Sheng, J., Liu, Z., Han, Y., Wang, L., Li, J., Deng L., Liu, Y.N. and Guo, S. (2016) Black Phosphorus Nanosheet-Based Drug Delivery System for Synergistic Photodynamic/Photothermal/Chemotherapy of Cancer. Advanced Materials, 29, Article ID: 1603864.
<br>https://doi.org/10.1002/adma.201603864Yin, F., Hu, K., Chen, S., Wang, D., Zhang, J., Xie, M., Yang, D., Qiu, M., Zhang, H. and Li, Z. (2017) Black Phosphorus Quantum Dot Based Novel siRNA Delivery Systems in Human Pluripotent Teratoma PA-1 Cells. Journal of Materials Chemistry B, 5, 5433-5440. <br>https://doi.org/10.1039/C7TB01068KSun, C., Wen, L., Zeng, J., Wang, Y., Sun, Q., Deng, L., Zhao, C. and Li, Z. (2016) One-Pot Solventless Preparation of PEGylated Black Phosphorus Nanoparticles for Photoacoustic Imaging and Photothermal Therapy of Cancer. Biomaterials, 91, 81-89. <br>https://doi.org/10.1016/j.biomaterials.2016.03.022Shao, J., Xie, H., Huang, H., Li, Z., Sun, Z., Xu, Y., Xiao, Q., Yu, X.F., Zhao, Y., Zhang, H., Wang, H. and Chu, P.K. (2016) Biodegradable Black Phosphorus-Based Nano-spheres for in Vivo Photothermal Cancer Therapy. Nature Communications, 7, Article No. 12967. <br>https://doi.org/10.1038/ncomms12967