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摘要: 近红外光热转换纳米晶材料因其在近红外区（普遍位于780~1 400 nm）的高效光热转换性能，已广泛应用于光热杀死癌细胞、肿瘤治疗、海水淡化等领域。因其多样的液相制备方法和形貌控制、纳米结构复合、逐渐提高的光热转换效率以及表面易于药物修饰等优点，该材料在光热成像诊断、光热治疗等领域引起了学术界的广泛关注。本文综述了近红外光热转换纳米晶的研究进展，主要包括贵金属纳米晶、铜硫族半导体纳米晶、碳相关纳米晶以及这些纳米晶材料构成的复合结构，同时介绍了具有较高光热转换效率的表面等离子体共振（SPR）材料的研究进展，尤其是双模态SPR性质的耦合在光热转换领域的应用前景。基于其性能协同耦合的特性，双模态表面等离子体共振耦合的复合纳米晶将是近几年光热转换纳米晶发展的重要方向。Abstract: Near-infrared photothermal(PT) conversion nanocrystals(NCs), due to their excellent PT conversion performance in near-infrared region(generally in range of 780-1 400 nm), has a wide application potential in the field of cancer cell killing, tumor therapy as well as desalination. These NCs attracted great attention on PT imaging and PT therapy, because of their diverse liquid phase synthesize methods, morphology-controll, nanostructure composite, increasing PT conversion efficiency and easy functionalization. This review aimed to summarize the research progress of near-infrared PT conversion NCs, including noble metal NCs, copper chalcogenide semiconductor NCs, carbon-related NCs, hybrid structure composed of nanocrystalline materials. In addition, the research progress of surface plasmon resonance(SPR) materials with high photothermal conversion efficiency is introduced, especially the application prospect of dual-mode SPR coupling in the field of photothermal conversion. Through the research on the literatures at home and abroad, it is known that the hybrid nanocrystals with dual mode surface plasmon resonance coupling will be an important direction for the development of photothermal conversion nanocrystals in recent years due to the characteristics of performance coordination and coupling.
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图 2 不同形貌的金纳米晶及对应光谱吸收图。(a, c)Au纳米棒(长径比为5.2) 的低分辨透射电子显微镜图片，以及不同长径比的Au纳米棒的消光光谱图[10]; (b, d)Au纳米笼的扫描电子显微镜图，以及置换反应程度的吸收光谱图[16]
Figure 2. LRTEM images of Au with various types of nanostructures and their plasmonic absorbance respectively. (a, c)LRTEM image of Au nanorods with aspect ratio 5.2 and the extinction of Au NRs with different aspect ratio[10]; (b, d)LRTEM image of Au nanocages and their plasmonic absorbance[16]
图 3 (a)疏水性Cu7S4纳米颗粒的低分辨透射电子显微镜图; (b)亲水性的Cu7S4纳米晶的低分辨透射显微镜图; (c)亲水性Cu7S4纳米晶形成机理; (d)两种材料的在808 nm的激光照射下的光热转换图谱; (e)光热成像指纹检测示意图[6]
Figure 3. (a)LRTEM image of hydrophobic Cu7S4 NPs. (b)LRTEM image of amphiphilic Cu7S4 NCs. (c)Fabrication strategy for Cu7S4 NCs. (d)PT activity of Cu7S4 NPs and NCs. (e)Schematic representation of photothermal imaging process[6]
图 4 (a)Au-Cu9S5异质二聚体纳米晶材料; (b)Au-Cu9S5元素分部图; (c)Au颗粒，Cu9S5纳米颗粒，Au-Cu9S5异质结构的UV-Vis吸收示意图; (d)Au-Cu9S5异质结构和Au与Cu9S5混合机构的光热准换效率对比图[33]
Figure 4. (a)Schematic representation of Au-Cu9S5 dual plasmonic hybrid NCs when irradiated by laser. (b)STEM image of Au-Cu9S5 NCs and their EDS element mapping images. (c)Molar extinction coefficient of Au-Cu9S5, Cu9S5 and Au colloidal respectively. (d)PT activity comparison of Au-Cu9S5 and physical mixture of Au and Cu9S5 at same concentration when irradiated by 808 nm, 0.7 W/cm2 laser[33]
图 7 (a)Au@Cu2-xS纳米棒，Au@Cu2-xS纳米颗粒，Au纳米棒以及Cu2-xS纳米颗粒溶胶的UV-Vis-NIR光谱图; (b)不同浓度的Au@Cu2-xS纳米棒胶体在0.7 W/cm2 1 064 nm的激光照射下的光热转换曲线; (c)Au@Cu2-xS与不同配比的Au，Cu2-xS的混合胶体的光热转换曲线对比; (d)Au@Cu2-xS纳米棒胶体在0.7 W/cm2 1 064 nm激光照射下的光热转换循环测试; (e)Au@Cu2-xS纳米棒和Cu2-xS纳米晶在808nm和1 064nm激光照射下赫拉细胞存活率对比[34]
Figure 7. (a)UV-Vis-NIR spectra of the as prepared Au@Cu2-xS nanorods, Au@Cu2-xS NPs, Au nanorods and Cu2-xS NPs colloidal respectively. (b)PT conversion curve of Au@Cu2-xS NRs by 0.7 W/cm2 1 064 nm laser. (c)PT activity of Au NRs, Cu2-xS nanoparticles and their physical mixtures for various ratios compared with Au@Cu2-xS nanorods. (d)PT cycling test of Au@Cu2-xS nanorods irradiated by 0.7 W/cm2 1 064 nm laser. (e)Hela cell viability of Au@Cu2-xS NRs under irradiation of 808 nm and 1 064 nm laser irradiation compared to Cu2-xS NPs[34]
图 8 (a)Au@Ag3AuTe2纳米晶效果图; (b)Au@Ag3AuTe2纳米晶的低分辨透射电子显微镜和高分辨透射电子显微镜图; (c, d)不同浓度下Au@Ag3AuTe2纳米晶在808 nm和1 064 nm激光照射下的光热转换曲线[52]
Figure 8. (a)Scheme of Au@Ag3AuTe2 NCs. (b)LRTEM and HRTEM images of Au@Ag3AuTe2 NCs. (c, d)PT conversion characterizations of Au@Ag3AuTe2 NCs colloid with various concentrations by 0.7 W/cm2 808 nm (c), 0.7 W/cm2 1 064 nm (d)[52]
图 10 (a)Cu2O@MS(M=Cd, Zn, Sn) yolk-shell纳米晶合成过程示意图; (b)Cu2O@CdS yolk-shell纳米晶低分辨透射电子显微镜图; (c)Cu2O@CdS yolk-shell纳米晶高分辨透射电子显微镜图; (d)Cu2O@CdS yolk-shell纳米晶STEM模式下的元素分布图[36]
Figure 10. (a)Synthesis scheme of Cu2O@MS (M=Cd, Zn, Sn) yolk-shell NCs. (b)LRTEM image of Cu2O@CdS yolk-shell NCs. (c)HRTEM image of Cu2O@CdS yolk-shell NCs. (d)Element mapping of Cu2O@CdS yolk-shell NCs[36]
图 11 PEG包附的石墨烯纳米片(NGS-PEG)。(a)Cy7修饰的NGS-PEG示意图; (b)NGS-PEG的原子力显微镜图; (c)NGS-PEG的UV-Vis-NIR吸收光谱图'; (d)808 nm，2 W/cm2激光照射下NGS-PEG的光热转换图谱[42]
Figure 11. NGS coated with PEG. (a)schematic diagram of NGS-PEG labeled with Cy7. (b)AFM image of NGS-PEG. (c)UV-Vis-NIR absorbance of NGS-PEG solution. (d)PT activity of NGS-PEG under 808 nm 2 W/cm2 laser treatment[42]
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