Ag2S纳米晶的制备及其近红外光热治疗应用

doi:10.15541/jim20170498

摘要/Abstract

摘要：

光热治疗是近年来受到广泛关注的一种低副作用的癌症治疗方法, 治疗中使用的纳米光热剂的制备和性能是决定光热治疗效应的关键因素。本研究采用热解和表面配体置换相结合的方法制备得到二氢硫辛酸(DHLA)修饰的Ag₂S纳米晶材料, 这种材料具有良好的水溶性、光热稳定性和生物相容性。研究结果显示浓度大于40 μg/mL的Ag₂S纳米晶在波长为980 nm、功率密度为5 W/cm²的红外激光照射下对宫颈癌细胞具有明显的杀伤效果, 且光热稳定性良好。Ag₂S纳米晶的光热效应与其良好的荧光成像功能相结合, 可实现光热治疗的可视化和精准化。

关键词: Ag₂S纳米晶, 光热效应, 980 nm激光, 可视化

Abstract:

Photothermal therapy (PTT) is a promising cancer treatment with both high effectiveness and low side effects. It is very important that the advancement of the NIR photothermal cancer therapy is dependent on the development of photothermal agents. Herein, this study developed hydrophilic DHLA-Ag₂S nanocrystals as a new photothermal agent, which were synthesized by combining a thermal decomposition and ligand exchange route. The as-prepared Ag₂S nanocrystals appear good water solubility, photo thermal stability and biocompatibility. Under irradiation of 980 nm laser with a power density of 5 W/cm², HeLa cancer cells in vitro can be efficiently killed by photothermal effects of the Ag₂S nanocrystals (40 μg/mL). The photothermal effect of Ag₂S nanocrystals and its good fluorescence imaging function can realize the visualization and precision of photothermal therapy.

Key words: Ag₂S nanocrystals, photothermal effect, 980 nm laser, visualization

中图分类号:

O614

邓立儿, 李妍, 巩蕾, 王佳. Ag₂S纳米晶的制备及其近红外光热治疗应用[J]. 无机材料学报, 2018, 33(8): 825-831.

DENG Li-Er, LI Yan, GONG Lei, WANG Jia. Preparation of Ag₂S Nanocrystals for NIR Photothermal Therapy Application[J]. Journal of Inorganic Materials, 2018, 33(8): 825-831.

图/表 8

图1 Ag2S纳米晶粉末及不同浓度水溶液照片(a)和Ag2S纳米晶的XRD图谱(b)及其TEM照片(插图)

Fig. 1 Photograph of DHLA-Ag2S nanocrystals aqueous dispersion (a) and XRD pattern (b) with inset showing TEM image of Ag2S nanocrystals

图2 Ag2S纳米晶HRTEM照片(a)及其水溶液的吸收光谱(b)

Fig. 2 HRTEM images of the synthesized Ag2S nanocrystals (a) and UV-Vis-NIR spectrum (b) of Ag2S nanocrystals suspended in water

图3 不同浓度Ag2S纳米晶水溶液在激光照射下的升温曲线(a)和相同光照时间下(5 min)的温升值随溶液的浓度变化曲线(b)

Fig. 3 Temperature elevation of the aqueous dispersion of Ag2S nanocrystals with different concentrations as a function of irradiation time (a) and plot of temperature change (∆T) over a period of 5 min versus the concentration of the Ag2S nanocrystals aqueous dispersion (b)

图4 80 μg/mL的Ag2S纳米晶水溶液在激光(980 nm, 5 W/cm2)照射下加热(激光开)和冷却(激光关)过程的温度变化曲线(a)及其t与lnθ的线性拟合曲线(b)

Fig. 4 Temperature evolution of Ag2S nanocrystals aqueous dispersion (80 μg/mL) during heating (laser on) and cooling (laser off) (a) and linear fitting curve between t and lnθ (b)

图5 三个周期激光开关过程的DHLA-Ag2S纳米晶水溶液温度值随时间的变化曲线

Fig. 5 Temperature varied with time of DHLA-Ag2S nanocrystals aqueous solution in three cycles of laser switching

图6 与不同浓度的Ag2S纳米晶水溶液共培养24 h后HeLa细胞的存活率

Fig. 6 Cell viability of HeLa cells incubated with different concentrations of Ag2S nanocrystal aqueous solutions for 24 h

图7 不同光照时间和不同浓度的Ag2S纳米材料光热治疗后HeLa细胞的存活率

Fig. 7 Cell viability of HeLa cells incubated with different concentrations of Ag2S nanomaterials and then being irradiated by a NIR laser for different time

图8 光照20 min后不同浓度Ag2S纳米晶材料杀灭肿瘤细胞效果的荧光照片

Fig. 8 Fluorescence images of HeLa cells after photothermal treatment with different concentrations of Ag2S nanomaterials under NIR irradiation for 20 min Green fluorecence: live cells; Red fluorescence: dead cells. All bars are 50 μm

参考文献 32

[1]	LU W, XIONG C, ZHANG G D,et al. Targeted photothermal abltion of murnemelanomas with melanocyte-stimulating hormone analog conjugated hollow gold nanospheres.Clin. Cancer. Res., 2009, 15(3): 876-886.
[2]	TAKOR A S, GAMBHIR S S.Nanooncology: the future of cancer diagnosis and therapy.CA. Cancer J. Clin., 2013, 63(6): 395-399.
[3]	VOGEL A, VENUGOPALAN V.Mechanisms of pulsed laser ablation of biological tissues.Chem. Rev., 2003, 103(2): 577-581.
[4]	YANG J, CHOI J, BANG D,et al. Convertible organic nanoparticles for near-infrared photothermal ablation of cancer cells.Angew. Chem. Int. Ed., 2011, 50(2): 441-444.
[5]	ZHAI YUN GANG, DONG WEN JIE, GAO YONG PING,et al. Preparation of superparamagnetic gold nanocomposites with different diameters and their imaging and therapy applications.Journal of Inorganic Materials, 2015, 30(9): 950-956.
[6]	YANG J, CHOI J, BANG D,et al. Convertible organic nanoparticles for near-infrared photothermal ablation of cancer cells.Angew. Chem. Int. Ed., 2011, 50(2): 441-444.
[7]	THAKARE V S, DAS M, JAIN A K,et al. Carbon nanotubes in cancer theragnosis.Nanomedicine, 2010, 5(8): 1277-1301.
[8]	HIESCH L R, STAFFORD R J, BANKSON J A.et al. Nanoshell- media-infrared thermal therapy of tumors under magnetic resonance guidance.Proc. Natl. Acad. Sci. USA, 2003, 100(23): 13549-13554.
[9]	HUANG X, JAIN P K, El-SAYED I H.et al. Plasmonic photo-thermal therapy (PPTT) using gold nanoparticles. Alex. J. Med., 2011, 47(15): 1-9.
[10]	HAO Y W, ZHANG B X, ZHENG C X,et al.The tumor-targeting core-shell structured DTX-loaded PLGA@Au nanoparticles for chemo-photothermal therapy and X-ray imaging. Journal of Controlled Release, 2015, 220: 545-555.
[11]	LI J L, GU M.Gold-nanoparticle-enhanced cancer photothermal therapy.IEEE J. Sel. Top Quant Electron., 2010, 16(4): 989-996.
[12]	LI Z, HUANG P, ZHANG X,et al.RGD-conjugated dendrimer-modified gold nanorods for in vivo tumor targeting and photothermal therapy. Mol. Pharmaceutics., 2010, 7(1): 94-104.
[13]	LI Z B, HUANG H, TANGS Y,et al. Small gold nanorods laden mac rophages for enhanced tumor coverage in photothermal therapy. Biomaterials, 2016, 74(30): 144-154.
[14]	CHAKRAVARTY P, MARCHES R, ZIMMERMAN N S,et al.Thermal ablation of tumor cells with anti body-functionalized single-walled carbon nanotubes.Proc. Natl. Acad. Sci. USA, 2008, 105(25): 8697-8702.
[15]	ZHANG Z, LIU S, XIONG H.Electrospun PLA/MWCNTs composite nanofibers for combined chemo- and photothermaltherapy.Acta Biomaterialia, 2015, 26(20): 115-123.
[16]	POLAND C A, DUFFIN R, KINLOCH I,et al.Carbon nanotubes introduced into the abdominal cavity of mice show asbestos-like pathogenicity in a pilot study. Nat. Nanotechnol., 2008, 3(7): 423-428.
[17]	LANBERT T N, ANDREWS N L, GERUNG H, et al. (CdSe)ZnS core-shell quantum dots: synthesis and characterization of a size series of highly luminescent nanocrystallites. Biomaterials, 2008, 29(5): 1912-1919.
[18]	DABBOUSI B O, RODRIGUEZVIEJO J, FV MIKULEC F V,et al.(CdSe) ZnS core-shell quantum dots: synthesis and optical and structural characterization of a size series of highly luminescent materials. J. Bacterior., 1997, 182(13): 3649-3654.
[19]	LEE C, KIM H, HONG C,et al.Porous silicon as an agent for cancer thermotherapy based on near-infrared light irradiation. J. Mater. Chem., 2008, 18(40): 4790-4795.
[20]	YANG K, ZHANG S A, ZHANG G X,et al.Graphene in mice: ultra hig in vivo tumor uptake and efficient photothermal therapy. Nano Lett., 2010, 10(9): 3318-3323.
[21]	SHARKER S M, KIM S M, LEE J E,et al.Functionalized biocom-patible WO3 nanoparticles for triggered and targeted in vitro and in vivo photothermal therapy. J. Control. Release, 2015, 217: 211-220.
[22]	YANG C, MA L, ZOU X J,et al.Surface plasmon-enhanced Ag/CuS nanocomposites for cancer treatment. Cancer Nano, 2013, 4(4/5): 81-89.
[23]	SHERLOCK S P, TABAKAN S M, XIE L,et al.Photothermally enhanced drug delivery by ultra-small multifunctional FeCo/ graphitic-shell nanocrystals. ACS Nano, 2011, 5(2): 1505-1512.
[24]	KRYUKOV A I, STROYUK A L, ZIN'CHUK N N,et al. Optical and catalytic properties of Ag2S nanoparticles. Journal of Molecular Catalysis A: Chemical, 2004, 221(1/2): 209-221.
[25]	WANG Q T, WANG X B, LOU W J,et al.Synthesis of bismuth sulfide nanostructures and their electrochemical hydrogen storage behavior. New Journal of Chemistry, 2010, 34(9): 1930-1935.
[26]	HONGG S, ROBINSON J T, ZHANG Y J,et al.In vivo fluorescence imaging with Ag2S quantum dots in the second near-infrared region. 2012, 51(39): 9818-9821.
[27]	LI C Y, ZHANG Y J, WANG M,et al.In vivo real-time visualization of tissue blood flow and angiogenesis using Ag2S quantum dots in the NIR-II window. Biomaterials, 2014, 35(1): 393-400.
[28]	ROPER D K, AHN W, HOEPFNER M.Microscale heat transfer transduced by surface plasmon resonant gold nanoparticles.J. Phys. Chem. C, 2007, 111(9): 3636-9641.
[29]	YUWEN L H, ZHOU J J, ZHANG Y Q,et al.Aqueous phase preparation of ultrasmall MoSe2 nanodots for efficient photothermal therapy of cancer cells. Nanoscale, 2016, 8: 2720-2726.
[30]	TIAN Q W, JIANG F R, ZOU R J,et al. Hydrophilic Cu9S5 nanocrystals: a photothermal agent with a 25.7% heat conversion efficiency for photothermal ablation of cancer cells in vivo.ACS Nano, 2011, 5(12): 9761-9771.
[31]	HONG G S, ROBINSON T J, ZHANG Y J,et al.In-vivo fluorescence imaging with Ag2S quantum dots in the second near-infrared region.Angew. Chem. Int. Ed., 2012, 51(39): 9818-9821.
[32]	DU Y P, XU B, FU T,et al.Near-infrared photoluminescent Ag2S quantum dots from a single source precursor.Journal of the American Chemical Society, 2010, 132(5): 1470-1471.

Ag₂S纳米晶的制备及其近红外光热治疗应用

Preparation of Ag₂S Nanocrystals for NIR Photothermal Therapy Application

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