水热法制备光热治疗剂纳米WO_(3-x)的组织结构与光热效应
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摘要
采用水热法制备表面活性剂聚甲基丙烯酸-季戊四醇四-3-巯基丙酸酯(PTMP-PMAA)修饰的具有光热效应的纳米WO_(3-x)粉末,通过X射线衍射(XRD)分析、透射电镜(TEM)观察、X射线光电子能谱(XPS)分析、傅里叶变换红外光谱(FT-IR)分析以及紫外-可见吸收光谱(UV-Vis谱)分析及光热性能测试等,研究所得纳米粉体材料的结构及其在不同浓度与pH值下的光热性能。结果表明,水热法制备的WO_(3-x)粉末为球形的非整比结构的W17O47,粒径小于10 nm。随WO_(3-x)的pH值降低或质量浓度降低,粉末的紫外吸光度增加,光热效应提高。pH值为6.4、质量浓度为800μg/mL的WO_(3-x)经光热转换后,可实现在5 min内约19℃的温度上升。考虑到人体体温为37℃,肿瘤部位的pH值为6.0～6.5之间,此质量浓度下纳米WO_(3-x)粉末可用于光热治疗并实现对肿瘤细胞的杀伤效果。
PTMP-PMAA modified Nano-WO_(3-x) powder was obtained by hydrothermal method.The effects of pH value and concentration on photothermal properties of the nano-WO_(3-x) powder materials were studied by X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV-vis spectroscopy and photothermal property testing.The results show that the powders prepared by hydrothermal method are spherical nonintegral structure W17 O48 with a particle size of less than 10 nm.The UV absorbance of the WO_(3-x) material increases and the photothermal effect increases with decreasing the pH value or concentration of WO_(3-x).When pH 6.4 and mass concentration is 800 μg/mL,the temperature of WO_(3-x) can rise nearly 19 ℃ in 5 minutes after photothermal conversion.Considering that the body temperature is 37 ℃ and the pH value of tumor site is between 6.0 and 6.5,nano-WO_(3-x) powders at this concentration can be used in photothermal therapy and achieve the killing effect on tumor cells.
PTMP-PMAA modified Nano-WO_(3-x) powder was obtained by hydrothermal method.The effects of pH value and concentration on photothermal properties of the nano-WO_(3-x) powder materials were studied by X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV-vis spectroscopy and photothermal property testing.The results show that the powders prepared by hydrothermal method are spherical nonintegral structure W17 O48 with a particle size of less than 10 nm.The UV absorbance of the WO_(3-x) material increases and the photothermal effect increases with decreasing the pH value or concentration of WO_(3-x).When pH 6.4 and mass concentration is 800 μg/mL,the temperature of WO_(3-x) can rise nearly 19 ℃ in 5 minutes after photothermal conversion.Considering that the body temperature is 37 ℃ and the pH value of tumor site is between 6.0 and 6.5,nano-WO_(3-x) powders at this concentration can be used in photothermal therapy and achieve the killing effect on tumor cells.
引文
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[2]吴一龙.恶性肿瘤治疗方法的发展及其认识论意义[J].医学与哲学,1994(11):9-11.WU Yilong.The development of cancer treatment and its epistemological significance[J].Medicine and Philosophy,1994(11):9-11.
[3]MELAMED J R,EDELSTEIN R S,DAY E S.Elucidating the fundamental mechanisms of cell death triggered by photothermal therapy[J].Acs Nano,2015,9(1):6-11.
[4]宋雪娇,刘庄.有机纳米材料在肿瘤光热治疗中的应用[J].化学通报,2015,78(4):292-298.SONG Xuejiao,LIU Zhuang.Organic nanomaterials for photothermal therapy of cancer[J].Chemistry Bulletin,2015,78(4):292-298.
[5]王新环,韩秋森,李婧影.无种子法纳米金棒的制备及其对肿瘤细胞光热治疗效应研究[J].物理化学学报,2014,30(7):1363-1369.WANG Xinhuan,HAN Qiusen,LI Jingying.Seedless synthesis of gold nanorods and applications in photo-thermal cancer therapy[J].Acta Physico-Chimica Sinica,2014,30(7):1363-1369.
[6]高振,魏勇,朱立新.金纳米笼-量子点-Anti-AFP复合探针对肝癌细胞株的靶向光热治疗[J].中华肿瘤防治杂志,2017,24(11):734-738.GAO Zhen,WEI Yong,ZHU Lixin.Targeted light heat treatment of gold nano cage-quantum dots-Anti-AFP composite probe on HepG-2 hepatocellular carcinoma cells[J].Chinese Journal of Cancer Prevention and Treatment,2017,24(11):734-738.
[7]TERENTYUK G,PANFILOVA E,KHANADEEV V.Gold nanorods with a hematoporphyrin-loaded silica shell for dual-modality photodynamic and photothermal treatment of tumors in vivo[J].Nano Research,2014,7(3):325-337.
[8]CHANDRA D,SAITO K,YUI T.Crystallization of tungsten trioxide having small mesopores:highly efficient photoanode for visible-light-driven water oxidation[J].Angew Chem,2013,52(48):12606-12609.
[9]LIU B J,ZHENG J,WANG J L.Ultrathin W18O49 nanowire assemblies for electrochromic devices[J].Nano Lett,2013,13(8):3589.
[10]HORPRATHUM M,SRICHAIYAPERK T,SAMRANSUK-SAMER B.Ultra sensitive hydrogen sensor based on pt-decorated WO3 nanorods prepared by glancing-angle DCmagnetron sputtering[J].Acs Appl Mater Interfaces,2014,6(24):22051-22060.
[11]钱静雯.含钨化合物纳米结构的合成及光电化学性能研究[D].北京:中国地质大学(北京),2017.QIAN Jinwen.Synthesis and photoelectrochemical properties of tungsten containing nanostructures[D].Beijing:China University of Geosciences(Beijing),2017.
[12]谢骥,谢祯芳,胡校兵.基于纳米WO3半导体材料的NO2气体传感器的研究进展[J].陶瓷学报,2016,37(6):593-602.XIE Ji,XIE Zhenfang,HU Xiaobing.The research progress of NO2 gas sensor based on the nano-WO3 semiconductor materials[J].Journal of Ceramics,2016,37(6):593-602.
[13]GUO C,YIN S,YAN M.Morphology-controlled synthesis of W18O49 nanostructures and their near-infrared absorption properties[J].Inorg Chem,2012,43(28):4763-4771.
[14]LIU J,MARGEAT O,DACHRAOUI W.Gram-scale synthesis of ultrathin tungsten oxide nanowires and their aspect ratio-dependent photocatalytic activity[J].Adv Funct Mater,2014,24(38):6029-6037.
[15]申永奇.氧化钨纳米材料的可控合成及光电性能研究[D].武汉:华中科技大学,2013.SHEN Yongqi.Controllable synthesis and photoelectric properties of tungsten oxide nanomaterials[D].Wuhan:Huazhong University of Science and Technology,2013.
[16]郝金玲,姜春萍,张艳辉.电沉积WO3薄膜及其光电性能的表征[J].化学研究与应用,2010,22(5):550-553.HAO Jinling,JIANG Chunping,ZHANG Yanhui.Electrodeposition and characterization of photoelectrochemical properties of WO3 thin films[J].Chemical Research and Application,2010,22(5):550-553.
[17]MAJEED M I,GUO J,YAN W.Preparation of magnetic iron oxide nanoparticles(MIONs)with Improved Saturation magnetization using multifunctional polymer ligand[J].Polymers,2016,8(11):392.
[18]黄鑫.多功能聚合物配体制备荧光纳米金颗粒及其生物应用[D].武汉:华中科技大学,2011.HUANG Xin.Preparation of fluorescent gold nanoparticles by multifunctional polymer ligands and their biological applications[D].Wuhan:Huazhong University of Science and Technology,2011.
[19]赵洁,姚秉华,贺友涛.简单水热法制备纳米WO3及其光催化性能[J].水处理技术,2012,38(10):42-46.ZHAO Jie,YAO Binghua,HE Youtao.Simple hydrothermal synthesis of nanosized WO3 and its photocatalytic activity[J].Technology of Water Treatment,2012,38(10):42-46.
[20]曾慧琳,王姗姗,符旭东.pH敏感脂质体在药物传递系统中的应用[J].医药导报,2014,33(3):348-351.ZENG Huilin,WANG Shanshan,FU Xudong.Application of p Hsensitive liposomes in drug delivery system[J].Herald of Medicine,2014,33(3):348-351.
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[22]TOH Y R,YU P,WEN X.Induced pH-dependent shift by local surface plasmon resonance in functionalized gold nanorods[J].Nanoscale Research Letters,2013,8(1):103-103.
[23]ZHU J,LI W,ZHU M.Influence of the pH value of a colloidal gold solution on the absorption spectra of an LSPR-assisted sensor[J].Aip Advances 2014,4(3):3722.
[24]BALITSKII O A,MOSZY?SKI D,ABBAS Z.Aqueous processable WO3-x nanocrystals with solution tunable localized surface plasmon resonance[J].Rsc Advances 2016,6(64):59050-59054.