CN111840548A - 一种层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体的制备方法 - Google Patents
一种层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体的制备方法 Download PDFInfo
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Abstract
本发明公开了一种层状双氢氧化物纳米片‑硫化铜量子点异质纳米复合体的制备方法,采用原位生长法,将硫化铜量子点生长于层状双氢氧化物纳米片上,利用聚合物限域作用,CuS独立地散步于LDH上而不发生团聚。本发明制得的层状双氢氧化物纳米片‑硫化铜量子点异质纳米复合体一方面具有光热性质,能将近红外光照后转化热能,发挥肿瘤光热治疗效果;另一方面,所形成的金属‑半导体异质结构有助于硫化铜在近红外光照下电子和空穴的分离,从而更高效地催化肿瘤细胞内产生具有生物毒性的活性氧,杀死肿瘤细胞。
Description
技术领域
本发明属于医用材料技术领域,具体涉及应一种层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体的制备方法。
背景技术
随着肿瘤治疗的发展,纳米材料具有优越的形态、理化和功能特性,各种治疗策略发生了广泛的变化。近年来,针对特定细胞器的各种主动靶向策略引起了越来越多的关注。尤其是溶酶体是细胞内吞作用后第一个运输纳米材料的细胞器。与正常细胞相比,癌细胞中溶酶体过度发育,体积大、数量多、组织蛋白酶活性高,显示了溶酶体作为靶向细胞器在肿瘤治疗中提高选择性和显著疗效的潜力。
硫化铜(CuS)由于其较好的近红外光吸收,基于其的肿瘤光热治疗和光动力治疗治疗已被广泛研究。但由于肿瘤组织内部的低氧,活性氧的生成效率往往成为动力治疗的最大限制。层状双氢氧化物(Layered double hydroxides,LDH)由于其生物相容性好也在生物医药学领域广泛关注。然而,LDH纳米片自身并没有抗癌作用,需要协同其他药物或材料才能发挥作用。
发明内容
本发明的目的在于克服现有技术缺陷,提供一种层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体的制备方法。
本发明的技术方案如下:
一种层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体的制备方法,包括如下步骤:
(1)将氢氧化钠溶解于去离子水中,得到氢氧化钠溶液;
(2)将第一金属盐、第二金属盐溶解于去离子水中,得到金属盐溶液;第一金属盐为二价金属盐,第二金属盐为三价金属盐或四价钛盐;
(3)在氮气气氛下,将上述氢氧化钠溶液缓慢滴加入上述金属盐溶液中,于室温下剧烈搅拌,接着离心得沉淀,再用水分别洗涤,收集得到层状双氢氧化物纳米片粗产物;
(4)将上述层状双氢氧化物纳米片粗产物分散于去离子水中,置于水热反应釜中,于60-140℃进行水热反应8-12h,得到层状双氢氧化物纳米片;
(5)将上述层状双氢氧化物纳米片、氯化铜和聚乙烯吡咯烷酮溶解于去离子水中,得到混合溶液;
(6)将硫化钠水溶液加入到上述混合溶液中,并于85-95℃剧烈搅拌,再置于冰水浴中冷却,离心收集得到所述层状双氢氧化物纳米片-硫化铜量子点纳米复合体。
在本发明的一个优选实施方案中,所述二价金属盐包括镁盐、铁盐、钴盐、镍盐、铜盐、锌盐、钙盐和锰盐。
进一步优选的,所述二价金属盐为镁盐。
更进一步优选的,所述镁盐为硝酸镁。
在本发明的一个优选实施方案中,所述三价金属盐包括铝盐、铁盐、钴盐、镍盐、铬盐、锰盐、钆盐和铟盐。
进一步优选的,所述三价金属盐为铝盐。
更进一步优选的,所述铝盐为硝酸铝。
在本发明的一个优选实施方案中,所述第一金属盐为硝酸镁,所述第二金属盐为硝酸铝。
在本发明的一个优选实施方案中,所述第一金属盐和第二金属盐的摩尔比为2-4∶1。
进一步优选的,所述层状双氢氧化物纳米片、氯化铜和聚乙烯吡咯烷酮的质量比为7.3-7.4∶6.7-6.9∶5-1000。
本发明的有益效果是:
1、本发明采用原位生长法,将硫化铜量子点(CuS)生长于层状双氢氧化物纳米片(LDH)上,利用聚合物限域作用,CuS独立地散步于LDH上而不发生团聚。
2、本发明制得的层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体(LDH-CuSNCs)一方面具有光热性质,能将近红外光照后转化热能,发挥肿瘤光热治疗效果;另一方面,LDH-CuS NCs所形成的金属-半导体异质结构有助于硫化铜在近红外光照下电子和空穴的分离,从而更高效地催化肿瘤细胞内产生具有生物毒性的活性氧,杀死肿瘤细胞。
3、本发明制得的层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体中的CuS在近红外光照射下加速铜离子的溢出,催化类芬顿反应进一步提升活性氧生产效率。
4、由于本发明制得的层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体中的二维形态,内化的LDH-CuS NCs容易富集于溶酶体中发挥效应,导致溶酶体膜通透性(LMP)途径相关的细胞死亡。
5、本发明制得的层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体能提升肿瘤细胞内氧气和过氧化氢的利用率,高效地将其转化为活性氧。
6、本发明制得的层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体能在外界近红外激光照射下在所需部位发挥效应,且具有光声成像功能,提高肿瘤治疗的精准性。
附图说明
图1为本发明实施例1的普通层状双氢氧化物纳米片以及层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体的透射电镜照片和层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体的元素定位图。
图2为本发明实施例2中层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体在不同光功率密度的808nm近红外激光照射下,随照射时间的溶液温度变化曲线。
图3为本发明实施例3中层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体与细胞共孵育不同时间后纳米复合体与溶酶体的共定位图。
图4为本发明实施例4中层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体与细胞共孵育后胞内ROS水平荧光强度图。
图5为普通硫化铜量子点和本发明实施例5中的层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体静脉注射进入肿瘤模型裸鼠不同时间后在肿瘤部位的富集情况和光声信号图。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
(1)将16.0mmol氢氧化钠溶解于37.5mL去离子水中,得到氢氧化钠溶液;
(2)将1.7mmol硝酸铝和5.1mmol硝酸镁溶解于12.5mL去离子水中,得到金属盐溶液;
(3)在氮气气氛下,将氢氧化钠溶液缓慢滴加入金属盐溶液中,于室温下剧烈搅拌1h,随后以12000rpm离心15min,并分别以水洗涤3遍,收集得到层状双氢氧化物纳米片粗产物;
(4)将层状双氢氧化物纳米片粗产物分散于40mL去离子水中,置于水热反应釜中,置于120℃烘箱中水热8h,得到层状双氢氧化物纳米片。
(5)取7.25mg所制得层状双氢氧化物纳米片,与6.8mg氯化铜,以及27mg聚乙烯吡咯烷酮溶解于9mL去离子水中,得到混合溶液。
(6)将40μL浓度为1mol/L的硫化钠水溶液加入混合溶液中,并置于90℃油浴中剧烈搅拌20min,最后置于冰水浴中冷却,离心收集得到所述层状双氢氧化物纳米片-硫化铜量子点纳米复合体。
图1A和B分别为本实施例中生长硫化铜量子点前的层状双氢氧化物纳米片以及生长硫化铜量子点后的层状双氢氧化物-硫化铜量子点纳米复合体的透射电镜图,图1C为本实施例获得的层状双氢氧化物-硫化铜量子点纳米复合体的元素定位。由图1看出硫化铜量子点分散生长于层状双氢氧化物纳米片上。
实施例2
取实施例1中制得的层状双氢氧化物-硫化铜量子点纳米复合体2mg,分散于2mL水中置于比色皿内,分别以功率密度为0.5,1.0,1.5,and 2.0W/cm2的808nm近红外激光照射溶液,监测溶液温度随时间变化。图2可看出所得纳米复合体在光照下发生明显的光热转换,溶液随光照时间延长,温度不断上升。
实施例3
取实施例1中制得的层状双氢氧化物-硫化铜量子点纳米复合体进行胞内溶酶体定位实验。
(1)将实施例1中制得的层状双氢氧化物-硫化铜量子点纳米复合体于等量绿色荧光标记物(FITC)的水溶液搅拌4h。将人乳腺癌细胞4T1接种于12孔板细胞培养板中,每孔1×105个细胞,每孔培养基中加入1mL的DMEM培养基,细胞培养贴壁24h后,取出原培养基,向实验组中分别加入500μL含10μg/mL标记有FITC的纳米复合体,继续培养4h;
(2)吸掉孔板中的上清液,使用磷酸盐缓冲溶液冲洗细胞,并用溶酶体探针LysoTracker Rad标记细胞溶酶体,并在激光共聚焦显微镜下观察并拍摄照片。
由图3看出,纳米复合体在3h已经开始进入细胞,并与溶酶体部分重合;在6h时大量富集与细胞中,并与溶酶体完全重合,表明其积累于溶酶体中;9h时,纳米复合体与溶酶体的重合度降低。
实施例4
取实施例1中制得的层状双氢氧化物-硫化铜量子点纳米复合体进行胞内活性氧(ROS)实验。
(1)将人乳腺癌细胞4T1接种于12孔板细胞培养板中,每孔1×105个细胞,每孔培养基中加入1mL的DMEM培养基,细胞培养贴壁24h后,取出原培养基,向实验组中分别加入500μL含10μg/mL的纳米复合体,继续培养4h;
(2)吸掉孔板中的上清液,使用磷酸盐缓冲溶液冲洗细胞,并用活性氧探针DCFH-DA标记胞内活性氧,并在激光共聚焦显微镜下观察并拍摄照片。
胞内ROS生成的实验结果如图4所示,对比有、无近红外激光照射条件下,层状双氢氧化物-硫化铜量子点纳米复合体与细胞共孵育后胞内ROS水平荧光强度图,可见本发明中制备的层状双氢氧化物-硫化铜量子点纳米复合体在近红外激光照射条件下能显著提高胞内ROS水平,对细胞造成氧化损伤杀死肿瘤;统计的荧光强度同时显示了胞内ROS胞内水平。
实施例5
取实施例1中制得的层状双氢氧化物-硫化铜量子点纳米复合体进行小鼠实体肿瘤光声成像实验。
(1)取取约18g裸鼠在其后腿侧注射0.1mL含有1×106个人乳腺癌细胞4T1的细胞悬液,待肿瘤生长至约100mm3。
(2)将1mg层状双氢氧化物-硫化铜量子点纳米复合体分散于0.1mL生理盐水中,并通过尾静脉注射于肿瘤模型裸鼠体内。在注射前和注射后2,4,6,12,24h时,使用光声成像系统观测肿瘤部位光声成像情况。
光声信号如图5所示,所制得的层状双氢氧化物-硫化铜量子点纳米复合体相较于普通硫化铜量子点在肿瘤部位的富集程度较高,产生较高的光声信号,并且信号强度在12h时达到最大,可见本发明中制备的层状双氢氧化物-硫化铜量子点纳米复合体能被应用于光声成像,同时发挥诊断和治疗功能。
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (10)
1.一种层状双氢氧化物纳米片-硫化铜量子点异质纳米复合体的制备方法,其特征在于:包括如下步骤:
(1)将氢氧化钠溶解于去离子水中,得到氢氧化钠溶液;
(2)将第一金属盐、第二金属盐溶解于去离子水中,得到金属盐溶液;第一金属盐为二价金属盐,第二金属盐为三价金属盐或四价钛盐;
(3)在氮气气氛下,将上述氢氧化钠溶液缓慢滴加入上述金属盐溶液中,于室温下剧烈搅拌,接着离心得沉淀,再用水分别洗涤,收集得到层状双氢氧化物纳米片粗产物;
(4)将上述层状双氢氧化物纳米片粗产物分散于去离子水中,置于水热反应釜中,于60-140℃进行水热反应8-12h,得到层状双氢氧化物纳米片;
(5)将上述层状双氢氧化物纳米片、氯化铜和聚乙烯吡咯烷酮溶解于去离子水中,得到混合溶液;
(6)将硫化钠水溶液加入到上述混合溶液中,并于85-95℃剧烈搅拌,再置于冰水浴中冷却,离心收集得到所述层状双氢氧化物纳米片-硫化铜量子点纳米复合体。
2.如权利要求1所述的制备方法,其特征在于:所述二价金属盐包括镁盐、铁盐、钴盐、镍盐、铜盐、锌盐、钙盐和锰盐。
3.如权利要求2所述的制备方法,其特征在于:所述二价金属盐为镁盐。
4.如权利要求3所述的制备方法,其特征在于:所述镁盐为硝酸镁。
5.如权利要求1所述的制备方法,其特征在于:所述三价金属盐包括铝盐、铁盐、钴盐、镍盐、铬盐、锰盐、钆盐和铟盐。
6.如权利要求5所述的制备方法,其特征在于:所述三价金属盐为铝盐。
7.如权利要求6所述的制备方法,其特征在于:所述铝盐为硝酸铝。
8.如权利要求1所述的制备方法,其特征在于:所述第一金属盐为硝酸镁,所述第二金属盐为硝酸铝。
9.如权利要求1至8中任一权利要求所述的制备方法,其特征在于:所述第一金属盐和第二金属盐的摩尔比为2-4∶1。
10.如权利要求9所述的制备方法,其特征在于:所述层状双氢氧化物纳米片、氯化铜和聚乙烯吡咯烷酮的质量比为7.3-7.4∶6.7-6.9∶5-1000。
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