CN109602919B - 一种核壳金属有机框架包覆的黑磷量子点及其制备方法与应用 - Google Patents
一种核壳金属有机框架包覆的黑磷量子点及其制备方法与应用 Download PDFInfo
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- CN109602919B CN109602919B CN201811454948.9A CN201811454948A CN109602919B CN 109602919 B CN109602919 B CN 109602919B CN 201811454948 A CN201811454948 A CN 201811454948A CN 109602919 B CN109602919 B CN 109602919B
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Abstract
本发明公开了一种核壳金属有机框架包覆的黑磷量子点,其特征在于,它是以金属有机框架为基体,包覆黑磷量子点,所述金属有机框架为HKUST‑1、MIL‑100中的一种或两种的复合物。相对于现有技术,本发明纳米材料靶向性强,毒副作用小,利用癌细胞的微环境降解金属有机框架,释放出铁离子和铜离子,并进一步将他们还原为亚铁离子和亚铜离子,诱导过氧化氢和亚硝基谷胱甘肽的分解,生成羟基自由基和一氧化氮。黑磷量子点可以在近红外辐照下产生热量,提高肿瘤细胞的温度,达到协同治疗的目的。最后,材料完全降解称为金属离子和磷酸根,并被排出体外。
Description
技术领域
本发明涉及一种核壳金属有机框架包覆的黑磷量子点及其制备方法和应用,属于纳米医学领域。
背景技术
恶性肿瘤己成为威胁人类健康和社会的重大疾病。在我国恶性肿瘤患者5年生存率仅为30.9%,农村肿瘤患者生存率仅是城市的一半。癌症超过了心血管疾病,成了致人死亡的“第一杀手”。癌症高发,增加的不仅仅是患者的伤痛,还给家庭和社会带来沉重的经济负担。目前许多肿瘤尚无有效的治疗方法,传统的治疗方法因疗效不佳、副作用和并发症等受到诸多限制。临床上使用最多的是化疗,但是化学药物特异性不高,在杀伤肿瘤细胞的同时对机体正常细胞,特别是对增殖旺盛的细胞也具有损害作用。明显的毒副作用导致患者生命质量下降,而且化学药物并不能精确达到肿瘤核心区域。由于肿瘤细胞在生物能量代谢上与正常细胞有所不同,所以肿瘤细胞只能通过无氧糖酵解产生大量乳酸和少量的ATP为细胞供能。许多学者希望找到作用于特有代谢途径的靶向抗肿瘤方法,从而达到控制肿瘤的目的。因此,临床上需要一种副作用低,更精确的替代疗法。靶向药物正逐渐代替传统化疗药物成为肿瘤治疗过程中的首选,科学家们正积极地研究肿瘤药物靶点和寻找靶向药物。
金属有机框架是近十年来迅猛发展的一种配位聚合物,其通常具有三维的孔结构,即以金属离子为中心原子,一种或者多种有机配体为支撑构成空间三维的延伸,这使得它成为沸石分子筛、大孔树脂以及碳材料之外的又一类新型的重要多孔材料,在催化、储能和分离中都有广泛应用。金属中心离子在骨架中既可以作为结点提供骨架的中枢,同时还能够拓展网络结构在中枢中形成无限的分支,从而提供金属有机框架独特的物理化学性质(如多孔性和手性等)。这类材料的比表面积远大于相似孔道的沸石材料,而且能够在移除孔道中的残存的溶剂小分子后仍然保持骨架结构的不被破坏。因此,金属有机框架具有许多特殊性能亟需开发。
发明内容
发明目的:针对现有技术中恶性肿瘤多模态诊疗的不足和存在的问题,本发明提供一种具有良好的靶向性以及生物相容性的核壳金属有机框架包覆的黑磷量子点,其对恶性肿瘤部位进行快速准确的靶向治疗。
技术方案:一种核壳金属有机框架包覆的黑磷量子点,它是以金属有机框架为基体,包覆黑磷量子点,所述金属有机框架为HKUST-1、MIL-100中的一种或两种的复合物所述核壳金属有机框架包覆的黑磷量子点能够利用肿瘤细胞的微环境触发连续反映,刺激羟基自由基和一氧化氮的生成,靶向性诱导癌细胞凋亡。
所述核壳金属有机框架包覆的黑磷量子点在400nm激发下发射460nm的荧光,并随着金属中心的还原而增强,因此可以用活体荧光成像来监测其在动物模型中的还原。所述核壳金属有机框架包覆的黑磷量子点在532nm存在吸收,因此可以用光声成像来监测材料在动物模型中的降解过程。
作为优选,所述黑磷量子点的尺寸为1~3纳米。
上述核壳金属有机框架包覆的黑磷量子点的制备方法,包括如下步骤:
(1)将黑磷量子点分散于甲醇中,向其中加入聚苯乙烯苯磺酸钠,得到表面修饰的黑磷量子点;
(2)将表面修饰的黑磷量子点分散于甲醇中,并加入硝酸锌和二甲基咪唑,反应,得到沸石咪唑酯骨架包覆的黑磷量子点;
(3)将沸石咪唑酯骨架包覆的黑磷量子点分散于乙醇中,在20~40℃(优选30℃),下与硝酸铜的乙醇溶液混合,优选反应温度为30℃,反应,离心,将沉淀物并重新分散于乙醇中,在40~70℃(优选60℃)下与均苯三甲酸的乙醇溶液反应,离心,将沉淀物分散于乙醇中并依次与氯化铁的乙醇溶液和均苯三甲酸的乙醇溶液在40~70℃(优选60℃)下反应,即得到核壳金属有机框架包覆的黑磷量子点。
步骤(1)中,聚苯乙烯苯磺酸钠与黑磷量子点的质量比是24:1~12:1,优选120:7。
步骤(2)中,硝酸锌与表面修饰的黑磷量子点的质量比是40:1~20:1,优选200:7;二甲基咪唑与表面修饰的黑磷量子点的质量比是90:1~40:1,优选440:7。
步骤(3)中,所述沸石咪唑酯骨架包覆的黑磷量子点的浓度为0.5~3mg/mL,优选1.5mg/mL;所述三水合硝酸铜的浓度为1~4mg/mL,优选2.4mg/mL;所述均苯三甲酸的浓度为1~4mg/mL,优选2.1mg/mL;所述氯化铁的浓度为1~4mg/mL,优选2.7mg/mL。
上述黑磷-金属有机框架复合物的制备方法制备得到的核壳金属有机框架包覆的黑磷量子点在本发明的保护范围之内。
上述核壳金属有机框架包覆的黑磷量子点在制备肿瘤细胞多模态诊疗药物中的应用在本发明的保护范围之内。
上述核壳金属有机框架包覆的黑磷量子负载亚硝基谷胱甘肽在制备肿瘤细胞多模态诊疗药物中的应用在本发明的保护范围之内。
有益效果:
本发明核壳结构金属有机框架包覆的黑磷量子点具有以下优势:
第一、本发明核壳结构金属有机框架包覆的黑磷量子点分散性好,具有良好的光热转换效率,并能够利用壳层的介孔孔道有效负载亚硝基谷胱甘肽。
第二、本发明核壳结构金属有机框架包覆的黑磷量子点,通过在黑磷周围包覆金属有机框架,能有效提高黑磷在水中以及各种生理介质中的稳定性。
第三、本发明核壳结构金属有机框架包覆的黑磷量子点,对pH值以及GSH具有灵敏的响应,通过肿瘤细胞微环境能快速诱导自由基和一氧化氮的生成。
第四、本发明核壳结构金属有机框架包覆的黑磷量子点,在400nm激发下发射460nm的荧光,并随着金属中心的还原而增强,因此可以用活体荧光成像来监测其在动物模型中的还原。
第五、本发明核壳结构金属有机框架包覆的黑磷量子点在532nm存在吸收,并随着材料的降解逐渐减弱,因此可以用光声成像来监测材料在动物模型中的降解过程。
第六、本发明核壳结构金属有机框架包覆的黑磷量子点,生物相容性好、细胞毒性低,可用于恶性肿瘤细胞的多模态靶向诊疗。
本发明中的本发明核壳结构金属有机框架包覆的黑磷量子点的具体特征如下:
该核壳结构金属有机框架包覆的黑磷量子点以沸石咪唑酯骨架作为母体,利用骨架交换得到金属有机框架包覆的黑磷量子点。再利用外延生长法在其外表包覆壳层形成核壳结构,并向壳层中的介孔负载亚硝基谷胱甘肽。纳米材料进入细胞之后,受到pH和GSH的双重刺激,释放出亚铁离子和亚铜离子,并以此作为催化剂诱导羟基自由基和一氧化氮的生成。通过结合光热治疗的手段,对恶性肿瘤达到多模态治疗的目的。该纳米颗粒在酸性条件下会逐渐降解称为金属离子以及有机配体,所释放的黑磷量子点最终转化成磷酸根,达到完全代谢的目的。
技术效果:相对于现有技术,本发明核壳结构金属有机框架包覆的黑磷量子点可以结合多模态治疗对肿瘤组织实现精准治疗,细胞毒性实验结果表明该材料对细胞几乎没有毒性,生物相容性和细胞渗透性。
附图说明:
图1是本发明的黑磷量子点的透射电子显微镜和紫外可见吸收光谱图。
图2是本发明的核壳结构金属有机框架包覆的黑磷量子点的X射线衍射图谱,透射电子显微镜图像,红外图谱以及紫外可见吸收光谱图,纵坐标为吸收强度。
图3是本发明的核壳结构金属有机框架包覆的黑磷量子点在不同条件下的羟基自由基以及一氧化氮释放曲线。其中横坐标为时间,纵坐标为释放量。
图4是本发明的核壳结构金属有机框架包覆的黑磷量子点(圆形)和黑磷量子点(方形)在波长为808纳米的近红外光照下的温度-时间曲线。
图5本发明的核壳结构金属有机框架包覆的黑磷量子点对SGC-7901细胞内活性氧的影响。向SGC-7901的培养基中加入200μg/mL的核壳结构金属有机框架包覆的黑磷量子点,孵育1小时(第一行)和3小时(第二行)后用DCFH-DA标记细胞内的活性氧。从左到右依次为Hoechst33342,DCFH-DA,Lyso-tracker和明场的图像。
图6是核壳结构金属有机框架包覆的黑磷量子点在SGC-7901荷瘤裸鼠体内的活体荧光图像。从左到右依次为注射前,注射后1,3,7,16,24,48小时后的图像。
图7是核壳结构金属有机框架包覆的黑磷量子点对SGC-7901荷瘤裸鼠的治疗效果。方形为对照组,圆形为注射核壳结构金属有机框架包覆的黑磷量子点的裸鼠,上三角为注射了负载亚硝基谷胱甘肽的核壳结构金属有机框架包覆黑磷量子点的裸鼠,下三角为注射了负载亚硝基谷胱甘肽的核壳结构金属有机框架包覆黑磷量子点的裸鼠在接受波长为808纳米的近红外光照治疗后的结果。
具体实施方式
根据下述实施例,可以更好地理解本发明。而本领域的技术人员容易理解,实施例所描述的具体试验结果仅用于说明本发明,而不应当也不会限制权利要求书中所描述的本发明。
实施例1:沸石咪唑酯骨架包覆的黑磷量子点的制备。
在氩气氛围下将50mg黑磷晶体置于玛瑙研钵内研磨15分钟,然后加入2mL二甲亚砜,在氮气氛围下探头超声15小时。将所得的混合物分散于20mL二甲亚砜中,在7500rpm下离心25分钟,将三分之二的上清液与等体积的甲醇混合,在9500rpm下离心25分钟,并重新分散于20mL甲醇中。黑磷量子点的透射电子显微镜和紫外可见吸收光谱图如图1所示。向黑磷量子点的甲醇溶液中加入聚苯乙烯苯磺酸钠。1小时后,在9500rpm下离心得到表面修饰的黑磷量子点,并用甲醇多次洗涤,最后将其分散于1mL甲醇中。
将上述混合物加入到2-甲基咪唑的甲醇溶液中,5分钟后加入硝酸锌的甲醇溶液。4小时后,在7500rpm下离心5分钟得到沸石咪唑酯骨架包覆的黑磷量子点。
实施例2:核壳金属有机框架包覆的黑磷量子点的制备。
将上述得到的沸石咪唑酯骨架包覆的黑磷量子点分散于乙醇中,在30℃下与硝酸铜的乙醇溶液混合,离心后重新分散于乙醇中,并在60℃下进一步与均苯三甲酸反应。将得到的材料分散于乙醇中并依次与氯化铁和均苯三甲酸的乙醇溶液在60℃下反应得到核壳机构金属有机框架包覆的黑磷量子点。核壳结构金属有机框架包覆的黑磷量子点的X射线衍射图谱,透射电子显微镜图像,红外图谱以及紫外可见吸收光谱图如图2所示。
实施例3:核壳金属有机框架包覆的黑磷量子点的结构、形貌和荧光特性。
将样品的粉末置于X射线粉末衍射仪的样品台上保持表面平滑,对其在5度到60度进行扫描。将样品超声后滴加于平整洁净的硅片表面,在扫描电镜下观察其形貌。将样品超声后滴加于铜网上,在透射电镜下观察其形貌。将样品与溴化钾粉末混合后充分研磨,在25MPa压力下压成片状以测试其红外光谱。将样品分散在超纯水或者磷酸缓冲溶液(pH7.4,7mM)配制成浓度为10mg/mL的母液。取一定量的母液用相应的溶剂如超纯水或者磷酸缓冲溶液稀释到实验所用的浓度200μg/mL。稀释后的悬浮液加到干净的4mL石英比色皿中,设置激发波长为400nm。实验结果如图1所示,从图中可以看到金属有机框架呈现HKUST-1和MIL-100的衍射峰,颗粒的大小在75nm左右。发射波长在465nm。
实施例4:核壳金属有机框架包覆的黑磷量子点在生理介质中的缓释以及降解。
将样品的粉末超声分散于缓冲溶液中,并将其稀释到实验所用的浓度200μg/mL,利用浓盐酸调节pH,或加入100毫摩尔每升的谷胱甘肽。在不同的时间点利用显色法测定上清液中的金属离子浓度或者释放出的自由基以及一氧化氮,结果如图3所示。同样地,将样品的粉末超声分散于缓冲溶液中,并将其稀释到实验所用的浓度200μg/mL,利用紫外可见吸收光谱以及透射电子显微镜观察材料在不同介质中的降解。
实施例5:核壳金属有机框架包覆的黑磷量子点在细胞中的缓释以及对于肿瘤细胞的杀灭效率。
胰蛋白酶消化处于对数生长期的SGC-7901细胞,制成浓度为1×105/mL单细胞悬液,接种于96孔板中,培养24h后,用不同浓度的纳米材料(10,20,30,40,50,80,100,150,200μg/mL)进行处理;然后继续于37℃、含有5%二氧化碳,95%湿度的培养箱中培养至24h,每个实验点设五个复孔。MTT比色法检测细胞生存率:培养时间终止后每孔加入5mg/mL的MTT溶液20μL继续培养4h;然后吸去上清液,每孔加入二甲基亚砜(DMSO)150μL,终止反应,将96孔板移入平板震荡器,水平震荡10min,使MTT还原产物完全溶解,然后用酶联免疫检测仪于492nm波长处测定每孔吸光度(OD值),并以空白对照孔的OD值调零。结果以每组5复孔的均数±标准误差表示,实验至少重复3次。细胞存活率用下式表示:
细胞生存率(%)=[OD实验值-OD空白值]492nm/[OD对照值-OD空白值]×100%
将SGC-7901细胞接种于共聚焦培养皿中,向其中加入不同的材料,利用DCFH-FDA以及DAF-FM来标记细胞中的活性氧和一氧化氮,在共聚焦显微镜下用488nm的激发波长进行观察,并用流式细胞分析仪定量分析荧光强度。如图5所示,从左到右依次为Hoechst33342,DCFH-DA,Lyso-tracker和明场的图像。
实施例6:核壳金属有机框架包覆的黑磷量子点在活体成像中的应用。
将荷SGC-7901肿瘤的裸鼠分为5组,分别通过尾静脉注射不同的材料。利用小动物活体荧光成像仪记录不同时间点的荧光,通过采集不同时段的光声图像来表征材料的降解和代谢。核壳结构金属有机框架包覆的黑磷量子点在SGC-7901荷瘤裸鼠体内的活体荧光图像如图6所示。
实施例7:核壳金属有机框架包覆的黑磷量子点对于恶性肿瘤治疗效果的评估。
将荷SGC-7901肿瘤的裸鼠分为5组,分别通过尾静脉注射不同的材料。每三天记录下每组裸鼠的体重以及肿瘤体积。肿瘤体积和治疗时间的关系如图7所示,方形为对照组,圆形为注射核壳结构金属有机框架包覆的黑磷量子点的裸鼠,上三角为注射了负载亚硝基谷胱甘肽的核壳结构金属有机框架包覆黑磷量子点的裸鼠,下三角为注射了负载亚硝基谷胱甘肽的核壳结构金属有机框架包覆黑磷量子点的裸鼠在接受波长为808纳米的近红外光照治疗后的结果。
Claims (6)
1.一种核壳金属有机框架包覆的黑磷量子点的制备方法,其特征在于,包括如下步骤:
(1) 将黑磷量子点分散于甲醇中,向其中加入聚苯乙烯苯磺酸钠,得到表面修饰的黑磷量子点;
(2) 将表面修饰的黑磷量子点分散于甲醇中,并加入硝酸锌和二甲基咪唑,反应,得到沸石咪唑酯骨架包覆的黑磷量子点;
(3) 将沸石咪唑酯骨架包覆的黑磷量子点分散于乙醇中,在20~40 ℃下与硝酸铜的乙醇溶液混合,反应,离心,将沉淀物并重新分散于乙醇中,在30~70 ℃下与均苯三甲酸的乙醇溶液反应,离心,将沉淀物分散于乙醇中并依次与氯化铁的乙醇溶液和均苯三甲酸的乙醇溶液在30~70 ℃下反应,即得到核壳金属有机框架包覆的黑磷量子点。
2.根据权利要求1所述核壳金属有机框架包覆的黑磷量子点的制备方法,其特征在于,步骤(1)中,聚苯乙烯苯磺酸钠与黑磷量子点的质量比是24:1~12:1。
3.根据权利要求1所述核壳金属有机框架包覆的黑磷量子点的制备方法,其特征在于,步骤(2)中,硝酸锌与表面修饰的黑磷量子点的质量比是40:1~20:1,二甲基咪唑与表面修饰的黑磷量子点的质量比是90:1~40:1。
4.根据权利要求1所述核壳金属有机框架包覆的黑磷量子点的制备方法,其特征在于,步骤(3)中,所述沸石咪唑酯骨架包覆的黑磷量子点的浓度为0.5~3mg/mL,所述硝酸铜的浓度为1~4mg/mL,所述均苯三甲酸的浓度为1~4mg/mL,所述氯化铁的浓度为1~4mg/mL。
5.权利要求1所述核壳金属有机框架包覆的黑磷量子点的制备方法制备得到的核壳金属有机框架包覆的黑磷量子点。
6.权利要求5 所述核壳金属有机框架包覆的黑磷量子点负载亚硝基谷胱甘肽在制备肿瘤细胞多模态诊疗药物中的应用。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8367419B2 (en) * | 2009-06-25 | 2013-02-05 | Rutgers, The State University Of New Jersey | Compositions and methods for detection of explosives |
CN108745404A (zh) * | 2018-06-14 | 2018-11-06 | 苏州大学 | 基于黑磷/金属有机框架修饰的氮化碳膜复合材料及其制备方法与在废气处理中的应用 |
-
2018
- 2018-11-30 CN CN201811454948.9A patent/CN109602919B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8367419B2 (en) * | 2009-06-25 | 2013-02-05 | Rutgers, The State University Of New Jersey | Compositions and methods for detection of explosives |
CN108745404A (zh) * | 2018-06-14 | 2018-11-06 | 苏州大学 | 基于黑磷/金属有机框架修饰的氮化碳膜复合材料及其制备方法与在废气处理中的应用 |
Non-Patent Citations (4)
Title |
---|
"Metal-organic frameworks join hands to create an anti-cancer nanoplatform based on 808 nm light driving up-conversion nanoparticles";Dan Yang et al;《Chemical Engineering Journal》;20180321;第344卷;第363-374页 * |
"Synthesis of hybrid nanocomposites of ZIF-8 with two-dimensional black phosphorus for photocatalysis";Lian Wang et al;《RSC Adv》;20160714;第6卷;第69033-69039页 * |
"The "Framework Exchange"-Strategy-Based MOF Platform for Biodegradable Multimodal Therapy";Tianyu Du et al;《Chem》;20190916;第5卷;第1-13页 * |
"一步法合成的黑磷烯掺杂的金属有机框架用于氧还原反应";鲁昆昆;《第三届中国国际复合材料科技大会摘要集-分会场46-50》;20171031;第138页 * |
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