CN113980059A - 一种铁基纳米催化治疗试剂及其制备方法和应用 - Google Patents
一种铁基纳米催化治疗试剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种铁基纳米催化治疗试剂及其制备方法和应用,所述铁基纳米催化治疗试剂包括纳米颗粒,所述纳米颗粒由摩尔比为2:1:1‑3:2:2的Fe金属离子、6‑硫鸟嘌呤和Meso‑四(4‑羧基苯基)卟吩反应获得。本发明通过水热法合成制备的铁基纳米催化治疗试剂是一种纳米催化药物,展现出较强的催化能力,可以催化过氧化氢产生氧气,改善肿瘤的乏氧环境;同时具有过氧化物模拟酶的性质,可以用于催化癌细胞内高氧化性羟基自由基的产生,继而诱导癌细胞凋亡,所含的6‑硫鸟嘌呤可用于肿瘤化疗,而Meso‑四(4‑羧基苯基)卟吩可用于肿瘤光动力学治疗。本发明的制备方法简单方便,原料来源广,成本低,可重复性,适用于工业化生产应用。
Description
技术领域
本发明涉及化学纳米材料领域,尤其涉及一种铁基纳米催化治疗试剂及其制备方法和应用。
背景技术
越来越多的证据表明,同正常细胞相比,肿瘤细胞由于遗传、代谢和微环境的改变,表现出持续较高的活性氧(ROS)水平。肿瘤细胞中过高的ROS水平可以诱导细胞死亡、衰老和细胞周期停滞。在高ROS水平下,致癌基因会诱导肿瘤细胞适应氧化应激(Oxidativestress)并上调抗氧化系统,导致ROS清除速率增加以维持ROS水平,从而允许激活促癌信号而不诱导细胞死亡。因此,高水平ROS以及高水平抗氧化系统维持的“脆弱的氧化还原稳态(Vulnerable redox homeostasis),为治疗肿瘤提供一种新的思路。
铁死亡治疗(Ferroptotic Therapy)是近几年受到关注的肿瘤治疗手段,主要基于铁依赖性芬顿反应(Fenton reaction)产生的羟基自由基(·OH,一种剧毒的ROS)以及对细胞抗氧化系统的消除用于诱导肿瘤调节性死亡。虽然铁死亡相比传统的凋亡依赖性肿瘤治疗策略有独特的优势,但是有许多的因素会限制铁死亡的治疗效果。与正常细胞相比,肿瘤细胞具有更高细胞内H2O2产生速率(0.2-0.5nmol/104cells/h),但是为了维持细胞存活,肿瘤通常会上调各种抗氧化机制,如:过氧化氢酶(Catalase),将H2O2的浓度限制在约10-50μM以维持氧化还原稳态。然而,根据Fenton反应的动力学研究,启动Fenton反应最低的H2O2浓度却需要100-500μM。因此,内源性产生的H2O2不足以获得令人满意的Fenton反应效率。在这方面,需要提高肿瘤细胞H2O2水平以增强铁死亡的抗癌效率。
传统纳米催化治疗试剂Fenton反应效率低,且不能协同药物治疗、光动力治疗、光热治疗以及放射疗法等其他治疗方法展开多模式治疗,实现癌症治疗效果最大化。
发明内容
发明目的:本发明的目的是提供一种催化性能强、反应效率高、协同效果好的铁基纳米催化治疗试剂;本发明的另一目的是提供一种铁基纳米催化治疗试剂的制备方法;本发明的另一目的是提供一种铁基纳米催化治疗试剂在制备抗癌药物中的应用。
技术方案:本发明的铁基纳米催化治疗试剂,包括纳米颗粒,所述纳米颗粒由摩尔比为2:1:1-3:2:2的Fe金属离子、6-硫鸟嘌呤和Meso-四(4-羧基苯基)卟吩反应获得。
优选地,Fe金属离子、6-硫鸟嘌呤和Meso-四(4-羧基苯基)卟吩摩尔比为2:1:1。
进一步地,所述的纳米颗粒为纳米花形状。
进一步地,所述的纳米颗粒的粒径为40-60nm,优选地,纳米颗粒的粒径为50nm;所述的纳米颗粒具有催化性能,纳米颗粒的吸收变化符合朗伯比尔定律,由Michaelis-Menten曲线和Lineweaver–Burk拟合可得其催化活性与过氧化物酶相当。
另一方面,本发明的铁基纳米催化治疗试剂的制备方法,包括如下步骤:
(1)将Fe盐试剂和稳定剂溶于水中进行搅拌反应,取去质子化剂加入溶液中继续搅拌反应,得到溶液A;
(2)另取TG和TCPP配体溶于水中,充分溶解得到溶液B;
(3)将溶液A和溶液B混合搅拌后得到混合液C,并进行水热反应;反应结束后,其中沉淀物经洗涤、烘干,得到铁基纳米催化治疗试剂。
进一步地,步骤(1)中,所述稳定剂为铅盐类稳定剂(比如说)、金属皂类稳定剂、有机锡稳定剂、稀土稳定剂或有机辅助稳定剂(环氧化合物类、多元醇类)其中,铅盐类稳定剂为三盐基硫酸铅或二盐基亚磷酸铅;金属皂类稳定剂为硬脂酸锌、硬脂酸钙;有机锡稳定剂为二月桂酸二丁基锡或二马来酸二丁基锡;稀土稳定剂为硫醇锑类或羧酸酯锑类;有机辅助稳定剂为环氧化合物类或多元醇类;优选地,稳定剂为有机辅助稳定剂。
进一步地,步骤(1)中,所述去质子化剂为甲酸、冰醋酸或者丙酸;优选地,去质子化剂为冰醋酸。
进一步地,步骤(1)中,溶液A的总搅拌时间为30min~150min;步骤(3)中,溶液A和溶液B混合搅拌的时间为1h~3h。
进一步地,步骤(3)中,水热反应为将溶液C倒入反应釜中,并在100℃-120℃条件下加热反应15h~17h。
优选地,在不同温度条件下100℃、110℃、120℃加热反应;最优选的为110℃反应时间为16h。
另一方面,本发明的铁基纳米催化治疗试剂在制备抗癌药物中的应用。所述抗癌药物借由铁基纳米催化治疗试剂展现出较强的催化性能,可以催化癌细胞内高氧化性羟基自由基的产生继而诱导细胞凋亡,应用于癌症诊疗。
本发中利用Fe金属离子、6-硫鸟嘌呤(TG)和Meso-四(4-羧基苯基)卟吩(TCPP),在聚四氟乙烯高温反应釜中进行反应,制得纳米颗粒。合成的纳米颗粒具有良好的催化性能,材料的吸收变化符合朗伯比尔定律,由Michaelis-Menten曲线和Lineweaver–Burk拟合可得其催化活性与过氧化物酶相当;同时,体外细胞的增殖抑制作用研究实验和体内抑制作用研究实验表明合成的纳米颗粒具有良好的生物抗肿瘤效应,可应用于制备抗癌药物。
本发明通过水热法合成制备的铁基纳米催化治疗试剂是一种纳米催化药物,制备的铁基纳米催化治疗试剂展现出较强的催化能力,可以催化过氧化氢产生氧气,改善肿瘤的乏氧环境。同时具有过氧化物模拟酶的性质,可以用于催化癌细胞内高氧化性羟基自由基的产生,继而诱导癌细胞凋亡,所含的TG可用于肿瘤化疗,TCPP可用于肿瘤光动力学治疗,因此,本铁基纳米催化治疗试剂可应用于癌症多模式治疗。
有益效果:与现有技术相比,本发明具有如下显著优点:
(1)纳米颗粒具有良好的催化性能和更好的多模式治疗效应,纳米颗粒作为过氧化物酶模拟物的含铁纳米催化剂可以用于催化癌细胞内高氧化性羟基自由基的产生,继而诱导癌细胞凋亡,发挥多模式治疗作用;
(2)通过水热法合成制备的铁基纳米催化治疗试剂,制备方法简单方便,原料来源广,成本低,可重复性,适用于工业化生产应用;
(3)纳米颗粒引入特定的生物环境可以通过驱动氧化还原反应来触发治疗效果,在癌细胞中引发类芬顿反应,特别是将过量的过氧化氢转化为高毒性的羟基,从而瞬间氧化和失活周围的细胞蛋白质和细胞器,可应用于抗癌药物。
附图说明
图1为实施例1制备的铁基纳米催化治疗试剂的TEM图;
图2为实施例1制备的铁基纳米催化治疗试剂的XRD图;
图3为实施例1制备的铁基纳米催化治疗试剂的XPS图;
图4为实施例1制备的铁基纳米催化治疗试剂的紫外吸收图谱;
图5为实施例1制备的铁基纳米催化治疗试剂的荧光发射图谱;
图6为实施例1制备的铁基纳米催化治疗试剂的红外光谱图;
图7为实施例1制备的铁基纳米催化治疗试剂的pH依赖性Fe离子释放实验;
图8为实施例1制备的铁基纳米催化治疗试剂的pH依赖性TG药物释放实验;
图9为实施例1制备的铁基纳米催化治疗试剂的酸响应实验;
图10为实施例1制备的铁基纳米催化治疗试剂的催化性能实验;
图11为实施例1制备的铁基纳米催化治疗试剂的溶解氧测定实验;
图12为实施例1制备的铁基纳米催化治疗试剂的细胞毒性实验;
图13为实施例1制备的铁基纳米催化治疗试剂的TCPP荧光成像实验;
图14为实施例1制备的铁基纳米催化治疗试剂的活性氧细胞成像实验;
图15为实施例1制备的铁基纳米催化治疗试剂的活/死细胞染色成像实验;
图16为对比例1纳米颗粒的TEM图;
图17为对比例2纳米颗粒的TEM图;
图18为对比例3纳米颗粒的TEM图;
图19为对比例4纳米颗粒的TEM图。
具体实施方式
下面结合附图对本发明的技术方案作进一步说明。
实施例1
本发明的铁基纳米催化治疗试剂,包括纳米颗粒,所述纳米颗粒由摩尔比为2:1:1的Fe金属离子、6-硫鸟嘌呤和Meso-四(4-羧基苯基)卟吩反应获得。
上述铁基纳米催化治疗试剂的制备方法,包括以下步骤:
(1)溶液A:称取0.016g的Pluronic F127和0.0107g的FeCl3与圆底烧瓶中,加15mlDI水超声溶解。在恒温磁力搅拌器上连接好装置,与25℃下剧烈搅拌1h;然后于烧瓶中加入15μl冰醋酸溶液,再搅拌1h。
(2)溶液B:取0.0261g TCPP和0.0055g TG到烧瓶中并溶于5ml DI水。
(3)混合液C进行水热反应:将溶液A和溶液B混合搅拌2h后得到混合液C,将溶液转移至高温反应釜,于鼓风干燥箱内110℃条件下反应16h达到结晶。反应结束后,10000r/min离心反应溶液3min,以去除反应过程中生成的大颗粒。丢弃上清液后,将得到的黑紫色固体产物用水清洗三次,去除多余的反应物和表面活性剂,并将所得的材料烘干收集,得到纳米颗粒;
图1是制备铁基纳米催化治疗试剂的TEM图(摩尔比2:1:1),可见制备材料为纳米花状,形貌均一,粒径为40-60nm。
可选的,步骤(1)中Pluronic F127可替换为其他类的稳定剂,如铅盐类稳定剂、金属皂类稳定剂、有机锡稳定剂、稀土稳定剂或有机辅助稳定剂,其中,铅盐类稳定剂为三盐基硫酸铅或二盐基亚磷酸铅;金属皂类稳定剂为硬脂酸锌、硬脂酸钙;有机锡稳定剂为二月桂酸二丁基锡或二马来酸二丁基锡;稀土稳定剂为硫醇锑类或羧酸酯锑类;有机辅助稳定剂为环氧化合物类或多元醇类。
表征测试:对上述方法制备的铁基纳米催化治疗试剂进行测试;
(1)XRD:图2为实施例1制备的铁基纳米催化治疗试剂的XRD图,可见纳米颗粒在33.0°,35.5°和49.0°时具有尖锐的衍射峰,表明得到的材料具有很好的晶形。26.8°处有峰,表面有FeCl3的峰,(300)锋面。
(2)XPS:图3为制备的铁基纳米催化治疗试剂的XPS图谱,图谱表明纳米颗粒中C、N、O、S、Fe五种元素的分峰。
(3)紫外吸收:图4为制备的铁基纳米催化治疗试剂的紫外吸收图谱,图谱表面纳米颗粒在415nm处具有强的吸收峰。
(4)荧光:图5为制备的铁基纳米催化治疗试剂的荧光图谱,图谱表面纳米颗粒在650nm有强的荧光发射峰,TCPP的荧光峰也位于650nm左右。
(5)红外吸收:图6为制备的铁基纳米催化治疗试剂的红外图谱,图中分别标明了各自的特征峰,表明金属离子和配体发生了反应。
性能测试:对上述方法制备的铁基纳米催化治疗试剂进行性能测试;
(1)测试铁基纳米催化治疗试剂的pH依赖性药物释放,图7为制备的铁基纳米催化治疗试剂的pH依赖性Fe离子释放实验;由图可得,pH为5.0时,Fe离子释放最多,释放量为35~40mg/l;图8为纳米颗粒的pH依赖性TG药物释放实验,由图可以得到一样的结论,,pH为5.0时,TG药物吸收最高,为0.7。
(2)测试铁基纳米催化治疗试剂的酸响应,图9为铁基纳米催化治疗试剂的酸响应实验;由图可得,在pH为6.5的条件下,纳米颗粒的荧光强度随时间的增长而加强。
(3)测试铁基纳米催化治疗试剂的催化性能,图10为铁基纳米催化治疗试剂的催化性能实验,材料的吸收变化符合朗伯比尔定律,由Michaelis-Menten曲线和Lineweaver–Burk拟合可得其催化活性与过氧化物酶相当,表明材料具有很好的催化性能。
(4)测试铁基纳米催化治疗试剂活性氧的产生,图11为铁基纳米催化治疗试剂的溶解氧测定情况,由图可知,同双氧水相比材料的活性氧产生量多。
(5)测试铁基纳米催化治疗试剂的细胞毒性,图12将不同浓度的铁基纳米催化治疗试剂、药物与HeLa细胞共同孵育及光照/不光照24h后的细胞毒性,由图可知材料细胞毒性较大。
(6)测试铁基纳米催化治疗试剂孵育细胞的细胞成像,图13将材料与HeLa细胞共同孵育后,用Hoechst 33342nucleus试剂对细胞核进行染色,拍摄TCPP荧光成像图片;图14用活性氧检测试剂盒检测活性氧的产生,由图可知材料产生了大量的活性氧;图15用活/死细胞检测试剂盒检测细胞存活率,绿色为存活细胞,红色为死亡细胞,由图可知材料加光照后细胞死亡率更多,说明协同治疗方式效果更好。
实施例2
本发明的铁基纳米催化治疗试剂,包括纳米颗粒,所述纳米颗粒由摩尔比为3:3:2的Fe金属离子、6-硫鸟嘌呤和Meso-四(4-羧基苯基)卟吩反应获得。
上述铁基纳米催化治疗试剂的制备方法,包括以下步骤:
(1)溶液A:称取0.016g的三羟甲基丙烷和0.0162g的FeCl3与圆底烧瓶中,加15mlDI水超声溶解。在恒温磁力搅拌器上连接好装置,与25℃下剧烈搅拌1.5h;然后于烧瓶中加入15μl甲酸溶液,再搅拌1.5h。
(2)溶液B:取0.0522g TCPP和0.0165g TG到烧瓶中并溶于5ml DI水。
(3)混合液C进行水热反应:将溶液A和溶液B混合搅拌3h后得到混合液C,将溶液转移至高温反应釜,于鼓风干燥箱内110℃条件下反应17h达到结晶。反应结束后,10000r/min离心反应溶液3min,以去除反应过程中生成的大颗粒。丢弃上清液后,将得到的黑紫色固体产物用水清洗三次,去除多余的反应物和表面活性剂,并将所得的材料烘干收集,得到纳米颗粒;制备材料为纳米花状,形貌均一,粒径为40-60nm。经性能测试,和实施例1制备的铁基纳米催化治疗试剂效果相似。
实施例3
本发明的铁基纳米催化治疗试剂,包括纳米颗粒,所述纳米颗粒由摩尔比为2:1:1的Fe金属离子、6-硫鸟嘌呤和Meso-四(4-羧基苯基)卟吩反应获得。
上述铁基纳米催化治疗试剂的制备方法,包括以下步骤:
(1)溶液A:称取0.016g的一缩二季戊四醇和0.0107g的FeCl3与圆底烧瓶中,加15ml DI水超声溶解。在恒温磁力搅拌器上连接好装置,与25℃下剧烈搅拌10min;然后于烧瓶中加入15μl丙酸溶液,再搅拌20min。
(2)溶液B:取0.0261g TCPP和0.0055g TG到烧瓶中并溶于5ml DI水。
(3)混合液C进行水热反应:将溶液A和溶液B混合搅拌1h后得到混合液C,将溶液转移至高温反应釜,于鼓风干燥箱内110℃条件下反应15h达到结晶。反应结束后,10000r/min离心反应溶液3min,以去除反应过程中生成的大颗粒。丢弃上清液后,将得到的黑紫色固体产物用水清洗三次,去除多余的反应物和表面活性剂,并将所得的材料烘干收集,得到纳米颗粒;制备材料为纳米花状,形貌均一,粒径为40-60nm。经性能测试,和实施例1制备的铁基纳米催化治疗试剂效果相似。
对比例1
称取0.016g的Pluronic F127和0.0107g的FeCl3与圆底烧瓶中,加15ml DI水超声溶解。在恒温磁力搅拌器上连接好装置,与25℃下剧烈搅拌1h。然后于烧瓶中加入15μl冰醋酸溶液,再搅拌1h。紧接着加入溶于5ml DI水的0.0055g TG于到烧瓶中,得到的溶液进一步搅拌2h。搅拌结束后,将溶液转移至高温反应釜,于鼓风干燥箱内110℃条件下反应16h达到结晶。反应结束后,10000r/min离心反应溶液3min,以去除反应过程中生成的大颗粒。丢弃上清液后,将得到的黑紫色固体产物用水清洗三次,去除多余的反应物和表面活性剂,并将所得的材料烘干收集,得到纳米颗粒;图16是制备纳米材料Fe-TG的TEM图(摩尔比为2:1),可见制备材料为片状。
对比例2
称取0.016g的Pluronic F127和0.0107g的FeCl3与圆底烧瓶中,加15ml DI水超声溶解。在恒温磁力搅拌器上连接好装置,与25℃下剧烈搅拌1h。然后于烧瓶中加入15μl冰醋酸溶液,再搅拌1h。紧接着加入溶于5ml DI水的0.0261g TCPP于到烧瓶中,得到的溶液进一步搅拌2h。搅拌结束后,将溶液转移至高温反应釜,于鼓风干燥箱内110℃条件下反应16h达到结晶。反应结束后,10000r/min离心反应溶液3min,以去除反应过程中生成的大颗粒。丢弃上清液后,将得到的黑紫色固体产物用水清洗三次,去除多余的反应物和表面活性剂,并将所得的材料烘干收集,得到纳米颗粒;图17是制备纳米材料Fe-TCPP的TEM图(摩尔比为2:1),可见制备材料为片状。
对比例3
称取0.016g的Pluronic F127和0.0054g的FeCl3与圆底烧瓶中,加15ml DI水超声溶解。在恒温磁力搅拌器上连接好装置,与25℃下剧烈搅拌1h。然后于烧瓶中加入15μl冰醋酸溶液,再搅拌1h。紧接着加入溶于5ml DI水的0.0261g TCPP和0.0055g TG于到烧瓶中,得到的溶液进一步搅拌2h。搅拌结束后,将溶液转移至高温反应釜,于鼓风干燥箱内110℃条件下反应16h达到结晶。反应结束后,10000r/min离心反应溶液3min,以去除反应过程中生成的大颗粒。丢弃上清液后,将得到的黑紫色固体产物用水清洗三次,去除多余的反应物和表面活性剂,并将所得的材料烘干收集,得到纳米颗粒;图18是制备纳米材料Fe-TG-TCPP的TEM图(摩尔比为1:1:1),可见制备材料为片状。
对比例4
称取0.016g的Pluronic F127和0.0214g的FeCl3与圆底烧瓶中,加15ml DI水超声溶解。在恒温磁力搅拌器上连接好装置,与25℃下剧烈搅拌1h。然后于烧瓶中加入15μl冰醋酸溶液,再搅拌1h。紧接着加入溶于5ml DI水的0.0261g TCPP和0.0055g TG于到烧瓶中,得到的溶液进一步搅拌2h。搅拌结束后,将溶液转移至高温反应釜,于鼓风干燥箱内110℃条件下反应16h达到结晶。反应结束后,10000r/min离心反应溶液3min,以去除反应过程中生成的大颗粒。丢弃上清液后,将得到的黑紫色固体产物用水清洗三次,去除多余的反应物和表面活性剂,并将所得的材料烘干收集,得到纳米颗粒;图19是制备纳米材料Fe-TG的TEM图(摩尔比为4:1:1),可见制备材料为片状。
对比例1-4制备的纳米颗粒,形貌为片状,说明其合成的物质均匀性差,在对比例1-4的条件下,无法制备得到本发明的铁基纳米催化治疗试剂。
Claims (9)
1.一种铁基纳米催化治疗试剂,其特征在于,包括纳米颗粒,所述纳米颗粒由摩尔比为2:1:1-3:2:2的Fe金属离子、6-硫鸟嘌呤和Meso-四(4-羧基苯基)卟吩反应获得。
2.根据权利要求1所述的铁基纳米催化治疗试剂,其特征在于,所述的纳米颗粒为纳米花形状。
3.根据权利要求1所述的铁基纳米催化治疗试剂,其特征在于,所述的纳米颗粒的粒径为40-60nm。
4.一种根据权利要求1-3任一所述的铁基纳米催化治疗试剂的制备方法,其特征在于,包括如下步骤:
(1)将Fe盐试剂和稳定剂溶于水中进行搅拌反应,取去质子化剂加入溶液中继续搅拌反应,得到溶液A;
(2)另取TG和TCPP配体溶于水中,充分溶解得到溶液B;
(3)将溶液A和溶液B混合搅拌后得到混合液C,并进行水热反应;反应结束后,其中得到的沉淀物经洗涤、烘干,得到铁基纳米催化治疗试剂。
5.根据权利要求4所述的制备方法,其特征在于,步骤(1)中,所述稳定剂为铅盐类稳定剂、金属皂类稳定剂、有机锡稳定剂、稀土稳定剂或有机辅助稳定剂。
6.根据权利要求4所述的制备方法,其特征在于,步骤(1)中,所述去质子化剂为甲酸、冰醋酸或者丙酸。
7.根据权利要求4所述的制备方法,其特征在于,步骤(1)中,溶液A的总搅拌时间为30min~150min;步骤(3)中,溶液A和溶液B混合搅拌的时间为1h~3h。
8.根据权利要求4所述的制备方法,其特征在于,步骤(3)中,水热反应为将溶液C倒入反应釜中,并在100℃-120℃条件下加热反应15h~17h。
9.一种根据权利要求1-3任一所述的铁基纳米催化治疗试剂在制备抗癌药物中的应用。
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