CN115415512B - 一种铂-氧化锌异质结纳米粒子的制备方法及其应用 - Google Patents
一种铂-氧化锌异质结纳米粒子的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种铂‑氧化锌异质结纳米粒子的制备方法及其应用。以醋酸锌为前体，氢氧化钠为pH调节剂反应合成Zn(OH)2，之后在甲醇体系中脱水合成ZnO。然后以ZnO为模板，硼氢化钠为还原剂，原位还原氯铂酸合成Pt‑ZnO纳米粒子。本发明通过调节NaOH的浓度、水与甲醇的体积比、还原时间可以控制Pt‑ZnO的尺寸和形貌，所制备的Pt‑ZnO水合粒径约为160nm。本方法操作简单、耗时短、合成条件温和可控、再现性强。在超声下，Pt‑ZnO能够表现出声敏剂特性，产生大量单线态氧(1O2)。并且Pt‑ZnO具有类过氧化物酶及类过氧化氢酶双重纳米酶活性，能够将过氧化氢催化产生羟基自由基(·OH)和氧气。
Description
技术领域
本发明属于生物医学纳米材料及其制备领域，更具体地，涉及一种半导体异质结声敏剂的制备方法与应用。
背景技术
超声(US)激活的声动力疗法(sonodynamic therapy，SDT)是一种非侵入性的疾病治疗方法，具有靶向性高、毒副反应小、可达深部肿瘤组织的优点，已成为肿瘤治疗的新方法(Angew.Chem.Int.Ed.2020,59,14212)。与光疗法(光热疗法、光动力疗法)相比，SDT以对人体无害的外源性超声波(US)激发声敏剂，产生高细胞毒性的活性氧(ROS)，破坏肿瘤细胞而不会对正常组织造成副作用。并且可以通过调节超声波的功率、频率和照射时间来调整组织穿透的深度，与近红外光相比，超声波不会因组织深度增加而显著衰减。由于其具有无创、成本低、组织穿透深度高等优点，SDT已被证明比光疗法更具发展潜力。
声敏剂作为声动力疗法最重要的介质，迫切需要高效的声敏剂以提高SDT的治疗效果。常见的声敏剂类型有有机声敏剂与无机声敏剂两种，传统的有机声敏剂分子生物利用度低，体内清除速度快，肿瘤积聚能力差。与有机声敏剂相比，无机纳米声敏剂具有较高的化学/生理稳定性和多功能性(Adv.Mater.2021,33,2101467)，许多无机纳米材料具有声学活化能力。但基于无机纳米粒子的声敏剂如二氧化钛纳米粒子等具有ROS的量子产率较低等局限性，阻碍了SDT的广泛临床应用，目前迫切需要高效的无机声敏剂以提高SDT的治疗效果。
本发明我们合成一种铂氧化锌异质结(Pt-ZnO)用于肿瘤声动力治疗的应用。Pt-ZnO是以(CH3COO)2Zn为前体，NaOH为pH调节剂，NaBH4为还原剂，原位还原H2PtCl6，在CH3OH与H2O体系中一步合成的。本发明通过调节(CH3COO)2Zn与NaOH的浓度、水与甲醇的体积比、还原时间可以有效控制Pt-ZnO的尺寸，所制备的Pt-ZnO水合粒径约为160nm。本方法操作简单、耗时短、耗材少、合成条件温和可控、再现性强。在超声作用下，Pt-ZnO能够表现出声敏剂特性，产生大量单线态氧，从而杀死肿瘤细胞，并且Pt-ZnO具有类过氧化物酶及类过氧化氢酶双重纳米酶活性双酶活性，可催化肿瘤细胞内源性过氧化氢产生氧气及羟基自由基，缓解肿瘤乏氧环境，协同增强声动力治疗效果。
发明内容
本发明的目的是提供一种具有声敏剂特性的金属-半导体异质结纳米粒子，用于抗肿瘤声动力-催化疗法协同治疗。即以ZnO纳米粒子(ZnO NPs)为模板，表面修饰铂纳米颗粒(Pt NPs)，实现声动力-催化疗法的协同治疗。
一种铂-氧化锌异质结纳米粒子的制备方法，其特征在于，醋酸锌与氢氧化钠反应生成氢氧化锌Zn(OH)2，其后在甲醇体系中脱水形成ZnO；使用还原剂硼氢化钠NaBH4将氯铂酸H2PtCl6原位还原于ZnO表面，离心去除上清，真空干燥后即得到Pt-ZnO异质结纳米粒子；
进一步，将(CH3COO)2Zn溶解在甲醇溶液中，搅拌至完全溶解；将NaOH溶解在甲醇水溶液中，搅拌至完全溶解；将(CH3COO)2Zn溶液滴入NaOH溶液中，搅拌反应3h生成ZnO溶液；将H2PtCl6水溶液加入至上述ZnO溶液中，搅拌1h；将NaBH4溶解在甲醇溶液中，将其加入到上述ZnO溶液中，反应1h，离心去除上清，清洗三次，真空干燥后得到Pt-ZnO纳米粒子；
所述的(CH3COO)2Zn甲醇溶液浓度为60mM，NaOH甲醇水溶液的浓度为60mM，甲醇与水的体积比为4：1，H2PtCl6水溶液浓度为50mM，NaBH4甲醇溶液浓度为160mM；所述的(CH3COO)2Zn甲醇溶液、NaOH甲醇水溶液、H2PtCl6水溶液、NaBH4甲醇溶液的体积比为1：1：0.005：0.25。
进一步，所述的离心转速为10000rpm，离心时间为5min；所述的真空干燥的温度为60℃，干燥时间为12h。
由所述制备方法制得的Pt-ZnO异质结纳米粒子。.所制备的Pt-ZnO异质结纳米粒子作为半导体异质结声敏剂。
该异质结纳米粒子具有如下特征：
(1)具有均一的尺寸，水合粒径约为160nm左右；
(2)有良好的声敏剂性质，超声作用下产生大量1O2；
(3)有良好的类过氧化氢酶纳米酶性质，能够改善肿瘤乏氧环境；
(4)有良好的类过氧化物酶纳米酶性质，可以催化过氧化氢产生大量·OH；
(5)有良好的体外细胞治疗效果；
附图说明
图1：本发明实施例1纳米粒子的粒径分布图。
图2：本发明实施例1纳米粒子的透射电镜图。
图3：本发明实施例2纳米粒子超声产生1O2图。
图4：本发明实施例3纳米粒子类过氧化物酶催化产生·OH图。
图5：本发明实施例4纳米粒子类过氧化氢酶催化产生氧气浓度图。
图6：本发明实施例5纳米粒子的细胞毒性图。
具体实施方式：
实施例1
(1)将1.2mmol(CH3COO)2Zn溶解在20mL甲醇溶液中，搅拌至完全溶解。
(2)将12mmolNaOH溶解在20mL甲醇水溶液中，甲醇与水体积比为4：1，搅拌至完全溶解。
(3)将(1)溶液滴入(2)溶液中，以1500rpm转速搅拌3h。
(4)将100μL，50mMH2PtCl6加入(3)溶液中，以1500rpm转速搅拌1h。
(5)将0.8mmolNaBH4溶解在5mL甲醇溶液中，搅拌至完全溶解。
(6)将(5)溶液加入(4)溶液中，以1500rpm转速搅拌反应1h，5min离心三次，60℃下真空干燥12h得到Pt-ZnO纳米粒子。
图1数据显示所得到的Pt-ZnO异质结纳米粒子的粒径约为160nm左右。图2的透射电镜图显示，本发明方法制备出Pt-ZnO异质结纳米粒子呈球形，且球形纳米粒子表面成功的负载铂纳米颗粒。
实施例2
(1)-(6)同实施例1步骤(1)-(6)
(7)电子自旋共振波谱仪(Electron spin-resonance Spectrometer，ESR)检测1O2：对照组设置为Control，ZnO+US，Pt-ZnO+US，Pt-ZnO+US+H2O2。3μL 2,2,6,6-四甲基哌啶(TEMP)分别加入到0.1mL水，ZnO(100μg/mL)，Pt-ZnO(100μg/mL)中，50mM H2O2加入到Pt-ZnO+US+H2O2组中，反应30min后，然后超声处理(1.0MHz，1.5W cm-2，1min)，1O2的信号通过ESR波谱显示。作为对比，ZnO+US，Pt-ZnO+US也在同样条件下检测1O2。图3数据显示材料在超声作用下，能产生较强的1O2信号，具有显著的声动力性能。并且由于材料具有类过氧化氢酶活性，加入H2O2后，提高了氧含量，进一步增强了声动力性能，产生更强的1O2信号。
实施例3
(1)-(6)同实施例1步骤(1)-(6)
(8)酶标仪检测类过氧化物酶产生·OH：将50μL的Pt-ZnO溶液(100μg/mL)与42.5μL的NaAc-HAc缓冲液(pH＝4.5)混合。并且将浓度为1M的5μL的H2O2溶液和浓度为8mg mL-1的2.5μL的3,3',5,5'-四甲基联苯胺(TMB)溶液加入上述反应体系中反应30min后，利用酶标仪测量652nm处吸光度进行类过氧化物酶活性测定。由于催化H2O2可使TMB氧化为在652nm有吸收峰的oxTMB，图4(a)数据显示在H2O2存在下，在625nm处显示出较高吸收，表明Pt-ZnO具有类过氧化物酶活性，可催化H2O2产生大量·OH。
(1)-(6)同实施例1步骤(1)-(6)
(9)电子自旋共振波谱仪(Electron spin-resonance Spectrometer，ESR)检测类过氧化物酶产生·OH：对照组设置为Control，ZnO+H2O2，Pt-ZnO+H2O2。10μL5,5-二甲基-1-吡咯啉-N-氧化物(DMPO)分别加入到0.1mL水，ZnO(100μg/mL)，Pt-ZnO(100μg/mL)中，50mMH2O2加入到ZnO组与Pt-ZnO组中，反应30min后，·OH的信号通过ESR波谱显示。图4(b)数据显示，材料具有类过氧化物酶活性，可催化过氧化氢产生·OH，能产生较强的·OH信号。
实施例4
(1)-(6)同实施例1步骤(1)-(6)
(10)溶氧仪测定类过氧化氢酶活性：在搅拌的作用下将0.5mL Pt-ZnO溶液(100μg/mL)添加到19.5mL 50mM H2O2稀溶液中，使用氧气探针记录不同时间点O2的浓度。图5数据显示在H2O2存在下，单纯ZnO纳米粒子在加入H2O2的条件下不能有效的产生氧气，而Pt-ZnO异质结纳米粒子能够有效产生氧气，说明本纳米粒子具有类过氧化氢酶活性，从而有助于缓解肿瘤组织的乏氧微环境。
实施例5
(1)-(6)同实施例1步骤(1)-(6)
(11)MTT法检测细胞活性：在细胞治疗实验中，将4T1细胞以10000个细胞每孔接种在96孔板中并培养24h，之后与不同浓度的Pt-ZnO共培养3h，然后用1.0MHz，50％占空比，1.5W cm-2的超声仪超声处理1min，再培养12h，并通过MTT测定检查细胞活力。细胞治疗实验中对细胞进行单独超声治疗，单独催化治疗，还有超声治疗和催化协同治疗，图6数据结果表明超声治疗和催化协同治疗具有最显著治疗效果。分析其原因为材料进入细胞之后，在超声作用下，产生大量活性氧，破坏细胞内氧化还原平衡，且纳米酶性质对声动力疗法具有增强效果，导致大量细胞凋亡。
Claims (4)
1.一种铂-氧化锌异质结纳米粒子的制备方法，其特征在于，将(CH3COO)2Zn溶解在甲醇溶液中，搅拌至完全溶解；将NaOH溶解在甲醇水溶液中，搅拌至完全溶解；将(CH3COO)2Zn甲醇溶液滴入NaOH甲醇水溶液中，搅拌反应3 h生成ZnO溶液；将H2PtCl6水溶液加入至上述ZnO溶液中，搅拌1 h；将NaBH4溶解在甲醇溶液中，将其加入到上述ZnO溶液中，反应1 h，离心去除上清，清洗三次，真空干燥后得到Pt-ZnO异质结纳米粒子；
所述的(CH3COO)2Zn甲醇溶液浓度为60mM，NaOH甲醇水溶液的浓度为60mM，甲醇与水的体积比为4：1，H2PtCl6水溶液浓度为50mM，NaBH4甲醇溶液浓度为160 mM；所述的(CH3COO)2Zn甲醇溶液、NaOH甲醇水溶液、H2PtCl6水溶液、NaBH4甲醇溶液的体积比为1：1：0.005：0.25。
2.权利要求1所述的制备方法，其特征在于：所述的离心转速为10000 rpm，离心时间为5 min；所述的真空干燥的温度为60°C，干燥时间为12h。
3.由权利要求1~2任一项所述制备方法制得的Pt-ZnO异质结纳米粒子。
4.权利要求1所述的制备方法所制备的Pt-ZnO异质结纳米粒子作为半导体异质结声敏剂。
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