CN111420707A - 丝素蛋白-二氧化铱多功能复合纳米团簇的制备 - Google Patents
丝素蛋白-二氧化铱多功能复合纳米团簇的制备 Download PDFInfo
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Abstract
本发明涉及纳米材料的合成领域,更具体地涉及利用丝素蛋白溶液模拟生物矿化过程来制备丝素蛋白‑二氧化铱多功能复合纳米团簇的方法,具体包括以下步骤:(1)从家蚕蚕茧中提取再生丝素蛋白溶液(2)在碱性环境下使用再生丝素蛋白溶液和氯化铱溶液制备丝素蛋白‑二氧化铱多功能复合纳米团簇(3)通过实验验证了丝素蛋白‑二氧化铱复合纳米团簇具有类过氧化物酶和类过氧化氢酶催化活性,以及一定的光热响应和作为超声治疗增敏剂的作用。
Description
技术领域
本发明涉及纳米材料的合成领域,更具体地涉及利用丝素蛋白溶液模拟生物矿化过程来制备丝素蛋白-二氧化铱多功能复合纳米团簇的方法。
背景技术
生物矿物提供是不仅是结构支撑和力学强度,而且是一种器官。作为天然建筑师,它包含了许多重要的生物学功能,具有许多其他特殊功能。如磁序菌中的磁传感器(Fe3O4);双壳动物的重力平衡器(CaCO3、CaSO4;防止其他动物捕食的甲壳(SiO2、CaCO3);血红蛋白的铁储存(Fe2O3·nH2O);三叶虫的眼晶状体(CaCO3)等。生物矿化作用区别于一般矿化作用的显著特征是通过有机大分子和无机离子在界面处的相互作用。从分子水平上控制无机矿物相的结晶、生长,从而使生物矿物具有特殊的分级结构和组装方式 。近年来研究表明,生物体对生物矿化过程的控制是一个复杂的多层次过程,其中,生物大分子产生排布以及它们与无机矿物相的持久作用是生物矿化过程的两个主要方面。一般认为生物体内的矿化过程分为四个阶段。
(1)有机质的预组织:生物体内不溶有机质在矿物沉积前构造一个有组织的微反应环境,该环境决定了无机物成核的位置和形成矿物的功能。该阶段是生物矿化进行的前提。
(2)界面分子识别:在已形成的有机大分子组装体的控制下,无机物在溶液中通过静电力作用、螯合作用、氢键、范德华力等作用在有机-无机界面处成核。分子识别是一种具有专一性功能的过程,它控制着晶体的成核、生长和聚集。
(3)生长调制:无机矿物相生长过程中,晶体的形态、大小、取向和结构受生物体有机质的调控,并初步组装得到亚单元。该阶段通过化学矢量调节赋予了生物矿化物质具有独特的结构和形态。
(4)外延生长:在细胞参与下,亚单元组装形成多级结构的生物成因矿物。该阶段是造成天然生物矿化材料与人工材料差别的主要原因。而且是复杂超精细结构在细胞活动中的最后修饰阶段。
生物矿化是一个复杂的动态的过程,受到生物有机质、晶体自身生长机制,以及外界环境等各方面的综合调控作用。仿生矿化模型的建立以及相关机理的深入研究.为在有机组分内合成无机材料,进而利用生物成因矿物的力学性质研究,制备具有高断裂韧性和高强度的仿生材料提供了理论基础。铱基纳米材料,近年来因其在广PH范围内高的催化析氧反应的能力而受到研究者们的关注。固有的高原子序数过渡金属元素(Z = 77)和IrO2相对于钨基氧化物的高稳定性使得铱基纳米材料在肿瘤治疗、CT成像和光声成像中展现出很好的性能。
发明内容
以再生丝素蛋白溶液、氯化铱溶液为原料合成了一种丝素蛋白-二氧化铱多功能复合纳米团簇。该纳米团簇具有良好的生物相容性、类过氧化氢酶催化活性、类过氧化物酶活性、声动力效应、光热效应及多功能造影能力,在多领域有很大的应用潜力。
本发明的技术方案具体如下:
1、丝素蛋白-二氧化铱多功能复合纳米团簇的制备方法,其特征在于,包含以下步骤:
(1)将蚕茧脱胶并分离纯化丝素蛋白,制备成稳定的再生丝素蛋白水溶液,并用冻干法确定丝素蛋白的含量;
(2)在快速磁力搅拌下向步骤(1)得到的再生丝素蛋白溶液中加入氯化铱溶液,接着搅拌30分钟使其充分混匀;使用氢氧化钠溶液将氯化铱与丝素蛋白混合溶液的PH值调至12,随后将溶液转移至密闭的玻璃瓶中,在80摄氏度油浴的条件下持续磁力搅拌12小时,再将溶液放在透析袋中透析24小时去除未反应完全的无机离子,最后将溶液离心收集丝素蛋白-二氧化铱多功能复合纳米团簇,并使用冷冻干燥机冻干后储存。
进一步,所述步骤(1)是将家蚕蚕茧按40克每升的比例置于沸腾的0.5%碳酸钠溶液中煮30分钟去除丝胶;随后将未溶解的蚕丝蛋白充分干燥后再溶解于90摄氏度且含有氯化钙:乙醇:水的摩尔比为1:2:8的溶液中,保持90摄氏度水浴两小时使其充分溶解;溶解后的丝素蛋白溶液经流水透析三天再经过抽滤,得到澄清的再生丝素蛋白溶液。
所述步骤(2)中的再生丝素蛋白溶液浓度为20 mg·mL-1,氯化铱溶液的浓度为50mM;再生丝素蛋白溶液与氯化铱溶液的体积比为4:1;透析袋的截留分子量为3500 kDa。
所述的丝素蛋白-二氧化铱多功能复合纳米团簇,具有催化过氧化氢生成氧气的类过氧化氢酶活性和催化过氧化氢生成羟基自由基的过氧化物酶活性,在近红外激光照射下该材料可产生显著的光热响应并提升其催化活性;在医用超声仪的刺激下该材料可高效产生单线态氧实现声动力治疗的效果。
本发明主要优点有:
利用受生物矿化作用启发的结晶方法,在再生丝素蛋白溶液中一步法不完全结晶生成了具有大量缺陷的丝素蛋白-二氧化铱多功能复合纳米团簇。该复合纳米团簇具有二氧化铱碎晶高的催化比表面积和丝素蛋白优良的生物相容性。目前已发现该材料至少具有高效的类过氧化氢酶催化活性、类过氧化物酶催化活性、超声产生单线态氧的声动力效应、光热转化能力和CT、光声等多功能造影能力。因此该复合纳米材料是一种很有应用潜力的功能材料,具有进一步开发的价值。
附图说明
为了使本发明的目的、技术方案和有益效果更加清楚,本发明提供如下附图:
图1为本发明实施例1中丝素蛋白-二氧化铱多功能复合纳米团簇的合成示意图。
图2为本发明实施例1中丝素蛋白-二氧化铱多功能复合纳米团簇的透射电镜图。
图3为本发明实施例1中丝素蛋白-二氧化铱多功能复合纳米团簇的热场发射扫描电镜图
图4为本发明实施例1中丝素蛋白-二氧化铱多功能复合纳米团簇的动态光散射水合粒径分布图。
图5为本发明实施例1中丝素蛋白-二氧化铱多功能复合纳米团簇的XPS能谱图。
图6为本发明实施例1中丝素蛋白-二氧化铱多功能复合纳米团簇与过氧化氢水溶液的溶氧变化图。
图7为本发明实施例1中丝素蛋白-二氧化铱多功能复合纳米团簇的光热升温曲线。
图8为本发明实施例1中丝素蛋白-二氧化铱多功能复合纳米团簇水溶液在超声处理后的ESR能谱图。
图9为本发明实施例1中丝素蛋白-二氧化铱多功能复合纳米团簇经不同处理后与OPD活性氧指示剂的反应结果。
具体实施方式
以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1丝素蛋白-二氧化铱多功能复合纳米团簇的制备
丝素蛋白-二氧化铱多功能复合纳米团簇的合成流程图如图1所示,包含如下的制备步骤:
(1)丝素蛋白的提取:取蚕茧用剪刀沿对称轴剖开,取出蚕蛹,随后将蚕茧剪为八分之一的小片。取80克蚕茧片加入2升的0.5%碳酸钠溶液中,在沸腾状态下煮30分钟。随后倒掉碳酸钠溶液,并用二次水反复冲洗丝素蛋白。冲洗干净的丝素蛋白放置于35摄氏度的鼓风干燥箱中干燥12小时。
(2)丝素蛋白的再溶解:按摩尔比为1:2:8的比例配置氯化钙、乙醇和水溶液50克,将2克步骤(1)制备的丝素蛋白加入溶液中,在90摄氏度的水浴锅中加热2小时使蛋白充分溶解。随后抽滤除杂,并在3500 kDa的透析袋中透析三天。使用冷冻干燥机确定少量丝素蛋白溶液样本中的丝素蛋白含量后,用纯净水将剩余丝素蛋白溶液的浓度稀释至20 mg·mL-1备用。
(3)复合纳米团簇的制备:在快速磁力搅拌下向16 mL步骤(1)得到的再生丝素蛋白溶液中加入4 mL氯化铱水溶液(50 mM),接着搅拌30分钟使其充分混匀。使用2 M浓度的氢氧化钠溶液将氯化铱与丝素蛋白混合溶液的PH值调至12,随后将溶液转移至密闭的玻璃瓶中于80摄氏度油浴的条件下持续磁力搅拌12小时,再将溶液放在3500 kDa透析袋中透析24小时去除未反应完全的无机离子,最后将溶液离心收集丝素蛋白-二氧化铱多功能复合纳米团簇并使用冷冻干燥机冻干后储存。
图2中展示了丝素蛋白-二氧化铱多功能复合纳米团簇的透射电镜图,可以看出其含有碎晶的团簇形貌。图3中展示了丝素蛋白-二氧化铱多功能复合纳米团簇的热场发射扫描电镜图,可以看出纳米团簇粒径较为均一,分散性良好。图4展示了纳米团簇在水溶液中的动态光散射水合粒径分布图。图5的XPS能谱图证明了丝素蛋白-二氧化铱多功能复合纳米团簇的化学组成。图6的溶氧曲线体现了纳米团簇高效的类过氧化氢酶催化能力。图7的光热升温曲线体现了纳米团簇的光热转化能力。图8的ESR能谱图证明了在医用超声探头的刺激下,纳米团簇可以高效地产生单线态氧,实现声动力治疗的效果。图9的活性氧指示剂OPD的紫外光吸收变化表明,单独纳米团簇具有类过氧化物酶的催化活性,且光照过后可以增强活性氧的产出能力。
最后说明的是,以上优选实施例仅用以说明本发明的技术方案而非限制,尽管通过上述优选实施例已经对本发明进行了详细的描述,但本领域技术人员应当理解,可以在形式上和细节上对其做出各种各样的改变,而不偏离本发明权利要求书所限定的范围。
Claims (4)
1.丝素蛋白-二氧化铱多功能复合纳米团簇的制备方法,其特征在于,包含以下步骤:
(1)将蚕茧脱胶并分离纯化丝素蛋白,制备成稳定的再生丝素蛋白水溶液,并用冻干法确定丝素蛋白的含量;
(2)在快速磁力搅拌下向步骤(1)得到的再生丝素蛋白溶液中加入氯化铱溶液,接着搅拌30分钟使其充分混匀;使用氢氧化钠溶液将氯化铱与丝素蛋白混合溶液的PH值调至12,随后将溶液转移至密闭的玻璃瓶中,在80摄氏度油浴的条件下持续磁力搅拌12小时,再将溶液放在透析袋中透析24小时去除未反应完全的无机离子,最后将溶液离心收集丝素蛋白-二氧化铱多功能复合纳米团簇,并使用冷冻干燥机冻干后储存。
2.根据权利要求1所述的丝素蛋白-二氧化铱多功能复合纳米团簇的制备方法,其特征在于,所述步骤(1)中再生丝素蛋白溶液的提取,是将家蚕蚕茧按40克每升的比例置于沸腾的0.5%碳酸钠溶液中煮30分钟去除丝胶;随后将未溶解的蚕丝蛋白充分干燥后再溶解于90摄氏度且含有氯化钙:乙醇:水的摩尔比为1:2:8的溶液中,保持90摄氏度水浴两小时使其充分溶解;溶解后的丝素蛋白溶液经流水透析三天再经过抽滤,得到澄清的再生丝素蛋白溶液。
3.根据权利要求1所述的丝素蛋白-二氧化铱多功能复合纳米团簇的制备方法,其特征在于:所述步骤(2)中的再生丝素蛋白溶液浓度为20 mg·mL-1,氯化铱溶液的浓度为50 mM;再生丝素蛋白溶液与氯化铱溶液的体积比为4:1;透析袋的截留分子量为3500 kDa。
4.根据权利要求1所述的丝素蛋白-二氧化铱多功能复合纳米团簇的制备方法,其特征在于,所述的丝素蛋白-二氧化铱多功能复合纳米团簇,具有催化过氧化氢生成氧气的类过氧化氢酶活性和催化过氧化氢生成羟基自由基的过氧化物酶活性,在近红外激光照射下该材料可产生显著的光热响应并提升其催化活性;在医用超声仪的刺激下该材料可高效产生单线态氧实现声动力治疗的效果。
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