CN109453794A - 一种Cu2ZnSn(SxSe1-x)4合金纳米材料作为模拟酶的应用 - Google Patents
一种Cu2ZnSn(SxSe1-x)4合金纳米材料作为模拟酶的应用 Download PDFInfo
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Abstract
本发明提供一种Cu2ZnSn(SxSe1‑x)4合金纳米材料作为模拟酶的应用。所述模拟酶材料为Cu2ZnSn(SxSe1‑x)4合金材料,通过溶剂热反应获得。本发明所述Cu2ZnSn(SxSe1‑x)4合金纳米材料具有良好的过氧化物酶催化性能,且制备方法工艺简单、易于控制、成本低廉,在免疫分析等领域具有潜在应用前景。
Description
技术领域
本发明属于模拟酶技术领域,具体涉及一种Cu2ZnSn(SxSe1-x)4合金纳米材料作为模拟酶的应用。
背景技术
过氧化物酶(Horseradish peroxidase,简称HRP)是由微生物或植物所产生的一类氧化还原酶,是以过氧化氢为电子受体催化底物氧化的酶,常被用于进行过氧化氢检测。然而作为天然酶,过氧化物酶本质上也是一种具有超分子结构的蛋白质,虽然它能够在温和的条件下高效、专一地催化各种生化反应,但是却对热、酸、碱不稳定而失去催化活性。此外,过氧化物酶由于提纯工艺复杂、成本高、不易保存,大大限制了其应用(Wei et al.,Chem.Soc.Rev.42(2013)6060-6093)。
由于纳米材料在尺寸、形状以及表面电荷方面与天然酶具有一定的相似之处,且比表面积大、表面活化中心多、催化活性高,因此,自从Gao等(Gao et al.,Nat.Nanotechnol.2(2007)577-583)首次报道了Fe3O4磁性纳米颗粒具有较高的过氧化物模拟酶催化活性后,研究者对于纳米材料模拟过氧化物酶进行了广泛的研究,并开发出许多新型纳米材料模拟酶,比如CeVO4(Ju et al.,J.Mater.Chem.B 4(2016)6316-6325)、MnSe(Qiao et al.,Sensor.Actuator.B:Chem.193(2014)255-262)、Cu2(OH)3Cl-CeO2(Wang etal.,Microchim.Acta 182(2015)1733-1738)、Fe3S4(Ding et al.,Microchim.Acta 183(2016)625-631)、ZnO(Dai et al.,J.Mater.Chem.18(2008)1919-1926)等。这些纳米材料在催化效率、机理和底物的专一性都与HRP相同,并且还具有稳定性高、制备工艺简单和可循环利用等优点
发明内容
本发明的目的在于提供一种Cu2ZnSn(SxSe1-x)4合金纳米材料作为模拟酶的应用,可以对H2O2进行快速检测,从而弥补现有技术的不足。
本发明所提供的Cu2ZnSn(SxSe1-x)4合金纳米材料,其制备方法如下:
1)将0.01~5g的聚乙烯吡咯烷酮PVP、0.01~1mmol的Cu(CH3COO)2·H2O、0.01~1mmol的Zn(CH3COO)2·2H2O和0.01~1mmol的SnCl2分散于乙醇胺中,磁力搅拌至完全溶解,得溶解液A;
2)将0.01~0.99mmol硫代乙酰胺TAA和0.01~0.99mmol Se粉加入到乙醇胺中,磁力搅拌至溶解,得溶解液B;
3)然后将将溶解液A和溶解液B混合,搅拌均匀后将混合液转移转移至反应釜中,放入150~200℃热处理24~72h;反应结束后,冷却至室温,经离心洗涤,40~80℃干燥得到化学组成为Cu2ZnSn(SxSe1-x)4的合金纳米材料,其中摩尔比x=S/(S+Se)为0~1;
所述Cu离子与Zn和Sn离子的摩尔比为0.1~1:1、Zn与Sn的摩尔比为1~2:1。
本发明的Cu2ZnSn(SxSe1-x)4合金纳米材料作为过氧化物模拟酶的应用。
所述Cu2ZnSn(SxSe1-x)4合金纳米材料在H2O2的快速检测中的应用。
所述Cu2ZnSn(SxSe1-x)4合金纳米材料模拟过氧化物酶性能具体测试方法为:依次向离心管中加入磷酸盐缓冲液(PBS)、待检测的样品溶液、TMB的乙醇溶液和Cu2ZnSn(SxSe1-x)4分散液,反应7min后观察溶液颜色变化,并记录400~800nm下的紫外可见吸收光谱;所述Cu2ZnSn(SxSe1-x)4终浓度为200μg/mL;所述H2O2终浓度为1.0mmol/L;所述TMB终浓度为0.8mmol/L。
本发明制备的Cu2ZnSn(SxSe1-x)4模拟酶材料具有良好的模拟过氧化物酶催化性能,可以通过比色法快速检测H2O2,并且具有良好的稳定性和重复利用性,制备工艺简单、易于控制、成本低廉,在免疫分析等领域具有潜在应用前景。
附图说明
图1为本发明实施例1制备的Cu2ZnSn(SxSe1-x)4(x=0.25)模拟酶材料的XRD图谱(A)和TEM照片(B)。
图2为本发明实施例1制备的Cu2ZnSn(SxSe1-x)4(x=0.25)模拟酶材料反应体系的紫外可见吸收光谱图。
具体实施方式
Cu2ZnSn(SxSe1-x)4合金材料作为一种功能半导体材料,其组成元素丰富、无毒、吸光性能好,具备获得高转化效率的理想带隙等条件,已经成为用于替代Cu(In,Ga)(Se,S)2和CdTe等传统薄膜太阳能电池材料的首选吸收层材料。然而Cu2ZnSn(SxSe1-x)4合金材料在生物免疫分析和环境检测等领域的应用潜能尚未开发。因此,本发明将Cu2ZnSn(SxSe1-x)4合金材料作为过氧化物模拟酶,通过对底物的催化氧化还原反应实现对H2O2快速检测,进一步扩展太阳能电池材料在生物免疫分析和环境检测等领域的应用。
以下通过具体的实施例对本发明作进一步说明,有助于本领域的普通技术人员更全面的理解本发明,但不以任何方式限制本发明。
实施例1:Cu2ZnSn(SxSe1-x)4纳米材料的制备
通过溶剂热法制备。将1.0g PVP、0.352mmol Cu(CH3COO)2·H2O、0.24mmol Zn(CH3COO)2·2H2O和0.2mmol SnCl2分散于15mL乙醇胺中,磁力搅拌至完全溶解,得溶解液A;同时将0.25mmol硫代乙酰胺(TAA)和0.75mmol Se粉加入到15mL乙醇胺中,磁力搅拌至溶解,得溶解液B;然后将将溶解液A和溶解液B混合,搅拌均匀后将混合液转移转移至反应釜中,放入电热恒温鼓风干燥箱180℃热处理48h;反应结束后,将反应釜冷却至室温,经离心洗涤,在60℃干燥12h,得到Cu2ZnSn(SxSe1-x)4的合金纳米材料(x=0.25),记为CZTSSe-0.25。
图1(A)为实施例1所制备样品的XRD图谱。由图可知,大部分衍射峰的位置与立方KS相CZTSe(JCPDS Card No.70-8930)的衍射峰位置相吻合,少数衍射峰与六角KS相CZTS相吻合,而且没有出现任何杂质相,可以确定实施例1制备的样品为CZTSSe纳米晶相结构。此外,由图可知,样品的衍射峰强度较大,衍射峰较尖,说明所制备的CZTSSe-0.25纳米材料具有较好的结晶度。图1(B)为实施例1所制备样品的TEM照片,由图可见,所制备的CZTSSe-0.25为纳米颗粒,结构尺寸较均一,约为5~10nm,稍有团聚的现象,这种纳米晶体结构将具有较大的比表面积。
实施例2:不同反应参数来制备Cu2ZnSn(SxSe1-x)4纳米材料
将0.01~5g PVP、0.01~1mmol Cu(CH3COO)2·H2O、0.01~1mmol Zn(CH3COO)2·2H2O和0.01~1mmol SnCl2分散于15mL乙醇胺中,磁力搅拌至完全溶解,得溶解液A;同时将0.01~0.99mmol硫代乙酰胺(TAA)和0.01~0.99mmol Se粉加入到15mL乙醇胺中,磁力搅拌至溶解,得溶解液B;然后将将溶解液A和溶解液B混合,搅拌均匀后将混合液转移转移至反应釜中,放入电热恒温鼓风干燥箱150~200℃热处理24~72h;反应结束后,将反应釜冷却至室温,经离心洗涤,在40~80℃干燥12h,得到化学组成为Cu2ZnSn(SxSe1-x)4的合金纳米材料(x=0、0.5、0.75、1),记为CZTSe、CZTSSe-0.5、CZTSSe-0.75、CZTS(参见表1)。
表1:不同反应条件制备的材料表
实施例3:Cu2ZnSn(SxSe1-x)4纳米材料模拟过氧化物酶
取1个1.5mL离心管,加入600μL 50mmol/L的磷酸盐缓冲液(PBS,pH=4.0)、100μL10mmol/L H2O2溶液和100μL 8mmol/L TMB的乙醇溶液,然后加入200μL实施例1制备的CZTSSe-0.25分散液(1.0mg/mL),反应7min后观察溶液变化,并记录400~800nm下的紫外可见吸收光谱(参见图2)。
图2是四种反应体系对应的紫外可见吸收光谱图,652nm是氧化态TMB的特征吸收峰。由图可见,H2O2+CZTSSe-0.25、TMB+CZTSSe-0.25和TMB+H2O2三个体系几乎没有吸收峰,而TMB+H2O2+CZTSSe-0.25体系在652nm处有明显的吸收峰,且峰形较好。此外,通过观察H2O2+CZTSSe-0.25、TMB+CZTSSe-0.25和TMB+H2O2三个体系的颜色变化,发现三个体系溶液颜色均为无色透明,未发生明显变化,而TMB+H2O2+CZTSSe-0.25体系中溶液呈现出明显的蓝色,说明CZTSSe-0.25在H2O2的存在下催化氧化TMB生成了蓝色氧化物。结果表明,本发明制备的CZTSSe-0.25纳米材料具有良好的模拟过氧化物酶催化活性,是一种过氧化物模拟酶材料,在H2O2存在下可以催化氧化TMB生成蓝色氧化物,通过这种显色反应可以实现快速检测H2O2,在生物免疫分析和环境检测等领域具有潜在应用前景。
Claims (8)
1.一种Cu2ZnSn(SxSe1-x)4合金纳米材料,其特征在于,所述的合金纳米材料的制备方法如下:
1)将0.01~5g的聚乙烯吡咯烷酮PVP、0.01~1mmol的Cu(CH3COO)2·H2O、0.01~1mmol的Zn(CH3COO)2·2H2O和0.01~1mmol的SnCl2分散于乙醇胺中,磁力搅拌至完全溶解,得溶解液A;
2)将0.01~0.99mmol硫代乙酰胺TAA和0.01~0.99mmol Se粉加入到乙醇胺中,磁力搅拌至溶解,得溶解液B;
3)然后将将溶解液A和溶解液B混合,搅拌均匀后将混合液转移转移至反应釜中,放入150~200℃热处理24~72h;反应结束后,冷却至室温,经离心洗涤,40~80℃干燥得到化学组成为Cu2ZnSn(SxSe1-x)4的合金纳米材料,其中摩尔比x=S/(S+Se)为0~1。
2.如权利要求1所述的合金纳米材料,其特征在于,所述的Cu离子与Zn和Sn离子的摩尔比为0.1~1:1;且Zn与Sn的摩尔比为1~2:1。
3.权利要求1所述的合金纳米材料作为过氧化物模拟酶的应用。
4.如权利要求3所述的应用,其特征在于,所述的应用是权利要求1所述的合金纳米材料作为过氧化物模拟酶在H2O2检测中的应用。
5.一种检测H2O2的方法,其特征在于,所述的方法中使用了权利要求1所述的合金纳米材料。
6.如权利要求5所述的方法,其特征在于,所述的检测方法,是向离心管中加入磷酸盐缓冲液PBS、待检测的样品溶液、TMB的乙醇溶液和权利要求1所述的合金纳米材料分散液,反应7min后观察溶液颜色变化,并记录400~800nm下的紫外可见吸收光谱。
7.如权利要求6所述的方法,其特征在于,所述Cu2ZnSn(SxSe1-x)4终浓度为200μg/mL。
8.如权利要求6所述的方法,其特征在于,所述的TMB的终浓度为0.8mmol/L。
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