CN109482207B - 一种Ag3PO4模拟酶材料及其应用 - Google Patents
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Abstract
本发明提供一种Ag3PO4模拟酶材料及其应用。所述模拟酶材料为具有纳米带缠绕的立方体结构的Ag3PO4,尺寸为2~8μm,通过共沉淀反应获得。所述Ag3PO4模拟酶材料可在氧气存在下催化氧化辣根过氧化物酶的特征底物3,3’,5,5’‑四甲基联苯胺,具有良好的催化性能,从而可以作为模拟酶。所述Ag3PO4模拟酶材料的应用,通过与Hg2+混合后提高模拟酶活性,从而可以根据特征底物的氧化产物的紫外可见吸收光谱信号和颜色变化测定Hg2+浓度。本发明不仅提供了一种新的模拟氧化酶材料,同时制备方法工艺简单、易于控制、成本低廉,可以简单、快速、灵敏地检测Hg2+,在环境监测、食品检验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Ag3PO4模拟酶材料及其应用。
背景技术
天然酶是一类具有特殊催化活性和特定空间构象的生物大分子,具有催化效率高、专一性强、反应条件温和等特点(Benkovic et al., Science 301(2003)1196-1202)。但是,由于大多数天然酶是蛋白质,对热、酸、碱不稳定,容易受到多种物理、化学因素的影响而失活。另外,天然酶在生物体内的含量很低,很难通过纯化大量获得,故价格昂贵,大大限制了实际应用。因此,合成在化学结构、催化效率、特异性和选择性上都和天然酶相似的模拟酶受到了研究者的广泛关注。
从尺寸、形状以及表面电荷来说,纳米材料与天然酶具有一定的相似之处,其比表面积大、表面活化中心多,催化活性和催化效率都大大增强,并且还克服了天然酶稳定性差、易变性失活、贮存困难、制备工艺复杂和价格昂贵等缺点。因此,自从Gao等(Gao etal.,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,纳米材料模拟酶的研究迅速堀起,在生物、医药、环境等领域取得了许多研究成果。目前,研究人员已开发出多种新型纳米材料模拟酶,比如金属纳米材料、碳基纳米材料、复合纳米材料等。其中,含银的金属纳米材料因催化效率高、性能稳定等优点受到了广泛关注,包括纳米Ag(Jiang et al.,Analyst 137(2012) 5560-5564)、AgVO3(Wang et al.,Microchim.Acta 185(2018)1)、 MoS2-Pt74Ag26(Cai et al.,Nanoscale 8(2016)3685-3693)等已经被证明具有高效的模拟酶催化活性,应用于分析检测葡萄糖和双氧水。
Ag3PO4材料由于其独特的物理化学特性,不仅在电学、光学、建筑等方面有很多用途,而且可以作为光催化剂、离子交换剂和低热膨胀率陶瓷材料用在玻璃工业和食品生产各个领域,对于食品品质的改良起着重要作用,是目前使用最广泛的食品品质改良剂,还可以做为一种新型无机粘结剂,具有无毒、无味、无公害以及良好的高温性能等优点。然而,其在生物免疫分析和环境检测等领域的应用潜能尚未开发。
发明内容
本发明的目的在于提供一种Ag3PO4模拟酶材料及其应用,从而弥补现有技术的不足。
本发明所提供的Ag3PO4模拟酶材料,其制备方法如下:
1)将AgNO3溶于超纯水中,随后加入浓氨水,得溶解液A;
2)将Na2HPO4·12H2O溶于超纯水得溶解液B;
3)然后将溶解液B在搅拌条件下逐滴滴加到溶解液A中得悬浮液,并在40~80℃水浴条件下继续搅拌0.5~2h;反应结束后,依次用超纯水、乙醇洗涤,过滤,40~80℃干燥6h,得到Ag3PO4模拟酶材料。
所述AgNO3与浓氨水的摩尔比为1:2~5。
所述AgNO3与Na2HPO4·12H2O的摩尔比为1:5~25。
本发明制备的Ag3PO4模拟酶材料作为氧化物酶的应用;
本发明的Ag3PO4材料作为氧化物酶用于对底物3,3’,5,5’-四甲基联苯胺(TMB)进行催化氧化,以实现对Hg2+的快速检测。
所述Ag3PO4材料模拟氧化物酶检测Hg2+的具体测试方法为:在室温下依次向离心管中加入磷酸盐缓冲液(PBS)、Ag3PO4分散液、Hg2+和TMB的乙醇溶液,反应10min后观察溶液颜色变化,并记录 400~800nm的紫外可见吸收光谱;所述Ag3PO4终浓度为10μg/mL,所述Hg2 +终浓度为40μmol/L,所述TMB终浓度为0.2mmol/L,所述PBS的终浓度为25mmol/L、pH=4。
本发明制备的Ag3PO4材料具有良好的模拟氧化物酶催化性能,可以通过比色法快速检测Hg2+,并且具有良好的稳定性,制备方法简单、易于控制、成本低廉,在环境监测、食品检验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Ag3PO4模拟酶材料的XRD图谱(A) 和SEM照片(B)。
图2为本发明实施例1制备的Ag3PO4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
本发明将Ag3PO4材料作为氧化物模拟酶,通过与Hg2+反应提高催化活性,实现对Hg2 +的快速检测。本发明制备的Ag3PO4材料,该材料具有良好的模拟氧化物酶催化活性,与Hg2+反应形成的产物能够在氧气的存在下催化氧化辣根过氧化物酶特征底物3,3’,5,5’-四甲基联苯胺(TMB),产生蓝色氧化产物,实现对Hg2+的快速检测,在环境监测、食品检验等领域具有潜在的应用前景。同时该材料具有制备方法简单易行、价格低廉和重复性好等特点。
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 Ag3PO4材料的制备
通过共沉淀法制备。将0.59mmol AgNO3溶于10mL超纯水中,随后加入1.09mmol浓氨水,得溶解液A,同时将8.38mmol Na2HPO4·12H2O溶于30mL超纯水得溶解液B;然后将上述溶解液B 在搅拌条件下逐滴滴加到上述溶解液A中得悬浮液,并在60℃水浴条件下继续搅拌1h;反应结束后,依次用超纯水、乙醇洗涤,过滤, 60℃干燥6h,得到化学组成为Ag3PO4的模拟酶材料。
图1(A)为实施例1所制备样品的XRD图谱。由图可知,所有衍射峰的位置与标准卡片JCPDS No.06-0505完全吻合,均归属于立方晶系Ag3PO4,而且没有出现任何杂质相,可以确定实施例1制备的样品为纯的体心立方结构Ag3PO4。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Ag3PO4具有较好的结晶度。图1(B)为实施例1所制备样品的SEM照片,由图可见,Ag3PO4材料为尺寸约为5μm的立方体状结构,表面有部分带状结构缠绕,结构与竹笼相似。
实施例2 Ag3PO4材料的制备
通过共沉淀法制备。将一定量的AgNO3溶于10mL超纯水中,随后加入浓一定量的氨水,得溶解液A,同时将一定量的 Na2HPO4·12H2O溶于30mL超纯水得溶解液B;然后将上述溶解液B 在搅拌条件下逐滴滴加到上述溶解液A中得悬浮液,并在40~80℃水浴条件下继续搅拌0.5~2h;反应结束后,依次用超纯水、乙醇洗涤,过滤,40~80℃干燥6h,得到化学组成为Ag3PO4的模拟酶材料 (参见表1)。
表1:制备Ag3PO4材料的不同反应参数
实施例3 Ag3PO4材料模拟酶检测Hg2+
取1个1.5mL离心管,加入500μL 50mmol/L的磷酸盐缓冲液(PBS,pH=4.0)、100μL实施例1制备的Ag3PO4分散液(100μg/mL)、 100μL 400μmol/L Hg2+溶液、100μL 2mmol/LTMB的乙醇溶液和 200μL超纯水,然后反应7min后观察溶液颜色变化,并记录400~800 nm的紫外可见吸收光谱(参见图2)。
图2是五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,Ag3PO4+Hg2+和TMB+Hg2+两个反应体系几乎没有吸收峰,Ag3PO4+TMB和Ag3PO4+TMB+ Hg2+体系在652nm处有明显的吸收峰,且峰形较好。此外,由图可见,在加入Hg2+后,反应体系的吸光度大大增加,这也说明了Hg2+与Ag3PO4发生反应后形成的产物模拟酶催化活性大大提高。通过观察Ag3PO4+Hg2+和TMB+Hg2+两个反应体系的颜色变化,发现两个体系溶液的颜色几乎无色透明,未发生明显变化,而Ag3PO4+TMB 和Ag3PO4+TMB+Hg2+体系中溶液呈现出明显的蓝色,且加入Hg2+后反应液的颜色进一步加深,说明Hg2+与Ag3PO4发生反应后形成的产物在O2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Ag3PO4立方体材料具有良好的模拟氧化物酶催化活性,是一种模拟酶材料,在O2存在下可以催化氧化TMB生成蓝色氧化物,并且在加入Hg2+后可以大大提高催化活性,通过这种显色反应可以实现快速检测Hg2+,在环境监测、食品检验等领域具有潜在应用前景。
Claims (7)
1.一种Ag3PO4模拟酶材料,其特征在于,所述的Ag3PO4模拟酶材料的制备方法如下:
1)将AgNO3溶于超纯水中,随后加入浓氨水,得溶解液A;
2)将Na2HPO4·12H2O溶于超纯水得溶解液B;
3)然后将溶解液B在搅拌条件下逐滴滴加到溶解液A中得悬浮液,并在40~80℃水浴条件下继续搅拌0.5~2h;反应结束后,依次用超纯水、乙醇洗涤,过滤,40~80℃干燥6h,得到Ag3PO4模拟酶材料;
所述的1)中AgNO3与浓氨水的摩尔比为1:2~5;
所述的AgNO3与Na2HPO4·12H2O的摩尔比为1:5~25。
2.权利要求1所述的Ag3PO4模拟酶材料作为模拟氧化物酶在 检测Hg2+中的应用。
3.一种检测Hg2+的方法,其特征在于,所述的方法,是使用权利要求1所述的Ag3PO4模拟酶材料进行检测。
4.如权利要求3所述的方法,其特征在于,所述的方法,是在室温下依次向离心管中加入磷酸盐缓冲液PBS、Ag3PO4分散液、待检测样品液和TMB的乙醇溶液,反应10min后观察溶液颜色变化,并记录400~800nm的紫外可见吸收光谱。
5.如权利要求4所述的方法,其特征在于,所述的Ag3PO4终浓度为10μg/mL。
6.如权利要求4所述的方法,其特征在于,所述的TMB终浓度为0.2mmol/L。
7.如权利要求4所述的方法,其特征在于,所述的PBS的终浓度为25mmol/L、pH=4。
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