CN109433227A - CdS@GR-CoOOH纳米复合材料的制备方法、光电化学生物传感器及其应用 - Google Patents
CdS@GR-CoOOH纳米复合材料的制备方法、光电化学生物传感器及其应用 Download PDFInfo
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Abstract
本发明属于纳米新材料技术领域,涉及一种CdS@GR‑CoOOH纳米复合材料的制备方法、光电化学生物传感器及其应用,本发明成功合成了CdS@GR‑CoOOH纳米复合材料,设计了用于监测ALP活性的简单PEC生物分析平台;本发明在GR(石墨烯)纳米膜表面上沉积CdS量子点和CoOOH纳米片,合成的CdS@GR‑CoOOH纳米复合材料具有强光电性,本发明同时提供一种光电化学生物传感器,即在工作电极上修饰有所制得的CdS@GR‑CoOOH纳米复合材料,光电化学生物传感器应用于碱性磷酸酶(ALP)的检测,实现了ALP的快速检测,检测稳定性好,检测限低。
Description
技术领域
本发明属于纳米新材料技术领域,涉及一种CdS@GR-CoOOH纳米复合材料的制备方法、光电化学生物传感器及其应用。
背景技术
碱性磷酸酶(ALP)是一种非特异性磷酸单酯酶,广泛存在于哺乳动物生物的各种组织中,包括肠,肝,骨,肾和胎盘。ALP能够催化核酸,蛋白质和一些小分子的去磷酸化过程。 ALP水平异常与许多疾病密切相关,如骨病,肝炎,糖尿病,阻塞性黄疸,前列腺癌和肝癌。因此,ALP通常被用作临床诊断中最重要的生物标志物之一。因此,非常需要在医学诊断和生物医学研究中建立用于ALP水平和活性测定的特异性和灵敏性探针。迄今为止,许多基于各种技术的方法已被用于检测ALP活性,例如,使用各种荧光,强化学发光,比色,电化学信号已被报道。然而,上述方法通常具有需要样品处理和昂贵仪器的限制。因此,实现ALP活动筛选的敏感,简单和快速平台仍然是一个挑战。
光电化学(PEC)传感技术作为一种新兴的蓬勃发现的检测技术,由于其灵敏度高,响应速度快,成本低,仪器简单等特点而受到越来越多的关注,它结合了光学方法和电化学传感的优点。为了制造典型的PEC系统,光活性材料是必不可少的元素。作为光子-电能转换层,在激发光照射下会发生光活性材料的电荷分离和转移,并产生光电流作为检测信号。作为窄带隙半导体,量子点(QD)已被广泛研究为流行的可见光光电化学纳米材料。由于其有效的光电转换元件和生物分子的独特生物相容性,通常采用CdS QD作为光活性材料,其可以光激发以产生光电流作为读出信号。具体地,氧化石墨烯(GO)是用于促进半导体性质的有用的纳米材料,当加入水合肼后把GO还原为GR(石墨烯),使其化学性质更加稳定,已经证明CdS@GR复合材料减少电子-空穴对的重组以增加PEC信号和改善CdS QD的稳定性的合适策略。
作为新兴的2D纳米材料,羟基氧化钴(CoOOH)纳米薄片已经显示出改善光电化学性能的显着优点。由于2D纳米片的超薄纳米结构,载流子传输距离缩短,有利于快速光电化学反应和减轻电子-空穴复合。同时,快速空穴迁移也可以增强光生电荷的分离。因此,CoOOH纳米片被认为是一种有效的空穴转移材料。然而,CoOOH纳米材料在光电化学中的发展仍处于起步阶段。主要通过使用CoOOH纳米薄片的有效光催化活性进行水解离和有机污染物降解来完成成果。据报道,在钒酸铋(BiVO4)上层状CoOOH的涂层可以有效地使BiVO4的表面俘获状态失活并促进光载流子在半导体/液体界面上的转移,从而实现更高的 PEC效率。
发明内容
本发明目的在于提供一种CdS@GR-CoOOH纳米复合材料的制备方法,在GR(石墨烯)纳米膜表面上沉积CdS量子点和CoOOH纳米片,合成的CdS@GR-CoOOH纳米复合材料具有强光电性,本发明同时提供一种光电化学生物传感器,即在工作电极上修饰有所制得的 CdS@GR-CoOOH纳米复合材料,光电化学生物传感器应用于碱性磷酸酶(ALP)的检测,实现了ALP的快速检测,检测稳定性好,检测限低。
本发明所述的CdS@GR-CoOOH纳米复合材料的制备方法,包括以下步骤:
(1)将GO分散于水中制备分散体溶液,调分散体溶液pH至碱性,投入Cd(NO3)2·4H2O 和CS(NH2)2搅拌得混合液,将混合液进行第一次回流后加入N2H4·H2O,然后进行第二次回流,第二次回流所得产物经离心、洗涤、干燥后得CdS@GR复合材料;
(2)制备NaOH与CoCl2·6H2O的混合水溶液,投入NaClO搅拌并超声处理,继续搅拌并用稀盐酸调体系pH为中性,然后将所得混合液离心、干燥,即得CoOOH纳米片材料;
(3)配制步骤(1)中CdS@GR复合材料的水溶液,配制步骤(2)中CoOOH纳米片材料的水溶液,将CoOOH纳米片材料的水溶液滴加至CdS@GR复合材料的水溶液得 CdS@GR-CoOOH纳米复合材料。
其中:步骤(1)中采用氨水调分散体溶液pH=122,使用氨来获得最大电荷密度,以防止由盐效应引起的GR聚集,这有利于CdS纳米颗粒在石墨烯纳米膜上的均匀分布。
步骤(1)中第一次回流工艺条件为:回流温度为85-90℃,回流时间为2.5-3.5h;步骤 (1)中第二次回流工艺条件为:回流温度为80-90℃,回流时间为4-5h。
步骤(1)中制得的混合液中,Cd(NO3)2·4H2O的浓度为0.006-0.007mol/L,CS(NH2)2浓度为0.024-0.026mol/L。
本发明所述的光电化学生物传感器,包括和电化学工作站连接的工作电极、参比电极 (Ag|AgCl|Cl-)、对电极(铂电极),采用氙灯照射为模拟光源,在工作电极上修饰有所制得的CdS@GR-CoOOH纳米复合材料,上述修饰工作电极的方法为:首先在工作电极表面滴加一层制备的CdS@GR复合材料水溶液,待完全干透前在其表面滴加制备的CoOOH纳米片水溶液并涂匀,然后将表面未完全干透的工作电极浸入Tris-HCl缓冲液中,取出清洗即可;其中:CdS@GR复合材料溶液浓度为0.8-1.2mg·mL-1;CoOOH纳米片水溶液的浓度为0.8-1.2mg·mL-1。
本发明所述光电化学生物传感器的应用,应用于对碱性磷酸酶的灵敏检测。
本发明所述光电化学生物传感器的应用时,将待测含碱性磷酸酶的水溶液滴加至工作电极表面,干燥后采用Tris-HCl缓冲液冲洗,晾干后将工作电极置于含2-磷酸-L-抗坏血酸的电解液中,接通电化学工作站,在氙灯下照射,光电流信号降低,实现对碱性磷酸酶的快速检测,电解液为0.1M的Tris-HCl缓冲液。
本发明在GR晶体的极性表面上选择性地沉积CdS量子点和CoOOH纳米片,合成一种新型的光电化学CdS@GR-CoOOH复合材料,CdS@GR-CoOOH复合材料包括GR和CdS两个分离的光化学系统和CoOOH纳米片电传送系统,由于GR和CdS的激发电子转移,使体系的光催化活性远远超过了单组分系统和双组分系统,提高了光电特性。
本发明光电化学生物传感器的工作原理为,2-磷酸-L-抗坏血酸(AAP)在ALP的催化下产生抗坏血酸(AA)生物还原CoOOH纳米片,使CoOOH纳米片被分解,光电流信号降低,实现快速简易检测碱性磷酸酶,开辟了基于半导体的生物还原电子设备的新路径。
本发明与现有技术相比,具有以下有益效果。
(1)本发明制备时在GR纳米薄膜表面沉积CdS量子点以形成CdS@GR纳米复合材料,使体系的光催化活性超过了单组分系统,并且通过物理吸附的方式将CoOOH纳米片附着在CdS@GR复合材料上,使光催化活性有了进一步的增强,提高了纳米材料的光电特性,本发明成功合成了CdS@GR-CoOOH纳米复合材料;
(2)本发明所制备的新型的用于快速检测碱性磷酸酶的光电化学生物传感器,对碱性磷酸酶的检测稳定性好,检测限低,检测下限为1.5U/L。
总之,基于使用CdS@GR-CoOOH纳米复合材料异质结的信号放大和CoOOH纳米片的酶诱导还原,设计了用于监测ALP活性的简单PEC生物分析平台;实验证实构建的光电化学生物传感器平台简单且经济,并且对于ALP检测具有高灵敏度,选择性和可靠性,更重要的是,CoOOH纳米片增强了光电流信号作为电子受体材料,这项工作是一种新的通用PEC 免疫分析格式的基础,可以扩展用于探测其他感兴趣的生物相互作用。
附图说明
图1、本发明实施例1中所制备的用于检测碱性磷酸酶的光电化学生物传感器的酶促过程示意图;
图2、本发明实施例1中所制备的CdS@GR-CoOOH纳米复合材料中电荷-载流子转移过程的示意图;
图3、(a)实施例1中GO纳米材料扫描电镜图(将实施例1中步骤(1)中GO分散体溶液滴加到硅板上,干燥后制得的GO纳米材料);(b)实施例1中制备的CdS@GR纳米复合材料的扫描电镜图;(c)实施例1中制备的CdS@GR纳米复合材料的透射电镜图;(d)实施例1制备的CoOOH纳米片材料的透射电镜图,插图为CoOOH纳米片高倍透射电镜图;(e) 实施例1中制备的CdS@GR纳米复合材料的X射线衍射谱;(f)实施例1中GO纳米材料和 CdS@GR纳米复合材料傅立叶转换红外线光谱图;
图4、实施例1制备的(a)CoOOH纳米片材料;(b)CdS@GR纳米复合材料的X射线能谱分析图,(b)中插图为相应的元素含量;
图5、实施例1制备的CdS@GR纳米复合材料的X射线光电子能谱分析图:(a)CoOOH纳米片的Co 2pXPS光谱;(b)CdS@GR的C 1sXPS光谱;(c)CdS@GR的O 1sXPS光谱;(d) CdS@GR的S 2pXPS光谱;(e)CdS@GR的Cd 3d和(f)CdS@GR的全XPS光谱;
图6、光电化学生物传感器中,以下工作电极的光电响应示意图,(a)ITO,(b)ITO/CdS@GR,(c)ITO/CdS@GR-CoOOH;(d)未向ITO/CdS@GR-CoOOH表面滴加含ALP溶液的ITO/CdS@GR-CoOOH光电响应曲线,(e)向ITO/CdS@GR-CoOOH表面滴加含ALP 溶液后CoOOH被AA还原后的光电响应曲线。
图7、实施例1制备的光电化学生物传感器用于检测ALP的电流响应(左图),和与之相对应的校正曲线(右图);
图8、实施例1制备的光电化学生物传感器用于检测ALP选择性的对照图;
图9、实施例1制备的光电化学生物传感器用于检测ALP活性孵育时间示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1
(1)将100mg的GO分散在100mL的水中超声处理30分钟获得GO分散体溶液,将氨水(按重量计28%)加入到GO分散体溶液中以将pH调节至12,然后将200mgCd(NO3)2·4H2O 和200mgCS(NH2)2加入到分散体溶液中搅拌得混合液,将混合液转移到250mL圆底烧瓶中在85℃下回流3小时,然后投入20μLN2H4·H2O(85%),在85℃下进行继续回流4.5小时,将回流所得产物,通过离心分离所得的黑色粉末,黑色粉末用水、乙醇依次洗涤,最后在真空烘箱中在60℃下干燥24小时,得到CdS@GR复合材料;
(2)将300μLNaOH溶液(1M)加入到1mL的浓度为10.0mM的CoCl2·6H2O溶液中搅拌的混合水溶液,然后将混合水溶液超声处理1分钟,然后投入50μLNaClO(0.9M)搅拌并超声处理10分钟,继续搅拌下并滴加1.0M HCl溶液将pH调节至7.0,然后将所得混合液离心、干燥,即得CoOOH纳米片材料;
(3)配制步骤(1)中CdS@GR复合材料的水溶液,配制步骤(2)中CoOOH纳米片材料的水溶液,将CoOOH纳米片材料的水溶液滴加至CdS@GR复合材料的水溶液得 CdS@GR-CoOOH纳米复合材料。
本发明所述的光电化学生物传感器,包括和电化学工作站连接的工作电极、参比电极 (Ag|AgCl|Cl-)、对电极(铂电极),采用氙灯照射为模拟光源,工作电极为ITO玻璃片,ITO玻璃片在修饰之前,依次用丙酮、乙醇/NaOH混合溶液(体积比为1:1)超声条件下清洗各15min,导电面向上,对其表面进行亲水化处理,再用去离子水超声清洗15min,分别在 60℃干燥2h,ITO电极的面积为1*1cm2。
本实施例所述的光电化学生物传感器在工作电极上修饰有所制得的CdS@GR-CoOOH纳米复合材料,上述修饰工作电极的方法为:取上述步骤(1)中CdS@GR复合材料制备浓度为1mg·mL-1的CdS@GR复合材料水溶液,取上述步骤)(2)中CoOOH纳米片材料制备浓度为1mg·mL-1的CoOOH纳米片水溶液,首先在工作电极表面滴加一层制备的CdS@GR 复合材料水溶液,待完全干透前在其表面滴加制备的CoOOH纳米片水溶液并涂匀,然后将表面未完全干透的工作电极浸入Tris-HCl缓冲液中,取出清洗即可;其中:CdS@GR复合材料溶液浓度为1mg·mL-1;CoOOH纳米片水溶液的浓度为1mg·mL-1;
本实施例所述光电化学生物传感器对碱性磷酸酶检测时,在修饰ITO玻璃片表面滴加含碱性磷酸酶(ALP)的待测溶液形成ITO/CdS@GR-CoOOH-ALP电极,并在室温下干燥2h以确保ALP的有效固定,干燥后采用0.1M Tris-HCl缓冲液彻底冲洗 ITO/CdS@GR-CoOOH-ALP电极,并在室温下自然干燥,干燥后将ITO/CdS@GR-CoOOH-ALP 电极置于含2-磷酸-L-抗坏血酸(AAP)的电解液(0.1M Tris-HCl缓冲液,pH=7.4)中,在 300W氙灯下照射,根据光电化学生物传感器光电信号变化对碱性磷酸酶进行检测。
如图1所示,基于CdS@GR-CoOOH复合材料的光电化学生物蚀刻建立了一个新的平台用于ALP的超灵敏检测:首先是AAP在ALP的催化作用下,产生AA,然后,通过AA对 CoOOH纳米片的还原,使CoOOH纳米片被分解,光电流信号降低,实现间接检测ALP;
如图2所示,示出了CdS@GR-CoOOH纳米复合材料光催化机理,CdS量子点通过吸附沉积到GR表面,来自CdS纳米颗粒的激发电子可以快速转移到GR纳米薄膜上,通过局域型表面等离子体共振(LSPR)效应促进光生载流子的分离和转移,修饰的CdS纳米颗粒能够增强光吸收,同时,CoOOH纳米片作为空穴转移共催化材料,通过钴离子的价循环实现有效空穴转移,抑制光生载流子的复合,从而提高整体光电催化效率,CdS@GR-CoOOH复合电极的能显著改善了光使用效率;
如图3所示,图3a中,GR纳米材料是一种薄膜状的,具有很大比表面积的薄膜纳米颗粒;图3b和3c,当GR表面沉积了CdS量子点之后,薄膜状的表面有明显的纳米粒子,并且所有的CdS量子点都固定在GR表面,没有游离的CdS量子点;沉积的CdS量子点的粒径在0.336nm左右;图3d所示为CoOOH纳米片,其为正六边形纳米颗粒;图3e是CdS@GR 纳米复合材料XRD测试结果,在2θ=24.8°,26.5°,28.2°,43.7°,47.8°和51.8°处的衍射峰指向(100),(002),(101),(110),(103)和(112)CdS平面(JCPDS No.10-0454),表明样品的成功合成;图3f是GR和CdS@GR纳米复合材料的傅立叶转换红外线光谱图,GR纳米薄膜的亲水基团清晰显示,包括1068cm-1(CO伸缩振动),1225cm-1 (酚醛C-OH伸缩振动),1389cm-1(羧基C-OH伸缩振动),3435cm-1(羟基OH伸缩振动),此外,1626cm-1处的峰可归因于吸附H2O的HOH弯曲带或未氧化石墨域的骨架振动,这与先前报道的结果一致,进一步证明了复合材料的合成;
如图4,显示了从CdS@GR-CoOOH纳米复合材料表面获得的能量色散X射线光谱(EDS)光谱,证实了产品中元素Co,O,C,S和Cd的存在。CoOOH记录Co,O的峰(图 4a),剩余的C,Cd和S峰归因于CdS@GR(图4b)。CdS@GR中S和Cd的原子百分比分别为3.82%和3.03%(图4b插图);
如图5,XPS通常用于识别元素组成和化学状态。图5a显示了CoOOH的曲线拟合Co2p1 /2和2p3/2光谱。曲线拟合的Co 2p3/2光谱在780.2eV处具有主峰,其分配给Co(III)离子而没有任何Co(II)氧化态的杂质和一个较小的峰位于781.7eV以及789.9eV。795.0eV的主峰是Co 2p1/2的光谱。图5b是来自CdS@GR复合物的C 1s的高分辨率XPS光谱。C 1s的C-O(286.7eV)和C-O(288.5eV)的峰可以分别与GR纳米薄膜的羟基和羧基相适应。此外,通过使用碳质C 1s线(284.8eV)作为参考来校准结合能(BE)值。在图5c中,O 1s 的一个峰值为531.8eV,应归入化学吸附的氧物种。此外,图5d和5e分别显示了来自CdS@ GR复合物的Cd3d和S 2p的高分辨率XPS光谱。位于162.0eV和163.2eV的结合能的主双峰(图5d)分别归因于S2-的S 2p3/2和S 2p1/2。在图5e中,Cd 3d5/2和Cd 3d3/2的峰值分别为405.4和411.7eV。最后,如图5f所示,制备的CdS@GR复合物的测量光谱表明存在C,O,Cd和S元素,证明了复合材料的成功合成;
如图6所示,光电流响应是检测CdS@GR-CoOOH电极组装的有效方法,曲线d中不检测ALP时,电解液中AAP不能产生AA还原CoOOH使信号降低,图中曲线b可以看出,ITO/ CdS@GR的电极光电流强度较小,而ITO/CdS@GR-CoOOH电极的电流强度增大(曲线c),这是因为GR来提高CdS量子点的稳定性,减少电子-空穴对的复合,从而增加PEC信号,同时由于2D纳米片的超薄纳米结构,载流子传输距离缩短,有利于快速光电化学反应和减轻电子-空穴复合。同时,快速空穴迁移也可以增强光生电荷的分离,因此CoOOH纳米片沉积在电极上后,光电流强度明显提高,见图中c,光电流响应可证明CdS@GR-CoOOH的合成是成功的,图中e光电流强度明显降低,原因为ALP与电解液中AAP反应产生AA,AA可以还原ITO/CdS@GR-CoOOH电极上的CoOOH纳米片,使工作电极光电流信号降低,证明光电化学生物传感器用于检测碱性磷酸酶是可行的;
如图7所示,配置不同浓度的ALP水溶液,测试光电化学生物传感器对不同浓度ALP的电流响应曲线,看以看出,ALP浓度之间呈现较好的相关性,线性回归方程为A=17.94-0.022CALP(R2=0.9922),在S/N=3时检测下限为1.5U/L。
对于新制备的传感体系,需要在分析实际样品时对目标分析物具有良好的选择性,为了验证新制备的光电化学生物传感器对ALP信号放大的特异性,我们使用兔抗人IgG、牛血清白蛋白、辣根过氧化物酶、β淀粉酶、人血清白蛋白、葡萄糖氧化酶和凝血酶作为干扰物,在相同的条件下,测试该传感器对ALP的选择性。由图8可以看出,与其他几种干扰物相比, ALP具有最好的选择性这表明该生物检测的选择性良好,具有高度特异可用于实际样本的检测。
同时我们对ALP的孵育时间进行优化,如图9所示,随着孵育时间延长,光电流强度逐渐增加,并且在90分钟后,较长时间不会影响光电流强度,因此,选择90分钟作为孵育时间,上述结果证明了使用该PEC系统检测ALP的可行性。
Claims (9)
1.一种CdS@GR-CoOOH纳米复合材料的制备方法,其特征在于:包括以下步骤:
(1)将GO分散于水中制备分散体溶液,调分散体溶液pH至碱性,投入Cd(NO3)2·4H2O和CS(NH2)2搅拌得混合液,将混合液进行第一次回流后加入N2H4·H2O,然后进行第二次回流,第二次回流所得产物经离心、洗涤、干燥后得CdS@GR复合材料;
(2)制备NaOH与CoCl2·6H2O的混合水溶液,投入NaClO搅拌并超声处理,继续搅拌并用稀盐酸调体系pH为中性,然后将所得混合液离心、干燥,即得CoOOH纳米片材料;
(3)配制步骤(1)中CdS@GR复合材料的水溶液,配制步骤(2)中CoOOH纳米片材料的水溶液,将CoOOH纳米片材料的水溶液滴加至CdS@GR复合材料的水溶液得CdS@GR-CoOOH纳米复合材料。
2.根据权利要求1所述的CdS@GR-CoOOH纳米复合材料的制备方法,其特征在于:步骤(1)中采用氨水调分散体溶液pH=12。
3.根据权利要求1所述的CdS@GR-CoOOH纳米复合材料的制备方法,其特征在于:步骤(1)中第一次回流工艺条件为:回流温度为85-90℃,回流时间为2.5-3.5h;步骤(1)中第二次回流工艺条件为:回流温度为80-90℃,回流时间为4-5h。
4.根据权利要求1所述的CdS@GR-CoOOH纳米复合材料的制备方法,其特征在于:步骤(1)中制得的混合液中,Cd(NO3)2·4H2O的浓度为0.006-0.007mol/L,CS(NH2)2浓度为0.024-0.026mol/L。
5.一种光电化学生物传感器,包括和电化学工作站连接的工作电极、参比电极、对电极,其特征在于:在工作电极上修饰有权利要求1-4任一所制得的CdS@GR-CoOOH纳米复合材料。
6.根据权利要求5所述的光电化学生物传感器,其特征在于:修饰工作电极的方法为:首先在工作电极表面滴加一层制备的CdS@GR复合材料水溶液,待完全干透前在其表面滴加制备的CoOOH纳米片水溶液并涂匀,然后将表面未完全干透的工作电极浸入Tris-HCl缓冲液中,取出清洗即可;其中:CdS@GR复合材料溶液浓度为0.8-1.2mg·mL-1;CoOOH纳米片水溶液的浓度为0.8-1.2mg·mL-1。
7.一种光电化学生物传感器的应用,其特征在于:应用于对碱性磷酸酶的灵敏检测。
8.根据权利要求7所述的光电化学生物传感器的应用,其特征在于:将待测含碱性磷酸酶的水溶液滴加至工作电极表面,干燥后采用Tris-HCl缓冲液冲洗,晾干后将工作电极置于含2-磷酸-L-抗坏血酸的电解液中,接通电化学工作站,在氙灯下照射,光电流信号降低,实现对碱性磷酸酶的快速检测。
9.根据权利要求8所述的光电化学生物传感器的应用,其特征在于:电解液为0.1M的Tris-HCl缓冲液。
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