CN111790450A - 一种铜基金属有机框架复合化学发光催化剂的制备及应用 - Google Patents
一种铜基金属有机框架复合化学发光催化剂的制备及应用 Download PDFInfo
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 10
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
本发明涉及的是一种铜基金属有机框架复合化学发光催化剂的制备及在化学发光检测甲胎蛋白中的应用技术,属于化学发光传感领域。主要技术特征是:制备金纳米粒子/铜基金属有机框架材料,再通过正负电荷相互作用复合氧化锌纳米粒子,得到氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂;本发明同时提供了一种将氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂应用于化学发光检测甲胎蛋白,结合磁性复合材料、适配体作为识别元件,该检测方法表现出高的选择性和灵敏度,为该方法进一步应用于临床甲胎蛋白的检测提供了理论支撑。
Description
技术领域
本发明涉及的是一种铜基金属有机框架复合化学发光催化剂的制备及在化学发光检测甲胎蛋白中的应用技术,属于化学发光传感领域,具体涉及氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂的制备及在化学发光检测甲胎蛋白中的应用。
背景技术
金属有机框架(MOFs)材料作为新型多孔功能材料之一,其次级构筑单元以及有机配体的类型对MOFs 材料的结构和性质有着显著的影响。过渡金属离子作为构筑MOFs次级构筑单元常用的一类金属离子,能够影响MOFs材料的催化性能、能量存储以及发光性能,尤其是不饱和金属节点与电子对配位显示出的Lewis酸性使MOFs材料作为多相催化剂在催化领域倍受青睐。其中,铜基MOFs材料作为多相催化剂之一已被应用于多种催化反应。在申请号为2017106620336的专利中公开了一种铜基金属有机框架材料的制备方法,该材料的化学分子式为[Cu3(Ddpb)1.5(H2O)3],该材料合成工艺简单、结晶纯度高;并且结构新颖,孔隙率大;具有高效的电催化析氢性能。申请号为2017114245101的专利中公开了一种基于铜基金属有机框架材料的制备方法以及在电催化分解水产氢中的应用技术,该材料的制备方法相对简单,所得到电催化剂具备较好的电解水析氢能力,是一种理想的高性能催化剂材料,可被用于电催化产氢等新能源领域。
化学发光法具有灵敏度高、线性范围宽、背景信号干扰小及操作简便等优点,以化学发光分析法为基础的生物传感器在疾病标志物的检测中也得到了广泛的应用。甲胎蛋白(AFP)是一种糖蛋白,它属于白蛋白家族,主要由胎儿肝细胞及卵黄囊合成。甲胎蛋白在胎儿血液循环中具有较高的浓度,出生后则下降,至生后2~3月甲胎蛋白基本被白蛋白替代,血液中较难检出,故在成人血清中含量极低。甲胎蛋白具有很多重要的生理功能,包括运输功能、作为生长调节因子的双向调节功能、免疫抑制、T淋巴细胞诱导凋亡等。甲胎蛋白与肝癌及多种肿瘤的发生发展密切相关,在多种肿瘤中均可表现出较高浓度,可作为多种肿瘤的阳性检测指标。目前临床上主要作为原发性肝癌的血清标志物,用于原发性肝癌的诊断及疗效监测。本发明旨在制备一种高催化性能的铜基金属有机框架复合化学发光催化剂;将该复合催化剂材料用于化学发光检测甲胎蛋白中,并结合磁性复合材料、适配体作为识别元件,实现对甲胎蛋白的高灵敏、高选择性、准确快速检测,发明了一种检测甲胎蛋白的新方法。
发明内容
本发明的目的之一是提供一种铜基金属有机框架复合化学发光催化剂的制备方法,首先制备金纳米粒子/铜基金属有机框架材料,再通过正负电荷相互作用复合氧化锌纳米粒子,得到氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂。
本发明的目的通过以下技术方案实现:
(1)金纳米粒子/铜基金属有机框架材料的制备:在室温下,向100 mL 0.01 ~ 0.05mol/L的硫酸铜溶液中加入0.2 ~ 0.5 g聚乙烯吡咯烷酮,然后加入25 mL 1.0 ~ 3.0 mol/L氢氧化钠溶液,有蓝色沉淀产生;然后加入25 mL 0.1 ~ 0.5 mol/L抗坏血酸溶液,搅拌反应10 ~ 15 min,沉淀的颜色由蓝变黄再变红;在8000 ~ 10000 rad/min的转速下离心分离3 ~ 5 min,收集沉淀;将沉淀放置于50 ~ 80 ºC的真空干燥箱中干燥8 ~ 12 h,得到中间产物正方体状氧化亚铜;向3 mL 0.1 ~ 0.5 mg/mL上述制备的正方体状氧化亚铜的乙醇溶液中加入3 mL 0.1 ~ 0.5 mmol/L的氯金酸溶液,搅拌反应1 ~ 5 min后,在8000 ~ 10000rad/min的转速下离心分离3 ~ 5 min,收集沉淀;将得到的沉淀分散到10 mL乙醇中,加入3mL 0.1 ~ 0.5 mol/L 均苯三甲酸和3 ~ 5 mL N,N-二甲基甲酰胺,将混合物搅拌反应12 ~24 h,在8000 ~ 10000 rad/min的转速下离心分离3 ~ 5 min,将沉淀放置于50 ~ 80 ºC的真空干燥箱中干燥8 ~ 12 h,得到金纳米粒子/铜基金属有机框架材料;
(2)氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂的制备:将5mL 0.01 ~ 0.05 g/mL的氧化锌纳米粒子分散到20 mL含有10 ~ 20 mmol/L三(羟甲基)胺基甲烷和10 ~ 20 mmol/L 氯化钠的质量分数为0.20%的聚二烯丙基二甲基氯化铵水溶液中,室温下搅拌反应2 ~ 4 h;然后在8000 ~ 10000 rad/min的转速下离心分离3 ~ 5 min,用去离子水离心清洗沉淀3 ~ 5次,得到带正电荷的氧化锌纳米粒子;然后将得到的正电荷的氧化锌纳米粒子分散到25 mL 0.1 ~ 0.5 mg/mL的金纳米粒子/铜基金属有机框架材料分散液中,室温下搅拌反应3 ~ 5 h,得到氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂。
本发明的另一个目的是将氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂应用于化学发光检测甲胎蛋白,互补链DNA修饰的磁性氧化石墨烯通过碱基互补配对作用和适配体修饰的鲁米诺分子连接在一起,形成磁性氧化石墨烯-互补链DNA/适配体-鲁米诺复合材料,将磁性氧化石墨烯-互补链DNA/适配体-鲁米诺复合材料置于甲胎蛋白样品中,室温下孵化1 ~ 2.5 h,使得甲胎蛋白与适配体充分识别和结合,形成甲胎蛋白@适配体-鲁米诺,此时适配体-鲁米诺从磁性氧化石墨烯-互补链DNA表面释放;用磁铁吸附样品液中的磁性氧化石墨烯-互补链DNA,上清液中仅存在被释放下来的甲胎蛋白@适配体-鲁米诺;向上清液中加入5 mL 0.1 ~ 0.5 mg/mL的金纳米粒子/铜基金属有机框架材料分散液,催化鲁米诺-过氧化氢的化学发光反应,产生化学发光I,以此实现对甲胎蛋白的检测。
本发明的优点及效果是:
(1)本发明制备了一种铜基金属有机框架复合化学发光催化剂,氧化锌纳米粒子、金纳米粒子和铜基金属有机框架材料间的协同催化作用显著提高了该复合化学发光催化剂的催化性能,合成可控性强;
(2)本发明制备的一种铜基金属有机框架复合化学发光催化剂,结合磁性复合材料、适配体作为识别元件,用于化学发光检测甲胎蛋白中,该检测方法表现出高的选择性和灵敏度,为该方法进一步应用于临床甲胎蛋白的检测提供了理论支撑;
(3)本发明制备的一种铜基金属有机框架复合化学发光催化剂用于化学发光检测甲胎蛋白中,通过改变适配体的种类,可以实现不同目标物的检测。
具体实施方式
实施例1
(1)金纳米粒子/铜基金属有机框架材料的制备:在室温下,向100 mL 0.01 mol/L的硫酸铜溶液中加入0.2 g聚乙烯吡咯烷酮,然后加入25 mL 1.0 mol/L氢氧化钠溶液,有蓝色沉淀产生;然后加入25 mL 0.1 mol/L抗坏血酸溶液,搅拌反应10 min,沉淀的颜色由蓝变黄再变红;在8000 rad/min的转速下离心分离5 min,收集沉淀;将沉淀放置于60 ºC的真空干燥箱中干燥10 h,得到中间产物正方体状氧化亚铜;向3 mL 0.1 mg/mL上述制备的正方体状氧化亚铜的乙醇溶液中加入3 mL 0.1 mmol/L的氯金酸溶液,搅拌反应1 min后,在8000 rad/min的转速下离心分离5 min,收集沉淀;将得到的沉淀分散到10 mL乙醇中,加入3 mL 0.1 mol/L 均苯三甲酸和3 mL N,N-二甲基甲酰胺,将混合物搅拌反应12 h,在8000rad/min的转速下离心分离5 min,将沉淀放置于60 ºC的真空干燥箱中干燥10 h,得到金纳米粒子/铜基金属有机框架材料;
(2)氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂的制备:将5mL 0.01 g/mL的氧化锌纳米粒子分散到20 mL含有10 mmol/L三(羟甲基)胺基甲烷和10mmol/L 氯化钠的质量分数为0.20%的聚二烯丙基二甲基氯化铵水溶液中,室温下搅拌反应2 h;然后在8000 rad/min的转速下离心分离5 min,用去离子水离心清洗沉淀3次,得到带正电荷的氧化锌纳米粒子;然后将得到的正电荷的氧化锌纳米粒子分散到25 mL 0.1 mg/mL的金纳米粒子/铜基金属有机框架材料分散液中,室温下搅拌反应3 h,得到氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂。
实施例2
(1)金纳米粒子/铜基金属有机框架材料的制备:在室温下,向100 mL 0.02 mol/L的硫酸铜溶液中加入0.3 g聚乙烯吡咯烷酮,然后加入25 mL 2.0 mol/L氢氧化钠溶液,有蓝色沉淀产生;然后加入25 mL 0.25 mol/L抗坏血酸溶液,搅拌反应10 min,沉淀的颜色由蓝变黄再变红;在8000 rad/min的转速下离心分离5 min,收集沉淀;将沉淀放置于80 ºC的真空干燥箱中干燥8 h,得到中间产物正方体状氧化亚铜;向3 mL 0.25 mg/mL上述制备的正方体状氧化亚铜的乙醇溶液中加入3 mL 0.25 mmol/L的氯金酸溶液,搅拌反应2 min后,在8000 rad/min的转速下离心分离5 min,收集沉淀;将得到的沉淀分散到10 mL乙醇中,加入3 mL 0.25 mol/L 均苯三甲酸和4 mL N,N-二甲基甲酰胺,将混合物搅拌反应18 h,在8000rad/min的转速下离心分离5 min,将沉淀放置于80 ºC的真空干燥箱中干燥8 h,得到金纳米粒子/铜基金属有机框架材料;
(2)氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂的制备:将5mL 0.025 g/mL的氧化锌纳米粒子分散到20 mL含有15 mmol/L三(羟甲基)胺基甲烷和15mmol/L 氯化钠的质量分数为0.20%的聚二烯丙基二甲基氯化铵水溶液中,室温下搅拌反应2.5 h;然后在8000 rad/min的转速下离心分离5 min,用去离子水离心清洗沉淀4次,得到带正电荷的氧化锌纳米粒子;然后将得到的正电荷的氧化锌纳米粒子分散到25 mL 0.25mg/mL的金纳米粒子/铜基金属有机框架材料分散液中,室温下搅拌反应4 h,得到氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂。
实施例3
(1)金纳米粒子/铜基金属有机框架材料的制备:在室温下,向100 mL 0.05 mol/L的硫酸铜溶液中加入0.5 g聚乙烯吡咯烷酮,然后加入25 mL 3.0 mol/L氢氧化钠溶液,有蓝色沉淀产生;然后加入25 mL 0.5 mol/L抗坏血酸溶液,搅拌反应15 min,沉淀的颜色由蓝变黄再变红;在10000 rad/min的转速下离心分离3 min,收集沉淀;将沉淀放置于50 ºC的真空干燥箱中干燥12 h,得到中间产物正方体状氧化亚铜;向3 mL 0.5 mg/mL上述制备的正方体状氧化亚铜的乙醇溶液中加入3 mL 0.5 mmol/L的氯金酸溶液,搅拌反应5 min后,在10000 rad/min的转速下离心分离3 min,收集沉淀;将得到的沉淀分散到10 mL乙醇中,加入3 mL 0.5 mol/L 均苯三甲酸和5 mL N,N-二甲基甲酰胺,将混合物搅拌反应24 h,在10000 rad/min的转速下离心分离3 min,将沉淀放置于50 ºC的真空干燥箱中干燥12 h,得到金纳米粒子/铜基金属有机框架材料;
(2)氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂的制备:将5mL 0.05 g/mL的氧化锌纳米粒子分散到20 mL含有20 mmol/L三(羟甲基)胺基甲烷和20mmol/L 氯化钠的质量分数为0.20%的聚二烯丙基二甲基氯化铵水溶液中,室温下搅拌反应4 h;然后在10000 rad/min的转速下离心分离3 min,用去离子水离心清洗沉淀5次,得到带正电荷的氧化锌纳米粒子;然后将得到的正电荷的氧化锌纳米粒子分散到25 mL 0.5 mg/mL的金纳米粒子/铜基金属有机框架材料分散液中,室温下搅拌反应5 h,得到氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂。
实施例4
将氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂应用于化学发光检测甲胎蛋白,互补链DNA修饰的磁性氧化石墨烯通过碱基互补配对作用和适配体修饰的鲁米诺分子连接在一起,形成磁性氧化石墨烯-互补链DNA/适配体-鲁米诺复合材料,将磁性氧化石墨烯-互补链DNA/适配体-鲁米诺复合材料置于甲胎蛋白样品中,室温下孵化2 h,使得甲胎蛋白与适配体充分识别和结合,形成甲胎蛋白@适配体-鲁米诺,此时适配体-鲁米诺从磁性氧化石墨烯-互补链DNA表面释放;用磁铁吸附样品液中的磁性氧化石墨烯-互补链DNA,上清液中仅存在被释放下来的甲胎蛋白@适配体-鲁米诺;向上清液中加入5 mL0.2 mg/mL的金纳米粒子/铜基金属有机框架材料分散液,催化鲁米诺-过氧化氢的化学发光反应,产生化学发光I,以此实现对甲胎蛋白的检测。
Claims (5)
1.一种铜基金属有机框架复合化学发光催化剂的制备方法,其特征是,在于该方法具有以下工艺步骤:
(1)金纳米粒子/铜基金属有机框架材料的制备:在室温下,向100 mL 0.01 ~ 0.05mol/L的硫酸铜溶液中加入0.2 ~ 0.5 g聚乙烯吡咯烷酮,然后加入25 mL 1.0 ~ 3.0 mol/L氢氧化钠溶液,有蓝色沉淀产生;然后加入25 mL 0.1 ~ 0.5 mol/L抗坏血酸溶液,搅拌反应10 ~ 15 min,沉淀的颜色由蓝变黄再变红;在8000 ~ 10000 rad/min的转速下离心分离3 ~ 5 min,收集沉淀;将沉淀放置于50 ~ 80 ºC的真空干燥箱中干燥8 ~ 12 h,得到中间产物正方体状氧化亚铜;向3 mL 0.1 ~ 0.5 mg/mL上述制备的正方体状氧化亚铜的乙醇溶液中加入3 mL 0.1 ~ 0.5 mmol/L的氯金酸溶液,搅拌反应1 ~ 5 min后,在8000 ~ 10000rad/min的转速下离心分离3 ~ 5 min,收集沉淀;将得到的沉淀分散到10 mL乙醇中,加入3mL 0.1 ~ 0.5 mol/L 均苯三甲酸和3 ~ 5 mL N,N-二甲基甲酰胺,将混合物搅拌反应12 ~24 h,在8000 ~ 10000 rad/min的转速下离心分离3 ~ 5 min,将沉淀放置于50 ~ 80 ºC的真空干燥箱中干燥8 ~ 12 h,得到金纳米粒子/铜基金属有机框架材料;
(2)氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂的制备:将5mL 0.01 ~ 0.05 g/mL的氧化锌纳米粒子分散到20 mL含有10 ~ 20 mmol/L三(羟甲基)胺基甲烷和10 ~ 20 mmol/L 氯化钠的质量分数为0.20%的聚二烯丙基二甲基氯化铵水溶液中,室温下搅拌反应2 ~ 4 h;然后在8000 ~ 10000 rad/min的转速下离心分离3 ~ 5 min,用去离子水离心清洗沉淀3 ~ 5次,得到带正电荷的氧化锌纳米粒子;然后将得到的正电荷的氧化锌纳米粒子分散到25 mL 0.1 ~ 0.5 mg/mL的金纳米粒子/铜基金属有机框架材料分散液中,室温下搅拌反应3 ~ 5 h,得到氧化锌纳米粒子/金纳米粒子/铜基金属有机框架复合化学发光催化剂。
2.根据权利要求1所述的一种铜基金属有机框架复合化学发光催化剂的制备方法所制备的复合化学发光催化剂,其特征是:氧化锌纳米粒子、金纳米粒子和铜基金属有机框架材料间的协同催化作用可以提高该复合化学发光催化剂的催化性能,合成可控性强。
3.根据权利要求1所述的一种铜基金属有机框架复合化学发光催化剂的应用,用于化学发光检测甲胎蛋白中。
4.根据权利要求3所述的一种铜基金属有机框架复合化学发光催化剂的应用,其特征是采用流动注射化学发光法,其具体的检测原理如下:
互补链DNA修饰的磁性氧化石墨烯通过碱基互补配对作用和适配体修饰的鲁米诺分子连接在一起,形成磁性氧化石墨烯-互补链DNA/适配体-鲁米诺复合材料;将磁性氧化石墨烯-互补链DNA/适配体-鲁米诺复合材料置于甲胎蛋白样品中,室温下孵化1 ~ 2.5 h,使得甲胎蛋白与适配体充分识别和结合,形成甲胎蛋白@适配体-鲁米诺,此时适配体-鲁米诺从磁性氧化石墨烯-互补链DNA表面释放;用磁铁吸附样品液中的磁性氧化石墨烯-互补链DNA,上清液中仅存在被释放下来的甲胎蛋白@适配体-鲁米诺;向上清液中加入5 mL 0.1 ~0.5 mg/mL的金纳米粒子/铜基金属有机框架材料分散液,催化鲁米诺-过氧化氢的化学发光反应,产生化学发光I,以此实现对甲胎蛋白的检测。
5.根据权利要求3所述的一种铜基金属有机框架复合化学发光催化剂的应用,其特征是:通过改变适配体的种类,可以实现不同目标物的检测。
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