CN111398381A - 一种识别非电活性氨基酸对映体的电化学识别方法 - Google Patents
一种识别非电活性氨基酸对映体的电化学识别方法 Download PDFInfo
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Abstract
本发明公开了一种识别非电活性氨基酸对映体的电化学识别方法及基于该方法用于识别非电活性天冬氨酸对映体的应用,属于纳米复合材料技术、电催化技术和手性识别技术领域。其主要步骤是配体溶液与醋酸铜和β‑环糊精的混合液共混,室温静置、微波活化制得Cu‑MOF负载β‑CD的纳米晶,制得β‑CD/Cu‑MOF纳米复合催化剂;采用电化学沉积法,制得β‑CD/Cu‑MOF/GCE负载RhB的电极,即RhB@β‑CD/Cu‑MOF/GCE电极,将该电极用于电化学识别非电活性天冬氨酸对映体,工艺简单,反应能耗低,电催化性能和反应稳定性好,具有工业前景。
Description
技术领域
本发明公开了一种识别非电活性氨基酸对映体的电化学识别方法及基于该方法用于识别非电活性天冬氨酸对映体的应用,属于纳米复合材料技术、电催化技术和手性识别技术领域。
背景技术
手性在自然界中普遍存在。很多具有生物活性的化合物(氨基酸、糖、肽、蛋白质、DNA等)和现代药物具有手性。识别和定量检测手性分子对映体在化学、生物和制药科学中非常重要。目前,手性分子的分析方法主要依赖于高效液相色谱、毛细管电泳和气相色谱。然而,由于这些方法具有复杂仪器、手性柱昂贵和分析时间较长的特点。因此,开发廉价且更方便的技术来进行手性识别以及手性分子的定量化分析极为必要。
近年来,电化学手性识别由于具有低成本、快速响应、廉价和小型化的仪器等受到了广泛的关注。例如,Kong等学者自组装了不同电荷状态的二苯丙氨酸和草酸,对色氨酸异构体具有手性识别能力[ Guo, L.; Yang, B.; Wu, D.; Tao, Y.; Kong, Y. Anal.Chem. 2018, 90 (8), 5451−5458.]。Dong等学者[Dong, L.; Zhang, Y.; Duan, X.;Zhu, X.; Sun, H.; Xu, J. Anal. Chem. 2017, 89 (18), 9695−9702.]通过电沉积R /S-2'-羟甲基,为D-/L-色氨酸,D-/L-3,4-二羟基苯丙氨酸和(R)-/(S)-普萘洛尔构建了一个手性电化学识别平台。但是,几乎所有这些方法都只能测量外消旋混合物中手性对映体的百分比,而不能直接实现手性对映体的选择性和定量测定。此外,大多数电化学传感器通常仅涉及一种信号机制,由于某些因素(例如检测环境和误差)可能会干扰检测结果,因此检测结果不够可靠,而具有多个响应信号的电化学传感平台,对手性对映体进行选择性和灵敏的定量测定,使检测结果更具说服力,并有望提供更多的响应信息,并改善传感器的选择性和灵敏度。
发明内容
本发明的技术任务之一是为了弥补现有技术的不足,提供一种β-CD/Cu-MOF纳米复合催化剂的制备方法,该方法室温短时间制备、成本低、能耗少、具有可观的工业前景。
本发明的技术任务之二是提供一种识别非电活性氨基酸对映体的电化学识别方法,即将β-CD/Cu-MOF纳米复合催化剂用于电化学识别非电活性天冬氨酸对映体的应用,该方法灵敏度高、操作简单,催化性能优异且稳定性良好。
为实现上述目的,本发明采用的技术方案如下:
(1)制备β-CD/Cu-MOF纳米复合催化剂
将1.0-1.5 mmol的醋酸铜和0.5-0.8 mmol的β-环糊精β-CD与10-12 mL水共混,180 W超声2-4 min,得到醋酸铜和β-环糊精的混合液;
将1.0-1.5 mmol 的配体H2sala和1.0-1.2 mmol 的LiOH加入到10-12 mL水中,搅拌25-30 min, 得到澄清的配体溶液;
将醋酸铜和β-环糊精的混合液和配体溶液共混,室温下静置5-10 min,离心分离,分别用水和乙醇洗涤三次,85 ℃干燥至恒重,制得Cu-MOF负载β-CD的纳米晶,即β-CD/Cu-MOF纳米晶;
将β-CD/Cu-MOF纳米晶250 W微波炉中活化3 min,制得活化β-CD/Cu-MOF纳米晶,即β-CD/Cu-MOF纳米复合催化剂;
(2)制备RhB@β-CD/Cu-MOF/GCE电极
将6 mg β-CD/Cu-MOF纳米复合催化剂与720 μL水、250 μL乙醇和30 μL Nafion共混,180 W超声30 min后制得β-CD/Cu-MOF悬浊液,取10 μL溶液滴涂在玻碳电极GCE上,室温过夜干燥,制得β-CD/Cu-MOF/GCE电极;
将0.5-0.8 mmol的RhB溶于10 mL pH 7.0、0.1 M的PBS缓冲液中,180 W超声2-4 min,得到含RhB的澄清混合液; 采用电化学工作站三电极体系,β-CD/Cu-MOF/GCE电极为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用线性扫描循环伏安法工艺,在含RhB的澄清混合液中循环扫描50-70圈,将得到的电极水洗3次,室温过夜干燥后,获得β-CD/Cu-MOF/GCE负载RhB的复合电极,即RhB@β-CD/Cu-MOF/GCE电极;
所述RhB,为罗丹明B;
(3)识别非电活性氨基酸
采用pH 7.0、0.1 M的PBS缓冲液,分别配制系列不同浓度的D-Asp和L-Asp标准溶液;
将RhB@β-CD/Cu-MOF/GCE作为工作电极,铂片为辅助电极、甘汞电极为参比电极,采用差分脉冲伏安法,分别测定不同浓度的D-Asp和L-Asp标准溶液的电流值,绘制基于RhB@β-CD/Cu-MOF/GCE电化学传感器的D-Asp和L-Asp对映体工作曲线;
将含D-Asp或L-Asp的样品溶于pH 7.0、0.1 M的PBS缓冲液中,以此缓冲溶液替换D-Asp或L-Asp的标准溶液,仍采用差分脉冲伏安法,测定其电流值,基于工作曲线,获得样品中D-Asp和L-Asp对映体的含量。
步骤(2)所述玻碳电极GCE,是将直径为4 mm的玻碳电极氧化铝抛光,分别用蒸馏水和乙醇180 W超声2-4 min清洗后制得。
步骤(2)中所述线性扫描循环伏安法工艺,扫描电压为-2.5—2.0 V,扫速为100mV/s。
所述Cu-MOF,其基本结构单元为[{Cu(sala)(H2O)}2]·2H2O,是由一个Cu2+,一个配体sala2-,2个主体水分子和2个客体水分子构成;所述sala2-,其构造式如下:
步骤(3)中所述RhB@β-CD/Cu-MOF/GCE电极,是玻碳电极GCE上负载了吸附β-CD 和RhB的Cu-MOF纳米复合膜电极。
RhB的浓度为0.65 mmol时,制得的基于RhB@β-CD/Cu-MOF/GCE电化学传感器在pH7.0、0.1 M的PBS缓冲液中有明显的RhB氧化峰;RhB@β-CD/Cu-MOF/GCE电化学传感器检测D-Asp或L-Asp对映体溶液时,由于L-Asp与β-CD之间的结合力较强,因此与β-CD腔发生竞争性相互作用,RhB被L-Asp取代,这导致RhB的峰值电流降低,并且L-Asp的峰值电流出现,出现RhB的氧化峰和L-Asp氧化峰的双信号,对L-Asp的检测范围为1.0×10-1~2.9×10-12 g/mL,双信号的变化与L-Asp的浓度线性相关;由于D-Asp和β-CD之间的结合力较弱,它不能替代RhB,未出现D-Asp的氧化峰。
本发明有益的技术效果如下:
(1)本发明RhB@β-CD/Cu-MOF/GCE的制备,是配体溶液与醋酸铜和β-环糊精的混合液共混,室温静置、微波活化制得Cu-MOF负载β-CD的纳米晶,即β-CD/Cu-MOF纳米复合催化剂;采用电化学沉积法,制得β-CD/Cu-MOF/GCE负载RhB的电极,即RhB@β-CD/Cu-MOF/GCE电极,该方法室温短时间制备、成本低、能耗少、具有可观的工业前景。
(2)本发明一种识别非电活性氨基酸对映体的电化学识别方法,是将RhB@β-CD/Cu-MOF用于电化学识别非电活性天冬氨酸对映体的应用,由于L-Asp与β-CD之间的结合力较强,因此与β-CD腔发生竞争性相互作用,RhB被L-Asp取代,这导致RhB的峰值电流降低,并且L-Asp的峰值电流出现,出现RhB的氧化峰和L-Asp氧化峰的双信号;由于D-Asp和β-CD之间的结合力较弱,它不能替代RhB,未出现D-Asp的氧化峰。该方法实现了电化学识别非电活性天冬氨酸对映体,该方法灵敏度高、操作简单,催化性能优异且稳定性良好。
具体实施方式
下面结合实施例对本发明作进一步描述,但本发明的保护范围不仅局限于实施例,该领域专业人员对本发明技术方案所作的改变,均应属于本发明的保护范围内。
实施例1 一种识别非电活性氨基酸对映体的电化学识别方法
(1)制备β-CD/Cu-MOF纳米复合催化剂
将1.0 mmol的醋酸铜和0.5 mmol的β-环糊精β-CD与10 mL水共混,180 W超声2 min,得到醋酸铜和β-环糊精的混合液;
将1.0 mmol 的配体H2sala和1.0 mmol 的LiOH加入到10 mL水中,搅拌25 min, 得到澄清的配体溶液;
将醋酸铜和β-环糊精的混合液和配体溶液共混,室温下静置5 min,离心分离,分别用水和乙醇洗涤三次,85 ℃干燥至恒重,制得Cu-MOF负载β-CD的纳米晶,即β-CD/Cu-MOF纳米晶;
将β-CD/Cu-MOF纳米晶250 W微波炉中活化3 min,制得活化β-CD/Cu-MOF纳米晶,即β-CD/Cu-MOF纳米复合催化剂;
(2)制备RhB@β-CD/Cu-MOF/GCE电极
将6 mg β-CD/Cu-MOF纳米复合催化剂与720 μL水、250 μL乙醇和30 μL Nafion共混,180 W超声30 min后制得β-CD/Cu-MOF悬浊液,取10 μL溶液滴涂在玻碳电极GCE上,室温过夜干燥,制得β-CD/Cu-MOF/GCE电极;
将0.5 mmol的RhB溶于10 mL pH 7.0、0.1 M的PBS缓冲液中,180 W超声2 min,得到含RhB的澄清混合液; 采用电化学工作站三电极体系,β-CD/Cu-MOF/GCE电极为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用线性扫描循环伏安法工艺,在含RhB的澄清混合液中循环扫描50圈,将得到的电极水洗3次,室温过夜干燥后,获得β-CD/Cu-MOF/GCE负载RhB的电极,即RhB@β-CD/Cu-MOF/GCE电极;
所述RhB,为罗丹明B;
(3) 识别非电活性氨基酸
采用pH 7.0、0.1 M的PBS缓冲液,分别配制系列不同浓度的D-Asp和L-Asp标准溶液;
将RhB@β-CD/Cu-MOF/GCE作为工作电极,铂片为辅助电极、甘汞电极为参比电极,采用差分脉冲伏安法,分别测定不同浓度的D-Asp和L-Asp标准溶液的电流值,绘制基于RhB@β-CD/Cu-MOF/GCE电化学传感器的D-Asp和L-Asp对映体工作曲线;
将含D-Asp或L-Asp的样品溶于pH 7.0、0.1 M的PBS缓冲液中,以此缓冲溶液替换D-Asp或L-Asp的标准溶液,仍采用差分脉冲伏安法,测定其电流值,基于工作曲线,获得样品中D-Asp和L-Asp对映体的含量。
实施例2 一种识别非电活性氨基酸对映体的电化学识别方法
(1)制备β-CD/Cu-MOF纳米复合催化剂
将1.3 mmol的醋酸铜和0.65 mmol的β-环糊精β-CD与11 mL水共混,180 W超声3 min,得到醋酸铜和β-环糊精的混合液;
将1.3 mmol 的配体H2sala和1.1 mmol 的LiOH加入到11 mL水中,搅拌27 min, 得到澄清的配体溶液;
将醋酸铜和β-环糊精的混合液和配体溶液共混,室温下静置8 min,离心分离,分别用水和乙醇洗涤三次,85 ℃干燥至恒重,制得Cu-MOF负载β-CD的纳米晶,即β-CD/Cu-MOF纳米晶;
将β-CD/Cu-MOF纳米晶250 W微波炉中活化3 min,制得活化β-CD/Cu-MOF纳米晶,即β-CD/Cu-MOF纳米复合催化剂;
(2)制备RhB@β-CD/Cu-MOF/GCE电极
将6 mg β-CD/Cu-MOF纳米复合催化剂与720 μL水、250 μL乙醇和30 μL Nafion共混,180 W超声30 min后制得β-CD/Cu-MOF悬浊液,取10 μL溶液滴涂在玻碳电极GCE上,室温过夜干燥,制得β-CD/Cu-MOF/GCE电极;
将0.65 mmol的RhB溶于10 mL pH 7.0、0.1 M的PBS缓冲液中,180 W超声3 min,得到含RhB的澄清混合液; 采用电化学工作站三电极体系,β-CD/Cu-MOF/GCE电极为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用线性扫描循环伏安法工艺,在含RhB的澄清混合液中循环扫描60圈,将得到的电极水洗3次,室温过夜干燥后,获得β-CD/Cu-MOF/GCE负载RhB的电极,即RhB@β-CD/Cu-MOF/GCE电极;
所述RhB,为罗丹明B;
(3) 识别非电活性氨基酸
采用pH 7.0、0.1 M的PBS缓冲液,分别配制系列不同浓度的D-Asp和L-Asp标准溶液;
将RhB@β-CD/Cu-MOF/GCE作为工作电极,铂片为辅助电极、甘汞电极为参比电极,采用差分脉冲伏安法,分别测定不同浓度的D-Asp和L-Asp标准溶液的电流值,绘制基于RhB@β-CD/Cu-MOF/GCE电化学传感器的D-Asp和L-Asp对映体工作曲线;
将含D-Asp或L-Asp的样品溶于pH 7.0、0.1 M的PBS缓冲液中,以此缓冲溶液替换D-Asp或L-Asp的标准溶液,仍采用差分脉冲伏安法,测定其电流值,基于工作曲线,获得样品中D-Asp和L-Asp对映体的含量。
实施例3 一种识别非电活性氨基酸对映体的电化学识别方法
(1)制备β-CD/Cu-MOF纳米复合催化剂
将1.5 mmol的醋酸铜和0.8 mmol的β-环糊精β-CD与12 mL水共混,180 W超声4 min,得到醋酸铜和β-环糊精的混合液;
将1.5 mmol 的配体H2sala和1.2 mmol 的LiOH加入到12 mL水中,搅拌30 min, 得到澄清的配体溶液;
将醋酸铜和β-环糊精的混合液和配体溶液共混,室温下静置10 min,离心分离,分别用水和乙醇洗涤三次,85 ℃干燥至恒重,制得Cu-MOF负载β-CD的纳米晶,即β-CD/Cu-MOF纳米晶;
将β-CD/Cu-MOF纳米晶250 W微波炉中活化3 min,制得活化β-CD/Cu-MOF纳米晶,即β-CD/Cu-MOF纳米复合催化剂;
(2)制备RhB@β-CD/Cu-MOF/GCE电极
将6 mg β-CD/Cu-MOF纳米复合催化剂与720 μL水、250 μL乙醇和30 μL Nafion共混,180 W超声30 min后制得β-CD/Cu-MOF悬浊液,取10 μL溶液滴涂在玻碳电极GCE上,室温过夜干燥,制得β-CD/Cu-MOF/GCE电极;
将0.8 mmol的RhB溶于10 mL pH 7.0、0.1 M的PBS缓冲液中,180 W超声4 min,得到含RhB的澄清混合液; 采用电化学工作站三电极体系,β-CD/Cu-MOF/GCE电极为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用线性扫描循环伏安法工艺,在含RhB的澄清混合液中循环扫描70圈,将得到的电极水洗3次,室温过夜干燥后,获得β-CD/Cu-MOF/GCE负载RhB的电极,即RhB@β-CD/Cu-MOF/GCE电极;
所述RhB,为罗丹明B;
(3) 识别非电活性氨基酸
采用pH 7.0、0.1 M的PBS缓冲液,分别配制系列不同浓度的D-Asp和L-Asp标准溶液;
将RhB@β-CD/Cu-MOF/GCE作为工作电极,铂片为辅助电极、甘汞电极为参比电极,采用差分脉冲伏安法,分别测定不同浓度的D-Asp和L-Asp标准溶液的电流值,绘制基于RhB@β-CD/Cu-MOF/GCE电化学传感器的D-Asp和L-Asp对映体工作曲线;
将含D-Asp或L-Asp的样品溶于pH 7.0、0.1 M的PBS缓冲液中,以此缓冲溶液替换D-Asp或L-Asp的标准溶液,仍采用差分脉冲伏安法,测定其电流值,基于工作曲线,获得样品中D-Asp和L-Asp对映体的含量。
实施例4 玻碳电极GCE的处理方法
实施例1-3步骤(2)所述玻碳电极GCE,是将直径为4 mm的玻碳电极氧化铝抛光,分别用蒸馏水和乙醇180 W超声2-4 min清洗后制得。
实施例5 实施例1-3步骤(2)中所述线性扫描循环伏安法工艺,扫描电压为-2.5—2.0 V,扫速为100 mV/s。
实施例6 实施例-3所述Cu-MOF,其基本结构单元为[{Cu(sala)(H2O)}2]·2H2O,是由一个Cu2+,一个配体sala2-,2个主体水分子和2个客体水分子构成;所述sala2-,其构造式如下:
实施例7
实施例1-3步骤(3)中所述RhB@β-CD/Cu-MOF/GCE电极,是玻碳电极GCE上负载了吸附β-CD 和RhB的Cu-MOF纳米复合膜电极。
实施例8
RhB的浓度为0.65 mmol时,制得的基于RhB@β-CD/Cu-MOF/GCE电化学传感器在pH 7.0、0.1 M的PBS缓冲液中有明显的RhB氧化峰;RhB@β-CD/Cu-MOF/GCE电化学传感器检测D-Asp或L-Asp对映体溶液时,由于L-Asp与β-CD之间的结合力较强,因此与β-CD腔发生竞争性相互作用,RhB被L-Asp取代,这导致RhB的峰值电流降低,并且L-Asp的峰值电流出现,出现RhB的氧化峰和L-Asp氧化峰的双信号,对L-Asp的检测范围为1.0×10-1~2.9×10-12 g/mL,双信号的变化与L-Asp的浓度线性相关;由于D-Asp和β-CD之间的结合力较弱,它不能替代RhB,未出现D-Asp的氧化峰。
Claims (5)
1.一种识别非电活性氨基酸对映体的电化学识别方法,其特征在于,步骤如下:
(1)制备β-CD/Cu-MOF纳米复合催化剂
将1.0-1.5 mmol的醋酸铜和0.5-0.8 mmol的β-环糊精β-CD与10-12 mL水共混,180 W超声2-4 min,得到醋酸铜和β-环糊精的混合液;
将1.0-1.5 mmol 的配体H2sala和1.0-1.2 mmol 的LiOH加入到10-12 mL水中,搅拌25-30 min, 得到澄清的配体溶液;
将醋酸铜和β-环糊精的混合液和配体溶液共混,室温下静置5-10 min,离心分离,分别用水和乙醇洗涤三次,85 ℃干燥至恒重,制得Cu-MOF负载β-CD的纳米晶,即β-CD/Cu-MOF纳米晶;
将β-CD/Cu-MOF纳米晶250 W微波炉中活化3 min,制得活化β-CD/Cu-MOF纳米晶,即β-CD/Cu-MOF纳米复合催化剂;
(2)制备RhB@β-CD/Cu-MOF/GCE电极
将6 mg β-CD/Cu-MOF纳米复合催化剂与720 μL水、250 μL乙醇和30 μL Nafion共混,180 W超声30 min后制得β-CD/Cu-MOF悬浊液,取10 μL溶液滴涂在玻碳电极GCE上,室温过夜干燥,制得β-CD/Cu-MOF/GCE电极;
将0.5-0.8 mmol的RhB溶于10 mL pH 7.0、0.1 M的PBS缓冲液中,180 W超声2-4 min,得到含RhB的澄清混合液; 采用电化学工作站三电极体系,β-CD/Cu-MOF/GCE电极为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用线性扫描循环伏安法工艺,在含RhB的澄清混合液中循环扫描50-70圈,将得到的电极水洗3次,室温过夜干燥后,获得β-CD/Cu-MOF/GCE负载RhB的复合电极,即RhB@β-CD/Cu-MOF/GCE电极;
所述RhB,为罗丹明B;
(3)识别非电活性氨基酸
采用pH 7.0、0.1 M的PBS缓冲液,分别配制系列不同浓度的D-Asp和L-Asp标准溶液;
将RhB@β-CD/Cu-MOF/GCE作为工作电极,铂片为辅助电极、甘汞电极为参比电极,采用差分脉冲伏安法,分别测定不同浓度的D-Asp和L-Asp标准溶液的电流值,绘制基于RhB@β-CD/Cu-MOF/GCE电化学传感器的D-Asp和L-Asp对映体工作曲线;
将含D-Asp或L-Asp的样品溶于pH 7.0、0.1 M的PBS缓冲液中,以此缓冲溶液替换D-Asp或L-Asp的标准溶液,仍采用差分脉冲伏安法,测定其电流值,基于工作曲线,获得样品中D-Asp和L-Asp对映体的含量。
2.根据权利要求1所述的一种识别非电活性氨基酸的电化学识别方法,其特征在于,步骤(2)所述玻碳电极GCE,是将直径为4 mm的玻碳电极氧化铝抛光,分别用蒸馏水和乙醇180W超声2-4 min清洗后制得。
3.根据权利要求1所述的一种识别非电活性氨基酸的电化学识别的方法,其特征在于,步骤(2)中所述线性扫描循环伏安法工艺,扫描电压为-2.5—2.0 V,扫速为100 mV/s。
5.根据权利要求1所述的一种识别非电活性氨基酸的电化学识别方法,其特征在于,步骤(3)中所述RhB@β-CD/Cu-MOF/GCE电极,是玻碳电极GCE上负载了吸附β-CD 和RhB的Cu-MOF纳米复合膜电极。
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CN114047238B (zh) * | 2021-10-22 | 2024-01-23 | 常州大学 | 一种L-His-ZIF-8手性材料、制备方法及应用 |
CN115015339A (zh) * | 2022-04-24 | 2022-09-06 | 东北林业大学 | 一种基于环糊精基mof手性传感器的制备方法及其对色氨酸对映体的电化学识别的应用 |
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