CN113433180A - 一种对芦丁检测的电化学传感方法 - Google Patents
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Abstract
本发明公开了一种对芦丁检测的电化学传感方法,该方法以磷掺杂分级多孔碳纳米球修饰电极作为工作电极,对芦丁检测。磷掺杂分级多孔碳纳米球是以β‑环糊精为碳源,通过水热法结合磷酸活化合成。磷掺杂分级多孔碳纳米球修饰玻碳电极进行电化学检测,修饰电极芦丁显示出良好的电催化活性和类氧化酶反应,实际检测药品芦丁片的测定时表现出更小的相对标准偏差。本发明制备的传感器具有传感器材料制备成本低、操作简单、快速高效、选择性强和灵敏度高等优点。
Description
技术领域
本发明涉及电化学传感技术领域,特别是一种对芦丁检测的电化学传感方法。
背景技术
芦丁又被称为芸香苷、维生素P,是一种天然的黄酮醇类化合物。芦丁广泛存在于多种野生植物中,是一种重要的野生植物资源。具有多种生理功能,如抗病毒、抗菌、镇痛、抗炎、抗辐射、抗心肌缺氧等,在临床医学上已占有重要地位。由于人们对天然芦丁的需求越来越大,因此对芦丁的检测需求也越来越严格。传统对芦丁的检测方法主要有化学荧光法、分光光度法、毛细管电泳法和高效液相色谱法。然而这些方法都因为仪器价格昂贵、操作步骤复杂而具有一定局限。大多数黄酮类化合物在适当的氧化电位具有电活性,因此电化学检测法更有利于检测这类物质。
黄酮类化合物具有充当抗氧化剂的作用,抗氧化剂在体内对氧自由基进行清除时需要依靠电子转移来完成,其中发生的反应和在电极上产生的氧化还原变化相似。可认为抗氧化活性本质上是一种电活性,这种活性很大程度上取决于氧化/还原电位、电子转移数、电子结构、活化能等电化学特征值。因此电化学分析检测已在黄酮类化合物检测中得到应用Yan等(L Yan,Niu X,Wang W,et al,Nanotechnology Weekly,2016,11:1738-1750.)制备了一种新型修饰电极,将GO和MWCNT纳米复合材料滴涂在碳离子液体电极(CILE)表面,用于芦丁的检测。芦丁浓度在0.08~80.0μmol/L范围内呈正比增长,检出限为0.02μmol/L。Yang等(Yang Haitang,Bingyue Li,Rongjing Cui,et al,Journal of NanoparticleResearch,2017,19(10):354-365.)用聚二烯丙基二甲基氯化铵(PDDA)功能化HCNTs并与AuNPs混合,成功制备了对芦丁检测敏感的AuNPs-PDDA-HCNTs纳米复合材料电化学传感器。在优化条件下,该传感器对芦丁的线性浓度响应范围为0.1~31μmol/L,检出限为81nmol/L。Zhang等(Zhang Bowen,Abdelhadi El-Jaouhari,Xiangrong Wu,et al,Journal ofElectroanalytical Chemistry,2020,877:114632-114639.)用聚乙烯二氧噻吩(PEDOT)与介孔碳(MC)复合,然后采用电沉积的方法引入AgNPs制备了PEDOT-MC/AgNPs复合材料修饰GCE用于检测芦丁。结果表明芦丁浓度在5~500nmol/L与0.5~100μmol/L这两段浓度范围内有较好的线性关系,检测限为3.5nmol/L。这些研究实例表明,电化学检测芦丁是一种非常具有潜力的检测方法,超微量浓度的检测具有很高的灵敏度。但是这些用于检测芦丁的化学修饰电极的原材料大多是贵金属纳米粒子、纳米碳材料和导电聚合材料,不仅价格昂贵、制备步骤也比较复杂。因此选择使用经济实惠的环糊精为碳源材料,用于修饰电极检测实际样品中芦丁含量仍然是一个挑战。
发明内容
本发明针对芦丁的测定、检测限偏高、修饰材料匮乏和价格昂贵这些难题,以及扩展多孔碳纳米球传感器应用途径,发明了一种磷掺杂分级多孔碳纳米球作为修饰材料的对芦丁的电化学传感方法。在本发明中碳源价格低廉获取途径广、制备方法流程简单、操作便捷、修饰电极具有高电催化性能,高效灵敏度和高选择性,适合推广。
本发明提供一种可对芦丁检测的电化学传感方法,其特征在于,该传感器以磷掺杂分级多孔碳纳米球作为修饰电极,包括以下步骤:
步骤1:修饰材料的制备
通过一定质量的β-环糊精为碳源,在一定温度下水热反应一定时间得到前驱体,使用乙醇和水反复离心清洗得到干净产物,干燥后的前驱体和磷酸按一定比例活化,最后在惰性气体保护下的管式炉中煅烧制备磷掺杂分级多孔碳纳米球。
步骤2:修饰电极的制备
磷掺杂分级多孔碳纳米球和超纯水按1mg/mL的比例超声分散后,在玻碳电极上滴涂5μL的分散液于红外干燥箱中烘干制备磷掺杂分级多孔碳纳米球修饰电极。
β-环糊精的质量为0.5~4g。
水热反应温度为433K,反应时间为24h。
前驱体和磷酸的比例为1:2~6,惰性气体为N2。
以磷掺杂分级多孔碳纳米球修饰电极为工作电极,铂丝电极为对电极,参比电极为饱和甘汞电极,组成传统三电极体系,采用磷酸盐缓冲溶液为电解质溶液。
磷酸盐缓冲溶液的pH为2,浓度为0.1M。
利用差分脉冲伏安法待测溶液中芦丁的含量。
本发明这种对芦丁电化学传感方法,具有以下优点:
1.本发明采用的碳源为β-环糊精来自天然植物可再生性强、其制备成本低廉和工艺简单,以及磷酸同时起到活化和掺杂作用。
2.本发明制备的电化学传感器能检测芦丁,而且检测浓度范围较宽,芦丁的检测限分别是8.3nM,并且具有良好的稳定性、重现性和抗干扰性,以及制备的电化学传感器可用于药品中芦丁的分析测定。
附图说明
图1修饰电极在含有10μM芦丁的磷酸盐缓冲溶液(0.1M,pH=2)中的差分脉冲伏安图。
图2磷掺杂分级多孔碳纳米球的扫描电镜图。
图3:磷掺杂分级多孔碳纳米球修饰电极在磷酸盐缓冲溶液(0.1M,pH=2)中的线性扫描伏安图,B:响应电流和浓度(0.01-100μM)的关系,C:响应电流和浓度(0.01-100μM)倒数的关系,D:响应电流和低浓度(0.01-7μM)的线性关系。
图4磷掺杂分级多孔碳纳米球修饰电极检测芦丁的抗干扰情况。
图5磷掺杂分级多孔碳纳米球修饰电极检测芦丁的稳定性。
表1磷掺杂分级多孔碳纳米球修饰电极在药品中芦丁的检测。
具体实施方式
下面结合附图对本发明做进一步的描述,本发明的保护范围不局限于以下所述:
实施例1
一种对芦丁检测的电化学传感方法,包括以下步骤:
步骤1:修饰材料的制备
以2gβ-环糊精溶于20mL超纯水中,超声溶解后,将得到的溶液转移到80mL聚四氟乙烯内衬不锈钢高压釜中,在433K下进行24h的水热处理。自然冷却至室温后,过滤所得的棕色混合物去除杂质,再用超纯水和乙醇反复高速离心清洗得到前驱体,于343K烘箱中干燥。之后在以N2保护下的管式炉中以1073K煅烧4h,278K/min,得到碳球。
步骤2:修饰电极的制备
称取1mg制备的碳球分散于1mL超纯水里,超声10分钟形成均匀分散稳定的混合溶液,取5μL混合溶液滴涂在玻碳电极表面,然后在红外干燥箱中干燥,得到碳球修饰电极。
以碳纳米球修饰电极为工作电极,铂丝电极为对电极,参比电极为饱和甘汞电极,组成传统三电极体系,采用磷酸盐缓冲溶液为电解质溶液,磷酸盐缓冲溶液的pH为2,浓度为0.1M。利用差分脉冲伏安法待测溶液中芦丁的含量。
如图1所示,β-环糊精碳球修饰电极对芦丁表现出比裸电极更好的峰值响应电流,但是由于没有磷酸活化,不能形成多级多孔结构,从而阻碍了电子传递,不利于芦丁的电催化氧化。
实施例2
一种对芦丁检测的电化学传感方法,包括以下步骤:
步骤1:修饰材料的制备
以2gβ-环糊精溶于20mL超纯水中,超声溶解后,将得到的溶液转移到80mL聚四氟乙烯内衬不锈钢高压釜中,在433K下进行24h的水热处理。自然冷却至室温后,过滤所得的棕色混合物去除杂质,再用超纯水和乙醇反复高速离心清洗得到前驱体,于343K烘箱中干燥。之后磷酸活化处理(质量比为磷酸(85%):前驱体=4:1),放入烘箱于373K干燥,最后在以N2保护下的管式炉中以1073K煅烧4h,278K/min,得到磷掺杂分级多孔碳球。
步骤2:修饰电极的制备
称取1mg制备的磷酸活化多孔碳纳米球分散于1mL超纯水里,超声10分钟形成均匀分散稳定的混合溶液,取5μL混合溶液滴涂在玻碳电极表面,然后在红外干燥箱中干燥,得到分级多孔碳纳米球修饰电极。
以磷掺杂分级多孔碳纳米球修饰电极为工作电极,铂丝电极为对电极,参比电极为饱和甘汞电极,组成传统三电极体系,采用磷酸盐缓冲溶液为电解质溶液,磷酸盐缓冲溶液的pH为2,浓度为0.1M。利用差分脉冲伏安法待测溶液中芦丁的含量。
如图1所示,磷酸活化的分级多孔碳球对芦丁具有更好的响应。
该类氧化酶传感器对芦丁的测定如图3A-D:不同浓度芦丁加入磷酸盐缓冲溶液(0.1M,pH=2)中,使用制备的修饰电极,利用DPV对芦丁测定,稳定其中某一个待检测物,随着另一个待检测物浓度的增加,开始响应电流随着浓度的增加呈现线性关系,继续增大浓度时,响应电流逐渐偏移线性,慢慢趋于平缓,并且浓度的倒数和响应峰值电流的倒数呈线性关系,表明制备的传感器具有类氧化酶特性。该传感器分别对芦丁有较宽的检测范围(0.01-7μM)、较高的灵敏度和较低的检测限(8.3nM)。
关于该传感器对芦丁检测的抗干扰性能评估,如图4,制备的传感器对芦丁具有很强的抗干扰性,诸多干扰物质都无明显的电化学响应,并且在有干扰物时的响应电流错误率小于5%。
关于该传感器对芦丁检测的性能评估稳定性评估,利用上述DPV检测方法,在含有5μM芦丁的磷酸盐缓冲溶液(0.1M,pH=2)中,修饰电极对芦丁连续进行30次循环检测。由结果图5可知,本发明制备的电化学传感器的稳定性较好。
使用制备的传感器测定了药片(复方芦丁片)中芦丁的含量,检测分析结果如表1所示,将复方芦丁片1片(每片含芦丁20mg)磨成粉末,用20ml乙醇溶解。将5μL溶解于0.1MPBS缓冲液中,采用标准添加法测定溶液中芦丁的含量。样品溶液中加入1μML芦丁标准溶液,加标回收率分别为102.83%、99.91%、97.00%,说明类氧化酶传感器电化学检测芦丁是可行的。此外,对每种芦丁的浓度进行3次平行检测,不同浓度的RSD分别为1.50%、1.28%和1.02%,说明类氧化酶传感器是可以接受的。
表1
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种对芦丁检测的电化学传感方法,其特征在于,方法以磷掺杂分级多孔碳纳米球修饰电极作为工作电极,对芦丁检测,且电化学传感方法包括以下步骤:
步骤1:修饰材料的制备
通过一定质量的β-环糊精为碳源,在一定温度下水热反应一定时间得到前驱体,使用乙醇和水离心清洗得到,干燥后的前驱体和磷酸按一定比例活化,最后在惰性气体保护下的管式炉中煅烧制备磷掺杂分级多孔碳纳米球;
步骤2:修饰电极的制备
磷掺杂分级多孔碳纳米球和超纯水按1mg/mL的比例超声分散后,在玻碳电极上滴涂5μL的分散液烘干制备磷掺杂分级多孔碳纳米球修饰电极。
2.根据权利要求1所述的一种对芦丁检测的电化学传感方法,其特征在于,所述步骤1中,β-环糊精质量为0.5~4g。
3.根据权利要求1所述的一种对芦丁检测的电化学传感方法,其特征在于,所述步骤1中,水热反应温度为433K,反应时间为24h。
4.根据权利要求1所述的一种对芦丁检测的电化学传感方法,其特征在于,所述步骤1中,前驱体和磷酸的比例为1:2~6,惰性气体为N2。
5.根据权利要求1所述的一种对芦丁检测的电化学传感方法,其特征在于,所述步骤2中,以磷掺杂分级多孔碳纳米球修饰电极为工作电极,铂丝电极为对电极,参比电极为饱和甘汞电极,组成传统三电极体系,采用磷酸盐缓冲溶液为电解质溶液。
6.根据权利要求1所述的一种对芦丁检测的电化学传感方法,其特征在于,所述步骤2中,磷酸盐缓冲溶液的pH为2,浓度为0.1M。
7.根据权利要求1所述的一种对芦丁检测的电化学传感方法,利用差分脉冲伏安法待测溶液中芦丁的含量。
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