CN111829866A - 一种循环式电化学萃取装置及其应用 - Google Patents
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Abstract
发明了一种电化学萃取装置。该装置可以在溶出伏安模式下完成复杂样品中目标物的电化学萃取或测定。该电化学萃取装置由电化学工作站、电化学萃取池、蠕动泵、输液导管、三通式流量控制阀和储液池等部件构成。随着样品溶液在微流电解池中的循环流动，该工作电极在富集电位下开始富集样品溶液中的目标物。达到所设置的时间后，通过流路切换使优化后的洗脱液在目标物溶出电位下流经该微池，这时电极上的富集物便会释放到微池中、最后经管路进入到洗脱液中完成微萃取。该发明有效地提高了萃取的选择性、萃取率，降低了样品处理成本和萃取产生的环境污染程度。
Description
技术领域
本发明涉及分析检测技术领域，具体涉及一种循环式电化学萃取装置及其使用方法。
背景技术
目前样品萃取的方法大多需要昂贵的仪器[1～3]、操作过程复杂繁琐、消耗长，且萃取率低不能满足检测的要求[4～10]。近年来，电化学方法在样品前处理过程的应用有了相关报道[11、12]。所报道的技术是利用电极的富集作用进行萃取，其方法简单有效。但选择性不够，并且也只是将目标物富集到电极表面、不能定量溶出。
发展富集倍数高、准确度和精密度好、简便快速、环境污染小、在线自动化操作的样品前处理技术已成为当今分析化学研究的前沿和热点。本发明集分子印迹、微萃取与电化学富集方法的优势，将选择性萃取电极与可交替进行富集/洗脱的循环式电解池联用，在溶出循环伏安模式下来完成复杂样品中选择性电化学萃取。这将在有效地解决单纯液、固相萃取法中目标物回收困难的问题，提高萃取的选择性、萃取率，降低样品处理成本和萃取产生的环境污染程度。
研究高效、快速、适于普及和推广的检测方法是保障食品、药品安全的关键，选择性萃取系统是目前最具发展前景的样品前处理方法。目前，灵敏度高、选择性好、简便迅速、价格低廉、适合现场检测的便携式、微型化、商品化的检测仪器目前还为数不多。为此，该发明对有效控制β-肾上腺素能激动剂类药物使用，保障食品、药品安全，具有十分重要的应用价值。
发明内容
本发明基于传统萃取装置和方法中，实验步骤繁琐、灵敏度和精密度不高、样品和试剂消耗量大以及容易产生误差等不足，制备了一种循环式电化学萃取装置。该发明可以应用于在线或即时分析条件下的样品前处理技术。
该装置由电化学工作站、电化学萃取池、蠕动泵、输液导管、三通式流量控制阀和储液池等部件构成。
1 电化学富集流程
样品溶液加入到待萃取溶液瓶3中，经三通式流量控制阀5 ，通过蠕动泵4定量输入到电化学萃取池7中在线性溶出伏安模式下进行动态电化学富集。流出液经8再次返回到3中。此时流体的流经路线是3-4-7-8-3。如此循环往复，直到所设置的富集时间为止。
2萃取电极表面电化学富集物的溶出或洗脱流程
待上述富集过程结束后，在设置的静置时间内将三通阀5换向，使洗脱液2流经5，由蠕动泵4定量输入7中。在所设置的的溶出电位下洗脱，洗脱液再经过三通控制阀8返回到2。洗脱过程流体流经路线是：2-5-4-7-8-2。如此循环往复，直到所设置的富集时间为止。该过程中同时由工作站1即时测定洗脱液中被萃取物的浓度、工作站6记录电化学萃取池中发生氧化还原反应的伏安曲线，当没有峰时停止溶出洗脱。溶出过程亦可实施对萃取物的在线含量测定。
3萃取过程的电化学实验条件
富集电位：由被萃取物电极电位确定。所设置电位比该萃取物的峰值电位低0.3～0.4V；溶出电位改变区间：0～2V；富集时间：总循环富集时间为1～10 min。具体时间取决于被萃取物质种类、浓度和电性状；静置时间：静置时间为富集与溶出操作的时间间隔设置为：30s～60s，并且每个萃取过程中静置时间保持一致。（静置时间过长峰电流会降低）；电压扫描速率：电压扫描速率以0～50mV/s。
图3示意了电化学富集和溶出过程。图中
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分别为富集和溶出电位。随着样品溶液在微流电解池中的循环流动，该工作电极在富集电位下开始富集样品溶液中的目标物。达到所设置的时间后，通过流路切换使优化后的洗脱液在目标物溶出电位下流经该微池，这时电极上的富集物便会释放到微池中、最后经管路进入到洗脱液中完成微萃取。
选择性萃取机制。如图4所示，在含有干扰物的待测溶液中，各种极性组分都会在静电场向萃取电极表面扩散。但由于该电极表面已经印迹有待测目标物（如廋肉精成分之一的盐酸克伦特罗）的空穴，所以只有分子或离子构型与其表面匹配的极性粒子才能稳定地吸附在电极表面、进而发生氧化还原反应。对于构型有微小差异的粒子，即使有表面吸附行为、但其稳定性差，很快就会被构型匹配的粒子所替换。从而使该分子印迹萃取电极对目标物具有选择性。
附图说明
图1 循环式电化学萃取装置的萃取过程示意图
1、6-电化学工作站；2-洗脱溶液储备池；3-待萃取溶液储备池；4-蠕动泵；5、8-三通控制阀；7-电化学萃取池；
图2 萃取装置7中的外观示意图；
图3 富集与洗脱过程示意图；
A 在装置7中的电化学富集过程；B 在装置7中的电化学溶出及洗脱过程。图中
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分别为富集和溶出电位；
图4 萃取前盐酸克伦特罗标准品的线性扫描伏安曲线；
图5 第一次溶出后盐酸克伦特罗标准品的线性扫描伏安曲线；
图6 萃取结束时盐酸克伦特罗标准品的线性扫描伏安曲线。
具体实施方式
盐酸克伦特罗标准品溶液配制：取上述标准品10微升、用上述缓冲液定容至10毫升。该测试液初始浓度为1×10-10克/微升。
萃取状态工作站6（图1）的运行模式：线性扫描溶出伏安法。对应的三电极系统为：工作电极-自制萃取电极[13]；辅助电极-铂丝电极；参考电极-银/氯化银电极。电解池体积：100微升。标准品：盐酸克伦特罗（100 μg/mL，0.5 mL）。缓冲溶液：0.1 mol/L的酒石酸钾钠缓冲液（pH 7）。
测定方法工作站运行模式。图1工作站1中的三电极系统为循环伏安法。
三电极系统：工作电极-玻碳电极；辅助电极-铂丝电极；参考电极-银/氯化银电极。
扫描速度100mv/s，最高电位1.5v，最低电位-1.5v，初始电位-1.5v，循环次数1圈。在上述优化条件下所建立的标准曲线方程为：Y=0.00002X+0.0002（R2=0.9734）。
电化学萃取的实验条件与实施方法
萃取的电化学实验条件。电化学工作站运行萃取模式：线性溶出伏安法；富集时间：300秒；富集电位：1v；扫描速度0.5mv/s；起始溶出电位1.0v、终止溶出电位2.0v。
实施步骤：
1）电化学工作站窗口中选择循环伏安模式，在两个体积相同的一个微型电解池中用玻碳电极做工作电极、测定萃取前配制的原溶液-盐酸克伦特罗标准溶液（pH 7酒石酸钾钠缓冲液做溶剂）中的的循环伏安图（如图4所示）并记录峰电流值为2.1826×10-4A/I、换算其在该系统中的测试浓度；
2）将自制的萃取电极置入上述电解池7中，将电化学工作站6设置为：“线性扫描溶出伏安”工作模式。富集时间设置为 5min，在该富集模式下电解池中的盐酸克伦特罗逐渐吸附到萃取电极表面，当到达预设时间后、再将该萃取电极切换到装有空白缓冲溶液的另一个体积相同的微电解池中进行电化学溶出。此时，萃取电极表面被富集的目标物便开始溶出。当溶出曲线接近平稳后，停止扫描。完成了第一次电化学萃取；
3）将步骤2中的工作站6及电极切换成工作站1及其配套电极系统、在循环伏安模式下测定该溶出池的电化学相应曲线（如图5所示）、记录峰电流值。完成第一次萃取过程的萃取率测定。
萃取结果：
在电化学循环伏安法和线性溶出伏安法模式下、该电极萃取效果良好。经标准品池（图4）和单次萃取后的电解池的循环伏安曲线（图5）对比表明，单次萃取前微池与溶出池后微池的峰电流有明显改变，其溶出池浓度是萃取前初使浓度的60 %，既单次萃取率为60 %。当累计循环次数5次后，在富集池中经检测已经无峰电流（图6），而溶出池CV曲线类似与萃取前的图4，其峰电流值为2.1846×10-4A/I）。
5次循环后溶出池中盐酸克伦特罗的浓度Ct=9.128×10-11微克/毫升；萃取前标准溶液的浓度测定值Ct=9.239×10-11微克/毫升（与配制浓度相比，该系统的测定相对负误差为7.61 %）。总萃取率计算的结果为：100×Ct/C0=98.79 %。
参考文献
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Claims (3)
1.本发明涉及一种循环式电化学萃取装置，该装置由电化学工作站、电化学萃取池、蠕动泵、输液导管、三通式流量控制阀和储液池所构成。
2.根据权利要求1所述的构造方法，其萃取过程的技术特征是：
样品溶液加入到待萃取溶液储备瓶中，经三通式流量控制阀 ，通过蠕动泵定量输入到电化学萃取池中，由电化学工作站在线性溶出伏安模式下进行动态电化学富集，直到所设置的富集时间为止；待上述富集过程结束后，在设置的静置时间内将三通阀换向，使洗脱液经由蠕动泵流入电化学萃取池中；在所设置的的溶出电位下洗脱，其洗脱液再经过三通控制阀返回到洗脱液储液瓶中；该过程中同时由工作站1即时测定洗脱液中被萃取物的浓度、工作站6记录电化学萃取池中发生氧化还原反应的伏安曲线，当没有峰时停止溶出洗脱。
3.根据权利要求2所述的萃取过程特征，其电化学条件的技术特征在于：所设置富集电位比该萃取物的标准电极电位低0.3～0.4V；溶出电位改变区间：0～2V；富集时间：总循环富集时间为1～10 min，具体时间取决于被萃取物质种类、浓度和电性状；静置时间：静置时间为富集与溶出操作的时间间隔设置为：30s～60s，并且每个萃取过程中静置时间保持一致；电压扫描速率：电压扫描速率以0～50mV/s。
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