CN115541551A - 一种阴离子功能化离子探针用于百草枯的快速现场检测 - Google Patents
一种阴离子功能化离子探针用于百草枯的快速现场检测 Download PDFInfo
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Abstract
本发明公开了一种阴离子功能化离子探针用于百草枯的快速现场检测,式(I)所示的阴离子功能化离子液体探针[Fluo][P66614]2作为荧光和比色双通道探针,能够快速灵敏地检测实际样品中痕量百草枯,并且具有热稳定性好、环境友好、对百草枯的特异性好等优点,能够在较宽线性范围内对百草枯进行有明显颜色变化的荧光和紫外定量检测;同时,该亲脂性离子液体探针在实际应用中有高回收率,还能组装成便捷可携带的检测纸基,从而实现了百草枯快速、可视化半定量检测,开辟了利用“富集‑检测”策略检测实际复杂样品中离子响应性分析物的新途径;
Description
技术领域
本发明涉及一种基于荧光素类的亲脂性荧光比色离子探针在实际环境和实际样品中对百草枯农药进行快速、灵敏的分析检测。
背景技术
百草枯(PQ)是一种廉价、高效非选择性除草剂,在世界各地的农业和园艺实践中广泛用于杂草控制。百草枯的不当使用不可避免地会造成农产品和生态环境中的过量残留,从而对生态环境以及人类构成巨大的隐患。百草枯对人体毒性极大,可通过皮肤接触、呼吸和消化道吸收,导致神经损伤、多器官衰竭,甚至死亡。基于这些风险,必须严格规定和监测百草枯在农产品和生态环境中的残留。目前,检测农药的方法有很多,主要有气相色谱-质谱、液相色谱-质谱和电化学方法等方法。虽然这些方法是灵敏和准确的,但是这些方法有着检测仪器昂贵、预处理或者分析检测分析步骤繁琐复杂、需要专业的检测技术人员等缺点,不适合低成本和现场分析检测。因此开发一种快速、简便、便携的百草枯实时、现场监测方法对百草枯农药的分析检测有着重要的指导意义。
离子液体作为一种功能材料,已成功应用于各个领域,已被广泛用于气体捕集、溶剂、催化剂和提取等领域,取得了良好的效果。而光学化学传感器具有操作简便、灵敏度高、检测直观等优点,已成为农药分析的首选材料。近年来,由于离子液体具有高度可调性,已显示出其作为荧光探针来检测目标对象,将离子液体应用于荧光比色法从而应用在农药检测方面有着巨大的发展前景。这与传统的荧光光感材料,如有机金属框架和金属纳米团簇等相比对呈现出更好的环境友好和安全性。同时,离子液体的结构稳定、热稳定性优异、生物相容性好,具有高度的可调性,对环境、农药等分析领域有着很大的发展前景。
在本发明中,通过酸碱中和反应设计了一种基于荧光素的阴离子功能化离子液体探针[Fluo][P66614]2(简称FIL),用于百草枯的荧光和比色检测。该探针通过静电吸引和π-π叠加双重作用,在较宽的线性范围内,对百草枯的加入表现出灵敏的绿色荧光猝灭,并且表现出很好的检测限。并且具有良好的选择性和抗干扰能力,能将百草枯与其他20种农药进行区分。同时,通过一步浸染法制备了便携式纸条,并成功应用于各种类型的实际样品,为百草枯现场实时检测提供了方便、有效、可行的策略。
发明内容
本发明提供了一种阴离子功能化离子探针用于百草枯的快速现场检测。本发明涉及的具有大共轭平面和富π电子的阴离子功能化离子液体探针([Fluo][P66614]2)作为荧光和比色双通道探针,具有选择性高、灵敏度高等优点。该探针在百草枯浓度0.1~7.0μM范围内线性良好,检出限为64.0nM(荧光)和0.1μM(比色法),且静电吸引和π-π叠加的双重作用,加入百草枯会表现出灵敏的绿色荧光猝灭,其荧光猝灭反应迅速(<5s)。同时,组装成方便的纸条,实现了百草枯的可视化半定量检测,能够灵敏、快速地检测环境和蔬菜水果中痕量百草枯,对百草枯的分析检测具有重要的现实指导意义。
本发明的技术方案如下:
一种离子液体FIL作为荧光比色探针用于实际样品中百草枯的快速灵敏检测,所述检测的方法如下:
(1)建立标准曲线
在离心管中加入离子液体FIL和不同浓度的百草枯,用乙醇稀释后,在激发光波长为454nm,激发和发射狭缝宽度为5nm的条件下测量荧光光谱,记录荧光强度和峰值位置;以加入百草枯前后的荧光强度变化ΔF为纵坐标,百草枯浓度为横坐标,构建标准曲线;
其中,ΔF=F0-F;F0为加入百草枯之前的荧光强度,F为加入百草枯之后的荧光强度;
(2)实际样品检测
对实际样品进行预处理得到样品溶液,在所得样品溶液中加入离子液体FIL,用乙醇稀释后,在激发光波长为454nm,激发和发射狭缝宽度为5nm的条件下进行荧光光谱数据的采集,之后根据步骤(1)建立的标准曲线,对样品溶液中百草枯的浓度进行定量,进而计算获得实际样品中百草枯的含量;
所述实际样品可以是环境水样、土壤或蔬果样品等。
本发明还提供了一种用于百草枯可视化半定量检测的便携式纸基。所述便携式纸基采用一步浸渍法制备,具体为:
将滤纸浸入2.5×10-5M离子液体FIL的乙醇溶液中10s左右,之后取出在空气中自然风干,即得便携式纸基;该纸基在365nm紫外灯下展现出绿色的荧光。
本发明所述的离子液体FIL的化学式为[Fluo][P66614]2,结构式如式(I)所示:
离子液体FIL的合成方法为:
以无水乙醇为溶剂,将[P66614][OH]与荧光素在50~80℃下搅拌反应6-24h,之后旋转蒸发除去溶剂,在60~80℃下氮气鼓泡干燥,得到棕红色粘性液体产物[Fluo][P66614]2;
所述荧光素与[P66614][OH]的摩尔比为1:2;
所述[P66614][OH]由三己基(十四烷基)氯化膦([P66614][Cl])经过强碱性阴离子交换树脂脱氯处理得到,具体的脱氯处理方法为:将[P66614][Cl]的乙醇溶液加入到装有强碱性阴离子交换树脂的层析柱中,收集流出液即为[P66614][OH]的乙醇溶液。
与现有技术相比,本发明的有益效果在于:
本发明将一种阴离子功能化荧光比色离子液体[Fluo][P66614]2应用于快速、准确定量检测百草枯。该探针在百草枯浓度0.1~7.0μM范围内线性良好,荧光信号和比色双信号的检出限分别为64.0nM和0.1μM。当加入一系列不同浓度的百草枯时,离子液体探针的颜色随着百草枯浓度的增加呈现出从绿色、橙色再到粉色的变化,并且离子液体的绿色荧光在小于5s的时间内发生明显的淬灭现象。同时,[Fluo][P66614]2探针对百草枯农药有着良好的特异性,表现为能够在20种农药中识别检测百草枯。
本发明涉及的[Fluo][P66614]2荧光离子液体有着热稳定性好、不易挥发、对环境污染性小等优点,对百草枯有良好的特异性和较高的灵敏度,能够在较宽范围内实现对百草枯的分析检测,组装成简便可携带的试纸为百草枯的低成本和现场分析提供了重要的指导意义。
附图说明
图1为本发明以[Fluo][P66614]2的荧光强度为纵坐标,波长为横坐标的荧光发射光谱图。
图2为本发明荧光淬灭强度与百草枯浓度(0~1.0μM)的线性校准曲图。
图3为本发明[Fluo][P66614]2溶液中加入不同百草枯浓度(0~100.0μM)后在365nm紫外灯下拍摄的荧光可视化
图4为本发明[Fluo][P66614]2溶液中加入不同百草枯浓度(0~8.0μM)后在日光下拍摄的比色照片。
图5为本发明以[Fluo][P66614]2荧光强度为纵坐标,响应时间为横坐标的曲线图谱。
图6为本发明以[Fluo][P66614]2荧光强度为纵坐标,不同农药的种类为横坐标绘制的柱状图。
图7为本发明在[Fluo][P66614]2的传感试纸检测不同百草枯浓度(0~100.0μM)后在365nm紫外灯下拍摄的荧光变化照片。
图8为本发明不同浓度(1.0×10-4M、1.0×10-5M、1.0×10-6M)下不同种类的农药对试纸条的响应荧光照片(365nm)。
图9为本发明用试验条检测水果番茄中不同农药对试纸条的响应。
具体实施方式
为了更好地理解本发明,下面结合具体实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例,不应理解以下内容是对本发明保护范围的限制。
实施例中所使用的化学试剂和溶剂均为分析纯。
实施例中用到阿拉丁化学有限公司的强碱阴离子交换树脂,型号为717强碱性I型阴离子交换树脂。
激发光波长设置为454nm(λex=454nm),激发和发射狭缝宽度设置为5nm。
实施例1
一种荧光比色离子液体的合成,具体合成方法如下:
(1)[P66614][Cl]的脱氯处理:
将[P66614][Cl]的乙醇溶液缓缓加入到装有强碱性阴离子交换树脂的层析柱中([P66614][Cl]与强碱性阴离子交换树脂的质量比为1:6),收集流出液得到[P66614][OH]的乙醇溶液,通过滴定得到相应的浓度。
(2)荧光比色离子液体[Fluo][P66614]2的合成:
通过一步酸碱中和反应合成了靶向FIL探针。首先,将步骤(1)中通过阴离子交换树脂制备的[P66614]OH乙醇溶液(含[P66614][OH]1.0010g)与称量好的0.3323g荧光素按照2:1的摩尔比加入到单颈烧瓶中,并加入乙醇溶解混合物。混合物在60℃油浴条件下搅拌12小时,随后旋转蒸发除去溶剂,再在80℃氮气鼓泡干燥,得到[Fluo][P66614]2为棕红色粘性液体产物,反应式如下:
实施例2
离子液体作为荧光比色探针用于实际样品中百草枯的快速灵敏检测,具体步骤包括:
(1)探针对百草枯的荧光检测:
在试验系统中,在离心管中加入配置好的0.01M FIL和不同浓度的百草枯,最后用乙醇调节总体积至1.0mL。将混合物混合均匀,然后倒入比色皿中测量它们的荧光光谱。激发光波长设置为454nm(λex=454nm),激发和发射狭缝宽度设置为5nm。记录荧光强度和峰值位置,结果如图1所示。
采用荧光法在最佳条件下对不同浓度的百草枯进行梯度实验可以直观的评价FIL探针对百草枯的灵敏度。在图1中,随着百草枯浓度在0.0~10.0μM范围内增加,荧光猝灭的程度也增加。荧光强度的变化(ΔF=F0-F)与百草枯浓度之间的关系见图2。线性范围(0~7.0×10-6M)的变化分为两段,其中2.5×10-6M处为分界点,线性相关方程分别为ΔF=68.61X+621.4(R2=0.9958)和ΔF=323.1X(R2=0.9974)。图3为0-100μM的百草枯与6.3×10-6M FIL在在365nm紫外线照射的图片。同时,图4所示为[Fluo][P66614]2溶液中加入不同百草枯浓度(0~8.0μM)后在日光下拍摄的比色照片。
(2)[Fluo[P66614]2的响应时间的研究
考虑到百草枯的稳定性和获得最佳的检测性能,将试验pH设置为7.0。随后,研究探针对百草枯的响应时间,如图5所示。在加入百草枯后5s内FIL的荧光猝灭,选择15s为合适的响应时间可以观察到荧光在90s内保持不变,表明探针具有实时检测能力。
(3)[Fluo][P66614]2对百草枯检测的选择性研究
为了评价FIL的选择性,我们通过平行实验测试了19种潜在农药的干扰,在探针溶液中分别加入5.0μM各类农药(百草枯,苄嘧磺隆,多菌灵,高效氟氯氰菊酯,苯草醚,高效氯氰菊酯,五氯硝基苯,三唑磷,溴氰菊酯,毒死蜱,氟磺胺草醚,辛硫磷,丙草胺,乙酰甲胺磷,二嗪磷,丁草胺,乙草胺,丙溴磷,敌敌畏),使用无水乙醇定容至1.0mL后检测荧光强度,以[Fluo][P66614]2荧光强度为纵坐标,不同农药的种类为横坐标绘制的柱状图绘制柱状图证明该探针对百草枯具有出色的选择性,如图6所示。
(4)[Fluo][P66614]2纸基的制备与应用
采用一步浸渍法制备了便携式纸基。通过将直径相同的滤纸浸入2.5×10-5M[Fluo][P66614]2乙醇溶液中10s左右,在空气中自然风干,该纸基在365nm紫外灯下展现出绿色的荧光。将不同浓度的农药溶液滴在试纸表面风干,在365nm紫外灯下试纸条绿色荧光变暗,可以观察到明显的颜色变化,如图7所示。
为检测便捷检测纸基对百草枯有良好的选择性,通过加入6种不同浓度的农药(百草枯、三唑磷、甲基苯磺隆、多菌灵、氟氯氰菊酯、丙烯虫胺)进行试纸条试验,如图8所示,只有百草枯使纸条的荧光颜色变绿,其他农药并没有引起明显的荧光颜色变化。同时,将纸条进一步应用于实际水果番茄样品中,在加入6种不同农药的番茄提取物溶液在试纸条上检测,在图9中可观察到含有百草枯的番茄提取液试条由原来的绿色变为较深的颜色,其他试条基本没有变化。
(5)实际样品中百草枯的检测
将河水和自来水、茶叶、生菜、番茄和土壤作为真实样品,通过加标回收实验测定回收率。对样品进行如下处理,得到样品溶液:
①先将水样在乙醇溶液中稀释10倍,得到待测水样。②取茶叶0.1g,用5.0ml乙醇浸泡,然后超声5min。③取生菜和番茄各取1.0g,切碎,加入10.0ml水。超声处理5min后滤除固体杂质,离心得到提取液。④取1.0g土壤,用10mL乙醇超声浸泡5min,得到提取物。
取100.0μL提取液,加入不同浓度的百草枯,然后加入[Fluo][P66614]2探针液,用乙醇稀释至1.0mL,最终百草枯浓度分别为5.0×10-7M、3.0×10-6M和7.0×10-6M,测定所有样品测试溶液的荧光光谱。结果如表1所示,该探针具有满意的回收率在98~102%之间,相对标准偏差(RSD)小于3.00%。
表1实际样品(河水、自来水、茶叶、生菜、西红柿、土壤)中的加标回收结果
Claims (3)
1.一种离子液体FIL作为荧光比色探针用于实际样品中百草枯的快速灵敏检测,其特征在于,所述检测的方法如下:
(1)建立标准曲线
在离心管中加入离子液体FIL和不同浓度的百草枯,用乙醇稀释后,在激发光波长为454nm,激发和发射狭缝宽度为5nm的条件下测量荧光光谱,记录荧光强度和峰值位置;以加入百草枯前后的荧光强度变化ΔF为纵坐标,百草枯浓度为横坐标,构建标准曲线;
其中,ΔF=F0-F;F0为加入百草枯之前的荧光强度,F为加入百草枯之后的荧光强度;
(2)实际样品检测
对实际样品进行预处理得到样品溶液,在所得样品溶液中加入离子液体FIL,用乙醇稀释后,在激发光波长为454nm,激发和发射狭缝宽度为5nm的条件下进行荧光光谱数据的采集,之后根据步骤(1)建立的标准曲线,对样品溶液中百草枯的浓度进行定量,进而计算获得实际样品中百草枯的含量;
上述检测方法中使用的离子液体FIL的化学式为[Fluo][P66614]2,结构式如式(I)所示:
2.如权利要求1所述的离子液体FIL作为荧光比色探针用于实际样品中百草枯的快速灵敏检测,其特征在于,所述实际样品为环境水样、土壤或蔬果样品。
3.一种用于百草枯可视化半定量检测的便携式纸基,所述便携式纸基按如下方法制备:
将滤纸浸入2.5×10-5M离子液体FIL的乙醇溶液中10s左右,之后取出在空气中自然风干,即得便携式纸基。
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