CN114989146A - “开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针及其制备方法和应用 - Google Patents
“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及Cu(Ⅱ)和草甘膦检测领域，尤其是一种“开‑关‑开”型连续识别Cu(Ⅱ)和草甘膦的喹啉类荧光探针及其制备方法和应用。本发明制备的喹啉类荧光探针能够高灵敏度的特异性识别Cu(Ⅱ)，是一类“开‑关”型荧光探针；在探针和Cu(Ⅱ)络合物中加入草甘膦，呈现明显的荧光恢复，不受其它有机磷农药、金属离子和阴离子的干扰，能够高灵敏性、高选择性的检测草甘膦，实现了草甘膦的痕量检测，又是一类“关‑开”型荧光探针。同时，“开‑关‑开”型喹啉类荧光探针的荧光变化过程中伴随着显著的颜色变化，能够“裸眼”识别并检测Cu(Ⅱ)和草甘膦。这种“开‑关‑开”型连续检测Cu(Ⅱ)和草甘膦的多功能喹啉类荧光探针具有良好的应用前景。
Description
技术领域
本发明属于Cu(Ⅱ)和草甘膦检测领域，尤其涉及一种“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针及其制备方法和应用。
背景技术
Cu(Ⅱ)既是生命体生长发育的必需微量元素，也是重金属污染物之一。地表水中过量的Cu(Ⅱ)不仅会对动植物产生毒害，同时能够通过食物链的富集作用，对人类健康造成严重威胁。我国生活饮用水卫生标准(GB5749-2006)中明确规定饮用水中铜的限量标准为1.0mg/L。因此，实现Cu(Ⅱ)的快速简便的灵敏性检测具有重要的现实意义。
草甘膦(Glyphosate，GLY)是一种广谱非选择性除草剂，由于其对哺乳动物的毒性相对较低、除草活性高，现已成为世界应用最广、生产量最大的除草剂。但是，由于草甘膦的滥用，导致水体中大量的草甘膦残留，严重威胁生态环境和人类健康。研究表明，草甘膦可能会损害中枢神经系统，导致呼吸、心肌及神经肌肉功能障碍等；另外，草甘膦具有致畸作用，对生物的遗传、发育和生殖都有一定的毒副作用。为此，我国生活饮用水卫生标准(GB5749-2006)中明确规定饮用水中草甘膦最大残留量不超过7.0mg/L。目前，已报道的草甘膦检测方法有气相色谱-质谱法、液相色谱-质谱法、酶联免疫吸附测定、毛细管电泳技术、基于量子点的分子印迹聚合物法等。这些方法虽然能够检测草甘膦，但是需要专业的样品处理及设备操作人员，检测费用昂贵。因此，仍缺乏一种简单有效、即用型、低成本的草甘膦识别检测方法。
荧光探针利用荧光性能可以对金属离子、阴离子和小分子进行检测，具有操作简便、灵敏度高、特异性强等优点，并且不需要借助昂贵的仪器，非常适用于实时或原位检测。喹啉类衍生物具有较大的共轭体系和良好的光热稳定性、易修饰性等优点，一直是荧光探针领域研究的热点。目前，报道的喹啉类荧光探针主要用于Zn2+、Cd2+、Cu2+、Hg2+、Fe3+等金属离子检测，以及在F-、CN-、羟基自由基等阴离子及有机小分子的检测；专利CN111925376A公开了喹啉-罗丹明衍生物荧光探针实现了对Cu2+和Hg2+的高灵敏度、高选择性识别；专利CN111620904A公开了基于8-羟基喹啉衍生物荧光探针实现了对F-的识别；专利CN112479998A公开了一种二氢喹啉类荧光探针能够高灵敏度且高选择性的检测羟基自由基。尽管喹啉类衍生物用于构建荧光探针已经得到了广泛应用，但是现有的喹啉类荧光探针主要用于单独检测一种或一类物质的应用，并不能连续检测两种或多种物质。本发明制备的基于喹啉衍生物的荧光探针能够在同一测试条件下实现Cu(Ⅱ)和草甘膦的“开-关-开”型连续检测。
发明内容
为解决上述技术问题，本发明提供了一种“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针及其制备方法和应用，该探针可以实现Cu(Ⅱ)和草甘膦的“开-关-开”型连续检测，并且能够“裸眼”识别并检测Cu(Ⅱ)和草甘膦，具有良好的应用前景。
本发明的技术方案：
“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针，其分子结构为：
所述“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针的制备方法：
氮气气氛下，将催化剂、喹啉-2-甲酰肼和7-(二乙氨基)香豆素-3-甲醛在乙醇中回流5～10h，进行醛胺缩合反应；反应产物过滤干燥得粗品，粗品经N,N-二甲基甲酰胺(DMF)重结晶提纯，即得荧光探针。
优选的，制备方法中催化剂为哌啶、哌嗪或吡咯烷，其中优选哌啶。
上述喹啉类荧光探针作为连续检测Cu(Ⅱ)和草甘膦的“开-关-开”型荧光检测试剂的应用。
本发明的原理：
本发明所制备的喹啉类荧光探针结构中具有较大的共轭体系和刚性共平面，探针自身显示出强烈的荧光，处于荧光“开”状态；当Cu(Ⅱ)存在时，探针与Cu(Ⅱ)络合后，荧光淬灭，处于荧光“关”状态；继续向探针和Cu(Ⅱ)络合体系中加入草甘膦，草甘膦能够夺取探针和Cu(Ⅱ)络合物中的Cu(Ⅱ)，使荧光恢复，处于荧光“开”状态。荧光探针实现了Cu(Ⅱ)和草甘膦的“开-关-开”型连续检测，其可能的响应机理见图1。
本发明的有益效果：
1)本发明制备的喹啉类荧光探针合成过程简单，易于制备。
2)本发明制备的喹啉类荧光探针对铜离子具有良好的选择性，不受其它常见金属离子及阴离子的干扰，在0～7μmol/L范围内，Cu(Ⅱ)浓度与探针荧光强度具有良好的线性关系，Cu(Ⅱ)检出限为3.9×10-8mol/L(即2.5×10-3mg/L)，能够满足我国生活饮用水卫生标准(GB5749-2006)的检测需求，具有较高的灵敏度，实现了Cu(Ⅱ)的痕量检测。
3)本发明制备的喹啉类荧光探针和Cu(Ⅱ)形成络合物后，对草甘膦具有良好的选择性，不受其它有机磷农药、金属离子及阴离子的干扰，在2～12μmol/L范围内,络合物荧光强度与草甘膦浓度具有良好的线性关系，草甘膦检出限为5.6×10-8mol/L(即9.5×10-3mg/L)，能够满足我国生活饮用水卫生标准(GB5749-2006)的检测需求，具有较高的灵敏度，实现了草甘膦的痕量检测。
4)本发明制备的喹啉类荧光探针在同一测试条件下实现了Cu(Ⅱ)和草甘膦的“开-关-开”型连续检测，操作简便。
5)本发明制备的喹啉类荧光探针能够“裸眼”识别并检测Cu(Ⅱ)和草甘膦，实用性强，具有良好的应用前景。
附图说明
图1为探针“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的响应机理；
图2为探针的1H NMR谱图；
图3为探针的13C NMR谱图；
图4为探针与Cu(Ⅱ)的Job’s plot图；
图5为探针和Cu(Ⅱ)络合物与草甘膦的Job’s plot图；
图6为探针对Cu(Ⅱ)的荧光选择性；
图7为共存金属离子及阴离子对探针检测Cu(Ⅱ)的影响(其中1.Cu2+、2.Co2+、3.Zn2 +、4.Ca2+、5.Cr3+、6.K+、7.Ni2+、8.Al3+、9.Fe3+、10.Mg2+、11.Pb2+、12.Na+、13.Sr3+、14.Ce3+、15.Ag+、16.Li+、17.Cd2+、18.Hg2+、19.SO4 2-、20.F-、21.SCN-、22.Br-、23.S2O3 2-、24.H2PO4 -、25.HPO4 2-、26.NO2 -、27.I-、28.HCO3 -、29.CO3 2-、30.Cl-、31.CH3COO-)；
图8为探针在530nm处荧光强度与Cu(Ⅱ)浓度的线性关系图；
图9为自然光下探针溶液颜色随Cu(Ⅱ)浓度的变化图；
图10为探针和Cu(Ⅱ)络合物对草甘膦的荧光选择性；
图11为共存有机磷农药、金属离子及阴离子对探针和Cu(Ⅱ)络合物检测草甘膦的影响(其中1.草甘膦、2.敌百虫、3.亚胺硫磷、4.敌敌畏、5.马拉硫磷、6.氧化乐果、7.乐果、8.灭线磷、9.杀螟硫磷、10.甲基对硫磷、11.对硫磷、12.草铵膦、13.SO4 2-、14.F-、15.SCN-、16.Br-、17.S2O3 2-、18.H2PO4 -、19.HPO4 2-、20.NO2 -、21.I-、22.HCO3 -、23.CO3 2-、24.Cl-、25.CH3COO-、26.Co2+、27.Zn2+、28.Ca2+、29.Cr3+、30.K+、31.Ni2+、32.Al3+、33.Fe3+、34.Mg2+、35.Pb2+、36.Na+、37.Sr3+、38.Ce3+、39.Ag+、40.Li+、41.Cd2+、42.Hg2+)；
图12为探针和Cu(Ⅱ)络合物在530nm处荧光强度与草甘膦浓度的线性关系图；
图13自然光下探针和Cu(Ⅱ)络合物溶液颜色随草甘膦浓度的变化图；
图14为pH对荧光探针“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的影响。
具体实施方式
下面将结合本发明的实施例，对本发明的技术方案进行清楚、完整地描述，显然，所有描述的实施例仅仅是本发明一部分实施例，而不是全部实施例。基于本发明中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其它实施例，都属于本发明的保护范围。
实施例1：本实施例“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针的制备方法：
氮气气氛下，100mL三颈瓶中加入喹啉-2-甲酰肼(0.39g,2.1mmol)、7-(二乙氨基)香豆素-3-甲醛(0.49g,2.0mmol)和无水乙醇50mL，再加入5滴哌啶，进行醛胺缩合反应；回流反应6h，冷却至室温后，过滤，N,N-二甲基甲酰胺(DMF)重结晶，得到荧光探针(0.56g，产率67.47％)。m.p.234.1～236.7℃.1H NMR(300MHz,DMSO-d6)δ:12.37(s,1H),8.77(s,1H),8.61(d,J＝8.5Hz,1H),8.43(s,1H),8.21(dd,J＝8.3,4.5Hz,2H),8.12(d,J＝8.1Hz,1H),7.92(ddd,J＝8.4,6.9,1.3Hz,1H),7.76(ddd,J＝8.0,7.0,1.0Hz,1H),7.69(d,J＝9.0Hz,1H),6.78(dd,J＝9.0,2.3Hz,1H),6.60(d,J＝2.1Hz,1H),3.48(q,J＝7.0Hz,4H),1.15(t,J＝7.0Hz,6H)；13C NMR(75MHz,DMSO-d6)δ:160.85,160.58,156.67,151.41,149.87,146.03,143.96,138.96,138.03,131.02,130.70,129.31,128.94,128.38,128.22,119.16,112.66,109.78,108.12,96.42,44.30,12.43；HRMS(ESI)[M-H]-cald for C24H21N4O3 413.1619,found 413.1628.
实施例2：荧光探针“开-关-开”型连续检测Cu(Ⅱ)和草甘膦响应机理
探针与Cu(Ⅱ)的Job’s plot曲线(图4)表明，在HEPES缓冲溶液(VTHF:V水＝3:7，HEPES10mmol/L，pH＝7.4)中，探针与Cu(Ⅱ)络合比为1:1；探针和Cu(Ⅱ)络合物与草甘膦的Job’s plot曲线(图5)表明，在HEPES缓冲溶液(VTHF:V水＝3:7，HEPES 10mmol/L，pH＝7.4)中，探针和Cu(Ⅱ)络合物与草甘膦作用比为1:1；在草甘膦检测过程中，草甘膦能够夺取探针和Cu(Ⅱ)络合物的Cu(Ⅱ)，每个荧光探针与Cu(Ⅱ)络合物中含有一个Cu(Ⅱ)，并被一分子草甘膦夺去，即草甘膦与Cu(Ⅱ)络合比为1:1。此外，探针自身显示出强烈的荧光，此时处于荧光“开”状态；当存在Cu(Ⅱ)时，探针与Cu(Ⅱ)络合荧光淬灭，此时处于荧光“关”状态；继续加入有机磷农药草甘膦后，草甘膦能够夺取探针与Cu(Ⅱ)络合物中的Cu(Ⅱ)，使荧光恢复，此时处于荧光“开”状态。荧光探针实现了Cu(Ⅱ)和草甘膦的“开-关-开”型连续检测(图1)。
实施例3：荧光探针对Cu(Ⅱ)的选择性
本实施例采用实施例1制备的荧光探针检测其对Cu(Ⅱ)的选择性。用四氢呋喃(THF)/H2O(V:V＝3:7，4-羟乙基哌嗪乙磺酸(HEPES)10mmol/L，pH＝7.4)缓冲溶液，将荧光探针配制成1.0×10-5mol/L储备液。每次取3mL浓度为1.0×10-5mol/L的荧光探针储备液于比色皿中，依次加入10μmol/L的常见金属离子Cu2+、Co2+、Zn2+、Ca2+、Cr3+、K+、Ni2+、Al3+、Fe3+、Mg2+、Pb2+、Na+、Sr3+、Ce3+、Ag+、Li+、Cd2+、Hg2+和常见阴离子SO4 2-、F-、SCN-、Br-、S2O3 2-、H2PO4 -、HPO4 2-、NO2 -、I-、HCO3 -、CO3 2-、Cl-、CH3COO-，在450nm激发光作用下，测量探针的荧光发射光谱，其结果如图6所示。探针中加入Cu(Ⅱ)后，具有明显的荧光猝灭效应，而加入其它离子未能引起明显的荧光变化，探针对Cu(Ⅱ)表现出优异的选择性识别能力。
实施例3：共存金属离子或阴离子对荧光探针检测Cu(Ⅱ)的影响
本实施例采用实施例2制备的荧光探针储备液测定共存金属离子或阴离子对荧光探针检测Cu(Ⅱ)的影响。每次取3mL浓度为1.0×10-5mol/L的荧光探针储备液于比色皿中，依次加入10μmol/L的常见金属离子Cu2+、Co2+、Zn2+、Ca2+、Cr3+、K+、Ni2+、Al3+、Fe3+、Mg2+、Pb2+、Na+、Sr3+、Ce3+、Ag+、Li+、Cd2+、Hg2+和常见阴离子SO4 2-、F-、SCN-、Br-、S2O3 2-、H2PO4 -、HPO4 2-、NO2 -、I-、HCO3 -、CO3 2-、Cl-、CH3COO-后，再加入10μmol/L的Cu(Ⅱ)，在450nm激发光作用下，测量Cu(Ⅱ)加入前后荧光探针在530nm处的荧光发射峰强度值，其结果如图7所示，
表示荧光探针+金属离子或阴离子；
表示荧光探针+金属离子或阴离子+Cu(Ⅱ)。在其它金属离子或阴离子存在下，探针的荧光强度均无明显变化；随后加入Cu(Ⅱ)，探针的荧光强度几乎完全猝灭。探针检测Cu(Ⅱ)具有优异的抗干扰能力。
实施例4：Cu(Ⅱ)浓度对探针荧光发射光谱的影响
本实施例采用实施例2制备的荧光探针储备液测定Cu(Ⅱ)浓度对探针荧光发射光谱的影响。每次取3mL浓度为1.0×10-5mol/L的荧光探针储备液于比色皿中，依次加入0、1.0、2.0……10.0μmol/L的Cu(Ⅱ)，在450nm激发光作用下，测量荧光探针在530nm处的荧光发射峰强度值，其结果如图8所示。Cu(Ⅱ)浓度在0～7μmol/L内，随Cu(Ⅱ)浓度的增大，探针在530nm处荧光发射峰强度值逐渐减小；Cu(Ⅱ)浓度与荧光发射峰强度值具有良好的线性关系，线性方程为：y＝425.8-55.9x，线性相关系数R2＝0.9903。根据检测限的计算公式：检测限＝3σ/k，计算出探针对Cu(Ⅱ)的检测限为3.9×10-8mol/L(即2.5×10-3mg/L)，能够满足我国生活饮用水卫生标准(GB5749-2006)的检测需求。这说明探针具有较高的灵敏度，可实现Cu(Ⅱ)的痕量检测。此外，探针溶液颜色随Cu(Ⅱ)浓度变化显著，能够“裸眼”识别检测Cu(Ⅱ)，见图9。
实施例5：探针和Cu(Ⅱ)络合物对草甘膦选择性
本实施例采用实施例2制备的荧光探针储备液测定探针和Cu(Ⅱ)络合物检测草甘膦的选择性。每次取3mL浓度为1.0×10-5mol/L的荧光探针储备液于比色皿中，加入10μmol/L的Cu(Ⅱ)孵育3～5min后，依次加入10μmol/L的草甘膦、敌百虫、亚胺硫磷、敌敌畏、马拉硫磷、氧化乐果、乐果、灭线磷、杀螟硫磷、甲基对硫磷、对硫磷、草铵膦等有机磷农药、常见阴离子SO4 2-、F-、SCN-、Br-、S2O3 2-、H2PO4 -、HPO4 2-、NO2 -、I-、HCO3 -、CO3 2-、Cl-、CH3COO-及常见金属离子Co2+、Zn2+、Ca2+、Cr3+、K+、Ni2+、Al3+、Fe3+、Mg2+、Pb2+、Na+、Sr3+、Ce3+、Ag+、Li+、Cd2+、Hg2+，在450nm激发光作用下，测量其的荧光发射光谱，其结果如图10所示。探针和Cu(Ⅱ)络合物中加入草甘膦后，呈现显著的荧光增强，而加入其它有机磷农药、阴离子或金属离子未能引起明显的荧光变化，探针和Cu(Ⅱ)络合物对草甘膦表现出优异的选择性识别能力。
实施例6：共存有机磷农药、阴离子、金属离子对探针和Cu(Ⅱ)络合物检测草甘膦的影响
本实施例采用实施例2制备的荧光探针储备液测定共存有机磷农药、阴离子、金属离子对探针和Cu(Ⅱ)络合物检测草甘膦的影响。每次取3mL浓度为1.0×10-5mol/L的荧光探针储备液于比色皿中，加入10μmol/L的Cu(Ⅱ)孵育3～5min后，依次加入10μmol/L的草甘膦、敌百虫、亚胺硫磷、敌敌畏、马拉硫磷、氧化乐果、乐果、灭线磷、杀螟硫磷、甲基对硫磷、对硫磷、草铵膦等有机磷农药、常见阴离子SO4 2-、F-、SCN-、Br-、S2O3 2-、H2PO4 -、HPO4 2-、NO2 -、I-、HCO3 -、CO3 2-、Cl-、CH3COO-及常见金属离子Co2+、Zn2+、Ca2+、Cr3+、K+、Ni2+、Al3+、Fe3+、Mg2+、Pb2+、Na+、Sr3+、Ce3+、Ag+、Li+、Cd2+、Hg2+后，再加入10μmol/L的草甘膦，在450nm激发光作用下，测量草甘膦加入前后探针和Cu(Ⅱ)络合物在530nm处的荧光发射峰强度值，其结果如图11所示，
表示探针和Cu(Ⅱ)络合物+有机磷农药、金属离子或阴离子；
表示探针和Cu(Ⅱ)络合物+有机磷农药、金属离子或阴离子+GLY。在其它有机磷农药、阴离子或金属离子存在下，探针和Cu(Ⅱ)络合物的荧光强度均无明显变化；随后加入草甘膦，探针和Cu(Ⅱ)络合物荧光强度均明显增强。共存有机磷农药、阴离子或金属离子对探针和Cu(Ⅱ)络合物检测草甘膦无明显干扰。
实施例7：草甘膦浓度对探针和Cu(Ⅱ)络合物荧光发射光谱的影响
本实施例采用实施例2制备的荧光探针储备液测定草甘膦浓度对探针和Cu(Ⅱ)络合物荧光发射光谱的影响。每次取3mL浓度为1.0×10-5mol/L的荧光探针储备液于比色皿中，加入10μmol/L的Cu(Ⅱ)孵育3～5min后，依次加入0、1.0、2.0……15.0μmol/L的草甘膦，在450nm激发光作用下，测量探针和Cu(Ⅱ)络合物在530nm处的荧光发射峰强度值，其结果如图12所示。草甘膦浓度在2～12μmol/L内，随草甘膦浓度的增大，探针和Cu(Ⅱ)络合物在530nm处荧光发射峰强度值逐渐增强；草甘膦浓度与荧光发射峰强度值具有良好的线性关系，线性方程为：y＝38.3x-52.7，线性相关系数R2＝0.9962。根据检测限的计算公式：检测限＝3σ/k，计算出探针和Cu(Ⅱ)络合物对草甘膦的检测限为5.6×10-8mol/L(即9.5×10- 3mg/L)，能够满足我国生活饮用水卫生标准(GB5749-2006)的检测需求。这说明探针和Cu(Ⅱ)络合物检测草甘膦具有较高的灵敏度，可实现草甘膦的痕量检测。此外，探针和Cu(Ⅱ)络合物体系颜色随草甘膦浓度变化显著，可“裸眼”识别检测草甘膦，见图13。
实施例8：pH对荧光探针“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的影响
本实施例采用实施例2制备的荧光探针储备液，测试了不同pH对荧光探针“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的影响，如图14所示，■表示荧光探针，▲表示探针+Cu(Ⅱ)，●表示探针+Cu(Ⅱ)+草甘膦。在强酸性条件下，探针中加入Cu(Ⅱ)后无明显的荧光变化，说明探针与Cu(Ⅱ)的配位能力消失；在强碱性条件下，探针的荧光强度明显降低，这可能是由于探针分子结构被破坏导致的。pH在4～10范围内，探针荧光性能稳定，加入Cu(Ⅱ)后具有显著的荧光猝灭，继续加入草甘膦后荧光恢复响应效果较佳。这些结果表明，荧光探针可在弱酸性、中性、弱碱性条件下“开-关-开”型连续检测Cu(Ⅱ)和草甘膦，具有较宽的pH适用范围.
实施例9：荧光探针在实际水样中检测草甘膦
为了考察探针在实际环境中的潜在应用，选取实验室自来水和松花江水(中国哈尔滨)两种水样，并对水样进行预处理：所取水样在转速12000rpm条件下离心10min，用0.45μm过滤器处理过滤，配制浓度分别为：3.0μmol/L、5.0μmol/L、7.0μmol/L、9.0μmol/L、11.0μmol/L的草甘膦溶液。
采用实施例2制备的荧光探针储备液，向荧光探针中加入10μmol/L的Cu(Ⅱ)孵育3～5min后，加入上述不同浓度的草甘膦溶液，在450nm激发光作用下，测量荧光探针在530nm处荧光发射峰强度值，并将其带入如下方程式，计算得到待测草甘膦溶液的浓度。检测结果如表1所示。
y＝38.3x-52.7
其中，x为草甘膦浓度，y为荧光发射峰强度值。
表1荧光探针在实际水样中检测草甘膦
通过表1可见，实际水样中草甘膦的回收率为90.67％～123.33％，相对标准偏差为0.16％～2.82％，这些结果表明本发明制备的荧光探针检测实际水样中的草甘膦具有较高的准确性、较佳的实用性能。
Claims (7)
1.“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针，其特征在于所述荧光探针的分子结构为：
2.根据权利要求1所述的“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针，其特征在于所述荧光探针的制备方法为：
氮气气氛下，将催化剂、喹啉-2-甲酰肼和7-(二乙氨基)香豆素-3-甲醛在乙醇中回流5～10h，进行醛胺缩合反应；反应产物过滤干燥得粗品，粗品经N,N-二甲基甲酰胺(DMF)重结晶提纯，即得荧光探针。
3.根据权利要求2所述的“开-关-开”型连续检测Cu(Ⅱ)和草甘膦的喹啉类荧光探针的制备方法，其特征在于所述催化剂为哌啶、哌嗪或吡咯烷。
4.如权利要求1所述的喹啉类荧光探针作为连续检测Cu(Ⅱ)和草甘膦的“开-关-开”型荧光检测试剂的应用。
5.根据权利要求3所述的荧光探针在连续检测Cu(Ⅱ)和草甘膦中的应用，其特征在于所述荧光探针能够“裸眼”识别并检测Cu(Ⅱ)和草甘膦。
6.根据权利要求3所述的荧光探针在连续检测Cu(Ⅱ)和草甘膦中的应用，其特征在于所述荧光探针检测Cu(Ⅱ)过程中不受其它金属离子Co2+、Zn2+、Ca2+、Cr3+、K+、Ni2+、Al3+、Fe3+、Mg2+、Pb2+、Na+、Sr3+、Ce3+、Ag+、Li+、Cd2+、Hg2+和阴离子SO4 2-、F-、SCN-、Br-、S2O3 2-、H2PO4 -、HPO4 2-、NO2 -、I-、HCO3 -、CO3 2-、Cl-、CH3COO-的干扰。
7.根据权利要求3所述的荧光探针在连续检测Cu(Ⅱ)和草甘膦中的应用，其特征在于所述荧光探针和Cu(Ⅱ)络合物检测草甘膦过程中不受其它有机磷农药敌百虫、亚胺硫磷、敌敌畏、马拉硫磷、氧化乐果、乐果、灭线磷、杀螟硫磷、甲基对硫磷、对硫磷、草铵膦、金属离子Co2+、Zn2+、Ca2+、Cr3+、K+、Ni2+、Al3+、Fe3+、Mg2+、Pb2+、Na+、Sr3+、Ce3+、Ag+、Li+、Cd2+、Hg2+和阴离子SO4 2-、F-、SCN-、Br-、S2O3 2-、H2PO4 -、HPO4 2-、NO2 -、I-、HCO3 -、CO3 2-、Cl-、CH3COO-的干扰。
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