CN115010732B - 一种检测三光气的荧光探针及其合成方法、试纸及其制备方法和应用 - Google Patents
一种检测三光气的荧光探针及其合成方法、试纸及其制备方法和应用 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 3',6' -bis (diethylamino) -2- { [ (E) - [4- (4, 5-dioxaborolan-2-yl) phenyl ] methylene ] amino } -2, 3-dihydro spiro [ isoindole-1, 9' -xanthene ] Chemical group 0.000 claims abstract description 6
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Abstract
本发明提出了一种检测三光气的荧光探针及其合成方法、试纸及其制备方法和应用,一种检测三光气荧光探针,该荧光探针为3',6'‑双(二乙基氨基)‑2‑{[(E)‑[4‑(4,4,5,5‑四甲基‑1,3,2‑二氧杂硼杂环戊‑2‑基)苯基]甲亚基]氨基}‑2,3‑二氢螺[异吲哚‑1,9'‑呫吨]‑3‑酮,本发明以罗丹明(Rhodamine)荧光染料为母体,设计合成了一种检测三光气的有机小分子荧光化合物(式Ⅰ所示化合物),实验发现,含有机小分子荧光探针的乙腈溶液无色,且无荧光;而与三光气反应后则可显示粉红色并且发出强烈的荧光。
Description
技术领域
本发明涉及三光气检测技术领域,特别是指一种检测三光气的荧光探针及其合成方法、试纸及其制备方法和应用。
背景技术
三光气(triphosgene),又名二(三氯甲基)碳酸酯(bis(trichloromethyl)carbonate,BTC),是一种优良的有机合成化合物,可以替代光气、双光气、氯化亚砜、三氯氧磷、三氯化磷、五氯化磷等传统与许多亲核试剂(如醇、醛、胺、酰胺、羧酸、苯酚、羟胺等)反应的酰化试剂。由于三光气有机合成计量准确、反应条件温和、选择性高、收率高、成本低、储运方便、安全可靠等优点,目前已在作为重要的基础化工原料,成功广泛应用于医药、农药、香料、染料和高分子材料等诸多领域。对三光气的检测和及时处理对预防此类安全事故极为关键,但目前用于检测三光气的方法经常需要繁琐的处理步骤、较长的检测时间和庞大笨重的精密仪器,很难实现现场方便快捷地检测三光气。
发明内容
本发明意在克服现有检测技术方法的不足,提出一种检测三光气的荧光探针及其合成方法、试纸及其制备方法和应用。本发明的有机小分子荧光探针试纸的具有合成简单,检测限低,反应灵敏,效率高等优点,能够实现现场快速检测三光气。本发明的有机小分子荧光探针试纸还具有适应范围广的特点,只需小型手持型紫外灯就可以检测出三光气的含量范围,具有广泛的应用前景。
本发明的技术方案是这样实现的:一种检测三光气荧光探针,该荧光探针为3′,6′-双(二乙基氨基)-2-{[(E)-[4-(4,4,5,5-四甲基-1,3,2-二氧杂硼杂环戊-2-基)苯基]甲亚基]氨基}-2,3-二氢螺[异吲哚-1,9′-呫吨]-3-酮,其结构式如式I所示:
本发明提出一种检测三光气荧光探针的合成方法,包含以下步骤:
1)将罗丹明B、水合肼和卡特缩合剂混匀进行反应,得到罗丹明中间体化合物a;
2)在催化剂存在的条件下,将中间体化合物a和4-甲酰基苯硼酸频哪醇酯混匀进行反应,得到式I所示化合物。
优选的,步骤1)中所述罗丹明B、水合肼和卡特缩合剂的投料摩尔比为1∶1~10∶1~5,所述反应的反应温度为10℃~50℃,反应时间为2~6小时,所述反应在有机溶剂中进行,所述有机溶剂选自无水乙醇和二氯甲烷中的一种或两种。有机溶剂的用量以完全溶解反应物为准,无需特别限定其用量。
优选的,所述罗丹明B、水合肼和卡特缩合剂的投料摩尔比为1∶5~10∶3~5,反应温度为室温。
优选的,步骤2)中所述催化剂选择三氟乙酸,所述中间体化合物a、4-甲酰基苯硼酸频哪醇酯的投料摩尔比为1∶0.5~5,反应温度为10℃~60℃,反应时间为8~16小时,反应时避光,所述反应在有机溶剂中进行,所述有机溶剂选择甲醇。甲醇的含水量极低,水的含量不超过0.003%,有机溶剂的用量以完全溶解反应物为准,无需特别限定其用量。
优选的,所述中间体化合物a、4-甲酰基苯硼酸频哪醇酯的投料摩尔比为1∶1。
本发明又提出一种检测三光气的试纸,其包括试剂储备液1和试剂储备液2;所述试剂储备液1为三光气的有机溶剂,所述试剂储备液2包含式I所示荧光探针化合物。
优选的,试剂储备液1和所述试剂储备液2的体积比为1mL∶10μL,
试剂储备液1中,所述三光气有机溶剂为分析纯,所述有机溶剂选自二氯甲烷和乙腈中的至少一种,三光气的浓度为500μg/mL;
所述试剂储备液2中,荧光探针的浓度为0.5~2mM,溶剂为二氯甲烷、或甲醇、或二甲基亚砜,助剂为聚环氧乙烷。
本发明提出一种检测三光气的试纸的制备方法,将试剂储备液2中荧光探针化合物与聚环氧乙烷溶解在二氯甲烷中,并通过搅拌和超声波处理使聚环氧乙烷彻底溶解,与荧光探针混合均匀,将滤纸片放入上述混合溶液中充分浸润,取出放置于干净通风处晾干,得到用于检测三光气的荧光探针试纸;
本发明还提出一种检测三光气的试纸的应用,取一张试纸,将待检测物用试剂储备液1中二氯甲烷或乙腈稀释或溶解,在紫外灯下将前述含待检测物溶液滴加到荧光探针试纸上观察对比,此时,三光气含量越高,荧光强度越强。
本发明的有益效果:
本发明以罗丹明(Rhodamine)荧光染料为母体,设计合成了一种检测三光气的有机小分子荧光化合物(式I所示化合物),实验发现,含有机小分子荧光探针的乙腈溶液无色,且无荧光;而与三光气反应后则可显示粉红色并且发出强烈的荧光。有机小分子荧光探针的乙腈溶液在紫外灯下几乎没有荧光,当在含有三光气的有机溶液逐渐滴入有机小分子荧光探针的乙腈溶液中后,荧光逐渐加强,当有机小分子荧光探针浓度达到5μM时,强度约为原来的100倍以上。因此,利用本发明提供的荧光探针试纸检测三光气现象明显,灵敏度高。本发明的三光气有机小分子荧光探针试纸,以及利用三光气有机小分子荧光探针试纸的检测方法,具有成本低,制备简单,容易操作,易于携带,抗干扰性好,可以达到肉眼识别及实施现场检验的目的,具有较好的应用前景。
试纸的制备过程中聚环氧乙烷的使用,是将荧光探针固定在滤纸上。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。
图1为本发明制备式I所示有机小分子荧光探针的化学反应方程式;
图2为有机小分子荧光探针在乙腈溶液中与不同浓度的三光气反应的荧光光谱;
图3为有机小分子荧光探针用于各种干扰物种反应的荧光发射光谱;
图4为荧光探针试纸在不同浓度三光气(0~100μM)下的荧光探针试纸对比图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和生物材料,如无特殊说明,均可从商业途径获得。
一种检测三光气荧光探针,式I所示3’,6’-双(二乙基氨基)-2-{[(E)-[4-(4,4,5,5-四甲基-1,3,2-二氧杂硼杂环戊-2-基)苯基]甲亚基]氨基}-2,3-二氢螺[异吲哚-1,9’-呫吨]-3-酮。
实施例一
按照图1所示的化学反应流程图进行制备,一种检测三光气荧光探针的合成方法,包含以下步骤:
1)将罗丹明B(364mg,0.76mmol)、水合肼(36.8μL,0.76mmol)、卡特缩合剂BOP(336.3mg,0.76mmol)添加到含有30mL二氯甲烷的50mL圆底烧瓶中充分溶解,常温搅拌2小时,反应温度为室温。反应结束后,通过旋转蒸发器除去溶剂,得到粗产物。然后用少量二氯甲烷溶解粗产物,用硅胶柱层析进行分离纯化,用洗脱剂二氯甲烷/甲醇(v/v,25∶1)进行洗脱,得到罗丹明中间体化合物a(208mg);
2)将得到的中间体化合物a(63.84mg,0.14mmol)和4-甲酰基苯硼酸频哪醇酯(16.25mg,0.07mmol)溶解在15mL甲醇中,并滴加三氟乙酸(7.8μL)。黑暗环境下室温搅拌过夜,反应温度为室温,反应结束后,通过旋转蒸发器去除所有挥发物,得到粗产物。然后用石油醚溶解粗产物,用硅胶柱层析进行分离纯化,用洗脱剂石油醚/乙酸乙酯(v/v,11∶1)进行洗脱,得到式I所示化合物(28mg)。
实施例二
一种检测三光气荧光探针的合成方法,按照图1所示的化学反应流程图进行制备。
操作步骤如下:
1)将罗丹明B(364mg,0.76mmol)、水合肼(368μL,7.6mmol)、卡特缩合剂BOP(1008.9mg,2.28mmol)添加到含有30mL二氯甲烷的50mL圆底烧瓶中充分溶解,常温搅拌2小时,反应温度为室温。反应结束后,通过旋转蒸发器除去溶剂,得到粗产物。然后用少量二氯甲烷溶解粗产物,用硅胶柱层析进行分离纯化,用洗脱剂二氯甲烷/甲醇(v/v,25∶1)进行洗脱,得到罗丹明中间体化合物a(256mg)。
2)将得到的中间体化合物a(63.84mg,0.14mmol)和4-甲酰基苯硼酸频哪醇酯(25.52mg,0.14mmol)溶解在15mL甲醇中,并滴加三氟乙酸(7.8μL)。黑暗环境下室温搅拌过夜,反应温度为室温,反应结束后,通过旋转蒸发器去除所有挥发物,得到粗产物。然后用石油醚溶解粗产物,用硅胶柱层析进行分离纯化,用洗脱剂石油醚/乙酸乙酯(v/v,11∶1)进行洗脱,得到式I所示化合物(42mg)。
实施例三
按照图1所示的化学反应流程图进行制备,一种检测三光气荧光探针的合成方法,包含以下步骤:
1)将罗丹明B(364mg,0.76mmol)、水合肼(368μL,7.6mmol)、卡特缩合剂BOP(1681.5mg,3.8mmol)添加到含有30mL二氯甲烷的50mL圆底烧瓶中充分溶解,常温搅拌2小时,反应温度为室温。反应结束后,通过旋转蒸发器除去溶剂,得到粗产物。然后用少量二氯甲烷溶解粗产物,用硅胶柱层析进行分离纯化,用洗脱剂二氯甲烷/甲醇(v/v,25∶1)进行洗脱,得到罗丹明中间体化合物a(248mg);
2)将得到的中间体化合物a(63.84mg,0.14mmol)和4-甲酰基苯硼酸频哪醇酯(162.46mg,0.7mmol)溶解在15mL甲醇中,并滴加三氟乙酸(7.8μL)。黑暗环境下室温搅拌过夜,反应温度为室温,反应结束后,通过旋转蒸发器去除所有挥发物,得到粗产物。然后用石油醚溶解粗产物,用硅胶柱层析进行分离纯化,用洗脱剂石油醚/乙酸乙酯(v/v,11∶1)进行洗脱,得到式I所示化合物(39mg)。
三个实施例制备出的产物的结构表征数据结果如下:
1H NMR(400MHz,298K,CDCl3):δ10.17(s,3H),8.40(d,J=8.7Hz,6H),8.08(d,J=8.8Hz,6H),1.60(s,4H),1.25(s,24H),0.88(s,4H)
13C NMR(101MHz,298K,CDCl3):δ153.05,148.96,146.59,137.87,134.64,133.41,128.26,128.00,126.72,123.43,108.05,105.92,97.88,83.81,77.34,77.02,76.70,44.32,31.94,29.71,29.67,29.37,24.83,22.70,14.13,12.61.
高分辨质谱(m/z):[M+H]+理论值:C41H47BN4O4:671.3763;实测值:671.3727。
由上可知,该产物结构正确,为式I所示的3′,6′-双(二乙基氨基)-2-{[(E)-[4-(4,4,5,5-四甲基-1,3,2-二氧杂硼杂环戊-2-基)苯基]甲亚基]氨基}-2,3-二氢螺[异吲哚-1,9′-呫吨]-3-酮。
式I所示化合物与不同浓度三光气反应的光谱性质
称取6.7mg试剂1,配成10mL二甲基亚砜溶液作为母液(1mM)。
将10μL的上述母液滴加到不同浓度的三光气溶液中,再用乙腈溶液定容到1mL。37℃下反应30min后,测量其紫外可见吸收光谱和荧光发射光谱。荧光发射光谱测定时以550nm去激发;激发和发射的狭缝宽度为10nm;电压400V。
图2为试剂1与0-7μM三光气反应的荧光光谱。
图2结果表明,本发明中的试剂1具有以下特点:
1)探针在溶液中呈无色并且无荧光,但随着三光气的加入,该探针在约558nm处产生吸收,并在581nm处产生红色荧光;
2)紫外可见吸收的强度和荧光强度随三光气浓度的增加而增加;
3)使用10μM的试剂1时,荧光增强与三光气的浓度在0.6-1.6μM范围内呈线性关系。
式I所示化合物与其他物种反应情况
在10μM的试剂1溶液中分别加入10μM各种物质:金属离子(Bi3+,Fe3+,Pd2+,Zn2+,Ag+,Zn2+,Cd2+,Sr2+,Ca2+,Cr3+,Ni2+,Mg2+,Cu2+,K+,Hg2+),葡萄糖,二硫苏糖醇,过氧化苯甲酰,阴离子(I-,HSO3 -),氨基酸(Leu,Ala,Asp,Arg,Ser,GSH,Cys,Hcy),活性氧(HClO,H2O2,·OH)和还原性物质(KI,NADH)和三光气(1μM)。在37℃下反应30min后,测量其荧光发射光谱。荧光发射光谱测定时以550nm去激发;激发和发射的狭缝宽度为10nm;电压400V。
在1mL混合了上述各种物质的溶液中加入10μl的试剂1母液(1mM),再加入三光气使其最终浓度为10μM。
图3为试剂1(5μM)与各种其他物质混合时得到的荧光发射光谱。
实验结果表明,只有三光气可引起试剂1产生明显的光信号响应,证明该试剂对三光气具有高度的选择性,而其他物种的存在不干扰三光气的测定。
有机小分子荧光化合物荧光探针试纸的制备
将5mg有机小分子荧光探针(即式I所示化合物)和250mg聚环氧乙烷(MV=300000)溶解在10mL二氯甲烷中,并通过搅拌和超声波处理使聚环氧乙烷彻底溶解与荧光探针分子混合。将滤纸切成4×4cm,放入溶液中充分浸润5min,取出晾干即制得有机小分子荧光化合物荧光探针试纸。
应用
将实施例4制得的荧光探针试纸12份,放置于15W 253.7nm的手提紫外灯照射下分别滴加三光气浓度为0μM、5μM、10gM、20μM、30μM、40μM、50μM、60μM、70μM、80μM、90μM、100μM的溶液,观察荧光强度。荧光探针试纸在紫外灯的照射下,呈现出不同的荧光强度,该条件下的荧光强度随着待检测的三光气的浓度增加,荧光强度明显增强。说明该荧光探针(即式I所示化合物)能很好的区分出不同的浓度的三光气溶液,结果见图4。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,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 (9)
1.一种检测三光气荧光探针,其特征在于,该荧光探针为3',6'-双(二乙基氨基)-2-{[(E)-[4-(4,4,5,5-四甲基-1,3,2-二氧杂硼杂环戊-2-基)苯基]甲亚基]氨基}-2,3-二氢螺[异吲哚-1,9'-呫吨]-3-酮,其结构式如式Ⅰ所示:
2.一种如权利要求1所述的检测三光气荧光探针的合成方法,其特征在于:包含以下步骤:
1)将罗丹明B、水合肼和卡特缩合剂混匀进行反应,得到罗丹明中间体化合物a;
2)在催化剂存在的条件下,将中间体化合物a和4-甲酰基苯硼酸频哪醇酯混匀进行反应,得到式Ⅰ所示化合物。
3.如权利要求2所述的一种检测三光气的荧光探针的合成方法,其特征在于:步骤1)中所述罗丹明B、水合肼和卡特缩合剂的投料摩尔比为1:1~10:1~5,所述反应的反应温度为10℃~50℃,反应时间为2~6小时,所述反应在有机溶剂中进行,所述有机溶剂选自无水乙醇和二氯甲烷中的一种或两种。
4.如权利要求2所述的一种检测三光气荧光探针的合成方法,其特征在于:步骤2)中所述催化剂选择三氟乙酸,所述中间体化合物a、4-甲酰基苯硼酸频哪醇酯的投料摩尔比为1:0.5~5,反应温度为10℃~60℃,反应时间为8~16小时,反应时避光,所述反应在有机溶剂中进行,所述有机溶剂选择为甲醇。
5.如权利要求4所述的一种检测三光气荧光探针的合成方法,其特征在于:所述中间体化合物a、4-甲酰基苯硼酸频哪醇酯的投料摩尔比为1:1。
6.一种检测三光气的试纸,其特征在于:其包括试剂储备液1和试剂储备液2;所述试剂储备液1为三光气的有机溶剂,所述试剂储备液2包含权利要求1所述的式Ⅰ所示荧光探针化合物。
7.如权利要求6所述的一种检测三光气的试纸,其特征在于:试剂储备液1和所述试剂储备液2的体积比为1mL:10μL,
试剂储备液1中,所述三光气有机溶剂为分析纯,所述有机溶剂选自二氯甲烷和乙腈中的至少一种,三光气的浓度为500μg/mL;
所述试剂储备液2中,所述荧光探针的浓度为0.5~2mM,溶剂为二氯甲烷、或甲醇、或二甲基亚砜,助剂为聚环氧乙烷。
8.如权利要求6或7中任一项所述的一种检测三光气的试纸的制备方法,其特征在于:将试剂储备液2中荧光探针化合物与聚环氧乙烷溶解在二氯甲烷中,并通过搅拌和超声波处理使聚环氧乙烷彻底溶解,与荧光探针混合均匀,将滤纸片放入上述混合溶液中充分浸润,取出放置于干净通风处晾干,得到用于检测三光气的荧光探针试纸。
9.如权利要求6或7中任一项所述的一种检测三光气的试纸的应用,其特征在于:取一张试纸,将待检测物用试剂储备液1中二氯甲烷或乙腈稀释或溶解,在紫外灯下将前述含待检测物溶液滴加到荧光探针试纸上观察对比,此时,三光气含量越高,荧光强度越强。
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