CN108059604A - 一种用于检测水合肼的荧光探针及其制备方法和应用 - Google Patents
一种用于检测水合肼的荧光探针及其制备方法和应用 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C223/00—Compounds containing amino and —CHO groups bound to the same carbon skeleton
- C07C223/06—Compounds containing amino and —CHO groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/04—Preparation of hydrazides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
- C07C243/26—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C243/28—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of a saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
- C07D237/30—Phthalazines
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Abstract
本发明属环境、材料分析检测技术领域,为解决现有检测水合肼的探针灵敏度差、制备方法复杂等问题,提供一种用于检测水合肼的荧光探针及其制备方法和应用,该荧光探针为4‑(二乙氨基)邻苯二甲醛,4‑(二乙氨基)水杨醛与等摩尔量的甲酰肼缩合反应得到N‑[(4‑二乙氨基‑2‑羟基苯基)亚甲基]甲酰肼,再与等摩尔量的四乙酸铅反应制得荧光探针。检测机理是4‑(二乙氨基)邻苯二甲醛与水合肼反应环化生成发蓝色荧光的6‑(二乙氨基)酞嗪,通过荧光强度的变化来实现对水合肼的定量检测。该检测方法具有高的灵敏度和选择性,检测限达1.9nM,不受常见阳离子、阴离子以及含氮类物质的干扰,检测过程简单、快速,检测结果准确度高。
Description
技术领域
本发明属于环境、材料分析检测技术领域,具体涉及一种用于检测水合肼的荧光探针及其制备方法和应用。
背景技术
水合肼,又称水合联氨,在医药、农药、化工合成等领域有广泛的用途,例如可用作热电厂循环水的防腐蚀添加剂、大型锅炉水的脱氧剂、合成发泡剂、偶氮引发剂、以及生产医药和农药的原料等。但是水合肼属高毒类物质,能引起皮肤过敏和全身性中毒,可经过皮肤、吸食进入人体,对血液系统、肝肾功能及中枢神经系统造成严重的伤害。随着现代工业的迅速发展,水合肼污染事件频发,对环境造成的污染和人体造成的危害已经受到广泛关注。我国国家环境标准规定地表水中的水合肼最高允许浓度为0.01 mg/L(GB 3838-2002地表水环境质量标准),而检测地表水中水合肼浓度的国标方法(HJ 674-2013水质 肼和甲基肼的测定 对二甲氨基苯甲醛分光光度法)的最低检测浓度为0.003 mg/L(以肼计),检出限接近标准限值,已不能满足环境监测和环境管理的需求。因此,寻找快速、超灵敏的水合肼检测方法在环境监测领域是迫切需要解决的问题。
水合肼的常用检测方法有:液相色谱法、比色法、离子色谱法、循环伏安法、荧光法、分光光度法等。其中荧光法由于具有操作简单、灵敏度高、能够实时、在线检测等优点,从众多水合肼检测方法中脱颖而出,成为目前水合肼检测方法的研究热点。本领域技术人员利用水合肼强的亲核特性、与卤代烃的亲核取代反应(Org. Lett.,2013,15,5412–5415;Sensors and Actuators B,2017,244,417–424等)、与醛酮的缩合反应(Chem. Sci.,2013,4,4121-4126;Tetrahedron Letters, 2014,55,2695–2699;Analytica Chimica Acta,2008,625,41–46等)以及酯(或者酰胺)的肼解反应(Anal. Chem.,2014,86,4611–4617;Anal. Chem.,2015,87,9101–9107等)设计合成了很多水合肼荧光探针,但是大多数水合肼荧光探针存在制备方法繁琐、操作复杂、反应时间长、有时需要借助掩蔽剂消除干扰等缺点,因此,合成快速、超灵敏、能满足环境监测需求的水合肼荧光探针一直是水合肼检测技术领域的研究热点。
申请号为:201710154914.7,发明名称为:一种可用于检测水合肼的新型荧光探针化合物及其制备方法,该专利公开了可用于检测水合肼的新型荧光探针化合物及其制备方法,以2-氨基吡啶为起始原料,经四步反应得到新型荧光探针化合物2-(4-(咪唑并[1,2-a]吡啶-3-基-乙炔基)苯亚甲基)丙二腈。经研究证明,该荧光探针化合物加入水合肼前后的紫外吸收和荧光光谱变化明显,是一个较为潜力的检测水合肼的荧光探针。但是该化合物制备方法复杂,原料繁杂,且灵敏度差等问题。但是该荧光探针制备方法复杂,而且也没有公开是否具有高的选择性和灵敏度,难以满足复杂环境水样检测的需求。
文献《一种检测水合肼荧光探针的合成与应用》(张琪等,分析测试学报,2017年7月,第36卷第7期,937-940),在该文献中公开了一种具有较高选择性和灵敏度,可在生理条件( pH7.4)下检测水合肼的荧光探针,同时利用核磁共振和高分辨质谱对探针的分子结构进行了表征。基于水合肼进攻探针分子结构中的4-丁酸酯,生成酚氧负离子,同时发生分子内环化反应后生成具有强烈荧光的亚胺香豆素,实现了探针分子对水合肼的检测。光谱学研究表明,当向探针溶液加入水合肼(0~100 mol/L)后,探针溶液在绿色光谱区域(502nm) 呈现一个显著的荧光增强响应(增强至55倍)。并且,探针可以检测相对较低浓度的水合肼,检出限为1.7×10-7mol/L。此外,相对于其他阴离子和亲核试剂,探针对水合肼的识别显示出较高的选择性和灵敏度。探针成功实现了细胞内水合肼的荧光成像,证明其在细胞成像中具有潜在的应用能力。但是该荧光探针与水合肼反应较慢,需要20分钟荧光强度才能恒定,不能满足环境监测领域快速检测的需求。
发明内容
本发明为了解决现有用于检测水合肼的荧光探针的灵敏度差、制备方法复杂等问题,提供了一种用于检测水合肼的荧光探针及其制备方法和应用,该制备方法原料易得,制备方便。该探针能定量检测水合肼。
本发明由如下技术方案实现的:一种用于检测水合肼的荧光探针,该荧光探针为4-(二乙氨基)邻苯二甲醛,其化学结构式如下:。
制备所述的用于检测水合肼的荧光探针的方法,以4-(二乙氨基)水杨醛为起始原料,与等摩尔量的甲酰肼缩合反应得到N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼,再与等摩尔量的四乙酸铅反应制得4-(二乙氨基)邻苯二甲醛。
具体步骤如下:
(1)制备N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼:将4-(二乙氨基)水杨醛溶于正丙醇中,然后加入等摩尔量的甲酰肼,加热回流反应5小时,冷却,减压去除溶剂得N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼;
(2)制备4-(二乙氨基)邻苯二甲醛:将步骤(1)制得的N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼溶于四氢呋喃中,边搅拌边加入等摩尔量的四乙酸铅,然后室温搅拌反应3小时,减压去除溶剂,残留物采用柱色谱分离得4-(二乙氨基)邻苯二甲醛。
步骤(1)中4-(二乙氨基)水杨醛与正丙醇的用量比例为:1mmol:3ml,加热回流反应的温度为97-100℃,减压去除溶剂的方法为:采用温度控制在55-60℃的旋转蒸发仪去除溶剂,蒸发至水泵真空度降至0.09 MPa没有液体流出为止。
步骤(2)中N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼与四氢呋喃的用量比例为:1mmol:5ml,该步骤中减压去除溶剂的具体方法为:用配备循环水真空泵的旋转蒸发仪减压去除溶剂,温度控制在40-45℃,蒸发至水泵真空度降至0.09 MPa没有液体流出为止。
柱色谱分离的方法为:用100-200目硅胶填充内径为40mm的具砂板闪式层析柱,充填高度为30cm,在硅胶上方加入待分离的残留物,用体积比为乙酸乙酯:石油醚=1:5作洗脱剂洗脱即可分离得到产物。
利用上述用于检测水合肼的荧光探针检测水体中水合肼的应用,检测方法为:配制4-(二乙氨基)邻苯二甲醛的二甲基亚砜溶液,配制体积比为4:6,pH值为7.4的DMSO/PBS缓冲液,将溶解于二甲基亚砜的4-(二乙氨基)邻苯二甲醛加入到缓冲液中,然后加入待检测水样,通过荧光强度的变化定量检测待测水样中水合肼的浓度。
本发明所述用于检测水合肼的荧光探针4-(二乙氨基)邻苯二甲醛的制备过程反应式如下:。
该探针能定量检测水合肼,而且检测机理新颖,是通过4-(二乙氨基)邻苯二甲醛与水合肼反应环化生成发蓝色荧光的6-(二乙氨基)酞嗪的反应机理来实现对水合肼的检测,反应原理如下:。
采用本发明所述荧光探针定量检测水合肼,包括高浓度水合肼的检测和低浓度水合肼的检测。
高浓度水合肼的检测方法包括如下操作步骤:
(1)用二甲基亚砜(DMSO)配制2 mM 4-(二乙氨基)邻苯二甲醛的荧光探针储备液;用蒸馏水配制1 mM的水合肼溶液。
(2)将2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和20 µL荧光探针储备液加入荧光比色皿中,在荧光分光光度仪上测定探针的荧光光谱,然后逐渐加入不同体积的水合肼溶液,在荧光分光光度仪上测定其荧光光谱,加入水合肼后探针在456 nm处出现了新的荧光发射峰,而且随着水合肼的加入荧光强度逐渐增强,加到荧光强度基本不发生变化为止;将探针在456 nm处的起始荧光强度记为F0,加入水合肼后探针在456 nm处的荧光强度记为F,以水合肼浓度C为横坐标,探针在456 nm处的相对荧光强度△F(即F-F0)为纵坐标,绘制图并进行线性拟合,得到该探针的最佳线性响应范围为0.5-20 µM,回归方程为:△F=137.568×C-48.901,线性相关系数R2=0.9988,检出限为0.05 µM。
(3)在盛有2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和20 µL荧光探针储备液的荧光比色皿中,加入V μL待测样品溶液,在荧光分光光度仪上测定探针在456 nm处的荧光强度F,将测得的荧光强度F代入步骤(2)的线性回归方程,即可求得待测样品溶液中水合肼的浓度。
高浓度水合肼的检测方法检测快速,在1分钟内即可反应完全。
低浓度水合肼的检测方法包括如下操作步骤:
(1)用二甲基亚砜(DMSO)配制2 mM 4-(二乙氨基)邻苯二甲醛的荧光探针储备液;用蒸馏水配制0.1 mM的水合肼溶液。
(2)将2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和1 µL荧光探针储备液加入荧光比色皿中,在荧光分光光度仪上测定探针的荧光光谱,分析方法同高浓度水合肼的检测方法中步骤(2)的分析方法,将探针在456 nm处的起始荧光强度记为F0,加入水合肼后探针在456 nm处的荧光强度记为F,以水合肼浓度C为横坐标,探针在456 nm处的相对荧光强度△F(即F-F0)为纵坐标,绘制工作曲线并进行线性拟合,得到该探针的最佳线性响应范围为0.01-0.6 µM, 回归方程为:△F=2524.679×C+20.468,线性相关系数R2=0.9930,检出限为1.9 nM。
(3)在盛有2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和1 µL荧光探针储备液的荧光比色皿中,加入V μL待测样品溶液,在荧光分光光度仪上测定探针在456 nm处的荧光强度F,将测得的荧光强度F代入步骤(2)的线性回归方程,即可求得待测样品溶液中水合肼的浓度。
低浓度水合肼的检测方法的反应速度比高浓度水合肼的检测方法要慢,但是在8分钟内也可反应完全。
经实验验证,常见阳离子、阴离子以及脂肪胺、芳香胺、尿素等其他含氮类物质不干扰体系对水合肼的检测,而且加标回收实验结果表明该检测方法具有较高的准确度,加标回收率为96.0-104.0%。
本发明所述的用于检测水合肼的荧光探针结构新颖、制备方便。检测方法具有高的灵敏度和选择性,检测限达1.9 nM,而且不受常见阳离子、阴离子以及脂肪胺、芳香胺、尿素等其他含氮类物质的干扰。本发明的检测方法检测快速,检测范围宽,浓度范围为0.01-20 µM。
附图说明
图1为本发明所述荧光探针检测高浓度水合肼的荧光滴定图;图2为本发明所述荧光探针检测高浓度水合肼的工作曲线;图3为本发明所述荧光探针检测高浓度水合肼的响应时间图;图4为本发明所述荧光探针检测低浓度水合肼的工作曲线;图5为本发明所述荧光探针检测低浓度水合肼的响应时间图;图6为常见阳离子对4-(二乙氨基)邻苯二甲醛荧光探针检测高浓度水合肼的荧光干扰图;图7为常见阴离子对4-(二乙氨基)邻苯二甲醛荧光探针检测高浓度水合肼的荧光干扰图;图8为脂肪胺、芳香胺、尿素等其他含氮类物质对4-(二乙氨基)邻苯二甲醛荧光探针检测高浓度水合肼的荧光干扰图。
具体实施方式
为更好地理解本发明,下面结合实施例对本发明作进一步地说明,本发明要求保护的范围并不局限于实施例表述的范围。
实施例1:一种用于检测水合肼的荧光探针,该荧光探针为4-(二乙氨基)邻苯二甲醛,其化学结构式如下:。
制备所述的用于检测水合肼的荧光探针的方法,以4-(二乙氨基)水杨醛为起始原料,与等摩尔量的甲酰肼缩合反应得到N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼,再与等摩尔量的四乙酸铅反应制得4-(二乙氨基)邻苯二甲醛。
具体步骤如下:
(1)N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼的制备:将1.93 g(10 mmol)4-(二乙氨基)水杨醛溶于30 mL正丙醇中,然后加入0.60 g(10 mmol)甲酰肼,加热回流反应5小时,冷却,减压去除溶剂得N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼。加热回流反应的温度为97-100℃,减压去除溶剂的方法为:采用温度控制在55-60℃的旋转蒸发仪去除溶剂,蒸发至水泵真空度降至0.09 MPa没有液体流出为止。
(2)4-(二乙氨基)邻苯二甲醛的制备:将步骤(1)制得的N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼10mmol溶于50 mL四氢呋喃中,搅拌下,分批加入4.43 g(10 mmol)四乙酸铅,加完后室温搅拌反应3小时,然后减压去除溶剂,方法为:采用温度控制在40-45℃的旋转蒸发仪去除溶剂,蒸发至水泵真空度降至0.09 MPa没有液体流出为止。残留物柱色谱分离,方法为:用100-200目硅胶填充内径为40mm的具砂板闪式层析柱,充填高度为30cm,在硅胶上方加入待分离的残留物,用体积比为乙酸乙酯:石油醚=1:5作洗脱剂洗脱,分离得0.48 g 4-(二乙氨基)邻苯二甲醛,收率23.4%。1H NMR (600 MHz, DMSO-d 6 ): δ 10.50(s, 1H), 10.15 (s, 1H), 7.84 (d, J = 9.0 Hz, 1H), 7.10 (s, 1H), 7.00 (d, J =9.0 Hz, 1H), 3.50 (m, 4H), 1.15 (t, J = 7.2 Hz, 6H). 13C NMR (150 MHz, DMSO-d 6 ): δ 194.6, 190.4, 151.5, 139.2, 134.2, 123.4, 114.3, 112.1, 44.6, 12.7.HRMS [M + H]+ m/z: calcd. For C12H16NO2 206.1181; found 206.1174。
实施例2:4-(二乙氨基)邻苯二甲醛荧光探针定量检测高浓度水合肼的实验方法,具体步骤如下:
(1)用二甲基亚砜(DMSO)配制2 mM 4-(二乙氨基)邻苯二甲醛的荧光探针储备液;用蒸馏水配制1 mM的水合肼溶液。
(2)将2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和20 µL荧光探针储备液加入荧光比色皿中,在荧光分光光度仪上测定探针的荧光光谱(激发波长410 nm),然后逐渐加入不同体积的水合肼溶液,在荧光分光光度仪上测定其荧光光谱,加入水合肼后探针在456 nm处出现了新的荧光发射峰,而且随着水合肼的加入荧光强度逐渐增强(见图1),加到荧光强度基本不发生变化为止;将探针在456 nm处的起始荧光强度记为F0,加入水合肼后探针在456 nm处的荧光强度记为F,以水合肼浓度C为横坐标,探针在456 nm处的相对荧光强度△F(即F-F0)为纵坐标,绘制图并进行线性拟合,得到该探针的最佳线性响应范围为0.5-20 µM,回归方程为:△F=137.568×C-48.901(见图2),线性相关系数R2=0.9988,检出限为0.05 µM。
(3)在盛有2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和20 µL荧光探针储备液的荧光比色皿中,加入V μL待测样品溶液,在荧光分光光度仪上测定探针在456 nm处的荧光强度F,将测得的荧光强度F代入步骤(2)的线性回归方程,即可求得待测样品溶液中水合肼的浓度。
实施例3:4-(二乙氨基)邻苯二甲醛荧光探针定量检测高浓度水合肼的响应时间实验
在荧光比色皿中,加入2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和20 µL荧光探针储备液,再加入1摩尔当量水合肼溶液,在荧光分光光度仪上测定探针在456 nm处的荧光强度变化(激发波长410 nm),随着反应时间的延长,荧光强度不断增大,反应进行到60 s时,荧光强度基本恒定(见图3),说明该检测方法检测快速,在1分钟内即可完全检测。
实施例4:4-(二乙氨基)邻苯二甲醛荧光探针定量检测低浓度水合肼的实验方法
(1)用二甲基亚砜(DMSO)配制2 mM 4-(二乙氨基)邻苯二甲醛的荧光探针储备液;用蒸馏水配制0.1 mM的水合肼溶液。
(2)将2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和1 µL荧光探针储备液加入荧光比色皿中,在荧光分光光度仪上测定探针的荧光光谱(激发波长327 nm),然后逐渐加入不同体积的水合肼溶液,在荧光分光光度仪上测定其荧光光谱,加入水合肼后探针在456nm处出现了新的荧光发射峰,而且随着水合肼的加入荧光强度逐渐增强,加到荧光强度基本不发生变化为止;将探针在456 nm处的起始荧光强度记为F0,加入水合肼后探针在456nm处的荧光强度记为F,以水合肼浓度C为横坐标,探针在456 nm处的相对荧光强度△F(即F-F0)为纵坐标,绘制工作曲线并进行线性拟合,得到该探针的最佳线性响应范围为0.01-0.6 µM, 回归方程为:△F=2524.679×C+20.468(见图4),线性相关系数R2=0.9930,检出限为1.9 nM。
(3)在盛有2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和1 µL荧光探针储备液的荧光比色皿中,加入V μL待测样品溶液,在荧光分光光度仪上测定探针在456 nm处的荧光强度F,将测得的荧光强度F代入步骤(2)的线性回归方程,即可求得待测样品溶液中水合肼的浓度。
实施例5:4-(二乙氨基)邻苯二甲醛荧光探针定量检测低浓度水合肼的响应时间实验
在荧光比色皿中,加入2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和1 µL荧光探针储备液,再加入1摩尔当量水合肼溶液,在荧光分光光度仪上测定探针在456 nm处的荧光强度变化(激发波长327 nm),随着反应时间的延长,荧光强度不断增大,反应进行到480 s时,荧光强度基本恒定(见图5),说明该检测方法检测快速,在8分钟内即可完全检测。
实施例6:4-(二乙氨基)邻苯二甲醛荧光探针定量检测高浓度水合肼的阳离子干扰实验
在不同的荧光比色皿中,分别加入2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和20µL荧光探针储备液,再分别加入常见阳离子水溶液,包括Na+、K+、Mg2+、Ca2+、Cr3+、Mn2+、Fe2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+、Hg2+、Pb2+、NH4 +,使其最终浓度为200 μM,在荧光分光光度仪上测定荧光光谱(激发波长410 nm),然后再分别加入水合肼溶液,使其最终浓度为20 μM,在荧光分光光度仪上测定荧光光谱,绘制加入不同阳离子和在不同阳离子存在时加入水合肼在456 nm处荧光强度的柱状图,见图6。实验证明,常见阳离子不干扰体系对水合肼的检测。
实施例7:4-(二乙氨基)邻苯二甲醛荧光探针定量检测高浓度水合肼的阴离子干扰实验
在不同的荧光比色皿中,分别加入2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和20µL荧光探针储备液,再分别加入常见阴离子水溶液,包括F-、Cl-、Br-、 I-、CO3 2-、NO3 -、NO2 -、AcO-、SO4 2-、SO3 2-、HSO3 -、S2-、CN-,使其最终浓度为200 μM,在荧光分光光度仪上测定荧光光谱(激发波长410 nm),然后再分别加入水合肼溶液,使其最终浓度为20 μM,在荧光分光光度仪上测定荧光光谱,绘制加入不同阴离子和在不同阴离子存在时加入水合肼在456 nm处荧光强度的柱状图,见图7。实验证明,常见阴离子不干扰体系对水合肼的检测。
实施例8:4-(二乙氨基)邻苯二甲醛荧光探针定量检测高浓度水合肼的其他含氮类物质干扰实验
在不同的荧光比色皿中,分别加入2 mL DMSO/PBS 缓冲液(v/v = 4/6,pH = 7.4)和20µL荧光探针储备液,再分别加入1摩尔当量的水合肼,使其最终浓度为20 μM,和10摩尔当量的其他含氮类物质水溶液,包括甲胺、乙胺、二甲胺、二乙胺、三甲胺、三乙胺、氨水、苯胺、乙醇胺、吡啶、二甲基甲酰胺、尿素,使其最终浓度为200 μM,然后在荧光分光光度仪上测定荧光光谱(激发波长410 nm),测定结果见图8。实验证明,其他含氮类物质不干扰体系对水合肼的检测。
实施例9:4-(二乙氨基)邻苯二甲醛荧光探针定量检测水合肼的加标回收实验
用4-(二乙氨基)邻苯二甲醛荧光探针定量检测低浓度水合肼的实验方法分别对加有0.25 μM、0.50 μM水合肼的自来水和矿泉水进行检测,实验结果见表1,加标回收率为96.0-104.0%,说明该检测方法具有较高的准确度。
表1加标回收实验结果
Claims (7)
1.一种用于检测水合肼的荧光探针,其特征在于:该荧光探针为4-(二乙氨基)邻苯二甲醛,其化学结构式如下:。
2.一种制备权利要求1所述的用于检测水合肼的荧光探针的方法,其特征在于:以4-(二乙氨基)水杨醛为起始原料,与等摩尔量的甲酰肼缩合反应得到N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼,再与等摩尔量的四乙酸铅反应制得4-(二乙氨基)邻苯二甲醛。
3.根据权利要求2所述的一种制备用于检测水合肼的荧光探针的方法,其特征在于:具体步骤如下:
(1)制备N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼:将4-(二乙氨基)水杨醛溶于正丙醇中,然后加入等摩尔量的甲酰肼,加热回流反应5小时,冷却,减压去除溶剂得N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼;
(2)制备4-(二乙氨基)邻苯二甲醛:将步骤(1)制得的N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼溶于四氢呋喃中,边搅拌边加入等摩尔量的四乙酸铅,然后室温搅拌反应3小时,减压去除溶剂,残留物采用柱色谱分离得4-(二乙氨基)邻苯二甲醛。
4.根据权利要求3所述的一种制备用于检测水合肼的荧光探针的方法,其特征在于:步骤(1)中4-(二乙氨基)水杨醛与正丙醇的用量比例为:1mmol:3ml,加热回流反应的温度为97-100℃,减压去除溶剂的方法为:采用温度控制在55-60℃的旋转蒸发仪去除溶剂,蒸发至水泵真空度降至0.09 MPa没有液体流出为止。
5.根据权利要求3所述的一种制备用于检测水合肼的荧光探针的方法,其特征在于:步骤(2)中N-[(4-二乙氨基-2-羟基苯基)亚甲基]甲酰肼与四氢呋喃的用量比例为:1mmol:5ml,所述减压去除溶剂的方法为:采用温度控制在40-45℃的旋转蒸发仪去除溶剂,蒸发至水泵真空度降至0.09 MPa没有液体流出为止。
6.根据权利要求3所述的一种制备用于检测水合肼的荧光探针的方法,其特征在于:步骤(2)中柱色谱分离的方法为:用100-200目硅胶填充内径为40mm的具砂板闪式层析柱,充填高度为30cm,在硅胶上方加入待分离的残留物,用体积比为乙酸乙酯:石油醚=1:5作洗脱剂洗脱即可分离得到产物。
7.利用权利要求1所述的一种用于检测水合肼的荧光探针检测水体中水合肼的应用,其特征在于:检测方法为:配制4-(二乙氨基)邻苯二甲醛的二甲基亚砜溶液,配制体积比为4:6,pH值为7.4的DMSO/PBS 缓冲液,将溶解于二甲基亚砜的4-(二乙氨基)邻苯二甲醛加入到缓冲液中,然后加入待检测水样,通过荧光强度的变化定量检测待测水样中水合肼的浓度。
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