CN109970600A - 一种三苯胺衍生物希夫碱类有机荧光探针及其制备方法 - Google Patents
一种三苯胺衍生物希夫碱类有机荧光探针及其制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/325—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups reduction by other means than indicated in C07C209/34 or C07C209/36
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
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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
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N21/64—Fluorescence; Phosphorescence
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- G01N2021/6432—Quenching
Abstract
本发明提供了一种三苯胺衍生物希夫碱类有机荧光探针及其制备方法。所述荧光探针是以N,N‑二苯基联苯二胺为原料，经取代、硝基还原，最后与水杨醛缩合反应而得。所述荧光探针分子对细胞内游离锌离子具有高选择性、高灵敏度、专一性、低检测限等优点，可用于机体内多种生理过程实时检测、查找多类病因等。
Description
技术领域
本发明涉及有机荧光探针领域，特别涉及一种三苯胺衍生物希夫碱类有机荧光探针及其制备方法，并将其应用于荧光法检测和分析Zn2+。
背景技术
Zn2+是生命体中重要的微量元素之一，其在生命体内分布广泛。其主要在酶催化、蛋白质测序、基因表达等生理过程中起着至关重要的作用，缺锌是儿童生长期的基因缺陷疾病的主要诱因之一。而Zn2+与Hg2+、Cd2+有着相似的化学结构，在性质上也有着相似性质，但是，它们对人体却是有害的，因此在低浓（PPM级）下有效识别对人体有益的Zn2+愈发显得重要。
有机荧光探针就是以荧光物质作为指示剂并在一定波长光的激发下使指示剂产生荧光，并通过检测所产生的荧光实现对被检测物质的定性或定量分析；有机荧光探针具有极好的生物传感性，具有灵敏度高、反应迅速、细胞内抗干扰能力强等特点。
因此，设计合成一种Zn2+敏感的有机荧光探针，特别是在较低浓度（PPM级）下对生命体中游离Zn2+产生独特识别效果的荧光探针分子显得尤为重要。
发明内容
本发明的目的在于提供一种三苯胺衍生物希夫碱类有机荧光探针N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺，其结构式如下：
其中，R为OH。
本发明的另一目的在于提供一种三苯胺衍生物希夫碱类有机荧光探针的制备方法，包括如下步骤：
（1）取0.250mol的氢化钠于300mL的二甲基亚砜（DMSO）中，室温搅拌；然后加入0.125mol的N，N-二苯基联苯二胺和0.250mol的对氟硝基苯，在100℃下搅拌反应1.5h；再将混合溶液倒入体积为2L的氯化钠饱和溶液中，乙腈重结晶得到47.1g橙红色固体，即为N，N-二（4-硝基甲苯)-N，N-二苯基联苯二胺，反应方程式如下：
（2）取N，N-二（4-硝基甲苯)-N，N-二苯基联苯二胺0.06mol的和0.4g 5%的钯碳于乙醇中，然后加入30mL水合肼，回流24h，反应完冷却至室温；过滤除去钯碳，将滤液倒入500mL水中，甲苯重结晶得到N，N-二（4-氨基甲苯)-N，N-二苯基联苯二胺，反应方程式如下：
（3）取0.259g N，N-二（4-氨基甲苯)-N，N-二苯基联苯二胺和过量的邻羟基苯甲醛或苯甲醛回流反应24h，萃取、柱层析，得到深黄色固体，即为目标产物，产率75%。
其中，R为OH。
优选的，步骤3中柱层析所需溶剂为石油醚和乙酸乙酯，其中石油醚：乙酸乙酯体积比为1:3。
本发明的又一目的在于三苯胺衍生物希夫碱作为有机荧光探针应用于荧光法检测Zn2+，所述的三苯胺衍生物希夫碱作为有机荧光探针对Zn2+有很好的络合作用，响应快、灵敏度高。
与现有技术相比本发明的优点：本发明的三苯胺衍生物希夫碱作为有机荧光探针合成方法简单、原料易得、收率高；且经过特定修饰的三苯胺衍生物希夫碱具有很高的量子产率、稳定的自由基性质、较高的空穴迁移率和良好的传输性，作为有机荧光探针可广泛应用于多种动植物机体内对Zn2+进行高效检测，所述荧光探针分子对细胞内游离锌离子具有高选择性、高灵敏度、专一性、低检测限（5*10-6M）等优点，可用于机体内多种生理过程实时检测、查找多类病因等。
附图说明
图1为实施例1中目标荧光探针分子N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺的核磁共振氢谱图；
图2为实施例1中目标荧光探针分子N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺的核磁共振碳谱图；
图3为实施例1中参比有机荧光染料分子N,N-二（4-氨基-苯甲醛)-N,N-二苯基联苯二胺的核磁共振氢谱图；
图4为实施例1中参比有机荧光染料分子N,N-二（4-氨基-苯甲醛)-N,N-二苯基联苯二胺的核磁共振碳谱图；
图5为实施例2中目标荧光探针分子N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺对Zn2+识别的紫外分析图谱；
图6为实施例2中参比有机荧光染料分子N,N-二（4-氨基-苯甲醛)-N,N-二苯基联苯二胺对Zn2+识别的紫外分析图谱；
图7为实施例2中目标荧光探针分子N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺Zn2+识别的荧光分析图谱；
图8为实施例2中参比有机荧光染料分子N,N-二（4-氨基-苯甲醛)-N,N-二苯基联苯二胺Zn2+识别的荧光分析图谱；
图9为实施例3中目标荧光探针分子N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺不同金属离子响应能力对比图；
图10为实施例4中目标荧光探针分子对Hela细胞中Zn2+ (5×10-6 mol.L-1) 的荧光检测；
具体实施方式
以下将结合实施案例进行具体说明：
实施例1:
1、目标荧光探针分子N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺的制备
（1）取0.250mol的氢化钠于300mL的二甲基亚砜（DMSO）中，室温搅拌；然后加入0.125mol的N，N-二苯基联苯二胺和0.250mol的对氟硝基苯，在100℃下搅拌反应1.5h；再将混合溶液倒入体积为2L的氯化钠饱和溶液中，乙腈重结晶得到47.1g橙红色固体，即为N，N-二（4-硝基甲苯)-N，N-二苯基联苯二胺；
（2）取N，N-二（4-硝基甲苯)-N，N-二苯基联苯二胺0.06mol的和0.4g 5%的钯碳于乙醇中，然后加入30mL水合肼，回流24h，反应完冷却至室温；过滤除去钯碳，将滤液倒入500mL水中，甲苯重结晶得到N，N-二（4-氨基甲苯)-N，N-二苯基联苯二胺；
（3）取0.259g N，N-二（4-氨基甲苯)-N，N-二苯基联苯二胺和过量的邻羟基苯甲醛回流反应24h，萃取、柱层析，柱层析所需溶剂为石油醚和乙酸乙酯，其中石油醚：乙酸乙酯体积比为1:3，得到深黄色固体，即为目标产物，产率75%，熔点：187.3-188.9℃，1H-NMR (400MHz, CDCl3-d 1 ) δ (ppm): 13.411(s,-OH,2H), 8.631(s, -N=CH, 2H), 7.383-7.337 (m,Ar-H, 4H), 7.308-7.269 (t, J＝7.8 Hz, Ar-H, 4H), 7.236-7.271 (d, J＝14.0Hz,Ar-H, 4H), 7.155-7.126 (m, Ar-H, 8H), 7.062-7.002 (m,Ar-H,8H),6.951-6.913(t,J=7.6Hz,Ar-H,2H). 13C-NMR(400MHz,CDCl3-d 1 )δ(ppm): 161.04, 160.42, 147.43,146.98, 142.80, 142.38, 132.74, 131.97, 129.38, 125.57, 124.21, 123.88,123.08, 122.11, 119.42, 119.02, 117.18, 77.22，其核磁共振氢谱如图1所示，其核磁共振碳谱如图2所示。
反应方程式如下：
2、参比有机荧光染料分子N,N-二（4-氨基-苯甲醛)-N,N-二苯基联苯二胺的制备
（1）取0.250mol的氢化钠于300mL的二甲基亚砜（DMSO）中，室温搅拌；然后加入0.125mol的N，N-二苯基联苯二胺和0.250mol的对氟硝基苯，在100℃下搅拌反应1.5h；再将混合溶液倒入体积为2L的氯化钠饱和溶液中，乙腈重结晶得到47.1g橙红色固体，即为N，N-二（4-硝基甲苯)-N，N-二苯基联苯二胺；
（2）取N，N-二（4-硝基甲苯)-N，N-二苯基联苯二胺0.06mol的和0.4g 5%的钯碳于乙醇中，然后加入30mL水合肼，回流24h，反应完冷却至室温；过滤除去钯碳，将滤液倒入500mL水中，甲苯重结晶得到N，N-二（4-氨基甲苯)-N，N-二苯基联苯二胺；
（3）取0.259g N，N-二（4-氨基甲苯)-N，N-二苯基联苯二胺和过量的苯甲醛回流反应24h，萃取、柱层析，柱层析所需溶剂为石油醚和乙酸乙酯，其中石油醚：乙酸乙酯体积比为1:3，得到深黄色固体，即为目标产物，产率75%，熔点：197.8-201.6℃。1H-NMR (400 MHz,CDCl3-d 1 ) δ (ppm): 8.516(s, N=CH, 2H), 7.912-7.888 (m, Ar-H, 4H), 7.479-7.462(t, J＝3.4 Hz, Ar-H, 9H), 7.300-7.281 (d, J＝7.6Hz,Ar-H,3H),7.210-7.139(m,Ar-H,16H),7.058-7.021(t,J=7.4Hz,Ar-H,4H).13C-NMR(400MHz,CDCl3-d 1 )δ(ppm):129.307,128.760,128.662,127.351,124.860,124.289,124.067,122.068,77.217其核磁共振氢谱如图3所示，其核磁共振碳谱如图4所示。
反应方程式如下：
实施例2:
1、目标荧光探针分子N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺检测Zn2+
配制浓度为1×10-5mol·l-1的N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺的乙酸乙酯中溶液，使用紫外-可见光谱仪，扫描200nm~600nm的紫外-可见吸收光谱。其紫外-可见吸收光谱如图5所示，最大吸收波长为402nm，其荧光光谱图如图7所示：在加入5*10-6mol/L的Zn2+后，目标荧光探针分子在560nm处的荧光发射峰消失了，这是由于Zn2+与目标荧光探针分子的N、O原子发生了有效络合所致，同时其紫外吸收峰也因离子络合作用发生了一定的红移。
2、参比有机荧光染料分子N,N-二（4-氨基-苯甲醛)-N,N-二苯基联苯二胺检测Zn2+
配制浓度为1×10-5mol·l-1 N,N-二（4-氨基-苯甲醛)-N,N-二苯基联苯二胺的乙酸乙酯中溶液，使用紫外-可见光谱仪，扫描200nm~600nm的紫外-可见吸收光谱。其紫外-可见吸收光谱如图6所示，最大吸收波长为396nm，其荧光光谱图如图8所示：可以看到在加入5*10- 6mol/L的Zn2+后，参比有机荧光染料分子由于不含有效络合官能结构-OH，所以其荧光发射峰没有明显变化，其紫外吸收峰同样没有发生明显变化。
实施例3:
目标荧光探针分子N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺的选择性：
常见的金属离子对Zn2+的检测可能存在干扰，因而要确定探针在识别Zn2+时能否具备良好的选择性。选取金属离子有：K+、Ca2+、Na+、Mg2+、Li+、Cu2+、Fe3+、Ni2+，选定激发波长，测定荧光发射光谱，以对比N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺探针分子对不同金属离子响应能力，响应结果如图9所示。可以看到加入Zn2+后的蓝色荧光明显增强，因Fe3+本身颜色较深，因此对实施例1有机荧光探针分子发生荧光淬灭干扰，而其它金属离子的加入没有明显变化。
实施例4:
N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺有机荧光探针的活细胞荧光成像实验。过程如下:
将人宫颈癌细胞（HeLa）用磷酸盐缓冲溶液(PBS)润洗后放置在培养皿中，基质用不同浓度的N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺探针分子(含有1%DMSO的PBS缓冲溶液)在37℃下培养培育6h，用PBS缓冲溶液清洗3次，除去多余的探针分子，再将人宫颈癌细胞分别用2×10-5mol.L-1、5×10-5 mol/L和5×10-6mol.L-1的Zn(OAc)2的PBS缓冲溶液37℃下培养30min，再次用PBS缓冲溶液清洗3次，用激光共焦显微镜观察共焦荧光成像，可以看到目标荧光探针分子能够对细胞内游离锌离子快速识别，并产生荧光响应信号。
Claims (3)
1.一种三苯胺衍生物希夫碱类有机荧光探针，该探针为N,N-二（4-氨基-2-羟基-苯甲醛)-N,N-二苯基联苯二胺，其特征在于，具有下式结构：
其中，R为OH。
2.一种权利要求1所述的三苯胺衍生物希夫碱类有机荧光探针的制备方法，其特征在于，步骤如下：
（1）取0.250mol的氢化钠于300mL的二甲基亚砜中，室温搅拌；然后加入0.125mol的N，N-二苯基联苯二胺和0.250mol的对氟硝基苯，在100℃下搅拌反应1-2h；再将混合溶液倒入体积为2L的氯化钠饱和溶液中，乙腈重结晶得到47.1g橙红色固体，即为N，N-二（4-硝基甲苯)-N，N-二苯基联苯二胺；
（2）取N，N-二（4-硝基甲苯)-N，N-二苯基联苯二胺0.06mol和0.3-0.5g催化剂于乙醇中，然后加入30mL水合肼，回流24h，反应完冷却至室温；过滤除去钯碳，将滤液倒入500mL水中，甲苯重结晶得到N，N-二（4-氨基甲苯)-N，N-二苯基联苯二胺；
（3）取0.259g N，N-二（4-氨基甲苯)-N，N-二苯基联苯二胺和过量的邻羟基苯甲醛回流反应24h，萃取、柱层析，柱层析所需溶剂为石油醚和乙酸乙酯，其中石油醚：乙酸乙酯体积比为1:3，得到深黄色固体，即为目标产物，产率75%。
3.一种权利要求1所述的三苯胺衍生物希夫碱类作为有机荧光探针应用于荧光法检测Zn2+。
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