CN106565679B - 一种铁离子检测试剂及其制备方法和应用 - Google Patents

一种铁离子检测试剂及其制备方法和应用 Download PDF

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CN106565679B
CN106565679B CN201610933781.9A CN201610933781A CN106565679B CN 106565679 B CN106565679 B CN 106565679B CN 201610933781 A CN201610933781 A CN 201610933781A CN 106565679 B CN106565679 B CN 106565679B
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徐括喜
王超玉
宋倩倩
刘晓燕
杨丽
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Abstract

本发明属于一种铁离子检测试剂，结构如下：；合成第一步：以无水乙腈为溶剂，无水碳酸钾为碱，2，9‑二溴甲基间基吖啶和邻氨基苯硫酚在加热回流的条件下反应12h，减压除去乙腈，加入用饱和NaHCO3溶液后经CH2Cl2萃取，收集有机相，经无水MgSO4干燥后，减压除去溶剂得到粗产品，粗产品经过柱分离提纯，得到化合物2；第二步：以乙醇为溶剂，把化合物2和2‑甲酰基吡啶在氮气保护、加热回流的条件下反应12h，加入硼氢化钠还原12h后减压除去乙醇，加入饱和NaHCO3溶液后经CH2Cl2萃取，收集有机相，经无水MgSO4干燥后，减压除去溶剂得到粗产物，粗产物经过柱分离提纯，即得。

Description

一种铁离子检测试剂及其制备方法和应用
技术领域
本发明属于金属离子检测领域，具体涉及一种铁离子检测试剂及其制备方法和应用。
背景技术
铁是生命体中必需元素之一，在生物体的生命活动中起着举足轻重的作用， 涉及生物体的各项生理活动，如肌肉的收缩、DNA 和RNA 的合成、酶催化、神经传导、细胞内渗透压调节以及维持酸碱平衡等。 细胞内铁含量的减少会导致生命体系的紊乱，而过量的铁同样对机体是有害甚至是致命的。因此，实现高选择性、高灵敏度地在活细胞中检测铁显得极其重要。现在常用的检测铁离子（III）的方法主要有原子吸收法、分光光度法、电感耦合等离子体发射光谱法、电感耦合等离子体质谱法、电化学法及荧光分析法等，这些方法各有优缺点。近几年，荧光探针法受到了极大的关注,由于该技术不仅操作简单、成本低、灵敏度高、选择性好、响应时间短等方面有突出优点。因此，对它的研究和探索，对于金属离子的定性和定量检测领域有着非常重要的意义，对开发新型铁离子（III）检测试剂也会产生很大的影响。
发明内容
本发明的目的是提供一种铁离子检测试剂及其制备方法和应用。
为实现上述目的，本发明采用的技术方案是，一种铁离子检测试剂，所述铁离子检测试剂的结构如下：
。
分两步合成所述铁离子检测试剂；第一步：以无水乙腈为溶剂，无水碳酸钾为碱，2，9-二溴甲基间基吖啶和邻氨基苯硫酚在加热回流的条件下反应12h，减压除去乙腈，加入用饱和NaHCO3溶液（20mL）后经CH2Cl2（3×20 mL）萃取，收集有机相，经无水MgSO4干燥后，减压除去溶剂得到粗产品，粗产品经过硅胶层析柱分离提纯（石油醚/乙酸乙酯 = 10:1），得到化合物2；化合物2的结构式如下：
；
第二步：以乙醇为溶剂，把化合物2和2-甲酰基吡啶在氮气保护、加热回流的条件下反应12h，加入硼氢化钠还原12h后减压除去乙醇，加入用饱和NaHCO3溶液（20mL）后经CH2Cl2（3×20 mL）萃取，收集有机相，经无水MgSO4干燥后，减压除去溶剂得到粗产物，粗产物经过硅胶层析柱分离提纯（石油醚/乙酸乙酯 = 5:1），得到所述铁离子检测试剂。
本发明产生的有益效果是：本发明提供的铁离子（III）检测试剂具有能在水溶液中定性和定量地检出Fe3+的性能，具有定性和定量地检出铁离子（III）的应用前景，检出极限可达4.60×10-7M.；并且本发明的铁离子检测试剂制备工艺简单，收率达80%。
具体实施方式
以下以具体实施例来说明本发明的技术方案，但本发明的保护范围不限于此。
实施例1
实施例1的铁离子检测试剂的合成路线如下：
。
化合物2的具体合成过程如下：取2,9-二溴甲基吖啶（化合物1，1mmol）、邻氨基苯硫酚(2.1mmol)和无水碳酸钾(2.1mmol)加入10毫升的无水乙腈中，然后在氮气保护下加热回流的条件下反应12h，减压除去乙腈，加入饱和NaHCO3溶液（20mL）后经CH2Cl2（3×20mL，分3次进行，每次20m）萃取，收集有机相，经无水MgSO4干燥后，减压除去溶剂得到粗产品，粗产品经过硅胶层析柱分离提纯（石油醚/乙酸乙酯 = 10:1），得到中间体化合物2，收率为88%。
取化合物2 (1.0 mmol)，2-甲酰基吡啶(2.1mmol)，10毫升乙醇中于50毫升烧瓶，
在氮气保护、加热回流的条件下反应12h，加入硼氢化钠(2.1mmol)还原12h后减压除去乙醇
，加入饱和NaHCO3溶液（20mL）后经CH2Cl2（3×20 mL）萃取，收集有机相，经无水MgSO4干燥后，减压除去溶剂得到粗产物，粗产物经过硅胶层析柱分离提纯（石油醚/乙酸乙酯 = 5:1），得到目标产物3，收率为91%。
目标产物3的表征结果
1）红外光谱测定：
用溴化钾压片法在400~4000cm–1范围内用美国Nicolet magna 750傅里叶红外光谱仪测定。所得化合物的主要红外吸收峰为：3358, 2976, 1604, 1522, 1473, 1391,946, 671 cm-1.
2）核磁共振氢谱测定：
用氘代氯仿为溶剂，四甲基硅烷为内标，用Bruker400核磁共振波谱仪测定氢谱。所得化合物的核磁共振氢谱为：
8.84(s, 1H), 7.93 (d, J = 1.7 Hz, 1H), 7.82(d, J = 1.7 Hz, 2H), 7.66–7.53(m, 4H), 7.47–7.32(m, 4H), 7.29 (s, 1H), 7.22(d, J = 1.4 Hz, 1H), 7.10(d, J = 8.0, 2H), 7.01–6.92(m, 4H), 6.77(d, J = 8.0, 1.1 Hz, 2H), 6.64(d, J =7.5, 1.2 Hz, 2H), 5.38(s, 4H), 4.82(s, 4H), 2.89(s, 2H).
3）核磁共振碳谱测定：
用氘代氯仿为溶剂，四甲基硅烷为内标，用Bruker400核磁共振波谱仪测定碳谱。所得化合物的核磁共振碳谱为：162, 158, 153, 150, 148, 145, 139, 136, 132, 129,128, 128, 125, 123, 121, 119, 117, 38.
4）元素分析测定：
元素分析用美国PE公司，PE2400-II 元素分析仪测定：所得化合物的元素分析值为：C, 76.62; H, 5.26; N, 11.00; S, 10.02。(理论值：C, 73.67; H, 5.23; N, 11.01;S, 10.09).
5）质谱测定：
质谱用Bruker Compass DataAnalysis质谱仪测定：所得化合物的质谱为：635.89[M]+(理论值：635.84) 。
目标产物3在检测Fe3+中的应用
将铁离子检测试剂（目标产物3）配制成3.0×10-5 mmol/L的DMSO溶液。在对分别含有(Li+, Na+, K+, Ag+, Mg2+, Ca2+, Ba2+, Pb2+, Zn2+, Co2+, Cd2+, Hg2+, Ni2+, Cu2+, Mn2 +, Cr3+, Al3+和Fe3+等)的DMSO溶液为检测对象。结果表明：在加入Fe3+离子时， 检测试剂的荧光猝灭，而加入其它离子时检测试剂的荧光几乎不变。实验中，取3 mL铁离子检测试剂加入到比色皿中，然后加入到含不同种类和浓度的金属离子均匀混合，测定各组溶液的荧光数据。经荧光滴定和拟合计算得测定其检出极限可达4.60×10-7M。本发明的铁离子检测试剂可定性和定量地检测铁离子（III）。

Claims (3)

1.一种铁离子检测试剂，其特征在于，所述铁离子检测试剂的结构如下：
。
2.如权利要求1所述铁离子检测试剂制备方法，其特征在于分两步合成所述铁离子检测试剂；
第一步：以无水乙腈为溶剂，无水碳酸钾为碱，2,9-二溴甲基吖啶和邻氨基苯硫酚在加热回流的条件下反应12h，反应产物经纯化处理得到化合物2；化合物2的结构式如下：
；
第二步：以乙醇为溶剂，把化合物2和2-甲酰基吡啶在氮气保护、加热回流的条件下反应12h，加入硼氢化钠还原12h，反应产物经纯化处理，得到所述铁离子检测试剂。
3.如权利要求1所述铁离子检测试剂在检测Fe3+中的应用。
CN201610933781.9A 2016-10-25 2016-10-25 一种铁离子检测试剂及其制备方法和应用 Expired - Fee Related CN106565679B (zh)

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WO2005043124A2 (en) * 2003-10-30 2005-05-12 Georgetown University Chiral 1,8-diarylnaphthalenes, methods of making them, and their use as sensors
CN103923017A (zh) * 2014-03-13 2014-07-16 华南师范大学 双丹酰基组氨酸及其应用
CN105917234A (zh) * 2014-01-17 2016-08-31 梅托珍尼克斯株式会社 铁(ii)离子检测剂以及使用其的检测方法

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Publication number Priority date Publication date Assignee Title
WO2005043124A2 (en) * 2003-10-30 2005-05-12 Georgetown University Chiral 1,8-diarylnaphthalenes, methods of making them, and their use as sensors
CN105917234A (zh) * 2014-01-17 2016-08-31 梅托珍尼克斯株式会社 铁(ii)离子检测剂以及使用其的检测方法
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