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