CN106565752A - 一种荧光化合物的合成及其在镍离子检测中的应用 - Google Patents
一种荧光化合物的合成及其在镍离子检测中的应用 Download PDFInfo
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract
本发明属于有机发光材料领域,公开了一种荧光化合物的合成及其在镍离子检测中的应用。所述荧光化合物为2,3′‑联(1,10‑菲罗啉),其具有式(I)所示的结构式。其制备方法为:在反应器中,加入邻菲罗啉、醇、金属催化剂和溶剂,再加入碱为促进剂,通入惰性气体,在100~160℃下搅拌反应1~48小时,反应结束后冷却至室温,稀释反应液,过滤,减压蒸馏得粗产物,经薄层层析或柱层析提纯得到产物。本发明的合成方法简单,所得荧光化合物2,3′‑联(1,10‑菲罗啉)的激发和发射光谱在可见光区,化学稳定性好,具有较好的水溶性,可以应用于中性条件下水环境体系中Ni2+的检测。
Description
技术领域
本发明属于有机发光材料领域,具体涉及一种荧光化合物的合成及其在镍离子检测中的应用。
背景技术
镍是人体必需的微量元素之一,是人类生活和工作中广泛接触的一种重金属元素,在现代工业如:镍的冶炼、提纯,电镀,镍络电池生产等行业中有广泛应用[张晓宇,张敬镶致癌的分子机制.国外医学卫生学分册,2005,32(6);365-370.]。当其浓度达到一定高度时,镍化合物可经多种途径进入机体,通过机体的膜屏障与组织细胞内的生物分子相互作用,导致各种毒效应。镍化合物是一类多器官毒物,可累及肝、肾、肺和血管系统、血液等多种重要器官。其中Ni2+是镍类化合物致癌的最终表现形式,Ni2+和染色质作用是镍类化合物致癌的关键。Ni2+通过与染色质结合,能直接或者间接地导致多种类型的染色质损伤,比如DNA损伤修复系统破坏、DNA氧化损伤、染色质浓缩、基因沉默等[马雪瑛.镍致癌的自由基机制.卫生研究,1997,26(3):168-171.]。
目前,用于检测镍离子的手段有很多种,比如化学发光法,电化学法,原子光谱法,色谱法等方法,这些方法都具有比较高的选择性与灵敏度,并且常用于定量分析,但是它们都不能实现对镍离子的可视化分析。而与上述几种检测方法相比,荧光分析法基于镍离子对邻菲罗啉的具有荧光猝灭作用,乔善宝等[乔善宝,黄天姿,孙国平.邻菲罗啉荧光淬灭法测定食用油中的镍.江南大学学报,2009,7(6):734-736.]建立了邻菲罗啉荧光猝灭测定镍的新方法。这种方法操作简便、测定快速、灵敏度也比较高。Aihua cui[Aihua Cui,Alllarjit Singh,and David L.Kaplan Enzyme-Based Moleeular ImPrinting withMetals.Biomacromolecules,2009,3:1353-1358.]等合成了一种新型的荧光分子传感器化合物,在过渡金属Ni2+存在下,荧光增强。在目前报道的Ni2+的荧光化学探针的应用仍受到一些限制:有的专一性不够,容易受其它金属离子的干扰;有的合成困难、结构复杂;有的膜渗透性能欠佳等。所以,优化Ni2+荧光化学探针分子的设计与合成,寻找灵敏性高、选择性好、性能优越的Ni2+荧光化学探针,具有非常重要的意义。
发明内容
为了解决以上现有技术的缺点和不足之处,本发明的首要目的在于提供一种荧光化合物。
本发明的另一目的在于提供上述荧光化合物的合成方法。
本发明的再一目的在于提供上述荧光化合物在镍离子检测中的应用。
本发明目的通过以下技术方案实现:
一种荧光化合物,所述荧光化合物为2,3′-联(1,10-菲罗啉),其具有式(I)所示的结构式:
上述荧光化合物的合成方法,包括以下步骤:
在反应器中,加入邻菲罗啉、醇、金属催化剂和溶剂,再加入碱为促进剂,通入惰性气体,在100~160℃下搅拌反应1~48小时,反应结束后冷却至室温,稀释反应液,过滤,减压蒸馏得粗产物,经薄层层析或柱层析提纯得到2,3′-联(1,10-菲罗啉)化合物。
上述合成反应如下式所示:
所述的反应器优选schlenk管(史兰克管);所述的惰性气体为氮气或氩气。
优选地,所述的醇是指甲醇、乙醇或异丙醇。
所述邻菲罗啉与醇的摩尔比为1:(1~20);优选1:4。
所述的金属催化剂为醋酸铜、醋酸钯、双三苯基膦二氯化钯、四三苯基磷钯、三氯化铱中的一种或两种以上的混合。
所述的溶剂为乙腈、1,4-二氧六环、甲苯、对二甲苯、甲醇、叔戊醇和水中的一种或两种以上的混合。
所述碱为碳酸钠、氢氧化钠、甲醇钠、叔丁醇钾、叔丁醇钠和三乙胺中的一种或两种以上的混合;碱的加入量与邻菲罗啉的摩尔比为(0.5~5):1;优选1:1。
所述的柱层析提纯所用的洗脱液为二氯甲烷:氨气甲醇的体积比为(20~100):1的混合溶剂。
上述荧光化合物作为荧光探针用于中性条件下的水环境体系中Ni2+的检测。
相对于现有技术,本发明具有如下优点及有益效果:
(1)本发明以邻菲罗啉为原料一步合成目标化合物,具有合成步骤简单、合成方法操作安全、原料无毒、价格低廉和对功能团适应性好的优点;
(2)本发明的荧光化合物2,3′-联(1,10-菲罗啉)的激发和发射光谱在可见光区,化学稳定性好,具有较好的水溶性,可以应用于中性条件下水环境体系中Ni2+的检测。
附图说明
图1为本发明实施例所得产物的核磁共振氢谱图;
图2为本发明实施例所得产物的核磁共振碳谱图;
图3为本发明实施例所得产物2,3′-联(1,10-菲罗啉)在不同金属离子条件下的荧光性能测试结果图;
图4为本发明实施例所得产物2,3′-联(1,10-菲罗啉)在不同浓度Ni2+时的荧光性能测试结果图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
在schlenk管中加入0.5毫摩尔邻菲罗啉、2.0毫摩尔异丙醇、0.5毫摩尔氢氧化钠,0.003毫摩尔醋酸钯,1.2毫升1,4-二氧六环,充入N2保护,在150℃搅拌反应16小时后,停止加热及搅拌,冷却至室温,稀释反应液,过滤,减压旋蒸去除溶剂,再通过柱层析分离纯化,所用的柱层析洗脱液为体积比为100:1的二氯甲烷:氨气甲醇混合溶剂,得到黄色固体目标产物,产率38%。
所得产物的核磁共振氢谱图和碳谱图分别如图1和图2所示,结构表征数据如下:
m.p:207-208℃;1H NMR(400MHz,CDCl3):9.87(s,1H),9.46(s,1H),9.26(d,J=2.9Hz,1H),9.20(d,J=3.1Hz,1H),8.39(d,J=8.3Hz,1H),8.31(d,J=8.4Hz,1H),8.26(t,J=6.7Hz,2H),8.02(d,J=8.8Hz,1H),7.86-7.75(m,3H),7.68-7.60(m,2H);
13C NMR(101MHz,CDCl3):δ154.53,150.45,150.33,148.90,146.45,146.27,146.15,146.06,137.32,136.30,136.05,136.04,135.78,134.26,129.20,129.10,128.69,128.06,127.33,126.93,126.36,123.21,120.84;
IR(KBr):3051,2985,2953,1511,1417,1266,854,740cm-1;
HRMS(ESI):Calcd.for C24H14N4[M+H]+:359.1291;found:359.1289。
根据以上数据推断所得产物为2,3′-联(1,10-菲罗啉),其结构如下式所示:
实施例2
在schlenk管中加入0.5毫摩尔邻菲罗啉、2.0毫摩尔异丙醇、0.5毫摩尔氢氧化钠,0.003毫摩尔醋酸钯,1.2毫升1,4-二氧六环,充入N2保护,在130℃搅拌反应16小时后,停止加热及搅拌,冷却至室温,稀释反应液,过滤,减压旋蒸去除溶剂,再通过柱层析分离纯化,所用的柱层析洗脱液为体积比为100:1的二氯甲烷:氨气甲醇混合溶剂,得到黄色固体目标产物,产物结构鉴定结果与实施例1相同,产率41%。
实施例3
在schlenk管中加入0.5毫摩尔邻菲罗啉、2.0毫摩尔异丙醇、0.5毫摩尔氢氧化钠,0.003毫摩尔双三苯基膦二氯化钯,1.2毫升1,4-二氧六环,充入N2保护,在130℃搅拌反应16小时后,停止加热及搅拌,冷却至室温,稀释反应液,过滤,减压旋蒸去除溶剂,再通过柱层析分离纯化,所用的柱层析洗脱液为体积比为100:1的二氯甲烷:氨气甲醇混合溶剂,得到黄色固体目标产物,产物结构鉴定结果与实施例1相同,产率37%。
实施例4
在schlenk管中加入0.5毫摩尔邻菲罗啉、2.0毫摩尔异丙醇、0.5毫摩尔氢氧化钠,0.003毫摩尔四三苯基磷钯,1.2毫升1,4-二氧六环,充入N2保护,在130℃搅拌反应16小时后,停止加热及搅拌,冷却至室温,稀释反应液,过滤,减压旋蒸去除溶剂,再通过柱层析分离纯化,所用的柱层析洗脱液为体积比为100:1的二氯甲烷:氨气甲醇混合溶剂,得到黄色固体目标产物,产物结构鉴定结果与实施例1相同,产率45%。
实施例5
在schlenk管中加入0.5毫摩尔邻菲罗啉、2.0毫摩尔异丙醇、0.5毫摩尔氢氧化钠,0.003毫摩尔醋酸钯,1.2毫升甲苯,充入N2保护,在130℃搅拌反应16小时后,停止加热及搅拌,冷却至室温,稀释反应液,过滤,减压旋蒸去除溶剂,再通过柱层析分离纯化,所用的柱层析洗脱液为体积比为100:1的二氯甲烷:氨气甲醇混合溶剂,得到黄色固体目标产物,产物结构鉴定结果与实施例1相同,产率49%。
实施例6
在schlenk管中加入0.5毫摩尔邻菲罗啉、2.0毫摩尔异丙醇、0.5毫摩尔氢氧化钠,0.003毫摩尔醋酸钯,1.2毫升对二甲苯,充入N2保护,在130℃搅拌反应16小时后,停止加热及搅拌,冷却至室温,稀释反应液,过滤,减压旋蒸去除溶剂,再通过柱层析分离纯化,所用的柱层析洗脱液为体积比为100:1的二氯甲烷:氨气甲醇混合溶剂,得到黄色固体目标产物,产物结构鉴定结果与实施例1相同,产率45%。
实施例7
在schlenk管中加入0.5毫摩尔邻菲罗啉、2.0毫摩尔异丙醇、0.5毫摩尔氢氧化钠,0.003毫摩尔醋酸钯,1.2毫升甲苯,充入N2保护,在110℃搅拌反应16小时后,停止加热及搅拌,冷却至室温,稀释反应液,过滤,减压旋蒸去除溶剂,再通过柱层析分离纯化,所用的柱层析洗脱液为体积比为100:1的二氯甲烷:氨气甲醇混合溶剂,得到黄色固体目标产物,产物结构鉴定结果与实施例1相同,产率31%。
实施例8
在schlenk管中加入0.5毫摩尔邻菲罗啉、2.0毫摩尔异丙醇、0.5毫摩尔氢氧化钠,0.003毫摩尔醋酸钯,1.2毫升甲苯,充入N2保护,在160℃搅拌反应16小时后,停止加热及搅拌,冷却至室温,稀释反应液,过滤,减压旋蒸去除溶剂,再通过柱层析分离纯化,所用的柱层析洗脱液为体积比为100:1的二氯甲烷:氨气甲醇混合溶剂,得到黄色固体目标产物,产物结构鉴定结果与实施例1相同,产率35%。
实施例所得产物2,3′-联(1,10-菲罗啉)的荧光性能测试:
(1)溶液的配制
探针溶液的配制:配置浓度为100μM的2,3′-联(1,10-菲罗啉)的甲醇原液,常温保存。
(2)各种金属离子溶液的配制:Fe2+,Mg2+,Cu+,Cu2+,Sn4+,Mn2+,Co2+,Li+,K+,Ba2+,Cd2 +,Ca2+,Hg2+,Al3+,Fe3+和Ni2+溶液由它们的盐酸盐制备。分别称取一定量的金属盐,溶于10mL蒸馏水中,配制成10-2mol/L的离子溶液,保存备用。
(3)荧光测试方法:通过荧光光谱对Fe2+,Mg2+,Cu+,Cu2+,Sn4+,Mn2+,Co2+,Li+,K+,Ba2 +,Cd2+,Ca2+,Hg2+,Al3+,Fe3+和Ni2+在CH3OH-H2O(v:v=1:1)溶液中与化合物的相互作用进行研究。其中待测液的配置:先准确配置浓度为100μM的2,3′-联(1,10-菲罗啉)的甲醇溶液,不含金属离子的待测液是取0.5mL原液、2.5mL水和2mL甲醇溶液,含有金属离子的待测液是0.5mL原液、0.5mL含有金属离子的水溶液和4mL CH3OH-H2O(v:v=1:1)溶液。将溶液混合后室温下静止10min再进行测试。
化合物2,3′-联(1,10-菲罗啉)的甲醇溶液具有强烈的蓝色荧光,当向化合物2,3′-联(1,10-菲罗啉)的甲醇溶液中加入1eq.的Fe2+,Mg2+,Cu+,Cu2+,Sn4+,Mn2+,Co2+,Li+,K+,Ba2+,Cd2+,Ca2+,Hg2+,Al3+,Fe3+时,其荧光强度变化较小,当加入1eq.的Ni2+时,其荧光强度出现明显的荧光衰减(如图3浅色柱状图所示)。此外,为了验证该化合物对镍离子的专一性,我们进行了竞争实验测试,将相同浓度的干扰离子(Fe2+,Mg2+,Cu+,Cu2+,Sn4+,Mn2+,Co2+,Li+,K+,Ba2+,Cd2+,Ca2+,Hg2+,Al3+,Fe3+)与镍离子(10μM)同时加入化合物2,3′-联(1,10-菲罗啉)的甲醇溶液中,检测结果如图3(深色柱状图)所示,由图中可以看出,加入其它竞争离子前后2,3′-联(1,10-菲罗啉)对Ni2+的检测几乎是没有变化的,这说明设计的探针对金属离子具有选择性响应,符合实际应用的要求。
通过在化合物2,3′-联(1,10-菲罗啉)甲醇水溶液中添加不同浓度的Ni2+测试其荧光性能,考察了该化合物对Ni2+的检测范围。结果如图4所示,由图中结果可以看出,化合物2,3′-联(1,10-菲罗啉)的荧光强度随着Ni2+浓度的增加逐渐减弱,当Ni2+浓度达到40μM时,该化合物的荧光强度出现了大幅度的衰减。该化合物对Ni2+的检测范围是从0.005μM到40μM,其检测限为5×10-9M,表明该化合物对Ni2+的检测能力已经达到ppm级别,可进行痕量检测,具有较高的实际应用价值。此外,化合物2,3′-联(1,10-菲罗啉)甲醇水溶液随着Ni2+浓度变化的荧光强度可以通过肉眼直接观察,说明将该化合物制成检测Ni2+的仪器是切实可行的。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种荧光化合物,其特征在于:所述荧光化合物为2,3′-联(1,10-菲罗啉),其具有式(I)所示的结构式:
2.权利要求1所述的一种荧光化合物的合成方法,其特征在于包括以下步骤:
在反应器中,加入邻菲罗啉、醇、金属催化剂和溶剂,再加入碱为促进剂,通入惰性气体,在100~160℃下搅拌反应1~48小时,反应结束后冷却至室温,稀释反应液,过滤,减压蒸馏得粗产物,经薄层层析或柱层析提纯得到2,3′-联(1,10-菲罗啉)化合物。
3.根据权利要求2所述的一种荧光化合物的合成方法,其特征在于:所述的反应器是指schlenk管,所述的惰性气体为氮气或氩气。
4.根据权利要求2所述的一种荧光化合物的合成方法,其特征在于:所述的醇是指甲醇、乙醇或异丙醇。
5.根据权利要求2所述的一种荧光化合物的合成方法,其特征在于:所述邻菲罗啉与醇的摩尔比为1:(1~20)。
6.根据权利要求2所述的一种荧光化合物的合成方法,其特征在于:所述的金属催化剂为醋酸铜、醋酸钯、双三苯基膦二氯化钯、三氯化铱中的一种或两种以上的混合。
7.根据权利要求2所述的一种荧光化合物的合成方法,其特征在于:所述的溶剂为乙腈、1,4-二氧六环、甲苯、对二甲苯、甲醇、叔戊醇和水中的一种或两种以上的混合。
8.根据权利要求2所述的一种荧光化合物的合成方法,其特征在于:所述碱为碳酸钠、氢氧化钠、甲醇钠、叔丁醇钾、叔丁醇钠和三乙胺中的一种或两种以上的混合,碱的加入量与邻菲罗啉的摩尔比为(0.5~5):1。
9.根据权利要求2所述的一种荧光化合物的合成方法,其特征在于:所述的柱层析提纯所用的洗脱液为二氯甲烷:氨气甲醇的体积比为(20~100):1的混合溶剂。
10.权利要求1所述的荧光化合物作为荧光探针用于中性条件下的水环境体系中Ni2+的检测。
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