CN110563751B - 一种苯腙类荧光探针及其制备和应用 - Google Patents
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Abstract
本发明公开了一种苯腙类荧光探针及其制备和应用，该苯腙类荧光探针在Al3+,Ba2+,Cu2+,Hg2+,Mg2+,Ag+,Ni2+,Zn2+中，荧光性都能得到增强，在Mg2+,Ni2+中甚至增强二十几倍。但在Fe3+中，其荧光几乎完全淬灭，由此表明，该络合苯腙对铁金属离子具有较好的选择性，可用于铁离子的裸眼定性鉴别。
Description
技术领域
本发明属于荧光化学传感技术领域，该类化合物以对铁离子有高选择性的荧光淬灭检测的荧光探针。
背景技术
苯腙结构及其络合物具有独特结构及催化活性,已成为配位化学研究的热点，2010年浙江大学倪旭峰等将稀土氯化物与苯腙钠盐的交换反应制备了一系列以3,5-二叔丁基水杨醛缩苯胺为主体分子的苯腙结构络合物，发现该系列络合物可以单组分催化ε-己内酯开环聚合，对单体转化率最高可达100％，2010年，日本的Shinya Handa在J.A.C.S上报道，同时含过渡金属Li与稀土金属La的双金属苯腙络合物在硝基-Mannich反应中有很好的不对称催化活性。报道了以N-甲酸甲酯取代苯腙类化合物为底物，经氯化、环合，制备了一系列1,4二取代甲酸酯-S-四嗪衍生物，并进行了生物活性测试，证明对P-388和A-549肿瘤细胞在固定浓度下有一定的抑制作用。
苯腙结构及其络合物还被广泛地应用于有机化学、无机化学、分析化学、生物化学、药物化学、电化学及染料化学等诸多行业中，如制备半导体材料、特种陶瓷及电致发光材料、烯烃的金属催化聚合中用作辅助催化剂、有机合成中作为重要的反应试剂等，2011年Ivan等在JOC上报道把腙的锌配合物作为参考的路易斯酸来比较常用的路易斯碱的碱性强度。目前，对过渡金属的苯腙结构及其络合物的报道很多，但苯腙结构氟硼荧络合的报道却不多，在荧光性能方面的研究则更少。本发明设计并合成一系列N-甲酸甲酯取代苯腙类化合物，并用BF3.Et2O络合得到苯腙硼络合物，测试苯腙及络合物的荧光性能，发掘在有机发光材料、荧光探针方面的应用潜力。
发明内容
本发明提供了一种苯腙类荧光探针及其制备和应用，该类化合物是对铁离子有高选择性荧光淬灭，可以用于铁离子的鉴别。
一种苯腙类荧光探针，为化合物IV-2或化合物IV-3；
化合物IV-2的结构式如下：
化合物IV-3的结构式如下：
其中，R1选自一个或者多个OH、甲氧基或甲基；
R2选自H或甲基；
R3选自H或羟基。
作为优选，所述的腙类荧光探针为化合物IV-2a、IV-2b、IV-2c、IV-2d、IV-2e或IV-3a；
化合物IV-2a、IV-2b、IV-2c、IV-2d和IV-2e的结构式如下：
化合物IV-3a结构式如下：
本发明的苯腙类化合物之一IV-2b在Al3+,Ba2+,Cu2+,Hg2+,Mg2+,Ag+,Ni2+,Zn2+中，荧光性都能得到增强，在Mg2+,Ni2+中甚至增强二十几倍。但在Fe3+中荧光几乎完全淬灭，由此表明，IV-2b对铁离子具有较好的选择性，可用于裸眼定性鉴别铁离子。
本发明还提供了一种所述的苯腙类荧光探针的制备方法，包括以下步骤：
碳酸二甲酯与水合肼经甲氧基化反应制得肼基甲酸甲酯，肼基甲酸甲酯与取代的芳香醛(酮)经缩合得到N-甲酸甲酯取代苯腙类化合物，在络合阶段，以N,N-二异丙基乙胺做缚酸剂，用甲苯做溶剂，反应结束后经过后处理得到所述的苯腙类氟硼荧光化合物。
反应方程式如下：
具体制备方法如下：
在三口圆底烧瓶中，投入水合肼、碳酸二甲酯。升温至80℃回流7小时。反应结束后减压蒸除甲醇和过量碳酸二甲酯，达到蒸馏终点，有大量泡沫产生后停止蒸馏，冷却至室温后析出白色固体，产物用乙醇重结晶，得白色晶体IV-1。
三口圆底烧瓶中，加入2,4-二羟基苯乙酮、肼基甲酸甲酯，乙醇，加热至回流。反应结束后，冷却到室温，放入冰箱，析出大量白色固体，抽滤，用少量乙醇淋洗，乙醇重结晶，得白色粉末IV-2a
在三口圆底烧瓶中，加入2,4-二羟基苯甲醛、肼基甲酸甲酯、甲醇，升温至回流。TLC跟踪检测，反应结束后，待冷却到室温，放入冰箱，析出大量白色固体，抽滤，用少量甲醇淋洗，乙醇重结晶，得白色晶体IV-2b三口圆底烧瓶中，加入4-甲氧基苯甲醛、肼基甲酸甲酯、乙醇，加热至回流。TLC跟踪检测(展开剂甲苯:乙酸乙酯＝7:3)，反应结束后，冷却到室温，放入冰箱，析出大量白色固体，抽滤，用少量乙醇淋洗，乙醇重结晶，得白色晶体IV-2c。
三口圆底烧瓶中，加入3,5-二甲氧基-4-羟基苯甲醛，肼基甲酸甲酯、乙醇，加热至回流。TLC跟踪检测(展开剂甲苯:乙酸乙酯＝7:3)，反应结束后，冷却至室温，放入冰箱，析出大量白色固体，抽滤，用少量乙醇淋洗，乙醇重结晶，得白色晶体IV-2d。
三口圆底烧瓶中，加入4-甲基苯甲醛、肼基甲酸甲酯、乙醇，加热至回流。TLC跟踪检测(展开剂甲苯:乙酸乙酯＝7:3)，反应结束后，冷却至室温，放入冰箱，析出大量白色固体，抽滤，用少量乙醇淋洗，乙醇重结晶，得白色晶体IV-2e。
在50mL史莱克管中加入IV-2a，抽换氮气数次，氮气保护下用注射器加入甲苯，加热至回流，再滴加N,N-二异丙基乙胺。10min后，缓慢滴入三氟化硼乙醚，反应4h后点板观察反应情况(展开剂石油醚:乙酸乙酯＝1:1)。反应结束后冷却至室温，有固体析出，抽滤除去甲苯，固体用甲醇溶解后加硅胶旋干，柱层析(油醚:乙酸乙酯＝1:1)分离，得黄色络合产物IV-3a。
本发明还提供了一种所述的苯腙类荧光探针在离子检测中的应用，将苯腙类荧光探针溶于有机溶剂中，然后加入待测溶液，对荧光变化进行检测，根据检测结果确定待测溶液中所含有的金属离子。
作为优选，所述的有机溶剂为THF。
作为优选，当加入待测溶液后，发生荧光淬灭现象，则确定待测溶液中所含有的铁离子。
同现有技术相比，本发明苯腙类荧光探针对铁离子有高选择性荧光淬灭，可以用于铁离子的鉴别。在进行鉴别的时候，能够有效避免Al3+,Ba2+,Cu2+,Hg2+,Mg2+,Ag+,Ni2+,Zn2+等离子的干扰。
附图说明
图1为THF溶液中络合苯腙IV-2b(10μM)加入不同离子的荧光性能。
图2化合物IV-2c和IV-3a(1×10-5mol·L-1)在不同溶剂中的吸收光谱和发射光谱。
表2化合物IV-2和IV-3的固体荧光数据。
图3化合物IV-2和IV-3固体荧光光谱。
图4苯腙IV-2和氟硼络合物IV-3的固体荧光照片。
具体实施方式
实施例1
在250mL三口圆底烧瓶中，投入80％的水合肼(31.25g,0.37mol)、碳酸二甲酯(54g,0.6mol)。升温至80℃回流7小时。反应结束后减压蒸除甲醇和过量碳酸二甲酯，达到蒸馏终点，有大量泡沫产生后停止蒸馏，冷却至室温后析出白色固体，产物用乙醇重结晶，得白色晶体IV-1 25.5g，收率74.91％，m.p.72-73℃。
实施例2
50mL三口圆底烧瓶中，加入2,4-二羟基苯乙酮(1.52g,10mmol)、肼基甲酸甲酯(0.92g,10mmo l)、乙醇(25mL)，加热至回流。TLC跟踪检测(展开剂甲苯:乙酸乙酯＝9:1)，反应结束后，冷却到室温，放入冰箱，析出大量白色固体，抽滤，用少量乙醇淋洗，乙醇重结晶，得白色粉末IV-2a 1.95g，收率87.1％，m.p.208.8℃-212.3℃。1H NMR(500MHz,DMSO)δ:13.04(s,1H),10.59(s,1H),9.72(s,1H),7.33(d,J＝8.7Hz,1H),6.29(dd,J＝8.7,2.4Hz,1H),6.23(d,J＝2.4Hz,1H),3.74(s,3H),2.23(s,3H)；HRMS(ESI)m/z calcd for:C10H13N2O4 +(M+H)+225.0869,found225.0869。
实施例3
在50mL三口圆底烧瓶中，加入2,4-二羟基苯甲醛(1.38g,10mmol)、肼基甲酸甲酯(0.92g,10mmo l)、甲醇(20mL)，升温至回流。TLC跟踪检测(展开剂甲苯:乙酸乙酯＝8:2)，反应结束后，待冷却到室温，放入冰箱，析出大量白色固体，抽滤，用少量甲醇淋洗，乙醇重结晶，得白色晶体IV-2b 1.77g，收率84.3％，m.p.109℃-113℃。1HNMR(500MHz,DMSO)δ:11.07(d,J＝42.9Hz,2H),9.81(s,1H),8.10(s,1H),7.20(dd,J＝8.3,2.8Hz,1H),6.44-6.20(m,2H),3.69(s,3H)；HRMS(ESI)m/z calcd for C9H11N2O4 +(M+H)+211.0713,found211.0713。
实施例4
50mL三口圆底烧瓶中，加入4-甲氧基苯甲醛(1.36g,10mmol)、肼基甲酸甲酯(0.92g,10mmo l)、乙醇(30mL)，加热至回流。TLC跟踪检测(展开剂甲苯:乙酸乙酯＝7:3)，反应结束后，冷却到室温，放入冰箱，析出大量白色固体，抽滤，用少量乙醇淋洗，乙醇重结晶，得白色晶体IV-2c1.69g，收率81.3％，m.p.140℃-142℃。1HNMR(500MHz,CDCl3)δ:12.45(s,1H),7.43(d,J＝7.7Hz,1H),7.29(dd,J＝9.1,2.1Hz,1H),7.00(dd,J＝8.2,1.1Hz,1H),6.93-6.84(m,1H),3.91(s,3H),2.30(s,3H)；HRMS(ESI)m/z calcd for C10H13N2O3 +(M+H)+209.0921,found209.0921。
实施例5
50mL三口圆底烧瓶中，加入3,5-二甲氧基-4-羟基苯甲醛(1.8g,10mmol)、肼基甲酸甲酯(0.92g,10mmo l)、乙醇(20mL)，加热至回流。TLC跟踪检测(展开剂甲苯:乙酸乙酯＝7:3)，反应结束后，冷却至室温，放入冰箱，析出大量白色固体，抽滤，用少量乙醇淋洗，乙醇重结晶，得白色晶体IV-2d 1.88g，收率74.0％，m.p.242.5℃-247.1℃。
实施例6
50mL三口圆底烧瓶中，加入4-甲基苯甲醛(1.2g,10mmol)、肼基甲酸甲酯(0.92g,10mmo l)、乙醇(20mL)，加热至回流。TLC跟踪检测(展开剂甲苯:乙酸乙酯＝7:3)，反应结束后，冷却至室温，放入冰箱，析出大量白色固体，抽滤，用少量乙醇淋洗，乙醇重结晶，得白色晶体IV-2e
1.73g，收率90.1％，m.p.157.2℃-160.3℃。
实施例7
在50mL史莱克管中加入IV-2a(210.0mg,1mmol)，抽换氮气数次，氮气保护下用注射器加入甲苯10mL，加热至回流，再滴加N,N-二异丙基乙胺(0.70mL，4.00mmol)。10min后，缓慢滴入三氟化硼乙醚(0.50mL，4.00mmol)，反应4h后点板观察反应情况(展开剂石油醚:乙酸乙酯＝1:1)。反应结束后冷却至室温，有固体析出，抽滤除去甲苯，固体用甲醇溶解后加硅胶旋干，柱层析(油醚:乙酸乙酯＝1:1)分离，得黄色络合产物IV-3a(80.0mg，收率31.0％)。m.p.233.5℃-235.1℃。1HNMR(500MHz,DMSO)δ:8.72(s,1H),7.36(d,J＝8.6Hz,1H),6.35(dd,J＝8.5,2.2Hz,1H),6.29(d,J＝2.1Hz,1H),4.03(d,J＝7.1Hz,1H),3.44(d,J＝7.0Hz,3H),2.51(s,3H)；HRMS(ESI)m/z calcd for C10H12BF2N2O4 +(M+H)+273.0853,found273.0867。
测试例1
检测方法如下：向苯腙类荧光探针IV-2b的THF溶液中，加入1.0当量的Al3+,Ba2+,Cu2+,Fe3+,Hg2+,Mg2+,Ag+,Ni2+,Zn2+，测试其荧光，在Al3+,Ba2+,Cu2+,Hg2+,Mg2+,Ag+,Ni2+,Zn2+中，IV-2b的荧光性都能得到增强，在Mg2+,Ni2+中甚至增强二十几倍。但在Fe3+中，其荧光几乎完全淬灭，根据探针溶液的荧光变化来判断是否含有铁离子。
向苯腙类荧光探针IV-2b的THF溶液中，加入1.0当量的Al3+,Ba2+,Cu2+,Fe3+,Hg2+,Mg2+,Ag+,Ni2+,Zn2+，测试其荧光数据(图1)。从图中可以看出，在Al3+,Ba2+,Cu2+,Hg2+,Mg2+,Ag+,Ni2+,Zn2+中，IV-2b的荧光性都能得到增强，在Mg2+,Ni2+中甚至增强二十几倍。但在Fe3+中，其荧光几乎完全淬灭，根据探针溶液的荧光变化来判断是否含有铁离子。由此表明，IV-2b对金属离子具有较好的选择性，在金属探针方面有应用的潜力。
测试例2
利用本发明的含对甲氧基的苯腙IV-2c和含对羟基的氟硼荧络合衍生物IV-3a研究不同溶剂中的吸收和荧光发射光谱。表1为化合物IV-2和IV-3在不同溶剂中和固体的光谱数据，图2是化合物IV-2c和IV-3a(1×10-5mol·L-1)在不同溶剂中的吸收光谱和发射光谱。
表1化合物IV-2和IV-3在不同溶剂中的光谱数据
由表1可知，苯腙化合物IV-2c在320nm左右出现一个明显的吸收峰，而氟硼络合分子IV-3a的最大吸收波长在368nm，较其对应苯腙IV-2a的最大吸收波长红移50nm。由图2可知，在吸收光谱中，不同溶剂对氟硼络合物及苯腙的紫外最大吸收波长影响不大。苯腙IV-2c在不同溶剂中的吸光度有较大差别，对于苯腙IV-2c，在CHCl3中的吸收最强，而不同溶剂对于氟硼络合物IV-3a吸光度的影响较小。在荧光性能方面，溶剂对苯腙及氟硼络合物的影响都很明显。对于苯腙IV-2c，其在THF中的荧光最强，而在DCM中荧光最弱，最大荧光发射波长均在350nm左右；对于氟硼络合物IV-3a，其在EA中的荧光最强，除EtOH外，在所选溶剂中的最大荧光发射波长均在405nm左右，较其苯腙红移了30nm左右。有意思的是氟硼络合物IV-3a在EtOH中的最大荧光发射波长为508nm，较其他溶剂整整红移134nm。
测试例3
本测试例研究了苯腙及其氟硼络合物的固体荧光性能，结果见表2和图3和图4。图3为化合物IV-2和IV-3固体荧光光谱，图4为苯腙IV-2和氟硼络合物IV-3的固体荧光照片(上排自然光，下排365nm紫外灯)。
表2化合物IV-2和IV-3的固体荧光数据
从表2、图3和图4中的IV-2和IV-3的固体荧光数据和照片可以看出，苯腙氟硼络合物IV-3a及苯腙在紫外灯下均有明显的荧光。且苯腙的氟硼络合物IV-3a的固体荧光较其苯腙IV-2a红移37nm，日光灯下，颜色也由苯腙的浅红色变成黄色。4个化合物中，IV-2b的固体荧光最强，而苯腙氟硼络合物IV-3a的荧光反应最弱，无论是苯腙还是氟硼络合物，均具有较大的斯托克斯位移(St)，其中IV-2c的斯托克斯位移高达200nm。
Claims (2)
1.一种苯腙类荧光探针在铁离子检测中的应用，其特征在于，将苯腙类荧光探针溶于有机溶剂中，然后加入待测溶液，对荧光变化进行检测，根据检测结果确定待测溶液中所含有的金属离子；
当加入待测溶液后，发生荧光淬灭现象，则确定待测溶液中含有铁离子；
所述的腙类荧光探针为化合物IV-2a、IV-2b或IV-2c；
化合物IV-2a、IV-2b或IV-2c的结构式如下：
2.根据权利要求1所述的苯腙类荧光探针在铁离子检测中的应用，其特征在于，所述的有机溶剂为THF。
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