CN107021967B - 基于罗丹明B的Fe3+荧光传感器、制备方法及应用 - Google Patents

基于罗丹明B的Fe3+荧光传感器、制备方法及应用 Download PDF

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CN107021967B
CN107021967B CN201710333989.1A CN201710333989A CN107021967B CN 107021967 B CN107021967 B CN 107021967B CN 201710333989 A CN201710333989 A CN 201710333989A CN 107021967 B CN107021967 B CN 107021967B
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包晓峰
华青涵
周彤
陈相雪
王宇
吴小磊
舒海
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Abstract

本发明公开了一种基于罗丹明B的Fe3+荧光传感器、制备方法及应用。本发明以罗丹明B（Rhodanmine B)为前体合成目标产物1,3‑双（2‑（3’，6’‑双（二乙基氨基）‑3‑氧杂螺[异吲哚‑1，9’–咕吨‑]咪唑‑2‑乙基硫脲））。本发明提供了目标产物在Fe3+检测中的应用，发现其对Fe3+有很好的检测效果，与现有技术相比，本发明采用的原料易得，合成步骤简单，后处理亦很方便，较易实现大规模生产，在检测Fe3+方面有很大的应用前景。

Description

基于罗丹明B的Fe3+荧光传感器、制备方法及应用
技术领域
本发明属于生物化学领域，具体涉及一种基于罗丹明B的Fe3+荧光传感器、制备方法及应用。
背景技术
目前，检测Fe3+的方法主要有：原子吸收分光光度法、伏安法、比色法和流动注射法，然而这些方法存在很多缺点，如所需仪器价格较为昂贵费时，携带不便，敏感性差，所测定的Fe3+浓度范围不大，对于含Fe3+量较小的细胞中测量则更是困难等。与此相反，由于化学发光不需要任何光源，因而在对荧光探针进行化学发光成像检测时，不存在荧光检测或者荧光成像时不可避免的光学背景的干扰，从而可以获得更低的检出限。
罗丹明类染料由于其摩尔吸光系数较大，荧光量子产率高、光谱性能优越、结构简单、易于修饰、吸收波长范围广等优势，已经被广泛应用与分子探针设计，目前，罗丹明类分子探针多用于检测Al3+，Cr3+，Zn2+等。
文献1(Weerasinghe AJ,Schmiesing C,Varaganti S,et al.Single-andmultiphoton turn-on fluorescent Fe(3+)sensors based on bis(rhodamine).[J].J.phys.chem.b,2010, 114(29):9413-9419..)报道了一种罗丹明酰肼和醛基物缩合反应，合成出一种新型的 Fe3+传感器的方法，产率85％。
文献2(Yang M,Meng W,Ding Q,et al.Novel fluorescent probes based onrhodamine for naked-eye detection of Fe3+and their application of imaging inliving cells[J].New Journal of Chemistry,2015,39.)报道了一种利用罗丹明B与氨基缩合反应合成出一种新型的Fe3+传感器的方法，产率49％。
上述文献所报道的合成方法存在以下缺陷
(1)如文献1中，合成的探针水溶性较差，75％都是乙腈。
(2)如文献2中，合成的探针的产率较低，仅为49％。
上述缺陷造成至今为止，应用现有工艺方法难以得到生产成本低、荧光强度高，选择性较好的Fe3+传感器制备方法。
发明内容
本发明目的是提供一种用于检测对Fe3+的分子探针、制备方法及应用。
实现本发明目的的技术解决方案是：
一种基于罗丹明B的Fe3+荧光传感器，该荧光传感器的结构如下：
基于罗丹明B的Fe3+荧光传感器的制备方法，包括如下步骤：
将罗丹明乙二胺与二硫化碳在0-5℃下溶于二氯甲烷，之后常温反应2-3h，反应完成之后，减压除去溶剂，萃取，硅胶柱分离，得到白色粉末即为所述Fe3+荧光传感器。
本发明中，罗丹明乙二胺与二硫化碳的摩尔比为2：1。
本发明中，反应得到的粗产物使用硅胶柱进行分离纯化，洗脱液为MeOH： CH2Cl2＝2：98(v/v)。
本发明中所述的基于罗丹明B的Fe3+荧光传感器用于检测Fe3+。
本发明与现有技术相比，其显著优点是：(1)本发明以罗丹明为主体合成了一种新型Fe3+荧光传感器，具有良好的光稳定性，长波长发射以及量子产率高等优点。(2 )本发明所选用原料成本低，合成步骤简单，后处理亦很方便，较易实现大规模生产。(3)本发明合成方法简单，反应条件温和，且产率较高。(4)本发明所涉及传感器能选择性检测Fe3+变化，且灵敏度较高，在检测环境中的Fe3+方面具有很大的应用前景。
附图说明
图1为本发明的化合物2 1H NMR。
图2为本发明的化合物2 13C NMR。
图3为本发明的化合物2的荧光选择性。
图4为本发明的化合物2的紫外选择性。
具体实施方式
(一)传感器化合物的合成
本发明提供了目标产物在Fe3+检测中的应用，发现其对Fe3+有很好的检测效果。本发明合成路线如下：
(二)荧光性能测试
将CdCl2·2.5H2O,CuCl2·2H2O,AlCl3,KCl,FeCl3·6H2O,PbCl2,AgNO3,HgCl2,NiCl2·6H2O,MgCl2·6H2O,NaCl,ZnCl2,CrCl3·6H2O,Ba(NO3)2,MnCl2·4H2O,CaCl2，CoCl2·6H2O,CaCl2等不同重金属离子加入化合物2的溶液中，进行荧光响应测试。 (三)紫外测试
将CdCl2·2.5H2O,CuCl2·2H2O,AlCl3,KCl,FeCl3·6H2O,PbCl2,AgNO3,HgCl2,NiCl2·6H2O,MgCl2·6H2O,NaCl,ZnCl2,CrCl3·6H2O,Ba(NO3)2,MnCl2·4H2O, CoCl2·6H2O,CaCl2等不同重金属离子加入化合物2的溶液中，进行紫外响应测试
下面结合附图和具体实施例对本发明作进一步详细说明。
实施例1
荧光化学传感器的合成
1.化合物1的合成
将罗丹明B(960mg，2mmol)与乙二胺(1.3ml，20mmol)在无水乙醇(40ml)中，控制反应温度在80℃，反应时间为12-13h。反应完成之后，减压除去溶剂，萃取，经硅胶柱分离得到淡黄色固体(880mg，92％)。
2.化合物2的合成
将化合物1(271.2mg,0.56mmol)与二硫化碳(15.7mg,0.28mmol)在0-5℃下溶于二氯甲烷(8ml),之后常温反应2-3h。反应完成之后，减压除去溶剂，萃取，经硅胶柱分离得到粉色粉末(226mg，81％)。化合物2 1H NMR，13C NMR分别如图1，图2所示。
实施例2
荧光选择性能测试
Fe3+荧光传感器2在乙醇中具有很好的溶解性，经验证，化合物2可以溶解在 EtOH：HEPES(1mM，pH＝7.2)＝2：1混合液中，配制500ml该溶液作为储备液 (pH＝7.26)。
精确配置Fe3+荧光传感器2为1×10-3mol/L EtOH-H2O混合液(2/1，V/V)， CdCl2·2.5H2O,CuCl2·2H2O,AlCl3,KCl,FeCl3·6H2O,PbCl2,AgNO3,HgCl2,NiCl2·6H2O, MgCl2·6H2O,NaCl,ZnCl2,CrCl3·6H2O,Ba(NO3)2,MnCl2·4H2O,CoCl2·6H2O,CaCl2等浓度为5×10- 3mol/L水溶液,以及用EtOH：HEPES(1mM,pH＝7.2，2/1,V/V)溶液。
荧光选择性实验如图3所示，取3ml储备液置于液体池中，加入60uL荧光传感器2，测其初始荧光强度值，然后分别加入配置好的各种阳60uL，测量其稳定时的荧光强度。观察图3可知，化合物2对Fe3+有明显响应效果，并且在582nm处荧光强度达到最大值，也即化合物2对Fe3+有很好的选择性。
实施例3
紫外选择性能测试
Fe3+荧光传感器2在乙醇中具有很好的溶解性，经验证，化合物2可以溶解在EtOH：HEPES(1mM，pH＝7.26)＝2：1混合液中，配制500ml该溶液作为储备液 (pH＝7.2)。
精确配置Fe3+荧光传感器2为1×10-3mol/L EtOH-H2O混合液(2/1，V/V)， CdCl2·2.5H2O,CuCl2·2H2O,AlCl3,KCl,FeCl3·6H2O,PbCl2,AgNO3,HgCl2,NiCl2·6H2O, MgCl2·6H2O,NaCl,ZnCl2,CrCl3·6H2O,Ba(NO3)2,MnCl2·4H2O,CoCl2·6H2O,CaCl2等浓度为5×10- 3mol/L水溶液,以及用EtOH：HEPES(1mM,pH＝7.2，2/1,V/V)溶液。
紫外选择性实验如图4所示，取3ml储备液置于液体池中，加入60uL荧光传感器2，测其初始吸光度，然后分别加入配置好的各种阳离子60uL，测量其稳定时的吸光度。观察图4可知，化合物2对Fe3+有明显响应效果，在558nm处出现一个新峰，也即化合物2对Fe3+有很好的选择性。

Claims (5)

1.基于罗丹明B的Fe3+荧光传感器，其特征在于，具有如下结构：
。
2.如权利要求1所述的基于罗丹明B的Fe3+荧光传感器的制备方法，其特征在于，将罗丹明乙二胺与二硫化碳在0-5℃下溶于二氯甲烷，之后常温反应2-3h，反应完成之后，减压除去溶剂，萃取，硅胶柱分离，得到所述Fe3+荧光传感器，其中，罗丹明乙二胺具有如下结构：
。
3.如权利要求2所述的制备方法，其特征在于，罗丹明乙二胺与二硫化碳的摩尔比为2：1。
4.如权利要求2所述的制备方法，其特征在于，硅胶柱分离采用的洗脱液是体积比为MeOH：CH2Cl2=2：98的混合液。
5.如权利要求1所述的基于罗丹明B的Fe3+荧光传感器在非诊断非治疗目的检测Fe3+上的应用。
CN201710333989.1A 2017-05-12 2017-05-12 基于罗丹明B的Fe3+荧光传感器、制备方法及应用 Expired - Fee Related CN107021967B (zh)

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