CN110746433B - 一种检测Al3+的罗丹明B类荧光传感器的制备及应用 - Google Patents
一种检测Al3+的罗丹明B类荧光传感器的制备及应用 Download PDFInfo
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Abstract
本发明提供一种罗丹明B类荧光传感器应用于水相中选择性强、响应时间短、灵敏度高的检测Al3+的方法。采用荧光分光光度计以及紫外‑可见分光光度计测定水相中罗丹明B类探针的特征峰的强度变化，进而确定Al3+的存在。本发明以罗丹明B(Rhodanmine B)为原料合成基于邻苯二胺和吡啶‑3‑磺酰氯的新型荧光传感器。本发明提供了该荧光传感器在Al3+检测中的应用，发现其对Al3+有很好的检测效果，并且响应很快。与现有技术相比，本发明研制成本低、易实现、操作简便，在Al3+的检测方面有很光明的应用前景。
Description
技术领域
本发明属于生物化学领域，具体涉及一种快速检测Al3+的罗丹明B类荧光传感器的制备及应用。
背景技术
铝是地壳中第三丰富的金属元素，天然存在于硅酸盐、冰晶石和铝土矿中。并且具有良好的导电导热性，高反射性和耐氧化性，因而在建筑建造等方面，到处都有铝的存在。铝元素主要以三价的形式存在于生活中，即Al3+。由于铝元素在地壳中的分布非常广泛，并且存在于我们的日常生产和生活中，因此，铝元素以及它的离子态广泛分布于空气、水和土壤中，人类便可以通过吃食物、饮水、呼吸空气等途径吸收一定量的Al3+。然而，铝元素并不是人体必需的金属元素，也不属于微量元素，当Al3+在人体中的含量积累到一定程度时，它就会对人体产生毒性。由于人体的脑组织对Al3+具有亲和性，大量的Al3+可以破坏人体的中枢神经系统和免疫系统，引起红细胞低色素性贫血，抑制体内多种酶的活性，加速人体的衰老，从而导致老年痴呆症、原发性帕金森症等疾病；大量的Al3+还可以影响人体中其它必需微量元素的吸收和利用，从而增加女性患乳腺癌的风险。由于Al3+在人体中是慢慢积蓄起来的，它引起的毒性非常缓慢，并且不容易被察觉出来。酸雨淋滤增加了土壤中Al3+的异常浓度，Al3+的含量达到一定程度时，会使土壤酸化，对植物根系和种子生长有明显的抑制作用，不利于植物生长。此外，当湖泊、河流、海洋中含有较多的Al3+时，还会抑制各种水生鱼类，包括淡水鱼的生长和发育，使这些鱼类因缺乏必需的营养素而死亡。因此，设计出来一种高选择性、高灵敏度检测环境中Al3+的含量也是非常关键的。
目前，广泛使用的检测技术主要包括电感耦合等离子体发射光谱法(ICP-OES)、电感耦合等离子体质谱法(ICP-MS)、石墨炉原子吸收光谱法(GF-AAS)和原子荧光光谱法(AFS)。然而，这些方法中的大多数都受到步骤繁琐、仪器昂贵或操作门槛高等短板限制，这也制约着它们的进一步发展和应用。这些方法的另一个缺点是高能量激发，高能激发会严重的损伤生物样本。因此，开发适用于自然环境和生物系统的新型铝离子(Al3+)检测手段是非常重要的，尤其是一些低成本和快速响应的检查手段的研发。与传统的铝离子的检测方法相比，近年来运用光学手段检测重金属离子的分子探针凭借其研制成本低、便捷、易实现、响应快、能适用于自然环境以及生物体系、检测限低、灵敏度高等优点得到了较多的关注。由于铝离子的配位能力较弱，而且容易水解，因此铝离子荧光探针的设计和合成一直以来是一个重大的问题。因此，开发出一种各方面性能都比较优秀的分子探针还是有一定难度的。
罗丹明B具有溶解性好、量子产率高、摩尔吸收系数大、激发波长长、发射波长延伸到可见区域等优良的光物理性质，是一种典型的荧光基团，可用于构建用于检测多种分析物的荧光化学传感器。基于罗丹明衍生物用于检测金属离子、阴离子、硫醇等的荧光探针相继被开发出来。
发明内容
本发明目的是提供一种快速检测Al3+的罗丹明B类荧光传感器的制备及其应用。
实现本发明目的的技术解决方案是：
一种检测Al3+的罗丹明B类荧光传感器RBLF，该荧光传感器RBLF的结构如下：
本发明中一种检测Al3+的罗丹明B类荧光传感器RBLF的制备方法，包括以下步骤：
将化合物1(532mg，1mmol)溶于适量二氯甲烷中，加入吡啶-3-磺酰氯(179.04μL，1.5mmol)和三乙胺(138.99μL，1mmol)，常温搅拌6h，TLC薄层色谱法监测反应进程。待反应结束后，减压蒸馏除去溶剂，最后使用CH2Cl2/乙酸乙酯(9∶1，v/v)作为洗脱液，经硅胶柱快速分离提纯化合物。得到淡粉色固体即为所述的Al3+荧光传感器。其中化合物1的结构如下：
本发明中，化合物1与吡啶-3-磺酰氯的摩尔比为1∶1.5。
本发明中，化合物1与三乙胺的摩尔比为1∶1。
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Al3+荧光传感器RBLF，具有选择性强，响应时间短，检出限较低，灵敏度高，可逆光谱性能优越，结构简单，生物相容性好等优点。(2)本发明所选用原料成本低，合成步骤简单，后处理步骤少。(3)本发明采用吡啶-3-磺酰氯与邻苯二胺缩合反应，合成方法简单，反应条件温和，且产率较高。(4)本发明所涉及荧光传感器能选择性检测Al3+变化，且灵敏度较高，在自然环境以及生物体系等诸多领域具有很好的应用前景。
附图说明
图1为本发明的化合物11H NMR。
图2为本发明的化合物荧光传感器RBLF1H NMR。
图3为本发明的化合物荧光传感器RBLF的荧光选择性。
图4为本发明的化合物荧光传感器RBLF的紫外选择性。
具体实施方式
(一)荧光传感器RBLF的合成
本发明提供了目标产物RBLF在Al3+检测中的应用，发现其对Al3+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Ag+，Al3+，Ca2+，Cd2+，Co2+，Cr3+，Fe2+，Fe3+，K+，Li+，Mg2+，Mn2+，Na+，Ni+，Pb2+，Zn2+等不同重金属离子加入化合物RBLF的溶液中，进行荧光选择性能测试。
(三)紫外测试
将Ag+，Al3+，Ca2+，Cd2+，Co2+，Cr3+，Fe2+，Fe3+，K+，Li+，Mg2+，Mn2+，Na+，Ni+，Pb2+，Zn2+等不同重金属离子加入化合物RBLF的溶液中，进行紫外选择性能测试。
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
荧光传感器的合成
1.化合物1的合成
在50mL的圆底烧瓶中将罗丹明B(960mg，2mmol)搅拌溶解于无水二氯乙烷中，在氮气保护下缓慢滴加三氯氧磷(1mL，11mmol)，随后体系回流6h。待反应结束后，减压除去溶剂和多余的三氯氧磷，得到紫色油状酰氯物。将紫色油状物重新溶解于40mL乙腈中，滴加溶解于10mL乙腈和三乙胺(1mL，7.2mmol)中的邻苯二胺(432mg，2mmol)，常温搅拌过夜，TLC薄层色谱法监测反应进程。待反应结束后，减压除去溶剂。粗产物用CH2Cl2/饱和食盐水萃取三次，反向萃取一次，有机相用无水硫酸镁干燥后，过滤，减压蒸馏除去溶剂得到化合物1。(787.8mg，74％)。化合物11HNMR如图1所示。
2.化合物RBLF的合成
将化合物1(532mg，1mmol)溶于适量二氯甲烷中，加入吡啶-3-磺酰氯(179.04μL，1.5mmol)和三乙胺(138.99μL，1mmol)，常温搅拌6h，TLC薄层色谱法监测反应进程。待反应结束后，减压蒸馏除去溶剂，最后使用CH2Cl2/乙酸乙酯(9∶1，v/v)作为洗脱液，经硅胶柱快速分离提纯化合物。得到紫色固体(342.4mg，51％)即为所述的Al3+荧光传感器RBLF。化合物RBLF的1H NMR如图2所示。
实施例2
荧光选择性能测试
荧光传感器RBLF在乙醇中具有很好的溶解性，经验证，化合物RBLF可以溶解在EtOH/H2O(2∶3，v/v)混合液中，配制400mL该溶液作为储备液。
精确配置荧光传感器RBLF为1×10-3mol/L EtOH/H2O混合液(2∶3，v/v)，CdCl2·2.5H2O，CuCl2·2H2O，AlCl3，KNO3，FeCl3·6H2O，AlCl2，NiCl2·6H2O，MgCl2·6H2O，NaCl，ZnCl2，CrCl3·6H2O，AgCl，MnCl2·4H2O，CoCl2·6H2O，CaCl2，PbCl2等浓度为5×10-3mol/L水溶液，以及EtOH/H2O(2∶3，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60μL荧光传感器RBLF，测其初始荧光强度值，然后分别加入配置好的各种阳离子60uL，测量其稳定时的荧光强度。观察图3可知，化合物RBLF对Al3+有明显的响应效果，并且在582nm处荧光强度达到最大值，也即化合物RBLF对Al3+有很好的选择性。
实施例3
紫外选择性能测试
荧光传感器RBLF在乙醇中具有很好的溶解性，经验证，化合物RBLF可以溶解在EtOH/H2O(2∶3，v/v)混合液中，配制400mL该溶液作为储备液。
精确配置荧光传感器RBLF为1×10-3mol/L的EtOH/H2O混合液(2∶3，v/v)，CdCl2·2.5H2O，CuCl2·2H2O，AlCl3，KNO3，FeCl3·6H2O，AlCl2，NiCl2·6H2O，MgCl2·6H2O，NaCl，ZnCl2，CrCl3·6H2O，AgCl，MnCl2·4H2O，CoCl2·6H2O，CaCl2，PbCl2等浓度为5×10-3mol/L水溶液，以及EtOH/H2O(2∶3，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60μL荧光传感器RBLF，测其初始吸光度，然后分别加入配置好的各种阳离子60μL，测量其稳定时的吸光度。观察图4可知，化合物RBLF对Al3+有明显的响应效果，在558nm处出现一个新峰，也即化合物RBLF对Al3+有很好的选择性。
Claims (4)
1.一种检测Al3+的罗丹明B类荧光传感器，其结构如下：
2.一种如权利要求1所述的检测Al3+的罗丹明B类荧光传感器的制备方法，包括以下步骤：在50mL的圆底烧瓶中将2mmol罗丹明B搅拌溶解于无水二氯乙烷中，在氮气保护下缓慢滴加11mmol三氯氧磷，随后体系回流6h；待反应结束后，减压除去溶剂和多余的三氯氧磷，得到紫色油状酰氯物；将紫色油状物重新溶解于40mL乙腈中，滴加溶解于10mL乙腈和1mL三乙胺中的2mmol邻苯二胺，常温搅拌过夜；待反应结束后，减压除去溶剂，将粗产物用CH2Cl2/饱和食盐水萃取三次，反向萃取一次，有机相用无水硫酸钠干燥后，过滤，减压蒸馏除去溶剂得到化合物1；将1mmol化合物1溶于适量二氯甲烷中，加入1.5mmol吡啶-3-磺酰氯和1mmol三乙胺，常温搅拌6h，待反应结束后减压蒸馏除去溶剂，最后使用CH2Cl2/乙酸乙酯作为洗脱液，经硅胶柱快速分离提纯后得到紫色固体即为权利要求1所述的检测Al3+的罗丹明B类荧光传感器；其中化合物1的结构如下：
3.如权利要求2所述的检测Al3+的荧光传感器的制备方法，其特征在于，硅胶柱分离采用的洗脱液中CH2Cl2/乙酸乙酯体积比为9∶1。
4.如权利要求1所述的检测Al3+的荧光传感器的应用，其特征在于：将权利要求1中所述的基于罗丹明B类的荧光传感器用于检测水相中的Al3+。
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