CN110746433A - 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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- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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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:
一种快速检测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:
本发明中一种快速检测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。
的Al3+。
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11H NMR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 (6)
2.一种快速检测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,有机相用无水硫酸钠干燥后,过滤,减压蒸馏除去溶剂得到化合物1。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。得到紫色固体即为所述的Al3+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Al3+荧光传感器的制备方法,其特征在于,罗丹明B与邻苯二胺的摩尔比为1∶2。
4.如权利要求2所述的Al3+荧光传感器的制备方法,其特征在于,化合物1与吡啶-3-磺酰氯的摩尔比为1∶1.5。
5.如权利要求2所述的Al3+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为CH2Cl2/乙酸乙酯=9∶1。
6.快速检测Al3+的罗丹明B类荧光传感器的应用,其特征在于:将权利要求1中所述的基于吡啶-3-磺酰氯的荧光传感器用于检测水相中的Al3+。
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