CN111423427A - 一种快速检测三价镓离子的荧光探针及其合成方法和应用 - Google Patents
一种快速检测三价镓离子的荧光探针及其合成方法和应用 Download PDFInfo
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Abstract
本发明公开了一种快速检测Ga3+离子的荧光探针及其合成方法和应用。该探针由4‑甲基‑7‑羟基‑8‑醛香豆素与2‑噻吩甲酰肼经席夫碱反应制备而成,不但能够实现Ga3+离子荧光光谱的检测,而且具有响应时间短、检测特异性好、抗干扰能力强的优点。
Description
技术领域
本发明涉及一种快速检测三价镓离子的荧光探针及其合成方法和应用,属于分析测试领域。
背景技术
镓离子作为一种稀土元素离子,具有优良的光电性能,已经倍广泛用于金属催化、磷光材料、低温发光材料、太阳能电池、上转换材料和长余辉材料等。镓离子的广泛使用给环境安全和生物体的健康带来了一定潜在威胁。研究表明,镓会导致钙和磷酸盐在小鼠肾脏堆积,堵塞肾腔。而人类在服用浓度高于750mg/kg镓时也会表现出对肾脏的毒性。但是,低浓度的镓离子及其配合物可以用于恶性肿瘤,晚期佩吉特氏骨病和血钙过多综合征等疾病的治疗。因此,开发一种可靠、简便的方法来检测Ga3+离子是非常重要的。
目前报道的用于Ga3+离子分析测试的方法荧光计和中子活化法,测量前需要对样品进行浓缩,通过溶剂提取,提高了灵敏度,或需要进行种子活化,预处理时间长,难以实时检测。
发明内容
本发明的目的是针对上述缺陷,提供一种Ga3+离子荧光探针,能够实现对Ga3+离子的快捷检测。本发明提供的荧光探针具有以下化学结构:
本发明所述的荧光探针的合成方法为:在乙醇溶液中,加入7-羟基-4-甲基-8-甲醛香豆素与1~1.2倍摩尔量的2-噻吩甲酰肼,然后在60~90℃条件下搅拌4~6小时后,冷却,减压抽滤除去溶剂。
本发明所述的荧光探针应用于各种介质中Ga3+离子的荧光光谱检测。
试验结果表明:
(1)该探针结构简单,易于制备。
(2)该探针对Ga3+离子具有良好荧光响应性,响应时间短。
(3)荧光选择性好,抗干扰能力强。
本发明的有益效果是:
(1)本发明探针能够实现对Ga3+离子的荧光定量检测。
(2)检测过程短,响应迅速,3分钟就能完成与Ga3+离子的相互作用。
(3)检测性能优良,其它金属离子没有显现出显著的干扰性。
附图说明
图1探针(20μmol/L)与Ga3+离子(50μmol/L)作用后紫外吸光谱的变化。
图2探针对Ga3+离子的荧光选择性(激发波长360nm)。
图3探针对Ga3+离子荧光检测效果的抗干扰性能(激发波长360nm,荧光强度468nm)。
图4探针与不同浓度Ga3+离子作用后的荧光光谱。
图5探针对于Ga3+离子的荧光响应线性关系。
图6探针对于Ga3+离子的强光强度随时间的变化情况。
具体实施方式
下面通过具体实施例对本发明进行详细地说明。
实施例1探针的合成和结构表征
由2-噻吩甲酰肼与7-羟基-4-甲基-8-甲醛香豆素经缩合反应最终得到目标产物。
探针的合成探针路线如下:
合成步骤:
目标化合物-肼探针的制备:将7-羟基-4-甲基-8-甲醛香豆素(0.41g,2mmol))和2-噻吩甲酰肼(0.30g,2.1mmol)溶于15mL无水乙醇中,65~85℃搅拌3小时,冷却,抽滤,冷乙醇洗涤一次得浅黄色固体,产率81%。
通过核磁共振氢谱、碳谱和质谱确认该探针的结构。
1H NMR(500MHz,DMSO-d6)δ12.64(s,1H),12.49(s,1H),9.11(s,1H),7.96,7.95(d,J=5Hz,2H),7.75,7.73(d,J=8Hz,1H),7.29,7.28(d,J=5Hz,1H),7.00,6.98(d,J=10Hz,1H),6.28(s,1H),2.42(s,3H).13C NMR(126MHz,DMSO-d6)δ161.45,159.71,157.84,154.41,152.97,143.74,137.36,133.22,130.10,128.90,128.67,113.94,112.37,111.23,106.05,18.81.EI-MS calcd for C16H12N2O4S328.05,found 329.05([M+H]+).
实施例2探针对Ga3+离子紫外吸收光谱的影响
1.如图1所示,在N,N-二甲基亚砜与水体积比为1:1组成的磷酸缓冲溶液(pH 7.4)中,探针(20μmol/L)本身紫外吸收在360nm处,加入50μmol/LGa3+后,位于360nm处的紫外吸收峰蓝移到310nm。
2.如图2所示,在N,N-二甲基亚砜与水体积比为1:1组成的磷酸缓冲溶液(pH 7.4,在360nm激发波长下,探针(20μmol/L)的荧光强度非常微弱,加入50μmol/L各金属离子包括Li+,K+,Na+,Ag+,Hg2+,Zn2+,Cu2+,Ca2+,Co2+,Ni2+,Pb2+,Mg2+,Cr3+,Fe3+,Mn2+,Ba2+,Cd2+,Al3+,In3 +和Ga3+后,只有Ga3+离子能引起探针荧光强度的显著增强,说明探针对Ga3+离子具有良好的荧光选择性。
3.如图3所示,在360nm激发波长下,当探针(20μmol/L)与Ga3+(50μmol/L)共存时,浓度均为50μmol/L的其它各金属离子包括1:Li+,2:K+,3:Na+,4:Ag+,5:Hg2+,6:Zn2+,7:Ca2+,8:Co2+,9:Pb2+,10:Mg2+,11:Cr3+,12:Ni2+,13:Fe3+,14:Cu2+,15:Mn2+,16:Ba2+,17:Cd2+,18:Al3 +和19:In3+都不能引起探针荧光强度的显著降低,说明其它常见的金属离子对探针检测Ga3+离子没有显著的干扰,该探针具有良好的抗干扰性能。
4.如图4所示,在N,N-二甲基亚砜与水体积比为1:1组成的磷酸缓冲溶液(pH 7.4,探针(20μmol/L)的荧光强度Ga3+离子浓度(0,2,4,6,8,10,12,15,20,25,30,35,40,45,50μmol/L)的增加逐渐增强。
5.如图5所示,Ga3+离子浓度在2~12μmol/L的范围内,探针在468nm处的荧光强度与Ga3+离子浓度之间满足良好的线性关系:y=-81.5+46.6x(R2=0.9914)。表明该探针(20μmol/L)可以在2~12μmol/L的范围内对Ga3+离子浓度进行定量检测。
6.如图6所示,探针(20μmol/L)与50μmol/L Ga3+离子混合后,3分钟探针在468nm的荧光强度能够接近最大值,表明该探针对Ga3+离子响应迅速。
实施例3探针对水中Ga3+离子的检测
通过加标回收的方式,分别向自来水和池塘水中加入4μmol/L,6μmol/L和10μmol/L的Ga3+离子,用磷酸缓冲溶液及N,N-二甲基亚砜调节至N,N-二甲基亚砜与水溶液体积比1:1,在比色皿中测试其荧光强度,把荧光强度带入探针与Ga3+离子的线性方程(如图5)即可求得待测样品溶液中Ga3+离子的浓度。回收率达可到87.5~95.4%的范围。
综上,该探针可以用于对Ga3+离子的荧光检测,并且响应时间短,选择性好,抗干扰能力强,能够实现水溶液中Ga3+离子的检测。
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