CN114539181B - 一种用于铝离子和锌离子快速检测的荧光探针及其制备方法 - Google Patents
一种用于铝离子和锌离子快速检测的荧光探针及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于铝离子和锌离子快速检测的荧光探针及其制备方法，属于荧光探针材料领域。该探针以苯酚腙亚胺配体为基本骨架，结构如式1所示，是一类打开型荧光传感器。本发明荧光探针合成路线短，简单易操作，对铝离子和锌离子有较高的选择性。X=O,S，
式1。
Description
技术领域
本发明涉及一种可用于铝离子和锌离子快速检测的双苯腙配体型荧光探针及制备方法，属于荧光探针材料领域。
背景技术
铝离子和锌离子在生命过程中起着重要作用，但高浓度离子会引起人体疾病和土壤污染，也会诱发精神疾病等，危害人体健康。世界卫生组织(WHO)制定了饮用水中铝含量不超过7.41μM的标准。此外，高浓度铝离子会使土壤呈酸性而抑制作物的生长，破坏生态系统。因此对环境及其生物体内铝离子浓度检测就显得尤为重要。
目前，原子荧光法、原子吸收法、电感耦合等离子体法、化学滴定法、电化学分析法和色谱分析法等金属离子检测方法被广泛用于金属离子检测。这些方法虽然有检测限低、灵敏度高等优点，但同时也存在仪器昂贵、操作复杂、前处理麻烦、时耗长、无法进行有机体内的实时测定等不足而限制了其应用。有机荧光探针具有检测限低、操作简单、成本低且能瞬时响应等特点，因此得到了越来越多科研工作者的重视，目前已有大量金属离子有机荧光探针被合成，并应用于定性识别细胞和生物体内的金属离子，但能同时实现铝离子和锌离子快速检测的荧光探针报道较少。论文(Journal of Photochemistry andPhotobiology A:Chemistry,2015,303/304:99-104)报道了一种双席夫碱型的荧光探针，在水溶液中Al3+的最低检测限为10-7M，但该探针本身有荧光，当加入Al3+后，溶液的荧光由黄色变成蓝色，并伴有约40nm的蓝移。中国发明专利201810105519.4公布了一种双通道荧光素类荧光探针，对Al3+和Zn2+离子的识别浓度为10-8M，但是需要在乙醇体系中进行测试，并且探针的合成路线较长，限制了其应用。论文(Luminescence,2016,31(3),851-855)报道了罗丹明酰肼和5-甲基噻吩甲醛反应得到荧光探针，该探针通过增强荧光发射选择性实现Al3+的检测。
含有酰肼结构的腙类席夫碱及其配合物具有生物活性，对许多生物酶有抑制作用，具有很高的研究应用价值,一直受到科学工作者的关注。但是,腙类席夫碱应用于荧光探针领域的报道较少。目前报道腙亚胺类分子对Al3+和Zn2+有着较好的识别性能，但其存在检测限低、荧光增强量小以及探针分子结构复杂、合成路线长等问题而限制了其应用。
发明内容
为了解决上述问题，本发明设计并合成了一类基于双腙亚胺的新型金属螯合打开型荧光探针，通过研究该类探针分子对Al3+和Zn2+的响应性进行筛查，开发出用于环境和生命体定向识别Al3+和Zn2+离子的荧光传感器。
为实现本发明目的，本发明以苯酚腙亚胺配体为基本骨架，设计合成一类新型的打开型荧光传感器并研究其对金属离子的识别性能，将其用于环境和生物体中铝和锌离子快速识别。
本发明采用的技术方案如下：
以邻苯二酚为原料制备4,5-二羟基间苯二甲醛，4,5-二羟基间苯二甲醛与苯并噁唑肼或者苯并噻唑肼反应生成苯酚腙亚胺类打开型荧光传感器。从探针合成、离子选择性、光谱滴定实验、络合比测定以及检测限研究，开发出可用于Al3+和Zn2+离子快速识别的高效探针。
本发明所述苯酚腙亚胺类荧光探针具有式I所示分子结构：
反应过程如下：
(1)邻苯二酚和乌洛托品在有机溶剂中反应，反应结束后蒸干溶剂，柱层析分离得4,5-二羟基间苯二甲醛；
所述有机溶剂为三氟乙酸或冰乙酸中的一种或两种。优选为三氟乙酸、冰乙酸混合液(体积比4:1)；所述反应温度为50-80℃，优选73℃；所述反应时间为2-6小时，优选5小时；柱层析采用200-600目柱硅胶，洗脱剂为乙酸乙酯、石油醚、乙醇、甲醇、冰乙酸或二氯甲烷中的一种或几种，优选300目柱硅胶，二氯甲烷/冰醋酸(体积比150/1)。
(2)4,5-二羟基间苯二甲醛与苯并噁唑肼或者苯并噻唑肼在溶剂中回流，产品析出，过滤后得黄色固体即为探针分子。
所述溶剂为所述溶剂为甲醇、乙醇、异丙醇、二氯甲烷、二甲基亚砜、四氢呋喃或二氧六环中的一种或几种，优选无水乙醇；反应时间为0.5-3小时，优选1小时。
本发明所述探针分子为双配体中心，能高效地响应铝离子和锌离子，对其他金属离子不敏感；可用于水中的铝离子和锌离子的快速检测。
与现有技术相比本发明具有如下优点：1、本发明荧光探针在水、乙醇、二甲基亚砜、甲醇中显示较好的荧光性能。特别是二甲基亚砜/水体系(体积比2/3)。在二甲基亚砜/水(2：3)的体系中与Al3+和Zn2+结合之后使得溶液的荧光分别增强了约41倍和10倍，并且不受其他金属离子干扰。探针和离子的最佳络合比为1:2；通过线性拟合得出最低检测限低达1.68×10-8mol/L远低于国家标准。
2、本发明所述苯酚腙亚胺类荧光探针的合成过程只需两步，原料廉价易得，反应条件温和，后处理简单易操作，收率高，达90％以上。
3、本发明制备的探针分子对Al3+和Zn2+离子有优越的选择性，响应时间短，荧光增强显著，具有潜在的开发价值和较好的应用前景。
附图说明
图1为本发明探针分子对金属离子选择性。
图2为本发明探针分子与Al3+的络合比测定。(a)本发明探针分子与不同浓度Al3+的荧光光谱；(b)本发明探针分子与Al3+的Job’s曲线图。
图3为本发明探针分子的荧光光谱滴定实验。
图4为本发明探针分子对Al3+最低检测限的测定。
图5为本发明探针分子对水中Al3+的响应性测定。
图6为本发明化合物3的HNMR图谱。
图7为本发明化合物4的HNMR图谱。
具体实施方式
为了更好地实施本发明，举实施例对本发明作进一步说明，但是这些实施例仅是用于说明本发明，但实施例不是对本发明的限制。
实施例1化合物2的制备
邻苯二酚和乌洛托品在三氟乙酸条件下80℃回流5h后，经TLC检测反应完全，以二氯甲烷、冰醋酸(150：1)为洗脱剂过硅胶层析柱，分离得4,5-二羟基间苯二甲醛，收率50％。1HNMR(400MHz,Chloroform-d)δ11.72(d,J＝0.8Hz,1H),10.00(s,1H),9.91(s,1H),7.76(d,J＝1.9Hz,1H),7.70(dd,J＝1.9,0.8Hz,1H).
实施例2化合物3和4的制备
4,5-二羟基间苯二甲醛与苯并噁唑肼在无水乙醇条件下，90℃回流1h后，经TLC检测反应完全。过滤，用少量无水乙醇洗涤滤饼，得到黄色固体。
化合物3，收率90％。1H NMR(400MHz,DMSO-d6)δ12.24(s,1H),11.98(s,1H),10.33(s,1H),9.84(s,1H),8.47(s,1H),8.08(s,1H),7.54(m,2H),7.45–7.35(m,3H),7.32(m,1H),7.27–7.18(m,2H),7.16–7.07(m,2H).
化合物4，收率95％。1H NMR(400MHz,DMSO-d6)δ12.19(s,2H),9.82(m,2H),8.46(s,1H),8.02(s,1H),7.87–7.67(m,2H),7.45(m,1H),7.38–7.16(m,5H),7.11(m,2H).
实施例3探针分子对金属离子选择性
探针溶液的制备:称取一定量本发明合成的探针，用二甲基亚砜(DMSO)配置成1.0x10-3 mol/L的储备液。然后将探针储备液稀释至二甲基亚砜：水体积比＝2：3的溶液中。称取一定量的Al3+、Ag+、Au3+、Ba2+、Co2+、Cd2+、Cr3+、Cu2+、Ca2+、Hg2+、Mg2+、Mn2+、K+、Pt4+、Ni2+、Na+、Zn2+、Fe2+、Fe3+盐，用二次蒸馏水溶解，配置成1.0x10-2 mol/L的金属离子储备液。
测试方法:在滴定实验中，每次向光程为1cm的石英光学元件中充入2mL稀释后的本发明探针溶液(1.0x10-5 mol/L)，然后将Al3+、Zn2+待测金属离子液体加入石英光学元件中。在选择性实验中，将2μL的金属离子储备液加入2mL的探针(1.0x10-5 mol/L)溶液中制备样品。对于荧光测量，激发波长为340nm，激发狭缝宽度为3nm，发射狭缝宽度为3nm，反应时间5min。
实施例4本发明探针分子与Al3+的络合比测定
使用Job’s法，逐渐改变Al3+浓度与本发明探针的浓度关系，分别测定其荧光光谱，得到本发明探针与Al3+的Job’s曲线图。如图2(b)所示，在0.66处左右出现了最大值，表明本发明探针与Al3+的配位比为1:2。本发明探针与Al3+的总浓度为1.0x10-5 mol/L，逐渐减小探针的浓度，增加Al3+的浓度，使两者的总浓度为1.0x10-5 mol/L，波长为482nm处的荧光强度也随着逐渐增强，当加入的Al3+的浓度达到探针的两倍量时，溶液的荧光强度将不再发生变化，趋近饱和，说明探针与Al3+的结合比为1:2。
实施例5荧光光谱滴定
在二甲基亚砜/水(体积比2：3)溶液中，使用紫外吸收光谱研究了该探针对Al3+的作用，发现该探针在329nm处有吸收带，在探针溶液中逐渐加入AI3+溶液时，329nm处的吸收峰逐渐减弱，447nm处的吸收峰逐渐增强，并且412nm处有一个等吸收点。
同样，在上述溶液中进行荧光光谱滴定实验，发现探针在488nm处有微弱的发射峰。往该探针中逐渐增加Al3+，发射峰蓝移到482nm，当AI3+的浓度达到探针浓度的两倍量时，体系的荧光强度基本不变，说明该探针与Al3+的配位达到了饱和，如图3所示。
实施例6 Al3+最低检测限的测定
配置10-6～10-4M的探针溶液，均加入2μl的Al3+(10-5M)，反应时间到达后，进行荧光光谱测试，根据实验结果计算检测限和结合常数。最低检出限的计算是基于荧光滴定实验得出的方程，公式为3S/m，其中S为对照组空白溶液测得荧光的标准方偏差(总计测量10次以上)，m为金属离子浓度与荧光强度线性方程的斜率。本发明探针与Al3+的结合常数通过Benesi-Hildebrand方程计算得出:c(LOD)＝KS/m＝3S/m。
实施例7水中Al3+的响应性测定
配制10-5M探针离子DMSO溶液和10-6M的金属离子水溶液。取1.5mL金属离子溶液加入到1mL探针离子溶液在中。5分钟后在365nm紫外灯下荧光效果，图5从左至右分别为空白探针、Al3+、Ag+、Au3+、Ba2+、Co2+、Cd2+、Cr3+、Cu2+、Ca2+、Hg2+、Mg2+、Mn2+、K+、Pt4+、Ni2+、Na+、Zn2+、Fe2+、Fe3+。结果表明，该探针可以识别Al3+和Zn2+，并且与Al3+和Zn2+反应后最大发射峰位置不同，在365nm紫外灯下荧光颜色也不同，Al3+为绿光，Zn2+为黄光可以达到区分Al3+和Zn2+的效果，见附图5。
Claims (3)
1.一种苯酚腙亚胺类荧光探针分子，其特征在于：具有通式1所示结构，
其中，X=O, S。
2.制备如权利要求1所述苯酚腙亚胺类荧光探针分子的方法，其特征在于，通过以下步骤实现：（1）邻苯二酚在三氟乙酸体系中回流与乌托洛品反应制备4,5-二羟基间苯二甲醛；
（2）4,5-二羟基间苯二甲醛与苯并噁唑肼或者苯并噻唑肼在溶剂中进行缩合反应，得到目标探针分子；所述溶剂为甲醇、乙醇、异丙醇、二氯甲烷、二甲基亚砜、四氢呋喃或二氧六环。
3.根据权利要求1所述的苯酚腙亚胺类荧光探针分子的应用，其特征在于，作为荧光探针用于水中的铝离子和锌离子的检测。
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