CN105820171A - 一种苯并吲哚啉螺吡喃比色探针、制备方法及应用 - Google Patents
一种苯并吲哚啉螺吡喃比色探针、制备方法及应用 Download PDFInfo
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Abstract
本发明涉及一种苯并吲哚啉螺吡喃比色探针，比色探针为：1’‑乙基‑3’，3’‑二甲基‑6‑硝基螺[4’，5’‑苯并吲哚啉‑2,2’[2H‑1]苯并吡喃]；探针的制备方法，包括步骤N‑乙基‑2,3,3‑三甲基‑4,5‑苯并吲哚啉‑N‑碘盐的制备、1’‑乙基‑3’，3’‑二甲基‑6‑硝基螺[4’，5’‑苯并吲哚啉‑2,2’[2H‑1]苯并吡喃]的制备和分离纯化，苯并吲哚啉螺吡喃比色探针用于识别溶液中的Al3+和Cr3+。本发明的有益效果是：(1)苯并吲哚啉螺吡喃探针合成过程较为简单，反应条件容易控制，通过简单的后处理就能够得到纯的产物，具有优良的化学稳定性和光致变色性能；(2)探针为固体粉末，便于储存，具有良好的前景；(3)探针在紫外和可见光照下都是无色的闭环体形式，只有在黑暗条件下为紫红色的开环体形式，这种性能可以用于检测光线的强度。
Description
技术领域
本发明涉及一种苯并吲哚啉螺吡喃比色探针、制备方法及应用。
背景技术
铝是地壳中含量最高的金属元素，在航空航天、汽车工业、冶金化工、农业生产，日常生活中大量被使用，但近些年来，越来越多的证据证明铝离子对人体中枢神经系统有很大的毒性。铬是维持人体正常生理机能和组织结构所必须的微量元素，其中铬在肌体的糖代谢和脂代谢中发挥特殊作用，研究表明铬元素会通过食物链在生物体内累积，体内铬含量过高会导致上呼吸道刺激反应、引起肝脏和肾脏等衰竭以及癌症。因此，研究高选择性高灵敏度检测Al3+和Cr3+离子的传感器具有重要意义。
近年来有关采用荧光或比色的化学传感器来识别Al3+和Cr3+的文献已经有所报道。Soma Mukherjee(Journal of Luminescence 172(2016)124–130)等人合成了一种发光萘酰腙染料，作为Al3+离子的荧光化学传感器，选择性好、灵敏度高，但是其抗干扰性能效果不佳。Muthaiah Shellaiah(Sensors andActuators B 226(2016)44–51)等人合成了一种金纳米颗粒，用于Cr3+离子的比色检测，检测效果好，但是成本高，不利于实际应用。
螺吡喃是一类研究最广泛、最深入的有机光致变色化合物，能够发生无色闭环体螺吡喃和有色开环体部花菁之间可逆的结构异构化。螺吡喃(350nm左右)随着C-O键的开裂，sp2杂化变成sp3杂化，形成有色的部花菁结构(560nm左右)，部花菁的酚氧基可与金属离子络合，形成的复合物紫外吸收峰在430nm左右，测量这一变化即可得到相应的信息，判断金属离子是否与染料络合。
本发明具体涉及一种用于Al3+和Cr3+检测的螺吡喃染料化学传感器，合成方法较为简单，反应条件容易控制，反应结束后通过简单的处理就能够得到纯的产物。当可见光照时，其溶液颜色接近无色，而在黑暗条件放置一段时间后，溶液转变为紫红色，在此条件下，可以选择性识别Al3+和Cr3+离子，加入上述离子后，溶液转变为黄色，而加入其他离子的溶液仍为紫红色。不仅可以检测光线的强度，也能作为Al3+和Cr3+的检测的化学传感器，本发明主要讲述的是其的金属离子检测性能。
发明内容
本发明要解决的技术问题是：基于上述问题，本发明提供一种苯并吲哚啉螺吡喃比色探针、制备方法及应用。
本发明解决其技术问题所采用的一个技术方案是：一种苯并吲哚啉螺吡喃比色探针，该比色探针为：1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]，结构式如下：
苯并吲哚啉螺吡喃比色探针的制备方法，包括以下步骤：
(1)N-乙基-2,3,3-三甲基-4,5-苯并吲哚啉-N-碘盐的制备
将2,3,3-三甲基-4,5-苯并吲哚和碘乙烷按摩尔比1：1.1～1.2加入到反应容器中，加入无水乙醇，75～79℃搅拌回流20～24h，冷却至室温，旋蒸，洗涤，干燥，得到蓝紫色固体，即N-乙基-2,3,3-三甲基-4,5-苯并吲哚啉-N-碘盐；
(2)1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]的制备
将步骤(1)制备的N-乙基-2,3,3-三甲基-4,5-苯并吲哚啉-N-碘盐和5-硝基水杨醛按摩尔比1：1加入到反应容器中，加入三乙胺和无水乙醇，75～79℃搅拌回流14～16h，冷却至室温，抽滤，干燥，得到深紫色粉末，即1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]粗品；
(3)将步骤(2)得到的1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]以乙酸乙酯和石油醚混合溶剂为洗脱剂，柱层析洗脱分离提纯后，得到淡黄色固体，即1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]产品。
进一步地，步骤(3)中乙酸乙酯和石油醚的体积比为1：9。
苯并吲哚啉螺吡喃比色探针的应用，比色探针用于识别溶液中的Al3+和Cr3+。
本发明的有益效果是：(1)染料合成过程较为简单，反应条件容易控制，通过简单的后处理就能够得到纯的产物，并且该苯并吲哚林螺吡喃染料具有优良的化学稳定性和光致变色性能；(2)染料为固体粉末，便于储存，具有良好的前景；(3)染料在紫外和可见光照下都是无色的闭环体形式，只有在黑暗条件下为紫红色的开环体形式，这种性能可以用于检测光线的强度。
附图说明
下面结合附图对本发明进一步说明。
图1为实施例1制备的苯并吲哚啉螺吡喃探针与不同浓度铝离子络合后的紫外吸收光谱图；
图2为加入EDTA后，实施例1制备的苯并吲哚啉螺吡喃探针与铝离子络合的可逆作用图；
图3为实施例1制备的苯并吲哚啉螺吡喃探针与不同浓度铬离子络合后的紫外吸收光谱图；
图4为加入EDTA后，实施例1制备的苯并吲哚啉螺吡喃探针与铬离子络合的可逆作用图。
具体实施方式
现在结合具体实施例对本发明作进一步说明，以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
称取6.28g的2,3,3-三甲基-4,5-苯并吲哚(0.030mol)和5.62g的碘乙烷(0.036mol)加入到100mL的三口烧瓶中，加入50mL无水乙醇，连接冷凝管，75℃下搅拌回流20h,溶液变为蓝紫色。反应结束后，停止加热，反应溶液冷却至室温后，转移至单口烧瓶，真空旋蒸得到蓝紫色粉末。烧瓶中加入少量乙酸乙酯并超声，待烧瓶壁上的固体剥落后，用布氏漏斗抽滤，同时用乙酸乙酯淋洗，待滴落的液体为无色时停止洗涤。滤饼放入烘箱60℃干燥。所得固体粉末即为中间体。
称取1.82g中间体(0.005mol)和0.84g 5-硝基水杨醛(0.005mol)加入到100mL的三口烧瓶中，加入10mL无水乙醇和1mL三乙胺，连接冷凝管，75℃下搅拌回流14h,溶液变为紫红色。反应结束后，停止加热，趁热过滤，滤饼中大部分为所需螺吡喃染料，滤饼放入烘箱60℃干燥。将烘干的紫红色粉末以乙酸乙酯和石油醚混合溶剂(体积比V乙酸乙酯：V石油醚＝1：9)作为洗脱剂，300-400目硅胶为固定相，柱层析洗脱分离提纯后，得到淡黄色固体，即苯并吲哚啉螺吡喃染料。
实施例2
称取4.18g的2,3,3-三甲基-4,5-苯并吲哚(0.020mol)和3.43g的碘乙烷(0.022mol)加入到100mL的三口烧瓶中，加入35mL无水乙醇，连接冷凝管，79℃下搅拌回流24h,溶液变为蓝紫色。反应结束后，停止加热，反应溶液冷却至室温后，转移至单口烧瓶，真空旋蒸得到蓝紫色粉末。烧瓶中加入少量乙酸乙酯并超声，待烧瓶壁上的固体剥落后，用布氏漏斗抽滤，同时用乙酸乙酯淋洗，待滴落的液体为无色时停止洗涤。滤饼放入烘箱60℃干燥。所得固体粉末即为中间体。
称取1.10g中间体(0.003mol)和0.50g 5-硝基水杨醛(0.003mol)加入到100mL的三口烧瓶中，加入10mL无水乙醇和1mL三乙胺，连接冷凝管，79℃下搅拌回流16h，溶液变为紫红色。反应结束后，停止加热，趁热过滤，滤饼中大部分为所需螺吡喃染料，滤饼放入烘箱60℃干燥。将烘干的紫红色粉末以乙酸乙酯和石油醚混合溶剂(体积比V乙酸乙酯：V石油醚＝1：9)作为洗脱剂，300-400目硅胶为固定相，柱层析洗脱分离提纯后，得到淡黄色固体，即苯并吲哚啉螺吡喃染料。
应用例1
为了检测实施例制备的苯并吲哚啉螺吡喃探针对铝离子的识别性能，以无水乙醇和水体积比为4：1的混合溶液作溶剂，将合成的苯并吲哚啉螺吡喃染料配置成浓度为4×10-5mol/L，取50mL，黑暗条件下放置6小时，并在暗光条件下向溶液中逐滴加入1×10-2mol/L的铝离子溶液，利用紫外-可见分光光度计依次测定其吸收光谱的变化，其吸收光谱如图1所示。由图可以看出，在黑暗条件下，该溶液在542nm处有较强的开环部花菁的特征峰，随着铝离子滴定量的增加，染料溶液的吸收光谱发生了改变：位于542nm处开环部花菁的吸收峰逐渐降低，而430nm处螺吡喃和铝离子络合物的吸收峰则逐渐增加。
为了检测EDTA对整个体系可逆性的影响，以无水乙醇和水体积比为4：1的混合溶液作溶剂，将合成的苯并吲哚啉螺吡喃染料配置成浓度为4×10-5mol/L，黑暗条件下放置6小时，并在暗光条件下分别取3mL配置的溶液于三支试管中，标号分别是1、2和3号。将2号试管滴入0.05mL 1×10-2mol/L的铝离子溶液，3号试管滴入0.05mL 1×10-2mol/L的铝离子溶液和0.1mL 1×10-2mol/L的EDTA溶液，分别测其吸光度，其吸收光谱如图2所示。由图可以看出，体系加入EDTA后，542nm处开环部花菁和430nm处螺吡喃和铝离子络合物特征峰的吸光度在1、2号吸光度之间。这说明，这个体系可以作为一种开关式的铝离子传感器。
应用例2
为了检测实施例制备的苯并吲哚啉螺吡喃探针对铬离子的识别性能，以无水乙醇和水体积比为4：1的混合溶液作溶剂，将合成的苯并吲哚啉螺吡喃染料配置成浓度为4×10-5mol/L，取50mL，黑暗条件下放置6小时，并在暗光条件下向溶液中逐滴加入1×10-2mol/L的铬离子溶液，利用紫外-可见分光光度计依次测定其吸收光谱的变化，其吸收光谱如图3所示。由图可以看出，在黑暗条件下，该溶液在542nm处有较强的开环部花菁的特征峰，随着铬离子滴定量的增加，染料溶液的吸收光谱发生了改变：位于542nm处开环部花菁的吸收峰逐渐降低，而430nm处螺吡喃和铬离子络合物的吸收峰则逐渐增加。
为了检测EDTA对整个体系可逆性的影响，以无水乙醇和水体积比为4：1的混合溶液作溶剂，将合成的苯并吲哚啉螺吡喃染料配置成浓度为4×10-5mol/L，黑暗条件下放置6小时，并在暗光条件下分别取3mL配置的溶液于三支试管中，标号分别是4、5和6号。将5号试管滴入0.05mL 1×10-2mol/L的铬离子溶液，6号试管滴入0.05mL 1×10-2mol/L的铬离子溶液和0.05mL 1×10-2mol/L的EDTA溶液，分别测其吸光度，其吸收光谱如图4所示。由图可以看出，体系加入EDTA后，542nm处开环部花菁和430nm处螺吡喃和铬离子络合物特征峰的吸光度在4、5号吸光度之间。这说明，这个体系可以作为一种开关式的铬离子传感器。
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。
Claims (4)
1.一种苯并吲哚啉螺吡喃比色探针，其特征是：该比色探针为：1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]，结构式如下：
。
2.权利要求1所述的苯并吲哚啉螺吡喃比色探针的制备方法，其特征是：包括以下步骤：
(1)N-乙基-2,3,3-三甲基-4,5-苯并吲哚啉-N-碘盐的制备
将2,3,3-三甲基-4,5-苯并吲哚和碘乙烷按摩尔比1：1.1～1.2加入到反应容器中，加入无水乙醇，75～79℃搅拌回流20～24h，冷却至室温，旋蒸，洗涤，干燥，得到蓝紫色固体，即N-乙基-2,3,3-三甲基-4,5-苯并吲哚啉-N-碘盐；
(2)1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]的制备
将步骤(1)制备的N-乙基-2,3,3-三甲基-4,5-苯并吲哚啉-N-碘盐和5-硝基水杨醛按摩尔比1：1加入到反应容器中，加入三乙胺和无水乙醇，75～79℃搅拌回流14～16h，冷却至室温，抽滤，干燥，得到深紫色粉末，即1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]粗品；
(3)将步骤(2)得到的1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]以乙酸乙酯和石油醚混合溶剂为洗脱剂，柱层析洗脱分离提纯后，得到淡黄色固体，即1’-乙基-3’，3’-二甲基-6-硝基螺[4’，5’-苯并吲哚啉-2,2’[2H-1]苯并吡喃]产品。
3.根据权利要求2所述的苯并吲哚啉螺吡喃比色探针的制备方法，其特征 是：所述的步骤(3)中乙酸乙酯和石油醚的体积比为1：9。
4.权利要求1所述的苯并吲哚啉螺吡喃比色探针的应用，其特征是：所述的比色探针用于识别溶液中的Al3+和Cr3+。
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| CN112724153A (zh) * | 2021-01-07 | 2021-04-30 | 郑州大学 | 三个具有线粒体/溶酶体双重靶向定位的溶致比色/溶致荧光探针 |
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