CN110256388A - 检测HClO的苯并吡喃腈类荧光探针分子的制备工艺 - Google Patents
检测HClO的苯并吡喃腈类荧光探针分子的制备工艺 Download PDFInfo
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Abstract
一种检测HClO的苯并吡喃腈类荧光探针分子的制备工艺,其制备工艺特征如下:在氮气保护下,准确称取化合物1(50mg,0.19mmol)和化合物DCM(39.6mg,0.19mmol),将上述两种化合物溶于10mL乙醇中,加热回流不少于12小时。待反应结束后,将反应液冷却至室温,抽滤后滤饼用冰无水乙醇洗三次,并用无水乙醇重结晶,得到黄色固体DCM‑Se(产率:30%)。所述产品DCM‑Se较易得,该探针分子主要用于选择性检测活性氧物质HClO。
Description
技术领域
本发明涉及一种检测HClO的苯并吡喃腈类荧光探针分子的制备工艺。
背景技术
HClO是一种含有超氧自由基(O2•-),羟基自由基(•OH),过氧化氢(H2O2),单线态氧(1O2)的活性氧(ROS),在生理和病理过程中起着重要作用。HClO是由过氧化氢和氯离子通过髓过氧化物酶(MPO)催化产生。与其他小生物分子相似,如果体内HClO浓度超过正常水平,则会引起如动脉粥样硬化、关节炎、类风湿性关节炎、肺部炎症、神经元变性和癌症等疾病。因此,为了准确地检测和鉴定体内HClO含量和位置,科学家们已经设计了多种荧光探针。Wang group开发了一种基于荧光素的“开启”荧光探针,其对ClO-具有高选择性,检测限低。由于ClO-的氧化性质,当检测ClO-时,它能够将探针的氨基氧化成亚氨基。同时,Guo组也具有良好的溶解性,快速响应和基于萘酰亚胺的“turn-on”荧光探针,对HClO/ClO鉴定具有高灵敏度和良好的选择性。2017年,Zhang组开发了一种聚集诱导发射(AIE)荧光开启探针,该探针显示出以前荧光探针无法获得的许多特征。更重要的是,探针还有可能测试饮用水中ClO-的存在和含量,这有可能进行现场检测。由于其众所周知的特性,近红外荧光探针已成为研究人员几十年来一直坚持的研究领域。2017年,Cui组合成了一种基于bodipy的近红外荧光探针,在ClO-检测过程中肉眼观察到ClO-检测前后探针的变化,探针可以应用于活细胞。在2018年,Wang 组也研究了一种基于卟啉的近红外荧光探针,它对ClO-具有极好的选择性,并且不受其他活性氧和典型亲核试剂的干扰。在检测到ClO-后,探针发射在近红外区域。近几年研究中发现,苯并吡喃腈也具有近红外吸收及发射性质,所以本发明根据该基团的这一特性设计并合成了一种二苯基硒醚修饰的苯并吡喃腈近红外探针分子。
发明内容
本发明的目的是公开一种检测HClO的苯并吡喃腈类荧光探针分子的制备工艺,以解决目前用于检测活性氧物质HClO方法的局限性,为拓展新的检测手段,制备一种苯并吡喃腈类荧光探针分子的工艺。
技术方案
一种检测HClO的苯并吡喃腈类荧光探针分子(DCM-Se)的制备工艺,其制备工艺如下:
步骤一,化合物1的合成,在氮气保护下,称取4-溴苯甲醛(370mg,2mmol)和二苯基二硒醚(312mg,1mmol)并将这两种化合物溶于5mL的无水二甲基亚砜中,再加入纳米粉末CuFe2O4(30mg,0.125mmol),并加热到120oC;搅拌不少于18小时并通过薄层层析色谱进行监测反应进度,待反应完全后,将反应液冷却至室温,加入足量冰水,用约300mL乙酸乙酯萃取三次,合并有机层并用无水硫酸钠进行干燥,减压旋干并柱色谱层析柱进行分离提纯。最终,得黄色粉末固体(化合物1,产率:65%);
步骤二,在氮气保护下,准确称取化合物1(50mg,0.19mmol)和化合物DCM(39.6mg,0.19mmol),将上述两种化合物溶于10mL乙醇中,加热回流不少于12小时。待反应结束后,将反应液冷却至室温,抽滤后滤饼用冰无水乙醇洗三次,并用无水乙醇重结晶,得到黄色固体DCM-Se反应式如下:
产率:30%。
按照上述工艺得到的黄色固体DCM-Se,即本发明所述的一检测HClO的苯并吡喃腈类荧光探针分子。
按照上述方式,取步骤1所给出的各反应物质的配量关系的整数倍数的量,按照步骤1给出的反应条件,制得对应倍数量的化合物1。
按照上述方式,取步骤2中化合物1(50mg,0.19mmol)和化合物DCM(39.6mg,0.19mmol)的n倍数量,把两种化合物溶于n倍的10mL乙醇中,按照步骤2的工艺能制得n倍数量的所述黄色固体DCM-Se。
发明的优点是工艺步骤简单,产物易得。获得的以新型结构苯并吡喃腈为荧光团、以C=C双键为桥梁连接二苯基二硒醚,在DMSO/HEPES体系中能够选择性识别活性氧物质HClO。
附图说明
图1目标化合物DCM-Se的核磁供振1H NMR谱。
图2目标化合物DCM-Se的核磁供振13C NMR谱。
图3化合物1的核磁供振1H NMR谱。
图4化合物DCM-Se溶于DMSO/HEPES溶液及化合物DCM-Se加入HClO以及其他离子(H2O2, ·OH, t-BuOOH, ClO-, NO3 -, NO2 -)之后的紫外光谱。
图5化合物DCM-Se溶于DMSO/HEPES溶液及化合物DCM-Se加入HClO以及其他离子(H2O2, OH, t-BuOOH, ClO-, NO3 -, NO2 -)之后的荧光光谱。
具体实施方式
下面结合具体实施例对本发明进一步说明。
实施例1
参见图11H NMR 谱和图213C NMR谱:目标化合物DCM-Se的制备工艺,如下步骤:
在氮气保护下,准确称取化合物1(50mg,0.19mmol)和化合物DCM(39.6mg,0.19mmol),将上述两种化合物溶于10mL乙醇中,加热回流12小时。待反应结束后,将反应液冷却至室温,抽滤后滤饼用冰无水乙醇洗三次,并用无水乙醇重结晶,得到黄色固体DCM-Se(产率:30%)。1H NMR (400 MHz, d6-DMSO) δ 8.74 – 8.68 (m, 1H), 7.95 – 7.88 (m, 1H),7.78 (d, J = 8.0 Hz, 1H), 7.72 – 7.64 (m, 3H), 7.63 – 7.55 (m, 3H), 7.52 –7.39 (m, 6H), 7.01 (s, 1H). 13C NMR (101 MHz, DMSO) δ 158.38, 153.36, 152.47,138.21, 135.95, 134.44 (3C), 134.22, 132.09 (2C), 130.40 (3C), 129.53 (2C),128.89 (2C), 126.68, 125.12, 120.28, 119.55, 117.54, 116.25, 107.42, 60.94。
实施例2
参见图31H NMR 谱,化合物1的制备,如下步骤:
在氮气保护下,称取4-溴苯甲醛(370mg,2mmol)和二苯基硒醚(312mg,1mmol)并将这两种化合物溶于5mL的无水二甲基亚砜中,再加入纳米粉末CuFe2O4(30mg,0.125mmol),并加热到120oC。搅拌并通过薄层层析色谱进行监测反应进度,待反应18小时后,将反应液冷却至室温,加入足量冰水,用300mL乙酸乙酯萃取三次,合并有机层并用无水硫酸钠进行干燥,减压旋干并柱色谱层析柱进行分离提纯。最终,得黄色粉末固体(化合物1,产率:65%)1H NMR(400 MHz, d6-DMSO) δ 9.93 (s, 1H), 7.79 (d, J = 8.0 Hz, 2H), 7.65 – 7.61 (m,2H), 7.49 – 7.43 (m, 5H)。
实施例3
参见图4和图5,化合物DCM-Se、化合物DCM-Se(DMSO/HEPES,0.01 M,pH=7.2,V/V =7:3)体系)中加入相同浓度的HClO以及其他离子(H2O2, ·OH, t-BuOOH, ClO-, NO3 -, NO2 -),分别表征混合溶液的紫外及荧光性质。
将化合物DCM-Se溶于DMSO/HEPES(0.01 M,pH=7.2,V/V =7:3)混合溶剂中,制备浓度为2X10-5 mol/L的溶液;将HClO以及其他离子(H2O2, ·OH, t-BuOOH, ClO-, NO3 -, NO2 -)溶于水中,制备浓度为0.2 mol/L的溶液。
向化合物DCM-Se溶于DMSO/HEPES(0.01 M,pH=7.2,V/V =7:3)混合溶剂中,分别加入96μL的HClO以及其他离子(H2O2, ·OH, t-BuOOH, ClO-, NO3 -, NO2 -)的水溶液,对化合物DCM-Se溶于DMSO/HEPES溶液及化合物DCM-Se加入上述离子之后的紫外及荧光性质分别进行表征。
Claims (1)
1.一种检测HClO的苯并吡喃腈类荧光探针分子的制备工艺,其特征在于步骤如下:
步骤一,化合物1的合成,在氮气保护下,称取4-溴苯甲醛(370mg,2mmol)和二苯基二硒醚(312mg,1mmol)并将这两种化合物溶于5mL的无水二甲基亚砜中,再加入纳米粉末CuFe2O4(30mg,0.125mmol),并加热到120oC;搅拌不少于18小时并通过薄层层析色谱进行监测反应进度,待反应完全后,将反应液冷却至室温,加入足量冰水,用约300mL乙酸乙酯萃取三次,合并有机层并用无水硫酸钠进行干燥,减压旋干并柱色谱层析柱进行分离提纯;最终,得黄色粉末固体即化合物1,产率:65%;
步骤二,在氮气保护下,准确称取化合物1(50mg,0.19mmol)和化合物DCM(39.6mg,0.19mmol),将上述两种化合物溶于10mL乙醇中,加热回流不少于12小时;待反应结束后,将反应液冷却至室温,抽滤后滤饼用冰无水乙醇洗三次,并用无水乙醇重结晶,得到黄色固体DCM-Se反应式如下:
产率:30%。
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