CN107936011B - 一种高选择性检测次氯酸根离子的四取代烯烃探针 - Google Patents
一种高选择性检测次氯酸根离子的四取代烯烃探针 Download PDFInfo
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Abstract
通过(Z)‑2‑芳甲叉基咪唑[1,2‑a]并吡啶‑3(2H)‑酮与取代吡唑酮在无催化剂的温和反应条件下的氧化偶联,高立体选择地制备了高度官能化的四取代烯烃衍生物,其代表性化合物可以作为一种高选择性检测次氯酸或次氯酸根的高效探针。该探针的优点是能够高选择性的检测次氯酸根,可用于环境样品、自来水、生物活细胞及活组织以及临床医学上病变组织中次氯酸根的检测。具有选择性高和灵敏度高的特点,其检测限为39nM。
Description
技术领域
本发明属于应用化学技术领域,具体涉及一类含有咪唑[1,2-a]并吡啶-3(2H)-酮和吡唑酮结构单元的四取代烯烃类化合物的制备及其应用于环境、医学、食品以及生物体中次氯酸根离子的选择性检测。
背景技术
次氯酸盐是广泛存在的一类物质,在日常生活中,常常用来漂白和自来水的消毒。在生物体系中,次氯酸根参与众多的生理和病理进程,在生物体内起到非常重要的作用。但一旦生物体系中次氯酸根离子的浓度过大,它们将氧化体内中的蛋白质和核酸等物质,严重阻碍体内正常生命活动过程,对生物体特别是人体产生严重的危害,产生动脉粥样硬化、神经衰退、关节炎和癌症等严重疾病。目前尚没有一种快速高效安全的检测方法,快速地对生物体系中次氯酸根离子的定量检测。在实际中,次氯酸根离子的传统的检测方法是利用次氯酸根的氧化还原反应进行检测,如利用次氯酸根在弱酸性条件下与碘化钾生成游离碘,以淀粉溶液为指示剂,硫代硫酸钠标准滴定溶液滴定,计算样品中次氯酸根的含量,此方法的优点是成本低,易于操作,但缺点是干扰大,选择性差,检测极限高。还有一些方法虽然成本低,如离子色谱,但操作复杂,重现性差。虽然文献中也报道过利用一些荧光探针来检测次氯酸根,但这些探针的合成往往困难,选择性和灵敏度也有较大的局限。因此,研究设计合成一种高选择性、高灵敏度、快速的检测次氯酸根的分子探针具有重要的理论研究意义和实际应用价值。
发明内容
本发明的目的是提供一种能够快速高效检测生物体系中或环境中次氯酸根的分子探针,所发明的一类含有咪唑[1,2-a]并吡啶-3(2H)-酮和吡唑酮结构单元的四取代烯烃类化合物具有快速高效选择性的检测次氯酸根离子的性能。
本发明包括以下技术方案:
1.所述的次氯酸根选择性检测的分子探针具有如下的结构:
2.一种所述用于检测次氯酸根的分子探针的制备步骤如下:
将咪唑并吡啶酮化合物1与吡唑酮化合物2在二氯甲烷中进行氧化偶联,室温搅拌反应48小时后终止反应。将上述反应物溶剂浓缩后,进行柱层析或重结晶分离得到目标化合物。
3.所述反应中,咪唑并吡啶酮化合物1与吡唑酮化合物2的摩尔比为1∶1.2-1∶1.5,优选的为1∶1.2。
4.所述反应中,所用的溶剂可以为二氯甲烷,1,2-二氯乙烷,甲苯,乙腈,四氢呋喃,乙酸乙酯,优选的为二氯甲烷和1,2-二氯乙烷。
5.所述反应中,反应温度为室温至回流,优选的为室温反应。
6.所述反应中,反应时间为24小时至96小时,优选地为48-72小时。
7.所述的含有咪唑[1,2-a]并吡啶-3(2H)-酮和吡唑酮结构单元的四取代烯烃类化合物具有快速高效选择性的从ClO-,AcO-,Br-,CO3 2-,C1O4 -,Cl-,F-,HSO4 -,HCO3 -,HPO4 2-,I-,NO2 -,H2PO4 -,NO3 -,PO4 3-,SO3 2-,S2-,SO4 2-等阴离子中选择性地检测次氯酸根离子,最低检测浓度为39nM。
附图说明:
图1.加入不同阴离子后,化合物5的紫外可见吸收光谱(1×10-5M)
图2.加入不同浓度的ClO-,化合物5的紫外可见吸收光谱(1×10-5M)
具体实施实例
为了更好的理解本发明专利的内容,下面通过实例来进一步说明本发明的技术方案,但这些实施实例并不限制本发明。
实施例1:咪唑并吡啶酮烯烃类化合物5的制备
向0.3mmol(52mg)5-甲基-2-苯基-2,4-二氢-3H-吡唑-3-酮2和1.5mL二氯甲烷中,加入0.2mol(44mg)(z)-2-苯甲叉基咪唑[1,2-a]并吡啶-3-(2H)-酮1,加完后,反应混合物在室温搅拌下反应,薄层色谱监控反应进程,约72小时后,加水终止反应,并用二氯甲烷(50mL)稀释反应液,分离有机相,无水硫酸钠干燥,减压浓缩,柱层析离提纯(洗脱液∶石油醚/乙酸乙酯=2∶1(V/V))得玫瑰红固体5,熔点258-260℃,收率70%。1H NMR(400MHz,CDCl3):δ1.43(s,3H),6.73(t,J=6.8Hz,1H),7.24(d,J=7.6Hz,1H),7.30(d,J=9.2Hz,1H),7.33-7.37(m.2H),7.45(t,J=7.6Hz,2H),7.50-7.54(m,4H),7.91(d,J=7.6Hz,2H),7.97(d,J=6.8Hz,1H),17.91(s,1H).13C NMR(100.6MHz,CDCl3):δ16.8,108.4,111.8,112.8,113.0,121.1,125.1,125.5,128.2,128.6,128.7,128.8,136.2,136.7,138.5,138.8,148.9,151.0,155.1,162.5.HRMS(ESI)m/z calc′d for C24H19N4O2[M+H]+:395.1503,found 395.1507.
实施例2:次氯酸根的选择性检测实验
将目标化合物5配成1×10-5M(ethanol-H2O(1∶1,v/v))的溶液,移取2.5mL所配的溶液加入到不同的比色皿中,向不同的比色皿中分别加入5当量的AcO-,Br-,CO3 2-,H2O2,ClO4 -,Cl-,F-,HSO4 -,HCO3 -,HPO4 2-,I-,NO2 -,H2PO4 -,NO3 -,PO4 3-,SO3 2-,S2-,SO4 2-,TBHP,ClO-,其中H2O2和叔丁基过氧化氢(TBHP)作为对照,分别测定其紫外可见光谱,结果如附图1所示,其它离子和H2O2与TBHP均没有明显影响,而对ClO-具有很好的选择性。
实施例3:目标化合物5对次氯酸根的浓度响应性实验
将目标化合物5配成1×10-5M(ethanol-H2O(1∶1,v/v))的溶液,移取适量所配的溶液加入到比色皿中,向该比色皿中分别加入不同当量(0-13equiv.)的ClO-,每次加完后测定其紫外可见光谱,结果如附图2所示。随着ClO-浓度的增加,522nm处的吸收降低,而560nm处的吸收增强,ClO-的检测极限为3.9×10-8M。
上述实施实例只是用来解释本发明,而非对本发明进行限制,在本发明的权利要求的保护范围内,对本发明所作出的任何修改和改变,都属于本发明所保护的范围。
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