CN110967325B - 一种巯基酯修饰的柱[5]芳烃超分子化合物及其合成和应用 - Google Patents
一种巯基酯修饰的柱[5]芳烃超分子化合物及其合成和应用 Download PDFInfo
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Abstract
本发明设计合成了一种巯基酯修饰的柱[5]芳烃超分子化合物，是以乙腈为溶剂，6‑溴己基功能化的柱[5]芳烃和巯基乙酸乙酯为底物，在70~80℃下反应20~24h；反应结束后除去溶剂，柱层析分离，即得超分子化合物。在DMF‑H2O溶液中具有良好的溶解性与荧光发射性能。在DMF‑H2O溶液中，该超分子化合物能与甲硫氨酸作用，同时发生荧光猝灭，因此可用于甲硫氨酸的单一选择性荧光识别，且最低检测线为2.84×10‑8 M。同时，其他常见的19种氨基酸的存在对甲硫氨酸的识别无影响。因此，该超分子化合物对人体必需氨基酸的高灵敏性专一性识别具有重要的应用价值。
Description
技术领域
本发明涉及一种用于单一选择性识别甲硫氨酸（L-Met）的超分子传感器及其合成方法；本发明同时还涉及该超分子传感器在DMF-H2O溶液中高效识别L-Met的应用，属于化学合成领域、分子识别领域。
背景技术
人体必需氨基酸，指人体不能合成或合成速度远不适应机体的需要，必须由食物蛋白供给，这些氨基酸称为必需氨基酸。共有赖氨酸（Lysine）、色氨酸（Tryptophan）、苯丙氨酸（Phenylalanine）、甲硫氨酸（Methionine）、苏氨酸（Threonine）、异亮氨酸（Isoleucine）、亮氨酸（Leucine）、缬氨酸（Valine）8种。对于L-Met甲硫氨酸（蛋氨酸），它能参与组成血红蛋白、组织与血清，有促进脾脏、胰脏及淋巴的功能。蛋氨酸是含硫必需氨基酸，与生物体内各种含硫化合物的代谢密切相关。当缺乏蛋氨酸时，会引起食欲减退、生长减缓或不增加体重、肾脏肿大和肝脏铁堆积等现象，最后导致肝坏死或纤维化。蛋氨酸还可利用其所带的甲基，对有毒物或药物进行甲基化而起到解毒的作用。因此，蛋氨酸可用于防治慢性或急性肝炎、肝硬化等肝脏疾病，也可用于缓解砷、三氯甲烷、四氯化碳、苯、吡啶和喹啉等有害物质的毒性反应。
氨基酸的测定方法有多种，如高效液相色谱法、分光度法、电化学法、质谱法、毛细管区法等。然而，这些方法具有成本高、灵敏度低、特异性差、样品预处理复杂等缺点。因此，研制一种简便、高效、低成本地化学荧光传感器检测氨基酸是非常必要的，且具有重要的现实意义。
柱芳烃是由对苯二酚或对苯酚醚通过亚甲基在苯环的对位连接而成的一类环状低聚物。柱芳烃作为一种新型的大环主体化合物分子，具有多种超分子自主装驱动力。虽然基于柱[5]芳烃的超分子传感器已经被报道过，但是基于巯基酯修饰的超分子传感器，以及它具有的分子识别尤其是对氨基酸的识别还没有被广泛的研究和报道。
发明内容
本发明的目的是提供一种巯基酯修饰的柱[5]芳烃超分子化合物及其合成方法；
本发明的另一目的是提供该巯基酯修饰的柱[5]芳烃超分子化合物作为传感器单一选择性荧光识别L-Met的具体应用。
一、巯基酯修饰的柱[5]芳烃超分子化合物
本发明巯基酯修饰的柱[5]芳烃超分子化合物的分子式为：C54H66O12S，标记为：SP5，其结构式为：
化合物SP5的和合成：以乙腈为溶剂，以单边溴代的柱[5]芳烃(C20H59O10Br)和巯基乙酸乙酯(C4H8O2S)为1:1.5~1:2的摩尔比投料，于70~80℃下反应20~24h；反应结束后除去溶剂，柱层析分离而得。
化合物SP5的氢谱谱图和质谱见图1和图2。
二、化合物SP5荧光识别L-Met
1、化合物SP5的荧光性能
图3为SP5在DMF-H2O溶液不同含水比的条件下的荧光发射性能。图3表明，SP5在DMF-H2O溶液的不同含水比中，H2O体积分数为10~40%时具有良好的溶解性与荧光发射性能。当激发波长为295nm时，SP5发出蓝紫色荧光（激发波长λex=295nm）。
2、SP5选择性荧光检测L-Met
在SP5的DMF-H2O溶液（VDMF:V水= 7:3）中，加入2倍当量的L-Phe，L-Gln，L-Ile，L-Thr，L-Glu，L-Ala，L-Ser，L-Met，L-Val，L-Tyr，L-Arg，L-Asp，L-Pro，L-His，L-Leu，L-Gly，L-Trp，L-Lys，L-Asn和L-Cys水溶液。图4为化合物SP5在DMF-H2O溶液中分别加入不同氨基酸的全扫描（λex=295 nm）。结果发现，只有L-Met的加入可使SP5荧光明显猝灭。而其他氨基酸的加入，不能使SP5荧光发生明显变化，说明SP5对L-Met具有单一选择性识别性能。
为了研究其它氨基酸对L-Met识别的干扰，我们做了抗干扰实验。图5为化合物SP5的DMF-H2O溶液中，分别加入不同氨基酸再加入L-Met的抗干扰图（从左到右依次为：SP5，SP5-Met，L-Phe，L-Gln，L-Ile，L-Thr，L-Glu，L-Ala，L-Ser，L-Val，L-Tyr，L-Arg，L-Asp，L-Pro，L-His，L-Leu，L-Gly，L-Trp，L-Lys，L-AsnandL-Cys）。结果表明，其它氨基酸的存在对超分子传感器SP5识别L-Met没有任何的干扰。
图6、7分别为SP5在DMF-H2O溶液中加入L-Met的荧光滴定图及L-Met的最低检测限。荧光滴定实验表明，超分子传感器SP5对L-Met的最低检测限为2.84×10-8mol。
图8为SP5的DMF-H2O中加入L-Met的核磁滴定图。（a）SP5；（b）L-Met；（c）0.2当量L-Met；（d）0.5当量L-Met；（e）1.0当量L-Met。核磁滴定实验表明，柱芳烃芳环上的质子H1和亚甲基桥联上的质子H2峰都发生了低场位移，甲硫氨酸上质子峰H5与H6发生了高场位移，说明L-Met进入了柱芳烃SP5的空腔，使SP5荧光猝灭，从而实现了对L-Met的荧光高效识别。
附图说明
图1为化合物SP5的氢谱图。
图2为化合物SP5的质谱图。
图3为SP5在DMF-H2O溶液不同含水比的条件下的荧光发射性能。
图4为化合物SP5的DMF-H2O溶液中分别加入不同氨基酸的全扫描（λex=295 nm）。
图5为化合物SP5的DMF-H2O溶液中分别加入不同氨基酸再加入L-Met的抗干扰图。
图6为SP5的DMF-H2O溶液中加入L-Met的荧光滴定图。
图7为SP5的DMF-H2O溶液中加入L-Met的最低检测限。
图8为SP5在加入L-Met的核磁滴定图。
具体实施方式
下面通过具体实施例对本发明超分子化合物SP5的制备和荧光高效识别L-Met的应用做进一步说明。
实施例1、SP5的合成
（1）单边溴代的柱[5]芳烃的合成：C20H59O10Br，根据文献，X. Q. Ma, Y. Wang, T.B. Wei, L. H. Qi, X. M. Jiang, J. D. Ding,W. B. Zhu, H. Yao, Y. M. Zhang, Q.Lin, Dyes Pigments, 2019,164, 279-286；
（2）巯基乙酸乙酯：C4H8O2S，从市场上购买；
（3）SP5的合成：取0.9g（1mmol）单边溴代的柱[5]芳烃，0.6g（1.5mmol）巯基乙酸乙酯；加入到150ml乙腈中，于80℃下反应24h；反应结束后除去溶剂，柱层析分离，得到白色粉末0.75g，即为化合物SP5，产率为80%。
实施例2、SP5识别L-Met
移取2.5ml超分子传感器分子SP5的DMF-H2O溶液（cSP5=1×10-4M，VDMF: V水= 7:3）于一系列比色管中，分别加入L-Phe，L-Gln，L-Ile，L-Thr，L-Glu，L-Ala，L-Ser，L-Met，L-Val，L-Tyr，L-Arg，L-Asp，L-Pro，L-His，L-Leu，L-Gly，L-Trp，L-Lys，L-Asn和L-Cys的水溶液（C=0.1mol/L），若SP5的DMF-H2O溶液荧光猝灭，说明加入的是L-Met，若SP5的DMF-H2O溶液荧光没有发生变化，则说明加入的不是L-Met。
Claims (5)
1.一种巯基酯修饰的柱[5]芳烃超分子化合物作为传感器在荧光识别甲硫氨酸中的应用，其特征在于：所述巯基酯修饰的柱[5]芳烃超分子化合物的分子式为C54H66O12S，结构式为：
2.如权利要求1所述巯基酯修饰的柱[5]芳烃超分子化合物作为传感器在荧光识别甲硫氨酸中的应用，其特征在于：在巯基酯修饰的柱[5]芳烃超分子化合物的DMF-H2O混合溶液中，分别加入L-Phe，L-Gln，L-Ile，L-Thr，L-Glu，L-Ala，L-Ser，L-Met，L-Val，L-Tyr，L-Arg，L-Asp，L-Pro，L-His，L-Leu，L-Gly，L-Trp，L-Lys，L-Asn和L-Cys水溶液，只有L-Met水溶液的加入能使巯基酯修饰的柱[5]芳烃超分子化合物的荧光猝灭。
3.如权利要求2所述巯基酯修饰的柱[5]芳烃超分子化合物作为传感器在荧光识别甲硫氨酸中的应用，其特征在于：所述DMF-H2O溶液中，H2O的体积百分数为10~40%。
4.如权利要求1所述巯基酯修饰的柱[5]芳烃超分子化合物作为传感器在荧光识别甲硫氨酸中的应用，其特征在于：巯基酯修饰的柱[5]芳烃超分子化合物的合成方法，是以乙腈为溶剂，6-溴己基功能化的柱[5]芳烃和巯基乙酸乙酯为底物，在70~80℃下反应20~24h；反应结束后除去溶剂，柱层析分离，即得巯基酯修饰的柱[5]芳烃超分子化合物。
5.如权利要求4所述巯基酯修饰的柱[5]芳烃超分子化合物作为传感器在荧光识别甲硫氨酸中的应用，其特征在于：巯基酯修饰的柱[5]芳烃超分子化合物的合成方法中，6-溴己基功能化柱[5]芳烃与巯基乙酸乙酯的摩尔比为1:1.5~1:2。
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Non-Patent Citations (2)
| Title |
|---|
| A novel AIE chemosensor based on quinoline functionalized Pillar[5]arene for highly selective and sensitive sequential detection of toxic Hg2+ and CN−;Xiao Qiang Ma et al.;《Dyes and Pigments》;20190531;第164卷;第279-286页 * |
| 基于对多底物检测识别的多功能柱[5]芳烃的合成;樊彦青 等;《中国化学会 全国第十五届有机合成化学学术研讨会》;20180802;第222页 * |
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