一种新型铱(Ⅲ)配合物探针分子的制备及其依次对铜离子和硫化氢的识别

doi:10.3969/j.issn.1006-7795.2021.01.010

首都医科大学学报 ›› 2021, Vol. 42 ›› Issue (1): 58-65.doi: 10.3969/j.issn.1006-7795.2021.01.010

一种新型铱(Ⅲ)配合物探针分子的制备及其依次对铜离子和硫化氢的识别

庞淇丹, 王天然, 肖猱^*

首都医科大学药学院化学生物学系, 北京 100069

收稿日期:2020-09-01 出版日期:2021-02-21 发布日期:2021-02-02
基金资助:
北京市自然科学基金青年项目(2174069),北京市教委科技计划面上项目(KM201510025007),首都医科大学科研培育基金(1200020248)。

Preparation of a novel iridium(Ⅲ) complex probe for sensing of copper ion and hydrogen sulfide in sequence

Pang Qidan, Wang Tianran, Xiao Nao^*

Department of Chemical Biology, School of Pharmaceutical Sciences, Capital Medical University, Beijing 100069, China

Received:2020-09-01 Online:2021-02-21 Published:2021-02-02
Contact: ^*E-mail:xiaonao@ccmu.edu.cn
Supported by:
Natural Science Foundation of Beijing (2174069), Scientific Research Common Program of Beijing Municipal Commission of Education (KM201510025007), Scientific Research Cultivating Fund of Capital Medical University (1200020248).

摘要/Abstract

摘要： 目的设计一个新型铱配合物荧光探针分子Ir-cyc,以质谱分析为主要手段确定产物的结构并分析其对Cu²⁺及H₂S的荧光响应。方法以2-苯基吡啶(2-phenylpyridine, ppy)及三氯化铱(iridium trichloride, IrCl₃)为原料,制备桥式铱前配物[Ir(ppy)₂Cl]₂;以5-氨基邻菲啰啉和溴乙酰溴为原料,通过亲核取代反应合成配体分子Phen-Br;通过[Ir(ppy)₂Cl]₂和Phen-Br在溶剂中螯合反应可得到溴功能化的铱配合物Ir-Br,Ir-Br进一步与轮环藤宁发生亲核取代反应后制备探针分子Ir-cyc。结果通过质谱分析确定了所合成各中间产物及最终产物的结构,通过荧光光谱及紫外-可见光谱分析掌握了配合物探针分子的基本光学性质。荧光光谱变化显示探针分子Ir-cyc可依次识别Cu²⁺及H₂S。结论通过经典的螯合反应和亲核取代反应制备了新型探针分子铱配合物Ir-cyc,该探针分子可在水溶液中依次识别Cu²⁺及H₂S,具备应用于环境监测及生物样品分析的潜力。

关键词: 铱配合物, 荧光探针, 铜离子, 硫化氢, 质谱

Abstract: Objective To synthesis a new water-soluble iridium complex Ir-cyc and explore the sensing properties of Ir-cyc towards Cu²⁺ and H₂S in sequence with fluorescence spectra. Methods Iridium complex [Ir(ppy)₂Cl]₂ was prepared from 2-phenylpyridine (ppy) and iridium trichloride (IrCl₃); the ligand Phen-Br was synthesized from 5-amino-o-phenanthroline and 2-bromoacetyl bromide by nucleophilic substitution; the bromine-functionalized iridium complex Ir-Br was obtained by chelation reaction of [Ir(ppy)₂Cl]₂ and Phen-Br; Ir-Br was further nucleophilically substituted with cyc to prepare the probe molecule Ir-cyc. Results The structures of the synthesized intermediates and final iridium complex were determined by mass spectrometry. The basic photophysical properties of the probe Ir-cyc were characterized by fluorescence spectroscopy and UV-Vis spectroscopy. The fluorescence spectral changes revealed that the probe Ir-cyc could detect Cu²⁺ and H₂S in sequence. Conclusion A novel iridium complex of probe Ir-cyc was prepared by classical chelation and nucleophilic substitution reactions, which could recognize Cu²⁺ and H₂S sequentially in aqueous solution and has potential application in environmental monitoring and biological sample analysis.

Key words: iridium complex, fluorescent probe, Cu²⁺ ion, hydrogen sulfide, MS analysis

中图分类号:

O654.9

庞淇丹, 王天然, 肖猱. 一种新型铱(Ⅲ)配合物探针分子的制备及其依次对铜离子和硫化氢的识别[J]. 首都医科大学学报, 2021, 42(1): 58-65.

Pang Qidan, Wang Tianran, Xiao Nao. Preparation of a novel iridium(Ⅲ) complex probe for sensing of copper ion and hydrogen sulfide in sequence[J]. Journal of Capital Medical University, 2021, 42(1): 58-65.

参考文献

[1] Xiao N, Zhang C. Selective monitoring of Cu(II) with a fluorescence-on naphthalene-based probe in aqueous solution[J]. Inorg Chem Commun, 2019, 107: 107467.
[2] Bao Z, Qin C, Wang J J, et al. A sensitive and selective probe for visual detection of Cu²⁺ based on 1, 8-naphthalimidederivative[J]. Sens Actuators B Clem, 2018, 265: 234-241.
[3] Nagarkar S S, Desai A V, Ghosh S K. A nitro-functionalized metal-organic framework as a reaction-based fluorescence turn-on probe for rapid and selective H₂S detection[J]. Chem Eur J, 2015, 21(28): 9994-9997.
[4] Wang W, Wu C, Yang C, et al. A dual-functional luminescent probe for imaging H₂S in living zebrafish and discrimination hypoxic cells from normoxic cells[J]. Sens Actuators B, 2018, 255: 1953-1959.
[5] Xiao N, Xie L, Zhi X, et al. A naphthol-based highly selective fluorescence turn-on and reversible sensor for Al(III) ion[J]. Inorg Chem Commun, 2018, 89: 13-17.
[6] Zhang X, Jiang Y, Xiao N, et al. Monitoring ADP and ATP in vivo using a fluorescent Ga(Ⅲ)-probe complex[J]. Chem Commun, 2018, 54(91): 12812-12815.
[7] Huang Q, Wang T, Xiao N. Selective monitoring ATP using a fluorogenic Al(Ⅲ)-probe complex in aqueous medium[J]. Spectrochim Acta A, 2020, 229: 117946.
[8] Zhang F, Liang X, Zhang W, et al. A unique iridium(Ⅲ) complex-based chemosensor for multi-signal detection and multi-channel imaging of hypochlorous acid in liver injury[J]. Biosens Bioelectron, 2017, 87: 1005-1011.
[9] Ohata J, Vohidov F, Aliyan A, et al. Luminogenic iridium azide complexes[J]. Chem Commun, 2015, 51(82): 15192-15915.
[10]Belhadj E, El-Ghayoury A, Cauchy T, et al. Tetrathiafulvalene-based phenanthroline ligands: synthesis, crystal structures, and electronic properties[J]. Eur J Inorg Chem, 2014, 2014(24): 3912-3919.
[11]Bos J, Fusetti F, Driessen A J, et al. Enantioselective artificial metalloenzymes by creation of a novel active site at the protein dimer interface[J]. Angew Chem Int Ed Engl, 2012, 51(30): 7472-7475.
[12]Sprouse S, King K A, Spellane P J, et al. Photophysical effects of metal-carbon σ bonds in ortho-metalated complexes of iridium(Ⅲ) and rhodium(Ⅲ)[J]. J Am Chem Soc, 1984, 106(22): 6647-6653.
[13]Schmittel M, Lin H. Luminescent iridium phenanthroline crown ether complex for the detection of silver(I) ions in aqueous media[J]. Inorg Chem, 2007, 46(22): 9139-9145.
[14]Lu F, Yamamura M, Nabeshima T. Luminescent biscyclometalated iridium(Ⅲ) complex for selective and switchable Cu²⁺ ion binding in aqueous media[J]. Tetrahedron Lett, 2013, 54(8): 779-782.
[15]Ye Z, An X, Song B, et al. A novel dinuclear ruthenium(II)-copper(II) complex-based luminescent probe for hydrogen sulfide[J]. Dalton Trans, 2014, 43(34): 13055-13060.
[16]Zhang C, Liu M, Liu S, et al. Phosphorescence lifetime imaging of labile Zn²⁺ in mitochondria via a phosphorescent iridium(Ⅲ) complex[J]. Inorg Chem, 2018, 57(17): 10625-10632.
[17]King K A, Spellane P J, Watts R J. Excited-state properties of a triply ortho-metalated iridium(Ⅲ) complex[J]. J Am Chem Soc, 1985, 107(5): 1431-1432.
[18]Dedeian K, Djurovich P I, Garces F O, et al. A new synthetic route to the preparation of a series of strong photoreducing agents-fac-tris-ortho-metalated complexes of iridium(Ⅲ) with substituted 2-phenylpyridines[J]. Inorg Chem, 1991, 30(8): 1685-1687.
[19]Colombo M G, Brunold T C, Riedener T, et al. Facial tris cyclometalated Rh³⁺ and Ir³⁺ complexes-their synthesis, structure, and optical spectroscopic properties[J]. Inorg Chem, 1994, 33(3): 545-550.
[20]Schmid B, Garces F O, Watts R J. Synthesis and characterization of cyclometalated iridium(Ⅲ) solvento complexes[J]. Inorg Chem, 1994, 33(1): 9-14.

一种新型铱(Ⅲ)配合物探针分子的制备及其依次对铜离子和硫化氢的识别

Preparation of a novel iridium(Ⅲ) complex probe for sensing of copper ion and hydrogen sulfide in sequence

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	朱晓蓉, 杨芳远, 卢晶, 曹曦, 杨光燃, 谢荣荣, 冯建萍, 杨金奎. 增殖期糖尿病视网膜病变的血清代谢组学研究[J]. 首都医科大学学报, 2020, 41(1): 1-7.
[2]	李鹏飞, 范家明, 刘河, 张茜, 安卓玲, 刘丽宏. 大鼠体内百草枯组织分布研究[J]. 首都医科大学学报, 2019, 40(5): 726-730.
[3]	杨一帆, 秦一, 徐唯哲, 徐平湘, 薛明. 吡硫醇在低氧与常氧环境下大鼠体内的药代动力学研究[J]. 首都医科大学学报, 2017, 38(2): 232-237.
[4]	胡立新, 宋文琪, 苏建荣, 董方, 王艳. 儿童感染沙门菌耐药特点及鉴定方法的研究[J]. 首都医科大学学报, 2016, 37(3): 364-369.
[5]	吴薇, 王利君, 隋文君, 张桂. 基质辅助激光解析电离飞行时间质谱技术早期筛查耐万古霉素屎肠球菌[J]. 首都医科大学学报, 2015, 36(3): 444-448.
[6]	黄雯, 陈燊, 李晓璐, 张红, 杨敏, 张梅. 内源性硫化氢在糖尿病大鼠肾脏的变化及作用[J]. 首都医科大学学报, 2015, 36(3): 505-507.
[7]	秦春雨, 周滔, 宫雯雯, 白露, 秦一, 徐唯哲, 徐平湘, 王晓民, 薛明. UPLC-MS/MS法测定大鼠血浆中雷公藤内酯醇及其药代动力学[J]. 首都医科大学学报, 2015, 36(1): 121-126.
[8]	陈宁, 王珊珊, 陈玉涵, 殷继明, 陈德喜, 丁惠国. 外源性硫化氢对肝癌细胞系HepG2自噬的影响[J]. 首都医科大学学报, 2015, 36(1): 116-120.
[9]	李鹏飞, 王淑民, 张茜, 安卓玲, 刘丽宏. LC-MS/MS法测定人血浆中氨基葡萄糖的浓度[J]. 首都医科大学学报, 2013, 34(5): 715-719.
[10]	何玥;吴玉梅;赵群;王晓丽;陈硕;钱小红;张玉祥. 宫颈上皮内瘤变与正常宫颈组织差异表达蛋白分析[J]. 首都医科大学学报, 2012, 33(1): 36-44.
[11]	刘治岐;王鸣刚;刘颖;李宇航;薛明. 两种β-环糊精对苯环壬酯手性识别的串联四极杆质谱研究[J]. 首都医科大学学报, 2012, 33(1): 89-93.
[12]	王新宝. 气体信号分子硫化氢与缺血再灌注损伤[J]. 首都医科大学学报, 2012, 33(1): 130-135.
[13]	孔明;时红波;陈宫;赵军;丁美;段钟平;陈煜. 复合花粉制剂改善CCl₄诱导肝硬化大鼠血浆氨基酸失衡[J]. 首都医科大学学报, 2011, 32(3): 331-336.
[14]	武彦宁;蔡照华_;孙海梅;尚宏伟;郝刚;张立新;孙琳;张华;丁惠国. 非酒精性脂肪性肝炎大鼠肝脏内源性H₂S合成减少[J]. 首都医科大学学报, 2010, 31(3): 287-292.
[15]	赵逸松;崔歆;梁堃;刘爽;杨琳;赵峰. 高效液相色谱-质谱联用分析法测定血清全氟辛烷磺酸[J]. 首都医科大学学报, 2009, 30(3): 336-340.