| 水溶性糖基铱配合物的合成、表征及成像分析 |
| Synthesis, Characterization and Imaging Analysis of Water-Soluble Iridium(Ⅲ) Complexes with Sugar Groups |
| 作者 | 单位 | E-mail | | 穆相君 | 福州大学化学学院, 食品安全与生物分析教育部重点实验室, 福建省食品安全分析与检测技术重点实验室, 福州 350116 | | | 冯青月 | 福州大学化学学院, 食品安全与生物分析教育部重点实验室, 福建省食品安全分析与检测技术重点实验室, 福州 350116 | | | 李梅金 | 福州大学化学学院, 食品安全与生物分析教育部重点实验室, 福建省食品安全分析与检测技术重点实验室, 福州 350116
福州大学, 能源与光催化国家重点实验室, 福州 350116 | mjli@fzu.edu.cn | | 易长青 | 中山大学生物医学工程学院, 广东省传感技术与生物医学仪器重点实验室, 深圳 518107 | | | 付凤富 | 福州大学化学学院, 食品安全与生物分析教育部重点实验室, 福建省食品安全分析与检测技术重点实验室, 福州 350116 | |
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| 摘要: 设计、合成了3种水溶性糖基金属铱配合物[（dfppy）2Ir（bpy-sugar）]Cl（1）、[（tpy-COOH）2Ir（bpy-sugar）]Cl（2）和[（mpbq）2Ir（bpy-sugar）]Cl（3）（dfppy=2-（2，4-二氟苯基）吡啶，tpy-COOH=4-（2'-吡啶基）苯甲酸，mpbq=2-甲基-3-苯基苯并[g]喹喔啉，bpy-sugar=4，4'-二（1-硫代-β-D-葡萄糖甲基）-2，2'-联吡啶），利用核磁共振波谱、高分辨质谱、红外光谱和元素分析对其进行结构表征，并研究其光物理性质及其在细胞成像中的应用。通过辅助配体的调控，可以实现配合物从黄色到近红外的不同波长发光。配合物1和2在水溶液中表现出黄色发光，发射波长分别为546和584 nm，配合物3在水和二甲基亚砜的混合溶液（39：1，V/V）中表现出近红外发光，发射波长为780 nm。配合物1和2具有相对较高的量子产率（16.9%和3.1%）和较长的发光寿命（0.22和0.10 μs）。在配体上修饰不同的基团可以增大配合物的细胞穿透性和水溶性，实现配合物在细胞内的成像分析。从细胞成像结果可以看出，金属铱配合物能够穿过细胞膜进入到细胞，且与4，6-联脒-2-苯基吲哚（DAPI）染色的细胞核部分有所重合，说明进入到了细胞核。同时配合物的发光情况良好，说明在细胞所在的生物环境中，这种配合物仍是稳定的。 |
| 关键词: 金属铱配合物 光致发光 成像分析 |
| 基金项目: 国家自然科学基金（No.21976029）和能源与环境光催化国家重点实验室开放基金（No.SKLPEE-202018）资助。 |
| Abstract: A series of cyclometalated iridium(Ⅲ) complexes,[(dfppy)2Ir(bpy-sugar)]Cl (1),[(tpy-COOH)2Ir(bpy-sugar)] Cl (2) and[(mpbq)2Ir(bpy-sugar)]Cl (3) (dfppy=2-(2,4-difluorophenyl)pyridine, tpy-COOH=4-(2'-pyridyl)benzoic acid, mpbq=2-methyl-3-phenylbenzo[g]quinoxaline, bpy-sugar=4,4'-bis(1-thio-β-D-glucosemethyl)-2,2'-bipyridine), were designed and synthesized with cyclometalated C^N ligand and bpy-sugar assistant ligands. Their structures were characterized by NMR, MS, IR spectroscopy and elemental analysis. Their photophysical properties and applications in cell imaging were studied. Through the regulation of auxiliary cyclometalated ligands, the photoluminescence of the complexes can be tuned from yellow to near-infrared light. In aqueous solution, complexes 1 and 2 displayed yellow emissions with the maximum wavelengths at about 546 and 584 nm, respectively. While complex 3 displayed near infrared emission with wavelength at about 780 nm in a mixed solution of H2O and dimethyl sulfoxide (39:1, V/V). The quantum efficiencies of complexes 1 and 2 were 16.9% and 3.1%, respectively. The quantum yield of complex 1 was significantly higher than that of ruthenium(Ⅱ) tris(2,2'-bipyridine). The photoluminescence of complex 3 was weak, and the integrating sphere cannot obtain accurate quantum yield. However, its photoluminescence in the near-infrared region was expected to be used as a near-infrared probe for biological analysis. The lifetimes of complexes 1 and 2 were 0.22 and 0.10 μs, respectively. Modifying different groups on the ligand can increase the cell penetration and water solubility of the complexes, and realize the imaging analysis of the complex in the cell. The iridium(Ⅲ) complexes could penetrate the cell membrane and enter the cell, and overlap with the part of the nucleus stained by 4,6-bialamidine-2-phenylindole (DAPI), indicating that it had entered the nucleus. The photoluminescence of the iridium(Ⅲ) complexes was good in living cells, showing that the iridium(Ⅲ) complexes was still stable in the biological environment. |
| Keywords: iridium(Ⅲ) complex photoluminescence imaging analysis |
| 投稿时间：2021-05-08 修订日期：2021-10-13 |
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| 穆相君,冯青月,李梅金,易长青,付凤富.水溶性糖基铱配合物的合成、表征及成像分析[J].无机化学学报,2021,37(12):2125-2132. |
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