新型水溶性吲哚花箐的合成及光谱性能研究  

Synthesis and Optical Properties of Novel Water-soluble Indocyanine Dyes

作　　者：陈正军 丁尚丽 吕佳佳 杨明焱 高杰 李洪玉 罗俊俊 袁泽利 CHEN Zhengjun;DING Shangli;LV Jiajia;YANG Mingyan;GAO Jie;LI Hongyu;LUO Junjun;YUAN Zeli(School of Pharmacy,Key Laboratory of Basic Pharmacology of Ministry of Education,Key Laboratory of Biocatalysis&Chiral Drug Synthesis of Guizhou Province,Guizhou International Scientific and Technological Cooperation Base for Medical Photo-theranostics Technology and Innovative Drug Development,Zunyi Medical University,Zunyi 563000,China)

机构地区：[1]遵义医科大学药学院,教育部基础药理重点实验室,贵州省生物催化与手性药物重点实验室,贵州省医用光学诊疗技术与创新药物国际科技合作基地,贵州遵义563000

出　　处：《合成化学》2023年第8期573-579,共7页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(82060626);贵州省创新群体重大资助项目(KY[2018]024);贵州省科技支撑计划资助项目([2020]4Y158);贵州省优秀青年科技人才资助项目([2021]5638);贵州省科技厅平台资助项目([2020]4104)。

摘　　要：近红外(NIR)荧光染料在体内成像方面具有巨大优势,在各种化学和生物学研究中引起了广泛关注。近红外波长可以穿透到更深的组织,具有更低的自发荧光,对体内成像至关重要。到目前为止,最著名、应用最广泛的近红外荧光染料吲哚菁绿(ICG),具有良好的临床应用和安全性。但由于其荧光量子产率低、荧光寿命短、光稳定性差和化学稳定性差等问题阻碍了ICG在化学和生命科学中的应用。因此,开发光学性能优异的近红外荧光染料是非常有意义的。以2,3,3-三甲基-3 H-吲哚和三溴丙基三甲基溴化铵为原料,合成得到了吲哚季胺盐(2)。用2与3-(羟基亚甲基)-2-氯环己-1-烯(1)缩合得到IR780类似物(3),再将3分别与3个芳基硼酸经Suzuki反应合成得到3个新型水溶性吲哚花箐染料(4~6)。上述中间体及目标染料的结构经^(1)H NMR、^(13)C NMR和HR-MS表征,并对中间体3及目标染料(4~6)的光谱性能进行了初步研究。结果表明:3个吲哚花箐染料分子均具有良好的水溶性和处于近红外区的吸收和发射性能,且化合物4和化合物6的单线态氧收率(ΦΔ)较高,分别为0.67%和0.52%。Near-infrared(NIR)fluorescent dyes have great superiority in vivo imaging and attracted extensive attention in various chemical and biological studies due to their great advantages in vivo imaging.Near-infrared wavelengths can penetrate deeper into tissues,and having lower autofluorescence is essential for in vivo imaging.So far,indocyanine green(ICG),the most famous and widely used near-infrared fluorescent dye,has good clinical application and safety.However,due to the low yield of fluorescence quantum,short fluorescence lifetime,poor photostability and poor chemical stability,the application of ICG in chemistry and life science is hindered.Therefore,it is very meaningful to develop near-infrared fluorescent dyes with excellent optical properties.Three cyanine dyes(4~6)were synthesized using cyanine dye(3)which respectively Suzuki reaction of arylboronic acid derivatives.3 was prepared from 2,3,3-trimethyl-1-[3-(trimethyl-ammonio)propyl]-3 H-indolium(2)and 3-(hydroxylmethylene)-2-chcloro-cyclohex-1-enealdehyde(1).Structures were confirmed by^(1)H NMR,^(13)C NMR and HR-MS spectrometry,and their spectral properities of dyes were examined.The results showed that the three indoline dyes had good water solubility,absorption and emission properties in the near infrared region,and compound 4(ΦΔ=0.67%)and compound 6(ΦΔ=0.52%)had high singlet oxygen yield.

关 键 词：吲哚花箐 荧光成像 近红外 SUZUKI反应 结构表征 光谱性能 单线态氧 

分 类 号：O622.6[理学—有机化学]