CN108034421A - 一种新型aie红光荧光染料 - Google Patents

一种新型aie红光荧光染料 Download PDF

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CN108034421A
CN108034421A CN201711467731.7A CN201711467731A CN108034421A CN 108034421 A CN108034421 A CN 108034421A CN 201711467731 A CN201711467731 A CN 201711467731A CN 108034421 A CN108034421 A CN 108034421A
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fluorescent dye
new
feux rouges
fluorescence
fluorescent dyes
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宋相志
龚隽
龚隽一
苏远安
廖立德
杨雷
张帆
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/88—Hydrazones having also the other nitrogen atom doubly-bound to a carbon atom, e.g. azines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B26/00—Hydrazone dyes; Triazene dyes
    • C09B26/02—Hydrazone dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

本发明公开了一种新型AIE红光荧光染料，其分子结构式如下：该荧光染料在固态状态下和聚集态下有红色荧光，发射峰位于617nm。此外，该荧光染料本身可用于细胞中的脂质体成像，具有比较高的选择性。

Description

一种新型AIE红光荧光染料
技术领域
本发明涉及的是荧光染料领域，涉及一种基于聚集诱导发光(AIE)及分子内激发态质子转移(ESIPT)机理的红光荧光染料。
背景技术
有机小分子荧光染料被广泛应用于生物成像，有机发光二极管，染料敏化太阳能电池，光动力抗肿瘤药物等领域。传统荧光染料如罗丹明，荧光素， BODIPY以及一部分香豆素染料虽然在稀溶液中有很高的荧光量子效率，但由于存在聚集导致淬灭(ACQ)现象，使这些染料在高浓度下以及固体状态下发光较弱或不发光，从而影响了其在上述领域的广泛应用。聚集诱导发光(AIE)现象则描述了一类与ACQ效应相反的荧光染料，其在稀溶液状态下荧光较弱或不发光，而在高浓度或者固态下，发较强的荧光。AIE效应和AIE荧光染料的发现为荧光研究开创了新的领域，提供了新的思路。
激发态分子内质子转移(ESIPT)机理是一类荧光染料的发光机理，其描述了一类在激发态会发生质子转移的化合物。该类化合物由于质子转移的存在，使得其Stokes位移显著的大于常规荧光染料，有利于降低染料本身的自吸收效应，特别适合基于此开发可应用于生物成像的长波长发光材料。
发明内容
本发明目的是提供一种基于AIE和ESIPT机理的新型易合成的有机小分子红光荧光染料。
本发明解决问题采取的技术方案为，一种新型有机小分子红光荧光染料，其分子结构式如下：具体合成路线如下：
具体合成方法如下：
(1)将272mg化合物1溶于10mL甲醇中，加入150mg 40％乙二醛，常温下反应12小时，观察体系有黄色沉淀生成；
(2)过滤并收集黄色沉淀，用50mL乙醇洗涤沉淀三次，得到黄色粉末状固体213mg，即为产品染料1，产率72.45％。
本发明的荧光染料的固体状态下荧光发射峰在617nm，荧光量子产率为 2.0％；
本发明的荧光染料在聚集状态下发射峰位于617nm，发光强度是同浓度染料完全溶解在溶剂中的溶液的40倍，具有显著的AIE效应；最大吸收峰位于 445nm，Stokes位移为172nm；
本发明所述的染料分子合成路线简单，Stokes位移172nm，发射位于红光区，可有效避免细胞自吸收和自身荧光的干扰，同时在生物体内有红光信号有更强的穿透力，该染料具有可以调节荧光的羟基可以做简单修饰为荧光探针，或直接用于细胞成像染色，以及其他领域的应用。
附图说明
图1为本发明荧光染料的固体荧光，横坐标为波长，纵坐标为荧光强度。
图2为本发明荧光染料的AIE效应，荧光染料(1.0×10-5mol/L)在含水量不同的水-四氢呋喃混合溶液中的荧光，横坐标为波长，纵坐标为荧光强度。
图3为本发明的荧光染料(1.0×10-5mol/L)在在含水量不同的水-四氢呋喃混合溶液中的荧光变化规律，横坐标为含水量，纵坐标为617nm处的荧光强度。
图4为本发明的荧光染料(1.0×10-5mol/L)在不同pH的PBS缓冲溶液中的荧光，横坐标为波长，纵坐标为荧光强度。
图5为本发明的荧光染料(1.0×10-5mol/L)在不同pH的PBS缓冲溶液中的荧光变化规律，横坐标为pH，纵坐标为发射峰处的荧光强度。
图6为本发明的荧光染料(1.0×10-5mol/L)的细胞(Hela细胞)成像(以等量pH＝7.4的PBS溶液为对照组)：图A对照组的红光通道信号成像，B对照组的明场成像，图C对照组的细胞复合场成像，图D染料处理的细胞中红光通道成像，图E染料溶液处理的细胞明场成像，图F染料溶液处理的细胞复合场成像。
具体实施实例
实施例1：染料的合成
将272mg化合物1溶于10mL甲醇中，加入150mg 40％乙二醛，常温下反应 12小时，观察体系有黄色沉淀生成；过滤黄色沉淀，用50mL乙醇洗涤沉淀三次，得到黄色粉末状固体213mg，即为产品染料1，产率72.45％。HRMS(ESI) m/z:calcd for[M+1]+,295.110；found,295.119.1H NMR(400MHz,DMSO-d6)δ10.99(s,2H), 8.97(s,2H),8.54(s,2H),7.76(dd,J＝7.7,1.5Hz,2H),7.57–7.24(m,2H),6.98(t,J＝7.8Hz, 4H).13C NMR(400MHz,CDCl3)168.01,160.55,159.99,134.35,133.23,119.96,117.46.
实施例2：本发明:荧光染料的细胞成像
将染料溶于DMSO溶液中，配制成2.0×10-5mol/L的溶液，将2μL上述溶液加入2mL细胞培养介质中，以此作为培养基在37℃下培养HeLa细胞1小时，通过激光共聚焦扫描显微镜，以425nm作为激发波长可以在红光通道下观察到在细胞的脂质体中有较强的信号，说明该探针可以选择性的在脂质体中聚集产生荧光，可用于成像并具有较高选择性。

Claims (1)

1.一种新型AIE红光荧光染料，其结构为：
CN201711467731.7A 2017-12-28 2017-12-28 一种新型aie红光荧光染料 Pending CN108034421A (zh)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103194215A (zh) * 2013-04-15 2013-07-10 武汉大学 一种聚集诱导发光分子及其制备方法和用途
CN106220583A (zh) * 2016-07-19 2016-12-14 华南理工大学 具有aie效应的苯并噻唑‑三苯胺染料及其制备方法与应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103194215A (zh) * 2013-04-15 2013-07-10 武汉大学 一种聚集诱导发光分子及其制备方法和用途
CN106220583A (zh) * 2016-07-19 2016-12-14 华南理工大学 具有aie效应的苯并噻唑‑三苯胺染料及其制备方法与应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WEIXIN TANG ET AL.: "Salicylaldehyde Azines as Fluorophores of Aggregation-Induced Emission Enhancement Characteristics", 《J. ORG. CHEM.》 *

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