CN108219774A - 一种吡啶并[1,2-a]苯并咪唑取代的喹啉类检测次氯酸的荧光探针及其应用 - Google Patents

一种吡啶并[1,2-a]苯并咪唑取代的喹啉类检测次氯酸的荧光探针及其应用 Download PDF

Info

Publication number
CN108219774A
CN108219774A CN201710976554.9A CN201710976554A CN108219774A CN 108219774 A CN108219774 A CN 108219774A CN 201710976554 A CN201710976554 A CN 201710976554A CN 108219774 A CN108219774 A CN 108219774A
Authority
CN
China
Prior art keywords
benzimidazole
fluorescence
formula
fluorescence probe
iodide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710976554.9A
Other languages
English (en)
Inventor
葛燕青
吉瑞雪
刘爱坤
曹晓群
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taishan Medical University
Original Assignee
Taishan Medical University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taishan Medical University filed Critical Taishan Medical University
Priority to CN201710976554.9A priority Critical patent/CN108219774A/zh
Publication of CN108219774A publication Critical patent/CN108219774A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • 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
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

Abstract

本发明公开了一种1‑乙基‑4‑（2‑（4‑苯基吡啶并[1,2‑a]苯并咪唑）乙烯基）喹啉‑1‑碘化物的分子荧光探针，其化学结构如式（1）所示。本发明的荧光探针在乙醇/水（体积比2:8）溶液中对次氯酸有好的荧光选择性、较高的灵敏度，有广阔的应用前景。

Description

一种吡啶并[1,2-a]苯并咪唑取代的喹啉类检测次氯酸的荧 光探针及其应用
背景技术
次氯酸作为活性氧化剂在日常生活中的应用非常广泛，如作为消毒剂用于日常的清洁，作为漂白剂用于工业、纺织业等行业。在生物体细胞中，次氯酸根离子在过氧化氢酶的催化下参与了许多重要的生理病理过程。在维持细胞内的氧化还原的平衡状态起到了重要的作用。正常状态下，一定浓度的次氯酸对生物体组织的修复、疾病的防御等是有益的，但是一旦细胞内次氯酸的浓度发生异常，就会导致一系列疾病的发生，如：关节炎、动脉粥样硬化、心血管疾病甚至癌症等。因此能够有效的检测环境及生物体中次氯酸浓度的变化已经成为一项重大的研究方向及课题。
有机小分子荧光探针检测方法以高灵敏度、高选择性、操作简单实用性强等优点被科学家们广泛关注并且积极应用。目前用荧光探针检测法来检测次氯酸是检测次氯酸根离子较为广泛的方法之一，但用于荧光探针的荧光团种类较少，主要是香豆素、罗丹明、1，8-萘二甲基酰亚胺等，需要发现新的荧光团来进行检测。
发明内容
对于上述情况，本发明的目的之一是提供一种合成简单，反应条件温和，成本较低的一种荧光探针的合成，目的二是提供一种新的荧光团来进行荧光检测，目的三是提供一种选择性好，灵敏度高的荧光探针来检测次氯酸根离子。
本发明的设计方案是：一种1 -乙基-4-（2-（4- 苯基吡啶并[1,2-a] 苯并咪唑）乙烯基）喹啉-1-碘化物荧光探针，用于检测次氯酸根例子，化学结构式如本式所示：
(1)
本发明主要是提供一种检测次氯酸的分子荧光探针，即1 -乙基-4-（2-（4- 苯基吡啶并[1,2-a] 苯并咪唑）乙烯基）喹啉-1-碘化物探针的应用，式（1）化合物在乙醇/水溶液中（体积比2:8）有特异的荧光选择性。
本发明还包括1 -乙基-4-（2-（4- 苯基吡啶并[1,2-a] 苯并咪唑）乙烯基）喹啉-1-碘化物荧光探针的合成方法，在乙醇溶液中4-苯基-吡啶并[1,2-a]苯并咪唑-3-甲醛与4-甲基-1-乙基喹啉-1-碘化物按照摩尔比1:1.5投料比例，加热回流12h,式（1）即为化合物。
配置式（1）化合物的乙醇/水（体积比2:8）溶液，分别加入10当量的NaCl、MgCl2·6H2O、Zn(CH3COO)2、FeCl3·6H2O、CuCl2、HO．、t-BuO·、KO2、1O2、NaOONO2、H2O2、t-BuOOH、HClO的水溶液，通过荧光光谱测试来研究对不同离子的选择性，测其荧光发射波谱强度变化发现：本发明所述的1 -乙基-4-（2-（4- 苯基吡啶并[1,2-a] 苯并咪唑）乙烯基）喹啉-1-碘化物荧光探针即式（1）化合物对次氯酸有独特的荧光选择性，如图1所示。逐渐加入次氯酸至1.5倍当量后，化合物1在504nm处荧光强度明显增强。1 -乙基-4-（2-（4- 苯基吡啶并[1,2-a]苯并咪唑）乙烯基）喹啉-1-碘化物分子荧光探针即式（1）化合物作为检测次氯酸的荧光探针具有较为明显的现象。
本发明提供了一种分子荧光探针即式（1）化合物，本实验证明本发明所述式（1）化合物可与次氯酸在乙醇/水（体积比2:8）溶液中以化学计量比1:1.5反应，在反应过程中，由于式（1）化合物在加入次氯酸后，水解氧化成酸，使得荧光强度增强。因此可以证明本发明所述的式（1）化合物在乙醇/水（体积比为2:8）中对次氯酸有独特的荧光选择性以及较高的灵敏度。
附图说明
图1：式（1）化合物（5×10-6M）的乙醇/水（体积比2:8）溶液中加入10当量的不同离子的荧光强度变化图。
图2：式（1）化合物（5×10-6M）的乙醇/水（体积比2:8）溶液中进行ClO-荧光滴定图。图中FL Intensity为荧光强度，Wavelength为波长，equ.为倍数。
图3：式（5×10-6M）的乙醇/水（体积比2:8）溶液中对ClO-反应的时间。
图4是式（1）化合物合成方法反应式图。
具体实施方式
实施例1：式（1）化合物合成方案如下是所示：
具体合成步骤如下：
在25 mL圆底烧瓶中依次加入0.1 g（0.36 mmol)（4-（二乙氨基）-2-羟基苯甲酰基）苯甲醛，0.17 g（0.55 mmol) 乙基噻唑, 20 mL乙醇，加热回流反应12小时。TLC检测反应完成，冷却析出大量结晶，洗涤，对溶液进行浓缩，柱层析得到0.13 g黑红色固体，产率59% 。
核磁共振氢谱测定：1H NMR（400MHz,CDCl3）：δ 9.19 (d, 1H), 8.39 (d, 2H),8.28 (m, 2H), 8.13 (s, 1H), 8.01 (d, 1H), 7.85 (m, 3H), 7.77 (t, 1H), 7.64(s, 5H), 7.49 (d, 2H), 5.13 (q, 2H), 4.01 (q, 1H), 3.23 (d, 1H), 1.66 – 1.49(m, 3H).
实施例2
向式（1）化合物（5×10-6M）的乙醇/水（体积比2:8）溶液，分别加入10当量的NaCl、MgCl2·6H2O、Zn(CH3COO)2、FeCl3·6H2O、CuCl2、HO．、t-BuO·、KO2、1O2、NaOONO2、H2O2、t-BuOOH、HClO后，测其在504nm荧光强度的变化，显示化合物对次氯酸具有的ClO-后，化合物1在504nm处荧光强度明显增强。如图2所示。
实施例3
向式（1）化合物（5×10-6M）的乙醇/水（体积比2:8）溶液，分别加入0、1.5倍当量的ClO-后，测其反应时间的快慢。如图3所示。

Claims (2)

1.一种种吡啶并[1,2-a]苯并咪唑取代的喹啉类检测次氯酸的荧光探针即1 -乙基-4-（2-（4- 苯基吡啶并[1,2-a] 苯并咪唑）乙烯基）喹啉-1-碘化物的荧光探针，其化学结构式如式（1）所示：
式（1）化合物在乙醇/水溶液中（体积比2:8）对次氯酸有独特的荧光选择性。
2.权利要求1所述中1 -乙基-4-（2-（4- 苯基吡啶并[1,2-a] 苯并咪唑）乙烯基）喹啉-1-碘化物荧光探针的合成方法，其特征在于：在乙醇溶液中，将4-苯基-吡啶并[1,2-a]苯并咪唑-3-甲醛与4-甲基-1-乙基喹啉-1-碘化物按照摩尔比1:1.5投料比例，加热回流12h,得到1 -乙基-4-（2-（4- 苯基吡啶并[1,2-a] 苯并咪唑）乙烯基）喹啉-1-碘化物。
CN201710976554.9A 2017-10-19 2017-10-19 一种吡啶并[1,2-a]苯并咪唑取代的喹啉类检测次氯酸的荧光探针及其应用 Pending CN108219774A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710976554.9A CN108219774A (zh) 2017-10-19 2017-10-19 一种吡啶并[1,2-a]苯并咪唑取代的喹啉类检测次氯酸的荧光探针及其应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710976554.9A CN108219774A (zh) 2017-10-19 2017-10-19 一种吡啶并[1,2-a]苯并咪唑取代的喹啉类检测次氯酸的荧光探针及其应用

Publications (1)

Publication Number Publication Date
CN108219774A true CN108219774A (zh) 2018-06-29

Family

ID=62654735

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710976554.9A Pending CN108219774A (zh) 2017-10-19 2017-10-19 一种吡啶并[1,2-a]苯并咪唑取代的喹啉类检测次氯酸的荧光探针及其应用

Country Status (1)

Country Link
CN (1) CN108219774A (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112143487A (zh) * 2020-09-25 2020-12-29 高伟健 一种用于化妆品中重金属离子检测的介孔硅荧光探针
CN112538051A (zh) * 2020-12-17 2021-03-23 桂林理工大学 一种用于氟乐灵检测的苯并咪唑荧光探针及其合成方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977130A (zh) * 2012-12-21 2013-03-20 天津理工大学 一种用于检测次氯酸根的分子荧光探针及其制备和应用
CN105968094A (zh) * 2016-05-30 2016-09-28 山西大学 一种测定ClO-的咔唑类荧光探针及其制备方法和应用
CN106544007A (zh) * 2015-09-23 2017-03-29 济南大学 一种检测生物体系内次氯酸的荧光探针及其应用
CN107021953A (zh) * 2017-05-15 2017-08-08 三峡大学 一种香豆素荧光探针和制备方法及其在检测次氯酸根离子上的应用
CN107325095A (zh) * 2017-07-04 2017-11-07 济南大学 一种溶酶体次氯酸荧光探针及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102977130A (zh) * 2012-12-21 2013-03-20 天津理工大学 一种用于检测次氯酸根的分子荧光探针及其制备和应用
CN106544007A (zh) * 2015-09-23 2017-03-29 济南大学 一种检测生物体系内次氯酸的荧光探针及其应用
CN106544007B (zh) * 2015-09-23 2018-07-31 济南大学 一种检测生物体系内次氯酸的荧光探针及其应用
CN105968094A (zh) * 2016-05-30 2016-09-28 山西大学 一种测定ClO-的咔唑类荧光探针及其制备方法和应用
CN107021953A (zh) * 2017-05-15 2017-08-08 三峡大学 一种香豆素荧光探针和制备方法及其在检测次氯酸根离子上的应用
CN107325095A (zh) * 2017-07-04 2017-11-07 济南大学 一种溶酶体次氯酸荧光探针及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AIKUN LIU等: "A ratiometric fluorescent probe for sensing sulfite based on a pyrido[1,2-a]benzimidazole fluorophore", 《NEW J. CHEM.》 *
SI ZHANG等: "A bright red fluorescent cyanine dye for live-cell nucleic acid imaging, with high photostability and a large Stokes shift†", 《JOURNAL OF MATERIAL CHEMISTRY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112143487A (zh) * 2020-09-25 2020-12-29 高伟健 一种用于化妆品中重金属离子检测的介孔硅荧光探针
CN112538051A (zh) * 2020-12-17 2021-03-23 桂林理工大学 一种用于氟乐灵检测的苯并咪唑荧光探针及其合成方法
CN112538051B (zh) * 2020-12-17 2022-03-22 桂林理工大学 一种用于氟乐灵检测的苯并咪唑荧光探针及其合成方法

Similar Documents

Publication Publication Date Title
Li et al. Highly selective and sensitive two-photon fluorescence probe for endogenous peroxynitrite detection and its applications in living cells and tissues
Guha et al. Thiophene anchored coumarin derivative as a turn-on fluorescent probe for Cr3+: cell imaging and speciation studies
Zhang et al. Development of a ruthenium (II) complex-based luminescent probe for hypochlorous acid in living cells
Shu et al. A novel visual and far-red fluorescent dual-channel probe for the rapid and sensitive detection of hypochlorite in aqueous solution and living cells
CN105385439B (zh) 检测汞离子的反应型罗丹明类荧光探针及其制备与应用
Lee et al. Zinc selective chemosensor based on pyridyl-amide fluorescence
Zang et al. A highly specific pyrene-based fluorescent probe for hypochlorite and its application in cell imaging
JP6275256B2 (ja) ボロンジピロメテン蛍光プローブ、その製造方法及び応用
Sheet et al. Ruthenium (II) complex-based luminescent bifunctional probe for Ag+ and phosphate ions: Ag+-assisted detection and imaging of rRNA
Choi et al. Selective perborate signaling by deprotection of fluorescein and resorufin acetates
Li et al. A novel optical probe for Hg2+ in aqueous media based on mono-thiosemicarbazone Schiff base
CN105017271A (zh) 一种次氯酸荧光比率探针及其应用
Gwon et al. Novel styrylbenzothiazolium dye-based sensor for mercury, cyanide and hydroxide ions
Xie et al. A highly selective fluorescent and colorimetric chemosensor for ZnII and its application in cell imaging
CN102603725A (zh) 水相中检测锌离子的近红外荧光探针及其制备和应用
CN110590753A (zh) 一种靶向线粒体的近红外so2衍生物比率荧光探针及其应用
CN106243154B (zh) 一种细胞膜靶向的磷光铱配合物探针及其制备方法和应用
Qu et al. A highly selective NIR fluorescent turn-on probe for hydroxyl radical and its application in living cell images
CN108219774A (zh) 一种吡啶并[1,2-a]苯并咪唑取代的喹啉类检测次氯酸的荧光探针及其应用
CN108191852A (zh) 一种用于检测次氯酸的分子荧光探针及其应用
Zhang et al. Development of an ultrasensitive Ru (II) complex-based fluorescent probe with phenothiazine unit for selective detection HOCl and its application in water samples
CN102818802A (zh) 一种检测次氯酸根的方法
Spiteri et al. A fluorescent combinatorial logic gate with Na+, H+-enabled OR and H+-driven low-medium-high ternary logic functions
EP3621622A1 (en) A probe for selective detection of hypochlorous acid (hoci) under physiological condition
CN114105927A (zh) 一种新型苯并吡喃腈类荧光分子探针的构建及其体外诊断应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180629