CN108558877A - 一种咪唑并[1,5-a]吡啶类的钯离子荧光探针及其应用 - Google Patents

一种咪唑并[1,5-a]吡啶类的钯离子荧光探针及其应用 Download PDF

Info

Publication number
CN108558877A
CN108558877A CN201810534701.1A CN201810534701A CN108558877A CN 108558877 A CN108558877 A CN 108558877A CN 201810534701 A CN201810534701 A CN 201810534701A CN 108558877 A CN108558877 A CN 108558877A
Authority
CN
China
Prior art keywords
phenyl
pyridine
fluorescence probe
formula
imidazos
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
CN201810534701.1A
Other languages
English (en)
Inventor
葛燕青
吉瑞雪
徐志扬
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 CN201810534701.1A priority Critical patent/CN108558877A/zh
Publication of CN108558877A publication Critical patent/CN108558877A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • G01N21/6402—Atomic fluorescence; Laser induced fluorescence
    • 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
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Optics & Photonics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Luminescent Compositions (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

本发明公开了一种1‑苯基‑3‑（2‑（丙基‑2‑炔氧基）苯基）H‑咪唑并[1,5‑a]吡啶的Pd2+荧光探针，其化学结构式如式（1）所示。本发明的荧光探针在PBS缓冲溶液（pH=7.40）中对Pd2+有较好的荧光选择性、较高的灵敏度及较强的抗其它离子干扰能力，应用前景广泛。

Description

一种咪唑并[1,5-a]吡啶类的钯离子荧光探针及其应用
技术领域
本发明涉及有机小分子荧光探针领域，尤其涉及一种Pd2+荧光探即1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶的合成及其应用。
背景技术
随着钯在医药、日用品、汽车尾气的催化转化剂及化学合成催化剂中广泛应用，有关钯对环境、人体健康的影响正引起越来越多的关注。已有研究标明: Pd2+ 可与含巯基的氨基酸、蛋白质( 酪蛋白、蚕丝蛋白和部分酶) 、DNA 及其它生物大分子结合而影响它们在体内的正常生理功能，进而对人体产生毒副作用，已有国家已经严格限制，食品摄入钯的最大量不得高于 1.5～15 μg/天/人。因此，研究对Pd2+具有灵敏度和选择性强的检测方法很有意义。
荧光探针往往具有高选择性，易实现可视化和实时检测，已被越来越多地应用于多种复杂生物、环境样品中的金属离子检测及成像分析。目前，已有一些关于Pd2+荧光探针报道，然而这些报道的Pd2+荧光探针有些尚不尽令人满意。
发明内容
针对现有技术的不足，本发明解决的问题是提供一种Pd2+的荧光探针即1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶的合成及其应用。
本发明的技术方案是：一种1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶的Pd2+荧光探针，其化学结构式如式（1）所示：
(1)
本发明还包括1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶的Pd2+荧光探针的应用，式（1）化合物在PBS缓冲溶液（pH=7.40）对Pd2+有较好的荧光选择性。
本发明还包括1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶的Pd2+荧光探针的合成方法，在乙腈溶液中，将2（1-苯基咪唑并[1,5-a]吡啶-3-基）苯酚与溴丙炔、碳酸钾按照摩尔比1:1.5:1.5投料比例，加热回流反应2小时，得到1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶化合物。
配制1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶化合物的二甲亚砜溶液，分别加入定量的MgCl2, CaCl2, AlCl3, SnCl2 .2H2O, PbSO4, CrCl3·6H2O,MnCl2·4H2O, FeCl3·6H2O, LiCl, KCl, CuCl2 .2H2O, FeCl2·4H2O, CoCl2·6H2O,NiCl2·6H2O, PdCl2, ZnCl2, HgCl2·2H2O, CdCl2·2½H2O, NaAc, NaBr, NaCl, NaHCO3,NaF, NaHS, NaI, NaNO2, NaNO3, Na2SO4, Na2SO3的水溶液，通过荧光光谱测试来研究对不同金属离子的选择性，测其荧光发射波谱强度变化发现：本发明所述1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶化合物即式（1）化合物对Pd2+有较好的荧光选择性，如图1所示。逐渐加入Pd2+至25当量后，化合物1在467nm处荧光强度明显降低，如图2所示。因此，1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶化合物作为Pd2+荧光探针具有巨大的应用。
附图说明
图1：式（1）化合物（1×10-6M）的PBS缓冲溶液中（pH=7.40）加入25当量的不同阴阳离子后的荧光强度变化比例柱状图，图1中纵坐标为467nm处的光强度。
图2：式（1）化合物（1×10-6M）的PBS缓冲溶液中（pH=7.40）进行Pd2+荧光滴定图。图中FL Intensity为光强，Wavelength为波长，equiv为倍数。
图3：式（1）化合物（1×10-6M）和25当量的金属离子共存的PBS缓冲溶液中（pH=7.40）加入25当量Pd2+的后荧光强度的变化柱状图。
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）化合物的合成方案如下式所示：
具体合成步骤如下：
在50 mL圆底烧瓶中依次加入0.14g（0.50 mmol）4-氰基-3-间苯酚-苯并咪唑并[1,2-a]吡啶-3-羧酸乙酯，0.18g（1.5 mmol）溴丙炔，0.2g (1.5 mmol)碳酸钾，20 mL乙腈，加热回流2小时。柱层析得0.22g固体，产率75%。
实施例2：
向式（1）化合物（10-6M）的PBS缓冲溶液中（pH=7.40）分别加入25当量Mg2+, Ca2+, Al3+,Pb2+, Cr3+, Mn2+, Fe3+, Fe2+，Co2+, Sn2+, Li+, Ni2+, Zn2+, Hg2+, Cd2+, Na+, K+, Cu2+,Ac-, NO2 -, SO4 2-, HCO3 -, F-, NO3 -, HS-, Br-, I-, SO3 2-后，测其在467nm荧光发射强度变化发现：式（1）化合物对Pd2+有较好的荧光选择性，加入25当量的Pd2+后，化合物1在467nm处荧光强度明显升高。如图1，图2所示。
实施例3：
分别于式（1）化合物（10-6M）和25当量的Mg2+, Ca2+, Al3+, Pb2+, Cr3+, Mn2+, Fe3+,Fe2+，Co2+, Sn2+, Li+, Ni2+, Zn2+, Hg2+, Cd2+, Na+, K+, Cu2+, Ac-, NO2 -, SO4 2-, HCO3 -,F-, NO3 -, HS-, Br-, I-, SO3 2-不同阴阳离子溶液中，加入25当量的Pd2+后，测其在467nm荧光发射强度变化发现：式（1）化合物对其它离子有较强的抗干扰能力，如图3所示。

Claims (2)

1.一种1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶化合物的Pd2+荧光探针，其特征在于：它是溴丙炔取代的4-氰基-3-间苯酚-苯并咪唑并[1,2-a]吡啶-3-羧酸乙酯化合物，其化学结构式如式（1）所示：
（1）
式（1）化合物在PBS缓冲溶液中（pH=7.40）对Pd2+有较好的荧光选择性。
2.权利要求1所述1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶化合物Pd2+荧光探针的合成方法，其特征在于：在二氯甲烷溶液中，将4-氰基-3-间苯酚-苯并咪唑并[1,2-a]吡啶-3-羧酸乙酯 与丙烯酰氯、碳酸钾按照摩尔比1:1.5:1.5投料，加热回流2小时，得到1-苯基-3-（2 -（丙基-2-炔氧基）苯基）H-咪唑并[1,5-a]吡啶。
CN201810534701.1A 2018-05-30 2018-05-30 一种咪唑并[1,5-a]吡啶类的钯离子荧光探针及其应用 Pending CN108558877A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810534701.1A CN108558877A (zh) 2018-05-30 2018-05-30 一种咪唑并[1,5-a]吡啶类的钯离子荧光探针及其应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810534701.1A CN108558877A (zh) 2018-05-30 2018-05-30 一种咪唑并[1,5-a]吡啶类的钯离子荧光探针及其应用

Publications (1)

Publication Number Publication Date
CN108558877A true CN108558877A (zh) 2018-09-21

Family

ID=63552414

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810534701.1A Pending CN108558877A (zh) 2018-05-30 2018-05-30 一种咪唑并[1,5-a]吡啶类的钯离子荧光探针及其应用

Country Status (1)

Country Link
CN (1) CN108558877A (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110257055A (zh) * 2019-07-29 2019-09-20 齐齐哈尔医学院 高选择性检测谷胱甘肽比率型荧光探针及合成方法与应用
CN112250681A (zh) * 2020-10-21 2021-01-22 浙江工业大学 一种咪唑并[1,5-a]吡啶类染料及其合成方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004018633A (ja) * 2002-06-14 2004-01-22 Kri Inc 新規な有機蛍光材料
CN106831771A (zh) * 2017-03-15 2017-06-13 贵州大学 一种可用于检测水合肼的新型荧光探针化合物及其制备方法
CN107163042A (zh) * 2017-06-07 2017-09-15 贵州大学 一种可用于检测联胺的新型荧光探针的制备工艺
CN107253961A (zh) * 2017-06-29 2017-10-17 湖南科技大学 一种可比率检测半胱氨酸的水溶性荧光传感器的制备及应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004018633A (ja) * 2002-06-14 2004-01-22 Kri Inc 新規な有機蛍光材料
CN106831771A (zh) * 2017-03-15 2017-06-13 贵州大学 一种可用于检测水合肼的新型荧光探针化合物及其制备方法
CN107163042A (zh) * 2017-06-07 2017-09-15 贵州大学 一种可用于检测联胺的新型荧光探针的制备工艺
CN107253961A (zh) * 2017-06-29 2017-10-17 湖南科技大学 一种可比率检测半胱氨酸的水溶性荧光传感器的制备及应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LEI CUIA等: "A novel ratiometric sensor for the fast detection of palladium species with large red-shift and high resolution both in aqueous solution and solid state", 《ANALYTICA CHIMICA ACTA》 *
SONG CHEN,等: "Imidazo[1,5-a]pyridine-derived fluorescent turn-on probe for cellular thiols imaging with a large Stokes shift", 《TETRAHEDRON LETTERS》 *
樊江莉 等: "改进的罗丹明类钯离子荧光分子探针", 《应用化学》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110257055A (zh) * 2019-07-29 2019-09-20 齐齐哈尔医学院 高选择性检测谷胱甘肽比率型荧光探针及合成方法与应用
CN110257055B (zh) * 2019-07-29 2022-11-15 齐齐哈尔医学院 高选择性检测谷胱甘肽比率型荧光探针及合成方法与应用
CN112250681A (zh) * 2020-10-21 2021-01-22 浙江工业大学 一种咪唑并[1,5-a]吡啶类染料及其合成方法和应用
CN112250681B (zh) * 2020-10-21 2022-01-04 浙江工业大学 一种咪唑并[1,5-a]吡啶类染料及其合成方法和应用

Similar Documents

Publication Publication Date Title
Wu et al. A specific turn-on fluorescent sensing for ultrasensitive and selective detection of phosphate in environmental samples based on antenna effect-improved FRET by surfactant
Wu et al. Sensors for determination of uranium: a review
Wang et al. Recent developments in lanthanide-based luminescent probes
Wei et al. Fluorometric determination of pesticides and organophosphates using nanoceria as a phosphatase mimic and an inner filter effect on carbon nanodots
Liu et al. Responsive lanthanide coordination polymer for hydrogen sulfide
Gupta et al. Fluorescent chemosensors for Zn2+ ions based on flavonol derivatives
Zhang et al. Fluorescence turn-on detection of alkaline phosphatase activity based on controlled release of PEI-capped Cu nanoclusters from MnO 2 nanosheets
Wang et al. Four novel lanthanide (III) metal–organic frameworks: tunable light emission and multiresponsive luminescence sensors for vitamin B6 and pesticides
He et al. A luminescent Eu3+-functionalized MOF for sensitive and rapid detection of tetracycline antibiotics in swine wastewater and pig kidney
Weng et al. A Eu (III) doped metal-organic framework conjugated with fluorescein-labeled single-stranded DNA for detection of Cu (II) and sulfide
Huang et al. Electrochemiluminescence biosensor for thrombin detection based on metal organic framework with electrochemiluminescence indicator embedded in the framework
Huo et al. State-of-the-art progress of switch fluorescence biosensors based on metal-organic frameworks and nucleic acids
CN102241970B (zh) 一种用于检测水相中锌离子的近红外荧光探针及其制备方法
Kulatilleke et al. A coumarin based fluorescent photoinduced electron transfer cation sensor
CN108558877A (zh) 一种咪唑并[1,5-a]吡啶类的钯离子荧光探针及其应用
Zheng et al. Prevailing paradigms in novel lanthanide optical probes from molecular complexes to hybrid materials
Yin et al. Bifunctional sensors based on phosphomolybdates for detection of inorganic hexavalent chromium and organic tetracycline
Yang et al. A red-emitting luminescent probe for sequentially detecting Cu2+ and cysteine/histidine in aqueous solution and its imaging application in living zebrafish
Khoshsafar et al. Enzymeless voltammetric sensor for simultaneous determination of parathion and paraoxon based on Nd-based metal-organic framework
Wang et al. Negatively charged molybdate mediated nitrogen-doped graphene quantum dots as a fluorescence turn on probe for phosphate ion in aqueous media and living cells
CN109294558A (zh) 基于均苯三甲酰氯功能化的主客体组装超分子凝胶及其制备和应用
Wang et al. A fluorescence sensor for lead (II) ions determination based on label-free gold nanoparticles (GNPs)-DNAzyme using time-gated mode in aqueous solution
Wang et al. Nanomaterials for molecular recognition: specific adsorption and regulation of nanozyme activities
Ullah et al. Heavy metal ions detection using nanomaterials-based aptasensors
Rayappa et al. Advances and effectiveness of metal–organic framework based bio/chemical sensors for rapid and ultrasensitive probing of antibiotic residues in foods

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: 20180921