CN106632406B - Indolizine rhodamine hydrazides Cu-like ion ratio fluorescent probe and its application - Google Patents

Indolizine rhodamine hydrazides Cu-like ion ratio fluorescent probe and its application Download PDF

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CN106632406B
CN106632406B CN201610385574.4A CN201610385574A CN106632406B CN 106632406 B CN106632406 B CN 106632406B CN 201610385574 A CN201610385574 A CN 201610385574A CN 106632406 B CN106632406 B CN 106632406B
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indolizine
rhodamine
formula
hydrazides
ratio fluorescent
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CN106632406A (en
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张萍
葛燕青
曹晓群
段桂运
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Taishan Medical University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • 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
    • G01N21/6428—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
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    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

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Abstract

The invention discloses a kind of indolizine rhodamine hydrazide derivatives class Cu2+Ratio fluorescent probe, the probe are the rhodamine hydrazides of indolizine substitution, chemical structural formula such as formula（1）It is shown.The fluorescence probe of the present invention is in ethanol solution to Cu2+There are unique fluorescence selectivity, higher sensitivity and stronger anti-other ion interference abilities, there is huge application prospect.

Description

Indolizine rhodamine hydrazides Cu-like ion ratio fluorescent probe and its application
Technical field
The present invention relates to organic molecule fluorescence probe field more particularly to a kind of Cu2+Ratio fluorescent probe indolizine takes The rhodamine hydrazides in generation and its application.
Background technology
Rhodamine fluorescent dyes are because of its absorption and emit in visible light region, and fluorescence quantum yield is high, Molar Extinction system Number is big, and photostability is high, convieniently synthesized etc., be widely used in being detected after structural modification the fluorescence probe of metal ion or The research of chemical sensor.
Cu2+It is the interior abundant transition metal element of third after iron, zinc of human body.It plays in many physiology courses Very important role, suitable copper can promote the absorption of ferro element, therefore copper content reduction is likely to result in anemicus disease Disease.Cu2+Internal enzyme reaction, enzyme transcription and some oxidation-reduction processes can be participated in, while being also in people under pressure and fear Physiological reaction is closely related.If internal Cu2+Metabolism it is abnormal, then may lead to various diseases, such as Menkes syndromes, family Race's property muscular atrophy, Wilson syndromes, Alzheimer's disease etc..As Cu in human body2+Too high levels, and organism can be produced Raw huge toxic action.Therefore, non-as chemists in recent years to the qualitative and quantitative detection of Copper in Body ion The field often paid close attention to.However, copper ion probe almost all is single signal enhancing or attenuated type probe at present, there are two tools Or the Ratiometric fluorescent probe of multiple signal response variations is very few.
Invention content
In view of the deficiencies of the prior art, problems solved by the invention is to provide a kind of Cu of two signals response variation2+Than The rhodamine hydrazides of rate fluorescence probe indolizine substitution and its application.
The technical scheme is that：A kind of rhodamine hydrazides Cu of indolizine substitution2+Ratio fluorescent probe, chemistry Structural formula such as formula（1）It is shown：
The invention also includes the rhodamine hydrazides Cu of indolizine substitution2+The application of ratio fluorescent probe, formula（1）Compound To Cu in ethanol solution2+There is unique fluorescence selectivity.
The invention also includes the rhodamine hydrazides Cu of indolizine substitution2+The synthetic method of ratio fluorescent probe, in dichloro In dichloromethane, by indolizine and rhodamine hydrazides according to 1:1 ingredient proportion, it is anti-under room temperature under EDC and DMAP catalytic conditions It answers 2-5 hours, obtains the rhodamine hydrazides of indolizine substitution.
The ethanol solution for preparing the rhodamine hydrazides of indolizine substitution, is separately added into quantitative MgCl2, CaCl2, AlCl3, SnCl2·2H2O,PbSO4, CrCl3·6H2O, MnCl2·4H2O, FeCl3·6H2O, CoCl2·6H2O, NiCl2· 6H2O, PdCl2, HgCl2, ZnCl2, CuCl2·2H2O, CdCl2·2½H2O, AgNO3Ethanol solution, pass through fluorescence light Spectrum tests to study the selectivity to different metal ions, surveys the discovery of its fluorescence emission spectrum Strength Changes：In of the present invention Rhodamine hydrazides, that is, formula of benzazole substitution（1）Compound is to Cu2+There is unique fluorescence selectivity, as shown in Figure 1.It is gradually added into Cu2+To 1 equivalent, the fluorescence intensity at 445nm of compound 1 is substantially reduced, meanwhile, fluorescence intensity is remarkably reinforced at 578nm, As shown in Figure 2.Therefore, the rhodamine hydrazides of indolizine substitution is as Cu2+Ratio fluorescent probe has huge application.
The present invention provides a kind of rhodamine hydrazides Cu of indolizine substitution2+Ratio fluorescent probe, experiments have shown that this hair The bright formula（1）Compound can be with Cu2+With stoichiometric ratio 1 in ethanol solution:1 reaction, during the reaction, due to Luo Dan Bright to be acted on copper ion, hydrolysis leads to compound 1 to make donor indolizine that energy transmission occur with receptor rhodamine Fluorescence intensity is substantially reduced at 445nm, meanwhile, fluorescence intensity is remarkably reinforced at 578nm.Thus susceptible of proof is of the present invention Formula（1）Compound is in ethanol solution to Cu2+There are unique fluorescence selectivity, higher sensitivity and stronger anti-other ions Interference performance has huge application prospect.
Description of the drawings
Fig. 1：Formula（1）Compound（10-5M）Ethanol solution in be added equivalent different metal ions after fluorescence intensity Change ratio bar graphs, ordinate is the light intensity at 578nm and the ratio between the light intensity at 445nm in Fig. 1.
Fig. 2：Formula（1）Compound（10-5M）Ethanol solution in carry out Cu2+Fluorescence titration figure.Intensity is light in figure By force, Wavelength is wavelength, and eq is multiple.
Fig. 3：Formula（1）Compound（10-5M）With the Cu of equivalent2+Other gold of equivalent are added in the ethanol solution coexisted The variation block diagram of fluorescence intensity ratio after category ion.
Fig. 4 is formula（1）Compound synthesis method reaction equation figure.
Specific implementation mode
Embodiment 1：Formula（1）The synthetic schemes of compound is shown below：
Specific synthesis step is as follows：
0.203g is sequentially added in 50 mL round-bottomed flasks（1.0 mmol）Indolizine carboxylic acid, 0.290g（1.5 mmol） 1-（3- dimethylamino-propyls）- 3- ethyl carbodiimides（EDC）, 0.180g（1.5 mmol）4-dimethylaminopyridine (DMAP), 20 mL anhydrous methylene chlorides react 30 minutes under room temperature, 0.470g are then added（1.0 mmol）Rhodamine hydrazides, under room temperature Reaction 2-5 hours.After the completion of TLC detection reactions, 100 mL dichloromethane are added, 30 mL are washed three times, dichloromethane layer sulfuric acid Sodium is dried, and concentration, column chromatography obtains 0.43g pale solids, yield 65%.
Nuclear magnetic resonance hydrogen spectruming determining：1H NMR（400 MHz, CDCl3）：δ7.93 (m, 2H), 7.85 (s, 1H), 7.53 (s, 1H), 7.47 (m, 2H), 7.08 (t, J = 4.0 Hz,1H), 6.95 (s, 1H), 6.69 (m, 2H), 6.56 (s, 2H), 6.46 (m, 2H), 6.31 (m, 1H), 3.81 (s, 4H), 3.35 (q, J = 8.0 Hz, 4H), 3.27 (s, 4H), 2.57 (s, 3H), 1.17 (t, J = 8.0 Hz, 6H)。
Embodiment 2：
To formula（1）Compound（10-5M）Ethanol solution in be separately added into the Cr of 2 equivalents3+, Mn2+, Fe3+, Co2+,Ni2+, Cu2+,Zn2+,Cd2+,Hg2+And Ag+Afterwards, it surveys it and changes discovery in 445nm and 578nm fluorescent emission intensity ratios：Formula（1）Change Object is closed to Cu2+There is unique fluorescence selectivity, the Cu of 1 equivalent is added2+Afterwards, the fluorescence intensity at 445nm of compound 1 obviously drops It is low, meanwhile, fluorescence intensity is remarkably reinforced at 578nm, I578/I445 =5.3, as shown in Figure 2.
Embodiment 3：
In formula（1）Compound（10-5M）With the Cu of 1 equivalent2+Ethanol solution in be separately added into the Mg of 2 equivalents2+, Ca2+, Al3+,Sn2+, Pb2+,Cr3+, Mn2+, Fe3+, Co2+,Ni2+,Zn2+,Cd2+,Pd2+,Hg2+And Ag+Afterwards, survey its in 445nm and The variation of 578nm fluorescent emission intensity ratios is found：Formula（1）Compound has stronger anti-interference ability to other ions, such as Fig. 3 institutes Show.

Claims (2)

1. a kind of indolizine-rhodamine hydrazide derivatives class Cu2+ ratio fluorescent probes, it is characterised in that：It is indolizine substitution Rhodamine hydrazides, chemical structural formula such as formula（1）It is shown：
Formula（1）Compound has unique fluorescence selectivity in ethanol solution to Cu2+.
2. the synthesis side of indolizine described in claim 1-rhodamine hydrazide derivatives class Cu2+ ratio fluorescent probes Method, it is characterised in that：In dichloromethane solution, by indolizineWith rhodamine hydrazidesAccording to molar ratio 1:1 ingredient proportion reacts under EDC and DMAP catalytic conditions under room temperature 2-5 hours, obtain the rhodamine hydrazides of indolizine substitution.
CN201610385574.4A 2016-06-03 2016-06-03 Indolizine rhodamine hydrazides Cu-like ion ratio fluorescent probe and its application Expired - Fee Related CN106632406B (en)

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CN107501285B (en) * 2017-09-08 2019-09-17 中国地质大学（武汉） A kind of the water-soluble rhodamine base ionic liquid probe and preparation method, application of bimetallic ion selectivity Division identification
CN108226106B (en) * 2017-11-07 2020-10-16 山东第一医科大学(山东省医学科学院) Ratiometric sulfite ion fluorescent probe based on indolizine-cyano furan hemicyanine
CN109749734A (en) * 2017-11-07 2019-05-14 泰山医学院 A kind of Ratiometric fluorescent probe can detecte sulfite ion and application
CN108586497A (en) * 2018-05-23 2018-09-28 泰山医学院 A kind of pyrazolo [1,5-a] pyridines mercury ion Ratiometric fluorescent probe and its application
CN108484644B (en) * 2018-05-23 2019-06-21 泰山医学院 The rhodamine hydrazides Cu that pyrazolo [1,5-a] pyridine replaces2+Ratiometric fluorescent probe and its application
CN109900664B (en) * 2019-02-19 2021-05-04 济南大学 Method for detecting copper ions by using non-traditional fluorescent micromolecular malonhydrazide
CN109824688B (en) * 2019-03-06 2020-07-31 华东理工大学 Internal standard ratio type fluorescent probe based on fluorescein derivative, preparation method and application thereof

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