CN106083897B - Imidazopyridine rhodamine salicylide Cu-like ion ratio fluorescent probe and its application - Google Patents

Imidazopyridine rhodamine salicylide Cu-like ion ratio fluorescent probe and its application Download PDF

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CN106083897B
CN106083897B CN201610347019.2A CN201610347019A CN106083897B CN 106083897 B CN106083897 B CN 106083897B CN 201610347019 A CN201610347019 A CN 201610347019A CN 106083897 B CN106083897 B CN 106083897B
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rhodamine
salicylide
pyridine
imidazo
formula
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CN106083897A (en
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曹晓群
葛燕青
段桂运
董建
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Taishan Medical University
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
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    • 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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    • C09K2211/1025—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 imidazo [1,5-a] pyridine-rhodamine salicylide Cu-like ion ratio fluorescent probe and its application, the probe is the rhodamine salicylide that imidazo [1,5-a] pyridine replaces, and chemical structural formula is as the formula (1).Fluorescence probe of the invention is in ethanol solution to Cu2+Have unique fluorescence selectivity, higher sensitivity and it is stronger resist other ion interference abilities, have huge application prospect.

Description

Imidazopyridine rhodamine salicylide Cu-like ion ratio fluorescent probe and its application
Technical field
The present invention relates to small organic molecule fluorescence probe field more particularly to a kind of Cu2+Ratio fluorescent probe imidazo [1, 5-a] pyridine replace rhodamine salicylide and its application.
Background technique
Rhodamine fluorescent dyes are because of its transmitting and absorb in visible light region, and molar extinction coefficient is big, photostability Height, fluorescence quantum yield is high, convieniently synthesized etc., and the fluorescence for being widely used in carrying out detection metal ion after structural modification is visited The research of needle or chemical sensor.
Cu2+It is the interior third transition metal element abundant after iron, zinc of human body.It plays in many physiology courses Very important role, copper content reduction are likely to result in anemic disorders.Cu2+It can participate in internal enzyme reaction, enzyme transcription and one A little oxidation-reduction processes, at the same be also in people pressure and it is panic under physiological reaction it is closely related.If internal Cu2+Metabolism not Normally, then various diseases be may cause, such as Menkes syndrome, familial amyotrophic disease, Wilson syndrome, alzheimer ' Mos disease etc..As Cu in human body2+Too high levels, and huge toxic action can be generated to organism.Therefore, to Copper in Body from The qualitative and quantitative detection of son becomes the field that chemists are paid special attention in recent years.However, copper ion probe is several at present All single signal enhancings or attenuated type probe, the Ratiometric fluorescent probe with the response variation of two or more signals It is very few.
Summary of the invention
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 salicylide and its application that rate fluorescence probe imidazo [1,5-a] pyridine replaces.
The technical scheme is that the rhodamine bigcatkin willow aldehydes Cu that a kind of imidazo [1,5-a] pyridine replaces2+Ratio is glimmering Light probe, chemical structural formula are as the formula (1):
The invention also includes the rhodamine bigcatkin willow aldehydes Cu that imidazo [1,5-a] pyridine replaces2+Ratio fluorescent probe is answered With formula (1) compound is in ethanol solution to Cu2+There is unique fluorescence selectivity.
The invention also includes the rhodamine bigcatkin willow aldehydes Cu that imidazo [1,5-a] pyridine replaces2+The conjunction of ratio fluorescent probe At method, in ethanol solution, by imidazo [1,5-a] pyridine-rhodamine hydrazides and salicylide according to 1:1 ingredient proportion, 80 degree back flow reaction 3-7 hours lower, obtains the rhodamine salicylide of imidazo [1,5-a] pyridine substitution.
The ethanol solution for preparing the rhodamine salicylide that imidazo [1,5-a] pyridine replaces, 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, AgNO3's Ethanol solution studies the selectivity to different metal ions by fluorescence spectrum test, surveys the change of its fluorescence emission spectrum intensity Change discovery: rhodamine salicylide, that is, formula (1) compound that imidazo [1,5-a] pyridine of the present invention replaces is to Cu2+There is uniqueness Fluorescence selectivity, as shown in Figure 1.It is gradually added into Cu2+To 1 equivalent, the fluorescence intensity at 465nm of compound 1 is substantially reduced, Meanwhile fluorescence intensity is remarkably reinforced at 585nm, as shown in Figure 2.Therefore, the rhodamine water that imidazo [1,5-a] pyridine replaces Poplar aldehyde is as Cu2+Ratio fluorescent probe has huge application.
The present invention provides the rhodamine bigcatkin willow aldehydes Cu that a kind of imidazo [1,5-a] pyridine replaces2+Ratio fluorescent probe, Experiments have shown that formula (1) compound of the present invention can be with Cu2+With stoichiometric ratio 1:1 reaction in ethanol solution, reacting Cheng Zhong, since rhodamine salicylide and copper ion act on, carbon-to-nitrogen double bon is broken, then hydrolysis, to make donor imidazo Energy transmission occurs for [1,5-a] pyridine and receptor rhodamine, causes the fluorescence intensity at 465nm of compound 1 to be substantially reduced, together When, fluorescence intensity is remarkably reinforced at 585nm.Thus susceptible of proof formula of the present invention (1) compound is in ethanol solution to Cu2+ Have unique fluorescence selectivity, higher sensitivity and it is stronger resist other ion interference abilities, have huge application prospect.
Detailed description of the invention
Fig. 1: formula (1) compound (10-5M the fluorescence intensity after the different metal ions of equivalent are added in ethanol solution) Change ratio bar graphs, ordinate is the ratio between the light intensity at 585nm and light intensity at 465nm in Fig. 1.
Fig. 2: formula (1) compound (10-5M Cu is carried out in ethanol solution)2+Fluorescence titration figure.Intensity is light in figure By force, Wavelength is wavelength, and eq is multiple.
Fig. 3: formula (1) compound (10-5) and the Cu of equivalent M2+Other gold of equivalent are added in the ethanol solution coexisted The variation histogram of fluorescence intensity ratio after category ion.
Specific embodiment
Embodiment 1: the synthetic schemes of formula (1) compound is shown below:
Specific synthesis step is as follows:
0.704g(1.0 mmol is sequentially added in 50 mL round-bottomed flasks) imidazo [1,5-a] pyridine rhodamine hydrazides, 0.122g(1.0 mmol) salicylide, 20 mL dehydrated alcohols, 80 degree are back flow reaction 3-6 hours lower.TLC is detected after the reaction was completed, It is concentrated under reduced pressure, column chromatographs to obtain 0.707g pale solid, yield 89.0%.
Nuclear magnetic resonance hydrogen spectruming determining:1H NMR(400 MHz, CDCl3): δ 11.03 (s, 1H), 8.43 (s, 1H), 7.95 (m, 1H), 7.72 (dd, J = 4.0 Hz, 8.0 Hz, 1H), 7.55-7.41 (m, 5H), 7.10-7.01 (m, 3H), 6.70-6.67 (m, 2H), 6.56 (m, 2H), 6.46 (d, J = 12.0 Hz, 1H), 6.42 (d, J = 4.0 Hz, 1H), 6.31 (dd, J = 2.8 Hz, 8.0 Hz, 1H), 3.82 (s, 4H), 3.34 (q, J = 8.0 Hz, 4H), 3.28 (s, 4H), 2.96 (d, J = 4.0 Hz, 4H), 1.82 (m, 2H), 1.62 (s, 2H), 1.44 (m, 2H), 1.17 (t, J = 8.0 Hz, 6H), 0.97 (t, J = 8.0 Hz, 3H)。
Embodiment 2:
To formula (1) compound (10-5M the Mg of 2 equivalents is separately added into ethanol solution)2+, Ca2+, Al3+,Sn2+, Pb2+, Cr3+, Mn2+, Fe3+, Co2+,Ni2+,Zn2+,Cd2+,Pd2+,Hg2+And Ag+Afterwards, it is strong in 465nm and 585nm fluorescent emission to survey it Spend ratio variation discovery: formula (1) compound is to Cu2+There is unique fluorescence selectivity, the Cu of 1 equivalent is added2+Afterwards, compound 1 exists Fluorescence intensity is substantially reduced at 465nm, meanwhile, fluorescence intensity is remarkably reinforced at 585nm, I585/I465 =3.35, such as Fig. 2 institute Show.
Embodiment 3:
In formula (1) compound (10-5) and the Cu of 1 equivalent M2+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 465nm and The variation discovery of 585nm fluorescent emission intensity ratio: formula (1) compound has stronger anti-interference ability to other ions, such as Fig. 3 institute Show.

Claims (2)

1. a kind of imidazo [1,5-a] pyridine-rhodamine bigcatkin willow aldehydes Cu2+Ratio fluorescent probe, it is characterised in that: it is imidazoles And the rhodamine salicylide that [1,5-a] pyridine replaces, chemical structural formula are as the formula (1):
Formula (1) compound is in ethanol solution to Cu2+There is unique fluorescence selectivity.
Imidazo described in claim 1 2. [1,5-a] pyridine-rhodamine bigcatkin willow aldehydes Cu2+The synthetic method of ratio fluorescent probe, It is characterized by: in ethanol solution, it willWith salicylide according to 1:1 ingredient proportion obtains the rhodamine salicylide of imidazo [1,5-a] pyridine substitution back flow reaction 3-7 hours under 80 degree.
CN201610347019.2A 2016-05-24 2016-05-24 Imidazopyridine rhodamine salicylide Cu-like ion ratio fluorescent probe and its application Expired - Fee Related CN106083897B (en)

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CN108219773A (en) * 2016-12-23 2018-06-29 泰山医学院 Pyridine [1,2-a] and benzimidizole derivatives class Hg2+Ratio fluorescent probe and its application
CN108219772A (en) * 2016-12-23 2018-06-29 泰山医学院 Imidazoles [1,5-a] and pyridine derived species Hg2+Ratio fluorescent probe and its application
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
CN109781678B (en) * 2017-11-14 2022-03-18 山东第一医科大学(山东省医学科学院) Preparation and application of ratiometric fluorescent probe applied to intramitochondrial hypochlorous acid detection
CN108299427A (en) * 2018-03-22 2018-07-20 泰山医学院 Imidazopyridine Ben Bing oxadiazole class cysteine ratio fluorescent probes and its application
CN110498794B (en) * 2018-05-18 2022-02-01 山东第一医科大学(山东省医学科学院) Imidazo [1,2-a ] pyridine derivative Pd2+ fluorescent probe and application thereof
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

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