CN108484644B - The rhodamine hydrazides Cu that pyrazolo [1,5-a] pyridine replaces2+Ratiometric fluorescent probe and its application - Google Patents

The rhodamine hydrazides Cu that pyrazolo [1,5-a] pyridine replaces2+Ratiometric fluorescent probe and its application Download PDF

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CN108484644B
CN108484644B CN201810501050.6A CN201810501050A CN108484644B CN 108484644 B CN108484644 B CN 108484644B CN 201810501050 A CN201810501050 A CN 201810501050A CN 108484644 B CN108484644 B CN 108484644B
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pyridine
phenylpyrazole
rhodamine
formula
fluorescence
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CN108484644A (en
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葛燕青
吉瑞雪
徐志扬
刘爱坤
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Taishan Medical University
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Abstract

The invention discloses a kind of 2- Phenylpyrazole simultaneously [1,5-a] pyridine rhodamine hydrazide derivatives Cu2+Ratiometric fluorescent probe, the fluorescence probe are that simultaneously [1,5-a] pyridine rhodamine hydrazides, chemical structural formula are as the formula (1) for 2- Phenylpyrazole.Fluorescence probe of the invention is in HEPES/CH3To Cu in CN (8/2, v/v, pH=7.30)2+There are preferable fluorescence selectivity and higher sensitivity, compared with existing probe, has the reaction time short, not by remarkable advantages such as background interferences, be with a wide range of applications.

Description

The rhodamine hydrazides Cu that pyrazolo [1,5-a] pyridine replaces2+Ratiometric fluorescent probe And its application
Technical field
The present invention relates to small organic molecule fluorescence probe field more particularly to a kind of novel C u2+Ratiometric fluorescent probe 2- The synthesis and its application of the Phenylpyrazole rhodamine hydrazides that simultaneously [1,5-a] pyridine replaces.
Background technique
Copper is microelement necessary to a kind of living organism, with the close phase of human health as a Heavy Metallic Elements It closes.But when internal copper content is excessively high, the organs such as liver can be caused to bear, metabolism gets muddled, and causes liver ascites, liver The diseases such as hardening.Currently, the excessive of copper product uses and inappropriate processing in the fields such as machine-building, building industry, medical treatment Cause it to become one of heavy metal contaminants, controls and monitors Cu in water body2+Content have become hot spot concerned by people and ask Topic.
For fluorescence probe because selectivity is good, high sensitivity is easy to operate, at low cost and real-time monitoring to may be implemented etc. excellent Point is now widely used in intracellular Cu2+Measurement.Although there are many Cu2+Fluorescence probe is reported, but most of at present Fluorescence probe almost all be single signal enhancing or attenuated type fluorescence probe, have two or more signal corresponding changes Ratiometric fluorescent probe it is less.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of Cu2+Ratiometric fluorescent probe 2- phenyl pyrazoline The synthesis and its application of azoles simultaneously [1,5-a] pyridine rhodamine hydrazide derivatives.
The technical scheme is that a kind of Cu of 2- Phenylpyrazole simultaneously [1,5-a] pyridine rhodamine hydrazide derivatives2+Than Rate type fluorescence probe, chemical structural formula are as the formula (1):
(1)
The invention also includes 2- Phenylpyrazole simultaneously [1,5-a] pyridine rhodamine hydrazide derivatives class Cu2+Ratio-type fluorescence is visited The application of needle, formula (1) compound is in HEPES/CH3To Cu in CN (8/2, v/v, pH=7.30) buffer solution2+Have preferable glimmering Light selectivity.
The invention also includes 2- Phenylpyrazole simultaneously [1,5-a] pyridine rhodamine hydrazide derivatives class Cu2+Ratio fluorescent probe Synthetic method, in dichloromethane solution, by 2- Phenylpyrazole simultaneously [1,5-a] pyridine -5- carboxylic acid and rhodamine hydrazides, EDC, DMAP feeds intake according to molar ratio 1:1:1.2:1.2, reacts 12 hours under room temperature, and obtaining 2- Phenylpyrazole, simultaneously [1,5-a] pyridine takes The rhodamine hydrazides in generation.
The acetonitrile solution for preparing 2- Phenylpyrazole simultaneously [1,5-a] pyridine rhodamine hydrazide derivatives, is separately added into quantitative MgCl2, CaCl2, AlCl3, SnCl2·2H2O, PbSO4, CrCl3·6H2O, MnCl2·4H2O, FeCl3·6H2O, FeCl2·4H2O, CuCl2 .2H2O, NaCl, CoCl2·6H2O, NiCl2·6H2O, PdCl2, ZnCl2, HgCl2· 2H2O, CdCl2·2½H2O, AgNO3Aqueous solution, the selection to different metal ions is studied by fluorescence spectrum test Property, survey its fluorescence emission spectrum Strength Changes discovery: the 2- Phenylpyrazole of the present invention rhodamine that simultaneously [1,5-a] pyridine replaces Hydrazides, that is, formula (1) compound is to Cu2+There is preferable fluorescence selectivity, as shown in Figure 1.It is gradually added into Cu2+To 1 equivalent, chemical combination The fluorescence intensity at 445nm of object 1 is substantially reduced, meanwhile, fluorescence intensity is remarkably reinforced at 570nm, as shown in Figure 2.Therefore, 2- Phenylpyrazole simultaneously [1,5-a] pyridine rhodamine hydrazide derivatives as Cu2+Ratio fluorescent probe has huge application.
Detailed description of the invention
Fig. 1: formula (1) compound (10-6M HEPES/CH)31 is added in CN (8/2, v/v, pH=7.30) buffer solution Fluorescence intensity change ratio bar graphs after the different metal ions of equivalent, in Fig. 1 ordinate be the place 570nm light intensity and The ratio between light intensity at 445nm.
Fig. 2: formula (1) compound (10-6M HEPES/CH)3It is carried out in CN (8/2, v/v, pH=7.30) buffer solution Cu2+Fluorescence titration figure.FL Intensity is light intensity in figure, and Wavelength is wavelength, and equiv is multiple.
Fig. 3: formula (1) compound (10-6) and the HEPES/CH that coexists of other metal ions of 1 equivalent M3CN(8/2, v/v, PH=7.30) 1 equivalent Cu is added in buffer solution2+Rear fluorescence intensity ratio variation histogram.
Fig. 4 is formula (1) compound synthesis method reaction equation figure.
Specific embodiment
Embodiment 1: the synthetic schemes of formula (1) compound is shown below:
Specific synthesis step is as follows:
0.16g(0.30 mmol is sequentially added in 50 mL round-bottomed flasks) rhodamine hydrazides, 0.08g(0.30 mmol) 2- Phenylpyrazole simultaneously [1,5-a] pyridine -5- formic acid, 0.07g (0.36 mmol) EDC, 0.04g (0.36 mmol) DMAP, 20 mL methylene chloride react 12 hours under room temperature.TLC is detected after the reaction was completed, and 100 mL methylene chloride, 30 mL water are added It washes three times, dichloromethane layer sodium sulphate is dry, and concentration, column chromatographs to obtain 0.13g white solid, yield 65%.
Embodiment 2:
To formula (1) compound (10-6M HEPES/CH)3It is separately added into CN (8/2, v/v, pH=7.30) buffer solution The Mg of 1 equivalent2+, Ca2+, Al3+, Pb2+, Cr3+, Mn2+, Fe3+, Na+, Fe2+, Co2+, Ni2+, Zn2+, Sn2+, Cd2+, Pd2+, Hg2+And Ag+Afterwards, it surveys it and changes discovery: formula (1) chemical combination in 445nm and 570nm fluorescent emission intensity ratio Object is to Cu2+There is preferable fluorescence selectivity, the Cu of 1 equivalent is added2+Afterwards, probe fluorescence intensity at 445nm is substantially reduced, together When, fluorescence intensity is remarkably reinforced at 570nm, I570/I445 =0.6, as shown in Figure 1 and Figure 2.
Embodiment 3:
Respectively at formula (1) compound (10-6) and the Mg of 1 equivalent M2+, Ca2+, Al3+, Pb2+, Cr3+, Mn2+, Fe3+, Na+, Fe2+, Co2+, Ni2+, Zn2+, Sn2+, Cd2+, Pd2+, Hg2+And Ag+In different metal ions solution, it is added 1 and works as The Hg of amount2+Afterwards, survey it and change discovery in 445nm and 570nm fluorescent emission intensity ratio: formula (1) compound is to other ions There is stronger anti-interference ability, as shown in Figure 3.

Claims (2)

1. a kind of 2- Phenylpyrazole simultaneously [1,5-a] pyridine rhodamine hydrazide derivatives class Cu2+Ratiometric fluorescent probe, feature exist In: it is the 2- Phenylpyrazole rhodamine hydrazides that simultaneously [1,5-a] pyridine replaces, and chemical structural formula is as the formula (1):
Formula (1) compound is in HEPES/CH3To Cu in CN buffer solution2+There is preferable fluorescence selectivity.
2. 2- Phenylpyrazole described in claim 1 simultaneously [1,5-a] pyridine rhodamine hydrazide derivatives class Cu2+Ratio-type fluorescence is visited The synthetic method of needle, it is characterised in that: in dichloromethane solution, by 2- Phenylpyrazole simultaneously [1,5-a] pyridine -5- formic acidWith rhodamine hydrazides, EDC, DMAP be according to molar ratio 1: 1:1.2:1.2 feeds intake, and reacts 12 hours under room temperature, obtains the 2- Phenylpyrazole rhodamine hydrazides that simultaneously [1,5-a] pyridine replaces.
CN201810501050.6A 2018-05-23 2018-05-23 The rhodamine hydrazides Cu that pyrazolo [1,5-a] pyridine replaces2+Ratiometric fluorescent probe and its application Expired - Fee Related CN108484644B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105754587A (en) * 2016-03-30 2016-07-13 泰山医学院 Imidazo pyridine rhodamine hydrazide type cupric ion ratio fluorescence probe and application thereof
CN105924457A (en) * 2016-05-24 2016-09-07 泰山医学院 Pyridino-benzo imidazole cupric ion rate fluorescence probe and application thereof
CN106083897A (en) * 2016-05-24 2016-11-09 泰山医学院 Imidazopyridine rhodamine salicylide Cu-like ion ratio fluorescent probe and application thereof
CN106632406A (en) * 2016-06-03 2017-05-10 泰山医学院 Indolizine-rhodamine hydrazide type cupric ion ratiometric fluorescent probe and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105754587A (en) * 2016-03-30 2016-07-13 泰山医学院 Imidazo pyridine rhodamine hydrazide type cupric ion ratio fluorescence probe and application thereof
CN105924457A (en) * 2016-05-24 2016-09-07 泰山医学院 Pyridino-benzo imidazole cupric ion rate fluorescence probe and application thereof
CN106083897A (en) * 2016-05-24 2016-11-09 泰山医学院 Imidazopyridine rhodamine salicylide Cu-like ion ratio fluorescent probe and application thereof
CN106632406A (en) * 2016-06-03 2017-05-10 泰山医学院 Indolizine-rhodamine hydrazide type cupric ion ratiometric fluorescent probe and application thereof

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