CN108102647A - Imidazopyridine cyanofuran class inferior sulfate radical fluorescence probe and its application - Google Patents

Imidazopyridine cyanofuran class inferior sulfate radical fluorescence probe and its application Download PDF

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Publication number
CN108102647A
CN108102647A CN201810181083.7A CN201810181083A CN108102647A CN 108102647 A CN108102647 A CN 108102647A CN 201810181083 A CN201810181083 A CN 201810181083A CN 108102647 A CN108102647 A CN 108102647A
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China
Prior art keywords
imidazos
piperazinyl
malononitrile
cyano
butyl
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葛燕青
段桂运
吉瑞雪
董建
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Taishan Medical University
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Taishan Medical University
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Abstract

The invention discloses a kind of imidazos [1; 5 a] pyridine cyanofuran class sulfite ion ratio fluorescent probe; the probe is 2 (4 (4 (4 (3 butyl, 1 chlorine, 7 imidazos [1; 5 a] picolinoyl) piperazinyl) phenylethylene) 3 cyano 5; 5 dimethyl furans) malononitrile, chemical structural formula such as formula（1）It is shown.The fluorescence probe is in PBS buffer solutions（pH=7.40）With in alcohol mixed solvent（Volume ratio 1：1）There are preferable fluorescence selectivity and higher sensitivity and stronger anti-other ion interference abilities to sulfite ion, there is huge application prospect.

Description

Imidazopyridine cyanofuran class inferior sulfate radical fluorescence probe and its application
Technical field
The present invention relates to organic molecule fluorescence probe field more particularly to a kind of new sulfite ion fluorescence probe 2- (4- (4- (4- (chloro- 7- imidazos [1,5-a] picolinoyls of 3- butyl -1-) piperazinyl) phenylethylene) -3- cyano -5,5- Dimethyl furan) malononitrile and its application.
Background technology
Food security has been a concern, and sulphite is a kind of common food additives, if its concentration level It is exceeded, then human body can be made to generate allergic reaction and asthma.So suitable sulphite detection method is found for consumer Safety plays a crucial role.In addition, epidemiological study shows that sulphite is related to some common diseases, such as Ischemic heart disease, myocardial ischemia, spontaneous hypertension and Hypoxic hypertension etc..Therefore, to the selectivity of inferior sulfate radical and Sensitivity detection is of great significance to human health.
There are some methods for quickly detecting sulfite ion in practical applications, such as：Analysis by titration, electrochemistry side Method, chromatography, capillary electrophoresis and flow injection analysis etc..However these conventional methods are time-consuming, cumbersome, it is necessary to sample Pretreatment and detection need the instrument of costliness, these shortcomings limit their extensive use.Fluorescence probe is because selectivity is good, spirit Sensitivity is high, easy to operate, at low cost and can realize real-time monitoring and other advantages, is now widely used in the measure of ion.Although It is reported there are many inferior sulfate radical fluorescence probe, but most probes are the enhancing of single signal or attenuated type probe at present, Ratio-type probe with the response variation of two or more signals is very few.
The content of the invention
In view of the deficiencies of the prior art, the present invention solves the problems, such as to be to provide a kind of sulfurous acid of two signals response variation Radical ion ratio fluorescent probe 2- (4- (4- (4- (chloro- 7- imidazos [1,5-a] picolinoyls of 3- butyl -1-) piperazinyl) Phenylethylene) -3- cyano -5,5- dimethyl furans) malononitrile and its application.
The technical scheme is that：A kind of imidazopyridine cyanofuran class sulfite ion ratio fluorescent probe, Its chemical structural formula such as formula（1）It is shown：
Present invention additionally comprises the application of imidazopyridine cyanofuran class sulfite ion ratio fluorescent probe, formulas（1）Chemical combination Object is in PBS buffer solutions（pH=7.40）With in alcohol mixed solvent（Volume ratio 1：1）There is preferable fluorescence to sulfite ion Selectivity.
It, will present invention additionally comprises the synthetic method of imidazopyridine cyanofuran class sulfite ion ratio fluorescent probe Chloro- 3- butyl -7- imidazos [1,5-a] pyridine carboxylic acids of 1- and 2- (3- cyano -5,5- dimethyl -4- (4- (piperazinyl) styrene Base) furans) malononitrile according to the amount of substance than 1:1 feeds intake, under EDC and DMAP catalytic conditions, when reaction 5-8 is small at room temperature, Obtain 2- (4- (4- (4- (chloro- 7- imidazos [1,5-a] picolinoyls of 3- butyl -1-) piperazinyl) phenylethylene) -3- cyanogen Base -5,5- dimethyl furans) malononitrile.
The dimethyl sulfoxide solution of imidazopyridine cyanofuran class sulfite ion ratio fluorescent probe is prepared, is added respectively Enter quantitative NaCl, MgCl2·6H2O, Zn(CH3COO)2, FeCl3·6H2O, CuCl2, F-, Br-, I-, HCO3 -, NO3 -, ClO-, SO4 2-, SCN-, S2O3 2-, S2-, SO3 2-Aqueous solution, studied by fluorescence spectrum test to different zwitterions Selectivity surveys the discovery of its fluorescence emission spectrum Strength Changes：Imidazopyridine cyanofuran class inferior sulfate radical of the present invention from Sub- ratio fluorescent probe, that is, formula（1）Compound has sulfite ion preferable fluorescence selectivity, as shown in Figure 1.Gradually add After entering sulfite ion to 40 equivalents, the fluorescence intensity at 468nm of compound 1 is remarkably reinforced, meanwhile, the fluorescence at 636nm Intensity substantially weakens, as shown in Figure 2.Therefore, imidazopyridine cyanofuran class sulfite ion ratio fluorescent probe has Huge application prospect.
Description of the drawings
Fig. 1：Formula（1）Compound（5×10-6M）PBS buffer solutions（pH=7.40）With in alcohol mixed solvent（Volume ratio 1：1）The fluorescence intensity change ratio bar graphs after the different zwitterions of 40 equivalents are added in, ordinate is at 636nm in Fig. 1 The ratio between light intensity at light intensity and 468nm.
Fig. 2：Formula（1）Compound（5×10-6M）PBS buffer solutions（pH=7.40）With in alcohol mixed solvent（Volume ratio 1：1）Carry out sulfite ion fluorescence titration figure.
Fig. 3：Formula（1）Compound（5×10-6M）The PBS buffer solutions coexisted with the sulfite ion of 40 equivalents（pH= 7.40）With in alcohol mixed solvent（Volume ratio 1：1）Add in the variation of fluorescence intensity ratio after other zwitterions of 40 equivalents Block diagram.
Fig. 4 is formula（1）Compound synthesis method reaction equation figure.
Specific embodiment
Embodiment 1：Formula（1）The synthetic schemes of compound is shown below：
Specific synthesis step is as follows：
0.253g is sequentially added in 50 mL round-bottomed flasks（1.0 mmol）Imidazo [1,5-a] picolinic 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, then add in 0.371g（1.0 mmol）2- (3- cyano- 5,5- dimethyl -4- (4- (piperazinyl) styryl) furans) malononitrile, react under room temperature 5-8 it is small when.TLC detections have been reacted Cheng Hou adds in 100 mL dichloromethane, and 30 mL are washed three times, the drying of dichloromethane layer sodium sulphate, concentration, and column chromatography obtains 0.46g Dark red solid, yield 75.4%.
Nuclear magnetic resonance hydrogen spectruming determining：1H NMR (DMSO-d6, 400 MHz), δ 7.74 (d, J = 8.0 Hz, 1H), 7.60 (m, 3H), 7.53 (s, 1H), 6.93 (d, J = 8.0 Hz, 2H), 6.83 (d, J = 12.0 Hz, 1H), 6.70 (d, J = 4.0 Hz, 1H), 3.88 (s, 4H), 3.55 (s, 4H), 2.96 (t, J = 8.0 Hz, 2H), 1.81 (m, 8H), 1.45 (m, 2H), 0.97 (t, J = 8.0 Hz, 3H).
Embodiment 2：
To formula（1）Compound（5×10-6M）PBS buffer solutions（pH=7.40）With in alcohol mixed solvent（Volume ratio 1：1） Add in the Na of 40 equivalents+, Mg2+, Zn2+, Fe3+, Cu2+, F-, Br-, I-, HCO3 -, NO3 -, ClO-, SO4 2-, SCN-, S2O3 2-, S2-And SO3 2-Afterwards, survey it and change discovery in 468nm and 636nm fluorescent emission intensities ratio：Formula（1）Compound pair SO3 2-There is preferable fluorescence selectivity, fluorescence intensity is remarkably reinforced at 468nm, meanwhile, fluorescence intensity is apparent at 636nm It reduces, I468/I636 =46.0, as shown in Figure 1.
Embodiment 3：
To formula（1）Compound（5×10-6M）With the SO of 40 equivalents3 2-PBS buffer solutions（pH=7.40）With alcohol mixed solvent In（Volume ratio 1：1）It is separately added into the Na of 40 equivalents+, Mg2+, Zn2+, Fe3+, Cu2+, F-, Br-, I-, HCO3 -, NO3 -, ClO-, SO4 2-, SCN-, S2O3 2-And S2-Afterwards, survey it and change discovery in 468nm and 636nm fluorescent emission intensities ratio：Formula（1） Compound has stronger antijamming capability to other ions, as shown in Figure 3.

Claims (2)

1. a kind of imidazo [1,5-a] pyridine cyanofuran class sulfite ion ratio fluorescent probe, it is characterised in that：It is 2- (4- (4- (4- (chloro- 7- imidazos [1,5-a] picolinoyls of 3- butyl -1-) piperazinyl) phenylethylene) -3- cyano -5, 5- dimethyl furans) malononitrile, chemical structural formula such as formula（1）It is shown：
Formula（1）Compound is in PBS buffer solutions（pH=7.40）With in alcohol mixed solvent（Volume ratio 1：1）To inferior sulfate radical from Son has preferable fluorescence selectivity.
2. (4- (the 4- (4- (chloro- 7- imidazos [1,5-a] picolinoyls of 3- butyl -1-) piperazinyl) of 2- described in claim 1 Phenylethylene) -3- cyano -5,5- dimethyl furan) malononitrile synthetic method, it is characterised in that：In dichloromethane solution In, by chloro- 3- butyl -7- imidazos [1, the 5-a] pyridine carboxylic acids of 1- and 2- (3- cyano -5,5- dimethyl -4- (4- (piperazinyl) Styryl) furans) malononitrile according to the amount of substance than 1:1 feeds intake, and under EDC and DMAP catalytic conditions, reacts 5-8 at room temperature Hour, obtain 2- (4- (4- (4- (chloro- 7- imidazos [1, the 5-a] picolinoyls of 3- butyl -1-) piperazinyl) phenylethylene) - 3- cyano -5,5- dimethyl furans) malononitrile.
CN201810181083.7A 2018-03-06 2018-03-06 Imidazopyridine cyanofuran class inferior sulfate radical fluorescence probe and its application Pending CN108102647A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3741390A1 (en) * 1987-12-07 1989-06-15 Wurz Dieter Sampling system for determining the SO3 and NH3 content of flue gases
CN102659677A (en) * 2012-04-28 2012-09-12 中南大学 Fluorescent molecular probe for detecting sulfite ions through naked eyes and fluorescence ratio as well as synthesis and application thereof
CN104946248A (en) * 2015-07-09 2015-09-30 山东大学 Water-soluble sulphurous acid hydrogen root ratiometric fluorescent probe and application thereof
CN105112049A (en) * 2015-09-23 2015-12-02 山东理工大学 Sulfite ratiometric fluorescence probe and preparation method thereof
CN106496197A (en) * 2016-10-27 2017-03-15 湖南师范大学 A kind of Fluorescence Increasing type quick detection sulfurous acid hydrogen radical ion or the synthesis and application of sulfite ion fluorescent molecular probe
CN106543166A (en) * 2016-11-07 2017-03-29 湖南师范大学 A kind of colorimetric and Ratio-type detection SO2And its synthesis and application of derivatives fluorescent probe
CN107417654A (en) * 2017-06-05 2017-12-01 河南农业大学 A kind of inferior sulfate radical fluorescence probe based on chromene nitrile and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3741390A1 (en) * 1987-12-07 1989-06-15 Wurz Dieter Sampling system for determining the SO3 and NH3 content of flue gases
CN102659677A (en) * 2012-04-28 2012-09-12 中南大学 Fluorescent molecular probe for detecting sulfite ions through naked eyes and fluorescence ratio as well as synthesis and application thereof
CN104946248A (en) * 2015-07-09 2015-09-30 山东大学 Water-soluble sulphurous acid hydrogen root ratiometric fluorescent probe and application thereof
CN105112049A (en) * 2015-09-23 2015-12-02 山东理工大学 Sulfite ratiometric fluorescence probe and preparation method thereof
CN106496197A (en) * 2016-10-27 2017-03-15 湖南师范大学 A kind of Fluorescence Increasing type quick detection sulfurous acid hydrogen radical ion or the synthesis and application of sulfite ion fluorescent molecular probe
CN106543166A (en) * 2016-11-07 2017-03-29 湖南师范大学 A kind of colorimetric and Ratio-type detection SO2And its synthesis and application of derivatives fluorescent probe
CN107417654A (en) * 2017-06-05 2017-12-01 河南农业大学 A kind of inferior sulfate radical fluorescence probe based on chromene nitrile and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LI D P. ET AL: ""A far-red ratiometric fluorescent probe for SO2 derivatives based on the ESIPT enhanced FRET platform with improved performance"", 《DYES AND PIGMENTS》 *
LIU C Y. ET AL: ""A highly selective colorimetric and far-red fluorescent probe for imaging bisulfite in living cells"", 《RSC ADV》 *
张伟杰等: ""比率型亚硫酸氢根荧光探针的构建及其生物成像"", 《中国科学：化学》 *

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