CN109722238A - Pyrido [1,2-a] the benzimidazole SO of pyridine modification32-Ratio fluorescent probe and its application - Google Patents
Pyrido [1,2-a] the benzimidazole SO of pyridine modification32-Ratio fluorescent probe and its application Download PDFInfo
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- CN109722238A CN109722238A CN201711022064.1A CN201711022064A CN109722238A CN 109722238 A CN109722238 A CN 109722238A CN 201711022064 A CN201711022064 A CN 201711022064A CN 109722238 A CN109722238 A CN 109722238A
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Abstract
The invention discloses a kind of pyridos [1 of pyridine modification, 2-a] benzimidazole inferior sulfate radical ratio fluorescent probe, the probe is 1-(2- pyridine) -3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone, chemical structural formula is as the formula (1).Fluorescence probe of the invention is in n,N-Dimethylformamide/water (volume ratio 1:4) solution to SO3 2‑There are specific recognition and higher sensitivity, sensitive can rapidly go out respectively sulfite ion from a variety of anion, have broad application prospects.
Description
Technical field
The present invention relates to the pyridos [1,2-a] that small organic molecule fluorescence probe field more particularly to a kind of pyridine are modified
Benzimidazole SO3 2-Ratio fluorescent probe and its application.
Background technique
Sulphite have suppresses growth of microorganism, prevent mildew ability, frequently as preservative be widely used in food and
In beverage.The sulphite of high concentration may cause the diseases such as diarrhea, low blood pressure, allergy and asthma.Modern industrial production mistake
The a large amount of sulphite discharged in journey causes serious environmental pollution problem.Endogenous sulphite horizontal abnormality usually with
The nervous system disease is related with lung cancer.So invention has the method for height sensitivity, convenient and efficient detection sulfite content
It is highly important to disease surveillance, food safety and environment measuring.
Fluorescence probe has easy to operate, high sensitivity, cheap, good selective, therefore is widely used in
The measurement of ion.In recent years, the document report fluorescence probe of many inferior sulfate radicals.But the overwhelming majority is in these probes
It is unimodal variation.A kind of Ratiometric fluorescent probe is constructed herein.Since the ratio fluorescent probe of detection sulphite is seldom.Cause
This, develops novel fluorescence dyestuff, and being one for constructing sulfite ion Ratiometric fluorescent probe significantly works.
In view of the deficiencies of the prior art, the present invention provides a kind of 1-(2- pyridines of two signals response variation) -3- (4-
Phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone SO3 2-Ratio fluorescent probe and its application.
The technical scheme is that a kind of 1-(2- pyridine) -3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -
2- propylene -1- ketone SO3 2-Ratio fluorescent probe, chemical structural formula are as the formula (1):
(1)
The invention also includes 1-(2- pyridines) -3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone SO3 2-
The application of ratio fluorescent probe, formula (1) compound is in n,N-Dimethylformamide/water (volume ratio 1:4) solution to SO3 2-
There is unique fluorescence selectivity.
The invention also includes 1-(2- pyridines) -3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone
SO3 2-The synthetic method of ratio fluorescent probe, in ethanol solution, by formylpyridine [1,2-a] and benzimidazole and acetyl group
Pyridine feeds intake according to molar ratio 1:2 ratio, using 1 milliliter of piperidines as catalyst, is heated to reflux 26 hours, obtains 1-(2- pyridine)-
3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone SO3 2-Ratio fluorescent probe.
Prepare 1-(2- pyridine) -3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone SO3 2-Ratio
The n,N-Dimethylformamide of fluorescence probe/water (volume ratio 1:4) solution, is separately added into quantitative Na2SO3, NaAcO,
NaBr, NaH2PO4, NaCl, Na2CO3, NaHCO3, NaF, Na2HPO4, NaHS, NaI, NaNO2, NaNO3, Na2S2O3, Na2SO4,
FeCl3, CaCl2, CuCl2, KCl, NaCl, ZnCl2, GSH, Hcy, the aqueous solution of Cys studied pair by fluorescence spectrum test
The selectivity of different ions and amino acid, fluorescence emission spectrum Strength Changes show: 1-(2- pyridine of the present invention) -3-
(4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone SO3 2-Ratio fluorescent probe, that is, formula (1) compound pair
SO3 2-There is unique fluorescence selectivity, as shown in Figure 1.It is gradually added into SO3 2-To 10 equivalents, the fluorescence at 510nm of compound 1
Intensity is substantially reduced, meanwhile, fluorescence intensity is remarkably reinforced at 450nm, as shown in Figure 1.Therefore, 1-(2- pyridine) -3- (4- benzene
Base -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone, that is, formula (1) compound is as SO3 2-Ratio fluorescent probe has
Huge application.
The present invention provides a kind of 1-(2- pyridines) -3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -
1- ketone SO3 2-Ratio fluorescent probe, that is, formula (1) compound, experiments have shown that formula of the present invention (1) compound can be with SO3 2-In N, N-
With stoichiometric ratio 1:10 reaction in dimethylformamide/water (volume ratio 1:4) solution, during the reaction, due to sulfurous
Acid ion destroys conjugated double bond of the 4- phenyl-pyridin simultaneously between [1,2-a] benzimidazole and 2- acetylpyridine, to make double
Key disconnects, and making donor 4- phenyl-pyridin, simultaneously [1,2-a] benzimidazole cannot be conjugated with receptor 2- acetylpyridine, lead to chemical combination
The fluorescence intensity at 510nm of object 1 is substantially reduced, meanwhile, fluorescence intensity is remarkably reinforced at 450nm.Thus the susceptible of proof present invention
Formula (1) compound is in n,N-Dimethylformamide/water (volume ratio 1:4) solution to SO3 2-There is unique fluorescence to select
Property, 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 10 are added in n,N-Dimethylformamide)/water (volume ratio 1:4) solution to work as
Measure SO3 2-And the figure of fluorescence intensity changes after the different anions of equivalent, cation, amino acid, FL Intensity in figure
For fluorescence intensity, Wavelength is wavelength, and equiv is multiple.
Fig. 2: formula (1) compound (10-5M SO is carried out in n,N-Dimethylformamide)/water (volume ratio 1:4) solution3 2-
Fluorescence titration figure.FL Intensity is fluorescence intensity in figure, and Wavelength is wavelength, and equiv is multiple.
Fig. 3: formula (1) compound (10-5M 10 are added in n,N-Dimethylformamide)/water (volume ratio 1:4) solution to work as
Measure SO3 2-And the UV intensity variation diagram after the different anions of equivalent, cation, amino acid.Abs. is extinction in figure
Degree, Wavelength is wavelength, and equiv is multiple.
Fig. 4: formula (1) compound synthesis method reaction equation figure.
Fig. 5: formula (1) compound (10-5M 10 are added in n,N-Dimethylformamide)/water (volume ratio 1:4) solution to work as
Measure SO3 2-And the figure of fluorescence intensity changes after the different anions of equivalent, cation, amino acid, FL Intensity in figure
For fluorescence intensity, Wavelength is wavelength, and equiv is multiple.
Specific embodiment
Embodiment 1: the synthetic schemes of formula (1) compound is shown below:
Specific synthesis step is as follows:
0.27g(1.0 mmol is sequentially added in 50 mL round-bottomed flasks) 4- phenyl-pyridin simultaneously [1,2-a] benzimidazole -3- first
Aldehyde, 0.24g(2.0 mmol) 2- acetylpyridine, 30 mL ethyl alcohol are heated to reflux 26 hours using 1 milliliter of piperidines as catalyst.
TLC is detected after the reaction was completed, is stopped heating, is filtered out solid after being cooled to room temperature, and with cold ethanol washing 3 times, drying is obtained
The orange red color solid of 0.16g, yield 42.7%.
Nuclear magnetic resonance hydrogen spectruming determining:1H NMR(400 MHz, CDCl3): δ 8.76 (d, 1H), 8.47 (d, 1H), 8.31
(d,1H), 8.15 (d,1H),7.97 (m,3H), 7.89 (m,1H), 7.58 (q,4H), 7.52 (t,3H), 7.43
(dd,2H)。
Embodiment 2:
To formula (1) compound (10-5M 10 equivalents are separately added into n,N-Dimethylformamide)/water (volume ratio 1:4) solution
SO3 2-, AcO-, Br-, H2PO4 -, Cl-, CO3 2-, HCO3 -, F-, HPO4 2-, HS-, I-, NO2 -, NO3 -, S2O3 2-, SO4 2-, Fe3+, Ca2 +, Cu2+, K+, Na+, Zn2+, it surveyed after GSH, Hcy and Cys to change in 450nm and 510nm fluorescent emission intensity ratio find:
Formula (1) compound is to SO3 2-There is unique fluorescence selectivity, the SO of 10 equivalents is added3 2-Afterwards, the fluorescence at 510nm of compound 1 is strong
Degree is substantially reduced, meanwhile, fluorescence intensity is remarkably reinforced at 450nm, I450/I510 =1.69, as shown in Figure 1.
Embodiment 3:
In formula (1) compound (10-5M it is separately added into n,N-Dimethylformamide)/water (volume ratio 1:4) solution different dense
The SO of degree3 2-, with the increase of inferior sulfate radical concentration, significant change occurs for the fluorescence spectrum of probe.As shown in Figure 2.
Claims (2)
1. the present invention relates to a kind of pyrido [1,2-a] benzimidazole Ratio-type inferior sulfate radical fluorescence probe of pyridine modification,
It is characterized by: it is 1-(2- pyridine) -3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone, change
It is as the formula (1) to learn structural formula:
(1)
Formula (1) compound is in n,N-Dimethylformamide/water (volume ratio 1:4) solution to SO3 2-There is unique fluorescence to select
Property.
2. 1-(2- pyridine described in claim 1) -3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone
SO3 2-The synthetic method of ratio fluorescent probe, it is characterised in that: in ethanol solution, by 4- phenyl-pyridin simultaneously [1,2-a] benzo
Imidazoles -3- formaldehyde and 2- acetylpyridine feed intake according to molar ratio 1:2 ratio, using 1 milliliter of piperidines as catalyst, are heated to reflux 26
Hour, obtain 1-(2- pyridine) -3- (4- phenyl -3- pyrido [1,2-a] benzimidazole) -2- propylene -1- ketone.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143487A (en) * | 2020-09-25 | 2020-12-29 | 高伟健 | Mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906623A (en) * | 2016-05-24 | 2016-08-31 | 泰山医学院 | Pyridino[1, 2-a]benzimidazole carboxylic acid pH 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 |
-
2017
- 2017-10-27 CN CN201711022064.1A patent/CN109722238A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906623A (en) * | 2016-05-24 | 2016-08-31 | 泰山医学院 | Pyridino[1, 2-a]benzimidazole carboxylic acid pH 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 |
Non-Patent Citations (2)
| Title |
|---|
| AIKUN LIU ET AL.: "A ratiometric fluorescent probe for sensing sulfite based on a pyrido[1,2-a]benzimidazole fluorophore", 《NEW J. CHEM.》 * |
| XIAOLIANG PEI ET AL.: "Colorimetric and fluorescent determination of sulfide and sulfite with kinetic discrimination", 《ANALYST》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143487A (en) * | 2020-09-25 | 2020-12-29 | 高伟健 | Mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics |
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