CN104804729A - Preparation and application of fluorescence-enhanced sulfite fluorescence probe - Google Patents
Preparation and application of fluorescence-enhanced sulfite fluorescence probe Download PDFInfo
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- CN104804729A CN104804729A CN201510205233.XA CN201510205233A CN104804729A CN 104804729 A CN104804729 A CN 104804729A CN 201510205233 A CN201510205233 A CN 201510205233A CN 104804729 A CN104804729 A CN 104804729A
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- sulfate radical
- inferior sulfate
- fluorescent probe
- fluorescence
- probe
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a novel compound which can be utilized for fluorescence detection of sulfite, particularly relates to preparation and application of a novel fluorescence probe, and belongs to the technical field of chemical analysis and detection. The novel fluorescence probe has a molecular structural formula shown in the description. The novel fluorescence probe is high in selectivity, anti-interference capability and sensitivity, can be utilized for the fluorescence detection of sulfite in a biological or environmental sample, and has an excellent application prospect.
Description
Technical field
What the present invention relates to is chemical analysis detection technique field, and the preparation method and this fluorescent probe that are specifically related to a kind of novel inferior sulfate radical fluorescent probe are detecting the application in inferior sulfate radical.
Background technology
Sulphite is just widely used in food-processing industry in period very early, as food bleaching agent and food preservatives.Industrially also have and apply very widely, such as, as the reductive agent of printing and dyeing industry, the SYNTHETIC OPTICAL WHITNER etc. of wool and silk fabric.Sulfurous acid ion as the product in Metabolism of Sulfur-Containing Amino Acids process, must be oxidized to the sulfate radical of toxicological harmless in human body by the sulfite oxidase in body.Heavy dose of sulphite can cause the anaphylaxis of people, may cause expiratory dyspnea, asthma, laryngitis, headache, nausea and vomiting time serious.Therefore, the interpolation of sulphite in foods needs strict criteria limit.Conventional inferior sulfate radical detection method has volumetry, red, orange, green, blue, yellow (ROGBY), electrochemical methods, capillary electrophoresis etc., but these methods mostly have length consuming time, need the shortcoming such as sample pretreatment and equipment and instrument costliness.Therefore, a kind of quick, convenient, reliable inferior sulfate radical qualitative and quantitative detection method for food safety and quality examination significant.Fluorescent probe detection method meets above-mentioned various requirement, the significant and practical value of inferior sulfate radical fluorescent probe of exploitation highly sensitive, highly selective.
Summary of the invention
One of the object of the invention is to provide one and synthesizes simple, gentle, the lower-cost fluorescent probe synthetic method of reaction conditions; Two of object be to provide a kind of highly sensitive, selectivity good, immunity from interference is strong, can realize the fluorescent probe of Fluorometric assay inferior sulfate radical.
The present invention uses Fluorometric assay inferior sulfate radical, with 2-hydroxyl-6-ethanoyl naphthalene derivatives for fluorophore, take levulinate as the recognition group of inferior sulfate radical.
The present invention's technical scheme taked of dealing with problems is, a kind of fluoroscopic examination inferior sulfate radical fluorescent probe, and its molecular structural formula is,
the synthetic route of this fluorescent probe is as follows,
Concrete preparation method comprises the following steps: 1) be dissolved in methylene dichloride by 2-methoxyl group-6-ethanoyl naphthalene; add mass fraction 36% concentrated hydrochloric acid again; be heated to 85 DEG C of backflow 4h, stop heating being cooled to room temperature, regulate pH to neutral with 50% sodium hydroxide solution; separate out solid; filter to obtain filter cake, with distilled water wash 3 times, vacuum-drying 24h; obtain white solid, be 2-hydroxyl-6-ethanoyl naphthalene.2) levulinic acid is slowly added drop-wise in sulfur oxychloride, stirring at room temperature 3h, revolves and steam the remaining sulfur oxychloride of removing, obtain levulinic acyl chlorides, do not purify further and directly carry out the next step.3) 2-hydroxyl-6-ethanoyl naphthalene is dissolved in anhydrous methylene chloride; add a small amount of triethylamine; again the levulinic acid that upper step obtains slowly is added drop-wise in reaction solution; reaction solution becomes dark-brown; stirring at room temperature 0.5h, stopped reaction, revolves and steams remove portion methylene dichloride; through column chromatography for separation, vacuum-drying 24h obtains light yellow solid.Synthesis and the detection method of this probe is illustrate in greater detail in the embodiment of this specification sheets.
Fluorescent molecular probe using method of the present invention is as follows, and being dissolved in by probe molecule containing 10% acetonitrile, pH is in the HEPES buffered soln of 7.4, tests under room temperature.When adding inferior sulfate radical, due to the cracking that levulinic acid ester group can occur under the induction of inferior sulfate radical, fluorescence is recovered.Probe molecule and inferior sulfate radical action principle as follows,
The specific features of inferior sulfate radical fluorescent probe of the present invention is as follows: probe molecule has faint emission peak at about 470nm, but with inferior sulfate radical effect after, probe molecule obviously strengthens at the emission peak of 451nm, and fluorescence intensity enhances more than 10 times.
Probe molecule of the present invention synthesis is simple, and cost is lower, good to the selectivity of inferior sulfate radical, immunity from interference strong, fast response time makes this fluorescent probe in biological chemistry, and the fields such as environmental science have actual using value.
Accompanying drawing explanation
Fig. 1 is the selectivity of fluorescent probe of the present invention, fluorescent probe (5.0 × 10
-6mol/L) at HEPES buffered soln (20mM, V
acetonitrile/
vHEPES=1/9, pH=7.4) in, from the fluorescence spectrum after different analyte effect, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 2 is the immunity from interference of fluorescent probe of the present invention, and inferior sulfate radical and other analytes coexist, with fluorescent probe 5.0 × 10
-6mol/L) at buffered soln (V
acetonitrile/ V
hEPES=1/9, pH=7.4) in effect after fluorescence intensity ratio (I/I
0) histogram.
Fig. 3 is fluorescent probe (5.0 × 10 of the present invention
-6mol/L) at HEPES buffered soln (20mM, V
acetonitrile/ V
hEPES=1/9, pH=7.4) in, change with the fluorescence spectrum after the effect of different concns inferior sulfate radical, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 4 is fluorescent probe (5.0 × 10 of the present invention
-6mol/L) at HEPES buffered soln (20mM, V
acetonitrile/ V
hEPES=1/9, pH=7.4) in, with the linear relationship of inferior sulfate radical concentration, X-coordinate is inferior sulfate radical concentration, and ordinate zou is fluorescence intensity.
Fig. 5 is fluorescent probe (5.0 × 10 of the present invention
-6mol/L) at HEPES buffered soln (20mM, V
acetonitrile/ V
hEPES=1/9, pH=7.4) in, with fluorescence intensity in inferior sulfate radical mechanism over time, X-coordinate is the time, and ordinate zou is fluorescence intensity.
Fig. 6 is fluorescent probe (5.0 × 10 of the present invention
-6mol/L) in different pH value buffered soln, with the fluorescence intensity before and after inferior sulfate radical effect, X-coordinate is pH, and ordinate zou is fluorescence intensity.
Embodiment
The synthesis of embodiment 1:2-hydroxyl-6-ethanoyl naphthalene
By 2-methoxyl group-6-ethanoyl naphthalene (1.5170g; 7.58mmol) be dissolved in 6mL methylene dichloride; add mass fraction 36% concentrated hydrochloric acid (100mL) again, be heated to 85 DEG C of backflow 4h, stop heating being cooled to room temperature; regulate pH to neutral with 50% sodium hydroxide solution; separate out solid, filtration, filter cake are product, distilled water wash 3 times; vacuum-drying 24h, obtains white solid.Output: 1.3552g.Output: 96%.This synthetic method reference
1.
Embodiment 2: the synthesis of levulinic acyl chlorides
Levulinic acid (0.5806g, 5mmol) is slowly added drop-wise in sulfur oxychloride (1.1897g, 10mmol), stirring at room temperature 3h, revolves and steam the remaining sulfur oxychloride of removing, obtain levulinic acyl chlorides, do not purify further and directly carry out the next step.
Embodiment 3: the synthesis of probe molecule
By 2-hydroxyl-6-ethanoyl naphthalene (0.2017g; 1.1mmol) be dissolved in 25mL anhydrous methylene chloride; add 1mL triethylamine, then the levulinic acid upper step obtained slowly is added drop-wise in reaction solution, reaction solution becomes dark-brown; stirring at room temperature 0.5h; stopped reaction, revolves and steams remove portion methylene dichloride, direct wet method loading; column chromatography for separation (eluent, V
methylene dichloride/ V
sherwood oil=1/1), vacuum-drying 24h obtains light yellow solid.Output: 0.1692g.Productive rate: 54.9%.
1H NMR(500MHz,CDCl
3)δ8.48(s,1H),8.07(d,J＝8.6Hz,1H),8.00(d,J＝8.9Hz,1H),7.87(d,J＝8.7Hz,1H),7.63(s,1H),7.34(d,J＝6.6Hz,1H),7.28(s,1H),2.92(s,4H),2.74(s,3H),2.27(s,3H).
13C NMR(126MHz,CDCl
3)δ206.36,197.85,171.41,150.39,136.15,134.41,131.09,130.51,129.92,128.17,124.66,122.19,118.57,37.95,29.86,28.24,26.67.
Embodiment 4: the performance test of inferior sulfate radical fluorescent probe of the present invention
Probe is dissolved in buffered soln (V
acetonitrile/ V
hEPES=2/8, pH=7.4) in be mixed with 5.0 × 10
-6the solution of mol/L, adds NaF, NaCl, NaBr, NaI, NaNO in solution
3, NaNO
2, AcONa, NaN
3, Na
2sO
4, Na
2s
2sO
3, NaClO, NaSCN, CN
-, H
2o
2, Cys, HCy, GSH, Na
3pO
4, Na
2cO
3, Na
2do not have obvious change in fluorescence after S, cause very significantly change in fluorescence after adding inferior sulfate radical, this fluorescent probe shows the identification of highly sensitive, highly selective to inferior sulfate radical.When inferior sulfate radical respectively with interfering substance NaF, NaCl, NaBr, NaI, NaNO
3, NaNO
2, AcONa, NaN
3, Na
2sO
4, Na
2s
2sO
3, NaClO, NaSCN, CN
-, H
2o
2, Cys, HCy, GSH, Na
3pO
4, Na
2cO
3, Na
2when S coexists, the impact of the interference-free factor of probe, shows good immunity from interference.
Embodiment 5: the practical application of inferior sulfate radical fluorescent probe of the present invention
Prepare a series of 5.0 × 10
-6buffered soln (the V of mol/L probe
acetonitrile/ V
hEPES=1/9, pH=7.4), add the inferior sulfate radical of 0-500 μM respectively, after complete reaction, the fluorescence intensity at the 516nm place recorded and inferior sulfate radical concentration have good linear in the scope of 0-300 μM, linearly dependent coefficient R=0.99191.Probe is dissolved in buffered soln (V
acetonitrile/ V
hEPES=1/9, pH=7.4) in be mixed with 5.0 × 10
-6the solution of mol/L, adds NaF, NaCl, NaBr, NaI, NaNO in solution
3, NaNO
2, AcONa, NaN
3, Na
2sO
4, Na
2s
2sO
3, NaClO, NaSCN, CN
-, H
2o
2, Cys, HCy, GSH, Na
3pO
4, Na
2cO
3, Na
2do not cause the change of fluorescence after S, add SO
3 2-after cause very significantly change in fluorescence, this fluorescent probe shows the identification of highly sensitive, highly selective to inferior sulfate radical.Work as SO
3 2-respectively with interfering substance NaF, NaCl, NaBr, NaI, NaNO
3, NaNO
2, AcONa, NaN
3, Na
2sO
4, Na
2s
2sO
3, NaClO, NaSCN, CN
-, H
2o
2, Cys, HCy, GSH, Na
3pO
4, Na
2cO
3, Na
2when S coexists, the impact of the interference-free factor of probe, shows good immunity from interference.Probe molecule to inferior sulfate radical Selective recognition, can show wider range of application in slightly acidic to weakly alkaline.
Claims (3)
1. an inferior sulfate radical fluorescent probe, its structure is:
2. the preparation method of inferior sulfate radical fluorescent probe as claimed in claim 1, is characterized in that being prepared according to the following steps:
A 2-methoxyl group-6-ethanoyl naphthalene is dissolved in methylene dichloride by (); add mass fraction 36% concentrated hydrochloric acid again; be heated to 85 DEG C of backflow 4h, stop heating being cooled to room temperature, regulate pH to neutral with 50% sodium hydroxide solution; separate out solid; filter to obtain filter cake, with distilled water wash 3 times, vacuum-drying 24h; obtain white solid, be 2-hydroxyl-6-ethanoyl naphthalene.
B levulinic acid is slowly added drop-wise in sulfur oxychloride by (), stirring at room temperature 3h, revolves and steams the remaining sulfur oxychloride of removing, obtain levulinic acyl chlorides, do not purify further and directly carry out the next step.
C 2-hydroxyl-6-ethanoyl naphthalene is dissolved in anhydrous methylene chloride by (); add a small amount of triethylamine; again the levulinic acid that upper step obtains slowly is added drop-wise in reaction solution; reaction solution becomes dark-brown; stirring at room temperature 0.5h, stopped reaction, revolves and steams remove portion methylene dichloride; through column chromatography for separation, vacuum-drying 24h obtains light yellow solid.
3. the purposes of inferior sulfate radical fluorescent probe according to claim 1, is characterized in that this inferior sulfate radical fluorescent probe is for the fluoroscopic examination of environment or biological sample sulfite root and analysis.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105466894A (en) * | 2015-11-18 | 2016-04-06 | 华南理工大学 | A method of detecting sulfite through applying triphenylamine dye |
| CN106928133A (en) * | 2017-03-23 | 2017-07-07 | 贺州学院 | A kind of switching mode bivalent cupric ion fluorescence probe and its preparation and application |
| 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 |
| CN108623575A (en) * | 2017-03-21 | 2018-10-09 | 泰山医学院 | A kind of fluorescence probe that is simple and effectively detecting sulphite |
| CN108640902B (en) * | 2018-07-04 | 2020-08-21 | 济南大学 | Fluorescent probe for identifying sulfur dioxide in pure water system and application thereof |
| CN112209898A (en) * | 2020-09-29 | 2021-01-12 | 华南理工大学 | Ratiometric fluorescent probe, preparation method thereof and application thereof in sulfite ion detection |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090155837A1 (en) * | 2007-12-18 | 2009-06-18 | Bong-Rae Cho | Two-photon fluorescent probes for acidic vesicles in live cells and tissue and method of imaging acidic vesicles in live cells and tissue using the same |
| US20120135532A1 (en) * | 2010-11-30 | 2012-05-31 | Chung-Ang University Industry-Academiy Cooperation Foundation | Sensor Comprising Resrufin Levulinate Having Sulfite Ion Selectivity and Method for Monitoring Sulfite Ion Using the Same |
| 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 |
| CN104262287A (en) * | 2014-09-02 | 2015-01-07 | 苏州罗兰生物科技有限公司 | Preparation and application of sulfite ratiometric fluorescent probe |
| CN104447421A (en) * | 2014-10-28 | 2015-03-25 | 苏州罗兰生物科技有限公司 | Preparation and application of novel cysteine and homocysteine fluorescence probe |
-
2015
- 2015-04-27 CN CN201510205233.XA patent/CN104804729A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090155837A1 (en) * | 2007-12-18 | 2009-06-18 | Bong-Rae Cho | Two-photon fluorescent probes for acidic vesicles in live cells and tissue and method of imaging acidic vesicles in live cells and tissue using the same |
| US20120135532A1 (en) * | 2010-11-30 | 2012-05-31 | Chung-Ang University Industry-Academiy Cooperation Foundation | Sensor Comprising Resrufin Levulinate Having Sulfite Ion Selectivity and Method for Monitoring Sulfite Ion Using the Same |
| 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 |
| CN104262287A (en) * | 2014-09-02 | 2015-01-07 | 苏州罗兰生物科技有限公司 | Preparation and application of sulfite ratiometric fluorescent probe |
| CN104447421A (en) * | 2014-10-28 | 2015-03-25 | 苏州罗兰生物科技有限公司 | Preparation and application of novel cysteine and homocysteine fluorescence probe |
Non-Patent Citations (2)
| Title |
|---|
| MYUNG GIL CHOI,ET AL.: "Chromogenic and Fluorogenic Signaling of Sulfite by Selective Deprotection of Resorufin Levulinate", 《ORG. LETT.》, vol. 12, 17 November 2010 (2010-11-17), pages 5624 - 5627 * |
| PENG HOU,ET AL.: "A colorimetric and ratiometric fluorescent probe for sulfite based on an intramolecular cleavage mechanism", 《LUMINESCENCE》, vol. 29, 20 December 2013 (2013-12-20), pages 749 - 753 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105466894A (en) * | 2015-11-18 | 2016-04-06 | 华南理工大学 | A method of detecting sulfite through applying triphenylamine dye |
| CN108623575A (en) * | 2017-03-21 | 2018-10-09 | 泰山医学院 | A kind of fluorescence probe that is simple and effectively detecting sulphite |
| CN108623575B (en) * | 2017-03-21 | 2020-04-10 | 山东第一医科大学(山东省医学科学院) | Simple and effective fluorescent probe for detecting sulfite |
| CN106928133A (en) * | 2017-03-23 | 2017-07-07 | 贺州学院 | A kind of switching mode bivalent cupric ion fluorescence probe and its preparation and application |
| 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 |
| CN107417654B (en) * | 2017-06-05 | 2020-03-10 | 河南农业大学 | Benzopyranonitrile-based sulfite fluorescent probe and preparation method thereof |
| CN108640902B (en) * | 2018-07-04 | 2020-08-21 | 济南大学 | Fluorescent probe for identifying sulfur dioxide in pure water system and application thereof |
| CN112209898A (en) * | 2020-09-29 | 2021-01-12 | 华南理工大学 | Ratiometric fluorescent probe, preparation method thereof and application thereof in sulfite ion detection |
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Application publication date: 20150729 |