CN105086995A - Preparation and application of probe for hydrogen sulfide (H2S) based on protection-deprotection mechanism - Google Patents
Preparation and application of probe for hydrogen sulfide (H2S) based on protection-deprotection mechanism Download PDFInfo
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- CN105086995A CN105086995A CN201510263490.9A CN201510263490A CN105086995A CN 105086995 A CN105086995 A CN 105086995A CN 201510263490 A CN201510263490 A CN 201510263490A CN 105086995 A CN105086995 A CN 105086995A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a fluorescent probe used for detecting hydrogen sulfide based on a protection-deprotection mechanism. The fluorescent probe provided by the invention has a highly-sensitive highly-selective recognition capacity for detection of hydrogen sulfide. The fluorescent probe provided by the invention is simple to synthesize and high in yield. According to the invention, due to presence of 2,4-dinitro benzenesulfonyl in the probe, the probe itself is free of fluorescence, and fluorescence rapidly increases when a protective group of hydroxy is deprotected after reaction with sulfur ions. The probe can detect hydrogen sulfide in chemical samples, biological samples or medical samples based on fluorescence enhancement or color enhancement, and is suitable for fluorescence imaging.
Description
Technical field
The invention belongs to fluorescent probe field, specific design is a kind of based on the preparation method and application of protection with the hydrogen sulfide fluorescent probe of deprotection mechanism.
Background technology
Sulfide is one of important parameter representing Water quality, and its existence can consume the oxygen in water body, causes hydrobiological death.Enrich at organism, waters that pH value is lower, sulfide very easily generates the toxic gas hydrogen sulfide (H with rotten egg smell
2s).H
2s generates the presoma with strong corrosive material sulfuric acid, has very large harm to environment; But also be a kind of strong neurotoxin, human body sucks the H of different concns
2s can produce headache, dizziness, vomiting, in a moment death etc.
[2]symptom, the survival and development of the mankind in serious threat.
Up-to-date research shows, H
2s is the third endogenous gas signaling molecule found after CO, NO; very important regulating effect is played in neural signaling process; be closely connected with physiological process and pathologic process, have and regulate Growth of Cells, protection cardiovascular systems and anti-oxidant etc.
[3]effect.H
2s horizontal abnormality is also considered to and alzheimer's disease, Down's syndrome, diabetes and liver cirrhosis etc.
[4]closely related.The physiology of hydrogen sulfide and pathology functional study have become the focus of chemistry and biological study at present.
Fluorescent probe has the feature that specificity is good, selectivity is high and identification response is fast in analyzing and testing; Fluorescent probe is easy to design, modifies and improve in chemical structure, can meet the needs of different detected object.The fluorescent probe detecting hydrogen sulfide has been reported, but mostly can be subject to the impact of sulfhydryl compound (as halfcystine, gsh, homocysteine, thiophenol), and selectivity is not high.We utilize the organic reaction mechanism of protection and remove-insurance to design the fluorescent probe of hydrogen sulfide, and utilize the nucleophilicity of hydrogen sulfide, thus improve the selectivity of fluorescent probe, the fluorescence intensity after deprotection significantly strengthens thus improves the sensitivity of analyzing and testing.
Summary of the invention
The object of the present invention is to provide a kind of based on protection and the fluorescent probe aimed detection hydrogen sulfide of deprotection mechanism and the Preparation method and use of this probe, thus detect quick and precisely, delicately the hydrogen sulfide in chemical example, biological sample or medical sample quantitatively and qualitative analysis and fluorescence imaging.
The present invention adopts following technical scheme to achieve these goals:
Based on the hydrogen sulfide fluorescent probe of protection with deprotection mechanism, it is characterized in that, the structural formula of described fluorescent probe is:
Described hydrogen sulfide fluorescent probe, is characterized in that hydroxyl protected group 2, the 4-dinitrobenzenesulfonyl of tonka bean camphor 7 in its structural formula protected, does not almost have fluorescence.
After the described fluorescent probe based on protection and deprotection and hydrogen sulfide effect, discharge the fluorescence of tonka bean camphor, fluorescence significantly strengthens, and has highly sensitive advantage.The selectivity of this probe is high in addition, halfcystine, gsh, and homocysteine, thiophenol are very little on the impact detecting hydrogen sulfide.
The preparation method of described hydrogen sulfide fluorescent probe, is characterized in that comprising following 2 steps:
2,4-Dihydroxy benzaldehyde and benzothiazole-2-acetonitrile are dissolved in ethanol, then drip piperidines, stirred overnight at room temperature.Next day, have a large amount of yellow mercury oxide to separate out in reaction system, suction filtration, the filter cake obtained joins in dilute hydrochloric acid solution, suspension liquid hydrolyse over night at 130 DEG C of formation.Filtering reacting liquid, filter cake is washed with water in neutral, after oil pump is drained, with silica gel column chromatography separating purification, obtains yellow compound
1solid.
Take 3-benzothiazole-umbelliferone and 2,4-dinitrophenyl chloride in the round-bottomed flask of 50ml, toward wherein adding DMF, catalyzer made by triethylamine, heated and stirred 2 hours at the temperature of 50 DEG C.Naturally cool to room temperature, reaction solution is gone in separating funnel, in funnel, add methylene dichloride and water extraction, collect methylene dichloride clear liquid, repeatedly until product is all extracted.Rotary evaporation makes it concentrate, and with silica gel column chromatography separating purification, with sherwood oil and dichloromethane as eluent, separation and purification obtains the solid chemical compound of light orange
2.
Probe provided by the invention is protection based on hydroxyl and de-protected novel structure; there is good light stability; higher molar extinction coefficient, higher fluorescence quantum yield, to the characteristic such as pH is insensitive; have water-soluble preferably, be applicable to quantitative and qualitative analysis and the fluorescence imaging of hydrogen sulfide in analyzing and testing biological sample.
Fluorescent probe provided by the invention may be used for quantitative analysis of hydrogen sulphide and fluorescence imaging in chemical example, biological sample or medical sample.
Probe provided by the invention, outstanding advantage is:
Fluorescent probe provided by the invention only has two step synthesis, and synthesis is simple, and productive rate is higher.
Design due to this probe is protection based on hydroxyl and deprotection reaction, so selectivity is high, wherein halfcystine, gsh, homocysteine, thiophenol are very little to probe response.
This probe is Fluorescence Increasing type, and with the probe solution not adding sulfonium ion, intensification factor reaches 20 times, highly sensitive.
Because blocking group is 2,4-dinitrobenzenesulfonyl in probe structure, the fluorescence of probe itself is quenched; after reacting with sulfonium ion, the blocking group deprotection of hydroxyl, fluorescence strengthens rapidly; under the hand-held fluorescent lamp of 365nm, naked eyes are visible, can be used for Visual retrieval hydrogen sulfide.
Accompanying drawing explanation
The synthetic route of Fig. 1 probe
The fluorescence spectrum that Fig. 2 probe 2 responds with the sulphur hydrogen radical ion of different concns
Fig. 3 probe 2 (5 μMs) responds various ion fluorescence.1:NO
2 -; 2:N
3 -; 3:HCO
3 -; 4:SCN
-; 5:ClO
-, 6:O
2 -; 7:NO; 8:H
2o
2; 9:SO
3 2-; 10:S
2o
3 2-; 11: halfcystine; 12: thiophenol; 13: gsh; 14:NaHS
Fig. 4 probe is at 490nm place fluorescence intensity response curve in time
Embodiment
The following examples just for describing the present invention in detail, and limit scope of invention never in any form.
The synthesis of embodiment probe:
In the round-bottomed flask of 50ml, add 2,4-Dihydroxy benzaldehyde (345.3mg, 2.5mmol) and benzothiazole-2-acetonitrile (435.6mg, 2.55mmol), add 5mL dissolve with ethanol, then drip 5 piperidines, stirred overnight at room temperature.Next day, have a large amount of yellow mercury oxide to separate out in reaction system, suction filtration obtains a large amount of yellow mercury oxides, joins in the dilute hydrochloric acid solution of 40mL10% by the filter cake obtained, and the suspension liquid of formation is at 130 DEG C of heated and stirred hydrolyse over night.Solution after acid being boiled is cooled to room temperature, regulates pH to neutral, filtering reacting liquid by NaOH dilute solution, and with a large amount of water washing filter cakes, after oil pump is drained, with silica gel column chromatography separating purification (methylene dichloride: ethanol=5:1, v/v), obtains yellow compound
1solid (530mg, 1.79mmol), productive rate: 71.6%.
Take 3-benzothiazole-umbelliferone 59mg(0.2mmol) and 2,4-dinitrophenyl chloride 80mg(0.6mmol) in the round-bottomed flask of 50ml, toward wherein adding 12mlN, dinethylformamide, catalyzer made by the triethylamine of 10, heated and stirred 2 hours at the temperature of 50 DEG C.Naturally cool to room temperature, reaction solution is gone in separating funnel, methylene dichloride and water extraction is added in funnel, water can dissolve each other with DMF, a large amount of yellow mercury oxide is separated out, and water and methylene dichloride can not dissolve each other, and product but dissolves in methylene dichloride, collect methylene dichloride clear liquid, repeatedly until product is all extracted.Rotary evaporation makes it concentrate, and with silica gel column chromatography separating purification, by sherwood oil and methylene dichloride proportioning polarity, is separated and obtains light saffron solution, be product, be spin-dried for the solid chemical compound obtaining light orange
2(73.6mg, 0.14mmol), productive rate is 70.0%.
The mensuration of embodiment spectrum:
0.03mL probe mother liquor (5 × 10 is added in test tube
-4mol/L), 0.27mL ethanol, and 2.7mLpH value is the PBS buffered soln of 7.4, mixes, and then adds the sulfonium ion/sulphur hydrogen radical ion solution of different concns, carries out spectrometry after reaction 5min.Excitation wavelength is 450nm, and exciting light slit width is 5.0nm, and emission peak slit width is 5.0nm.Fig. 2-3 is known, highly sensitive to hydrogen sulfide of probe.
Concentration and probe concentration (5 μMs), various relative species 1mMNO
2 -, N
3 -, HCO
3 -, SCN
-, 50 μMs of ClO
-, O
2 -, NO, 100 μMs of H
2o
2, SO
3 2-, S
2o
3 2-, 1mM halfcystine, thiophenol, 10mM gsh, 25 μMs of NaHS, survey their uv-absorbing and fluorescence spectrum.Excitation wavelength is 450nm, and exciting light slit width is 5.0nm, and emission peak slit width is 5.0nm.The known probe of Fig. 4 has very strong selectivity to sulphur hydrogen radical ion.
Claims (3)
1., based on the hydrogen sulfide fluorescent probe of protection with deprotection mechanism, its structure is as follows:
2. the preparation method of fluorescent probe described in claim 1, its characterization step comprises following step:
2,4-Dihydroxy benzaldehyde and benzothiazole-2-acetonitrile are dissolved in ethanol, then drip piperidines, stirred overnight at room temperature.Next day, have a large amount of yellow mercury oxide to separate out in reaction system, suction filtration, the filter cake obtained joins in dilute hydrochloric acid solution, suspension liquid hydrolyse over night at 130 DEG C of formation.Filtering reacting liquid, filter cake is washed with water in neutral, after oil pump is drained, with silica gel column chromatography separating purification, obtains yellow compound 1 solid.
Take 3-benzothiazole-umbelliferone and 2,4-dinitrophenyl chloride in the round-bottomed flask of 50ml, toward wherein adding DMF, catalyzer made by triethylamine, heated and stirred 2 hours at the temperature of 50 DEG C.Naturally cool to room temperature, reaction solution is gone in separating funnel, in funnel, add methylene dichloride and water extraction, collect methylene dichloride clear liquid, repeatedly until product is all extracted.Rotary evaporation makes it concentrate, and with silica gel column chromatography separating purification, with sherwood oil and dichloromethane as eluent, separation and purification obtains the solid chemical compound 2 of light orange.
3. fluorescent probe described in claim 1 is used for quantitative analysis of hydrogen sulphide and fluorescence imaging in chemical example, biological sample or medical sample.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419788A (en) * | 2015-12-25 | 2016-03-23 | 济南大学 | Small-molecular fluorescent probe for recognizing H2S, preparation method and application thereof |
| CN105928914A (en) * | 2016-04-15 | 2016-09-07 | 安徽师范大学 | Hydrogen sulfide detection sensor, preparation method thereof, quantitative detection method of hydrogen sulfide, and qualitative detection method of hydrogen sulfide in cells |
| CN108840818A (en) * | 2018-06-25 | 2018-11-20 | 山西大学 | It is a kind of for detecting the synthesis and application of the ratio colour pattern carbazoles fluorescence probe of hydrogen sulfide |
| CN109422738A (en) * | 2017-08-24 | 2019-03-05 | 北京工商大学 | A kind of Coumarins hydrogen sulfide fluorescence probe |
| CN109879851A (en) * | 2019-04-11 | 2019-06-14 | 济南大学 | A kind of near infrared fluorescent probe of specific detection benzenethiol |
| CN110143931A (en) * | 2019-06-18 | 2019-08-20 | 济南大学 | A kind of targeting lysosome detects fluorescence probe and its application of hydrogen sulfide |
| CN111777605A (en) * | 2020-07-21 | 2020-10-16 | 南通大学 | Coumarin fluorescent probe and preparation method and application thereof |
| CN111875561A (en) * | 2020-07-20 | 2020-11-03 | 中南林业科技大学 | Naphthalene derivative two-photon probe for specifically recognizing selenocysteine and preparation and application thereof |
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| 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 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419788B (en) * | 2015-12-25 | 2017-12-29 | 济南大学 | A kind of small-molecule fluorescent probe for identifying hydrogen sulfide and its preparation method and application |
| CN105419788A (en) * | 2015-12-25 | 2016-03-23 | 济南大学 | Small-molecular fluorescent probe for recognizing H2S, preparation method and application thereof |
| CN105928914A (en) * | 2016-04-15 | 2016-09-07 | 安徽师范大学 | Hydrogen sulfide detection sensor, preparation method thereof, quantitative detection method of hydrogen sulfide, and qualitative detection method of hydrogen sulfide in cells |
| CN105928914B (en) * | 2016-04-15 | 2019-09-27 | 安徽师范大学 | The qualitative checking method of sulfurated hydrogen detection sensor and preparation method thereof, the quantitative detecting method of hydrogen sulfide and intracellular hydrogen sulfide |
| CN109422738A (en) * | 2017-08-24 | 2019-03-05 | 北京工商大学 | A kind of Coumarins hydrogen sulfide fluorescence probe |
| CN108840818A (en) * | 2018-06-25 | 2018-11-20 | 山西大学 | It is a kind of for detecting the synthesis and application of the ratio colour pattern carbazoles fluorescence probe of hydrogen sulfide |
| CN108840818B (en) * | 2018-06-25 | 2021-09-28 | 山西大学 | Synthesis and application of colorimetric carbazole fluorescent probe for detecting hydrogen sulfide |
| CN109879851B (en) * | 2019-04-11 | 2021-08-31 | 济南大学 | Near-infrared fluorescent probe for specifically detecting thiophenol |
| CN109879851A (en) * | 2019-04-11 | 2019-06-14 | 济南大学 | A kind of near infrared fluorescent probe of specific detection benzenethiol |
| CN110143931A (en) * | 2019-06-18 | 2019-08-20 | 济南大学 | A kind of targeting lysosome detects fluorescence probe and its application of hydrogen sulfide |
| CN111875561A (en) * | 2020-07-20 | 2020-11-03 | 中南林业科技大学 | Naphthalene derivative two-photon probe for specifically recognizing selenocysteine and preparation and application thereof |
| CN111777605A (en) * | 2020-07-21 | 2020-10-16 | 南通大学 | Coumarin fluorescent probe and preparation method and application thereof |
| CN111777605B (en) * | 2020-07-21 | 2022-04-01 | 南通大学 | Coumarin fluorescent probe and preparation method and application thereof |
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