CN106632266A - Switching mode thiol fluorescent labeling reagent as well as synthetic method and application thereof - Google Patents

Switching mode thiol fluorescent labeling reagent as well as synthetic method and application thereof Download PDF

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Publication number
CN106632266A
CN106632266A CN201610828240.XA CN201610828240A CN106632266A CN 106632266 A CN106632266 A CN 106632266A CN 201610828240 A CN201610828240 A CN 201610828240A CN 106632266 A CN106632266 A CN 106632266A
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mercaptan
fluorescent labeling
labeling reagent
switching mode
carbazoles
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尤进茂
吕政贤
路帅敏
窦昆
孙志伟
李国梁
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Qufu Normal University
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Qufu Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • G01N21/6402—Atomic fluorescence; Laser induced fluorescence

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Abstract

The invention relates to fluorescent labeling reagents, in particular to a switching mode thiol fluorescent labeling reagent as well as a synthetic method and application thereof. The fluorescent labeling reagent is N-(9-ethyl-carbazole)-maleimide. The reagent does not emit fluorescence and can selectively react with a thiol compound under neutral conditions so as to produce a derived product with strong fluorescence, and background interference in the thiol detection process is greatly reduced. According to the reagent, a carbazole ring serves as a fluorescent group, a maleimide ring serves as a reactive active group, the synthesis steps are simple and convenient, and the synthesis can be completed by a two-step reaction. The fluorescent labeling reagent disclosed by the invention is stable in chemical property, reaches the chemical purity of 99.6% or higher after separation and purification, has the advantages of high labeling reaction rate, high labeling yield, high thiol selectivity and the like, contributes to enhancing of the accuracy and sensitivity of thiol compound analysis and can be applied to the research fields of life analysis, environment analysis, food analysis and the like.

Description

Switching mode mercaptan fluorescent labeling reagent and its synthetic method and application
Technical field
The present invention relates to fluorescent labeling reagent, and in particular to a kind of switching mode mercaptan fluorescent labeling reagent and its synthetic method And application.
Background technology
In the efficient liquid phase chromatographic analysis of mercaptan compound, maleimide fluorescent labeling reagent has the excellent of uniqueness Gesture：(1) compared with the reagents such as traditional aryl halide, benzofuran sulfonic acid halide, they are fast with thiol reactant speed, in room temperature And can carry out under physiological pH.(2) selectivity to sulfydryl is high, and addition compound product is more stable.(3) itself unstressed configuration or fluorescence is very Weak, the Fluorescence Increasing after with mercaptan addition, the background signal that this fluorescent switch effect is significantly reduced in detection process is done Disturb.
But current applicable maleimide fluorescent labeling reagent limited amount, and it is glimmering with mercaptan addition compound product Photoswitch effect is not obvious, and synthesis step is complicated, it is therefore necessary to a kind of mark of exploitation is swift in response, fluorescent switch effect is good, The switching mode maleimide fluorescent labeling reagent of simple synthetic method.
The content of the invention
It is an object of the invention to provide a kind of mark be swift in response, it is high to thiol-selective, without ambient interferences, synthetic method Easy switching mode mercaptan fluorescent labeling reagent；Present invention simultaneously provides its synthetic method and application.
Switching mode mercaptan fluorescent labeling reagent of the present invention is that, with carbazole as fluorophor, maleimide is reaction Active group, its chemistry is entitled：N- (9- Ethy-Carbazoles)-maleimide, its chemical structural formula is：
The synthetic method of described switching mode mercaptan fluorescent labeling reagent, comprises the following steps：
(1) maleic anhydride is dissolved into acetonitrile, the acetonitrile containing 3- amino -9- Ethy-Carbazoles is added dropwise under normal temperature Solution is reacted, and reaction is finished, and removes solvent, obtains intermediate N (9- Ethy-Carbazoles)-maleamic acid；
(2) N- (9- Ethy-Carbazoles)-maleamic acid is dissolved with acetic anhydride, adds anhydrous sodium acetate to be reacted, instead Cooling should be finished, then be poured into water reaction is quenched, after reclaiming solid, drying, be recrystallized to give target product N- (9- ethyls- Carbazole)-maleimide.
Wherein：
The mol ratio of maleic anhydride and 3- amino -9- Ethy-Carbazoles is 1.1～1.4 in step (1):1.
In step (1) after completion of dropping, continue to react 0.8～1 hour.
In step (1) after completion of the reaction, solvent is removed by rotary evaporation.
Anhydrous sodium acetate and the mol ratio of N- (9- Ethy-Carbazoles)-maleamic acid are 1 in step (2):5～8.
Add in step (2) after anhydrous sodium acetate, react 0.8～1 hour at 100 DEG C.
Using recrystallized from acetonitrile three times in step (2).
The application of described switching mode mercaptan fluorescent labeling reagent, that is, the method for detecting concentrations of mercaptans, comprises the steps：
(1) the PBS cushioning liquid of pH=7.4, concentration for 10mM is prepared；The acetonitrile solution of 5 parts of mercaptan standard items is prepared, it is dense Degree is respectively 1 μM, 10 μM, 100 μM, 1mM, 10mM；Compound concentration is N- (9- the Ethy-Carbazoles)-maleimide of 100mM Acetonitrile solution；
(2) successively by 50 μ L PBS cushioning liquid, the acetonitrile solution of 100 μ L mercaptan standard items and 50 μ L N- (9- ethyls- Carbazole) acetonitrile solution of-maleimide is added to the peace of 2mL and cuts open in bottle, react 10 minutes in 40 DEG C of water-bath, and reaction is finished Afterwards, take 10 μ L to analyze into high performance liquid chromatograph, setting fluorescence exciting wavelength is 274nm, fluorescence emission wavelengths are 363nm, obtains mercaptan standard items chromatogram, with concentrations of mercaptans as abscissa, by ordinate of peak area concentrations of mercaptans work is drawn Make curve；
(3) after sample is marked with switching mode mercaptan fluorescent labeling reagent, analyze into high performance liquid chromatograph, by institute The peak area for obtaining is substituted into concentrations of mercaptans working curve, you can try to achieve the concentration of mercaptan in sample.
Beneficial effects of the present invention are as follows：
The switching mode mercaptan fluorescent labeling reagent of the present invention is that, with carbazole as fluorogen, maleimide is reactivity base Group, wherein maleimide ring is joined directly together with carbazole fluorogen, due to the strong sucting electronic effect of maleimide ring, makes mark The quantum yield of reagent is remarkably decreased, and shows as unstressed configuration.
Reagent of the present invention itself does not fluoresce, can in neutral conditions optionally with mercaptan compound react, generate tool There are the derivative products of hyperfluorescence, greatly reduce the ambient interferences in mercaptan detection process；Mark reaction has high selectivity, Lower of physiological ph and mercaptan react；Mark reaction speed is fast, and the mark reaction to mercaptan can be completed in 10 minutes；Mark Note tube- nursery step is simple, and stable chemical nature, yield is higher, and after separated purification, chemical purity has up to more than 99.6% Have the advantages that mark reaction rate is fast, mark yield high, high to thiol-selective, be conducive to strengthening what sulfur alcohol compound was analyzed Accuracy and sensitivity, in can be applicable to the research fields such as life analysis, environmental analysis, food analysis, with wide application Prospect.
Description of the drawings
Fig. 1 is the synthetic route chart of embodiment 1N- (9- Ethy-Carbazoles)-maleimide.
Fig. 2 is the nuclear-magnetism of embodiment 1N- (9- Ethy-Carbazoles)-maleimide1HNMR schemes.
Fig. 3 is the fluorescent emission figure of the reagent of embodiment 2 and its thiol derivative.
Fig. 4 is the reaction scheme figure of the reagent of embodiment 3 and sulfhydryl compound.
Fig. 5 is the chromatogram that the reagent of embodiment 3 derives 5 kinds of mercaptan standard items.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
As shown in figure 1, the synthesis of the switching mode mercaptan fluorescent labeling reagent of the present invention has 2 steps, with maleic anhydride It is raw material with 3- amino -9- Ethy-Carbazoles, concrete synthetic operation is as follows：
1st, the preparation of intermediate N (9- Ethy-Carbazoles)-maleamic acid：
5g maleic anhydrides and 100mL acetonitriles are added in the round-bottomed flask of 250mL, starts stirring；In maleic two After acid anhydrides is completely dissolved, the acetonitrile solution containing 9.7g 3- amino -9- Ethy-Carbazoles is added dropwise, obtains the suspension of white, and Continue to stir 1 hour；React rear rotary evaporation and removed solvent, obtain intermediate N (9- Ethy-Carbazoles)-maleamic acid 13.7g, yield 96%.
2nd, the preparation of target product N- (9- Ethy-Carbazoles)-maleimide：
N- (9- the Ethy-Carbazoles)-maleamic acid of gained is dissolved with 70mL acetic anhydrides, adds 0.7g anhydrous acetic acids Sodium, reacts 1 hour under 100 DEG C of oil baths；After cooling, it is poured into water and reaction is quenched, it is by solid suction filtration and dry, tied again with acetonitrile It is brilliant three times, light yellow crystal is obtained, it is target product N- (9- Ethy-Carbazoles)-maleimide.9.6g, yield 74%.
Characterization of The Products is as follows：
1HNMR(CDCl3,400MHz,ppm)δ8.41(d,1H,Ar-H),8.16(d,1H,Ar-H),7.80-7.85(dd, 2H ,-CH-CH-, J=8.0Hz), 7.53 (m, 1H, Ar-H), 7.45 (dd, 2H, J=8.0Hz), 7.41 (s, 1H, Ar-H), 7.3 (m,1H,Ar-H),4.4(m,2H,-CH2-),1.47(t,2H,-CH3). (Fig. 2)
IR(KBr):3470(NH2),2962(-CH3), 2875,3056,1600 (ph), 1644 (- C=O)；
Found:C 74.44,H 4.72,N 9.74,O 11.16；Calculated:C 74.47,H 4.86,N 9.65, O 11.05；MS:m/z 290.1[M+H]+.
Embodiment 2
In order to verify the photoluminescent property of fluorescent labeling reagent, with the N- (9- Ethy-Carbazoles) that acetontrile concentration is 1 μM- The hexyl mercaptan derivative solution of maleimide amine aqueous solution and same concentrations, as shown in figure 3, before reacting with hexyl mercaptan, the reagent Almost unstressed configuration, fluorescence is significantly increased after reaction.Fluorescence is most preferably excited and is respectively 274nm and 363nm with launch wavelength.Meanwhile, With tryptophan standards solution as reference solution, N- (9- Ethy-Carbazoles)-maleimides are calculated glimmering with its thiol derivative Quantum yield.It is computed, the quantum yield of N- (9- Ethy-Carbazoles)-maleimide is to measure behind 0.004, with thiol reactant Sub- yield is 0.388.
Embodiment 3
Using the mercaptans content in the fluorescent labeling reagent detection coffee, prepare the PBS that pH=7.4, concentration are 10mM and delay Rush solution；Prepare 5 kinds of mercaptan standard items (3- sulfydryls-toluic acid butyl ester, the methyl butyl alcohol of 3- sulfydryls -3,2- methyl -3- tetrahydrochysenes Furanthiol, furfuryl mercaptan, 3- sulfydryls-hexanol) a series of concentration acetonitrile solution, concentration be respectively 1 μM, 10 μM, 100 μM, 1mM, 10mM, the acetonitrile solution of different types of mercaptan standard items of same concentrations is mixed, and obtains 5 mercaptan mixing marks Quasi- product solution；Compound concentration is the acetonitrile solution of N- (9- the Ethy-Carbazoles)-maleimide of 100mM.
(2) successively by 50 μ L PBS cushioning liquid, 100 μ L mercaptan hybrid standard product solution and 50 μ L N- (9- ethyls-click Azoles)-maleimide amine aqueous solution is added to the peace of 2mL and cuts open in bottle, react 10 minutes in 40 DEG C of water-bath.N- (9- Ethy-Carbazoles)- Maleimide and thiol reactant formula such as Fig. 4.10 μ L are taken after the completion of reaction to analyze into high performance liquid chromatograph, and fluorescence is set Excitation wavelength is 274nm, and fluorescence emission wavelengths are 363nm, obtains mercaptan standard items chromatogram, and 5 kinds were realized in 10 minutes Thiol analytes are kept completely separate, and it is 1 × 10 that Fig. 5 is concentration-6The mercaptan hybrid standard product chromatogram of mol/L.With concentrations of mercaptans For abscissa, the calibration curve of concentrations of mercaptans is drawn as ordinate with peak area.
(3) after coffee samples are marked with fluorescent labeling reagent, analyze into high performance liquid chromatograph, will be resulting Peak area is substituted into working curve, you can try to achieve the concentration of mercaptan in coffee samples.

Claims (10)

1. a kind of switching mode mercaptan fluorescent labeling reagent, it is characterised in that：With carbazole as fluorophor, maleimide is reaction Active group, its chemical name is：N- (9- Ethy-Carbazoles)-maleimide, its chemical structural formula is：
2. the synthetic method of the switching mode mercaptan fluorescent labeling reagent described in a kind of claim 1, it is characterised in that including following Step：
(1) maleic anhydride is dissolved into acetonitrile, the acetonitrile solution containing 3- amino -9- Ethy-Carbazoles is added dropwise under normal temperature Reacted, reaction is finished, removed solvent, obtained intermediate N (9- Ethy-Carbazoles)-maleamic acid；
(2) N- (9- Ethy-Carbazoles)-maleamic acid is dissolved with acetic anhydride, adds anhydrous sodium acetate to be reacted, reacted Finish cooling, then be poured into water reaction is quenched, after recovery solid, drying, be recrystallized to give target product N- (9- ethyls-click Azoles)-maleimide.
3. the synthetic method of switching mode mercaptan fluorescent labeling reagent according to claim 2, it is characterised in that：Step (1) The mol ratio of middle maleic anhydride and 3- amino -9- Ethy-Carbazoles is 1.1～1.4:1.
4. the synthetic method of switching mode mercaptan fluorescent labeling reagent according to claim 2, it is characterised in that：Step (1) After middle completion of dropping, continue to react 0.8～1 hour.
5. the synthetic method of switching mode mercaptan fluorescent labeling reagent according to claim 2, it is characterised in that：Step (1) In after completion of the reaction, solvent is removed by rotary evaporation.
6. the synthetic method of switching mode mercaptan fluorescent labeling reagent according to claim 2, it is characterised in that：Step (2) Middle anhydrous sodium acetate is 1 with the mol ratio of N- (9- Ethy-Carbazoles)-maleamic acid:5～8.
7. the synthetic method of switching mode mercaptan fluorescent labeling reagent according to claim 2, it is characterised in that：Step (2) After middle addition anhydrous sodium acetate, react 0.8～1 hour at 100 DEG C.
8. the synthetic method of switching mode mercaptan fluorescent labeling reagent according to claim 2, it is characterised in that：Step (2) Middle employing recrystallized from acetonitrile three times.
9. the application of the switching mode mercaptan fluorescent labeling reagent described in a kind of claim 1, it is characterised in that：For detection sample The concentration of middle mercaptan.
10. the application of switching mode mercaptan fluorescent labeling reagent according to claim 9, it is characterised in that including following step Suddenly：
(1) the PBS cushioning liquid of pH=7.4, concentration for 10mM is prepared；Prepare the acetonitrile solution of 5 parts of mercaptan standard items, concentration point Wei not 1 μM, 10 μM, 100 μM, 1mM, 10mM；Compound concentration is the acetonitrile of N- (9- the Ethy-Carbazoles)-maleimide of 100mM Solution；
(2) successively by 50 μ L PBS cushioning liquid, the acetonitrile solution of 100 μ L mercaptan standard items and 50 μ L N- (9- ethyls-click Azoles) acetonitrile solution of-maleimide is added to the peace of 2mL and cuts open in bottle, react 10 minutes in 40 DEG C of water-bath, and reaction is finished Afterwards, take 10 μ L to analyze into high performance liquid chromatograph, setting fluorescence exciting wavelength is 274nm, fluorescence emission wavelengths are 363nm, obtains mercaptan standard items chromatogram, with concentrations of mercaptans as abscissa, by ordinate of peak area concentrations of mercaptans work is drawn Make curve；
(3) after sample is marked with switching mode mercaptan fluorescent labeling reagent, analyze into high performance liquid chromatograph, will be resulting Peak area substitute into concentrations of mercaptans working curve in, you can try to achieve the concentration of mercaptan in sample.
CN201610828240.XA 2016-09-18 2016-09-18 Switching mode thiol fluorescent labeling reagent as well as synthetic method and application thereof Pending CN106632266A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108490093A (en) * 2018-03-29 2018-09-04 曲阜师范大学 A kind of fluoroscopic examination application of switching mode mercaptan fluorescent labeling reagent and its synthetic method
CN108484478A (en) * 2018-05-10 2018-09-04 曲阜师范大学 A kind of novel carbazoles fluorescence mercaptan labelled reagent and its synthetic method and application

Citations (2)

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CN103013497A (en) * 2012-12-21 2013-04-03 武汉大学 Sulfydryl fluorescent probe and preparation method thereof
CN103575727A (en) * 2013-10-18 2014-02-12 山西大学 Reagent and method for detecting thiol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103013497A (en) * 2012-12-21 2013-04-03 武汉大学 Sulfydryl fluorescent probe and preparation method thereof
CN103575727A (en) * 2013-10-18 2014-02-12 山西大学 Reagent and method for detecting thiol

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Title
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梁淑彩等: "N-取代马来酰亚胺巯基荧光探针的研究进展", 《化学通报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108490093A (en) * 2018-03-29 2018-09-04 曲阜师范大学 A kind of fluoroscopic examination application of switching mode mercaptan fluorescent labeling reagent and its synthetic method
CN108484478A (en) * 2018-05-10 2018-09-04 曲阜师范大学 A kind of novel carbazoles fluorescence mercaptan labelled reagent and its synthetic method and application

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