CN108484478A - A kind of novel carbazoles fluorescence mercaptan labelled reagent and its synthetic method and application - Google Patents
A kind of novel carbazoles fluorescence mercaptan labelled reagent and its synthetic method and application Download PDFInfo
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- CN108484478A CN108484478A CN201810443306.2A CN201810443306A CN108484478A CN 108484478 A CN108484478 A CN 108484478A CN 201810443306 A CN201810443306 A CN 201810443306A CN 108484478 A CN108484478 A CN 108484478A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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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
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- 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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- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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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
- 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
Abstract
The present invention provides a kind of novel carbazoles fluorescence mercaptan labelled reagent and its synthetic method and application, the fluorescent labeling reagent is using carbazole as fluorescent parent ring, and the C=C double bonds of activation are reaction active groups, and synthesis step is easy, easily operated, a large amount of synthesis can be realized in two-step reaction：(1) carbazole is reacted with 4 bromobenzaldehydes, obtains intermediate (4 (9 base of 9H carbazoles) benzaldehydes；(2) by intermediate, (4 (9 base of 9H carbazoles) benzaldehydes are reacted with malononitrile, obtain target product (4 (9 base of 9H carbazoles) benzylidene) malononitrile, through recrystallized from acetonitrile 3 times, yellow needles body is obtained.Fluorescent labeling reagent chemical purity of the present invention up to 99%, stablize by chemical property.Novel carbazoles fluorescence mercaptan labelled reagent of the present invention can fast and accurately mark the degradation thiol product of organophosphor mercaptan ester pesticide in a mild condition, to realize the quantitative analysis of organophosphor mercaptan ester pesticide content in reagent sample.
Description
Technical field
The invention belongs to organic molecule fluorescent labelling techniques fields, and in particular to a kind of novel carbazole is fluorescence marked
The synthetic method of reagent and its application in the detection of organophosphor mercaptan ester pesticide.
Background technology
Organophosphorus insecticide is widely used in agricultural production, is the maximally efficient method of pre- preventing disease and pest, and improves grain
Yield is to meet the effective way of growing population demand.However, due to the excess application in agricultural, there is also latent
Organophosphorus insecticide residual.The remaining presence of organophosphorus insecticide is a major issue in food security.The mankind are logical
Cross the organophosphorus insecticide residual of intake low concentration, it is possible to lead to immune and internal system destruction.In Acute exposure
When can cause human body inability or muscular paralysis, and Chronic exposure can influence neurodevelopment and growth.It rapidly and accurately measures organic
Phosphorus pesticide residual has great importance for food security.Organophosphorus insecticide does not have fluorescence radiation property, main to transport
Organophosphorus insecticide is detected with efficient liquid phase-mass spectrometry combination method.But mass signal interference is stronger, while instrument
Cost is high, needs special technical operation personnel, this limits mass spectrometric analysis method in organophosphorus insecticide to a certain extent
Application in detection.Develop a kind of new method based on HPLC-fluorescence detection, improves the sensitive of organophosphorus insecticide detection
Property is particularly important.Organophosphorus insecticide is the compound of the amide of a kind of organic phosphoric acid, ester, mercaptan ester, can pass through drop
Solution generates corresponding amine, alcohol, thiol derivative.As a kind of feasible approach, by detecting organic phosphorous insecticide degradation production
The fluorescent marker of object can be realized indirectly to organic phosphorous insecticide fluoroscopic examination.
Invention content
The object of the present invention is to provide a kind of label, reaction rate is fast, sensitivity is high, the novel sulphur of simple synthetic method
Alcohol fluorescent labeling reagent.Novel carbazoles fluorescence mercaptan labelled reagent of the present invention, be using carbazole as fluorescent parent ring,
Using the C=C double bonds of activation as reaction active groups, its chemical name is：(4- (9H- carbazole -9- bases) benzylidene) malononitrile,
Its chemical structural formula is：
It is a further object of the present invention to provide a kind of synthesis sides of the novel carbazoles fluorescence mercaptan labelled reagent
Method includes the following steps：
(1) substitution reaction：Carbazole, 4- bromobenzaldehydes are dissolved into dimethyl sulfoxide, cuprous iodide, 18- [hat] -6 is added
Ether and potassium carbonate, oil bath reaction；After reaction, it waits for that reaction solution is cooled to room temperature, filters, then by smoke filtrate and (10-30)
Solid is precipitated in the mixing of wt%NaCl aqueous solutions, recycles solid and drying obtains intermediate (4- (9H- carbazoles-with recrystallized from acetonitrile
9- yls) benzaldehyde；
(2) nucleophilic addition：By intermediate, (4- (9H- carbazole -9- bases) dissolution of benzaldehyde is added dropwise in anhydrous acetonitrile
A small amount of anhydrous pyridine makees catalyst, and malononitrile is added, and heating reflux reaction waits for that reaction solution is cooled to room temperature, so after reaction
Solution is mixed with (10-30) wt%NaCl aqueous solutions afterwards, solid is precipitated, recycled solid and drying is obtained with recrystallized from acetonitrile
Target product (4- (9H- carbazole -9- bases) benzylidene) malononitrile.
Preferably, carbazole and 4- bromobenzaldehyde molar ratios are 1 in the step (1):1.3, cuprous iodide, 18- [hat] -6
The addition of ether and potassium carbonate is respectively 25%, 20% and the 50% of carbazole quality.
Preferably, step (1) reaction temperature is 130 DEG C, and the reaction time is for 24 hours.
Using acetonitrile, by gained intermediate in step (1), (4- (9H- carbazole -9- bases) benzaldehyde recrystallizes 3 times, obtains Huang
Color acicular crystal product.
Preferably, (molar ratio of 4- (9H- carbazole -9- bases) benzaldehydes and malononitrile is 1 in the step (2):1.2, pyrrole
The addition of pyridine is (the 5% of 4- (9H- carbazole -9- bases) benzaldehyde quality.
Preferably, in the step (2), under reflux condition, reaction time 4h.
Gained target product (4- (9H- carbazole -9- bases) benzylidene) malononitrile in step (2) is recrystallized using acetonitrile
3 times, obtain yellow needles product.
Another object of the present invention is to provide a kind of application of the novel carbazoles fluorescence mercaptan labelled reagent,
By marking the degradation of thiols product of organophosphor mercaptan ester pesticide to realize the fluorescence point to organophosphor mercaptan ester pesticide
Analysis, the content for detecting organophosphor mercaptan ester pesticide in sample.
Specifically include following steps：
(1) phenyl butane -1,2 of 2.0nM is prepared, 3- triketone -2- oxime solution is used for catalyzing hydrolysis organophosphor mercaptan esters
Insecticide generates degradation of thiols derivative；The solution of 5 parts of organophosphor mercaptan ester pesticide standard items is prepared, concentration is respectively 1 μ
M、10μM、100μM、1mM、10mM；Compound concentration is the acetonitrile of (4- (9H- carbazole -9- bases) benzylidene) malononitrile of 100mM
Solution prepares the 4-dimethylaminopyridine solution of 3.0nM, is the degradation of thiols of labelled reagent and organophosphor mercaptan ester pesticide
The label reaction of product provides suitable alkaline environment；
(2) successively by the solution and 200 μ L phenyl butanes -1,2,3- of 100 μ L organophosphor mercaptan ester pesticide standard items
The peace that triketone -2- oxime solution is added to 2mL is cutd open in bottle, and 20min is reacted in 40 DEG C of water-bath, after completion of the reaction so that organophosphor sulphur
The degradation of alcohol ester insecticides is complete, and 150 μ L (4- (9H- carbazole -9- bases) benzylidene) malononitrile solution, 50 μ L4- are then added
Dimethylamino naphthyridine solution reacts 15min in 40 DEG C of water-bath, after the completion of reaction to be marked, 10 μ L is taken to carry out efficient liquid phase-
Fluorescence analysis draws organophosphor mercaptan ester with a concentration of abscissa of organophosphor mercaptan ester pesticide by ordinate of peak area
Insecticides concentration working curve；
(3) sample containing organophosphor mercaptan ester pesticide is degraded and is marked according to the method described in step (2)
Afterwards, high performance liquid chromatography-fluorescence analysis is carried out, obtained peak area is substituted into the work of organophosphor mercaptan ester pesticide concentration
In curve, you can acquire the concentration of organophosphor mercaptan ester pesticide in sample.
Beneficial effects of the present invention are as follows：Novel carbazoles fluorescence mercaptan labelled reagent of the present invention is with carbazole
For fluorescent parent ring, using the C=C double bonds of activation as reaction active groups.The C=C double bonds of activation exist as reaction active groups
When marking mercaptan compound, flag condition is mild, the label time is short, label yield is high.Therefore, labelled reagent of the present invention
Can quickly, it is accurate, delicately mark mercaptan compound, be particularly suitable for micro, trace mercaptan compound in complex system
Separation detection.As a kind of new application, we are applied to the detection of organophosphor mercaptan ester pesticide.Concrete operations
For：Organophosphor mercaptan ester pesticide by with phenyl butane -1,2, the nucleophilic substitution of 3- triketone -2- oximes releases drop
Solve thiol product, then with novel carbazole class fluorescence mercaptan labelled reagent of the present invention to thiol product of degrading into rower
Note, then efficient liquid phase-fluorescence analysis is carried out, and then realize the quantitative inspection to organophosphor mercaptan ester pesticide content in sample
It surveys.The present invention provides a detection organic phosphorous insecticide new approaches, i.e., by the fluorescent marker to corresponding catabolite,
It realizes to organic phosphorous insecticide quantitative analysis：Using fluorescent labelling techniques to corresponding amine, alcohols, thio-alcohol catabolite
Label, realize quantitative analysis to organic phosphoramide types, organophosphor esters, organophosphor mercaptan ester pesticide.
Description of the drawings
Fig. 1 is the synthetic route chart that embodiment 1 prepares (4- (9H- carbazole -9- bases) benzylidene) malononitrile.
Fig. 2 is the nuclear-magnetism 1HNMR figures that embodiment 1 prepares (4- (9H- carbazole -9- bases) benzylidene) malononitrile.
Fig. 3 is the marker of 2 labelled reagent of embodiment and the thiol derivative of organophosphor mercaptan ester pesticide degradation
The online spectrogram of efficient liquid phase-fluorescence excitation.
Fig. 4 is the efficient liquid phase-of 2 labelled reagent of embodiment and the thiol derivative of organophosphor mercaptan ester pesticide degradation
The online spectrogram of fluorescent emission.
Fig. 5 is the schematic diagram that 2 labelled reagent of embodiment is used to detect organophosphor mercaptan ester pesticide new strategy.
Fig. 6 is 3 representative 5 kinds of organophosphor mercaptan ester pesticides and its thiol products of degrading accordingly of embodiment.
Fig. 7 is the chromatographic isolation that 3 labelled reagent of embodiment derives 5 kinds of organophosphor mercaptan ester pesticide degradation of thiols products
Figure, wherein A：(4- (9H- carbazole -9- bases) benzylidene) malononitrile；B：Methyl mercaptan (methamidophos degradation thiol product)；C：Rosickyite
Alcohol (Toyodan catabolite)；D：2- sulfydryls butane (cadusafos degradation thiol product)；E：2- ehtylmercapto ethyl mercaptan (disulfotons
Degradation thiol product)；F：Benzenethiol (Dyfonate degradation thiol product).
Specific implementation mode
The present invention is described further with reference to embodiments.
Embodiment 1
The preparation of (4- (9H- carbazole -9- bases) benzylidene) malononitrile
(1) 10g carbazoles are added in 250mL three-necked flasks, 13.2g 4- bromobenzaldehydes, 5g potassium carbonate, 2.5g iodate are sub-
150mL dimethyl sulfoxides are added as solvent in copper and -6 ethers of 2g18- [hat], and 130 DEG C of reactions of oil bath are for 24 hours；After reaction, it waits for anti-
It answers liquid to be cooled to room temperature, filters, smoke filtrate is mixed with 20wt%NaCl aqueous solutions then, solid is precipitated, recycle solid and do
It is dry, with recrystallized from acetonitrile 3 times, obtain intermediate (4- (9H- carbazole -9- bases) benzaldehyde, yield 85%；
(2) 7.5g (4- (9H- carbazole -9- bases) benzaldehyde, use are added into three-necked flasks of the 100ml equipped with electromagnetic agitation
20mL anhydrous acetonitriles are completely dissolved, and 2mL anhydrous pyridines make catalyst, then addition 2.8g malononitrile, heating reflux reaction 4h, instead
After answering, reaction solution is mixed with 15wt%NaCl aqueous solutions, solid is precipitated, solid and drying are recycled, with recrystallized from acetonitrile 3
It is secondary, obtain target product (4- (9H- carbazole -9- bases) benzylidene) malononitrile, yield 83%.
As shown in Fig. 2, the characterize data of target product is as follows：
1HNMR(500MHz,CDCl3) δ 8.14 (d, J=7.7Hz, 2H), 7.59 (d, J=8.2Hz, 2H), 7.55 (d, J=
8.3Hz,2H),7.42–7.35(m,4H),7.28(m,2H),4.81(s,2H),1.79(s,1H).
Found:C 82.76,H 4.08,N 13.17；Calculated:C 82.74,H 4.10,N 13.16.
Embodiment 2
By fluorescence mercaptan labelled reagent to the label of organophosphor mercaptan ester pesticide degradation thiol product, realize to having
The quantitative analysis of machine phosphorus mercaptan ester pesticide, except the complete hydrolysis of organophosphor mercaptan ester pesticide and to degradation mercaptan production
The complete label of object is outer, accurately obtains the fluorescence maximum excitation and emission maximum of labelled reagent and thiol product marker of degrading
Wavelength is to improve detection sensitivity, reduces the key of detection limit.
The present invention is taken using the nucleophilic between phenyl butane -1,2,3- triketone -2- oximes and organophosphor mercaptan ester pesticide
Generation reaction, hydrolysis organophosphor mercaptan ester pesticide release degradation thiol product, by optimizing phenyl butane -1,2,3- triketones -
The amount of 2- oximes and organophosphor mercaptan ester pesticide, may be implemented the complete hydrolysis to organophosphor mercaptan ester pesticide.Simultaneously
Using sensitive nucleophilic addition between activation C=C double bonds in catabolite and labelled reagent molecule, passes through and optimize label examination
The amount and label reaction condition of agent, can also realize complete label of the labelled reagent to thiol product of degrading.
The present embodiment is with Dyfonate to degrading and marking whether to evaluate completely.Because there is phenyl ring knot in Dyfonate molecule
Structure, there are certain UV absorptions and its degradation thiol product benzenethiol also UV absorption.Under optimum conditions：
The molar ratio of phenyl butane -1,2,3- triketone -2- oximes and organophosphor mercaptan ester pesticide is 5:1；Labelled reagent and organophosphor
The molar ratio of the degradation thiol product of mercaptan ester pesticide is 7:1, it being capable of complete hydrolysis with organophosphor mercaptan ester pesticide
For measurement criteria.Efficient liquid phase-ultra-violet analysis is carried out to hydrolyzate and label reaction solution, does not find Dyfonate and benzenethiol
Absorption peak further illustrates under optimum conditions, is that can ensure that degradation is complete with label.We are to labelled reagent and drop
The marked product for solving thiol product benzenethiol carries out high phase liquid phase-fluorescence analysis, and the fluorescence maximum for respectively obtaining marked product swashs
It is respectively 260nm and 435nm that wavelength, which is sent out, with maximum emission wavelength.
Embodiment 3
(1) drop of (4- (9H- carbazole -9- bases) benzylidene) malononitrile fluorescent marker organophosphor mercaptan ester insecticide is utilized
Thiol product is solved, the quantitative analysis of organophosphor mercaptan ester pesticide in agricultural product is realized, prepares the phenyl butane -1 of 2.0nM,
2,3- triketone -2- oxime solution, and generate degradation thiol product for catalyzing hydrolysis organophosphor mercaptan ester pesticide.Prepare 5 parts
The solution of organophosphor mercaptan ester pesticide standard items, concentration are respectively 1 μM, 10 μM, 100 μM, 1mM, 10mM；Compound concentration is
The acetonitrile solution of (4- (9H- carbazole -9- bases) benzylidene) malononitrile of 100mM, the 4-dimethylaminopyridine for preparing 3.0nM are molten
Liquid reacts with the label of the degradation of thiols product of organophosphor mercaptan ester pesticide for labelled reagent and provides suitable alkaline ring
Border；
(2) by the solution and 200 μ L phenyl butane -1,2,3- triketones-of 100 μ L organophosphor mercaptan ester pesticide standard items
The peace that 2- oxime solution is added to 2mL is cutd open in bottle, and 20min is reacted in 40 DEG C of water-bath, after completion of the reaction so that organophosphor mercaptan ester
Insecticides degradation is complete, and 150 μ L (4- (9H- carbazole -9- bases) benzylidene) malononitrile solution, 50 μ L4- diformazans are then added
Aminopyridine solution reacts 15min in 40 DEG C of water-bath, after the completion of reaction to be marked, 10 μ L is taken to carry out efficient liquid phase-fluorescence
Analysis is drawn organophosphor mercaptan esters as ordinate using peak area and is killed with a concentration of abscissa of organophosphor mercaptan ester pesticide
Worm agent concentration working curve；
(3) acetonitrile/water (2/1) is added in agricultural product wild cabbage sample and carries out ultrasonic extraction 10min, then in 15000rpm
Lower centrifugation 3min, supernatant are adsorbed and removed the agricultural product matrix in extract liquor through excessive empty carbon nanotube solid phase adsorption pillar, use
Acetonitrile is eluted, and the extraction sample of organophosphor mercaptan ester pesticide is obtained；Then according to the method described in step (2) into
Row hydrolysis, hydrolyzate silver ion solid phase extraction column are enriched with degradation thiol product, are eluted with methanol, obtain organophosphor mercaptan ester
The degradation thiol product sample of insecticides；It is marked according still further to the method described in step (2), finally carries out efficient liquid phase
Chromatography-fluorescence analysis substitutes into obtained peak area in working curve, you can in the hope of organophosphor mercaptan esters in agricultural product
The content of insecticide.
The present invention has also expanded the application of fluorescence mercaptan labelled reagent successively, and the labelled reagent can sensitively mark it
The fragrant sulphur in mercaptan metabolin, food in mercaptan compound in his sample, such as glutathione, cysteine life entity
Toxic mercaptan compound in alcoholic compound and environment can be applied to life analysis, food science research, environment point
A variety of research fields such as analysis, food security, have broad application prospects.
Claims (9)
1. a kind of novel carbazoles fluorescence mercaptan labelled reagent, it is characterised in that：Using carbazole as fluorescent parent ring, with activation
C=C double bonds are reaction active groups, its chemical name is：(4- (9H- carbazole -9- bases) benzylidene) malononitrile, chemistry knot
Structure formula is：
2. a kind of synthetic method of novel carbazoles fluorescence mercaptan labelled reagent described in claim 1, it is characterised in that packet
Include following steps：
(1) substitution reaction：Carbazole, 4- bromobenzaldehydes are dissolved into dimethyl sulfoxide, be added cuprous iodide, -6 ethers of 18- [hat] with
Potassium carbonate, oil bath reaction；After reaction, it waits for that reaction solution is cooled to room temperature, filters, then by smoke filtrate and (10-30) wt%
Solid is precipitated in the mixing of NaCl aqueous solutions, recycles solid and drying obtains yellow needles intermediate (4- with recrystallized from acetonitrile
(9H- carbazole -9- bases) benzaldehyde；
(2) nucleophilic addition：By intermediate, (4- (9H- carbazole -9- bases) dissolution of benzaldehyde is added dropwise a small amount of in anhydrous acetonitrile
Anhydrous pyridine makees catalyst, and malononitrile, heating reflux reaction is added；After reaction, it waits for that reaction solution is cooled to room temperature, then will
Solution is mixed with (10-30) wt%NaCl aqueous solutions is precipitated solid, recycles solid and drying obtains yellow with recrystallized from acetonitrile
Acicular crystal target product (4- (9H- carbazole -9- bases) benzylidene) malononitrile.
3. the synthetic method of novel carbazoles fluorescence mercaptan labelled reagent according to claim 2, it is characterised in that：Institute
It states in step (1), the molar ratio of carbazole and 4- bromobenzaldehydes is 1:1.3, cuprous iodide, -6 ethers of 18- [hat] and potassium carbonate plus
Enter amount is respectively carbazole quality 25%, 20% and 50%.
4. the synthetic method of novel carbazoles fluorescence mercaptan labelled reagent according to claim 3, it is characterised in that：Institute
It states in step (1), oil bath reaction temperature is 130 DEG C, and the reaction time is for 24 hours.
5. the synthetic method of novel carbazoles fluorescence mercaptan labelled reagent according to claim 2, it is characterised in that：Institute
It states in step (2), (molar ratio of 4- (9H- carbazole -9- bases) benzaldehydes and malononitrile is 1:1.2, the addition of pyridine is (4-
The 5% of (9H- carbazole -9- bases) benzaldehyde quality.
6. the synthetic method of novel carbazoles fluorescence mercaptan labelled reagent according to claim 5, it is characterised in that：Institute
It states in step (2), the reaction time being heated to reflux is 4h.
7. a kind of application of novel carbazoles fluorescence mercaptan labelled reagent described in claim 1, it is characterised in that：Pass through mark
Organophosphor mercaptan ester pesticide content in sample is determined in the degradation thiol product realization of note organophosphor mercaptan ester pesticide
Amount analysis.
8. the application of novel carbazoles fluorescence mercaptan labelled reagent according to claim 7, it is characterised in that：Including with
Lower step：
(1) phenyl butane -1,2,3- triketone -2- oxime solution of 2.0nM is prepared；Prepare 5 parts of organophosphor mercaptan ester pesticide marks
The solution of quasi- product, concentration are respectively 1 μM, 10 μM, 100 μM, 1mM, 10mM；Compound concentration is the (4- (9H- carbazoles -9- of 100mM
Base) benzylidene) malononitrile acetonitrile solution, prepare the 4-dimethylaminopyridine solution of 3.0nM for labelled reagent with it is organic
The label of the degradation of thiols product of phosphorus mercaptan ester pesticide reacts；
(2) successively by the solution and 200 μ L phenyl butane -1,2,3- triketones-of 100 μ L organophosphor mercaptan ester pesticide standard items
The peace that 2- oxime solution is added to 2mL is cutd open in bottle, and 20min is reacted in 40 DEG C of water-bath, after completion of the reaction so that organophosphor mercaptan ester
Insecticides degradation is complete, and 150 μ L (4- (9H- carbazole -9- bases) benzylidene) malononitrile solution, 50 μ L 4- bis- are then added
Methylamino pyridine solution reacts 15min in 40 DEG C of water-bath, after the completion of reaction to be marked, takes 10 μ L to carry out efficient liquid phase-glimmering
Light is analyzed, and with a concentration of abscissa of organophosphor mercaptan ester pesticide, organophosphor mercaptan esters are drawn by ordinate of peak area
Insecticide concentration working curve；
(3) after the sample containing organophosphor mercaptan ester pesticide being degraded and is marked according to the method described in step (2), into
Obtained peak area is substituted into organophosphor mercaptan ester pesticide concentration working curve by row high performance liquid chromatography-fluorescence analysis
In, you can acquire the concentration of organophosphor mercaptan ester pesticide in sample.
9. the application of novel carbazoles fluorescence mercaptan labelled reagent according to claim 8, which is characterized in that the step
Suddenly in (3), the molar ratio of phenyl butane -1,2,3- triketone -2- oximes and organophosphor mercaptan ester pesticide is 5:1, (4- (9H- clicks
Azoles -9- bases) benzylidene) molar ratio of degradation thiol product of malononitrile and organophosphor mercaptan ester pesticide is 7:1.
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| CN110054644A (en) * | 2019-05-22 | 2019-07-26 | 武汉天马微电子有限公司 | Compound, display panel and display device |
| CN110793950A (en) * | 2019-08-16 | 2020-02-14 | 东莞伊元生物科技有限公司 | Method for detecting organophosphorus pesticide residues |
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| CN109824533B (en) * | 2019-03-19 | 2022-09-06 | 曲阜师范大学 | Preparation method of (E) -1- (3-bromomethylene) -3-acylindene compounds |
| CN110054644A (en) * | 2019-05-22 | 2019-07-26 | 武汉天马微电子有限公司 | Compound, display panel and display device |
| CN110054644B (en) * | 2019-05-22 | 2021-08-27 | 武汉天马微电子有限公司 | Compound, display panel and display device |
| CN110793950A (en) * | 2019-08-16 | 2020-02-14 | 东莞伊元生物科技有限公司 | Method for detecting organophosphorus pesticide residues |
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