CN102634333B - High-sensitive-polarity fluorescent probe by taking acenaphtho-pyrazine as mother body and preparation method and application thereof - Google Patents
High-sensitive-polarity fluorescent probe by taking acenaphtho-pyrazine as mother body and preparation method and application thereof Download PDFInfo
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- CN102634333B CN102634333B CN201210095991.7A CN201210095991A CN102634333B CN 102634333 B CN102634333 B CN 102634333B CN 201210095991 A CN201210095991 A CN 201210095991A CN 102634333 B CN102634333 B CN 102634333B
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Abstract
The invention relates to an acenaphtho-pyrazine compound which is sensitive to the environment in the field of fluorescent probe application, characterized in that an amino straight chain of a flexible side chain is used as an electron-donating group at one end, and two cyans are used as an electron-withdrawing group at the other end, so that a push-pull electron large-plane conjugated system is formed. The compound is extremely high in dipole moment and has unique photophysical chemical performance. The compound is extremely sensitive to the polarity of the environment and can be used for detecting trace water in an organic solvent, for example, for measuring the trace water content in tetrahydrofuran and 1,4-dioxane.
Description
Technical field
The invention belongs to fluoroscopic examination application field, and in particular to a class is using acenaphthene and pyrazine as the Polar fluorescence probe of parent, and the application in environment measuring.
Background technology
Water content in organic solvent has a significant impact to the usual tool of organic chemical reactionses, or even can determine product, yield and the selectivity of reaction, therefore significant to the detection of Water in Organic Solvents content.Especially in anhydrous and oxygen-free experiment, water content directly determines the success or failure of experiment, and tetrahydrofuran and Isosorbide-5-Nitrae-dioxane are commonly used solvents in anhydrous and oxygen-free experiment, therefore detect that their water content is particularly important.
Fluorescent spectrometry is a very important instrument in biochemical research ion identification, small molecule detection and bioprocess (such as the interaction and phosphorylation between protein folding, protein).Environmentally sensitive fluorogen is the special chromophore of a class, and their spectrum property changes with the change of the physicochemical characteristics of surrounding environment.Of particular interest are solvatochromic fluorescence probe; their polar sensitives to local environment; such as 2- propiono -6- dimethylamine naphthalenes (PRODAN), 4- dimethylamine phthalimide (4-DMAP) and 4- amino -1,8-naphthalimide derivative.Fluorescence quantum yield is very low in aqueous for these usual molecules, and being combined rear fluorescence in non-polar solven or with the hydrophobic site of protein or cell membrane becomes very strong.Therefore it is eaily method to carry out detection to the minor amount of water in environment using such fluorescence probe.
Due to ground state and the high degree of symmetry of minimum singlet excited state, unsubstituted aromatics is insensitive to environment.Electron donating group and electron withdraw group on aromatic ring make it that the excitation state of minimum energy has significant charge transfer characteristic.Generally, Polar fluorescence probe is connected with a power supplying groups and an electron-withdrawing group in same aromatic ring system, and the distance for suitably increasing both groups can be so that sensitivity of the probe to polarity be increased.Using naphthalene as parent and with amino-substituent fluorogen, because of its high sensitivity to solvent effect, receive much concern, for example 6-N, chloro- 2, the 3- naphthalimides of TMSDMA N dimethylamine -2,3- naphthalimide (6DMN), 6-, 1- methylamino -5- cyano group naphthalenes.Based on this, the present invention has designed and synthesized a class, and using acenaphthene, simultaneously pyrazine is parent, and fatty amine is electron-donating group, and cyano group is the Polar fluorescence probe of electron-withdrawing group, and successfully have detected the water content in tetrahydrofuran and Isosorbide-5-Nitrae-dioxane.
The content of the invention
The invention aims to detect micro-water content in the minor amount of water in organic solvent, particularly tetrahydrofuran and Isosorbide-5-Nitrae-dioxane, a kind of highly sensitive Polar fluorescence probe is invented.
The technical solution for realizing the object of the invention is：Using acenaphthene, simultaneously pyrazine is parent to the class of the present invention, and fatty amine is electron-donating group, and cyano group is electron-withdrawing group, the Polar fluorescence probe of the big planar conjugate system of push-and-pull electronics is formed, with following general structure：
And prepared by following steps：
R is C1~C12Straight chained alkyl.
Step 1: the synthesis of 5- bromines acenaphthenequinone (2)：
By acenaphthenequinone and bromine heating stirring, stop filtering after being washed with aqueous solution of sodium bisulfite after reaction, and recrystallize；
Step 2: the synthesis of the bromo- acenaphthenes of 3- and pyrazine -8,9 dintrile (3)：
5- bromines acenaphthenequinone and diaminomaleonitrile are added in glacial acetic acid, heating stirring, stop cooling down after reaction, be poured into water, filter, silicagel column separating-purifying after drying；
Step 3: the synthesis of 3- amidos-acenaphthene and pyrazine -8,9 dintrile (4)：
Fatty amine is added dropwise into the ethylene glycol monomethyl ether solution of the bromo- acenaphthenes of 3- and pyrazine -8,9 dintrile, is heated to reflux under Ar protections, glycol monoethyl ether is evaporated off after stopping reaction, then silicagel column separating-purifying.
The mol ratio of bromine and acenaphthenequinone described in step one is 4~5: 1, and described reaction temperature is 60~70 DEG C, and the reaction time is 2~3h.
Diaminomaleonitrile and the mol ratio of 5- bromine acenaphthenequinones described in step 2 are 1~2: 1, and described reaction temperature is 116~118 DEG C, and the reaction time is 2~4h.
Heating-up temperature described in step 3 is 124~126 DEG C, and the reaction time is 1~3h, and the mol ratio of the bromo- acenaphthenes of described 3- and pyrazine -8,9 dintrile and fatty amine is 1: 4~6, and described fatty amine is methylamine, ethamine, n-propylamine or n-butylamine.
By 3- amidos-acenaphthene made from step 3, simultaneously pyrazine -8,9 dintrile (4) is used to determine the micro-water content in tetrahydrofuran or Isosorbide-5-Nitrae-dioxane.
Beneficial effects of the present invention are：The acenaphthene of the present invention and synthetic method of Pyrazine Polar fluorescence probe is simple, raw material is easy to get, light and heat stability, Stokes displacements be big and excited by visible light and transmitting, polarity to environment is extremely sensitive, minor amount of water in detectable organic solvent, such as tetrahydrofuran or 1, the measure of micro-water content in 4- dioxane, the fluorescent spectrometry sensitivity is high, efficient and convenient, low cost.
Brief description of the drawings
Fig. 1 is the 3- n-butylamine-baseds-acenaphthene and fluorescence spectrum (λ ex=440nm) of pyrazine -8,9 dintrile (4d) in different solvents of the embodiment of the present invention 4.
Fig. 2 (a) is the 3- n-butylamine-baseds-acenaphthene and pyrazine -8 of the embodiment of the present invention 4,9 dintrile (4d) (10 μM) are in (the fluorescence spectrum change (λ ex=455nm) in V/V, 0~tetrahydrofuran solution 9.00%) of different water contents.
Fig. 2 (b) be the embodiment of the present invention 4 3- n-butylamine-baseds-acenaphthene and pyrazine -8,9 dintrile (4d) 613nm locate standardized fluorescent signal response with tetrahydrofuran in water volume fraction change.
Fig. 3 (a) is the 3- n-butylamine-baseds-acenaphthene and pyrazine -8 of the embodiment of the present invention 4,9 dintrile (4d) (10 μM) are in different water content (V/V, fluorescence spectrum change (λ ex=440nm) in 0~Isosorbide-5-Nitrae-dioxane solution 9.00%)；
Fig. 3 (b) is the change of 3- n-butylamine-baseds-acenaphthene and pyrazine -8,9 dintrile (4d) water volume fraction during fluorescence intensity is with Isosorbide-5-Nitrae-dioxane at the 582nm of the embodiment of the present invention 4.
Fig. 4 is nucleus magnetic hydrogen spectrum figure (the solvent DMSO-d of 3- n-butylamine-baseds-acenaphthene of the embodiment of the present invention 4 and pyrazine -8,9 dintrile (4d)6)。
Embodiment
Below by embodiment, the present invention is further illustrated, the purpose is to be best understood from present disclosure, but for embodiment be not intended to limit protection scope of the present invention：
Embodiment 1：The synthesis of 3- methylaminos-acenaphthene and pyrazine -8,9 dintrile (4a)
(1) synthesis of 5- bromines acenaphthenequinone (2)
In two mouthfuls of flasks of 500mL, acenaphthenequinone (20g, 110mmol) and bromine (25mL, 467mmol) are added, stirring, oil bath heating after reaction backflow 2h, stops reaction, add aqueous solution of sodium bisulfite to 60~70 DEG C, is colourless to reaction solution.After being diluted with water, suction filtration is depressurized, and mashing is washed with massive laundering, to pH=7.0.Filter cake recrystallizes 4 times to obtain 5- bromine acenaphthenequinones, brown color acicular crystal, yield 80% in glacial acetic acid.
1H NMR (400MHz, DMSO-d6)δ(ppm)：(d, J=7.6Hz, the 1H) of 8.39 (d, J=8.4Hz, 1H), 8.21 (d, J=7.6Hz, 1H), 8.15 (d, J=7.2Hz, 1H), 8.04 (t, J=7.8Hz, 1H), 7.96
(2) synthesis of the bromo- acenaphthenes of 3- and pyrazine -8,9 dintrile (3)
5- bromine acenaphthenequinones (400mg is added in two mouthfuls of flasks of 50mL, 1.54mmol) with diaminomaleonitrile (220mg, 2.14mmol), 20mL glacial acetic acid is then added, it is stirred and heated to 116~118 DEG C of backflow 2h, during cooling is fallen back, filtering, silicagel column separating-purifying (dichloromethane/petroleum ether after drying, 3: 1), obtain the bromo- acenaphthenes of foresythia 3- and pyrazine -8,9 dintrile, yield 67.7%.
1H NMR (400MHz, CDCl3)δ(ppm)：(t, J=8.4Hz, the 1H) of 8.57 (d, J=6.8Hz, 1H), 8.49 (d, J=8.4Hz, 1H), 8.34 (d, J=7.6Hz, 1H), 8.19 (d, J=7.2Hz, 1H), 8.04
(3) synthesis of 3- methylaminos-acenaphthene and pyrazine -8,9 dintrile (4a)
Take the bromo- acenaphthenes of 3- and pyrazine -8; 9 dintrile (1mmol) add 20mL glycol monoethyl ethers, under stirring in 50mL round-bottomed flasks; methylamine (6mmol) is added dropwise; 124 DEG C of backflow 1h are heated under Ar protections, solution graduates into peony by light yellow, and vacuum rotary steam removes glycol monoethyl ether; obtain red solid; silicagel column separating-purifying, obtains red powder solid, yield 61.8%.
1H NMR (400MHz, DMSO-d6)δ(ppm)：8.80 (d, 1H), 8.54 (d, 1H), 8.45 (s, 1H), 8.32 (d, 1H), 7.86 (t, 1H), 6.93 (d, 1H), 3.49 (t, 3H) .TOF MS (ES-) m/z [C20H14N5]-Calcd for 282.0785, found：282.0780.
Embodiment 2：The synthesis of 3- ethylamino-s-acenaphthene and pyrazine -8,9 dintrile (4b)
First two steps reaction is in the same manner as in Example 1, takes the bromo- acenaphthenes of 3- and pyrazine -8,9 dintrile (1mmol) is in 50mL round-bottomed flasks; add 20mL glycol monoethyl ethers; under stirring, ethamine (5mmol) is added dropwise, 125 DEG C of backflow 2h are heated under Ar protections; solution graduates into peony by light yellow; vacuum rotary steam removes glycol monoethyl ether, obtains red solid, silicagel column separating-purifying; obtain red powder solid, yield 60.5%.
1H NMR (400MHz, DMSO-d6)δ(ppm)：8.78 (d, J=8.4,1H), 8.56 (d, J=7.2,1H), 8.48 (s, 1H), 8.31 (d, J=8.4,1H), 7.87 (t, J=7.8,1H), 6.89 (d, J=8.4,1H), 3.46 (m, 2H), 1.77 (t, 3H) .TOF MS (ES-) m/z [C20H14N5]-calcd for 296.0942, found：296.0938.
Embodiment 3：The synthesis of 3- Propylaminos-acenaphthene and pyrazine -8,9 dintrile (4c)
First two steps reaction is in the same manner as in Example 1, takes the bromo- acenaphthenes of 3- and pyrazine -8,9 dintrile (1mmol) is in 50mL round-bottomed flasks; add 20mL glycol monoethyl ethers; under stirring, n-propylamine (4mmol) is added dropwise, 126 DEG C of backflow 3h are heated under Ar protections; solution graduates into peony by light yellow; vacuum rotary steam removes glycol monoethyl ether, obtains red solid, silicagel column separating-purifying; red powder solid, yield 62.3%.
1H NMR (400MHz, DMSO-d6)δ(ppm)：8.83 (d, 1H), 8.50 (d, 1H), 8.49 (s, 1H), 8.29 (d, 1H), 7.85 (t, 1H), 6.92 (d, 1H), 3.47 (m, 2H), 1.72 (m, 2H), 1.49 (t, 3H) .TOF MS (ES-) m/z [C20H14N5]-Calcd for 310.1098, found：310.1091.
Embodiment 4：The synthesis of 3- n-butylamine-baseds-acenaphthene and pyrazine -8,9 dintrile (4d)
First two steps reaction is in the same manner as in Example 1, takes the bromo- acenaphthenes of 3- and pyrazine -8,9 dintrile (1mmol) is in 50mL round-bottomed flasks; add 20mL glycol monoethyl ethers; under stirring, n-butylamine (4mmol) is added dropwise, 126 DEG C of backflow 3h are heated under Ar protections; solution graduates into peony by light yellow; vacuum rotary steam removes glycol monoethyl ether, obtains red solid, silicagel column separating-purifying; obtain red powder solid, yield 58.8%.Its nucleus magnetic hydrogen spectrum figure is as shown in Figure 4.
1H NMR (400MHz, DMSO-d6)δ(ppm)：8.82 (d, J=8.4,1H), 8.55 (d, J=7.2,1H), 8.49 (s, 1H), 8.30 (d, J=8.4,1H), 7.88 (t, J=7.8,1H), 6.90 (d, J=8.4,1H), 3.48 (m, 2H), 1.74 (m, 2H), 1.47 (dd, J=15.0,7.4,2H), 0.97 (t, J=7.3,3H) .TOF MS (ES-) m/z [C20H14N5]-Calcd for 324.1255, found：324.1249.
Embodiment 5：The test of probe 4d Photophysics in different solvents
Comprise the following steps that：
(1) the compound 4d synthesized in 3.25mg embodiments 1 is weighed with the balance for being accurate to 0.01mg, is added in 10mL volumetric flask, then 1.00 × 10 are made into dichloromethane constant volume-3Mol/L mother liquor.
(2) the above-mentioned μ L of mother liquor 100 are pipetted respectively with microsyringe to be added in the volumetric flask as done 10mL, then dichloromethane is evaporated, it is slightly cold, it is configured to prepare liquid with different solvents constant volume respectively.
(3) ultraviolet measurement：First neat solvent is placed in 1cm quartz colorimetric utensils and sweeps blank, then solution to be measured is placed in same quartz colorimetric utensil and measured.
(4) measurement of fluorescence：Solution to be measured is placed in 1cm quartz colorimetric utensils, in excitation wavelength 440nm, slit width (Ex)：5nm, (Em)：Measured under conditions of 3nm.
(5) test of fluorescence quantum yield：With the fluorescein (Φ=0.9) that is dissolved in the 0.1mol/L NaOH aqueous solution for standard.The first step, ultraviolet test is carried out by above-mentioned (3), the concentration of fluorescein is adjusted, until obtained the maximum absorption is between 0.05~0.1.Second step, will adjust the luciferin solution of concentration in the first step, carry out fluorometric investigation, adjust excitation wavelength and test condition to ensure that fluorescence spectrum has complete peak type.3rd step, above two steps (excitation wavelength being removed during fluorometric investigation, other parameters can not change) is repeated by the prepare liquid in above-mentioned (2).4th step, is calculated according to below equation (1).
Φ in formulas, Φr--- the fluorescence quantum yield for treating test sample and reference material is represented respectively；
As, Ar--- represent treat the absorbance of test sample and reference material under used excitation wavelength respectively；
Fs, Fr--- the peak area in the fluorescence spectrum for treating test sample and reference material is represented respectively；
λs, λr--- the excitation wavelength for treating test sample and reference material is represented respectively；
ns, nr--- the refractive index for treating test sample and reference material solvent for use is represented respectively.
Test carbon tetrachloride, toluene, ether, 1,4- dioxane, chlorobenzene, butyl chloride, tetrahydrofuran, ethyl acetate, dichloromethane, chloroform, 1,2- dichloroethanes, methyl acetate, acetone, N, influence of the solvent of 15 kinds of opposed polarities of dinethylformamide (DMF) and acetonitrile (polarity is from small to large) to fluorescence probe 4d Photophysics, as a result as shown in table 1.Fluorescence probe 4d maximum emission wavelength has 100nm or so Stokes displacements.Generally, with the increase of solvent polarity, compound 4d ultraviolet maximum absorption band and fluorescence maximum emission peak all there occurs red shift, and quantum yield is significantly reduced, weaken from carbon tetrachloride (Φ f=0.3642) to acetonitrile (Φ f=0.0006) fluorescence quantum yield more than 600 times.
Photophysics of the compound 4d of table 1 in different solvents
* fluorescence quantum yield test is for standard with the fluorescein (Φ=0.9) being dissolved in the 0.1mol/L NaOH aqueous solution.In addition, influence of the solvent of this 15 kinds of opposed polarities to fluorescence probe 4d fluorescence spectrum, as shown in Figure 1.With the increase of solvent polarity, fluorescence intensity is significantly reduced.Because fluorescence probe 4d one end is using the amino straight chain of flexible side-chains as electron-donating group, the other end is using two cyano group as electron withdraw group, form the big planar conjugate system of push-and-pull electronics, this make it that 4d has very strong dipole moment, this fluorescence probe with strong dipole most possibly shows very strong dependence to solvent, and medium polarity increase can promote nonradiative relaxation process, radiation transistion is accordingly reduced.Probe 4d maximum emission wavelength 118nm from carbon tetrachloride to DMF red shifts, similar probe 1- methylaminos -5- cyano group naphthalene (from n-hexane to bright pink shifting 99nm) effect than it is more preferable；Widely used polarity probes PRODAN (from hexamethylene to bright pink shifting 130nm), from toluene to acetonitrile ability red shift 41nm, and probe 4d from toluene to acetonitrile red shift 82nm, be twice of PRODAN.
Embodiment 6：The measure of water content in tetrahydrofuran
In anhydrous and oxygen-free reaction, tetrahydrofuran is that a kind of success or not of how many pairs of experiments of moisture in conventional solvent, tetrahydrofuran solvent often plays conclusive effect.In order to further study fluorescence probe 4d property and application value, the water content using fluorescence probe 4d to this sensitive nature examination of solvent polarity in tetrahydrofuran is comprised the following steps that：
(1) take 1mL water to be added in 100mL volumetric flask, use tetrahydrofuran constant volume.
(2) the μ L of mother liquor 100 in embodiment 2 (1) are pipetted respectively with microsyringe to be added in the volumetric flask as done 10mL, then dichloromethane is evaporated, it is slightly cold.
(3) the μ L of solution 100 prepared in (1), 200 μ L, 300 μ L, 500 μ L, 700 μ L, 1mL, 2mL, 3mL, 5mL, 7mL are pipetted respectively to be added in the volumetric flask in (2), are then configured to prepare liquid with tetrahydrofuran constant volume.
(4) the μ L of water 100,200 μ L, 300 μ L, 500 μ L, 700 μ L are pipetted respectively to be added in the volumetric flask in (2), are then configured to prepare liquid with tetrahydrofuran constant volume.
(5) measurement of fluorescence：Solution to be measured is placed in 1cm quartz colorimetric utensils, in excitation wavelength 455nm, slit width (Ex)：5nm, (Em)：Measured under conditions of 10nm.
With the increase of water content in tetrahydrofuran, fluorescence intensity is gradually reduced, shown in such as accompanying drawing 2 (a), and red shift occurs for maximum emission wavelength.When water content volume fraction from 0% increases to 1.00%, fluorescence intensity drops quickly to 163 by 429；When water content volume fraction increases to 9.00% by 1.00%, the trend that fluorescence intensity reduces weakens, and 34 are down to from 163.When water content volume fraction from 0% increases to 9.00%, maximum emission wavelength red shift 19nm altogether.Pass through fluorescence datas of the sniffing probe 4d in the tetrahydrofuran solution of different water contents, it was found that good linear relationship is presented between the logarithm value of tetrahydrofuran water content and the fluorescence intensity of standardization, obtain shown in linear regression curves such as accompanying drawing 2 (b), linear equation is：(Imax-I)/(Imax-Imin)=1.37771+0.37055log [H2O], coefficient correlation is 0.97751.Water content corresponding to the intersection point of the straight line and abscissa is 0.019%, so the detectable limit for understanding the method is 0.019%.
Embodiment 7：The measure of water content in Isosorbide-5-Nitrae-dioxane
In anhydrous and oxygen-free reaction, except tetrahydrofuran, Isosorbide-5-Nitrae-dioxane is also a kind of conventional solvent.Renatus W.Sinkeldam et al. have synthesized the probe 2- phenylene-ethynylene Fluorenones to water sensitive, and have studied spectrum change of the probe in water and Isosorbide-5-Nitrae-dioxane mixed solvent, but not used for the detection of water content in Isosorbide-5-Nitrae-dioxane.The present invention determines the water content in Isosorbide-5-Nitrae-dioxane with probe 4d, comprises the following steps that：
(1) 1mL water is taken to be added in 100mL volumetric flask, with Isosorbide-5-Nitrae-dioxane constant volume.
(2) the μ L of mother liquor 100 in embodiment 2 (1) are pipetted respectively with microsyringe to be added in the volumetric flask as done 10mL, then dichloromethane is evaporated, it is slightly cold.
(3) the μ L of solution 50 prepared in (1), 100 μ L, 200 μ L, 300 μ L, 500 μ L, 700 μ L, 1mL, 1.5mL, 2mL, 3mL, 5mL, 7mL, 9mL are pipetted respectively to be added in the volumetric flask in (2), then it is configured to prepare liquid with Isosorbide-5-Nitrae-dioxane constant volume.
(4) the μ L of water 100,150 μ L, 200 μ L, 300 μ L, 500 μ L, 700 μ L, 900 μ L are pipetted respectively to be added in the volumetric flask in (2), are then configured to prepare liquid with Isosorbide-5-Nitrae-dioxane constant volume.
(5) measurement of fluorescence：Solution to be measured is placed in 1cm quartz colorimetric utensils, in excitation wavelength 440nm, slit width (Ex)：5nm, (Em)：Measured under conditions of 5nm.
With the increase of water content in Isosorbide-5-Nitrae-dioxane, fluorescence intensity is gradually reduced, shown in such as accompanying drawing 3 (a).As water content volume fraction from 0% increases to 1.00%, fluorescence intensity drops quickly to 233 by 861；When water content volume fraction increases to 9.00% by 1.00%, the trend that fluorescence intensity reduces weakens is down to 10 from 233.When water content volume fraction from 0% increases to 9.00%, maximum emission wavelength red shift 38nm altogether.Pass through fluorescence datas of the sniffing probe 4d in the tetrahydrofuran solution of different water contents, it was found that 1, water content volume fraction in 4- dioxane is at 0~1.00%, good linear relationship is presented between water content and fluorescence intensity, obtain shown in linear regression curves such as Fig. 3 (b), linear equation is：I=823.58414-6.58346 [H20], coefficient correlation is 0.97087.Empirically method carries out 11 blank assays, and it is 1.67 to try to achieve standard deviation S, and it is 0.0076% to calculate this law detectable limit according to 3SPK.
Claims (1)
1. it is a kind of using acenaphthene and pyrazine as the application of the highly sensitive Polar fluorescence probe of parent, it is characterised in that described fluorescence probe has following general structure：
Wherein, R is normal-butyl, and described fluorescence probe is applied in the micro-water content of tetrahydrofuran or Isosorbide-5-Nitrae-dioxane is determined.
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| CN104804723A (en) * | 2014-01-28 | 2015-07-29 | 中国科学院大连化学物理研究所 | DCDHF chromophore-based solvatochromic fluorescence probes, and preparation method and application thereof |
| CN104531134B (en) * | 2014-12-16 | 2016-08-31 | 北京理工大学 | The fluorescent probe of a kind of polar sensitive, preparation method and application |
| CN111995589B (en) * | 2015-11-10 | 2023-12-05 | 国立大学法人九州大学 | Process for producing 2, 5-dicyano-3, 6-dihalopyrazine |
| CN109796435B (en) * | 2016-06-08 | 2020-05-12 | 中节能万润股份有限公司 | Organic photoelectric material and organic electroluminescent device including the same |
| CN106433186B (en) * | 2016-09-05 | 2018-01-30 | 大连理工大学 | Fluorescence dichroic dye of the one kind containing the 4 biphenyl acetylene acenaphthenes simultaneously dintrile of [1,2 b] pyrazine 8,9, its preparation method and application |
| CN108558702B (en) * | 2018-05-11 | 2020-07-17 | 郑州大学 | Naphthoquinone-based bisulfite fluorescent probe and preparation and application thereof |
| CN109912617B (en) * | 2019-04-03 | 2021-05-07 | 山东大学 | Fluorescence ratio probe for reversibly detecting water content in organic solvent and application thereof |
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| CN102634333A (en) | 2012-08-15 |
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