CN107721837A - That detects more nitrogen azole heterocyclic compounds lights type fluorescence probe and preparation method thereof - Google Patents
That detects more nitrogen azole heterocyclic compounds lights type fluorescence probe and preparation method thereof Download PDFInfo
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Abstract
Type fluorescence probe and preparation method thereof is lighted the present invention relates to a kind of more nitrogen azole heterocyclic compounds of detection, belongs to fluorescence chemical sensor technical field.The fluorescence probe is formulated by HPB ID, organic solvent and water, and for the fluorescence probe for containing more than 3 nitrogen-atoms and for more nitrogen azole heterocyclic compounds of 5 ring structures there is type of lighting to respond, detection limit reaches ng levels；And the fluorescence probe can exclude the interference of other orthodox explosives and phenodiazine azole compounds for having good specific selectivity containing more than 3 nitrogen-atoms and for more nitrogen azole heterocyclic compounds of 5 ring structures.Fluorescence probe preparation method of the present invention is simple, and detection is easy to operate, practical, easy to spread.
Description
Technical field
It is more particularly to a kind of to be used to detect with height the present invention relates to a kind of fluorescence probe for detecting high Energy Density Materials
More nitrogen azole heterocyclic compounds of energy density light type fluorescence probe and preparation method thereof, belong to fluorescence chemical sensor skill
Art field.
Background technology
High Energy Density Materials (high energy density material, HEDM) are made up of high energy component, are referred to
Unit volume/quality contains the material of high potential, the i.e. energetic material with high-energy-density, available for manufacture explosive, promotes
Agent or priming system.Because more nitrogen azole heterocyclic compound nitrogen contents are high, the high energy such as substantial amounts of N-N keys and N-C keys are contained in molecule
The chemical bond of amount, have the advantages that generation heat is high, density is high and is easier to reach zero oxygen balance, and catabolite pollution journey
Spend low.Therefore, more nitrogen azole heterocyclic compounds turn into one of study hotspot of current high-energy-density energetic material.
In more nitrogen azole heterocyclic compounds, 3- nitros -1,2, the ketone of 4- triazoles -5 (3-nitro-1,2,4-triazol-5-
One, abbreviation NTO) it is to be up to 1.93g/ by a kind of representative high Energy Density Materials of most attention, its density in recent years
cm3.It is reported that NTO detonation energies are close to hexogen (RDX), but sensitivity is similar to photoacoustic spectroscopy (TATB), is one
Kind has feels explosive immediately very much using the Low vulnerability to advance.NTO small toxicities, raw material are cheap and easy to get, easily prepare, with other materials
Compatibility is preferable, and the research about its synthesis, performance and application etc. have received concern universal both at home and abroad, and obtain extensively
Application.Equally, other derivatives of triazole are also good explosive candidate material.And 1,5- diaminourea tetrazolium (DAT) contains
Nitrogen quantity is higher, while has the higher positive enthalpy of formation and good heat endurance, is tetrazole high-energy-density energetic material
Representative.
Because it is certain that more nitrogen azole heterocyclic compounds in the outstanding application in explosive field, make it have in daily life
Danger, at present the crowded place such as airport, subway station, market and cinema be both provided with explosive detection approach,
But detection method is complicated, cost height adds the difficulty to safety guarantee so that criminal has an opportunity to take advantage of, and gives life safety
Certain threat is brought with government utility.
The method of currently used detection explosive has chromatogram mass spectrography, colorimetric method, fluorescence method, FRET
Method, electrochemical process and Surface Plasmon Resonance etc..Wherein, fluorescence method due to it is simple to operate, cost is low, detection speed soon with
And the advantages that high sensitivity and be used widely.At present, explosive is mainly utilized using the method for fluoroscopic examination explosive
Contained nitro acts on chromophore in light emitting molecule in molecule, its fluorescence efficiency is quenched, so as to reach detected purpose.
But what this detection method was applied to detection is trinitro- benzene derivate, such as trinitrophenol (PA) and trinitrotoluene
(TNT), because the nitrogen content of trinitrobenzen derivative is relatively low, with the development of science and technology, PA and TNT are gradually nitrogenous by other height
The high Energy Density Materials of amount are substituted；In addition, this detection method based on Fluorescence quenching mechanism be vulnerable to application environment with
The interference of condition, testing result should not be observed, or even easily produce false detection signal, limit further application
(Dongdong Li,Jianzhao Liu,Ryan T.K.Kwok,Zhiqiang Liang,Ben Zhong Tang and
Jihong Yu,Supersensitive detection of explosives by recyclable AIE luminogen-
functionalized mesoporous materials.Chem.Commun.,2012,48,7167-7169；Yingxin
Ma,Hao Li,Shan Peng,and Leyu Wang,Highly Selective and Sensitive Fluorescent
Paper Sensor for Nitroaromatic Explosive Detection.Anal.Chem.2012,84,8415-
8421；Jianzhao Liu,Yongchun Zhong,Ping Lu,Yuning Hong,Jacky W.Y.Lam,Mahtab
Faisal,Yong Yu,Kam Sing Wong and Ben Zhong Tang,A superamplification effect
in the detection of explosives by a fluorescent hyperbranched poly
(silylenephenylene)with aggregation-enhanced emission
characteristics.Polym.Chem.,2010,1,426-429；Shu-Ran Zhang,Dong-Ying Du,Jun-
Sheng Qin,Shao-Juan Bao,Shun-Li Li,WenWen He,Ya-Qian Lan,Ping Shen,and Zhong-
Min Su,A Fluorescent Sensor for Highly Selective Detection of Nitroaromatic
Explosives Based on a 2D,Extremely Stable,Metal–Organic
Framework.Chem.Eur.J.2014,20,3589-3594).Due to the limitation of the two defects, Fluorometric assay blast
Thing, especially high Energy Density Materials, although of great interest in recent years, never obtain adequate solution and
Break through.
Disadvantages mentioned above can largely be overcome by lighting the fluorescent method of type detection explosive, because it is with higher
Detection sensitivity and stronger specificity.Chemistry institute of Beijing Institute of Technology Wang Bo professors et al. synthesized one kind in 2014
Metal organic framework (Metal Organic Framework, MOF) material, realize that there is NTO and light type detection, be mesh
Before almost unique " turn-on " type fluorescent chemicals (Yuexin Guo, Xiao in the relevant explosive detection that can retrieve
Feng,Tianyu Han,Shan Wang,Zhengguo Lin,Yuping Dong,and Bo Wang,Tuning the
Luminescence of Metal-Organic Frameworks for Detection of Energetic
Heterocyclic Compounds.J.Am.Chem.Soc.2014,136,15485-15488).However, the MOF materials can only
Realized for NTO and light type detection, that is, there is very strong specificity, it is impossible to realize the detection to more nitrogen azoles, this is unfavorable for reality
Apply on border.Therefore, realize that the detection that quick, sensitive " lighting " type fluorescence is carried out to explosive increasingly turns into research work at this stage
The popular research of person.
The content of the invention
Because current most of detections to explosive are required for large-scale equipment, complicated program, wherein using more
Fluorometric assay nearly all be quenching, the difficulty added to explosive detection of these problem high degrees.For upper
State problem, it is an object of the invention to provide it is a kind of detect more nitrogen azole heterocyclic compounds light type fluorescence probe, it is described glimmering
Light probe has for more nitrogen azole heterocyclic compounds lights type response and good specific selectivity, and test limit reaches ng
Level；The fluorescence probe preparation method is simple, easy to operate, practical, easy to spread.
The purpose of the present invention is realized by following technical scheme：
A kind of more nitrogen azole heterocyclic compounds of detection light type fluorescence probe, and the fluorescence probe is by HPB-ID, had
What solvent and water were formulated；
Wherein, organic solvent is tetrahydrofuran, dimethyl sulfoxide (DMSO), acetonitrile or DMF, preferably tetrahydrochysene furan
Mutter；The volume ratio of organic solvent and water is 1:9, HPB-ID the concentration of organic solvent and the in the mixed solvent of water be 1 × 10- 3Mol/L~1 × 10-5Mol/L, HPB-ID, 2,2'- ((1E, 3E) -1,2,3,4- tetraphenyls -1,3-butadiene-Isosorbide-5-Nitrae-substitution)
Two -1.3 indandione rodenticides, its structural formula are as follows：
The nitrogen-atoms numbers contained in more nitrogen azole heterocyclic compounds are no less than 3, and are five-membered ring structure, such as substituted
Triazole, tetrazole etc..
A kind of preparation method for lighting type fluorescence probe of the more nitrogen azole heterocyclic compounds of detection of the present invention, it is described
Method comprises the following steps that：
(1) catalyst I, good solvent I, 4- formylphenylboronic acids and tolans are added in reactor, and is passed through protection
Gas, at 90 DEG C~120 DEG C after stirring reaction 40min~80min, filtering, the filtrate of collection is spin-dried for, obtains crude product I；Will
Crude product I is dissolved in good solvent II, separating-purifying, is dried, is obtained product I；
Wherein, the catalyst I is the mixture of silver carbonate and palladium, the ratio between amount of material of silver carbonate and palladium
It is preferred that 1:(0.025~0.035)；
The mixed solvent of the I preferred normal propyl alcohol of good solvent and water, or acetonitrile；Wherein, the volume ratio of normal propyl alcohol and water is excellent
Select 9:1；
The mol ratio preferably 1 of the 4- formylphenylboronic acids, tolans and silver carbonate:(1~1.2):1；
II preferred dichloromethane of good solvent, chloroform, tetrahydrofuran or the ethyl acetate；
The separating-purifying preferably uses pillar layer separation, using petroleum ether and dichloromethane as eluant, eluent；Wherein, petroleum ether
With the mass ratio preferably 1 of dichloromethane:2.5；
The preferred N of protective gas2Or Ar；
(2) product I, indandione rodenticide and solvent III are added in reaction vessel, after reacting 3h~5h at 70 DEG C~90 DEG C, taken out
Filter, separating-purifying, dry, obtain HPB-ID；
Or add product I, indandione rodenticide, solvent III and catalyst II in reaction vessel, reacted at 50 DEG C~70 DEG C
After 1h~3h, filter, separating-purifying, dry, obtain HPB-ID；
Wherein, the mol ratio of product I and indandione rodenticide is 1:(2~3), preferably 1:2.4；Catalyst II is morpholine or three
The weak alkali catalyst such as ethamine, the mol ratio with product I are 1~5:100；Solvent III is that ethanol or methanol etc. can dissolve production
The organic solvent of thing I but insoluble product HPB-ID, the addition of solvent III are product I and indandione rodenticide is fully dissolved；
(3) HPB-ID is dissolved in the in the mixed solvent of organic solvent and water, is well mixed, obtains the fluorescence probe.
Beneficial effect：
(1) fluorescence probe of the present invention has aggregation-induced emission property, miscellaneous to more nitrogen azoles of high-energy-density
Cycle compound (such as NTO, DTA), which has, lights type response, and detection limit reaches ng levels；
(2) fluorescence probe of the present invention has good specific selectivity, can exclude other high density material containing energy
Material, such as TNT, HMX, RDX etc. interference；
(3) fluorescence probe preparation method of the present invention is simple, easy to operate.
Brief description of the drawings
Fig. 1 is HPB-ID in THF/H2Fluorescence intensity spectrogram inside O different mixing proportions；
Fig. 2 is the fluorescence intensity of HPB-ID fluorescence probes with the increasing of NTO (ketone of 3- nitro -1,2,4- triazoles -5) content
Add and increased fluorogram；
Fig. 3 is the fluorescence intensity (I-I to HPB-ID fluorescence probes0)/I0Relation between NTO content is fitted straight
Line chart；
Fig. 4 is addition 2 × 10-7After mol (2.6ng) NTO, the fluorescence intensity of HPB-ID fluorescence probes increases over time
And increased fluorogram；
Fig. 5 is addition 2 × 10-7After mol (2.0ng) DAT (1,5- diaminourea tetrazolium), the fluorescence of HPB-ID fluorescence probes is strong
Degree increases over time and increased fluorogram；
Fig. 6 is addition 2 × 10-7After mol (2.3ng) NT (3- nitros -1,2,4- triazoles), the fluorescence of HPB-ID fluorescence probes
Intensity increases over time and increased fluorogram；
Fig. 7 is addition 2 × 10-7After mol (2.7ng) CTO (3- chloroethyls -1,2, the ketone of 4- triazoles -5), HPB-ID fluorescence is visited
The fluorescence intensity of pin increases over time and increased fluorogram；
Fig. 8 is addition 2 × 10-7After mol (4.6ng) PA (trinitrophenol), the fluorescence intensities of HPB-ID fluorescence probes with
The fluorogram the increase of time and reduced；
Fig. 9 is addition 2 × 10-7Mol (4.5ng) TNT (trinitrotoluene), the fluorescence intensities of HPB-ID fluorescence probes with
The fluorogram the increase of time and reduced；
Figure 10 is addition 2 × 10-7After mol (5.9ng) HMX (cyclotetramethylene-tetranitramine), HPB-ID fluorescence probes it is glimmering
Luminous intensity increases over time and almost unchanged fluorogram；
Figure 11 is addition 2 × 10-7After mol (4.4ng) RDX (cyclotrimethylene trinitramine), HPB-ID fluorescence probes it is glimmering
Luminous intensity increases over time and increased fluorogram；
Figure 12 is addition 2 × 10-7After mol (3.1ng) CL-20 (Hexanitrohexaazaisowurtzitane), HPB-ID fluorescence is visited
The fluorescence intensity of pin increases over time and almost unchanged fluorogram；
Figure 13 is addition 2 × 10-7After mol (1.6ng) N-IM (N- methylimidazoles), the fluorescence intensity of HPB-ID fluorescence probes
Increase over time and almost unchanged fluorogram；
Figure 14 is addition 2 × 10-7After mol (3.2ng) 2N-IM (carbonyl dimidazoles), the fluorescence of HPB-ID fluorescence probes is strong
Degree increases over time and increased fluorogram；
Figure 15 is addition 2 × 10-7After mol (1.3ng) IM (imidazoles), the fluorescence intensity of HPB-ID fluorescence probes is over time
Increase and almost unchanged fluorogram；
After Figure 16 is adds above-mentioned substance, the change in fluorescence of the fluorescence intensities of HPB-ID fluorescence probes after 270s collects
Figure.
Figure 17 is in the case of the presence of other explosives, and NTO anti-interference is detected.
Embodiment
The present invention is described in detail with reference to specific embodiment, wherein, methods described is conventional method unless otherwise instructed,
The raw material can obtain from open commercial sources unless otherwise instructed.
The main agents information mentioned in following examples is shown in Table 1, and key instrument is shown in Table 2 with facility information.
Table 1
Table 2
Embodiment 1
A kind of preparation process for lighting type fluorescence probe of the more nitrogen azole heterocyclic compounds of detection is as follows：
(1) by 2.00mmol 4- formylphenylboronic acids, 2.00mmol tolans, 0.05mmol palladiums, 2.00mmol
Silver carbonate, 4.5mL normal propyl alcohols and 0.5mL water are added in 25mL there-necked flask, and are passed through nitrogen, the stirring reaction at 120 DEG C
After 60min, filter and be spin-dried for filtrate, obtain crude product I；Crude product I is dissolved in 5mL dichloromethane, with petroleum ether and
Dichloromethane is eluant, eluent (mPetroleum ether：mDichloromethane=1:2.5), purified with pillar layer separation, obtain yellow product I；
(2) 0.1mmol products I and 0.24mmol indandione rodenticides are added in 25mL three-necked flasks, it is anhydrous adds 10mL
Ethanol, under agitation in 80 DEG C of back flow reaction 5h, filter, and the solid matter collected is rinsed with absolute ethyl alcohol, obtain red solid
Body HPB-ID；
(3) HPB-ID is dissolved in THF (tetrahydrofuran), obtained containing 2 × 10-4Mol/L HPB-ID THF solution；
The 300 above-mentioned THF solutions of μ L are mixed with 2700 μ L deionized waters, obtained containing 2 × 10-5Mol/L HPB-ID mixed solution,
The solution is the fluorescence probe.
Embodiment 2
A kind of preparation process for lighting type fluorescence probe of the more nitrogen azole heterocyclic compounds of detection is as follows：
(1) by 2.00mmol 4- formylphenylboronic acids, 2.00mmol tolans, 0.05mmol palladiums, 2.00mmol
Silver carbonate, 4.5mL normal propyl alcohols and 0.5mL water are added in 25mL there-necked flask, and are passed through nitrogen, the stirring reaction at 120 DEG C
After 60min, filter and be spin-dried for filtrate, obtain crude product I；Crude product I is dissolved in 5mL dichloromethane, with petroleum ether and
Dichloromethane is eluant, eluent (mPetroleum ether：mDichloromethane=1:2.5), purified with pillar layer separation, obtain yellow product I；
(2) 0.1mmol products I and 0.24mmol indandione rodenticides are added in 25mL three-necked flasks, it is anhydrous adds 10mL
Ethanol and 0.05mL triethylamines, under agitation in 70 DEG C of back flow reaction 2h, filter, and the solids collected is rinsed with absolute ethyl alcohol
Matter, obtain red solid HPB-ID；
(3) HPB-ID is dissolved in THF (tetrahydrofuran), obtained containing 2 × 10-4Mol/L HPB-ID THF solution；
The 300 above-mentioned THF solutions of μ L are mixed with 2700 μ L deionized waters, obtained containing 2 × 10-5Mol/L HPB-ID mixed solution,
The solution is the fluorescence probe.
Performance characterization
(1) nucleus magnetic hydrogen spectrum and mass spectral characteristi
By nuclear magnetic resonance chemical analyser and mass-spectroscopic characterization, it is prepared into (2) the step of embodiment 1 and embodiment 2
To red solid be HPB-ID, its nucleus magnetic hydrogen spectrum and mass spectrometric data are as follows：
1H-NMR(400MHz,DMSO)δ(ppm)：8.61 (s, 1H), 8.59 (s, 1H), 8.23 (s, 4H), 8.21 (s,
4H), 8.05-7.96 (m, 4H), 7.84-7.77 (m, 4H), 7.20-6.94 (m, 10H)；
MS(MALDI-TOF):Calculated value C48H30N4, 822.28；Test value 822.3.
(2) aggregation-induced emission (Aggregation-induced emission abbreviation AIE) property representation
HPB-ID is dissolved in the in the mixed solvent of 10 parts of tetrahydrofurans and deionized water respectively, is well mixed, the 10 of gained
HPB-ID even concentration is 2 × 10 in part mixed solution-5, the body of deionized water and tetrahydrofuran in above-mentioned 10 parts of mixed solutions
Product ratio is followed successively by 0:100、10:90、20:80、30:70、40:60、50:50、60:40、70:30、80:20、90:10；Use again
Fluorophotometric instrument tests the fluorescence intensity of above-mentioned 10 parts of mixed solutions respectively, and test result is as shown in Figure 1.As a result show, work as water
When content is less than 70%, mixed solution almost have fluorescence, when water content is higher than 70%, on fluorescence intensity is notable
Rise.It is typical AIE materials in the system of THF and water to illustrate HPB-ID.
(3) fluorescence intensity and the relation of content of material to be detected
The fluorescence probe (90% water content) prepared in 3mL embodiments 1 is taken, and its initial fluorescence is detected with fluorophotometric instrument
Intensity I0；Divide 10 tetrahydrofuran solutions that NTO is added into the probe, the NTO added every time tetrahydrofuran solution body again
Product is 10 μ L, contains 1 × 10 in the NTO added every time tetrahydrofuran solution-7mol(1.3ng)NTO；Add NTO's every time
After tetrahydrofuran solution, the fluorescence intensity I of the mixed solution is tested with fluorophotometric instrumenti(i is the NTO added tetrahydrofuran
The volume number of solution).Fluorescence probe according to prepared by testing result draws embodiment 1 is glimmering in the presence of different NTO contents
Spectrogram, refer to Fig. 2,3.
From figure 2 it can be seen that with the increase of NTO contents, fluorescence intensity increases therewith；When NTO molal quantity reaches 1
×10-6During mol, fluorescence intensity I100For 4967, (I100-I0)/I0For 2.5, illustrate that the fluorescence probe there is type of lighting to ring NTO
Should.From figure 3, it can be seen that the molal quantity in NTO is 0~6 × 10-7During mol, NTO molal quantity and fluorescence intensity ratio have
There is good linear relationship, the NTO of response content as the working curve of response, can be calculated according to fluorescence intensity.
(4) relation of fluorescence intensity and detection time
The fluorescence probe (90% water content) prepared in 3mL embodiments 1 is taken, and its initial fluorescence is detected with fluorophotometric instrument
Intensity I0；Then, 2.6ng NTO, and the fluorescence intensity I that test is added after NTO immediately are added into the fluorescence probeNTO,
Fluorescence intensity I after 30s tests once add NTO againi(i is to add after NTO the time tested).Painted according to testing result
Fluorogram of the fluorescence probe under different time is made, as shown in Figure 4.After 270s, (I270-I0)/I0For 2.4, illustrate this
Response of the probe to NTO has time dependence, is not instant response
On the basis of above-mentioned method of testing, 2.6ng NTO are replaced with into other more nitrogen azole compounds respectively：2.0ng
DAT, 2.3ng NT, 2.7ng CTO, other common explosives：4.6ng PA、4.5ng TNT、5.9ng HMX、4.4ng
RDX, 3.1ng CL-20, and the nitrogen azole compounds containing 2 nitrogen：1.6ng N-IM, 3.2ng 2N-IM, 1.3ng IM, other behaviour
Make step and test condition be constant, fluorogram of the fluorescence probe to compound under different time is drawn according to test result,
Refer to Fig. 5~15.It can be seen from test result, when being detected to DAT, NT, CTO, fluorescence intensity is with the increasing of detection time
Add and strengthen, after 270s, DTA (I270-I0)/I0For 1.1, NT (I270-I0)/I0For 1.93, CTO (I270-I0)/I0
For 1.63, illustrate that the probe all has to the nitrogen azoles that other contain more than three nitrogen and light type response；To other explosives PA,
When TNT, HMX, RDX, CL-20 are detected, PA and TNT fluorescence intensity decline to a great extent, HMX, and RDX and CL-20's is glimmering
Intensity variation is little, illustrates that the fluorescence probe has specificly-response for more nitrogen azoles explosives containing more than three nitrogen, and
Other explosives are not responded to, can be used as the probe for distinguishing explosive；To nitrogen azoles N-IM, 2N- containing 2 nitrogen
When IM, IM are detected, fluorescence intensity is almost unchanged, illustrates that the probe does not respond to ribavirin.
Fluorescence probe is aggregated into block diagram to the fluorescence after above-mentioned all kinds of material detection 270s, as shown in figure 16.Thus
Understand, fluorescence probe of the present invention has to more nitrogen azole heterocyclic compounds lights type test, to other common explosives
And phenodiazine azole compounds do not respond to.
(5) to the anti-interference research of other materials
60 μ L, which are prepared, with THF contains NTO (1.3ng), PA (2.3ng), TNT (2.3ng), HMX (2.9ng), RDX
(2.2ng) and CL-20 (1.5ng) solution I；40 μ L, which are prepared, with THF contains NTO (1.3ng), N-IM (0.8ng), 2N-IM
(1.6ng) and IM (0.7ng) solution II；50 μ L, which are prepared, with THF contains NTO (1.3ng), N-IM (0.8ng), 2N-IM
(1.6ng), HMX (2.9ng) and RDX (2.2ng) solution III；Contain NTO (1.3ng) solution with 10 μ L of THF preparations, as
Comparative solution；The fluorescence probe (90% water content) prepared in 4 parts of 3mL embodiments 1 is taken, and it is initial with fluorophotometric instrument to detect its
Fluorescence intensity I0；A fluorescence probe mixes with a above-mentioned solution, after mixing 270s, then detects the fluorescence of 4 parts of mixed solutions
Intensity, the results detailed in Figure 17,0,1,2,3 are corresponding in turn to comparative solution, solution I, solution II, the fluorescence intensity of solution III in figure.
From testing result as can be seen that the fluorescence intensity that the fluorescence probe detects to solution I, solution II, solution III and comparative solution
Almost almost, illustrate that the fluorescence probe has very strong anti-interference.
The present invention include but is not limited to above example, it is every carried out under the principle of spirit of the present invention it is any equivalent
Replacement or local improvement, all will be regarded as within protection scope of the present invention.
Claims (10)
1. a kind of more nitrogen azole heterocyclic compounds of detection light type fluorescence probe, it is characterised in that：The fluorescence probe be by
What HPB-ID, organic solvent and water were formulated；
Wherein, the organic solvent is tetrahydrofuran, dimethyl sulfoxide (DMSO), acetonitrile or DMF；The HPB-ID
For 2,2'- ((1E, 3E) -1,2,3,4- tetraphenyls -1,3-butadiene-Isosorbide-5-Nitrae-substitution) two -1.3 indandione rodenticides, its structural formula is as follows,
2. a kind of more nitrogen azole heterocyclic compounds of detection according to claim 1 light type fluorescence probe, its feature exists
In：The volume ratio of organic solvent and water is 1:9.
3. a kind of more nitrogen azole heterocyclic compounds of detection according to claim 1 light type fluorescence probe, its feature exists
In：HPB-ID is 1 × 10 in the concentration of organic solvent and the in the mixed solvent of water-3Mol/L~1 × 10-5mol/L。
4. a kind of more nitrogen azole heterocyclic compounds of detection according to claim 1 light type fluorescence probe, its feature exists
In：The fluorescence probe for nitrogen-atoms numbers no less than 3 and for five-membered ring structure more nitrogen azole heterocyclic compounds have light
Type responds.
5. a kind of more nitrogen azole heterocyclic compounds of detection as described in any one of Claims 1-4 light type fluorescence probe
Preparation method, it is characterised in that：Methods described comprises the following steps that,
(1) catalyst I, good solvent I, 4- formylphenylboronic acids and tolans are added in reactor, and is passed through protection gas,
At 90 DEG C~120 DEG C after stirring reaction 40min~80min, filtering, the filtrate of collection is spin-dried for, obtains crude product I；To slightly it produce
Thing I is dissolved in good solvent II, separating-purifying, is dried, is obtained product I；
(2) product I, indandione rodenticide and solvent III are added in reaction vessel, after reacting 3h~5h at 70 DEG C~90 DEG C, filtered,
Separating-purifying, dry, obtain HPB-ID；
Or will product I, indandione rodenticide, solvent III and catalyst II add reaction vessel in, at 50 DEG C~70 DEG C react 1h~
After 3h, filter, separating-purifying, dry, obtain HPB-ID；
(3) HPB-ID is dissolved in the in the mixed solvent of organic solvent and water, is well mixed, obtains the fluorescence probe；
Wherein, catalyst I is silver carbonate and the mixture of palladium；4- formylphenylboronic acids, tolans and silver carbonate rub
You are than being 1:(1~1.2):1；Protective gas is nitrogen or argon gas；The mol ratio of product I and indandione rodenticide is 1:(2~3)；Catalysis
Agent II is morpholine or triethylamine, and the mol ratio of catalyst II and product I is 1~5:100；Solvent III is being capable of lysate
I, but insoluble HPB-ID organic solvent.
6. the preparation method for lighting type fluorescence probe of the more nitrogen azole heterocyclic compounds of detection according to claim 5, its
It is characterised by：The good solvent I is the mixed solvent of normal propyl alcohol and water, or acetonitrile；Wherein, the volume ratio of normal propyl alcohol and water is 9:
1。
7. the preparation method for lighting type fluorescence probe of the more nitrogen azole heterocyclic compounds of detection according to claim 5, its
It is characterised by：The good solvent II is dichloromethane, chloroform, tetrahydrofuran or ethyl acetate.
8. the preparation method for lighting type fluorescence probe of the more nitrogen azole heterocyclic compounds of detection according to claim 5, its
It is characterised by：In catalyst I, the ratio between amount of material of silver carbonate and palladium is 1:(0.025~0.035).
9. the preparation method for lighting type fluorescence probe of the more nitrogen azole heterocyclic compounds of detection according to claim 5, its
It is characterised by：Separating-purifying is carried out using pillar layer separation, using petroleum ether and dichloromethane as eluant, eluent；Wherein, petroleum ether with
The mass ratio of dichloromethane is 1:2.5.
10. the preparation method for lighting type fluorescence probe of the more nitrogen azole heterocyclic compounds of detection according to claim 5, its
It is characterised by：Solvent III is methanol or ethanol.
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| PCT/CN2017/000748 WO2019051627A1 (en) | 2017-09-13 | 2017-12-25 | Fluorogenic probe for detecting polyazole heterocyclic compound and preparation method therefor |
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| CN111307773A (en) * | 2020-03-13 | 2020-06-19 | 北京理工大学 | Application of fluorescent compound in detecting and/or distinguishing natural plant compounds |
| CN114034656A (en) * | 2021-11-10 | 2022-02-11 | 国网四川省电力公司电力科学研究院 | Probe for detecting fluorine ions, preparation method and application of probe |
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