CN109897041A - A kind of near-infrared zinc ion fluorescent compound and its preparation method and application - Google Patents
A kind of near-infrared zinc ion fluorescent compound and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of near-infrared zinc ion fluorescent compounds and preparation method thereof.Reacting the preparation method comprises the following steps: malononitrile, isophorone are dissolved in organic solvent with piperidines, acetic acid, acetic anhydride, parahydroxyben-zaldehyde for the compound, is dissolved in trifluoroacetic acid for product and reacts with methenamine, obtains II intermediate of formula；By 5- amino -4,6- dichloro pyrimidine, naphthalidine is added in organic solvent, concentrated hydrochloric acid is added, reflux, is dissolved in phosphorus oxychloride for reaction product, acetic acid, polyphosphoric acids and dodecyl trimethyl ammonium chloride, and reaction product is dissolved in organic solvent and hydration hydrazine reaction obtains III intermediate of formula；Organic solvent is added in II intermediate of formula, III intermediate of formula to react to obtain the near-infrared zinc ion fluorescent compound (formula I).Near-infrared zinc ion fluorescent compound high sensitivity of the invention, strong interference immunity can be widely used for zinc ion detection.
Description
Technical field
The invention belongs to the fluorescent probe technique fields of metal ion detection, and in particular to a kind of near-infrared zinc ion fluorescence
Probe compound and its preparation method and application.
Background technique
Zinc (Zn) is play in many bioprocess as the second metallic element abundant for following iron in human body closely to pass
Important role, including gene expression, cell growth, cell division, cell metabolism, DNA replication dna and reparation.Zinc ion it is excessive or
Shortage can cause many diseases, such as Alzheimer disease, and this disease is increasing the disease incidence of multiple types cancer, such as insane
Epilepsy, ishemic stroke and infantile diarrhea.Therefore, in order to keep human health, zinc in effectively identification drinking water and living cells is developed
The method of ion is extremely important.
Currently used zinc ion detection method includes atomic absorption spectrography (AAS) (AAS), atomic emission spectrometry (AES) electricity
Feel coupled plasma mass probe and electrochemical method, however all these methods need complicated and expensive tool, rigorously
Experiment condition, and prolonged detection.Compared with these methods, fluorescence probe is due to its excellent selective sensitivity
Height, detection time is short, easy to operate, and monitoring cost is low and superiority and is concerned.
Dicyano isophorone derivative has some excellent properties, good glimmering including big Stokes shift
Photostability, launch wavelength in the near infrared region, furthermore have good binding ability with heteroatomic purine analog derivative,
Therefore composite structure stabilization, high sensitivity, visualization and the fluorescence probe of detectable zinc ion that can be used in aqueous phase system
Have great importance.
Nevertheless, many reported zinc ion fluorescents still have poor selectivity, reaction time length, water solubility
The problems such as poor.
Summary of the invention
In order to overcome the above-mentioned problems of the prior art and deficiency, an object of the present invention is to provide a kind of near-infrared
Zinc ion fluorescent compound.
To achieve the above object, the specific technical solution that the present invention uses is as follows:
A kind of near-infrared zinc ion fluorescent compound, the compound have the following structure general formula I:
The second object of the present invention is to provide a kind of preparation method of above-mentioned near-infrared zinc ion fluorescent compound.Its
Synthetic route is as follows:
Wherein, IV intermediate of formula is that (3- (4-Vinyl phenol base) -5,5- dimethyleyelohexane -2- alkene -1- is sub- by (E) -2-
Base) malononitrile, II intermediate of formula is (E) -2- (3- (3- formoxyl -4- hydroxyl) vinyl) -5,5- dimethyleyelohexane -2- alkene -
1- subunit) malononitrile, V intermediate of formula is the chloro- N of 6-4(naphthalene -1- base) pyrimidine -4,5- diamines, VI intermediate of formula are the chloro- 8- of 6-
Methyl -9- (naphthalene -1- base) -9H- purine, III intermediate of formula are 6- diazanyl -8- methyl -9- (naphthalene -1- base) -9H- purine, and formula I is changed
Conjunction object is near-infrared zinc ion fluorescent compound of the present invention.
To achieve the above object, another technical solution that the present invention uses is as follows:
A kind of preparation method of near-infrared zinc ion fluorescent compound, comprising the following steps:
(1) II intermediate of preparation formula ((E) -2- (3- (3- formoxyl -4- hydroxyl) vinyl) -5,5- dimethyleyelohexane -2-
Alkene -1- subunit) malononitrile),
By malononitrile, isophorone is dissolved in organic solvent, and piperidines, acetic acid, acetic anhydride is added, after 1~2h is stirred at room temperature,
Continue 1~2h of stirring at 80~85 DEG C, parahydroxyben-zaldehyde is then added in a nitrogen atmosphere, stirs 1 at 80~85 DEG C
Reactant is poured into the aqueous solution that concentrated sulfuric acid volume content is 3.0-3.5% while hot, is stirred, filtered, and be washed with water by~2h
It washs solid 6~8 times, obtained solid recrystallized from acetonitrile obtains IV intermediate of formula.
Methenamine is added after IV intermediate of formula is dissolved in trifluoroacetic acid, 3~4h of return stirring at 72~74 DEG C,
It then cools to room temperature, reactant is poured into mixture of ice and water, filter, and be washed with water solid 3~4 times, consolidate what is obtained
Body is dried at 45~50 DEG C, is carried out chromatography using eluant ethyl acetate/petroleum ether and is obtained II intermediate.
(2) III intermediate of preparation formula (6- diazanyl -8- methyl -9- (naphthalene -1- base) -9H- purine)
5- amino -4,6- dichloro pyrimidine, naphthalidine are added in organic solvent, are added concentrated hydrochloric acid after being completely dissolved, 78
~80 DEG C of 24~26h of back flow reaction, it is cooling, solvent is removed under reduced pressure, is dissolved with the NaOH that concentration is 1M, is then extracted with ethyl acetate
It takes, 45~55 DEG C are evaporated off ethyl acetate, are recrystallized with methanol and water, and 45~55 DEG C of drying obtain V intermediate of formula；
V intermediate of formula, acetic acid, polyphosphoric acids, dodecyl trimethyl ammonium chloride are dissolved in phosphorus oxychloride, 78
~80 DEG C of 20~36h of reflux, after reactant is cooled to room temperature, 68~72 DEG C are evaporated off solvent, to anti-under 0~5 DEG C of ice-water bath
It answers and mixture of ice and water is added in system, filter, washing, 45~55 DEG C of drying obtain VI intermediate of formula；
After VI intermediate of formula is dissolved in organic solvent, hydrazine hydrate is added, it, will in 78~80 DEG C of 3~4h of back flow reaction
Reactant is cooled to room temperature, and is filtered, is washed solid 3~4 times with organic solvent, obtain III intermediate of formula.
(3) near-infrared zinc ion fluorescent compound is prepared
II intermediate of formula in step (1), III intermediate in step (2) are added in organic solvent, 78~80 DEG C
Flow back 12~14h, is cooled to room temperature, and filters, is washed solid 3~4 times with organic solvent, obtain red solid, i.e., the described near-infrared
Zinc ion fluorescent compound.
Preferably, organic solvent described in step (1) is n,N-Dimethylformamide, organic described in step (2)
Solvent is methanol, and organic solvent described in step (3) is ethyl alcohol.
Preferably, malononitrile described in step (1), isophorone, piperidines, acetic acid, acetic anhydride, parahydroxyben-zaldehyde rub
You are than being 1: 1~1.2: 0.13~0.16: 0.005~0.009: 0.017~0.024: 1~1.3.
Preferably, step (1) IV intermediate, trifluoroacetic acid, methenamine molar ratio be 1: 60~70: 0.97~
1.16。
Preferably, step (2) 5- amino -4,6- dichloro pyrimidine, naphthalidine, concentrated hydrochloric acid, NaOH molar ratio be 1:
1.8~2.2: 1.8~2.2: 1.6~2.0.
Preferably, the volume ratio of step (2) recrystallization in methanol and water is VMethanol:VWater=1: 4.5~5.5.
Preferably, step (2) V intermediate of formula, acetic acid, polyphosphoric acids, dodecyl trimethyl ammonium chloride mole
Than being 1: 5~5.5: 3.8~4.2: 0.002~0.007.
Preferably, step (2) VI intermediate, hydrazine hydrate molar ratio are 1: 5~6.
Preferably, the volume ratio of step (1) described eluant, eluent is VEthyl acetate:VPetroleum ether=1:10~15, step (2) is described to wash
The volume ratio of de- agent is VMethanol:VMethylene chloride=1:95~110.
Preferably, step (3) II intermediate of formula, III intermediate of formula molar ratio be 1: 1~1.2.
The third object of the present invention is to provide the application of above-mentioned near-infrared zinc ion fluorescent compound.
Specific technical solution is as follows:
A kind of application of the near-infrared zinc ion fluorescent compound in zinc ion detection.
Preferably, using the near-infrared zinc ion fluorescent compound as the detection substance of zinc ion fluorescent.
The invention has the following advantages:
For the present invention using dicyano isophorone derivative as fluorophor, hydrazine hydrate is linking group, the chloro- 8- methyl-of 6-
9- (naphthalene -1- base) -9H- purine is that recognition group has synthesized a kind of near-infrared zinc ion fluorescent compound.This method raw material
It is easy to get, synthetic method is simple, and products obtained therefrom is solid powder, is easy to store；Prepared near-infrared zinc ion fluorescent
Closing object has specific recognition to zinc ion, and the reaction time is short, high sensitivity, strong antijamming capability, can be used for making zinc ion
Fluorescence probe, can with real-time qualitative under fluorescence on site and the visual fluorescence of sxemiquantitative detection zinc ion and for organism zinc from
Son detection.
Detailed description of the invention
Fig. 1 is that zinc ion (Zn is added in near-infrared zinc ion fluorescent compound in embodiment 22+) before and after UV absorption
And fluorescence spectra；
Fig. 2 is near-infrared zinc ion fluorescent compound in embodiment 2 in DMSO-H2It is right in O (v/v=3:2) solution
Different metal ions selectivity fluorescence spectra；
Fig. 3 is near-infrared zinc ion fluorescent compound in implementation 2 in DMSO-H2To not in O (v/v=3:2) solution
With concentration zinc ion (Zn2+) fluorescence spectrum response diagram；
Fig. 4 is near-infrared zinc ion fluorescent compound in embodiment 2 in DMSO-H2It is right in O (v/v=3:2) solution
Different metal ions select the fluorescence response figure of interference detection；
Fig. 5 is near-infrared zinc ion fluorescent compound in embodiment 2 in DMSO-H2O (v/v=3:2) and zinc ion
(Zn2+) Job ' the s plot curve of ratio is complexed；
Fig. 6 is that (Fig. 6 a is to combine to near-infrared zinc ion fluorescent compound for front and back in conjunction with zinc ion in embodiment 2
Before, Fig. 6 b is after combining) image in HeLa cell；
Fig. 7 is the nuclear magnetic resonance of near-infrared zinc ion fluorescent compound in embodiment 21H-NMR spectrum.
Fig. 8 is the nuclear magnetic resonance of near-infrared zinc ion fluorescent compound in embodiment 213C-NMR spectrogram.
Fig. 9 is mass spectrogram of the near-infrared zinc ion fluorescent compound in conjunction with zinc ion in embodiment 2.
Figure 10 is mass spectrogram of the near-infrared zinc ion fluorescent compound in conjunction with zinc ion in embodiment 2.
Specific embodiment
To better understand the essence of the present invention, the invention will be further elaborated combined with specific embodiments below.
Reagent employed in embodiment is that commercially available analysis is pure or chemical pure.
Embodiment 1
(1) (E) -2- (3- (3- formoxyl -4- hydroxyl) vinyl) -5,5- dimethyleyelohexane -2- alkene -1- base is prepared) third
Dintrile (II intermediate of formula)
Malononitrile (1.87g, 28.3mmol) is added into 100mL round-bottomed flask, isophorone (3.9g, 28.3mmol),
After n,N-Dimethylformamide (10mL), piperidines (380 μ L, 3.84mmol), acetic acid (28 μ L, 0.19mmol), acetic anhydride is added
(18 μ L, 0.5mmol), is stirred at room temperature 1~2h, continues 1~2h of stirring at 80~85 DEG C, then addition pair in a nitrogen atmosphere
Hydroxy benzaldehyde (3.45g, 28.7mmol) stirs 1~2h at 80~85 DEG C, while hot pours into reactant dense containing 6~8mL
It in 200~220mL water of hydrochloric acid, stirs, filters, and be washed with deionized solid 6~8 times, obtained solid acetonitrile weight
Crystallization, obtains (E) -2- (3- (4-Vinyl phenol base) -5,5- dimethyleyelohexane -2- alkene -1- subunit) malononitrile (among formula IV
Body).
(E) -2- (3- (4-Vinyl phenol base) -5,5- dimethyleyelohexane -2- alkene -1- is added into 100mL round-bottomed flask
Subunit) malononitrile (1.16g, 4mmol), be dissolved in trifluoroacetic acid (20mL, 269mmol) be added afterwards methenamine (0.544g,
3.88mmol), 3~4h of return stirring at 72~74 DEG C, then cools to room temperature, reactant is poured into mixture of ice and water,
It filters, and is washed with deionized solid 3~4 times, 50 DEG C of solid obtained are dried, eluant ethyl acetate/petroleum is used
Ether (VEthyl acetate: VPetroleum ether=1:10) carry out chromatography obtain (E) -2- (3- (3- formoxyl -4- hydroxyl) vinyl) -5,5- two
Methyl cyclohexane -2- alkene -1- base) malononitrile (II intermediate of formula).
(2) 6- diazanyl -8- methyl -9- (naphthalene -1- base) -9H- purine (III intermediate of formula) is prepared
5- amino -4,6- dichloro pyrimidine (5g, 30mmol) is added into 100mL round-bottomed flask, and naphthalidine (8.584g, 60
Mmol), it is dissolved in methanol (50mL), concentrated hydrochloric acid (5mL, 60mmol) is added after being completely dissolved, 78~80 DEG C of back flow reactions 24~
26h, it is cooling, solvent is removed under reduced pressure, NaOH (1M, 50mL) dissolution is added, is extracted with 400mL ethyl acetate, 50 DEG C are evaporated off acetic acid
Ethyl ester recrystallizes (volume ratio V with methanol and waterMethanol:VWater=100: 500), filtering, 50 DEG C of drying obtain light purple solid,
That is the chloro- N of 6-4(naphthalene -1- base) pyrimidine -4,5- diamines (V intermediate of formula).
Acetic acid (5.882g, 98mmol), polyphosphoric acids (25g, 74mmol), dodecane are added into 100mL round-bottomed flask
Base trimethyl ammonium chloride (0.5g, 0.1mmol), the chloro- N of 6-4(naphthalene -1- base) pyrimidine -4,5- diamines (5g, 18.5mmol) is dissolved in
Phosphorus oxychloride (60mL, concentration 98%), 78~80 DEG C of 20~36h of reflux, the reaction is cooled to after room temperature, 70 DEG C be evaporated off it is molten
90mL mixture of ice and water is added in agent under 0~5 DEG C of ice-water bath into reaction system, filters and is washed with 100mL deionized water solid
Body, 50 DEG C dry to obtain yellow solid, use eluant, eluent ethanol/methylene (volume ratio VMethanol:VMethylene chloride=1: 100) carrying out
Column chromatography for separation obtains the chloro- 8- methyl -9- of 6- (naphthalene -1- base) -9H- purine (VI intermediate of formula).
Into 100mL round-bottomed flask be added the chloro- 8- methyl -9- of 6- (naphthalene -1- base) -9H- purine (1.187g,
4.04mmol), after being dissolved in methanol (40mL), be added hydrazine hydrate (1.264g, 20.2mmol), 78~80 DEG C of back flow reactions 3~
Reactant is cooled to room temperature by 4h, is filtered, is washed solid 3~4 times with methanol, obtain 6- diazanyl -8- methyl -9- (naphthalene -1- base) -
9H- purine (III intermediate of formula).
(3) near-infrared zinc ion fluorescent compound is prepared
(E) -2- (3- (3- formoxyl -4- hydroxyl) vinyl) -5,5- diformazan basic ring is added into 100mL round-bottomed flask
Hex- 2- alkene -1- base) malononitrile (1.64g, 5.15mmol), 6- diazanyl -8- methyl -9- (naphthalene -1- base) -9H- purine
(1.418g, 5.15mmol), ethyl alcohol (20mL), 78~80 DEG C of 12~14h of reflux are cooled to room temperature, and are filtered, are washed solid with ethyl alcohol
3~4 times, red solid is obtained, i.e., the described near-infrared zinc ion fluorescent compound.
Embodiment 2
It is tested using near-infrared zinc ion fluorescent compound described in embodiment 1.
The near-infrared zinc ion fluorescent compound is dissolved in DMSO-H2In O (v/v=3:2) solution, concentration 10
μM, other concentration of metal ions are 50 μM, are tested with Fluorescence Spectrometer and ultraviolet specrophotometer, the maximum of fluorescence probe
Excitation wavelength is 502nm, maximum emission wavelength 670nm.
Such as Fig. 1, zinc ion (Zn is added for near-infrared zinc ion fluorescent compound of the invention2+) before and after ultraviolet suction
It receives and fluorescence spectra, probe compound itself has a ultraviolet absorption peak at 434nm, but probe compound molecule and zinc ion
After complexing, occur new ultraviolet absorption peak at 502nm, probe compound almost unstressed configuration 670nm at itself, but spy
After needle compound molecule and zinc ion complexing, strong fluorescence is generated at 670nm, is near infrared region, and this holds in the palm
Ke Si displacement reaches 168nm.
Such as Fig. 2, the fluorescence light after each metal ion species is added for near-infrared zinc ion fluorescent compound of the invention
Spectrogram, the results showed that when each metal ion species are added, fluorescence spectrum is substantially unchanged, and when zinc ion is added, fluorescence significantly increases
By force, i.e., fluorescence probe of the invention has good selectivity to zinc ion.
It is near-infrared zinc ion fluorescent compound of the invention to various concentration zinc ion (Zn such as Fig. 32+) fluorescence
Spectral response figure.0~15 μM of zinc ion is added into the near-infrared zinc ion fluorescent compound of the present invention containing 10 μM
When, the fluorescence probe almost unstressed configuration in the solution itself, but with the increase of zinc ion concentration, the fluorescence enhancement at 670nm,
Apparent red fluorescence can be observed directly with naked eye under 365nm ultraviolet lamp.
It is near-infrared zinc ion fluorescent compound feelings existing for disturbance metal ion of the invention such as Fig. 4
Fluorescence intensity histogram after being reacted under condition with zinc ion, the results showed that, the presence of other metal ions is to zinc ion of the present invention
Fluorescent probe compounds identify zinc ion without significantly interfering with.
It is 50 μM for the concentration summation of near-infrared zinc ion fluorescent compound and zinc ion of the invention such as Fig. 5, leads to
Cross change both concentration ratio (near-infrared zinc ion fluorescent compound and zinc ion the mass ratio of the material are followed successively by 1: 9,2: 8,
3: 7,4: 6,5: 5,6: 4,7: 3,8: 2,9: 1) obtaining zinc ion fluorescent chemical combination under the fluorescence intensity and the concentration at 670nm
The difference of object autofluorescence intensity, the scale of total concentration is accounted for ion.By this figure it is found that when zinc ion proportion is
Ordinate reaches peak when 0.5, can determine between near-infrared zinc ion fluorescent compound and zinc ion mainly with 1: 1
Form combines and forms stable complex compound.
Such as Fig. 6, be near-infrared zinc ion fluorescent compound of the invention with zinc ion in conjunction with before and after in HeLa cell
In image.It can be seen that near-infrared zinc ion fluorescent compound unstressed configuration in HeLa cell itself, figure in Fig. 6 a
It can be seen that near-infrared zinc ion fluorescent compound generates strong fluorescence in HeLa cell in 6b, the results showed that close red
Outer zinc ion fluorescent compound can be applied to organism experiment.
It is near-infrared zinc ion fluorescent compound of the invention such as Fig. 71H NMR spectra,1H NMR(400MHz,
DMSO-d6) δ 8.33 (s, 1H), 8.25-8.18 (m, 2H), 8.14 (d, J=8.2Hz, 1H), 7.75 (s, 1H), 7.73 (dd, J
=5.4,2.1Hz, 2H), 7.67-7.50 (m, 4H), 7.25-7.09 (m, 4H), 6.98 (d, J=8.5Hz, 1H), 6.78 (s,
1H), 2.57(s,4H),2.31(s,3H),1.00(s,6H).
It is near-infrared zinc ion fluorescent compound of the invention such as Fig. 813C NMR(101MHz,DMSO-d6)δ
170.62,158.75,156.76,152.38,151.41,144.63,137.81,134.35,130.80,130.54,
130.11,128.97,128.32,127.91,127.54,127.42,127.32,126.26,122.44,122.22,119.79,
118.18,114.45,113.69,75.68,42.76,38.65,32.09,27.93,14.52.
It is the mass spectrogram of near-infrared zinc ion fluorescent compound of the invention such as Fig. 9, MS (ESI) m/z:
589.2471 [M-H]+。
It is the mass spectrogram of near-infrared zinc ion fluorescent compound of the invention such as Figure 10.As we can see from the figure plus
Entering after zinc ion to relative molecular mass is 653.1765, as a result further demonstrate that near-infrared zinc ion fluorescent compound with
Zinc ion combination ratio is 1:1.
In DMSO-H2O (v/v=3:2) system, zinc ion can be with near-infrared zinc ion fluorescent chemical combination of the invention
Hydroxyl, diazanyl in object and the nitrogen effect on purine, form stable hexatomic ring, strong fluorescence, fluorescence are generated at 670nm
Color becomes red by colourless, and excellent linear relationship is presented in fluorescence intensity and zinc ion concentration in a certain range, can
With in 1-10 μM of quantitative detection zinc ion, while fluorescent probe molecule and zinc ion complexation constant are 8.33 × 104M-1, minimum
Detection is limited to 12nM.
Claims (10)
1. a kind of near-infrared zinc ion fluorescent compound, which is characterized in that the compound has the following structure general formula I:
2. a kind of preparation method of near-infrared zinc ion fluorescent compound according to claim 1, which is characterized in that
The following steps are included:
(1) II intermediate of preparation formula
By malononitrile, isophorone is dissolved in organic solvent, piperidines, acetic acid, acetic anhydride is added, after 1~2h is stirred at room temperature, 80
Continue 1~2h of stirring at~85 DEG C, parahydroxyben-zaldehyde be then added in a nitrogen atmosphere, 1~2h is stirred at 80~85 DEG C,
Reactant is poured into the aqueous solution that concentrated sulfuric acid volume content is 3.0-3.5%, stirred while hot, filtered, and solid 6 is washed with water
~8 times, obtained solid recrystallized from acetonitrile obtains IV intermediate of formula；
Methenamine is added after IV intermediate of formula is dissolved in trifluoroacetic acid, 3~4h of return stirring at 72~74 DEG C, then
It is cooled to room temperature, reactant is poured into mixture of ice and water, filter, and be washed with water solid 3~4 times, obtained solid is existed
45~50 DEG C of drying carry out chromatography using eluant ethyl acetate/petroleum ether and obtain II intermediate of formula；
(2) III intermediate of preparation formula
5- amino -4,6- dichloro pyrimidine, naphthalidine are added in organic solvent, are added concentrated hydrochloric acid after being completely dissolved, 78~80
DEG C 24~26h of back flow reaction, it is cooling, solvent is removed under reduced pressure, is dissolved with the NaOH that concentration is 1M, is then extracted with ethyl acetate,
45~55 DEG C are evaporated off ethyl acetate, are recrystallized with methanol and water, and 45~55 DEG C of drying obtain V intermediate of formula；
V intermediate of formula, acetic acid, polyphosphoric acids, dodecyl trimethyl ammonium chloride are dissolved in phosphorus oxychloride, 78~80
DEG C reflux 20~36h, after reactant is cooled to room temperature, 68~72 DEG C are evaporated off solvent, to reactant under 0~5 DEG C of ice-water bath
Mixture of ice and water is added in system, filters, washing, 45~55 DEG C of drying obtain VI intermediate of formula；
After VI intermediate of formula is dissolved in organic solvent, hydrazine hydrate is added will react in 78~80 DEG C of 3~4h of back flow reaction
Object is cooled to room temperature, and is filtered, is washed solid 3~4 times with organic solvent, obtain III intermediate of formula；
(3) near-infrared zinc ion fluorescent compound is prepared
II intermediate of formula in step (1), III intermediate in step (2) are dissolved in organic solvent, 78~80 DEG C of reflux 12~
14h is cooled to room temperature, and is filtered, is washed solid 3~4 times with organic solvent, obtain red solid, i.e., the described near-infrared zinc ion is glimmering
Light probe compound.
3. a kind of preparation method of near-infrared zinc ion fluorescent compound according to claim 2, which is characterized in that
Organic solvent described in step (1) is n,N-Dimethylformamide, and organic solvent described in step (2) is methanol, step
(3) organic solvent described in is ethyl alcohol.
4. a kind of preparation method of near-infrared zinc ion fluorescent compound according to claim 2, which is characterized in that
Malononitrile described in step (1), isophorone, piperidines, acetic acid, acetic anhydride, parahydroxyben-zaldehyde molar ratio be 1: 1~1.2:
0.13~0.16: 0.005~0.009: 0.017~0.024: 1~1.3；Step (1) IV intermediate, trifluoroacetic acid, Wu Luo
The molar ratio of tropine is 1: 60~70: 0.97~1.16.
5. a kind of preparation method of near-infrared zinc ion fluorescent compound according to claim 2, which is characterized in that
Step (2) 5- amino -4,6- dichloro pyrimidine, naphthalidine, concentrated hydrochloric acid, NaOH molar ratio be 1: 1.8~2.2: 1.8~
2.2: 1.6~2.0；Step (2) V intermediate of formula, acetic acid, polyphosphoric acids, dodecyl trimethyl ammonium chloride molar ratio
It is 1: 5~5.5: 3.8~4.2: 0.002~0.007；Step (2) VI intermediate, hydrazine hydrate molar ratio are 1: 5~6.
6. a kind of preparation method of near-infrared zinc ion fluorescent compound according to claim 2, which is characterized in that
Step (3) II intermediate of formula, III intermediate of formula molar ratio be 1: 1~1.2.
7. a kind of preparation method of near-infrared zinc ion fluorescent compound according to claim 2, which is characterized in that
The volume ratio of step (1) described eluant, eluent is VEthyl acetate:VPetroleum etherThe volume ratio of=1:10~15, step (2) described eluant, eluent is
VMethanol:VMethylene chloride=1:95~110.
8. a kind of preparation method of near-infrared zinc ion fluorescent compound according to claim 2, which is characterized in that
The volume ratio of step (2) recrystallization in methanol and water is VMethanol:VWater=1: 4.5~5.5.
9. application of the near-infrared zinc ion fluorescent compound described in claim 1 in zinc ion detection.
10. detection substance of the near-infrared zinc ion fluorescent compound described in claim 1 as zinc ion fluorescent.
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| CN112110922A (en) * | 2020-08-28 | 2020-12-22 | 江苏科技大学 | Purine matrix-based aluminum ion detection fluorescent probe and preparation method and application thereof |
| CN112321588A (en) * | 2020-11-27 | 2021-02-05 | 江苏科技大学 | Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof |
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| CN113980023A (en) * | 2021-11-25 | 2022-01-28 | 江苏科技大学 | Compound PHA, preparation method thereof and application thereof in detection of copper ions |
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| CN111018773A (en) * | 2019-12-13 | 2020-04-17 | 长江师范学院 | Malononitrile phorone zinc ion fluorescent probe and preparation method and application thereof |
| CN112341463A (en) * | 2020-03-17 | 2021-02-09 | 江苏科技大学 | Purine parent-based fluorescent probe compound and preparation method and application thereof |
| CN112094270A (en) * | 2020-08-28 | 2020-12-18 | 江苏科技大学 | Purine parent-based cadmium ion detection fluorescent probe and preparation method and application thereof |
| CN112110922A (en) * | 2020-08-28 | 2020-12-22 | 江苏科技大学 | Purine matrix-based aluminum ion detection fluorescent probe and preparation method and application thereof |
| CN112110922B (en) * | 2020-08-28 | 2021-11-16 | 江苏科技大学 | Purine matrix-based aluminum ion detection fluorescent probe and preparation method and application thereof |
| CN112094270B (en) * | 2020-08-28 | 2021-12-07 | 江苏科技大学 | Purine parent-based cadmium ion detection fluorescent probe and preparation method and application thereof |
| CN112321588A (en) * | 2020-11-27 | 2021-02-05 | 江苏科技大学 | Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof |
| CN112321588B (en) * | 2020-11-27 | 2021-12-07 | 江苏科技大学 | Purine matrix-based zinc ion detection fluorescent probe and preparation method and application thereof |
| CN113980023A (en) * | 2021-11-25 | 2022-01-28 | 江苏科技大学 | Compound PHA, preparation method thereof and application thereof in detection of copper ions |
| CN113980023B (en) * | 2021-11-25 | 2022-12-02 | 江苏科技大学 | Compound PHA, preparation method thereof and application thereof in detection of copper ions |
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