CN107501252A - A kind of cadmium ion fluorescent probe and its preparation method and application - Google Patents
A kind of cadmium ion fluorescent probe and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of cadmium ion fluorescent probe and its preparation method and application, the probe has single-minded combination selectivity and fluorescence response to cadmium ion, using the Xiao Ji Ben oxadiazoles of 4 amino 7 as fluorogen in probe, acid amides DPA is acceptor, the tautomerism of amide functional group causes acceptor to have modification ability, i.e. with the isomers combination cadmium ion of imidic acid, and other metal ions are combined with the structure of amide isomers, show as the single-minded combination selectivity to cadmium ion.The present invention realizes specific recognition of the probe to cadmium ion, can be used in the detection of cadmium ion in cell, due to its wider pH working range, also can be used in the detection of cadmium ion in other biological and environment.
Description
Technical field
The invention belongs to chemical analysis detection field, and in particular to a kind of cadmium ion fluorescent probe and its preparation
Methods and applications, the cadmium ion fluorescent probe can detect the cadmium ion detection of wide pH working ranges.
Background technology
Cadmium is a kind of heavy metal to health with serious toxic action, can cause renal insufficiency,
Metabolic calcium disorder, increase the incidence of lung cancer, prostate cancer, cancer of pancreas and kidney.Cadmium is widely used in
In industry and agricultural, a large amount of accumulations in soil and waters are caused, is absorbed by various animals and plants and passes through food
Thing chain is enriched with and enters human body.Although cadmium ion has undesirable effect to environment and health,
The pathogenesis of cadmium ion is still unclear.Therefore seek fast and efficiently cadmium ion detection method, make
It is very necessary that it, which is applied to the fields such as medicine, environment, food,.Fluorescence detection method is easy, and
And there are outstanding advantages in sensitivity, selectivity, response time and biologic applications etc., in recent years
It is used widely.
At present, most of cadmium ion fluorescent probes reported are mainly based upon EDTA amide derivatives and are
Part or the cadmium ion probe that DPEA/DPA is part, by the way that being quenched for fluorescence occurs after being complexed with cadmium ion
Or enhancing, fluorescence emission wavelengths red shift or blue shift come realize detection cadmium ion [(a) Gunnlaugsson,
T.；Lee,T.C.；Parkesh,R.Org.Lett.2003,5,4065.(b)Yang,Y.-Y.；Cheng,T.-Y.；
Zhu,W.-P.；Xu,Y.-F.；Qian,X.-H.Org.Lett.2011,13,264.(c)Taki,M.；Desaki,M.；
Ojida,A.；Iyoshi,S.；Hirayama,T.；Hamachi,I.；Yamamoto,Y.J.Am.Chem.Soc.
2008,130,12564.(d)Liu,Z.P.；Zhang,C.L.；He,W.J.；Yang,Z.H.；Gao,X.；
Guo,Z.J.Chem.Commun.2010,46,6138.].These cadmium ion probes generally have preferably spirit
Sensitivity and quick response time, but the combination selectivity ratios to cadmium ion are poor, easily by it
His metal ion is particularly the interference of metallic zinc of the same clan and mercury ion.In order to combining unfavorable target analysis
Thing has special combination selectivity, and acceptor, which is preferably able to have target analytes, is different from general knot
Syntype.In other words, acceptor can convert configuration for different target analytes to improve with reference to choosing
Selecting property, that is, become receptor.Common combination configuration can be taken Competing Species by becoming receptor, and is directed to
Target analytes can then change configuration and use optimum combination pattern, so as to realize to the special of target analytes
One identification.Acid amides DPA is a kind of tautomerism by the use of acid amides as the modification factor come design variant acceptor,
Single-minded combination selectivity can be shown to metal ion in the example reported.
Absorption of the cadmium in soil and animals and plants and accumulative, and cadmium ion is to the toxicity of organism, sternly
The pH of environment is depended on again.Such as Bervoets et al. inhales to cadmium of the river mosquito larvae under condition of different pH
Receipts are studied, and are found in the range of pH 5.5-9, and the absorption with pH increase cadmium also increases；And
In the range of pH 9-10, the absorption with pH increase cadmium declines.Many research verified reduction pH
The toxicity of cadmium can be reduced.Fertile step on et al. confirms that cadmium exists in the Escherichia coli Poisoning ratio that pH value is 5
PH be 7 in it is much lower.However, the cadmium ion probe reported can only be in the range of very narrow pH
Detect cadmium ion.
Cadmium ion fluorescent probe of the present invention becomes receptor using acid amides DPA and solves selection well
The problem of property and pH detection ranges.
The content of the invention
It is an object of the invention to provide a kind of cadmium ion fluorescent probe and its preparation method and application, the probe
There is single-minded combination selectivity and fluorescence response to cadmium ion, with 4- amino -7- Xiao Ji Ben Evil bis- in probe
Azoles is fluorogen, and acid amides DPA is acceptor, and the tautomerism of amide functional group enables acceptor to have modification
Power, i.e., with the isomers combination cadmium ion of imidic acid, and other metals are combined with the structure of amide isomers
Ion, show as the single-minded combination selectivity to cadmium ion.Fluorescence intensity strengthens after probe combination cadmium ion
65 times；There is no obvious change in fluorescence after being combined with other metal ions particularly congeners, show as
To the single-minded fluorescence signal of cadmium ion selectivity, suitable for wider pH detection ranges (pH 4.5-11.5),
And sensitivity is higher, preparation method is simple, is adapted to amplification synthesis and practical application.
The technical solution adopted by the present invention：
A kind of cadmium ion fluorescent probe, the fluorescence probe structure are as follows：
The preparation method of the cadmium ion fluorescent probe, is comprised the following steps that：
(1) synthesis of intermediate 4- amino -7- Xiao Ji Ben oxadiazoles：The chloro- 7- Xiao Ji Ben oxadiazoles of 4- are dissolved in
Methanol, add ammoniacal liquor and obtain reaction solution, reaction solution reacts 12-36 hours under nitrogen protection, after reaction terminates
Reaction solution, crude product purified by silica gel post separation are spin-dried for, gained solid is 4- amino -7- Xiao Ji Ben oxadiazoles；
(2) synthesis of the chloro- N- of intermediate 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：4- amino -7- Xiao Ji Ben Evil
Diazole and 4-dimethylaminopyridine, which are dissolved in dichloromethane, obtains solution A, and solution A is placed in ice bath and stirred,
2- chloracetyl chlorides are dissolved in dichloromethane again and obtain solution B, solution B is added dropwise in solution A, are stirred at room temperature
Reaction 1-5 hours are mixed, reaction solution is spin-dried for and obtains crude product, crude product is by pillar layer separation, gained solid
For the chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides；
(3) synthesis of probe：By the chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides, 2,2 '-bipyridyl amine,
Potassium carbonate and KI are added in acetonitrile, after nitrogen protection lower 50-80 DEG C of reaction 5-12 hour, are cooled to
Room temperature, it is spin-dried for reaction solution and obtains crude product, by silica gel column separating purification crude product, obtaining product is
Cadmium ion fluorescent probe.
In step (1), the mass ratio of the chloro- 7- Xiao Ji Ben oxadiazoles of 4- and methanol is 1：The chloro- 7- of 20-80,4-
The mass ratio of Xiao Ji Ben oxadiazoles and ammonia spirit is 1：8-15；React at room temperature；
In step (2), the mol ratio of 4- amino -7- Xiao Ji Ben oxadiazoles and 4-dimethylaminopyridine is 1：
The mass ratio of 1-1.5,4- amino -7- Xiao Ji Ben oxadiazoles and dichloromethane is 1：80-150,4- amino -7- nitre
The mol ratio of Ji Ben oxadiazoles and 2- chloracetyl chlorides is 1：The quality of 1-1.5,2- chloracetyl chloride and dichloromethane
Than for 1：30-50；
In step (3), the chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：2,2 '-bipyridyl amine：Carbonic acid
The mol ratio of potassium is 1：1-1.2：2-2.5；The chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：The matter of KI
Amount is than being 1：0.3-1；The chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：The mass ratio of acetonitrile is 1：200-700.
Ammonia concn described in step (1) is 28wt.%.
The eluant, eluent of post separation described in step (1), step (2) and step (3) be dichloromethane, petroleum ether,
One or two or more kinds in ethyl acetate, chloroform, methanol, triethylamine or glacial acetic acid.
Cadmium ion fluorescent probe provided by the invention is applied to the detection of cadmium ion.
Specifically include the cadmium ion in the different pH value aqueous solution of detection and in biological specimen, the pH value model
Enclose includes living cells for 4.5-11.5, the biological specimen.
Beneficial effects of the present invention and advantage：
Probe molecule raw material is easy to get, and synthetic route is simple, reaction condition is gentle, post processing is simple and convenient,
Good light stability, single-minded to cadmium ion recognition capability, response speed is very fast, and acid amides-DPA acceptors, which exist, to be become
The combination of type function, acceptor and cadmium ion is imidic acid form.Probe is at HEPES (pH=7.4)
Dissolubility is preferable in solution, and maximum emission wavelength is in 560nm, and fluorescence signal is weaker, with cadmium ion
Add, probe molecule fluorescence signal at 560nm strengthens.Fluorescence probe in the present invention can be wider
PH scopes (pH 4.5-11.5) detect cadmium ion, therefore can be applicable to the detection of cadmium ion among environment.
In addition this probe can effectively detect the cadmium ion in living cells.
Brief description of the drawings
Fig. 1 is fluorescence probe prepared by embodiment 11H NMR spectras；
Fig. 2 is fluorescence probe prepared by embodiment 113C NMR spectras；
Fig. 3 is the abosrption spectrogram after the effect of the cadmium ion of fluorescence probe and various concentrations in embodiment 2,
Abscissa is wavelength, and ordinate is absorption intensity, and the concentration of fluorescence probe is 10 μM.
Fluorescence spectra in Fig. 4 embodiments 3 after the effect of the cadmium ion of fluorescence probe and various concentrations, it is horizontal
Coordinate is wavelength, and ordinate is fluorescence intensity, and the concentration of fluorescence probe is 10 μM of m.
Fig. 5 is J-P curves in embodiment 4, and the concentration summation of probe and cadmium ion is 10 μM, abscissa
For probe concentration from 0 μM -10 μM, ordinate is fluorescence intensity.
Fig. 6 is that the nuclear-magnetism of embodiment 5 titrates, solvent for use DMSO-d6, the initial concentration of probe is
0.5mg/mL, thereto titrate various concentrations cadmium ion nuclear magnetic spectrogram-1H is composed；
Fig. 7 is the fluorescence spectra situation of change that fluorescence probe is added after different metal ions in embodiment 6；
Fig. 8 is to be in embodiment 7 after (10 μM) of fluorescence probe adds different metal ions (10 μM)
The competition block diagram of cadmium ion (10 μM) is added, abscissa is metal species, and ordinate is that fluorescence is strong
Degree.
Fig. 9 is the fluorescence intensity of probe-cadmium-ion solution of different pH value in embodiment 9, and abscissa is
PH value, ordinate are fluorescence intensity.
Figure 10 is the fluorescence co-focusing imaging results (bar=20 μM) of Chinese hamster ovary celI in embodiment 9, its
In (a) be the cell imaging added after probe culture 30 minutes, after (b) is adds cadmium ion culture 30 minutes
Cell imaging, (c) be (b) light field figure.
Embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Concrete operation step is：
(1) synthesis of intermediate 4- amino -7- Xiao Ji Ben oxadiazoles：The chloro- 7- Xiao Ji Ben oxadiazoles of 4- are dissolved in
The methanol of 20-80 times of quality, the ammonia spirit of 8-15 times of quality is added at room temperature.Reaction solution is protected in nitrogen
Lower room temperature reaction 12-36 hours.Reaction is spin-dried for reaction solution, crude product purified by silica gel post separation after terminating.Elution
Agent is petroleum ether and ethyl acetate, and the two volume ratio is 1：0.5-3, obtain brown solid.
(2) synthesis of the chloro- N- of intermediate 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：4- amino -7- Xiao Ji Ben Evil
Diazole and 1-1.5 times of mole 4-dimethylaminopyridine, it is dissolved in equivalent to 4- amino -7- Xiao Ji Ben oxadiazoles
In the dry methylene chloride of 80-150 times of quality, solution is placed in ice bath and stirred.Equivalent to 4- amino -7- nitros
The 2- chloracetyl chlorides of 1-1.5 times of mole of Ben oxadiazoles, the dichloromethane that itself 30-50 times of quality is dried is dissolved in,
It is added dropwise in above-mentioned solution.Stirring reaction 1-5 hours at room temperature, it is spin-dried for reaction solution and obtains pale solid.
Crude product is by pillar layer separation, and eluant, eluent is petroleum ether and ethyl acetate, the two volume ratio 3-10:1, obtain
To yellow solid.
(3) synthesis of probe：By the chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides, 1-1.2 times of mole
2,2 '-bipyridyl amine, 2-2.5 times of mole potassium carbonate and equivalent to the chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acyl
0.3-1 times of quality KI of amine, add N- chloro- equivalent to 2- (7- Xiao Ji Ben oxadiazoles -4-) 200-700 times of acid amides
In the acetonitrile of quality, after nitrogen protection lower 50-80 DEG C of reaction 5-12 hour, room temperature is cooled to, is spin-dried for reacting
Liquid obtains crude product.By silica gel column separating purification crude product, eluant, eluent is methylene chloride/methanol, volume
Than for 50-200:1, obtain yellow solid.
Embodiment 1：The basic building-up process of cadmium ion fluorescent probe is as follows：
(1) synthesis of intermediate 4- amino -7- Xiao Ji Ben oxadiazoles：The chloro- 7- nitros of 400mg (1mmol) 4-
Ben oxadiazoles are dissolved in 20mL methanol, add 4mL 28wt.% ammonia spirit at room temperature.Reaction solution is in nitrogen
The lower room temperature reaction of protection 24 hours.Reaction is spin-dried for reaction solution, crude product purified by silica gel post separation after terminating.Wash
De- agent is petroleum ether：Ethyl acetate 1:1, obtain brown solid 194mg, yield 54%.
(2) synthesis of the chloro- N- of intermediate 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：194mg(1.08mmol)4-
Amino -7- Xiao Ji Ben oxadiazoles and 171mg (1.40mmol) 4-dimethylaminopyridine are dissolved in 20mL dryings
In dichloromethane, solution is placed in ice bath and stirred.146mg (1.30mmol) 2- chloracetyl chlorides are dissolved in 5mL
Dry dichloromethane, it is added dropwise in above-mentioned solution.Stirring reaction 2 hours at room temperature, are spin-dried for reaction solution
Obtain pale solid.For crude product by pillar layer separation, eluant, eluent is petrol ether/ethyl acetate 5:1, obtain
To yellow solid 119mg, yield 43%.1H NMR(500MHz,CDCl3):δ9.52(s,1H,NH),
8.58 (d, J=8.0Hz, 1H), 8.48 (d, J=8.5Hz, 1H), 4.35 (s, 1H)；13C NMR(125
MHz,CDCl3):δ167.5,145.9,143.8,136.1,134.3,130.8,114.6,43.9.HRMS
(ESI):Calcd for C8H6ClN4O4[M+H]+257.0078；found 257.0080.
(3) synthesis of probe：By the chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides 100mg (0.39mmol),
2,2 '-bipyridyl amine 42mg (0.39mmol), potassium carbonate 107mg (0.78mmol) and KI 50mg are added
In 50mL acetonitriles, after lower 60 DEG C of nitrogen protection is reacted 10 hours, room temperature is cooled to, reaction solution is spin-dried for and obtains
Crude product.By silica gel column separating purification crude product, eluant, eluent is methylene chloride/methanol 100:1, obtain Huang
Color solid 101mg, yield 62%.Fig. 1：1H NMR(500MHz,CDCl3):δ12.37(s,1H,NH),
8.58 (d, J=4.5Hz, 2H), 8.53 (d, J=8.0Hz, 1H), 8.45 (d, J=8.5Hz, 1H), 7.62 (t,
J=7.5Hz, 2H), 7.39 (d, J=8.0Hz, 2H), 7.17 (t, J=6.0Hz, 2H), 4.05 (s, 4H),
3.62(s,2H)；Fig. 2：13C NMR(125MHz,CDCl3):δ172.3,157.6,149.6,145.4,
143.3,136.8,134.4,134.3,130.5,123.2,122.7,112.8,60.6,58.9.HRMS(ESI):
Calcd for C20H18N7O4[M+H]+420.1420；found 420.1423.
Embodiment 2：
The absorption titration of fluorescence probe 4 prepared by embodiment 1 to cadmium ion
0.0042g probes 4, which are dissolved in 5mL DMSO, is made into 2mM mother liquors.With HEPES (pH=7.4)
10 μM of solution are made into, 2mM Cd (ClO are gradually added dropwise4)2Solution.Test its Change of absorption.As a result such as
Shown in Fig. 3.
Embodiment 3：
Fluorescence probe 4 prepared by embodiment 1 titrates to the fluorescence response of cadmium ion
0.0042g probes 4, which are dissolved in 5mL DMSO, is made into 2mM mother liquors.With HEPES (pH=7.4)
10 μM of solution are made into, 2mM Cd (ClO are gradually added dropwise4)2Solution.Test its change in fluorescence.(excite
Wavelength is 468nm, slit [5,5].) result is as shown in Figure 4.
Embodiment 4：
The complexing ratio of fluorescence probe 4 and cadmium ion
Keep probe and Cd (ClO4)2Concentration summation be 10 μM, regulation probe and Cd (ClO4)2Ratio
Example (probe：Cd(ClO4)2Concentration ratio 1:9,2:8,3:7,4:6,5:5,6:4,7:3,8:2,9:1), as a result as schemed
Shown in 5,5:Fluorescence intensity most shows by force that probe and cadmium ion are 1 when 5:1 complexing, wherein horizontal seat
Target [4] represents probe.
Embodiment 5：
Fluorescence probe 4 prepared by embodiment 1 is in DMSO-d6In with cadmium ion complexing nuclear-magnetism titrate
In DMSO-d6In, concentration and probe concentration prepared by embodiment 1 is 0.5mg/mL, is added dropwise thereto not
With the Cd of equivalent2+, nucleus magnetic hydrogen spectrum is done respectively.As a result as shown in fig. 6, nuclear magnetic spectrogram from top to bottom as
Add 0eq, 0.2eq, 0.4eq, 0.5eq, 0.6eq, 0.8eq, 1eq probe and Cd2+Ion,
Show probe and Cd2+Mol ratio is 1:When 1, stable complex compound can be formed.
Embodiment 6：
Selectivity of the fluorescence probe 4 to cadmium ion
10 μM of probe solutions are made into HEPES (pH=7.4) using foregoing 2mM probes mother liquor, then
Add the perchlorate HEPES solution (concentration is 2mM) of different metal, the different metal ions
Including：Cd2+、Pb2+、Hg2+、Zn2+、Li+、Na+、K+、Mg2+、Ca2+、Cr3+、Fe2+、Fe3+、
Cu2+、Co2+、Ni2+、Ag+、Pd2+, final concentration is 10 μM.As shown in fig. 7, add Cd (ClO4)2
Solution fluorescence is remarkably reinforced, the no too significant change of other metal ions, therefore in above-mentioned interference
Under the conditions of ion is existing, probe still has preferably selectivity to cadmium ion.
Embodiment 7：
The competitive relation of fluorescence probe 4 and cadmium ion and other ions
10 μM of probe solutions are made into HEPES (pH=7.4) using foregoing 2mM probes mother liquor, then
The perchlorate HEPES solution (concentration is 2mM) of different metal is added, final concentration is 10 μM,
It is eventually adding 10 μM of Cd (ClO of final concentration4)2Solution.As shown in Figure 8, the results showed that cadmium ion can be
Most of metal cements out from part, simply Zn2+,Cu2+There is interference to result.
Embodiment 8：
Probe 4 is used for the detection of cadmium ion in different pH solution
10 μM of probe solutions are prepared with pure water, equimolar amounts cadmium ion are added, with hydrochloric acid solution and hydrogen-oxygen
Change sodium solution and adjust pH from 1 to 12.5, test the fluorescence of cadmium-ion solution under different pH.As a result as schemed
Shown in 9, show that probe has wide pH working ranges, disclosure satisfy that and test concentration of cadmium ions under different condition
Requirement.
Embodiment 9：Fluorescence probe detects cadmium ion in the cell
Chinese hamster ovary celI is layered in culture dish, the DMEM culture mediums containing 10% hyclone in ware,
Cultivated 48 hours under 37 DEG C and 5% carbon dioxide conditions, be separately added into the 2mM of probe thereto
The μ L of DMSO mother liquors 20, cultivate 30 minutes, sop up culture medium with suction pipe, washed carefully with PBS
Born of the same parents 3 times, add fresh culture and 2mM Cd (ClO4)2The μ L of solution 20 continue culture 30 minutes, enter
Row imaging experiment, as a result as shown in Figure 10 (bar=20 μM).
Claims (7)
- A kind of 1. cadmium ion fluorescent probe, it is characterised in that：The fluorescence probe structure is as follows：
- A kind of 2. preparation method of cadmium ion fluorescent probe described in claim 1, it is characterised in that：Specifically Step is as follows：(1) synthesis of intermediate 4- amino -7- Xiao Ji Ben oxadiazoles：The chloro- 7- Xiao Ji Ben oxadiazoles of 4- are dissolved in Methanol, add ammoniacal liquor and obtain reaction solution, reaction solution reacts 12-36 hours under nitrogen protection, after reaction terminates Reaction solution, crude product purified by silica gel post separation are spin-dried for, gained solid is 4- amino -7- Xiao Ji Ben oxadiazoles；(2) synthesis of the chloro- N- of intermediate 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：4- amino -7- Xiao Ji Ben Evil Diazole and 4-dimethylaminopyridine, which are dissolved in dichloromethane, obtains solution A, and solution A is placed in ice bath and stirred, 2- chloracetyl chlorides are dissolved in dichloromethane again and obtain solution B, solution B is added dropwise in solution A, are stirred at room temperature Reaction 1-5 hours are mixed, reaction solution is spin-dried for and obtains crude product, crude product is by pillar layer separation, gained solid For the chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides；(3) synthesis of probe：By the chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides, 2,2 '-bipyridyl amine, Potassium carbonate and KI are added in acetonitrile, after nitrogen protection lower 50-80 DEG C of reaction 5-12 hour, are cooled to Room temperature, it is spin-dried for reaction solution and obtains crude product, by silica gel column separating purification crude product, obtaining product is Cadmium ion fluorescent probe.
- 3. preparation method according to claim 2, it is characterised in that：In step (1), the chloro- 7- of 4- The mass ratio of Xiao Ji Ben oxadiazoles and methanol is 1：The chloro- 7- Xiao Ji Ben oxadiazoles of 20-80,4- and ammonia spirit Mass ratio is 1：8-15；React at room temperature；In step (2), the mol ratio of 4- amino -7- Xiao Ji Ben oxadiazoles and 4-dimethylaminopyridine is 1： The mass ratio of 1-1.5,4- amino -7- Xiao Ji Ben oxadiazoles and dichloromethane is 1：80-150,4- amino -7- nitre The mol ratio of Ji Ben oxadiazoles and 2- chloracetyl chlorides is 1：The quality of 1-1.5,2- chloracetyl chloride and dichloromethane Than for 1：30-50；In step (3), the chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：2,2 '-bipyridyl amine：Carbonic acid The mol ratio of potassium is 1：1-1.2：2-2.5；The chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：The matter of KI Amount is than being 1：0.3-1；The chloro- N- of 2- (7- Xiao Ji Ben oxadiazoles -4-) acid amides：The mass ratio of acetonitrile is 1：200-700.
- 4. according to the preparation method of cadmium ion fluorescent probe described in claim 2, it is characterised in that：Step (1) ammonia concn described in is 28wt.%.
- 5. according to the preparation method of cadmium ion fluorescent probe described in claim 2, it is characterised in that：Step (1), the eluant, eluent of post separation described in step (2) and step (3) be dichloromethane, petroleum ether, acetic acid second One or two or more kinds in ester, chloroform, methanol, triethylamine or glacial acetic acid.
- 6. the cadmium ion fluorescent probe described in a kind of claim 1 is applied to the detection of cadmium ion.
- 7. application according to claim 6, it is characterised in that：It is water-soluble including detecting different pH value Cadmium ion in liquid and in biological specimen.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586459A (en) * | 2018-01-14 | 2018-09-28 | 常州大学 | Sour cyanines probe in a kind of side based on guanine and its preparation method and application |
| CN111875597A (en) * | 2020-08-05 | 2020-11-03 | 国家纳米科学中心 | Hypoxic fluorescent imaging probe and preparation method and application thereof |
| CN111892584A (en) * | 2020-08-05 | 2020-11-06 | 国家纳米科学中心 | Fluorescent probe and preparation method and application thereof |
-
2016
- 2016-06-14 CN CN201610411319.2A patent/CN107501252A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586459A (en) * | 2018-01-14 | 2018-09-28 | 常州大学 | Sour cyanines probe in a kind of side based on guanine and its preparation method and application |
| CN108586459B (en) * | 2018-01-14 | 2019-07-26 | 常州大学 | Sour cyanines probe in a kind of side based on guanine and its preparation method and application |
| CN111875597A (en) * | 2020-08-05 | 2020-11-03 | 国家纳米科学中心 | Hypoxic fluorescent imaging probe and preparation method and application thereof |
| CN111892584A (en) * | 2020-08-05 | 2020-11-06 | 国家纳米科学中心 | Fluorescent probe and preparation method and application thereof |
| CN111875597B (en) * | 2020-08-05 | 2022-01-11 | 国家纳米科学中心 | Hypoxic fluorescent imaging probe and preparation method and application thereof |
| CN111892584B (en) * | 2020-08-05 | 2022-01-11 | 国家纳米科学中心 | Fluorescent probe and preparation method and application thereof |
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Application publication date: 20171222 |