CN103923636B - Fluorescent small-molecule probe with CL-20 sensing function as well as preparation method and application method - Google Patents
Fluorescent small-molecule probe with CL-20 sensing function as well as preparation method and application method Download PDFInfo
- Publication number
- CN103923636B CN103923636B CN201410140349.5A CN201410140349A CN103923636B CN 103923636 B CN103923636 B CN 103923636B CN 201410140349 A CN201410140349 A CN 201410140349A CN 103923636 B CN103923636 B CN 103923636B
- Authority
- CN
- China
- Prior art keywords
- cyclodextrin
- methylpiperazine
- molecule probe
- fluorescent small
- naphthalimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a fluorescent small-molecule probe with a CL-20 sensing function as well as a preparation method and an application method. The fluorescent small-molecule probe is 4-methyl piperazine-1,8-naphthalimide-gamma-cyclodextrin. The fluorescent small-molecule probe is prepared by firstly preparing paratoluensulfonyl-gamma-cyclodextrin with gamma-cyclodextrin and paratoluensulfonyl chloride, then preparing N3-gamma-cyclodextrin with paratoluensulfonyl-gamma-cyclodextrin and NaN3 and then reacting N3-gamma-cyclodextrin with N-propargyl-4-methyl piperazine-1,8-naphthalimide and Cu(PPh3)3Br. The fluorescent small-molecule probe is used for detecting CL-20. The small-molecule probe prepared by utilizing the 1,8-naphthalimide preparation material with higher fluorescence quantum yield has higher limit of detection and sensitivity. Click reaction can ensure the stability of the fluorescent material in water solutions, thus improving the detection sensitivity. The fluorescent small-molecule material provided by the invention has the characteristics of simplicity in synthesis and easiness in synthesis in quantity, thereby providing a technical support for eliminating deep potential terroristic threats.
Description
Technical field
Embodiments of the present invention relate to the preparation of chemical field Small-molecule probe, and more specifically, embodiments of the present invention relate to a kind of in aqueous to CL-20 fluorescent small molecule probe having sensing function and preparation method thereof and using method.
Background technology
The high energy such as CL-20, highdensity poly-ammonium nitrate compound are a kind of novel energetic materials.To the detection of CL-20 to Homeland Security, warlike operation and environment measuring significant.Existing multiple method is used for the detection of CL-20 at present, as high performance liquid chromatography, mass spectrum, capillary electrophoresis etc.These methods present good detectability and wide linearity range, but when using these methods, usually need costly equipment or carry out loaded down with trivial details sample pretreatment.
Fluorescent optical sensor based on Fluorescence Increasing can perform well in the detection of explosive substance.Because this sensor selectivity and highly sensitive and can reduce interfering factors impact.Fluorescent material 1,8-naphthalimide and derivative thereof act on and electrostatic interaction mainly through π-π the detection of nitro-aromatic explosive substance in aqueous.But this method is infeasible to the detection of Cl-20 in aqueous, because the strong polarity of the aqueous solution will destroy the motivating force of catching Cl-20.In order to strengthen in aqueous to the binding ability of Cl-20, a kind of binding site CL-20 being carried out to effectively combine must be introduced in 1,8-naphthalimide detection system.
Cyclodextrin is a kind of important macrocyclic host, it have some important character as water-soluble, nontoxic, be easy to modify and with guest molecule as fluorescence dye forms complex compound.The clathration of fluorescence dye and cyclodextrin easily causes the noticeable change of its fluorescence property, the particularly change of fluorescence intensity.On the contrary, its resolving then can recover this change, and its process can be monitored and accurately for the detection of analyte.At present, the cyclodextrin/dye complexes connected by covalent linkage has successfully been applied to the detection of analyte.Such as pyrene, naphthalene, dansyl, the cyclodextrin derivative that the fluorophores such as naphthalimide are modified is for the detection of organic molecule.In testing process, cyclodextrin hole is as binding site, and fluorophore is signal element.
Summary of the invention
Instant invention overcomes the deficiencies in the prior art, there is provided a kind of in aqueous to the embodiment of CL-20 fluorescent small molecule probe having sensing function and preparation method thereof, using method, this fluorescent small molecule probe has strong capture ability to CL-20 in aqueous, can be simple and efficient CL-20 is detected and is not needed costly equipment and loaded down with trivial details sample pretreatment.
For solving above-mentioned technical problem, one embodiment of the present invention by the following technical solutions:
In aqueous CL-20 is had to a fluorescent small molecule probe for sensing function, described fluorescent small molecule probe is 4-methylpiperazine-1,8-naphthalimide-γ-cyclodextrin, and concrete structure is as follows:
In aqueous CL-20 is had to a preparation method for the fluorescent small molecule probe of sensing function, comprise the steps:
(1) γ-cyclodextrin is scattered in suitable quantity of water, and in ice-water bath, slowly drip the acetonitrile solution of sodium hydroxide, the acetonitrile solution of Tosyl chloride is slowly dripped again when solution is clarified completely, now adularescent precipitation occurs, at room temperature 3.5 ~ 4.5h is reacted after dropwising, adjust ph to 5.8 ~ 6.2, after filtration, recrystallization, obtain p-toluenesulfonyl-γ-cyclodextrin, the mol ratio of described γ-cyclodextrin, sodium hydroxide, Tosyl chloride is 1:1.2 ~ 1.3:1.4 ~ 1.5;
(2) p-toluenesulfonyl-γ-cyclodextrin is dissolved in appropriate DMF, then adds sodiumazide, in nitrogen protection, after reacting 3.5 ~ 4.5h at 104 ~ 108 DEG C, obtain 6 γ CDN through sedimentation, filtration, recrystallization
3, described p-toluenesulfonyl-γ-cyclodextrin and the mol ratio of sodiumazide are 1:1.5 ~ 2.5;
(3) by bromo-for 4-1,8-naphthalic anhydride is dissolved in appropriate pyridine, 4-methylpiperazine and triethylamine is added after dissolving completely, backflow 7.5 ~ 8.5h, through concentrated, sedimentation, filtration obtains 4-methylpiperazine-1,8-naphthalic anhydride, the mol ratio of bromo-1, the 8-naphthalic anhydride of described 4-, 4-methylpiperazine and triethylamine is 1:1.2 ~ 1.5:0.001 ~ 0.002;
(4) by 4-methylpiperazine-1,8-naphthalic anhydride is scattered in ethanol, add 2-propargyl-1-amine under nitrogen protection, by mixture backflow 5.5 ~ 6.5h, N-propargyl-4-methylpiperazine-1 is obtained with freezing absolute ethanol washing after filtration, 8-naphthalimide, the mol ratio of described 4-methylpiperazine-1,8-naphthalic anhydride and 2-propargyl-1-amine is 1:1.1 ~ 1.3;
(5) by 6 γ CDN
3, N-propargyl-4-methylpiperazine-1,8-naphthalimide, Cu (PPh
3)
3br is dissolved in appropriate DMF, in nitrogen protection, reacts 11.5 ~ 12.5h at 50 ~ 60 DEG C, obtains 4-methylpiperazine-1,8-naphthalimide-γ-cyclodextrin, 6 described γ CDN after sedimentation, filtration, recrystallization
3, N-propargyl-4-methylpiperazine-1,8-naphthalimide, Cu (pph
3)
3the mol ratio of Br is 1:1:0.02.
Further technical scheme is: described 6 γ CDN
3structure be:
6 γ CDN
3structure and 6 β CDN
3structure substantially identical, but cyclodextrin structure partial lumen size is different, because the molecular size that detected by Small-molecule probe and cyclodextrin structure cavity size determine the ability to function of Small-molecule probe to detection molecules simultaneously, therefore, when detecting for different materials, need the cyclodextrin structure corresponding to its molecular size, make Small-molecule probe realize catching effect to tested substance molecule.
In aqueous CL-20 is had to a using method for the fluorescent small molecule probe of sensing function, comprises following steps:
A. detection reaction system is prepared: system cumulative volume is 3mL, and wherein the concentration of fluorescent small molecule probe is 1.2 × 10
-4mol/L, surplus is water;
The detection of b.CL-20: take 390nm as fluorescence exciting wavelength, 390 ~ 650nm is fluoroscopic examination wavelength, carries out fluoroscopic examination to the detection reaction system adding CL-20;
C. the fluoroscopic examination curve of each detection reaction system is recorded.
Further technical scheme is: the fluoroscopic examination of described CL-20 is limited to 7.7 × 10
-7mol/L.
CL-20 is had to an application for the fluorescent small molecule probe of sensing function, for detecting the concentration of CL-20.
Compared with prior art, one of beneficial effect of the present invention is: 1, the 8-naphthalimide that present method utilizes fluorescence quantum yield higher prepares material, has higher detectability and sensitivity than prior art.The present invention introduces nitrine functional group by introducing on alkynyl and γ-cyclodextrin on 1,8-naphthalimide skeleton, and utilizes Click to react to modify on γ-cyclodextrin by 1,8-naphthalimide, and obtaining take 1,8-naphthalimide as the fluorescent small molecule material of parent.Click reaction can ensure fluorescent material stability in aqueous, thus improves detection sensitivity.The raising of sensitivity makes to develop sensitiveer explosive detection instrument becomes possibility, and meanwhile, fluorescent small molecule material provided by the invention has the feature of the simple and easily a large amount of synthesis of synthesis, and this provides technical support for the threat of terrorism eliminating deep layer potential.
Accompanying drawing explanation
Fig. 1 is the structure of CL-20.
Fig. 2 is the present invention has the fluorescent small molecule probe of sensing function in aqueous structure to CL-20.
Fig. 3 is the synthetic route that one embodiment of the invention prepares fluorescent small molecule probe.
Fig. 4 is one embodiment of the invention fluorescent small molecule probe and the interactional spectrum change figure of CL-20.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
(1) preparation of intermediate p-toluenesulfonyl-γ-cyclodextrin
γ-cyclodextrin (12.0g, 6.4mmol) is scattered in 100mL water, and slowly drips 1mL aqueous sodium hydroxide solution (8.2mol/L in ice-water bath.), γ-cyclodextrin is dissolved completely.Now Tosyl chloride (1.748g, 9.2mmol) be dissolved in 4mL acetonitrile solution and be slowly added drop-wise in the above-mentioned mixed solution dissolving γ-cyclodextrin, in the process of dropping, the precipitation of adularescent produces.After this mixture is at room temperature reacted 4h, be adjusted between 5.8 ~ 6.2 with the hydrochloric acid soln of 3mol/L by pH value, filter, in water, recrystallization obtains target product.
(2) intermediate p-toluenesulfonyl-γ-cyclodextrin is utilized to prepare N
3-γ-cyclodextrin (6 γ CDN
3)
By p-toluenesulfonyl-γ-cyclodextrin (1.73g, 1.34mmol), NaN
3(174mg, 2.68mmol) is dissolved in 10mL DMF, and under nitrogen protection, reflux this mixing solutions at 106 DEG C 4h.After completion of the reaction solution is cooled to room temperature, and carries out sedimentation in acetone, solid collected by filtration, collected solid is carried out recrystallization in acetone.
(3) preparation of 4-methylpiperazine-1,8-naphthalic anhydride
In round-bottomed flask, add bromo-1, the 8-naphthalic anhydride (1.5g, 5.4mmol) of 4-, pyridine 10mL, after bromo-1, the 8-naphthalic anhydride of 4-dissolves completely, drip 4-methylpiperazine (0.6g, 6.6mmol) again, triethylamine (1mL is about 0.001mmol).Concentration of reaction solution after 106 DEG C of backflow 8h, and in concentrated solution, add water, solid collected by filtration, vacuum-drying obtains target product 0.78g.
(4) 4-methylpiperazine-1,8-naphthalic anhydride is utilized to prepare N-propargyl-4-methylpiperazine-1,8-naphthalimide
4-methylpiperazine-1,8-naphthalic anhydride (415mg, 1.4mmol) is scattered in 7mL ethanol, vacuumizes, add 2-propargyl-1-amine (0.1mL, 1.54mmol) when nitrogen protection, and 6h that reaction solution is refluxed at 90 DEG C.After completion of the reaction reaction solution is cooled to room temperature, filters, and with freezing absolute ethanol washing, collect filter residue vacuum-drying.
(5) 6 γ CDN are utilized
3with N-propargyl-4-methylpiperazine-1,8-naphthalimide, Cu (PPh
3)
3br prepares 4-methylpiperazine-1,8-naphthalimide-γ-cyclodextrin
6 γ CDN
3(179mg, 0.13mmol), N-propargyl-4-methylpiperazine-1,8-naphthalimide (43mg, 0.13mmol), Cu (pph
3)
3br (2.6mg, 0.0026mmol) joins in 4mL DMF, and nitrogen protection reacts 12h at 55 DEG C.After being cooled to room temperature, reaction solution is added drop-wise in 200mL acetone and carries out sedimentation, filter, washing with acetone, collect solid, and the solid of collection is carried out recrystallization in water or acetone.
Fig. 2 is the structure of final obtained fluorescent small molecule probe 4-methylpiperazine-1,8-naphthalimide-γ-cyclodextrin, and Fig. 3 is the schema of above-mentioned preparation process.
After fluorescent small molecule probe preparation completes, above-mentioned fluorescent small molecule probe can be utilized in water to detect CL-20, and the structure of CL-20 as shown in Figure 1.
Its detection method is: the total system of reaction first preparing 3mL, and the Small-molecule probe concentration of the total system of this reaction is 1.2 × 10
-4mol/L, surplus is water, Small-molecule probe is placed in fluorescence pond, and to add concentration wherein be respectively 0,1.5,3.3,6.6,9.9,13.2,16.6,19.8 (× 10
-5mol/L) CL-20, with 390nm fluorescence excitation, 390nm fluoroscopic examination, obtains spectrum change figure as shown in Figure 4.
Fluorescent small molecule probe prepared by the present embodiment is for detecting the concentration of CL-20, and the Cmin of its fluoroscopic examination is 7.7 × 10
-7mol/L.
Embodiment 2
12.8mmol γ-cyclodextrin is scattered in 180mL water, and in ice-water bath, slow dropping 2mL concentration is the aqueous sodium hydroxide solution of 8.5mol/L, and γ-cyclodextrin is dissolved completely.19.2mmol Tosyl chloride is dissolved in 9mL acetonitrile solution, strict control is there is no to the concentration of the acetonitrile solution of Tosyl chloride herein, but concentration when being just all dissolved in acetonitrile solution with Tosyl chloride is advisable.Slowly be added drop-wise to by the acetonitrile solution of Tosyl chloride in the above-mentioned mixed solution dissolving γ-cyclodextrin, in the process of dropping, the precipitation of adularescent produces.After this mixture is at room temperature reacted 3.5h, be adjusted between 5.8 ~ 6.2 with the hydrochloric acid soln of 3.5mol/L by pH value, filter, in water, recrystallization obtains p-toluenesulfonyl-γ-cyclodextrin.
By 1.32mmol p-toluenesulfonyl-γ-cyclodextrin, 3.3mmol NaN
3be dissolved in 10mL dimethyl formamide (DMF), under nitrogen protection, reflux this mixing solutions at 104 DEG C 4.5h.After completion of the reaction solution is cooled to room temperature, and carries out sedimentation in acetone, solid collected by filtration, collected solid is carried out in water recrystallization and obtain 6 γ CDN
3.
Bromo-1, the 8-naphthalic anhydride of 10.8mmol4-is all dissolved in after in 23mL pyridine and instills 16mmol4-methylpiperazine, 4mL triethylamine (being about 0.004mmol) again.Concentration of reaction solution after 115 DEG C of backflow 8.5h, and in concentrated solution, add water, solid collected by filtration, vacuum-drying obtains 4-methylpiperazine-1,8-naphthalic anhydride 1.5g.
1.3mmol4-methylpiperazine-1,8-naphthalic anhydride is scattered in 7mL ethanol, vacuumizes, add 1.65mmol2-propargyl-1-amine when nitrogen protection, and 5.5h that reaction solution is refluxed at 85 DEG C.After completion of the reaction reaction solution is cooled to room temperature, filters, and with freezing absolute ethanol washing, collect filter residue vacuum-drying and obtain N-propargyl-4-methylpiperazine-1,8-naphthalimide.
By 2mmol6 γ CDN
3, 2mmol N-propargyl-4-methylpiperazine-1,8-naphthalimide, 0.04mmolCu (pph
3)
3br joins in 25mL DMF, and nitrogen protection reacts 12.5h at 50 DEG C.After being cooled to room temperature, reaction solution is added drop-wise in 300mL acetone and carries out sedimentation, filter, washing with acetone, collect solid, and the solid of collection is carried out in water or acetone recrystallization and obtain 4-methylpiperazine-1,8-naphthalimide-γ-cyclodextrin, i.e. fluorescent small molecule probe.
The total system of reaction of preparation 3mL, the Small-molecule probe concentration of the total system of this reaction is 1.2 × 10
-4mol/L, surplus is water, Small-molecule probe is placed in fluorescence pond, and to add concentration wherein be respectively 0,1.5,3.3,6.6,9.9,13.2,16.6,19.8 (× 10
-5mol/L) CL-20, with 390nm fluorescence excitation, 523nm fluoroscopic examination.
Embodiment 3
Adopt the preparation method identical with embodiment 1 or embodiment 2; γ-cyclodextrin is 12.8mmol; the aqueous sodium hydroxide solution 2mL of 8mol/L; after 17.92mmol Tosyl chloride is dissolved in and reacts 4.5h under room temperature after 9mL acetonitrile solution prepares mixture; with the hydrochloric acid soln of 2.5mol/L, pH value is adjusted between 5.8 ~ 6.2; filter, in water, recrystallization obtains p-toluenesulfonyl-γ-cyclodextrin.
1.32mmol p-toluenesulfonyl-γ-cyclodextrin, 2mmol NaN
3, 10mL dimethyl formamide mixing solutions under nitrogen protection, react 3.5h at 108 DEG C.After completion of the reaction solution is cooled to room temperature, and carries out sedimentation in acetone, solid collected by filtration, collected solid is carried out in water recrystallization and obtain 6 γ CDN
3.
Bromo-1, the 8-naphthalic anhydride of 10.8mmol4-, 25mL pyridine, 13mmol4-methylpiperazine, 3mL triethylamine (being about 0.003mmol).Concentration of reaction solution after 115 DEG C of backflow 7.5h, and in concentrated solution, add water, solid collected by filtration, vacuum-drying obtains 4-methylpiperazine-1,8-naphthalic anhydride 1.48g.
1.3mmol4-methylpiperazine-1,8-naphthalic anhydride, 1.56mmol2-propargyl-1-amine and ethanol in proper amount preparation feedback liquid, nitrogen protection, 88 DEG C of backflow 6.5h.After completion of the reaction reaction solution is cooled to room temperature, filters, and with freezing absolute ethanol washing, collect filter residue vacuum-drying and obtain N-propargyl-4-methylpiperazine-1,8-naphthalimide.
1mmol6 γ CDN
3, 1mmol N-propargyl-4-methylpiperazine-1,8-naphthalimide, 0.02mmolCu (pph
3)
3br joins in 15mL DMF, and nitrogen protection reacts 11.5h at 60 DEG C.After being cooled to room temperature, reaction solution is added drop-wise in 200mL acetone and carries out sedimentation, filter, washing with acetone, collect solid, and the solid of collection is carried out in water or acetone recrystallization and obtain 4-methylpiperazine-1,8-naphthalimide-γ-cyclodextrin, i.e. fluorescent small molecule probe.
The total system of reaction of preparation 3mL, the Small-molecule probe concentration of the total system of this reaction is 1.2 × 10
-4mol/L, surplus is water, Small-molecule probe is placed in fluorescence pond, and to add concentration wherein be respectively 0,1.5,3.3,6.6,9.9,13.2,16.6,19.8 (× 10
-5mol/L) CL-20, with 390nm fluorescence excitation, 650nm fluoroscopic examination.
Although with reference to multiple explanatory embodiment of the present invention, invention has been described here, but, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.More particularly, in the scope of, accompanying drawing open in the application and claim, multiple modification and improvement can be carried out to the building block of subject combination layout and/or layout.Except the modification of carrying out building block and/or layout is with except improvement, to those skilled in the art, other purposes also will be obvious.
Claims (6)
1. CL-20 is had to a fluorescent small molecule probe for sensing function, it is characterized in that: described fluorescent small molecule probe is 4-methylpiperazine-1,8-naphthalimide-γ-cyclodextrin, and concrete structure is as follows:
2. CL-20 is had to a preparation method for the fluorescent small molecule probe of sensing function, it is characterized in that: its preparation method comprises the steps:
(1) γ-cyclodextrin is scattered in suitable quantity of water, and in ice-water bath, slowly drip the acetonitrile solution of sodium hydroxide, the acetonitrile solution of Tosyl chloride is slowly dripped again when solution is clarified completely, now adularescent precipitation occurs, at room temperature 3.5 ~ 4.5h is reacted after dropwising, adjust ph to 5.8 ~ 6.2, after filtration, recrystallization, obtain p-toluenesulfonyl-γ-cyclodextrin, the mol ratio of described γ-cyclodextrin, sodium hydroxide, Tosyl chloride is 1:1.2 ~ 1.3:1.4 ~ 1.5;
(2) p-toluenesulfonyl-γ-cyclodextrin is dissolved in appropriate DMF, then adds sodiumazide, in nitrogen protection, after reacting 3.5 ~ 4.5h at 104 ~ 108 DEG C, obtain 6 γ CDN through sedimentation, filtration, recrystallization
3, described p-toluenesulfonyl-γ-cyclodextrin and the mol ratio of sodiumazide are 1:1.5 ~ 2.5;
(3) by bromo-for 4-1,8-naphthalic anhydride is dissolved in appropriate pyridine, 4-methylpiperazine and triethylamine is added after dissolving completely, backflow 7.5 ~ 8.5h, through concentrated, sedimentation, filtration obtains 4-methylpiperazine-1,8-naphthalic anhydride, the mol ratio of bromo-1, the 8-naphthalic anhydride of described 4-, 4-methylpiperazine and triethylamine is 1:1.2 ~ 1.5:0.001 ~ 0.002;
(4) by 4-methylpiperazine-1,8-naphthalic anhydride is scattered in ethanol, add 2-propargyl-1-amine under nitrogen protection, by mixture backflow 5.5 ~ 6.5h, N-propargyl-4-methylpiperazine-1 is obtained with freezing absolute ethanol washing after filtration, 8-naphthalimide, the mol ratio of described 4-methylpiperazine-1,8-naphthalic anhydride and 2-propargyl-1-amine is 1:1.1 ~ 1.3;
(5) by 6 γ CDN
3, N-propargyl-4-methylpiperazine-1,8-naphthalimide, Cu (PPh
3)
3br is dissolved in appropriate DMF, in nitrogen protection, reacts 11.5 ~ 12.5h at 50 ~ 60 DEG C, obtains 4-methylpiperazine-1,8-naphthalimide-γ-cyclodextrin, 6 described γ CDN after sedimentation, filtration, recrystallization
3, N-propargyl-4-methylpiperazine-1,8-naphthalimide, Cu (pph
3)
3the mol ratio of Br is 1:1:0.02.
3. preparation method CL-20 being had to the fluorescent small molecule probe of sensing function according to claim 2, is characterized in that: described 6 γ CDN
3structure be:
4. using method CL-20 being had to the fluorescent small molecule probe of sensing function as claimed in claim 1, is characterized in that: comprise following steps:
A. detection reaction system is prepared: system cumulative volume is 3mL, and wherein the concentration of fluorescent small molecule probe is 1.2 × 10
-4mol/L, surplus is water;
The detection of b.CL-20: take 390nm as fluorescence exciting wavelength, 390 ~ 650nm is fluoroscopic examination wavelength, carries out fluoroscopic examination to the detection reaction system adding CL-20;
C. the fluoroscopic examination curve of each detection reaction system is recorded.
5. according to claim 4 CL-20 is had to the using method of the fluorescent small molecule probe of sensing function, it is characterized in that: the fluoroscopic examination of described CL-20 is limited to 7.7 × 10
-7mol/L.
6. application CL-20 being had to the fluorescent small molecule probe of sensing function as claimed in claim 1, is characterized in that: for detecting the concentration of CL-20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410140349.5A CN103923636B (en) | 2014-04-09 | 2014-04-09 | Fluorescent small-molecule probe with CL-20 sensing function as well as preparation method and application method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410140349.5A CN103923636B (en) | 2014-04-09 | 2014-04-09 | Fluorescent small-molecule probe with CL-20 sensing function as well as preparation method and application method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103923636A CN103923636A (en) | 2014-07-16 |
| CN103923636B true CN103923636B (en) | 2015-07-08 |
Family
ID=51142038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410140349.5A Active CN103923636B (en) | 2014-04-09 | 2014-04-09 | Fluorescent small-molecule probe with CL-20 sensing function as well as preparation method and application method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103923636B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371042A (en) * | 2014-11-07 | 2015-02-25 | 中国工程物理研究院化工材料研究所 | Functional monomer, preparation method of functional monomer as well as fluorescent imprinted membrane and preparation method of fluorescent imprinted membrane |
| CN109651533A (en) * | 2018-12-27 | 2019-04-19 | 浙江外国语学院 | A kind of the beta-cyclodextrin fluorescent optical sensor and its synthetic method of naphthylamino modification |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134289A (en) * | 2010-12-28 | 2011-07-27 | 南开大学 | Perylene bisimide bridged full-methylated beta-cyclodextrin assembly and application thereof |
| CN102532347A (en) * | 2011-12-28 | 2012-07-04 | 华东师范大学 | Synthesis method of tri(terpyridyl ruthenium)beta-cyclodextrin compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090013826A (en) * | 2006-05-15 | 2009-02-05 | 닛토덴코 가부시키가이샤 | Light emitting devices and compositions |
-
2014
- 2014-04-09 CN CN201410140349.5A patent/CN103923636B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134289A (en) * | 2010-12-28 | 2011-07-27 | 南开大学 | Perylene bisimide bridged full-methylated beta-cyclodextrin assembly and application thereof |
| CN102532347A (en) * | 2011-12-28 | 2012-07-04 | 华东师范大学 | Synthesis method of tri(terpyridyl ruthenium)beta-cyclodextrin compound |
Non-Patent Citations (1)
| Title |
|---|
| 苝酰亚胺共价、非共价连接环糊精设计及合成研究;马亭亭;《山东师范大学硕士学位论文》;20120831;第二章第26-56页，及其第三章3.4.2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103923636A (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | A novel reaction-based colorimetric and ratiometric fluorescent sensor for cyanide anion with a large emission shift and high selectivity | |
| Sun et al. | A novel oligothiophene-based colorimetric and fluorescent “turn on” sensor for highly selective and sensitive detection of cyanide in aqueous media and its practical applications in water and food samples | |
| Huang et al. | Multisignal chemosensor for Cr3+ and its application in bioimaging | |
| Jamkratoke et al. | ADA sensors based on naphthoimidazoledione and boronic acid as turn-on cyanide probes in water | |
| CN102876323B (en) | Cadmium ion fluorescence probe, preparation method and application | |
| Krasnoperov et al. | Luminescent probes for ultrasensitive detection of nucleic acids | |
| Khandare et al. | Fluorescence turn-on chemosensor for the detection of dissolved CO2 based on ion-induced aggregation of tetraphenylethylene derivative | |
| CN103214428B (en) | Benzothiazole-cyanophenyl compound serving as hydrazine fluorescence probe as well as preparation method and application method of benzothiazole-cyanophenyl compound | |
| CN102942537B (en) | Benzothiazole-aniline compound used as pH fluorescent probe and preparation method thereof | |
| Xu et al. | A colorimetric and fluorometric dual-modal chemosensor for cyanide in water | |
| CN102898353B (en) | Carbazole benzaldehyde o-phenylenediamine bis-schiff base and preparation method thereof | |
| Ozdemir et al. | Phenanthroimidazole and dicyanovinyl-substituted triphenylamine for the selective detection of CN−: DFT calculations and practically applications | |
| Xing et al. | UV–vis spectral property of a multi-hydroxyl Schiff-base derivative and its colorimetric response to some special metal ions | |
| Dong et al. | A new naphthopyran-based chemodosimeter with aggregation-induced emission: Selective dual-channel detection of cyanide ion in aqueous medium and test strips | |
| Rathikrishnan et al. | 4, 7-Diaryl indole-based fluorescent chemosensor for iodide ions | |
| Yin et al. | A new aggregation-induced emission active red-emitting fluorescent sensor for ultrarapidly, selectively and sensitively detecting hydrazine and its multiple applications | |
| Bar et al. | Asymmetric bimetallic ruthenium (II) complexes selectively sense cyanide in water through significant modulation of their ground and excited state properties | |
| Zuo et al. | Ratiometric fluorescence sensing of formaldehyde in food samples based on bifunctional MOF | |
| Bu et al. | A phenanthro [9, 10-d] imidazole-based AIE active fluorescence probe for sequential detection of Ag+/AgNPs and SCN− in water and saliva samples and its application in living cells | |
| Guo et al. | A Zn-based coordination polymer as a luminescent sensor for simple and sensitive detecting of sulfonamides antibiotics and nitroaromatic | |
| Liu et al. | A new “turn-on” fluorescent sensor for highly selective sensing of H2PO4− | |
| CN104151867B (en) | Temperature response type cyclodextrin probe double with pH and preparation method thereof | |
| CN103937487B (en) | A kind of phosphorescence fluorion probe and Synthesis and applications thereof | |
| CN103923636B (en) | Fluorescent small-molecule probe with CL-20 sensing function as well as preparation method and application method | |
| CN101672780B (en) | Analytical method for detecting trace mercury in aqueous medium based on the color change of fluorescence |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |