CN104860840A - Preparation and application of fluorescence enhancement type hydrogen sulfide fluorescent probe - Google Patents
Preparation and application of fluorescence enhancement type hydrogen sulfide fluorescent probe Download PDFInfo
- Publication number
- CN104860840A CN104860840A CN201510205626.0A CN201510205626A CN104860840A CN 104860840 A CN104860840 A CN 104860840A CN 201510205626 A CN201510205626 A CN 201510205626A CN 104860840 A CN104860840 A CN 104860840A
- Authority
- CN
- China
- Prior art keywords
- hydrogen sulfide
- fluorescent probe
- dissolved
- distilled water
- sulfide fluorescent
- 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.)
- Pending
Links
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a novel compound for hydrogen sulfide fluorescent recognition, particularly relates to a preparation method and application of a novel fluorescent probe, and belongs to the technical field of chemical analysis and detection. The molecular structural formula of the novel fluorescent probe is shown in the specification. The fluorescent probe is used for fluorescence sensing analysis of hydrogen sulfide in the environment or biological samples, is good in selectivity and high in anti-jamming capacity, can flexibly and rapidly discover the hydrogen sulfide in the samples through detection, has good water solubility, and has the good application prospect in the aspect of biomedical research.
Description
Technical field
What the present invention relates to is chemical analysis detection technique field, and the preparation method and this fluorescent probe that are specifically related to a kind of novel hydrogen sulfide fluorescent probe are detecting the application in hydrogen sulfide.
Background technology
Hydrogen sulfide (H
2s) be a kind of hypertoxic gas, its smell shows as rotten egg smell when lower concentration, has impact to human eye, respiratory tract and central nervous system.Hydrogen sulfide is as the 3rd gaseous signal molecule be found after carbon monoxide and nitrogen protoxide in recent years, receives the extensive concern of scientific researcher.Biological study shows, the physiology of hydrogen sulfide in human body and pathological process have vital effect, and it has vital role in the pathogenic process of the disease such as hypertension, heart trouble.Up to now, the method detecting hydrogen sulfide has had a variety of, wherein has electrochemical method, colorimetry, vapor-phase chromatography etc.But fluorescent probe analytical technology relies on its highly sensitive and convenient easy-operating feature to attract the sight of numerous investigator.Fluorescent probe at present for hydrogen sulfide has had a variety of, and the principle of work of most of hydrogen sulfide fluorescent probe introduces azido-or nitro quench fluorescence, then by hydrogen sulfide by after azido-or nitroreduction, fluorescence is recovered.Secondly fluorescent probe needs the detection that good cell membrane permeability could realize in active somatic cell, so the water miscible raising of fluorescent probe is also one of goal in research.
Summary of the invention
One of the object of the invention is to provide one and synthesizes simple, gentle, the lower-cost fluorescent probe synthetic method of reaction conditions; Two of object be to provide a kind of highly sensitive, selectivity good, immunity from interference is strong, can realize the fluorescent probe of Fluorometric assay hydrogen sulfide.
The present invention uses Fluorometric assay hydrogen sulfide, with acetonaphthone derivative for fluorophore, take azido-as the recognition group of hydrogen sulfide.
The present invention's technical scheme taked of dealing with problems is, a kind of fluoroscopic examination hydrogen sulfide fluorescent probe, and its molecular structural formula is,
the synthetic route of this fluorescent probe is as follows,
Concrete preparation method comprises the following steps: 1) be dissolved in methylene dichloride by 2-methoxyl group-6-ethanoyl naphthalene; add mass fraction 36% concentrated hydrochloric acid again; be heated to 85 DEG C of backflow 4h, stop heating being cooled to room temperature, regulate pH to neutral with 50% sodium hydroxide solution; separate out solid; filter to obtain filter cake, with distilled water wash 3 times, vacuum-drying 24h; obtain white solid, be compound 1.2) by previous step products therefrom 1, Sodium Pyrosulfite and strong aqua are placed in autoclave, are heated to 140 DEG C in air dry oven baking oven, constant temperature 96h, stop heating, be cooled to room temperature, adularescent solid is separated out, suction filtration, filter cake is product, distilled water wash 3 times, vacuum-drying 24h, obtains white solid and is compound 2.3) upper step is obtained product 2 to be dissolved in concentrated hydrochloric acid, then Sodium Nitrite is dissolved in distilled water, under ice-water bath, and it is slowly added drop-wise in reaction solution, stir 0.5h; Sodiumazide is dissolved in distilled water, and it is slowly added drop-wise in reaction solution, there is a large amount of bubble formation, stir 0.5h, regulate pH to neutral with sodium carbonate, dichloromethane extraction, revolve and steam to obtain oily crude product, add a small amount of methylene dichloride again, wet method loading column chromatography for separation, vacuum-drying obtains milk yellow solid and is probe molecule.Synthesis and the detection method of this probe is illustrate in greater detail in the embodiment of this specification sheets.
Fluorescent molecular probe using method of the present invention is as follows, and being dissolved in by probe molecule containing 30% acetonitrile, pH is in the HEPES buffered soln of 7.4, tests under room temperature.When adding sulfonium ion, because azido-is reduced to amino through hydrogen sulfide, fluorescence is recovered.Probe molecule and hydrogen sulfide action principle as follows,
The specific features of hydrogen sulfide fluorescent probe of the present invention is as follows: probe molecule without obvious emission peak, but with hydrogen sulfide effect after, there is emission peak at 490nm place in probe molecule, fluorescence intensity strengthens more than 200 times.
Probe molecule of the present invention synthesis is simple, and cost is lower, good to the selectivity of hydrogen sulfide, immunity from interference strong, fast response time, and in biological chemistry, the fields such as environmental science have actual using value.
Accompanying drawing explanation
Fig. 1 is the selectivity of fluorescent probe of the present invention, fluorescent probe (5.0 × 10
-6mol/L) at HEPES buffered soln (20mM, V
acetonitrile/ V
hEPES=3/7, pH=7.4) in, with the fluorescence spectrum after different anions effect, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 2 is the immunity from interference of fluorescent probe of the present invention, and sulfonium ion and other negatively charged ion coexist, with fluorescent probe (5.0 × 10
-6mol/L) at buffered soln (V
acetonitrile/ V
hEPES=3/7, pH=7.4) in effect after fluorescence intensity ratio (I/I
0) histogram, the interfering substance of selection is respectively: 1, NaF; 2, NaCl; 3, NaBr; 4, NaI; 5, NaNO
3; 6, NaNO
2; 7, AcONa; 8, NaN
3; 9, Na
2sO
4; 10, Na
2s
2sO
3; 11, NaClO; 12, NaSCN; 13, CN
-; 14, H
2o
2; 15, Cys; 16, HCy; 17, GSH; 18, Na
3pO
4; 19, Na
2cO
3; 20, Na
2sO
3.
Fig. 3 is fluorescent probe (5.0 × 10 of the present invention
-6mol/L) at HEPES buffered soln (20mM, V
acetonitrile/ V
hEPES=3/7, pH=7.4) in, change with the fluorescence spectrum after the effect of different concns sulfonium ion, X-coordinate is wavelength, and ordinate zou is fluorescence intensity.
Fig. 4 is fluorescent probe (5.0 × 10 of the present invention
-6mol/L) at HEPES buffered soln (20mM, V
acetonitrile/ V
hEPES=3/7, pH=7.4) in, with the linear relationship of sulfonium ion concentration, X-coordinate is sulfonium ion concentration, and ordinate zou is fluorescence intensity.
Fig. 5 is fluorescent probe (5.0 × 10 of the present invention
-6mol/L) at HEPES buffered soln (20mM, V
acetonitrile/v
hEPES=3/7, pH=7.4) in, with fluorescence intensity in sulfonium ion mechanism over time, X-coordinate is the time, and ordinate zou is fluorescence intensity.
Fig. 6 is fluorescent probe (5.0 × 10 of the present invention
-6mol/L) in different pH value buffered soln, with the fluorescence intensity before and after sulfonium ion effect, X-coordinate is pH, and ordinate zou is fluorescence intensity.
Embodiment
Embodiment 1: the synthesis of compound 1
By 2-methoxyl group-6-ethanoyl naphthalene (1.5170g; 7.58mmol) be dissolved in 6mL methylene dichloride, then add mass fraction 36% concentrated hydrochloric acid (100mL), be heated to 85 DEG C of backflow 4h; heating is stopped to be cooled to room temperature; regulate pH to neutral with 50% sodium hydroxide solution, separate out solid, filter; filter cake is product; distilled water wash 3 times, vacuum-drying 24h, obtains white solid.Output: 1.3552g.Output: 96%.The synthetic method reference of this compound
1.
Embodiment 2: the synthesis of compound 2
Upper step gained compound 1 (0.5200g, 2.8mmol), Sodium Pyrosulfite (1.3300g, 7.0mmol) and strong aqua 15mL, as in autoclave, are heated to 140 DEG C in air dry oven baking oven, and constant temperature 96h, stops
1w.Yao, Y.Yan, L.Xue, C.Zhang, G.Li, Q.Zheng, Y.S.Zhao, H.Jiang, J.N.Yao, Angew.Chem.Int.Ed.2013,52,8713 – 8717. are heating only, is cooled to room temperature, adularescent solid is separated out, suction filtration, and filter cake is product, distilled water wash 3 times, vacuum-drying 24h, obtains white solid.Output 0.2585g.Productive rate: 49.7%.
1H NMR(400MHz,CDCl
3)δ8.30(d,J＝1.6Hz,1H),7.91(dd,J＝8.8,2.0Hz,1H),7.74(d,J＝8.6Hz,1H),7.58(d,J＝9.2Hz,1H),6.97(dd,J＝8.6,2.2Hz,1H),6.95(d,J＝2.2Hz,1H),4.05(s,2H),2.66(s,3H).
13C NMR(100MHz,CDCl
3)δ198.1,147.0,137.8,131.6,131.4,130.7,126.7,126.2,124.9,118.9,108.1,26.7.
Embodiment 3: the synthesis of probe molecule
Upper step gained compound 2 (0.0930g, 0.5mmol) is dissolved in 3mL concentrated hydrochloric acid; Again Sodium Nitrite (0.0690g, 1.0mmol) is dissolved in 0.5mL distilled water, under ice-water bath, and it is slowly added drop-wise in reaction solution, stir 0.5h; By sodiumazide (0.1630g, 5mmol) be dissolved in 1mL distilled water, and it is slowly added drop-wise in reaction solution, there is a large amount of bubble formation, stir 0.5h, regulate pH to neutral with sodium carbonate, dichloromethane extraction, revolves and steams methylene dichloride and obtain oily crude product, then add a small amount of methylene dichloride, wet method loading column chromatography for separation, vacuum-drying obtains milk yellow solid.Output: 0.0472g.Output: 39.1%.
1H NMR(500MHz,CDCl
3)δ8.45(s,2H),8.45(s,1H),8.08(d,J＝8.6Hz,1H),7.98(d,J＝8.7Hz,1H),7.83(d,J＝8.6Hz,1H),7.50(s,1H),7.25(d,J＝8.7Hz,1H),2.74(s,3H).
13C NMR(126MHz,CDCl
3)δ197.65,140.31,136.31,134.06,131.61,130.01,127.42,125.22,119.76,115.64,26.63.
Embodiment 5: the application of hydrogen sulfide fluorescent probe of the present invention
Probe is dissolved in buffered soln (V
acetonitrile/ V
hEPES=3/7, pH=7.4) in be mixed with 5.0 × 10
-6the solution of mol/L, adds NaF, NaCl, NaBr, NaI, NaNO in solution
3, NaNO
2, AcONa, NaN
3, Na
2sO
4, Na
2s
2sO
3, NaClO, NaSCN, CN
-, H
2o
2, Cys, HCy, GSH, Na
3pO
4, Na
2cO
3, Na
2sO
3do not cause the change of fluorescence afterwards, add S
2-after cause very significantly change in fluorescence, this fluorescent probe shows the identification of highly sensitive, highly selective to hydrogen sulfide.Work as S
2-respectively with interfering substance NaF, NaCl, NaBr, NaI, NaNO
3, NaNO
2, AcONa, NaN
3, Na
2sO
4, Na
2s
2sO
3, NaClO, NaSCN, CN
-, H
2o
2, Cys, HCy, GSH, Na
3pO
4, Na
2cO
3, Na
2sO
3when coexisting, the impact of the interference-free factor of probe, shows good immunity from interference.This probe to sulfonium ion generation response clearly, can both have certain practical value for realizing intracellular fluorometric analysis in slightly acidic to alkaline environment.
Claims (3)
1. a Fluorescence Increasing type hydrogen sulfide fluorescent probe, its structure is:
。
2. the preparation method of hydrogen sulfide fluorescent probe as claimed in claim 1, is characterized in that being prepared according to the following steps:
A 2-methoxyl group-6-ethanoyl naphthalene is dissolved in methylene dichloride by (); add mass fraction 36% concentrated hydrochloric acid again; be heated to 85 DEG C of backflow 4h, stop heating being cooled to room temperature, regulate pH to neutral with 50% sodium hydroxide solution; separate out solid; filter to obtain filter cake, with distilled water wash 3 times, vacuum-drying 24h; obtain white solid, be compound 1.
B () is by previous step products therefrom 1, Sodium Pyrosulfite and strong aqua are placed in autoclave, are heated to 140 DEG C in air dry oven baking oven, constant temperature 96h, stop heating, be cooled to room temperature, adularescent solid is separated out, suction filtration, filter cake is product, distilled water wash 3 times, vacuum-drying 24h, obtains white solid and is compound 2.
C upper step is obtained product 2 and is dissolved in concentrated hydrochloric acid by (), then be dissolved in distilled water by Sodium Nitrite, under ice-water bath, and it is slowly added drop-wise in reaction solution, stirs 0.5h; Sodiumazide is dissolved in distilled water, and it is slowly added drop-wise in reaction solution, there is a large amount of bubble formation, stir 0.5h, regulate pH to neutral with sodium carbonate, dichloromethane extraction, revolve steaming removing methylene dichloride and obtain oily crude product, add a small amount of methylene dichloride again, wet method loading column chromatography for separation, vacuum-drying obtains milk yellow solid and is probe molecule.
3. the purposes of hydrogen sulfide fluorescent probe according to claim 1, is characterized in that this hydrogen sulfide fluorescent probe is for the fluoroscopic examination of hydrogen sulfide in environment or biological sample and analysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510205626.0A CN104860840A (en) | 2015-04-27 | 2015-04-27 | Preparation and application of fluorescence enhancement type hydrogen sulfide fluorescent probe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510205626.0A CN104860840A (en) | 2015-04-27 | 2015-04-27 | Preparation and application of fluorescence enhancement type hydrogen sulfide fluorescent probe |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104860840A true CN104860840A (en) | 2015-08-26 |
Family
ID=53907079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510205626.0A Pending CN104860840A (en) | 2015-04-27 | 2015-04-27 | Preparation and application of fluorescence enhancement type hydrogen sulfide fluorescent probe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104860840A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418662A (en) * | 2015-10-14 | 2016-03-23 | 济南大学 | Preparation and application of cysteine fluorescent probe compound based on BODIPY |
| CN105837609A (en) * | 2016-04-01 | 2016-08-10 | 济南大学 | Preparation and application of fluorescent probe capable of rapidly detecting cysteine |
| CN106866437A (en) * | 2015-12-11 | 2017-06-20 | 中国科学院大连化学物理研究所 | The PRODAN fluorochromes and its synthetic method and application of red fluorescence and big Stokes shift |
| CN107286186A (en) * | 2016-04-12 | 2017-10-24 | 中国科学院化学研究所 | Hydrogen sulfide fluorescence probe and its preparation method and application |
| CN108840818A (en) * | 2018-06-25 | 2018-11-20 | 山西大学 | It is a kind of for detecting the synthesis and application of the ratio colour pattern carbazoles fluorescence probe of hydrogen sulfide |
| CN109422721A (en) * | 2017-08-23 | 2019-03-05 | 北京工商大学 | A kind of hydrogen sulfide fluorescence probe |
| CN111039866A (en) * | 2019-12-16 | 2020-04-21 | 济南大学 | Golgi-targeted hydrogen sulfide fluorescent probe, and preparation method and application thereof |
| CN111116433A (en) * | 2018-10-31 | 2020-05-08 | 北京工商大学 | Double-recognition-site hydrogen sulfide fluorescent probe |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850272A (en) * | 2012-09-26 | 2013-01-02 | 华东理工大学 | Azido-containing naphthalimide compound and applications thereof in detecting hydrogen sulfide |
| WO2015020281A1 (en) * | 2013-08-06 | 2015-02-12 | 아주대학교산학협력단 | Variable color two-photon fluorescent probe for detecting hydrogen sulfate, method for manufacturing same, and method for quantitatively imaging in vivo hydrogen sulfate using same |
| CN104419401A (en) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | Fluorescent probe for detecting hydrogen sulfide by virtue of fluorescence enhancement as well as synthetic method and application of fluorescent probe |
| CN104479669A (en) * | 2014-11-18 | 2015-04-01 | 辽宁大学 | Preparation method and applications of enhanced type fluorescent probe for detecting hydrogen sulfide |
-
2015
- 2015-04-27 CN CN201510205626.0A patent/CN104860840A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850272A (en) * | 2012-09-26 | 2013-01-02 | 华东理工大学 | Azido-containing naphthalimide compound and applications thereof in detecting hydrogen sulfide |
| WO2015020281A1 (en) * | 2013-08-06 | 2015-02-12 | 아주대학교산학협력단 | Variable color two-photon fluorescent probe for detecting hydrogen sulfate, method for manufacturing same, and method for quantitatively imaging in vivo hydrogen sulfate using same |
| CN104419401A (en) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | Fluorescent probe for detecting hydrogen sulfide by virtue of fluorescence enhancement as well as synthetic method and application of fluorescent probe |
| CN104479669A (en) * | 2014-11-18 | 2015-04-01 | 辽宁大学 | Preparation method and applications of enhanced type fluorescent probe for detecting hydrogen sulfide |
Non-Patent Citations (5)
| Title |
|---|
| HWAN MYUNG KIM 等: "Two-PhotonFluorescent Probes for Long-Term Imaging of Calcium Waves in Live Tissue", 《CHEM.EUR.J.》 * |
| SAMONINA-KOSICKA, JELENA 等: "Dual-emissive difluoroboron naphthyl-phenyl β-diketonate polylactide materials: Effects of heavy atom placement and polymer molecular weight", 《MACROMOLECULES》 * |
| SINGHA, SUBHANKAR 等: "Toward a Selective, Sensitive, Fast-Responsive, and Biocompatible Two-Photon Probe for Hydrogen Sulfide in Live Cells", 《ANALYTICAL CHEMISTRY》 * |
| 张伟红: "硫化氢荧光探针的研究进展", 《科技信息》 * |
| 高敏 等: "检测硫化氢分子的荧光探针", 《化学进展》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418662B (en) * | 2015-10-14 | 2017-06-23 | 济南大学 | A kind of preparation and application of the cysteine fluorescent probe compounds based on BODIPY |
| CN105418662A (en) * | 2015-10-14 | 2016-03-23 | 济南大学 | Preparation and application of cysteine fluorescent probe compound based on BODIPY |
| CN106866437B (en) * | 2015-12-11 | 2018-12-07 | 中国科学院大连化学物理研究所 | The PRODAN fluorochrome and its synthetic method and application of red fluorescence and big Stokes shift |
| CN106866437A (en) * | 2015-12-11 | 2017-06-20 | 中国科学院大连化学物理研究所 | The PRODAN fluorochromes and its synthetic method and application of red fluorescence and big Stokes shift |
| CN105837609A (en) * | 2016-04-01 | 2016-08-10 | 济南大学 | Preparation and application of fluorescent probe capable of rapidly detecting cysteine |
| CN107286186A (en) * | 2016-04-12 | 2017-10-24 | 中国科学院化学研究所 | Hydrogen sulfide fluorescence probe and its preparation method and application |
| CN109422721A (en) * | 2017-08-23 | 2019-03-05 | 北京工商大学 | A kind of hydrogen sulfide fluorescence probe |
| CN109422721B (en) * | 2017-08-23 | 2021-07-23 | 北京工商大学 | Hydrogen sulfide fluorescent probe |
| CN108840818A (en) * | 2018-06-25 | 2018-11-20 | 山西大学 | It is a kind of for detecting the synthesis and application of the ratio colour pattern carbazoles fluorescence probe of hydrogen sulfide |
| CN108840818B (en) * | 2018-06-25 | 2021-09-28 | 山西大学 | Synthesis and application of colorimetric carbazole fluorescent probe for detecting hydrogen sulfide |
| CN111116433A (en) * | 2018-10-31 | 2020-05-08 | 北京工商大学 | Double-recognition-site hydrogen sulfide fluorescent probe |
| CN111039866A (en) * | 2019-12-16 | 2020-04-21 | 济南大学 | Golgi-targeted hydrogen sulfide fluorescent probe, and preparation method and application thereof |
| CN111039866B (en) * | 2019-12-16 | 2022-02-25 | 济南大学 | Golgi-targeted hydrogen sulfide fluorescent probe, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104860840A (en) | Preparation and application of fluorescence enhancement type hydrogen sulfide fluorescent probe | |
| CN104447421B (en) | The preparation and application of a kind of novel cysteine and homocysteine fluorescent probe | |
| CN109608414B (en) | Fluorescent probe for detecting peroxynitrite and preparation method and application thereof | |
| CN104262287A (en) | Preparation and application of sulfite ratiometric fluorescent probe | |
| CN105419788A (en) | Small-molecular fluorescent probe for recognizing H2S, preparation method and application thereof | |
| CN104419401A (en) | Fluorescent probe for detecting hydrogen sulfide by virtue of fluorescence enhancement as well as synthetic method and application of fluorescent probe | |
| CN108129428A (en) | A kind of ratio fluorescent probe for detecting bisulfite and its application | |
| CN102603725A (en) | Near-infrared fluorescence probe used for detecting zinc ions in water phase, preparation method thereof, and application thereof | |
| CN105693655A (en) | Aminobenzothiazole-modified column aromatic hydrocarbons and synthesis thereof, and application of column aromatic hydrocarbons in continuous fluorescent recognition of Fe<3+> and F<-> in water phase | |
| CN104804729A (en) | Preparation and application of fluorescence-enhanced sulfite fluorescence probe | |
| CN105802606A (en) | Preparation method and use of mercapto-containing amino acid fluorescent probe | |
| CN104804728A (en) | Preparation and application of fluorescence-enhanced thiophenol fluorescence probe | |
| CN104560027A (en) | Fluorescent probe capable of distinguishing and detecting biological mercaptans and preparation method thereof | |
| CN105038295A (en) | Near-infrared fluorescent compounds using cyanine dyes as skeleton, and preparation and application thereof | |
| CN105985769B (en) | A kind of preparation and application of benzenethiol fluorescence probe | |
| CN105111415B (en) | Polythiophene derivative with side chain containing naphthalene groups and preparing method and application of polythiophene derivative | |
| CN109134441A (en) | A kind of novel fluorescence probe and its preparation method and application detecting cysteine | |
| CN102391150B (en) | Iron-ion fluorescent probe compound and preparation method thereof | |
| CN109942508B (en) | Ratio type carbon monoxide fluorescent probe and preparation method and application thereof | |
| CN110818646A (en) | Aggregation-induced emission-based small-molecule fluorescent probe and preparation method and application thereof | |
| CN104529841A (en) | Salen-like compound as well as preparation method and application thereof | |
| CN106083870A (en) | A kind of Novel phosphoric acid two hydrogen radical fluorescent ion probe and preparation method and application | |
| CN103130827A (en) | Compound for detecting fluoride ion and preparation method and application thereof | |
| CN105669689A (en) | Preparation and application of mercury ion fluorescent probe compound based on rhodamine B | |
| CN103113259B (en) | O-nitrophenyl azo salicylaldehyde phenoxy acetyl hydrazone, and synthesis and application thereof in CN<-> colorimetric detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150826 |
|
| WD01 | Invention patent application deemed withdrawn after publication |