CN107033158B - A kind of colorimetric fluorescence probe and preparation method thereof of hypersensitive analysis mercury ion - Google Patents
A kind of colorimetric fluorescence probe and preparation method thereof of hypersensitive analysis mercury ion Download PDFInfo
- Publication number
- CN107033158B CN107033158B CN201611246359.2A CN201611246359A CN107033158B CN 107033158 B CN107033158 B CN 107033158B CN 201611246359 A CN201611246359 A CN 201611246359A CN 107033158 B CN107033158 B CN 107033158B
- Authority
- CN
- China
- Prior art keywords
- ion
- mercury ion
- probe
- mercury
- preparation
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to a kind of colorimetric fluorescence probes and preparation method thereof of hypersensitive analysis mercury ion.Specifically, probe of the invention is a kind of thiocarbonic acid benester compound, can be used as detection of the mercury ion colorimetric fluorescence probe for mercury ion.This kind of probe can realize following at least one of technical effect: identify mercury ion with high selectivity；Quickly mercury ion can be realized and be responded；The High Sensitive Analysis to mercury ion may be implemented；Property is stablized, and can be used with long-term preservation；And it has strong anti-interference ability.
Description
Technical field
The present invention relates to thiocarbonic acid benester compounds as mercury ion fluorescence probe, can be rapidly to mercury ion Gao Xuan
Select intelligent quick identification or its concentration that can measure mercury ion in sample.
Background technique
Mercury is a kind of metallic element with serious physiological-toxicity, since it is with persistence, property easy to migrate and height
Bioconcentration becomes one of environmental contaminants most noticeable at present.Inorganic mercury ion in environment can be certain
Under the conditions of by organism conversion be severe toxicity methyl mercury.Inorganic mercury mainly influences kidney, and methyl mercury is mainly invaded after entering human body
Evil nervous system, especially central nervous system.Both can be highly enriched in biological tissue by food chain, thus to people
Huge harm is caused with nature.Mercury poisoning can generate extremely bad influence, present mercury to entire society and be existed by dominated column
On global environment monitoring system inventory, therefore, to the in situ, real-time, online of the Selective recognition of mercury ion, especially mercury ion
Monitoring is all of great significance for medicine, biology and environmental science.
In consideration of it, it is of crucial importance and significant that development, which can effectively detect the analysis method of mercury ion,.Nowadays
The analysis method of the detection mercury ion of report include Atomic absorption-emission spectrometry, high performance liquid chromatography, inductive coupling etc. from
(such as anodic stripping voltammetry, oxidation are also for daughter mass spectrum, nuclear magnetic resonance, colorimetric method (such as traditional dithizone method), electrochemical method
Former current potential method etc.), colorimetric fluorescence probe is researcher since its peculiar advantage forms in these numerous detection methods
Focus of attention.However, there are still some problems for the colorimetric and fluorescence probe reported at present, including selectivity is not good enough, response
Speed is not fast enough, synthesis is complicated.Due to intracorporal other ions such as bicarbonate ion of life, sulfate ion, bromide ion, chlorine
Other metal ions such as ion, nitrate ion, nitrite ion and phosphate anion, it can be constituted the detection of mercury ion
Potential interference, therefore, development the analysis method of mercury ion can be necessary in high sensitivity detection life entity.In short, development
Quickly, highly selective, highly sensitive, the simple mercury ion colorimetric fluorescence binary channels probe of synthesis is that those skilled in the art are badly in need of
It solves.
Summary of the invention
This field be badly in need of it is a kind of prepare simple highly sensitive mercury ion colorimetric fluorescence probe, so as to effectively detect mercury
Ion.For this purpose, the present invention has synthesized the colorimetric fluorescence probe of a kind of novel detection mercury ion, synthesis is simple, selectivity is high,
High sensitivity can identify mercury ion at once.Specifically, being fluorescence the present invention provides a kind of mercury ion fluorescence probe
Chlorins compound, structure are as follows:
Preferably, fluorescence probe of the invention is:
It is the phase by the way that probe of the present invention will be corresponded to the present invention also provides the preparation method of mercury ion fluorescence probe
Answer fluoresceins compound and thio phenyl chloroformate in dichloromethane solution stirring at normal temperature 6 hours and synthesize and be made.It is preferred that
, the corresponding fluoresceins compound corresponding to probe of the present invention of the invention is the fluorescein of rhodamine B hydridization.
The present invention also provides the detection preparations or kit for detecting ion concentration of mercury in sample, and it includes the present invention
Probe.Preferably, detection preparation of the invention or kit also include the operation instructions of product.It is further preferred that of the invention
Kit also include buffer for measuring the ion concentration of mercury in sample.
The present invention also provides the methods of ion concentration of mercury in detection sample comprising by probe of the invention and to test sample
The step of this contact.
The present invention also provides probe of the invention in preparation for detecting the use in sample in the preparation of ion concentration of mercury
On the way.
It is dense for detecting mercury ion in sample (such as water sample sample) in preparation that the present invention also provides probes of the invention
Purposes in the kit of degree.
Mercury ion colorimetric fluorescence probe of the invention can be acted on mercury ion, generate fluorescence spectrum and UV absorption light
The variation of spectrum, to realize the quantitative detection to mercury ion.
Specifically, mercury ion colorimetric fluorescence probe of the invention respectively with aluminium ion, copper ion, magnesium ion, potassium ion,
Zinc ion, nickel ion, sodium ion, nitrite ion, bicarbonate ion, sulfate ion, carbanion, chloride ion,
Other ions such as nitrate ion, fluorine ion, which are acted on, cannot cause fluorescence spectrum and the obvious of ultra-violet absorption spectrum to change
Become, to realize to the Selective recognition of mercury ion, and then can be optionally used for excluding in these ions and human body other from
Interference of the presence of son to the quantitative determination of mercury ion.
Selectively, the stability of mercury ion fluorescence probe of the invention is good, and then being capable of long-term preservation use.
Further, mercury ion colorimetric fluorescence probe of the invention is the high mercury ion colorimetric fluorescence probe of sensitivity,
And synthesis is simple, is conducive to commercialized popularization and application.
Detailed description of the invention
Fig. 1 is (5 μM) addition Hg of probe2+Fluorescence spectrum before and after (10 μM).
Fig. 2 a is various concentration Hg2+The influence of (0-0.8 μM) to probe (5 μM) fluorescence spectrum；Fig. 2 b is various concentration
Hg2+The influence of (0-10 μM) to probe (10 μM) absorption spectrum.
Fig. 3 a and Fig. 3 b are Hg2+The fluorescence intensity of (5 μM) and other different ions analytes (50 μM) to probe (5 μM)
Influence, in which: a. probe, b. mercury ion, c. aluminium ion, d. copper ion, e. magnesium ion, f. potassium ion, h. zinc ion, i.
Nickel ion, j. sodium ion, k. nitrite ion, l. bicarbonate ion, m. sulfate ion, n. carbanion, o. chlorine
Ion, p. nitrate ion, q. fluorine ion.
Specific embodiment:
The present invention provides synthetic route, method and its spectrum of above-mentioned quick high-selectivity mercury ion fluorescence probe
Energy.
Mercury ion colorimetric fluorescence probe of the invention is a kind of fluoresceins compound, has following structure general formula
In above formula: R1, R2, R3, R4, R5, R6And R7For hydrogen atom, linear or branched alkyl group, straight or branched alkoxyl, sulphur
Acidic group, ester group, carboxyl；R1, R2, R3, R4, R5, R6And R7It can be identical or different.
The synthetic route and method of such mercury ion colorimetric Fluorescence Fluorescence probe are as follows:
Specifically, colorimetric fluorescence probe of the invention can be prepared via a method which, by certain mol proportion (example 1:1.5-
Fluoresceins compound (such as fluorescein of rhodamine B hydridization) and thio phenyl chloroformate 1:3) is in methylene chloride, and two
The molar ratio of person is that (1:2) then stirring at normal temperature for a period of time (such as 6h), is then rotated using revolving instrument, added after being spin-dried for
Enter a small amount of methylene chloride to be dissolved, Guo Zhuhou obtains product, if to obtain purer product, can be used methylene chloride
It carries out being recrystallized to give sterling with the mixed system (such as v/v, 1:5) of petroleum ether.
Therefore, the present invention also provides thio phenyl chloroformates in preparing the colorimetric fluorescence probe for detecting mercury ion
Purposes.
The present invention also provides fluoresceins compound (such as fluorescein of rhodamine B hydridization) in preparation for detecting mercury
Purposes in the colorimetric fluorescence probe of ion.
The highly sensitive identification mercury ion colorimetric fluorescence probe of quick high-selectivity of the invention is noteworthy characterized by can be quick
Highly selective sensitive identification mercury ion and in the presence of other ions can accurately to mercury ion carry out quantitative analysis.
It below will be by the way that the present invention be described in more detail by following embodiment.Following embodiment is merely illustrative,
It should be understood that the present invention is not limited by following embodiments.
Embodiment 1
The fluorescein of 387mg (1mmol) rhodamine B hydridization is dissolved in 15mL methylene chloride by (scheme 1), is added
The thio phenyl chloroformate stirring at normal temperature 6h of 337mg (2mmol) is then rotated using revolving instrument, obtains crude product.If wanted
Purer product is obtained, it can be recrystallized in the mixed system (such as v/v, 1:5) of methylene chloride and petroleum ether
Obtain sterling.Obtain red pure product 364mg, yield 64%.
The fluorescein of 387mg (1mmol) rhodamine B hydridization is dissolved in 15mL methylene chloride by (scheme 2), is added
Thio 6 h of phenyl chloroformate stirring at normal temperature of 252.7mg (1.5mmol) is then rotated using revolving instrument, obtains crude product.
If obtaining purer product, it can be carried out in the mixed system (such as v/v, 1:5) of methylene chloride and petroleum ether
It is recrystallized to give sterling.Obtain red pure product 297mg, yield 52%.
The fluorescein of 387mg (1mmol) rhodamine B hydridization is dissolved in 15mL methylene chloride by (scheme 3), then plus
The thio phenyl chloroformate stirring at normal temperature 6h of 421.3mg (2.5mmol) is then rotated using revolving instrument, obtains crude product.Such as
Fruit will obtain purer product, it can be carried out to weight in the mixed system (such as v/v, 1:5) of methylene chloride and petroleum ether
Crystallization obtains sterling.Obtain red pure product 483mg, yield 85%.
The fluorescein of 500mg (1mmol) rhodamine B hydridization is dissolved in 20mL methylene chloride by (scheme 4), is added
The thio phenyl chloroformate stirring at normal temperature 6h of 505.5mg (3mmol) is then rotated using revolving instrument, obtains crude product.If
Purer product is obtained, it can be tied again in the mixed system (such as v/v, 1:5) of methylene chloride and petroleum ether
Crystalline substance obtains sterling.Obtain red pure product 503mg, yield 89%.
The fluorescein of 500mg (1mmol) rhodamine B hydridization and 173mg (1 mmol) are dissolved in 15mL dichloromethane by (scheme 5)
In alkane, the thio phenyl chloroformate stirring at normal temperature 10h of 421.3mg (2.5mmol) is added, is then rotated using revolving instrument,
Obtain crude product.If obtaining purer product, can by its methylene chloride and petroleum ether mixed system (such as v/
V, 1:5) in carry out being recrystallized to give sterling.Obtain red pure product 497mg, yield 88%.
1H-NMR(400MHz,DMSO-d6)δ(*10-6): 1.20 (t, J=6Hz, 6H), 3.36-3.45 (m, 4H),
6.39-6.49(m,2H),6.59-6.62(m,1H),6.86-6.91(m,2H), 7.22-7.29(m,3H),7.32-7.38(m,
1H), 7.49 (t, J=8Hz, 2H), 7.63-7.73 (m, 3H), 8.05 (d, J=8Hz, 1H)
Embodiment 2
Fig. 1 is (5 μM) addition Hg of probe2+Fluorescence spectrum before and after (10 μM).As can clearly be seen from Figure, mercury ion
Addition causes fluorescence intensity to enhance.
Embodiment 3
Fig. 2 a is various concentration Hg2+The influence of (0-0.8 μM) to probe (5 μM) fluorescence spectrum；Fig. 2 b is various concentration
Hg2+The influence of (0-10 μM) to probe (10 μM) ultra-violet absorption spectrum.
Along with Hg in probe solution it can be seen from Fig. 2 a2+The increase of concentration, fluorescence intensity gradually increase, and in (0-
0.8μM)Hg2+In concentration range, Hg2+Concentration and fluorescence intensity good linear relationship is presented.This is proved by means of the fluorescence
Probe can be to Hg2+Carry out quantitative analysis, and sensitivity with higher.Hg in Drinking Water in China standard2+Standard limited value be
Therefore, probe of the invention can relatively accurately determine Hg in sample to be tested to 0.001 mg/L2+Content.In addition, with Hg2+It is dense
The increase of degree, absorption spectrum also gradually increase therewith, this shows to can be realized the colorimetric method for determining to mercury ion using the probe.
Embodiment 4
Fig. 3 a and Fig. 3 b are Hg2+(5 μM) and other different ions analytes (50 μM) are strong to the fluorescence of probe (5 μM)
The influence of degree.Analyte includes: that concentration is 50 μM of aluminium ions, copper ion, magnesium ion, potassium ion, zinc ion, nickel ion, sodium
Ion, nitrite ion, bicarbonate ion, sulfate ion, carbanion, chloride ion, nitrate ion, fluorine from
The mercury ion that son and concentration are 5 μM.All test conditions are completed in pure water, and used probe is institute in embodiment 1
The probe of preparation, and all spectrum are all that analyte measures after being added at 25 DEG C.Specifically, the 1mM probe of 50 μ L is pipetted
Stock solution is put into 10mL colorimetric cylinder, and the PBS buffer solution of 5mL pure water and the pH=7.4 of 0.5mL is then added, fixed with pure water
Hold to 10mL, then pipette the above-mentioned 10mM analyte stock solution of 50 μ L and be added in colorimetric cylinder, shakes up, measured after 30min.As a result as schemed
Shown in 3.
Can be seen that existing other common ions in organism from Fig. 3 a will not have apparent response to probe；From figure
3b, which can be seen that existing other common ions in organism, will not significantly interfere with measurement of the probe to mercury ion, therefore probe
It has good selectivity.
Although with above embodiments describe the present invention, it should be appreciated that before without departing substantially from spirit of the invention
It puts, the present invention further can be modified and be changed, and these modifications and variation all belong to the scope of protection of the present invention it
It is interior.
Claims (9)
1. compound is the compound such as flowering structure:
2. preparation or kit for detecting mercury ion content in sample, it includes the compounds of claim 1.
3. preparation according to claim 2 or kit, wherein the sample is water sample sample.
4. the compound of claim 1 is in preparation for detecting the purposes in sample in the preparation or kit of ion concentration of mercury.
5. purposes according to claim 4, wherein the sample is water sample sample.
6. the method for preparing the compound of claim 1 comprising following steps:
The fluorescein of rhodamine B hydridization is dissolved in methylene chloride with thio phenyl chloroformate and is reacted, wherein the Luo Dan
The fluorescein of bright B hydridization are as follows:
7. method according to claim 6, wherein the molar ratio of the fluorescein of the rhodamine B hydridization and thio phenyl chloroformate
For 1:1.5-1:3.
8. method according to claim 6, wherein the time of the reaction is 6-10 hour.
9. method according to claim 8, wherein the time of the reaction is 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611246359.2A CN107033158B (en) | 2016-12-29 | 2016-12-29 | A kind of colorimetric fluorescence probe and preparation method thereof of hypersensitive analysis mercury ion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611246359.2A CN107033158B (en) | 2016-12-29 | 2016-12-29 | A kind of colorimetric fluorescence probe and preparation method thereof of hypersensitive analysis mercury ion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107033158A CN107033158A (en) | 2017-08-11 |
| CN107033158B true CN107033158B (en) | 2019-04-12 |
Family
ID=59530841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611246359.2A Expired - Fee Related CN107033158B (en) | 2016-12-29 | 2016-12-29 | A kind of colorimetric fluorescence probe and preparation method thereof of hypersensitive analysis mercury ion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107033158B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746406B (en) * | 2017-11-22 | 2021-02-09 | 济南大学 | Preparation and application of ultrasensitive high-selectivity hypochlorous acid fluorescent probe |
| CN108918482A (en) * | 2018-05-07 | 2018-11-30 | 济南大学 | A kind of kit of the highly selective mercury ion fluorescence probe based on fluorescein |
| CN109438426B (en) * | 2018-11-05 | 2021-04-27 | 湖北大学 | Half-cyanine-based reactive type Hg2+ fluorescent probe Cy-PT and preparation method and application thereof |
| CN110938051B (en) * | 2019-12-19 | 2022-05-10 | 济南大学 | Probe for efficiently detecting mercury ions, preparation method and application |
| CN115477657B (en) * | 2022-10-06 | 2023-10-31 | 中国药科大学 | Coumarin prodrug and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101471527B1 (en) * | 2014-01-29 | 2014-12-12 | 중앙대학교 산학협력단 | Rhodol thiophosphinate compound having selectivity for mercury and method for monitoring mercury ion using the same |
| CN106117230B (en) * | 2016-06-29 | 2018-07-06 | 河南师范大学 | Replace rhodamine B amide groups Thiourea fluorescent probe compounds and its preparation method and application |
| CN106220640B (en) * | 2016-06-29 | 2018-06-01 | 河南师范大学 | A kind of mercury ion fluorescence probe and its preparation method and application |
| CN106243123B (en) * | 2016-08-01 | 2017-12-26 | 济南大学 | A kind of fluorescence probe for detecting hydrogen peroxide and its application |
-
2016
- 2016-12-29 CN CN201611246359.2A patent/CN107033158B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN107033158A (en) | 2017-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107033158B (en) | A kind of colorimetric fluorescence probe and preparation method thereof of hypersensitive analysis mercury ion | |
| CN106220640B (en) | A kind of mercury ion fluorescence probe and its preparation method and application | |
| CN104017568B (en) | -Application of fluorescent probe containing rhodamine in detecting Hg2+ | |
| CN107417671B (en) | Coumarin derivative containing quinoline substitution, preparation method thereof and application of coumarin derivative on ratio type pH fluorescent probe | |
| CN109336835B (en) | Fluorescent probe for detecting activity of myeloperoxidase and preparation method and application thereof | |
| CN107033177B (en) | It is a kind of using pinacol borate as the hypersensitive high selection peroxynitrite colorimetric ratio fluorescent probe of identification receptor | |
| CN107141256A (en) | A kind of quick high-selectivity hypersensitive hydrogen sulfide ratio fluorescent probe and preparation method thereof | |
| CN110563708B (en) | Turn-on type fluorescent probe for rapidly detecting sulfite (hydrogen) salt, and synthesis method and application thereof | |
| CN106800548B (en) | 8- benzimidazole quinoline Ratio-type pH probe and its preparation method and application | |
| CN104132920A (en) | Method for measuring Ag<+> or F<-> through fluorescence quenching | |
| CN110964044B (en) | Peroxynitrite fluorescent probe based on dicoumarin derivative, preparation method and application | |
| CN105669689A (en) | Preparation and application of mercury ion fluorescent probe compound based on rhodamine B | |
| CN111362900A (en) | Responding to ONOO-Ratio type small molecule fluorescent probe and preparation method and application thereof | |
| CN109096180B (en) | H2S fluorescent probe based on 4-styryl pyridinium long wave emission recognition, and synthetic method and application thereof | |
| CN111349071A (en) | For detecting ONOO-Xanthene derivative, and synthetic method and application thereof | |
| CN111349101A (en) | Turn-on type fluorescent molecular probe responding to biological cell viscosity and preparation method and application thereof | |
| CN113402470B (en) | Multichannel reversible colorimetric mercury ion fluorescent probe, preparation method and application | |
| CN106841132B (en) | Method for detecting concentration of mercury ions in sample | |
| CN108640885B (en) | A kind of colorimetric fluorescence probe of the hypersensitive analysis mercury based on resorufin | |
| CN107098852B (en) | Di (2-methylpyridine) amine modified pyrene derivative fluorescent probe and synthetic method and application thereof | |
| CN108774514A (en) | A method of detection mercury ion | |
| CN112500382B (en) | Ratiometric fluorescent probe for reversible detection of sulfur dioxide/formaldehyde, preparation method and application | |
| CN110156858B (en) | Water-soluble hydrogen sulfide fluorescent probe, preparation method thereof and application thereof in detection of water quality sulfide and cell hydrogen sulfide | |
| CN108299396B (en) | Organic compound for detecting metal ions in water environment and application thereof | |
| CN108570029A (en) | A kind of two-photon fluorescence probe of highly selective Sensitive Detection mercury |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190412 Termination date: 20191229 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |