CN115246831B - Hg system 2+ Sensitive hydrazone derivative and preparation and application thereof - Google Patents
Hg system 2+ Sensitive hydrazone derivative and preparation and application thereof Download PDFInfo
- Publication number
- CN115246831B CN115246831B CN202111585067.2A CN202111585067A CN115246831B CN 115246831 B CN115246831 B CN 115246831B CN 202111585067 A CN202111585067 A CN 202111585067A CN 115246831 B CN115246831 B CN 115246831B
- Authority
- CN
- China
- Prior art keywords
- probe
- sensitive hydrazone
- hydrazone derivative
- sensitive
- solution
- 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
- 150000007857 hydrazones Chemical class 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- DMZATVKONWVLBE-UHFFFAOYSA-N (4-nitro-2,1,3-benzoxadiazol-7-yl)hydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C2=NON=C12 DMZATVKONWVLBE-UHFFFAOYSA-N 0.000 claims description 26
- 239000007850 fluorescent dye Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- PFMTUGNLBQSHQC-UHFFFAOYSA-N 4,5-diazafluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CN=C3C2=N1 PFMTUGNLBQSHQC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 239000000523 sample Substances 0.000 abstract description 47
- 238000001514 detection method Methods 0.000 abstract description 22
- 238000002474 experimental method Methods 0.000 abstract description 16
- IGHBXJSNZCFXNK-UHFFFAOYSA-N 4-chloro-7-nitrobenzofurazan Chemical compound [O-][N+](=O)C1=CC=C(Cl)C2=NON=C12 IGHBXJSNZCFXNK-UHFFFAOYSA-N 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 5
- 238000012512 characterization method Methods 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 229940008718 metallic mercury Drugs 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 238000010521 absorption reaction Methods 0.000 description 19
- 239000002904 solvent Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000825 ultraviolet detection Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- -1 but not limited to Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001917 fluorescence detection Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000007995 HEPES buffer Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
-
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
-
- 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"
- G01N2021/6443—Fluorimetric titration
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention relates to Hg 2+ Sensitive hydrazone derivative is synthesized by using 4-chloro-7-nitrobenzofurazan and 4, 5-diazafluorene-9-ketone as substrates through modification, and can be found that the compound is exclusively used for Hg in the reaction process of the compound with a series of metal ions through a series of characterization 2+ The reaction of (2) has high selectivity, the obvious change of color can be observed by naked eyes in a selectivity experiment, the emission wavelength can be obviously red-shifted by the detection patterns on ultraviolet and fluorescence, and the probe L can be completely used as Hg according to the intramolecular charge transfer mechanism 2+ Is a colorimetric probe of (a). From the characterization result, it was found that probe L was specific to Hg 2+ Has high selectivity and forms stable compound with the fluorescent sensor in the coordination ratio of 1:1, and is a good fluorescent sensor for specifically identifying metallic mercury.
Description
Technical Field
The invention belongs to the technical field of fluorescent molecular probe preparation, and relates to Hg 2+ Sensitive hydrazone derivatives, and preparation and application thereof are provided.
Background
Mercury in the environment has durability, easy migration and high biological enrichment, and is the most attractive environmental pollutant. Hg of Hg 2+ Is a chemical substance with extremely physiological toxicity, and is concentrated in nervous system, digestive system and internal organs due to Hg 2+ Is easy to combine with sulfhydryl groups in proteins in human bodies, thereby affecting the functions and growth of cells.
Compared with the traditional detection means, such as Atomic Emission Spectrometry (AES), atomic Absorption Spectrometry (AAS), atomic Fluorescence Spectrometry (AFS), plasma mass spectrometry (ICP-MS) and electrochemical methods, the fluorescent probe detection technology has the characteristics of good selectivity and high sensitivity, and is easy to realize the remote, real-time and online automatic detection of analysis objects in chemical and biological systems, so that the fluorescent probe detection technology is widely focused by scientists.
At present, the problems of poor water solubility, long response time, influence of coexisting ions on detection and the like exist in the probe, so that a novel fluorescent probe is developed to realize Hg in water 2+ The detection has important significance.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art and provides the Hg 2+ Sensitive hydrazone derivatives. The compound has good water solubility, short response time to metal ions, and no influence of coexisting ions on detection, and is a good fluorescent probe.
The invention also provides the Hg 2+ The preparation method of the sensitive hydrazone derivative is simple and has low raw material cost.
The invention further provides the Hg 2+ Application of sensitive hydrazone derivatives.
To this end, the invention provides a Hg 2+ The structural formula of the sensitive hydrazone derivative is shown as (I):
the compound of this structure may be referred to as Hg 2+ The sensitive hydrazone derivative has good water solubility, short response time to metal ions, and no influence of coexisting ions on detection, and can be used as a fluorescent probe for detecting metal ions in aqueous solution or organic solvent.
The invention further provides the Hg 2+ A process for the preparation of a sensitive hydrazone derivative comprising: preparation of Hg 2+ Step of preparing Hg by sensitive hydrazone derivative 2+ Step of sensitive hydrazone derivatives 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD-NH) 2 ) Mixing the solution with 4, 5-diazafluorene-9-ketone solution, uniformly stirring, fully reacting, filtering and washing to obtain Hg 2+ Crude sensitive hydrazone derivatives.
In the above reaction, the 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD-NH) 2 ) The structural formula of the (B) is shown as (II), and the structural formula of the 4, 5-diazafluorene-9-ketone is shown as (III). Hg was prepared in the above procedure 2+ The chemical reaction formula of the sensitive hydrazone derivative is shown in figure 2.
In the preparation of Hg according to the present invention 2+ In the step of the sensitive hydrazone derivative, the 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD)-NH-NH 2 ) The molar ratio of the fluorine-containing compound to the 4, 5-diazafluorene-9-ketone is 1: (0.9-1.1), and is preferably 1:1.1.
In one embodiment of the present invention, hg is prepared as described above 2+ In the step of the sensitive hydrazone derivative, the 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD-NH) 2 ) The solution is prepared from 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD-NH) 2 ) Is dissolved in the I solvent to form.
The I-th solvent is an organic solvent including, but not limited to, dimethyl sulfoxide, methanol, and the like.
In another embodiment of the present invention, hg is prepared as described above 2+ In the step of the sensitive hydrazone derivative, the 4, 5-diazafluorene-9-one solution is formed by dissolving 4, 5-diazafluorene-9-one in a II solvent.
The II solvent is an organic solvent including, but not limited to, methanol, ethanol, and the like.
The amounts of the first solvent and the second solvent used in the present invention are not particularly limited, as long as the reactants can be dissolved well and the reaction can be smoothly carried out.
In the preparation of Hg according to the present invention 2+ The step of separating and purifying Hg is also included after the step of sensibility hydrazone derivatives 2+ Step of sensitive hydrazone derivatives: hg produced 2+ Separating and purifying the crude product of the sensitive hydrazone derivative to prepare Hg 2+ Pure sensitive hydrazone derivative.
For example, in some specific examples, hg is produced 2+ After the coarse product (sediment) of the sensitive hydrazone derivative is recrystallized, hg is obtained 2+ Pure sensitive hydrazone derivative.
In the present invention, hg is prepared 2+ In the step of the sensitive hydrazone derivative, the 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD-NH) 2 ) Can be obtained by commercial method or directly prepared.
In one embodiment of the invention, hg is prepared 2+ The step of preparing the sensitive hydrazone derivative also comprises the steps of preparing 4-hydrazino-7-nitro-2, 1,3Benzoxadiazole (NBD-NH) 2 ) Comprises the steps of: uniformly mixing 4-chloro-7-nitrobenzofurazan (NBD-Cl) solution and 80% hydrazine hydrate solution, stirring for 1h at room temperature to form a tan precipitate, and separating and purifying the reaction product to obtain 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD-NH) 2 ) The reaction formula is shown in figure 1.
In the present invention, the 4-chloro-7-nitrobenzofurazane (NBD-Cl) solution is formed by dissolving 4-chloro-7-nitrobenzofurazane (NBD-Cl) in a III solvent, wherein the III solvent is an organic solvent, which includes but is not limited to dichloromethane, chloroform, etc.
In the present invention, the 80% hydrazine hydrate solution is formed by dissolving 80% hydrazine hydrate in an IV solvent, wherein the IV solvent is an organic solvent, which includes but is not limited to methanol, ethanol, etc.
The amounts of the III solvent and the IV solvent used in the present invention are not particularly limited as long as the reactants can be well dissolved so that the reaction can be smoothly performed.
In one embodiment of the present invention, hg is prepared using the process of the present invention 2+ Sensitive hydrazone derivatives are as follows:
1. preparation of intermediate 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD-NH) 2 )
(1) 0.1g of 4-chloro-7-nitrobenzofurazane (NBD-Cl) was dissolved in 30mL of methylene chloride to form a solution A.
(2) 0.8mL of hydrazine hydrate was added to 50mL of methanol to form solution B.
(3) The solution A, B is mixed, stirred for 1-2h at room temperature, filtered and dried to form solid C.
2. Preparation of Hg 2+ Sensitive hydrazone derivatives
(1) 0.1g of solid C is weighed and dissolved in 10mL of dimethyl sulfoxide, and a solution D is obtained after heating and dissolving. Then 0.0934g of 4, 5-diazafluorene-9-ketone is weighed and dissolved in 10mL of ethanol, 4, 5-diazafluorene-9-ketone is slowly dripped into the solution D, and the mixture is uniformly mixed for full reaction.
(2) The mixed solution is evenly stirred for 8 hours at 90 ℃, the coarse product is obtained by suction filtration and washing, and the black solid is obtained after recrystallization.
The invention also provides the Hg 2+ Application of sensitive hydrazone derivatives as fluorescent probes, based on application of sensitive hydrazone derivatives in Hg (Hg) in the invention 2+ The sensitive hydrazone derivative is also called a fluorescent probe L or a hydrazone fluorescent probe L.
As can be seen from the above, the molecular structure of the probe L of the invention is shown in the formula I, the synthetic route is shown in the figures 1 and 2, firstly, 4-chloro-7-nitrobenzofurazane (NBD-Cl) is taken as a raw material to generate an intermediate product 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD-NH) with 80% hydrazine hydrate 2 ) Intermediate NBD-NH 2 And reacting with 4, 5-diazafluorene-9-ketone for 8 hours to synthesize the hydrazone probe L.
According to the invention Hg is used 2+ The sensitive hydrazone derivative is used as a fluorescent probe for detecting metal ions.
Hg due to the present invention 2+ The sensitive hydrazone derivative has good water solubility, short response time to metal ions and no influence of coexisting ions on detection, so that the sensitive hydrazone derivative can be used as a fluorescent probe for detecting metal ions in aqueous solution or organic solvent.
In one embodiment of the present invention, the metal ions comprise Cu 2+ 、Hg 2+ 、Fe 3+ The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the metal ion is Hg 2+ 。
The invention also provides the Hg 2+ The application of sensitive hydrazone derivatives in the biological fluorescent stain.
In a specific embodiment of the invention, hg produced according to the method of the invention 2+ The sensitive hydrazone derivative is used for detecting mercury ions in water. Hg is added to 2+ Sensitive hydrazone derivative used as fluorescent probe and containing Hg 2+ Is added to an aqueous solution containing 10% strength -5 ～10 -6 The mol/L fluorescent probe molecules were reacted in HEPES buffer solution of pH 7.4 for 1-5 minutes, and then the system was tested for fluorescence intensity or ultraviolet absorption.
In another embodiment of the invention, the process according to the invention is carried outHg obtained 2+ The sensitive hydrazone derivative is used for detecting mercury ions in an organic solvent. Hg is added to 2+ Sensitive hydrazone derivative used as fluorescent probe and containing Hg 2+ Is added into the organic solvent with the concentration of 10 -5 ～10 -6 The fluorescence intensity or ultraviolet absorption of the system was then tested in a solution of mol/L fluorescent probe molecules in the same organic solvent.
The term "mercury ion" as used herein means "Hg 2+ ”。
The term Hg in the present invention 2+ Sensitive hydrazone derivative refers to the hydrazone derivative meeting Hg 2+ A visual color change or a fluorescent reaction or a shift in the ultraviolet absorption peak occurs.
The term "water" in the present invention refers to one or more of natural environmental water, domestic water and medical water without particular limitation and explanation.
The invention synthesizes an intermediate product 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole by using NBD-Cl as a raw material and hydrazine hydrate, and then reacts with 4, 5-diazafluorene-9-ketone to synthesize a novel mercury ion fluorescent probe L. Hg was found in a number of metals by investigation 2+ The fluorescent probe L has good selectivity, and Hg is added 2+ After that, the ultraviolet-visible absorption peak of the fluorescent probe L is red-shifted, and Hg 2+ The linear relation in a certain concentration range is better, and the working curve can know that the probe L and Hg 2+ Complexing in an amount of 1:1 of the substance and the probe is reversible and recyclable. The probe meets the requirements of energy conservation and environmental protection, and can be Hg 2+ Provides a feasible and effective way for identification and detection.
Drawings
The invention is described in further detail below with reference to the accompanying drawings:
FIG. 1 shows the chemical reaction scheme for the preparation of the intermediate 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole.
FIG. 2 shows the production of Hg 2+ Chemical reaction formula of sensitive hydrazone derivatives.
Fig. 3 shows the color change when metal ions are added to the aqueous solution of the probe.
FIG. 4 is an ultraviolet visible spectrum of metal ions added to an aqueous solution of a probe.
FIG. 5 is a fluorescence spectrum of a metal ion added to an aqueous solution of a probe.
FIG. 6 shows addition of Hg to probe L in ethanol (2. Mu.L) 2+ (0-23. Mu.L) ultraviolet titration chart.
FIG. 7 is a graph of Hg 2+ Ultraviolet fitting curve of probe L in aqueous solution in the presence of (1. Mu.L to 23. Mu.L).
FIG. 8 shows probes L and Hg 2+ Is described herein).
FIG. 9 is Hg 2+ Competing histograms in the presence of interference from other metal ions.
FIG. 10 is a chart of the ultraviolet visible spectrum of the reversible reaction.
FIG. 11 shows probes L and Hg 2+ Is a graph of the operation of (1).
Detailed Description
In order that the invention may be more readily understood, a detailed description of the invention will be provided below with reference to the accompanying drawings and examples, which are given by way of illustration only and are not limiting the scope of the invention, as to the specific experimental methods not mentioned in the examples below, which are generally carried out in accordance with conventional experimental methods.
Examples
In order that the invention may be more readily understood, the invention will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present invention may be prepared by commercial or conventional methods unless specifically indicated.
In the following examples, hg was prepared by using an ultraviolet-visible spectrophotometer (UV 8000, mepuda, china) 2+ And carrying out ultraviolet absorption spectrum analysis on the pure product of the sensitive hydrazone derivative.
Hg was prepared by a pair of fluorescent spectrophotometers (F7000 type, hitachi, japan) 2+ And (5) performing fluorescence spectrum analysis on the pure sensitive hydrazone derivative.
Example 1: preparation of Hg 2+ Sensitive hydrazone derivatives
1. Preparation of intermediate 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole (NBD-NH-NH 2)
(1) 0.1g of 4-chloro-7-nitrobenzofurazane (NBD-C1) was dissolved in 30mL of methylene chloride to form a solution A.
(2) 0.8mL of hydrazine hydrate was added to 50mL of methanol to form solution B.
(3) The solution A, B is mixed, stirred for 1-2h at room temperature, filtered and dried to form solid C.
2. Preparation of Hg 2+ Sensitive hydrazone derivatives
(1) 0.1g of solid C is weighed and dissolved in 10mL of dimethyl sulfoxide, and a solution D is obtained after heating and dissolving. Then 0.0934g of 4, 5-diazafluorene-9-ketone is weighed and dissolved in 10mL of ethanol, 4, 5-diazafluorene-9-ketone is slowly dripped into the solution D, and the mixture is uniformly mixed for full reaction.
(2) The mixed solution is evenly stirred for 8 hours at 90 ℃, the coarse product is obtained by suction filtration and washing, and the black solid is obtained after recrystallization.
After the synthesis reaction, hg was prepared by a nuclear magnetic resonance apparatus (Bruker AVANCE 300MHz type nuclear magnetic resonance apparatus, bruker Co., switzerland) 2+ Nuclear magnetic resonance analysis is carried out on the pure product of the sensitive hydrazone derivative, and the result is as follows:
1 H NMR(300MHz，DMSO-D6)δ12.15，8.81，8.66，8.25，7.36，7.47。
example 2: investigation of the selectivity of Probe L for Metal ions
Whether the synthesized compound can specifically and specifically select our target metal is one of important detection indexes for measuring whether the synthesized product is successful or not, so that the compound is subjected to a selection experiment (a naked eye color comparison experiment and ultraviolet visible spectrum analysis) comprising two parts, and the color change of metal ions when the metal ions are added into an ethanol solution of a probe is examined. The prepared concentration is 1.0X10 -3 To an aqueous solution (2 mL) of a mol/L probe L (10. Mu.L) was added 100. Mu.t at a concentration of 1.0X10 -3 mol/L of metal ion (blank, al 3+ ，Ca 2+ ，Cd 2+ ，Co 2+ ，Cr 3+ ，Cu 2+ ，Mg 2+ ，Na + ，Ni 2+ ，K + ，Pb 2+ ，Ba 2+ And Zn 2+ ) The color reaction occurring after the addition is shown in FIG. 3, and only Hg is found by direct visual observation 2+ The color of the solution changed from yellow to light pink immediately after the probe was added.
And then respectively carrying out ultraviolet-visible spectrum analysis on the solutions, repeating the macroscopic comparison experiment steps, adding the prepared solution into a cuvette, waiting for the metal ion solution to fully react with the probe L, and then putting the solution into an ultraviolet-visible spectrophotometer for detection, wherein the result is shown in figure 4. As a result of the analysis, probe L was found to have only one absorption peak having an absorbance of 0.2488 at 376 nm. To select the metal ions that can be recognized by the probe L, we will prepare in advance metal ions (Al 3+ ，Ca 2+ ，Cd 2+ ，Co 2+ ，Cr 3+ ，Hg 2+ ，Cu 2+ ，Mg 2+ ，Na + ，Ni 2+ ，K + ，Pb 2+ ，Ba 2+ And Zn 2+ ) And (5) respectively adding the detection and recording the result. It was found that only Hg in the reaction with these metal ions 2+ The absorbance thereof is affected by the addition of (1) to (1) (the absorption peak at 376nm disappears, and a new absorption peak at 464nm appears). Through the two selection experiments, it is not difficult to find that the probe L only reacts with Hg during the reaction with a plurality of metal ions 2+ Exhibiting good selectivity. In addition, we detected the selectivity of probe L with a fluorescence spectrophotometer and prepared the solution as above, hg had been detected on an ultraviolet-visible spectrophotometer 2+ Since the absorption peak of (2) is 464nm and the absorption peaks of the rest of the metal ions are 376nm, the absorption wavelength should be set at 450nm and the excitation wavelength at 470nm in the case of fluorescence detection, and the detection data can be recorded. The experimental data are processed to obtain the result shown in fig. 5, and the analysis chart can be used for knowing that the fluorescence detection result is basically consistent with the ultraviolet detection result, and the selectivity result of the probe L is more accurate.
Example 3: titration experiments
The following experiments we done UV-dropThe results of the assay and the fluorescence titration assay are shown in FIGS. 6 and 8, respectively. As can be seen from the results, hg was found in the UV titration experiment 2+ In the process of gradually increasing the concentration of (1), the peak of the ultraviolet spectrogram at 376nm is continuously weakened, and the absorption at 464nm is gradually enhanced, when Hg is absorbed 2+ When the concentration of (2) was increased to 23. Mu.L, the absorption peaks at both sites were not changed. In the fluorescence titration experiment, the excitation wavelength of the fluorescence spectrophotometer was set at 450nm, and the absorption wavelength was set at 470 nm. The procedure in the UV titration experiment was repeated and the results showed Hg 2+ The concentration and fluorescence intensity of (2) exhibit a proportional relationship. But when Hg is added 2+ After reaching 20. Mu.L, the fluorescence intensity remained substantially constant.
Next, we performed data processing on the uv titration experimental curves, and obtained the titration fitting curves of fig. 7, respectively. By fitting a curve, the probe L and Hg can be visually seen 2+ Has good linear relation and can be quantitatively analyzed.
Example 4: competing with each other
Whether the preparation of the compound is successful or not should not be disturbed in complex chemical environments in addition to good selectivity, so that a competition experiment is also required to determine whether the probe L can exclude the interference of other metal ions, and whether the target metal ions can still be rapidly and accurately identified from the situation that a plurality of ions are already present in the competition experiment is a key point of whether the probe L is successfully prepared or not. Firstly, adding solvent water (2 mL) and a probe L (10 mu L) into a cuvette, and then adding 100 mu L (Al) of any other metal ion which can influence the probe L to recognize target metal ions 3+ ，Ca 2+ ，Cd 2+ ，Co 2+ ，Cr 3+ ，Cu 2+ ，Mg 2+ ，Na + ，Ni 2+ ，K + ，Pb 2+ ，Ba 2+ And Zn 2+ ) Finally Hg is added 2+ And after being fully and uniformly mixed, the mixture is placed into an ultraviolet-visible spectrometer for scanning. Scanning and analyzing the ultraviolet visible spectrum to obtain Al 3+ ，Ca 2+ ，Cd 2+ ，Co 2+ ，Cr 3+ ，Cu 2 + ，Mg 2+ ，Na + ，Ni 2+ ，K + ，Pb 2+ ，Ba 2+ And Zn 2+ Is added to the probe L to recognize Hg 2+ The final result is shown in figure 9. The results show that in the presence of other metal ion interference, probe L is relative to Hg 2+ The specificity of (2) is not substantially affected.
Example 5: reversibility of
Characterization of whether the probe L can be very stably applied to life practice, a reversibility experiment can be used to infer that it recognizes Hg 2+ Is used for the practical application of the product. In the reversibility test, we selected distilled water as the solvent, added 2mL of the solvent into a cuvette, and then added with accurately measured 10. Mu.L of 1.0X10% concentration -3 And (3) the mol/L probe L is put into an ultraviolet visible spectrum instrument for detection after the mixed solution is uniformly diffused in the aqueous solution system, and an ultraviolet detection result is stored. Taking out the just detected cuvette containing the liquid to be detected, adding 100 mu L Hg into the system to be detected 2+ Solution, repeating the steps, and recording the result; finally, 100 mu L of EDTA aqueous solution is continuously added into the system to be detected, ultraviolet scanning detection is carried out, the ultraviolet detection result under the system is recorded, and in order to ensure that sufficient EDTA reacts with the solution to be detected, a group of 200 mu L of EDTA is supplemented for ultraviolet scanning detection. The result of analysis of the above-stored detection result is shown in FIG. 10, in which a normal absorption peak appears at 376nm with the addition of only probe L, and Hg is added thereto 2+ After the full mixing reaction, the absorption peak of the detection system at 375nm is red shifted, the absorption peak appears at 464nm, the absorption peak is basically unchanged after EDTA which is equal to the metal ion is added into the same system, and the absorption peak is unchanged after excessive EDTA is added into the system. Thus we infer that probe L is an irreversible type of fluorescent probe.
Example 6: working curve
Job's Plot is a method for determining the coordination ratio of a compound in the liquid phase by which we can easily operate but with high accuracyTo determine the probe L in a liquid phase with Hg in an aqueous solution as a solvent 2+ How to complex the most stable and efficient. The data required by the Job's Plot curve can be obtained by ultraviolet detection or fluorescence detection, and the data is obtained by ultraviolet detection in the laboratory. In the whole experiment process, the concentration of the metal ions and the probe L is 1 multiplied by 10 - 3 mol/L, hg is changed in sequence 2+ And the volume of probe L, hg 2+ The volumes of the probes L are sequentially 10, 20, 30, 40, 50, 60, 70, 80, 90 (unit: μL), and the volumes of the probes L are sequentially 90, 80, 70, 60, 50, 40, 30, 20, 10 (unit: μL). And then sequentially putting the materials into an ultraviolet-visible spectrophotometer for scanning, and recording data. The detection result obtained by processing the data is shown in FIG. 11, which shows that when [ L/L+Hg ] 2+ ]The ultraviolet scan showed the highest absorbance at a value of about 0.5, indicating that probe L and Hg in an aqueous system 2+ The optimal coordination ratio of (2) is 1:1.
Example 7: time dependence
To a known concentration of 1X 10 -3 1X 10 concentration of the probe L (10. Mu.L) was added to an aqueous solution (2 mL) of the probe L in mol/L - 3 mol/L (100. Mu.L) Hg 2+ The fluorescence intensity was measured at each operation interval of 30 seconds, and the fluorescence intensity was substantially stabilized when the total recording time was 5 minutes. The experimental results were recorded, and the results showed that the trend of the change in fluorescence intensity was gradually decreased with the lapse of time, and after the whole reaction time was accumulated to 5min, the fluorescence intensity was not significantly decreased after decreasing to 7.859, and the response time of the fluorescent probe L was found to be 5min.
From the above examples, the invention synthesizes intermediate 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole with hydrazine hydrate by using NBD-Cl as raw material, and then reacts with 4, 5-diazafluorene-9-ketone to synthesize a novel mercury ion fluorescent probe L. Hg was found in a number of metals by investigation 2+ The fluorescent probe L has good selectivity, and Hg is added 2+ After that, the ultraviolet-visible absorption peak of the fluorescent probe L is red-shifted, and Hg 2+ The linear relation in a certain concentration range is better, and the working curve can know that the probe L and Hg 2+ Complexing in an amount of 1:1 of the substance and the probe is reversible and recyclable. The probe meets the requirements of energy conservation and environmental protection, and can be Hg 2+ Provides a feasible and effective way for identification and detection.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (5)
1. Hg system 2+ The molecular structure of the sensitive hydrazone derivative is shown as a formula (I):
2. hg as claimed in claim 1 2+ A method for synthesizing a sensitive hydrazone derivative, comprising: preparation of Hg 2+ The sensitive hydrazone derivative is prepared through mixing 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole solution with 4, 5-diazafluorene-9-ketone solution, stirring, reaction, suction filtering and washing 2+ Crude sensitive hydrazone derivatives.
3. The synthesis method according to claim 2, characterized in that: in the production of Hg 2+ In the step of the sensitive hydrazone derivative, the molar ratio of the 4-hydrazino-7-nitro-2, 1, 3-benzoxadiazole to the 4, 5-diazafluorene-9-one is 1 (0.9-1.1).
4. A synthetic method according to claim 2 or 3, characterized in that: in the production of Hg 2+ The step of separating and purifying Hg is also included after the step of sensibility hydrazone derivatives 2+ Step of sensitive hydrazone derivatives: hg produced 2+ Separating and purifying the crude product of the sensitive hydrazone derivative to prepare Hg 2+ Pure sensitive hydrazone derivative.
5. Hg of claim 1 2+ The application of the sensitive hydrazone derivative as a fluorescent probe is characterized in that: hg is added to 2+ The sensitive hydrazone derivative is used as a fluorescent probe for detecting metal ions; the metal ion is Hg 2+ 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111585067.2A CN115246831B (en) | 2021-12-20 | 2021-12-20 | Hg system 2+ Sensitive hydrazone derivative and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111585067.2A CN115246831B (en) | 2021-12-20 | 2021-12-20 | Hg system 2+ Sensitive hydrazone derivative and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115246831A CN115246831A (en) | 2022-10-28 |
| CN115246831B true CN115246831B (en) | 2023-07-07 |
Family
ID=83698261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111585067.2A Active CN115246831B (en) | 2021-12-20 | 2021-12-20 | Hg system 2+ Sensitive hydrazone derivative and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115246831B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327846A (en) * | 2014-11-18 | 2015-02-04 | 河南农业大学 | Hg<2+> ratio fluorescence probe containing rigid structure rhodamine and preparation method of Hg<2+> ratio fluorescence probe |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8541555B2 (en) * | 2006-04-18 | 2013-09-24 | Solulink Biosciences, Inc. | Hydrazone-based and oxime-based fluorescent and chromophoric/pro-fluorescent and pro-chromophoric reagents and linkers |
| CN102633795B (en) * | 2012-04-02 | 2014-06-11 | 湘潭大学 | [4,5-dinitrogen-9-fluorenone] hydrazone compound and method of compound for determining concentration of free cyanide ions in acetonitrile |
| CN108373916A (en) * | 2018-05-24 | 2018-08-07 | 泰山医学院 | Imidazo [1,5-a] pyridine hydrazide derivatives class mercury ion fluorescence probe and its application |
| CN110229147A (en) * | 2019-06-21 | 2019-09-13 | 安徽大学 | A kind of cumarin-benzothiazolyl hydrazone compounds and its preparation method and application |
-
2021
- 2021-12-20 CN CN202111585067.2A patent/CN115246831B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327846A (en) * | 2014-11-18 | 2015-02-04 | 河南农业大学 | Hg<2+> ratio fluorescence probe containing rigid structure rhodamine and preparation method of Hg<2+> ratio fluorescence probe |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115246831A (en) | 2022-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111423423B (en) | Application of ratiometric fluorescent probe in detecting peroxynitrite anion | |
| CN113121513B (en) | Carbazole-coumarin hydrazone compound as well as preparation method and application thereof | |
| CN109970600B (en) | Triphenylamine derivative Schiff base organic fluorescent probe and preparation method thereof | |
| CN107698557B (en) | Pyridine bipyrazole acylhydrazone derivative-based fluorescent probe and preparation method and application thereof | |
| CN108383823B (en) | Naphthopyran carbazone derivatives, and preparation method and application thereof | |
| CN107417681B (en) | Fluorescent probe compound containing coumarin-thiadiazole Schiff base and preparation method and application thereof | |
| CN110172070B (en) | Fluorescent probe for detecting viscosity and hydrogen peroxide as well as synthesis method and application thereof | |
| CN108640867B (en) | Fluorescent probe compound containing cyano-carbazolyl Schiff base as well as preparation method and application thereof | |
| CN107382977B (en) | Pyrazinepyrazole acylhydrazone derivative-based fluorescent probe and preparation method and application thereof | |
| CN110878085B (en) | Rapid high-selectivity hypobromous acid fluorescent probe, preparation method and application | |
| CN110964044B (en) | Peroxynitrite fluorescent probe based on dicoumarin derivative, preparation method and application | |
| CN110627737B (en) | Water-soluble benzoxazole fluorescent probe for detecting zinc ions as well as preparation method and application thereof | |
| CN115246831B (en) | Hg system 2+ Sensitive hydrazone derivative and preparation and application thereof | |
| CN109810692B (en) | Fluorescent probe based on 3-aminopyrazine acylhydrazone derivative and preparation method and application thereof | |
| CN116496233A (en) | PH fluorescent probe with aggregation-induced emission property and preparation and application thereof | |
| CN108558839B (en) | Coumarin-pyridine compound, preparation method and application thereof | |
| CN107831165B (en) | Double-channel copper ion detection test paper and preparation method thereof | |
| CN114380792B (en) | Off-on type ion detection fluorescent probe, ion detection kit, preparation method and application | |
| CN110981857A (en) | Ultrasensitive ferrous ion fluorescent probe, preparation method and application | |
| CN114031532B (en) | Thiourea-modified pyrene derivative fluorescent probe and preparation method and application thereof | |
| CN111662279B (en) | Naphthalene-substituted carbazole-benzothiazolyl hydrazone compound and preparation method and application thereof | |
| CN113402470B (en) | Multichannel reversible colorimetric mercury ion fluorescent probe, preparation method and application | |
| CN109721592B (en) | Fluorescent probe containing aminopyrazine acylhydrazone derivatives of coumarin as well as preparation method and application of fluorescent probe | |
| CN114835636A (en) | Naphthalene-vinyl pyridyl double-response type fluorescent probe and preparation method and application thereof | |
| CN114518333A (en) | Method for rapidly detecting F ions in food by using cholesteric chiral molecular clamp |
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 |