CN110028952B - Iodide ion recognition probe and preparation method thereof - Google Patents
Iodide ion recognition probe and preparation method thereof Download PDFInfo
- Publication number
- CN110028952B CN110028952B CN201910301562.2A CN201910301562A CN110028952B CN 110028952 B CN110028952 B CN 110028952B CN 201910301562 A CN201910301562 A CN 201910301562A CN 110028952 B CN110028952 B CN 110028952B
- Authority
- CN
- China
- Prior art keywords
- detection
- probe
- under
- taking
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
-
- 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"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides an iodide ion recognition probe and a preparation method thereofThe preparation method comprises the following steps: taking (9, 9-di (6-bromohexyl) -2, 7-bifluorenal) as a raw material, and reacting with 2, 5-diaminopyridine under the condition of taking anhydrous LiCl as a catalyst to obtain an intermediate product: and reacting the intermediate product with trimethylamine to obtain the pyridine fluorenyl fluorescent conjugated polymer under the condition of taking N, N-dimethylacetamide as a solvent. The method is simple, easy for industrial production, can realize rapid, sensitive, accurate and economic detection of iodide ions, has high efficiency in practical application, and is particularly suitable for detection of trace and trace iodide ions. The fluorescent probe has high selectivity on the detection of iodide ions, and the lowest detection limit is 4.688 multiplied by 10‑7The mol/L is in a range of 0-25 mu mol/L, presents a good linear quantitative relation, and is suitable for trace detection.
Description
Technical Field
The invention relates to an identification probe and a preparation method thereof, in particular to an iodide ion identification probe and a preparation method thereof, and belongs to the field of analysis and detection.
Background
Iodine is one of important essential trace elements of human body, and excessive or insufficient iodine intake can induce various thyroid related diseases. The detection of the iodine content in human bodies has very important clinical significance in medicine, and can evaluate the iodine nutrition status of people in regions in time, guide and correctly adjust the iodine intake in diet in time, further reduce the disease incidence caused by iodine deficiency, and have important significance for improving the population quality of the whole nation. In addition, China has abundant brine resources, and the determination of the content of iodine in brine plays an important role in iodine extraction and brine development and utilization.
There are many conventional detection methods for iodide ions, such as chemical analysis, atomic spectrometry, spectrophotometry, inductively coupled plasma mass spectrometry, and the like. Chemical analysis methods generally have more steps, have larger errors on trace detection results, and have larger influence on the detection results by coexisting impurities such as iron ions, alkaline calcium ions and sulfides. When the arsenic-cerium catalytic kinetics method is adopted to measure the content of iodide ions in brine, the toxicity of a reaction reagent is high, and the actual detection requirement is not met. In addition, some scholars adopt an electrochemical method, an atomic spectrometry method, an inductively coupled plasma mass spectrometry method to measure the content of iodine ions, and the like, and the methods need expensive instruments and equipment, have high requirements on sample treatment, are complicated in procedure and do not have the requirement of rapid detection.
The method is very important for realizing rapid, sensitive, accurate and economic detection of iodide ions.
Disclosure of Invention
The invention aims to provide an iodide ion recognition probe with simple system, convenient operation and high selectivity and a preparation method thereof.
The purpose of the invention is realized as follows:
an iodide ion recognition probe P is a pyridine fluorenyl fluorescent conjugated polymer and has the following structural formula:
a preparation method of an iodide ion recognition probe comprises the following steps:
the method comprises the following steps: taking I (9, 9-di (6-bromohexyl) -2, 7-bifluorenal) as a raw material, and reacting with 2, 5-diaminopyridine under the condition of taking anhydrous LiCl as a catalyst to obtain an intermediate product II:
step two: and reacting the intermediate product II with trimethylamine to obtain the pyridine fluorenyl fluorescent conjugated polymer under the condition of taking N, N-dimethylacetamide as a solvent.
The invention also includes such features:
1. in the first step, the molar ratio of 2, 5-diaminopyridine to (9, 9-bis (6-bromohexyl) -2, 7-bifluorenal) is 1: 1-1: 3;
2. the reaction temperature in the first step is 100-120 ℃ under the protection of nitrogen, and the reaction time is 8-24 h;
3. the second step is carried out under the conditions of sealing, normal temperature and normal pressure;
4. the solvent in the second step is a DMF solvent, and the reaction time of the second step is 48-72 hours.
Compared with the prior art, the invention has the beneficial effects that:
the method is simple, easy for industrial production, can realize rapid, sensitive, accurate and economic detection of iodide ions, has high efficiency in practical application, and is particularly suitable for detection of trace and trace iodide ions. The fluorescent probe has high selectivity on the detection of iodide ions, and the lowest detection limit is 4.688 multiplied by 10-7The mol/L is in a range of 0-25 mu mol/L, presents a good linear quantitative relation, and is suitable for trace detection.
The pyridine fluorenyl copolymer is a conjugated polymer which can emit fluorescence under the excitation of a light source, and can be selectively combined with iodide ions to quench the fluorescence of the polymer. The test method has strong anti-interference capability on other ions, and can realize specific detection and identification on iodide ions.
Drawings
FIG. 1 shows the selective fluorescence spectrum recognition of iodide ions by the probe P of the present invention, with an excitation wavelength of 330 nm;
FIG. 2 is a bar graph of fluorescence quenching efficiency of the probe P of the present invention for different anions;
FIG. 3 shows the selective recognition of I for probe P when other coexisting anions are present in the solution-Influence graph of (2);
FIG. 4 is I-An image of the reaction time with probe P versus the fluorescence intensity of the solution;
FIG. 5 shows probe P in different concentration solutions I-Fluorescence quenching efficiency map of (1).
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention designs and synthesizes a fluorescent probe for identifying iodide ions, namely a pyridine fluorenyl fluorescent conjugated polymer P with a brand new structure.
The invention takes I (9, 9-di (6-bromohexyl) -2, 7-bifluorenal) and 2, 5-diaminopyridine as raw materials to carry out polymerization reaction, an intermediate product II is obtained and is a neutral polymer, and then bromine on a side chain of the intermediate product II is subjected to substitution reaction to generate the ionized pyridine fluorenyl fluorescent conjugated polymer P-ion recognition probe. Then, through a fluorescence detection means, the change of a fluorescence signal is detected after various anions are added into the final product polymer P for anion recognition: the polymer P is specifically combined with iodide ions to generate a fluorescence quenching phenomenon, and the specific recognition result is not interfered by other anions; meanwhile, the lowest detection limit and linear measurement range of the polymer P for the identification of the iodide ions are determined by data calculation.
The purpose of the invention can be realized by the following technical scheme:
a fluorescent probe for identifying iodide ions has the following structural formula:
the preparation method of the probe for identifying iodide ions comprises the following synthetic technical route:
the first step is as follows:
the second step is that:
the specific method comprises the following steps:
the first step is as follows: the method takes (9, 9-di (6-bromohexyl) -2, 7-bifluorenal) as a raw material to react with 2, 5-diaminopyridine under the condition of taking anhydrous LiCl as a catalyst to obtain an intermediate product II.
In some embodiments: the molar ratio of the 2, 5-diaminopyridine to the compound I in the first step is 1: 1-1: 3, the reaction temperature in the first step needs to reach 100-120 ℃ under the protection of nitrogen, and the reaction time in the first step is 8-24 hours.
The second step is that: intermediate II and trimethylamine (NMe) in N, N-dimethylacetamide (DMAc) as solvent3) Reacting to obtain a polymerP。
In some embodiments: the second reaction step is carried out under sealed conditions. The second step is carried out at normal temperature and normal pressure. The solvent in the second step is a DMF solvent, and the reaction time of the second step is 48-72 hours.
The reaction product was structurally characterized by nuclear magnetic resonance spectroscopy (NMR).
Example 1
Preparing and characterizing an iodide ion recognition probe P:
0.02667g of 9, 9-di (6-bromohexyl) -2, 7-bifluorenal is taken as a raw material, 0.0159g (0.15mmoL) of 2, 5-diaminopyridine which is excessive by 3 times is weighed, 25mL of DMF (water is removed) is added into a reaction eggplant bottle, 0.5g (0.0118moL) of anhydrous LiCl of a catalyst is added, and the mixture is placed in an oil bath pot under the protection of nitrogen and heated to 110 ℃ for reaction for 12 hours. After the reaction, the reaction mixture was slowly dropped into 500mL of an ice-water mixture to be settled, and then the precipitate was centrifuged, washed with deionized water to clarify the precipitate until the supernatant was clear, and freeze-dried. Intermediate II was obtained as a brown powder in a yield of 48% and 0.0204 g.
0.02g (32.2. mu. moL) of the intermediate II was put into a 100mL eggplant-shaped flask, and then 15mL of DMAc was measured, and then 15mL of a 30% aqueous solution of trimethylamine was added thereto, and the mixture was stirred and reacted for 3 days under normal temperature and pressure in a sealed apparatus. And after the reaction is finished, removing the solvent DMAc, and drying to obtain a powder product, namely the identification probe P.
Characterization of intermediate II:
hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,CDCl3,TMS,20℃,ppm)：δ＝8.20–8.18(d,CH＝N,2H),8.09-7.90(m,pH-H,6H),7.18-6.51(m,Py-H,3H),4.30(s,-CH2-Br,4H),2.20-1.80(t,-CH2-CH2-Br,4H),1.52-1.2(t,-CH2-(CH2)4-Br,4H),1.25-0.21(m,-CH2-CH2-(CH2)2-Br,-CH2-(CH2)5-Br,12H)。
characterization of Polymer P:
hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz,DMSO,TMS,20℃,ppm)：δ＝8.30-8.20(s,CH＝N,2H),7.92-7.63(m,Ph-H,6H),7.95-7.32(m,Py-H,3H),3.54-3.42(m,-CH2-Br,4H),3.12(s,-N-CH3,18H),2.05-1.81(m,-CH2-CH2-Br,4H),1.30-1.11(m,-CH2-(CH2)4-Br,4H),1.12-0.21(m,-(CH2)2-(CH2)2-Br,-CH2-(CH2)5-Br,12H)。
example 2:
and (3) fluorescent identification and detection of the probe P on iodide ions:
as shown in FIG. 1, to a 10. mu. mol/L PBS (pH 7) buffer solution system of the probe molecule P, an anion Solution (SO) was added4 2-、ClO4 -、HCO3 -、OH-、F-、Cl-、Br-、I-) The concentration was brought to 100mmol/L, and the fluorescence test was carried out on a fluorescence spectrophotometer model LS55 manufactured by PE company, USA. From the figure we can see that the non-anions are all capable of quenching the probe P to different degrees, with iodide being the most significant. This phenomenon indicates that the probe molecule P has a unique response to iodide ions.
As shown in FIG. 2, the fluorescence quenching efficiency was calculated at an anion concentration of 100mmol/L, and it can be seen from the graph that different anions can quench the fluorescence of the probe molecule P to different degrees, but the addition of I-The fluorescence quenching effect of the sample is obvious, and the fluorescence quenching efficiency is as high as 68.8%. It shows that the probe molecule P can obviously identify I-。
As shown in fig. 3, the fluorescence intensity of the blank was measured using a 10 μmol/L PBS (pH 7) buffer solution system of the probe molecule P without adding an anion as a blank; then 100mmol/L I is added to the buffer system of the probe molecule P-Testing the fluorescence intensity; followed by the addition of a further anion (SO) dissolved in a 10-fold molar amount4 2-、ClO4 -、HCO3 -、NO3-、OH-、F-、Cl-、Br-) The fluorescence intensity of the solution was measured at an excitation wavelength of 330 nm. Calculating to obtain the fluorescence burst of the added interference ionsThe quenching efficiency is different from the fluorescence quenching efficiency of the non-added interference ions by 2.4 percent at most. As can be seen from FIG. 3, when other anions are present in the solution in large amounts, the selective recognition of iodide ions by the probe molecule P does not affect. As shown in FIG. 4, the blank was prepared by using 10. mu. mol/L of probe molecule P in PBS (pH 7) buffer, and the fluorescence intensity of the blank was measured first, followed by addition of 10-fold molar amount of I-The change in fluorescence intensity with time was monitored immediately.
As shown in FIG. 4, 100mmol/L of I was added to a solution of the probe molecule P-After 1min, the fluorescence intensity is basically unchanged with time, so that the probe molecule P can be obtained to I-The method realizes quick detection and has high efficiency in practical application.
As shown in FIG. 5, I was gradually added to 10. mu. mol/L of probe molecule P in PBS (pH 7) buffer-The concentrations of which were 0, 5, 10, 15, 0, 25, 30, 40, 50, 60, 70, 80, 90, 100. mu. mol/L, respectively, and the fluorescence intensity of the solution was measured at an excitation wavelength of 330 nm. It can be seen from the figure that when I-The concentration of the compound shows a good linear relationship (R is 0.99724) in the range of 0-25 mu mol/L, and the detection limit calculated by using IUPAC standard of 3 sigma is 4.688 multiplied by 10-7mol/L。
Claims (1)
1. The application of the pyridine fluorenyl fluorescent conjugated polymer in preparing the iodide ion recognition probe is characterized in that the structural formula is as follows:
the preparation method of the iodide ion recognition probe comprises the following steps:
the method comprises the following steps: taking (9, 9-di (6-bromohexyl) -2, 7-bifluorenal) as a raw material, and reacting with 2, 5-diaminopyridine under the condition of taking anhydrous LiCl as a catalyst to obtain an intermediate product:
step two: under the condition that N, N-dimethylacetamide is used as a solvent, the intermediate product reacts with trimethylamine to obtain a pyridine fluorenyl fluorescent conjugated polymer;
in the first step, the molar ratio of (9, 9-di (6-bromohexyl) -2, 7-bifluorenal) to 2, 5-diaminopyridine is 1: 1-1: 3; the reaction temperature in the first step is 100-110 ℃ under the protection of nitrogen, and the reaction time is 12 h;
and the second step is carried out under the conditions of sealing, normal temperature and normal pressure, the solvent in the second step is a DMF solvent, and the reaction time in the second step is 3 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910301562.2A CN110028952B (en) | 2019-04-16 | 2019-04-16 | Iodide ion recognition probe and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910301562.2A CN110028952B (en) | 2019-04-16 | 2019-04-16 | Iodide ion recognition probe and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110028952A CN110028952A (en) | 2019-07-19 |
| CN110028952B true CN110028952B (en) | 2022-01-14 |
Family
ID=67238505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910301562.2A Active CN110028952B (en) | 2019-04-16 | 2019-04-16 | Iodide ion recognition probe and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110028952B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029075A (en) * | 2020-08-24 | 2020-12-04 | 哈尔滨工程大学 | Ionized fluorenyl pyridine conjugated polymer and preparation method and application thereof |
| CN112029094B (en) * | 2020-08-24 | 2023-05-05 | 哈尔滨工程大学 | Ionic fluorenyl melamine hyperbranched conjugated polymer and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276383A (en) * | 2018-02-10 | 2018-07-13 | 贵州大学 | A kind of fluorescence probe and preparation method thereof of identification iodide ion and recognition methods |
-
2019
- 2019-04-16 CN CN201910301562.2A patent/CN110028952B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276383A (en) * | 2018-02-10 | 2018-07-13 | 贵州大学 | A kind of fluorescence probe and preparation method thereof of identification iodide ion and recognition methods |
Non-Patent Citations (1)
| Title |
|---|
| "离子型聚芴的制备及其光学性能研究";付苗;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20190115(第01期);第B014-762页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110028952A (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chandra et al. | A simple benzildihydrazone derived colorimetric and fluorescent ‘on–off-on’sensor for sequential detection of copper (II) and cyanide ions in aqueous solution | |
| Bhatti et al. | New water soluble p-sulphonatocalix [4] arene chemosensor appended with rhodamine for selective detection of Hg2+ ion | |
| CN110028952B (en) | Iodide ion recognition probe and preparation method thereof | |
| CN113121513B (en) | Carbazole-coumarin hydrazone compound as well as preparation method and application thereof | |
| CN104829589B (en) | A kind of mercury ion probe and its preparation method and application | |
| CN110964515B (en) | double-Schiff base aluminum ion fluorescent probe, and synthesis method and application thereof | |
| CN113527698B (en) | Europium (III) metal organic framework Eu-MOF probe material and preparation method and application thereof | |
| CN108088828B (en) | Double-column aromatic mercury ion fluorescent sensor and preparation and application thereof | |
| CN110003095B (en) | Cd with AIE properties2+Fluorescent probe and preparation method and application thereof | |
| CN111393461A (en) | Palladium ion fluorescent probe compound based on BODIPY and synthetic method thereof | |
| CN108148575A (en) | A kind of bivalent cupric ion fluorescence probe and its preparation method and application | |
| CN105319194B (en) | A kind of method that I and Hg2+ are continuously detected using aggregation-induced emission type fluorescence sense molecule | |
| CN113004256B (en) | Ratio type probe for detecting mercury ions and preparation method and application thereof | |
| CN108658806B (en) | Supermolecular sensor based on 2-hydroxynaphthalimide functionalized column [5] arene, and synthesis and application thereof | |
| Esteves et al. | A squaraine-based dipicolylamine derivative acting as a turn-on mercury (II) fluorescent probe in water | |
| CN113278157A (en) | Cadmium coordination polymer and preparation method and application thereof | |
| CN113087651A (en) | Compound containing indole group and preparation method and application thereof | |
| CN107831165B (en) | Double-channel copper ion detection test paper and preparation method thereof | |
| CN109370573B (en) | Fluorescent probe for detecting bivalent mercury ions and temperature, preparation method and application thereof | |
| CN108051415B (en) | Method for detecting hexavalent chromium ions by fluorescence ratio | |
| CN110423609A (en) | A kind of fluorescence probe identifying thiocyanate radical and its preparation and recognition methods | |
| CN113201132B (en) | Rhodamine B derivative fluorescent probe molecule based on monodisperse four-arm polyethylene glycol and preparation method thereof | |
| CN110408023A (en) | A kind of fluorenyl fluorescent polymer and preparation method thereof | |
| CN103012375B (en) | Pyridyl triazole methyl substituted acridine derivative, preparation method and application thereof | |
| CN112142764B (en) | Zinc complex and synthesis and fluorescence recognition Fe thereof 3+ Method for ion |
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 |