CN107290323B - Near-infrared fluorescent probe and preparation method and application technology thereof - Google Patents
Near-infrared fluorescent probe and preparation method and application technology thereof Download PDFInfo
- Publication number
- CN107290323B CN107290323B CN201710681508.6A CN201710681508A CN107290323B CN 107290323 B CN107290323 B CN 107290323B CN 201710681508 A CN201710681508 A CN 201710681508A CN 107290323 B CN107290323 B CN 107290323B
- Authority
- CN
- China
- Prior art keywords
- fluorescent probe
- infrared fluorescent
- probe
- probe according
- detecting
- 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
-
- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- 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
Abstract
The invention belongs to the technical field of fluorescent probe sensing in analytical chemistry, and relates to a novel near-infrared fluorescent probe, a preparation method thereof and application thereof in polysulfide detection. The method comprises the step of reacting a nile red derivative with 2-fluoro-4-nitrobenzoic acid to obtain the probe molecule. The probe is simple in preparation method and stable in structure, and can be used for rapidly detecting sodium disulfide with high selectivity and high sensitivity through a fluorescence spectrophotometer. The probe provides a novel method for detecting polysulfide, and has a good application prospect.
Description
Technical Field
The invention relates to the technical field of fluorescent probe sensing in analytical chemistry, and relates to a near-infrared fluorescent probe for detecting polysulfide, a preparation method and an application technology thereof.
Background
With the development of industry and agriculture, polysulfides are used in large quantities such as: as polymerization terminators, depilatories in the leather industry, agriculturally as insecticides, petroleum refining aids, etc. The problem of environmental impact is not insignificant, and qualitative and quantitative detection of polysulfides is therefore important.
In addition, active sulfur compounds including hydrogen sulfide, hydrogen peroxide, mercapto amino acids, etc. play an important role in the metabolism of cells (function of proteins, redox signaling, etc.). As one of the important signaling molecules, hydrogen sulfide is considered as a third class of gas transmitter in biological systems, and too high or too low a hydrogen sulfide content may affect the central nervous system, which is associated with many serious diseases, such as: down syndrome, Alzheimer's disease, etc. However, recent studies have shown that intracellular signaling is likely to be achieved by the co-action of hydrogen sulfide (generated by oxidation of hydrogen sulfide by a bioactive oxygen) and hydrogen sulfide, and that hydrogen sulfide is capable of activating tumor suppressor, ion channel, transcription factor and has more efficient sulfation than hydrogen sulfide. However, studies on the biological functions of hydrogen polysulfide are still in the early stage, and many problems are urgently needed to be solved. The traditional method for determining polysulfide mainly relies on a gas-mass combination method, and although the method can determine hydrogen polysulfide, the method also has certain defects, such as poor selectivity, complex sample preparation, complex operation, expensive instrument cost, time consumption and difficult popularization and application. Therefore, it is important to develop a method for detecting hydrogen polysulfide effectively, accurately and conveniently, which not only has important significance for environmental monitoring, but also has very important significance for the early clinical diagnosis of some serious diseases.
The invention relates to a near-infrared fluorescent probe for detecting polysulfide and a preparation method and application technology thereof. The novel near-infrared fluorescent probe is designed through the reaction of a nile red derivative, 2-fluoro-4-nitrobenzoic acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 4-dimethylaminopyridine. The probe has the advantages of high selectivity, high sensitivity and quick detection in the detection of hydrogen polysulfide. In addition, the near infrared fluorescence has small damage to a living organism when biological tissues or cells are detected. Meanwhile, the biological tissue absorbs the fluorescence in the near infrared region at the minimum, the distance that the near infrared light can penetrate the biological tissue is large, and deep tissues and organs can be detected and imaged. Therefore, the probe has potential application prospect.
Disclosure of Invention
The invention aims to provide a near-infrared fluorescent probe, a preparation method of the probe and application of the probe in polysulfide detection.
According to the invention, the probe molecule is obtained by the reaction of the hydroxyl-bearing nile red derivative and 2-fluoro-4-nitrobenzoic acid, and the synthesis steps specifically comprise: (1) in an ice bath, dissolving 5-diethylamino-2-nitrosophenol hydrochloride and 1, 6-dihydroxynaphthalene in an N, N-dimethylformamide solvent, and stirring under the protection of argon to react to finally obtain a nile red derivative with hydroxyl; (2) and (2) dissolving the nile red derivative obtained in the step (1), 2-fluoro-4-nitrobenzoic acid and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in dichloromethane, adding a proper amount of catalyst, stirring for reaction at room temperature, and separating and purifying to finally obtain the near-infrared fluorescent probe.
Compared with the prior art, the patent technology has the following advantages:
1. the selectivity is good, and the anti-interference capability is strong;
2. the sensitivity is high, and the detection of a trace target object can be realized;
3. the response is quick, and quick detection can be realized;
3. the synthesis is simple, and the detection is convenient;
4. the near infrared light detection has small damage to organisms and potential application prospect.
Drawings
FIG. 1 is a fluorescent titration chart of sodium disulfide detection by probe
FIG. 2 is a response time fluorescence spectrum of polysulfide detected by probe
FIG. 3 is a pH optimized fluorescence spectrum of the probe
FIG. 4 is a fluorescence spectrum of a probe for selective assay
Detailed Description
The present invention will be further described with reference to the following examples, which are only for illustrating the technical solutions of the present invention and are not to be construed as limiting the present invention.
Example 1
Dissolving 5-diethylamino-2-nitrosophenol hydrochloride (0.5g, 2.6mmol) and 1, 6-dihydroxynaphthalene (0.41g, 2.6mmol) in 8mL of N, N-dimethylformamide under ice bath, refluxing at 140 ℃ for 5 hours under the protection of argon, cooling the reaction solution to room temperature, and adding 100mL of H2And O, extracting with dichloromethane, drying with anhydrous sodium sulfate, spin-drying, and separating and purifying by a chromatographic column to finally obtain the hydroxyl-containing nile red derivative. Dissolving the nile red derivative (110mg, 0.33mmol), 2-fluoro-4-nitrobenzoic acid (74mg, 0.4mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (126mg, 0.66mmol) in 10mL of dichloromethane, adding a catalyst 4-dimethylaminopyridine (40mg, 0.33mmol), stirring at room temperature for reaction, pouring the reaction solution into 40mL of water, extracting with dichloromethane, drying with anhydrous sodium sulfate, spin-drying, and separating and purifying by a chromatographic column to obtain a final product, namely the near-infrared fluorescent probe.
Example 2
Dissolving 5-diethylamino-2-nitrosophenol hydrochloride (1.15g, 6.0mmol) and 1, 6-dihydroxynaphthalene (0.82g, 5.2mmol) in 12mL of N, N-dimethylformamide under ice bath, refluxing at 140 ℃ for 8 hours under the protection of argon, cooling the reaction solution to room temperature, and adding 100mL of H2O, extraction with dichloromethane, noDrying with sodium sulfate, spin-drying, and separating and purifying with chromatographic column to obtain hydroxyl-containing Nile red derivative. Dissolving the nile red derivative (330mg, 0.99mmol), 2-fluoro-4-nitrobenzoic acid (370mg, 2.0mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (530mg, 3.3mmol) in 20mL of dichloromethane, adding a catalyst 4-dimethylaminopyridine (50mg, 0.39mmol), stirring at room temperature for reaction, pouring the reaction solution into 50mL of water, extracting with dichloromethane, drying with anhydrous sodium sulfate, spin-drying, and separating and purifying by a chromatographic column to obtain a final product, namely the near-infrared fluorescent probe.
Example 3
Dissolving 5-diethylamino-2-nitrosophenol hydrochloride (0.5g, 2.6mmol) and 1, 6-dihydroxynaphthalene (0.41g, 2.6mmol) in 8mL of N, N-dimethylformamide under ice bath, refluxing at 140 ℃ for 3 hours under the protection of argon, cooling the reaction solution to room temperature after the reaction is finished, and adding 100mL of H2And O, extracting with dichloromethane, drying with anhydrous sodium sulfate, spin-drying, and separating and purifying by a chromatographic column to finally obtain the hydroxyl-containing nile red derivative. Dissolving the nile red derivative (110mg, 0.33mmol), 2-fluoro-4-nitrobenzoic acid (74mg, 0.4mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (126mg, 0.66mmol) in 10mL of dichloromethane, adding a catalyst 4-dimethylaminopyridine (20mg, 0.17mmol), stirring at room temperature for reaction, pouring the reaction solution into 40mL of water, extracting with dichloromethane, drying with anhydrous sodium sulfate, spin-drying, and separating and purifying by a chromatographic column to obtain a final product, namely the near-infrared fluorescent probe.
The probes obtained in examples 1-3 were the same substance by TLC monitoring, and successful preparation of the probes was confirmed by nuclear magnetic characterization, with the following characterization data:1H NMR(400MHz,CDCl3)δ9.10-9.07(q,1H),8.56-8.52(m,2H),8.42(d,J＝8.0Hz,1H),7.60(d,J＝8.0Hz,1H),7.54-7.51(q,1H),7.45(t,J＝9.2Hz,1H),6.70-6.67(q,1H),6.49(d,J＝2.8Hz,1H),6.41(s,1H),3.51-3.46(q,4H),1.27(t,J＝7.2Hz,6H).13C NMR(100MHz,CDCl3)δ182.6,166.9,164.1,160.3,152.5,151.1,147.0,138.8,133.9,131.4,130.5,130.3,130.0,128.7,127.9,125.0,123.1,118.9,118.7,116.3,110.0,105.6,96.3,45.2,12.6.
application example 1: as shown in FIG. 1, the probe detects the fluorescence titration chart of sodium disulfide. When a probe (5. mu.M) was added to a mixed solution of dimethyl sulfoxide and water, the fluorescence of the probe itself was very weak under excitation with light having a wavelength of 550 nm. After the probe and the sodium disulfide respond, the fluorescence intensity at 655nm of the near infrared region is enhanced, and the fluorescence intensity is also continuously increased along with the increase of the concentration of the sodium disulfide, and a good linear relation is formed. The probe is proved to be well applicable to the detection of sodium disulfide.
Application example 2: as shown in fig. 2, the probe detects the response time fluorescence spectrum of sodium disulfide. When a probe (5. mu.M) is added to a mixed solution of dimethyl sulfoxide and water, the fluorescence of the probe itself is very weak under the excitation of light with the wavelength of 550nm, but after the addition of sodium disulfide, the fluorescence intensity at 655nm in the near infrared region begins to gradually increase, and the fluorescence intensity is completely responded within 6 minutes, and the fluorescence intensity does not change any more. Therefore, the probe has the performance of realizing the rapid detection of the sodium disulfide.
Application example 3: the probe pH-optimized fluorescence spectrum, as shown in fig. 3. Adding a probe (5 mu M) and a target substance sodium disulfide into a mixed solution of dimethyl sulfoxide and water (the pH value of the solution is adjusted to be 3-10 respectively), keeping other test conditions unchanged, and measuring the condition that the probe responds to the sodium disulfide under different pH values, wherein the probe can keep good stability between pH values of 5-10 and can respond to the sodium disulfide well.
Application example 4: FIG. 4 shows the fluorescence spectra of the probe in the selectivity experiment. Adding different interferents (1-29 are respectively: probe itself and HCO) under the same test system and test conditions3 -、Br-、HPO4 2-、I-、NO3 -、NO2 -、H2PO4 -、Ac-、K+、Thr、Mg2+、Zn2+、Pro、SO4 2-、Gly、Ca2+、Na+、Trp、Arg、Ala、Na2S2O3、Hcy、SO3 2-、GSH、Cys、S2-、HS-、Na2S2). The experimental result proves that the selectivity of the probe is very good, the probe does not respond to the interferents, and the fluorescence intensity is almost unchanged. The probe responded rapidly to sodium disulfide only when present in solution and showed a dramatic increase in fluorescence intensity in the near infrared region at 655 nm. The probe has high selectivity for detecting sodium disulfide.
Claims (6)
1. A near-infrared fluorescent probe is characterized in that the molecular structural formula is as follows:
2. the method for preparing the near-infrared fluorescent probe according to claim 1, characterized in that the preparation process comprises the following steps:
a: dissolving 5-diethylamino-2-nitrosophenol hydrochloride and 1, 6-dihydroxynaphthalene in an N, N-dimethylformamide solvent in an ice bath, carrying out reflux reaction for a certain time under the protection of argon, and separating and purifying to finally obtain a hydroxyl nile red derivative;
b: and (b) dissolving the nile red derivative obtained in the step (a), 2-fluoro-4-nitrobenzoic acid and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in dichloromethane, adding a proper amount of catalyst, stirring for reaction at room temperature, and separating and purifying to finally obtain the near-infrared fluorescent probe as claimed in claim 1.
3. The method for preparing a near-infrared fluorescent probe according to claim 2, wherein the catalyst in the step b is 4-dimethylaminopyridine.
4. Use of the near-infrared fluorescent probe according to claim 1 for detecting polysulfides.
5. The use of the near-infrared fluorescent probe according to claim 4 for detecting polysulfides, wherein the excitation light has a wavelength of 520nm to 580nm and the collected emission light has a wavelength of 630nm to 660 nm.
6. The use of the near-infrared fluorescent probe according to claim 4 for detecting polysulfide, wherein the solvent system used for detection is a mixed solution of dimethyl sulfoxide and water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710681508.6A CN107290323B (en) | 2017-08-10 | 2017-08-10 | Near-infrared fluorescent probe and preparation method and application technology thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710681508.6A CN107290323B (en) | 2017-08-10 | 2017-08-10 | Near-infrared fluorescent probe and preparation method and application technology thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107290323A CN107290323A (en) | 2017-10-24 |
| CN107290323B true CN107290323B (en) | 2020-01-14 |
Family
ID=60104800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710681508.6A Active CN107290323B (en) | 2017-08-10 | 2017-08-10 | Near-infrared fluorescent probe and preparation method and application technology thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107290323B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108226377B (en) * | 2018-01-08 | 2019-08-23 | 浙江新和成特种材料有限公司 | The detection method of sodium polysulfide |
| CN109851677B (en) * | 2019-02-26 | 2022-02-25 | 山东大学 | Protein fluorescent probe for specifically detecting polysulfide and preparation method and application thereof |
| CN110511742A (en) * | 2019-09-04 | 2019-11-29 | 中南大学 | A kind of near infrared fluorescent probe of specific recognition hydrogen polysulfide |
| CN113698379B (en) * | 2021-10-20 | 2022-02-11 | 中国科学院烟台海岸带研究所 | Fluorescent probe for detecting hydrogen polysulfide and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016038040A2 (en) * | 2014-09-08 | 2016-03-17 | Landsteiner Genmed, S.L. | Dipeptidyl ketoamide compounds and their use for the treatment and/or prevention of fat accumulation |
| CN106967038A (en) * | 2017-04-10 | 2017-07-21 | 台州学院 | A kind of synthesis and application of the fluorescence probe of Dual channel detection hydrogen sulfide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241970B (en) * | 2011-02-25 | 2014-11-05 | 苏州大学 | Near infrared fluorescent probe for detecting zinc ions in water phase and preparation method thereof |
| CN104419401A (en) * | 2013-08-28 | 2015-03-18 | 苏州罗兰生物科技有限公司 | Fluorescent probe for detecting hydrogen sulfide by virtue of fluorescence enhancement as well as synthetic method and application of fluorescent probe |
| CN106753337B (en) * | 2016-12-01 | 2018-06-29 | 济南大学 | A kind of near-infrared and two-photon Double-mode imaging fluorescence probe and its preparation and application |
-
2017
- 2017-08-10 CN CN201710681508.6A patent/CN107290323B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016038040A2 (en) * | 2014-09-08 | 2016-03-17 | Landsteiner Genmed, S.L. | Dipeptidyl ketoamide compounds and their use for the treatment and/or prevention of fat accumulation |
| CN106967038A (en) * | 2017-04-10 | 2017-07-21 | 台州学院 | A kind of synthesis and application of the fluorescence probe of Dual channel detection hydrogen sulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107290323A (en) | 2017-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107290323B (en) | Near-infrared fluorescent probe and preparation method and application technology thereof | |
| CN110540837B (en) | Preparation and application of hydrogen peroxide near-infrared fluorescent probe | |
| CN111205280B (en) | Ratio type fluorescent probe for detecting hypochlorous acid and preparation method and application thereof | |
| CN106946902B (en) | A kind of sulfur dioxide near-infrared-two-photon ratio fluorescent probe and preparation method thereof | |
| CN108117544B (en) | Reversible sulfur dioxide/sulfite (hydrogen) salt fluorescent probe | |
| CN104418874B (en) | Fluorescent molecular probe for detecting fluoride ions in aqueous solutions as well as synthesis method and application thereof | |
| CN104419401A (en) | Fluorescent probe for detecting hydrogen sulfide by virtue of fluorescence enhancement as well as synthetic method and application of fluorescent probe | |
| CN109336835B (en) | Fluorescent probe for detecting activity of myeloperoxidase and preparation method and application thereof | |
| CN110028463B (en) | Fluorescent probe with large Stokes displacement and synthetic method and application thereof | |
| CN107721922B (en) | Quinoline biological thiol fluorescent probe and preparation and application thereof | |
| CN110698401A (en) | Novel fluorescent probe for detecting biological thiol and preparation method and application thereof | |
| CN109266331A (en) | A kind of near infrared fluorescent probe, preparation method and application for surveying hypochlorite ion based on half flower cyanines structure | |
| CN105524055A (en) | Preparation and application of fluorescent probe capable of being used for distinguishing cysteine/homocysteine and glutathione | |
| CN106749034A (en) | Ratio-type fluorescent labeling reagent and its synthetic method and application are answered to bisulfite and hypochlorite double-bang firecracker | |
| CN114181204B (en) | Near infrared fluorescent probe for detecting viscosity and preparation and application thereof | |
| CN114605343A (en) | Fluorescent group LAN-OH, fluorescent sensor LAN-beta gal, preparation method and application thereof | |
| CN113004258B (en) | Preparation method and application of hydrogen sulfide ratio type fluorescent molecular probe based on ESIPT effect | |
| CN110964044B (en) | Peroxynitrite fluorescent probe based on dicoumarin derivative, preparation method and application | |
| CN110669503B (en) | Preparation and application of carbon monoxide near-infrared fluorescent probe | |
| CN114644646B (en) | Near infrared fluorescent probe with benzyl boric acid pinacol esters as detection groups and preparation method and application thereof | |
| CN110563609B (en) | Preparation method and application of near-infrared fluorescent probe for detecting selenious acid roots | |
| CN113735796A (en) | Design synthesis and property research based on phenothiazine reversible fluorescent probe | |
| CN113956274A (en) | Design and synthesis method of fluorescent probe capable of responding to viscosity and peroxynitrite change in epileptic diseases | |
| CN111039866A (en) | Golgi-targeted hydrogen sulfide fluorescent probe, and preparation method and application thereof | |
| CN115894427B (en) | Near-infrared frequency up-conversion fluorescent probe, preparation method thereof and application thereof in detection of biological mercaptan |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210810 Address after: 318000 east 4 and east 5, building 27, Jianan community, Taizhou Development Zone, Zhejiang Province (office only) (self declaration) Patentee after: Taizhou Xuefu Ecological Environment Research Center Co.,Ltd. Address before: 318000 No. 1139, Shifu Road, Jiaojiang District, Taizhou, Zhejiang. Patentee before: TAIZHOU University |
|
| TR01 | Transfer of patent right |