CN112608256B - AIE probe and preparation method and application thereof - Google Patents
AIE probe and preparation method and application thereof Download PDFInfo
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- CN112608256B CN112608256B CN202011396621.8A CN202011396621A CN112608256B CN 112608256 B CN112608256 B CN 112608256B CN 202011396621 A CN202011396621 A CN 202011396621A CN 112608256 B CN112608256 B CN 112608256B
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- C07—ORGANIC CHEMISTRY
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- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/11—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- 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"
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- 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"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
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Abstract
The invention discloses an AIE probe, which is a compound with the following structural formula:
wherein R is a sulfur-containing group, and the AIE probe can quantitatively detect spermine in urine with high sensitivity.
Description
Technical Field
The invention belongs to the technical field of biochemical detection, and particularly relates to an AIE probe and a preparation method and application thereof.
Background
Biological polyamines are widely present in the human body, especially in some rapidly growing tissues, and play an important role in many important cellular activities. Spermine, due to its positively charged nature, readily binds to cellular components and regulates cellular physiological activities, playing an important role in immune responses, neuronal regulation and certain pathological events. In recent years, some studies have determined that spermine in urine can be a potential biomarker for prostate cancer (PCa), the level of which can reflect the risk of prostate carcinogenesis.
The mainstream technologies for quantitatively detecting spermine at present comprise capillary electrophoresis, chromatography-mass spectrometry and the like, although the methods can accurately perform quantitative analysis of spermine, analytical instruments are expensive and the operation process is complex, so that the wide application of the methods in clinical quantitative analysis of spermine in urine is limited to a certain extent. Meanwhile, because spermine does not have a chromophore, is not sensitive to light, does not have ultraviolet absorption or fluorescence property, and is difficult to realize by analyzing and detecting spermine by an optical method, the development of a high-sensitivity quantitative detection method for spermine in urine has important significance for human disease diagnosis and health monitoring.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides an AIE probe, a preparation method and an application thereof, and the AIE probe can quantitatively detect spermine in urine with high sensitivity.
The technical purpose of the invention is realized by the following technical scheme:
an AIE probe that is a compound having the following structural formula:
Preferably, R is a sulfite-containing group.
Preferably, R is-SO3Na、-SO3K.
Another object of the present invention is to provide a method for preparing the above AIE probe, comprising:
a method for preparing the AIE probe comprises the following steps:
(1) mixing 4- (1,2, 2-triphenylvinyl) phenol with methanol, adding methoxide, and stirring to obtain a mixture A;
(2) dissolving 1, 3-propane sultone in methanol, and stirring to obtain a mixture B;
(3) and adding the mixture B into the mixture A, stirring until a solid appears, filtering and washing to obtain the AIE probe.
Preferably, the mass ratio of the 4- (1,2, 2-triphenylvinyl) phenol to the 1, 3-propane sultone is (2.5-3.5): 1.
preferably, the stirring time in the step (3) is 12 to 15 hours.
Preferably, the method specifically comprises the following steps:
(1) adding 4- (1,2, 2-triphenylvinyl) phenol (0.375-0.56g) into a suspension of 15-25mL of methanol at room temperature, slowly adding 0.08-0.12g of sodium methoxide or potassium methoxide after 10-15 minutes, and stirring to obtain a mixture A;
(2) dissolving 1, 3-propane sultone (0.15-0.16g) in 5-10ml of methanol at room temperature, and stirring to obtain a mixture B;
(3) and (3) adding the mixture B into the mixture A at room temperature, stirring for 12-15 hours until a solid appears, filtering, and washing with ethanol or acetone to obtain the AIE probe.
The application of the AIE probe in spermine detection.
The application of the AIE probe in spermidine detection.
The invention has the beneficial effects that:
(1) the AIE probe has excellent spermine and spermidine detection capability, can quantitatively detect spermine with high sensitivity, and has the detection limit of 1.54 mu M;
(2) the AIE probe has stronger selectivity, can effectively resist interference factors in a sample, and ensures the accuracy of a detection result.
Drawings
FIG. 1 is a test chart in a limit of detection test of spermine by the AIE probe of the present invention;
FIG. 2 is a graph of the fluorescence spectra of the AIE probes of the present invention reacted with various amines and inorganic salts;
FIG. 3 is a graph of the fluorescence response of AIE probes of the invention reacted with various amines and inorganic salts;
FIG. 4 is a graph of the fluorescence spectra of AIE probes of the present invention tested in artificial urine.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
an AIE probe that is a compound having the following structural formula:
the preparation method of the AIE probe comprises the following steps:
(1) adding 4- (1,2, 2-triphenylvinyl) phenol (0.375g) into a suspension of 15mL of methanol at room temperature, slowly adding 0.12g of potassium methoxide after 10 minutes, and stirring to obtain a mixture A;
(2) dissolving 1, 3-propane sultone (0.15g) in 5ml of methanol at room temperature, and stirring to obtain a mixture B;
(3) and (3) adding the mixture B into the mixture A at room temperature, stirring for 12 hours until a solid appears, filtering, and washing with ethanol to obtain the AIE probe.
Example 2:
an AIE probe that is a compound having the following structural formula:
the preparation method of the AIE probe comprises the following steps:
(1) 4- (1,2, 2-triphenylvinyl) phenol (0.56g) is added into a suspension of 25mL methanol at room temperature, 0.08g of sodium methoxide is slowly added after 15 minutes, and a mixture A is obtained after stirring;
(2) dissolving 1, 3-propane sultone (0.16g) in 10ml of methanol at room temperature, and stirring to obtain a mixture B;
(3) and (3) adding the mixture B into the mixture A at room temperature, stirring for 15 hours until a solid appears, filtering, and washing with acetone to obtain the AIE probe.
Example 3:
an AIE probe that is a compound having the following structural formula:
the preparation method of the AIE probe comprises the following steps:
(1) adding 4- (1,2, 2-triphenylvinyl) phenol (0.46g) into a suspension of 20mL of methanol at room temperature, slowly adding 0.10g of sodium methoxide after 15 minutes, and stirring to obtain a mixture A;
(2) dissolving 1, 3-propane sultone (0.155g) in 5ml of methanol at room temperature, and stirring to obtain a mixture B;
(3) and (3) adding the mixture B into the mixture A at room temperature, stirring for 12 hours until a solid appears, filtering, and washing with acetone to obtain the AIE probe.
Example 4:
an AIE probe that is a compound having the following structural formula:
the preparation method of the AIE probe comprises the following steps:
(1) 4- (1,2, 2-triphenylvinyl) phenol (0.45g) is added into a suspension of 18mL of methanol at room temperature, 0.09g of sodium methoxide is slowly added after 15 minutes, and a mixture A is obtained after stirring;
(2) dissolving 1, 3-propane sultone (0.158g) in 6ml of methanol at room temperature, and stirring to obtain a mixture B;
(3) and adding the mixture B into the mixture A at room temperature, stirring for 13 hours until a solid appears, filtering, and washing with acetone to obtain the AIE probe.
Test example:
the AIE probe prepared in example 3 is taken to carry out a detection limit test of the probe on spermine, a selectivity test of the probe on spermine and a performance test of the probe in artificial urine respectively, wherein the AIE probe prepared in example 3 is marked as AIE-SO 3.
(1) Detection limit test of probe for spermine
The fluorescence intensity (F/F0) of AIE-SO3 (20. mu.M) was tested at 25 ℃ with the addition of different concentrations of spermine (c [ Spm ]/c [ AIE-SO3] ═ 0-8 equiv). The specific steps of the test are as follows: HEPES buffer (10mm, pH7.4), spermine (0-160. mu.M) and AIE-SO3 (20. mu.M) were added to a quartz cuvette, mixed for a reaction period, and subjected to fluorescence spectroscopy and analysis. The fluorescence spectrum test conditions are as follows: the excitation wavelength was 319nm, the emission test range was 350-650nm, and the intensity of the maximum emission peak was monitored at 470 nm. The limit of detection (LOD) is determined by the following formula, where k is the slope of the curve, SD is the standard deviation of the AIE-SO3 fluorescence intensity (470nm) measured in the absence of spermine, and LOD is (3 SD)/k.
The results of the fluorescence spectroscopy are shown in FIG. 1, and the LOD was calculated to be 1.54. mu.M.
(2) Probe for the selective testing of spermine
A fluorescence intensity test method similar to the detection limit test was used. The fluorescence response of AIE-SO3(20 μ M in 10mM HEPES, pH7.4) was studied at 25 ℃ in different amines and inorganic salts (spermine, spermidine, propylamine, butylamine, benzylamine, hexylamine, aniline, 1, 3-propylamine, 1, 2-ethylenediamine, cyclopropylamine, ethanolamine, 3-amino-1-propanol, diisopropylamine, dibutylamine, cyclohexylamine, 2-pyridine, dopamine, lysine, urea, sodium chloride, magnesium chloride, calcium chloride, lithium chloride, potassium chloride, zinc chloride, ammonium chloride, all at a concentration of 0.2 equiv.). The test conditions were: the excitation wavelength was 319nm and the intensity of the maximum emission peak was monitored at 470 nm.
The fluorescence spectra of the reaction of AIE-SO3 with various amines and inorganic salts are shown in FIG. 2, and the fluorescence response of the reaction of AIE-SO3 with various amines and inorganic salts is shown in FIG. 3.
As can be seen from FIGS. 2 and 3, the probe has high interference resistance and the best ability to recognize spermine, and as can be seen from FIGS. 2 and 3, the probe also has good ability to recognize spermidine and can detect spermidine in urine more sensitively.
(3) Performance testing of probes in artificial urine
The synthesis of Artificial Urine (AU) comprises the following steps: an artificial urine was prepared by adding 0.12g of calcium chloride, 0.75g of creatinine, 0.25g of magnesium chloride hexahydrate, 1.01g of potassium chloride, and 0.38g of urea to deionized water (500 mL). The pH was adjusted to 7.4 using either Tris buffer or uric acid.
AIE-SO3 (20. mu.M) was added to HEPES buffer and artificial urine solution, respectively, at 25 ℃ and incubated for a period of time to test for fluorescent response. The test conditions were: the excitation wavelength was 319nm, and the intensity of the maximum emission peak at 470nm was monitored, wherein spermine was added to the artificial urine at various concentrations (0-40. mu.M), and the fluorescence emission spectrum of AIE-SO3 (20. mu.M) is shown in FIG. 4.
As can be seen from FIG. 4, the probe has strong selectivity in artificial urine, and can sensitively test spermine in artificial urine.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (2)
1. The application of the compound in preparing the AIE probe for spermine detection is characterized in that: the compound is:
2. The application of the compound in preparing the AIE probe for spermidine detection is characterized in that: the compound is:
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012051816A (en) * | 2010-08-31 | 2012-03-15 | Tokyo Institute Of Technology | Discrimination method of biogenic amine |
| JP6859053B2 (en) * | 2016-09-08 | 2021-04-14 | 東芝テック株式会社 | Amine compound detection marker |
| US11332449B2 (en) * | 2017-05-17 | 2022-05-17 | The Hong Kong University Of Science And Technology | AIE-active chemo sensors for amine detection and related food-safety monitoring |
| CN108586290B (en) * | 2018-07-09 | 2019-12-17 | 北京师范大学 | Amino-substituted tetraphenylethylene derivative, preparation method thereof and application thereof in gas detection |
| CN109836414B (en) * | 2019-03-26 | 2020-06-02 | 北京大学深圳研究生院 | Pentapylene derivative, preparation method thereof and application thereof in polyamine detection |
| CN110174386B (en) * | 2019-06-11 | 2021-11-23 | 青岛科技大学 | Host-guest sensor pair for detecting spermine and application thereof |
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