CN110078716B - Fluorescent probe for detecting glutathione and preparation method and application thereof - Google Patents
Fluorescent probe for detecting glutathione and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorescent probe for detecting glutathione and a preparation method and application thereof, belonging to the technical field of analysis and detection. The fluorescent probe is 2,2 '- (((1E, 1' E) - ((((((((disulfide (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide, and the structural formula is shown as a formula (I).
Compared with the existing fluorescence detection technology, the fluorescent probe disclosed by the invention is easy to synthesize, simple in detection means and intuitive in result, can be used for qualitatively and quantitatively analyzing the glutathione through fluorescence intensity, has good accuracy and anti-interference performance, and can be applied to detection of the glutathione in the fields of cosmetics, foods and the like.
Description
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to a fluorescent probe for detecting glutathione as well as a preparation method and application thereof.
Background
Glutathione exists mainly in two forms, namely reduced Glutathione (GSH) and oxidized glutathione (GSSG), wherein reduced glutathione is the main form, so glutathione is generally referred to as reduced glutathione. Glutathione is tripeptide composed of three amino acids (glutamic acid, cysteine and glycine), and the sulfydryl on the cysteine is an active group, so that the glutathione can play a role in resisting oxidation and is widely applied to the fields of foods, cosmetics, health-care products and the like. In the field of food, the glutathione can prevent food from browning, prolong the shelf life and strengthen the mouthfeel of the food. In the field of cosmetics, the glutathione can play a role in resisting aging while whitening and preventing wrinkles. In the field of health care products, glutathione can remove free radicals in vivo and has the function of detoxification. Therefore, qualitative and quantitative detection of glutathione has great significance in relevant fields.
The current detection method for glutathione mainly comprises the following steps: spectrophotometry, enzyme cycling, high performance liquid chromatography, fluorescence, etc.
Spectrophotometry mainly uses the Ellman reagent, 5-dithiobis (2-nitrobenzoic acid), also known as DTNB. At pH 8.0, the reagent reacts with thiol groups to form 4-nitrothiophenol compounds, also known as TNB, which have a strong absorption peak at 412 nm. The content of sulfhydryl can be known by detecting the absorption at 412nm after the reaction of the substance to be detected and DTNB, and then the content of glutathione can be known. However, this method has a disadvantage that all thiol-group-containing substances can react with DTNB, and thus external interference cannot be overcome.
The enzyme cycling method is based on Ellman reagent color development, and adds oxidized glutathione reductase and NADPH, and can continuously convert oxidized glutathione into reduced glutathione. The production rate of TNB is proportional to the total glutathione content while maintaining reduced glutathione unchanged. The total glutathione content can then be determined by measuring the absorption of TNB at 412 nm. The method has the advantages of high detection speed, high sensitivity and the like. However, the method still does not solve the problem that DTNB can react with other thiol-bearing substances, and the activity of the enzyme has certain influence on the result.
High performance liquid chromatography is a method for separating a detection substance into single substances respectively for detection by utilizing the difference of various properties of the detection substance in a stationary phase and a mobile phase, such as partition coefficient, intermolecular force and the like. The mobile phase is liquid, and can be passed through chromatographic column at high speed under high pressure to separate the detected substance with high sensitivity. The method can distinguish reductive glutathione from oxidative glutathione, can clearly distinguish other sulfhydryl-containing substances, and has the advantages of difficult destruction and easy recovery of samples. However, this method is long in operation time and requires a high level of equipment.
Fluorescence is an important method for detecting glutathione as a detection means. This method has many advantages such as short reaction time, long maintenance of fluorescence of the reactant (stable for at least half an hour), no interference of related amino acids to detection, etc. Through the development of many years, the method has attracted extensive attention of researchers in the field of glutathione detection. Chinese patent (application No. 201810636563.8) prepared a probe containing a 2, 4-dinitrobenzenesulfonyl group. The probe is subjected to nucleophilic attack in the presence of glutathione to break a phenyl ether bond, so that the probe can emit strong near-infrared fluorescence under the excitation wavelength of 350-360nm, thereby realizing the detection of the glutathione. However, the probe is complicated to synthesize, has low detection sensitivity, and is difficult to realize accurate detection. A research paper (ACS Applied Materials & Interfaces, 2015, 7, 12809-12813) reported a coumarin-based fluorescence-recovering probe that did not fluoresce due to the heavy atom effect. However, in the presence of glutathione, the bromide part of the probe is substituted by sulfhydryl, and the probe can emit strongest fluorescence at 510nm under the excitation wavelength of 454nm, thereby realizing the fluorescence recovery type detection of the glutathione. However, the fluorescent probe is easily interfered by external substances, and accurate analysis of glutathione is difficult to realize.
Therefore, the development of a detection method with fast response, high sensitivity and strong interference resistance is urgently needed in the field.
Disclosure of Invention
In order to solve the above disadvantages and drawbacks of the prior art, a primary object of the present invention is to provide a fluorescent probe for detecting glutathione, i.e., a fluorescent compound.
Another object of the present invention is to provide a method for preparing the above fluorescent probe.
The invention further aims to provide application of the fluorescent probe, and application of the fluorescent probe in glutathione detection.
The purpose of the invention is realized by the following technical scheme.
A fluorescent probe for detecting glutathione, the compound of the fluorescent probe being 2,2 '- ((1E, 1' E) - (((((((dithio (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide, of the formula:
the preparation method of the fluorescent probe for detecting glutathione comprises the following steps:
(1) under the protection of inert gas, dissolving triphosgene and N, N-diisopropylethylamine in an organic solvent, respectively dripping into 2-hydroxyethyl disulfide dissolved in the organic solvent, reacting at low temperature, reacting at room temperature, and performing decompression and drying to obtain a reaction intermediate product;
(2) dissolving N, N-diisopropylethylamine and (E) -2- (2- (6-hydroxy-2, 3-dihydro-1H-anthracene-4-yl) vinyl) -1,3, 3-trimethyl-3H-indole-1-iodide in an organic solvent to obtain a solution A; under the protection of inert gas, dissolving the reaction intermediate product obtained in the step (1) in an organic solvent, then dropwise adding the solution A, reacting at room temperature, separating and purifying to obtain the product 2,2 '- ((1E, 1' E) - ((((((((disulfide (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide.
Preferably, in the step (1), the molar ratio of the 2-hydroxyethyl disulfide to the triphosgene is 1 (3.0-3.2); the molar volume ratio of the 2-hydroxyethyl disulfide to the N, N-diisopropylethylamine is 1 mmol: (400-500) μ L.
Preferably, the molar ratio of the 2-hydroxyethyl disulfide to (E) -2- (2- (6-hydroxy-2, 3-dihydro-1H-anthracen-4-yl) vinyl) -1,3, 3-trimethyl-3H-indole-1-iodide is 1 (2.0-2.1); the molar volume ratio of the 2-hydroxyethyl disulfide to the N, N-diisopropylethylamine in the step (2) is 1 mmol: (200-300). mu.L.
Preferably, the organic solvent is anhydrous dichloromethane.
Preferably, the temperature of the low-temperature reaction in the step (1) is 0-10 ℃; further preferably 0 ℃.
Preferably, the low-temperature reaction time in step (1) is 15 to 25 minutes.
Preferably, the reaction time at room temperature in step (1) is 4 to 6 hours.
Preferably, the reaction time at room temperature in the step (2) is 18 to 24 hours.
Preferably, the separation and purification step in step (2) is: removing the organic solvent by rotary evaporation, and purifying by column chromatography to obtain the final product.
The fluorescent probe is applied to glutathione detection.
The product obtained by the invention is 2,2 '- ((1E, 1' E) - ((((((((disulfide (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide, the molecular formula of which is C58H58I2N2O8S2The compound is stable and non-toxic with a relative molecular mass of 1228.
The fluorescent probe can perform qualitative and quantitative detection on the glutathione through fluorescence intensity. In the presence of glutathione, the probe reacts with glutathione to generate (E) -2- (2- (6-hydroxy-2, 3-dihydro-1H-anthracene-4-yl) vinyl) -1,3, 3-trimethyl-3H-indole-1-iodide, and the substance can emit strong near infrared fluorescence at 710nm under the excitation wavelength of 680 nm. The fluorescent compound can be used for qualitative and quantitative analysis of glutathione.
The disulfide bond of the fluorescent probe can be broken under the condition of existence of glutathione, so that the fluorescence of (E) -2- (2- (6-hydroxy-2, 3-dihydro-1H-anthracene-4-yl) vinyl) -1,3, 3-trimethyl-3H-indole-1-iodide is recovered, and qualitative detection of the glutathione can be well realized. The fluorescence intensity is gradually enhanced along with the increase of the concentration of the glutathione and has a better linear relation, so that the quantitative detection of the glutathione can be realized. The detection is simple to operate, visual in result and good in accuracy.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the probe can specifically detect glutathione, other ions and amino acids, can not cause the breakage of the disulfide bond of the probe, does not generate fluorescence, and has strong anti-interference performance.
(2) The probe of the invention can react with glutathione to emit near infrared fluorescence, and qualitatively detect glutathione. With the increase of the concentration of the glutathione, the fluorescence intensity is gradually enhanced and has a better linear relation, so that the glutathione can be quantitatively detected through the fluorescence intensity.
(3) The probe provided by the invention constructs a method for detecting glutathione, and the method is simple in detection means, intuitive in result and convenient to apply and popularize.
(4) The probe of the invention has low cost, easy synthesis and higher yield.
Drawings
FIG. 1 is a scheme showing the synthesis of fluorescent compounds according to the present invention;
FIG. 2 is a NMR spectrum of 2,2 '- ((1E, 1' E) - (((((((disulfide (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide of example 1;
FIG. 3a is a graph showing fluorescence spectra of the fluorescent probe of example 1 in response to glutathione for different periods of time;
FIG. 3b is a graph showing the relationship between the fluorescence intensity at 710nm and the response time of the fluorescent probe of example 1;
FIG. 4a is a graph of the fluorescence spectra of the fluorescent probe of example 1 in response to different concentrations of glutathione;
FIG. 4b is a graph of the fluorescence intensity at 710nm of the fluorescent probe of example 1 as a function of glutathione concentration;
FIG. 5 is a graph showing the relationship between the fluorescence intensity and pH before and after the reaction of the fluorescent probe of example 1 with glutathione;
FIG. 6 is a bar graph of the anti-interference test of the fluorescent probe of example 1, i.e., the relationship between the fluorescence intensity of the probe and different ions and compounds (1.PBS, 2. glutathione, 3. valine, 4. aspartic acid, 5. glycine, 6. threonine, 7. alanine, 8. arginine, 9. leucine, 10 FeCl)3，11.H2O2，12.NaClO，13.NaNO3，14.CaCl2，15.NaCl)。
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
FIG. 1 shows a synthetic scheme of a fluorescent probe, i.e., a fluorescent compound according to the present invention.
Example 1
Dissolving 0.077g of 2-hydroxyethyl disulfide in anhydrous dichloromethane, dissolving 0.444g of triphosgene and 400 mu L N of N-diisopropylethylamine in the anhydrous dichloromethane under the protection of inert gas, then respectively and slowly dripping, reacting at low temperature of 0 ℃ for 20 minutes, reacting at room temperature for 4 hours, and carrying out decompression and drying to obtain a reaction intermediate product. Mu. L N, N-diisopropylethylamine and 0.537g of (E) -2- (2- (6-hydroxy-2, 3-dihydro-1H-anthracen-4-yl) vinyl) -1,3, 3-trimethyl-3H-indole-1-iodide were dissolved in anhydrous dichloromethane, the reaction intermediate was dissolved in anhydrous dichloromethane under protection of inert gas and slowly added dropwise to the solution, the reaction was carried out at room temperature for 24 hours, the organic solvent was removed by rotary evaporation, and the mixture was purified by column chromatography (dichloromethane: ethyl acetate: methanol, V/V/V ═ 8:4:1) to obtain a probe 2,2 '- ((1E, 1' E) - (((((((((disulfide (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2 for detecting glutathione, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide 0.411g (yield 66.9%); the product was characterized by nmr hydrogen spectroscopy, which is shown in fig. 2;
from the test results of fig. 2, it can be seen that:1H NMR(600MHz,DMSO)δ8.49(d,J＝15.3Hz,2H) 7.76(dd, J ═ 10.7,8.0Hz,4H), 7.57-7.54 (m,4H), 7.51-7.47 (m,4H),7.37(s,2H),7.17(dd, J ═ 8.4,2.2Hz,2H),6.67(d, J ═ 15.3Hz,2H),4.55(t, J ═ 6.1Hz,4H),3.95(s,6H),3.20(t, J ═ 6.2Hz,4H), 2.74-2.72 (m,4H), 2.69-2.67 (m,4H),1.83(dd, J ═ 11.9,6.1Hz,4H),1.72(s, 12H); wherein 8.49ppm, 7.76ppm, 7.57-7.54 ppm, 7.51-7.47 ppm, 7.37ppm, 7.17ppm and 6.67ppm correspond to a proton characteristic peak and a vinyl proton characteristic peak on a benzene ring, 4.55ppm, 3.20ppm, 2.74-2.72 ppm, 2.69-2.67 ppm and 1.83ppm correspond to a methylene proton characteristic peak, and 3.95ppm and 1.72ppm correspond to a methyl proton characteristic peak; the synthesized product can be confirmed to be a final product by nuclear magnetic analysis.
Example 2
Dissolving 0.077g of 2-hydroxyethyl disulfide in anhydrous dichloromethane, under the protection of inert gas, dissolving 0.474g of triphosgene and 450 mu L N of N-diisopropylethylamine in the anhydrous dichloromethane, then respectively and slowly dripping, reacting at the low temperature of 10 ℃ for 15 minutes, reacting at the room temperature for 6 hours, and carrying out decompression and drying to obtain a reaction intermediate product. Mu. L N, N-diisopropylethylamine and 0.511g of (E) -2- (2- (6-hydroxy-2, 3-dihydro-1H-anthracen-4-yl) vinyl) -1,3, 3-trimethyl-3H-indole-1-iodide were dissolved in anhydrous dichloromethane, the reaction intermediate was dissolved in anhydrous dichloromethane under protection of an inert gas and slowly added dropwise to the solution, the reaction was carried out at room temperature for 18 hours, the organic solvent was removed by rotary evaporation, and the mixture was purified by column chromatography (dichloromethane: ethyl acetate: methanol, V/V/V ═ 8:4:1) to obtain a probe 2,2 '- ((1E, 1' E) - (((((((((disulfide (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2 for detecting glutathione, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide 0.393g (yield 64.0%); the product was characterized by nmr hydrogen spectroscopy, which is shown in fig. 2;
the characterization of the intermediates of the fluorescent compound obtained in this example and the final compound is the same as the results in example 1.
Example 3
Dissolving 0.077g of 2-hydroxyethyl disulfide in anhydrous dichloromethane, under the protection of inert gas, dissolving 0.459g of triphosgene and 500 mu L N of N-diisopropylethylamine in the anhydrous dichloromethane, then respectively and slowly dripping, firstly reacting at the low temperature of 5 ℃ for 25 minutes, then reacting at the room temperature for 5 hours, and decompressing and draining to obtain a reaction intermediate product. 200 mu. L N N-diisopropylethylamine and 0.524g (E) -2- (2- (6-hydroxy-2, 3-dihydro-1H-anthracen-4-yl) vinyl) -1,3, 3-trimethyl-3H-indole-1-iodide were dissolved in anhydrous dichloromethane, the reaction intermediate was dissolved in anhydrous dichloromethane under protection of inert gas and slowly added dropwise to the solution, the reaction was carried out at room temperature for 20 hours, the organic solvent was removed by rotary evaporation, and the mixture was purified by column chromatography (dichloromethane: ethyl acetate: methanol, V/V/V ═ 8:4:1) to obtain a probe 2,2 '- ((1E, 1' E) - (((((((((disulfide (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2 for detecting glutathione, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide 0.370g (yield 60.3%); the product was characterized by nmr hydrogen spectroscopy, which is shown in fig. 2;
the characterization of the intermediates of the fluorescent compound obtained in this example and the final compound is the same as the results in example 1.
And (3) performance testing:
the fluorescent probe 2,2 '- ((1E, 1' E) - ((((((((disulfide (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide prepared in example 1 was subjected to a performance test, and the test results are shown in fig. 3a to fig. 6.
1. The test steps and conditions were respectively: 1.228mg of the probe obtained in example 1 was dissolved in 10mL of dimethyl sulfoxide to prepare a 100. mu.M probe stock solution. Glutathione (30.7 mg) was dissolved in 5mL of PBS solution with pH 7.4 to prepare a 20mM glutathione stock solution. 10mL sample bottles are taken, 100 mu L of glutathione mother liquor and 7500 mu L of PBS with the pH value of 7.4 are respectively added, then 400 mu L of probe mother liquor is respectively added, and the probe and the glutathione react for 0min, 2min, 5min, 10min, 15min, 30min, 45min, 60min, 90min and 120min respectively. The fluorescence intensity of these 10 samples was measured at an excitation wavelength of 680nm, and the results are shown in FIG. 3 a. The results are plotted as fluorescence intensity at 710nm versus response time according to FIG. 3a and FIG. 3 b. FIG. 3a is a graph showing fluorescence spectra of the fluorescent probe of example 1 in response to glutathione for various periods of time. FIG. 3b is a graph showing the relationship between the fluorescence intensity at 710nm and the response time of the fluorescent probe of example 1.
2. The test steps and conditions were respectively: 1.228mg of the probe obtained in example 1 was dissolved in 10mL of dimethyl sulfoxide to prepare a 100. mu.M probe stock solution. Glutathione (30.7 mg) was dissolved in 5mL of PBS solution with pH 7.4 to prepare a 20mM glutathione stock solution. 10mL sample bottles were taken, and 0. mu.L, 2. mu.L, 4. mu.L, 8. mu.L, 10. mu.L, 20. mu.L, 30. mu.L, 40. mu.L, 80. mu.L, and 100. mu.L of glutathione mother liquor were added, 7600. mu.L, 7598. mu.L, 7596. mu.L, 7592. mu.L, 7590. mu.L, 7580. mu.L, 7570. mu.L, 7560. mu.L, 7520. mu.L, and 7500. mu.L of PBS with pH 7.4 was added, and finally 400. mu.L of probe mother liquor was added, and the probe was allowed to react with glutathione for 60 min. The fluorescence intensity of these 10 samples was measured at an excitation wavelength of 680nm, and the results are shown in FIG. 4 a. A corresponding fit curve can be made to the fluorescence intensity at 710nm according to FIG. 4a, and the result is shown in FIG. 4 b. FIG. 4a is a graph showing the fluorescence spectrum of the fluorescent probe of example 1 responding to different concentrations of glutathione, and FIG. 4b is a graph showing the relationship between the fluorescence intensity at 710nm and different concentrations of glutathione for the fluorescent probe of example 1.
3. The test steps and conditions were respectively: 1.228mg of the probe obtained in example 1 was dissolved in 10mL of dimethyl sulfoxide to prepare a 100. mu.M probe stock solution. Glutathione (30.7 mg) was dissolved in 5mL of PBS solution with pH 7.4 to prepare a 20mM glutathione stock solution. 13 10mL sample bottles were taken, 100. mu.L of glutathione stock solution was added, 7500. mu.L of PBS with pH 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0 was added, and finally 400. mu.L of probe stock solution was added. The probe was allowed to react with glutathione for 60 min. The fluorescence intensity at 710nm before and after the reaction of these 13 samples was measured at an excitation wavelength of 680nm, and the results are shown in FIG. 5. FIG. 5 is a graph showing the relationship between the fluorescence intensity and pH before and after the reaction between the probe of example 1 and glutathione.
4. Test procedures andthe conditions are respectively as follows: 1.228mg of the probe obtained in example 1 was dissolved in 10mL of dimethyl sulfoxide to prepare a 100. mu.M probe stock solution. Glutathione (30.7 mg) was dissolved in 5mL of PBS solution with pH 7.4 to prepare a 20mM glutathione stock solution. 15 10mL sample bottles were taken, and 7500. mu.l of PBS (pH 7.4) was added thereto. Then adding 100 μ L250 μ M PBS, glutathione, valine, aspartic acid, glycine, threonine, alanine, arginine, leucine, and FeCl3、H2O2、NaClO、NaNO3、CaCl2And NaCl, and finally adding 400 mu L of probe mother liquor respectively, and allowing the probe to react with the glutathione for 60 min. The fluorescence intensities of the 15 samples before and after reaction were measured at an excitation wavelength of 680nm to obtain a histogram of fluorescence intensity at 710nm, and the results are shown in FIG. 6. FIG. 6 is a bar graph of the anti-interference test of the probe of example 1, i.e., the relationship between the fluorescence intensity of the probe and different amino acids and compounds (1.PBS, 2. glutathione, 3. valine, 4. aspartic acid, 5. glycine, 6. threonine, 7. alanine, 8. arginine, 9. leucine, 10 FeCl)3，11.H2O2，12.NaClO，13.NaNO3，14.CaCl2，15.NaCl)。
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 (9)
1. A fluorescent probe for detecting glutathione, wherein the compound of the fluorescent probe is 2,2 '- ((1E, 1' E) - ((((((((dithio (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide, and the structural formula is as follows:
2. the method for preparing the fluorescent probe for detecting glutathione, which is described in the claim 1, is characterized by comprising the following steps:
(1) under the protection of inert gas, dissolving triphosgene and N, N-diisopropylethylamine in an organic solvent, respectively dripping into 2-hydroxyethyl disulfide dissolved in the organic solvent, reacting at low temperature, reacting at room temperature, and performing decompression and drying to obtain a reaction intermediate product;
(2) dissolving N, N-diisopropylethylamine and (E) -2- (2- (6-hydroxy-2, 3-dihydro-1H-anthracene-4-yl) vinyl) -1,3, 3-trimethyl-3H-indole-1-iodide in an organic solvent to obtain a solution A; under the protection of inert gas, dissolving the reaction intermediate product obtained in the step (1) in an organic solvent, then dropwise adding the solution A, reacting at room temperature, separating and purifying to obtain the product 2,2 '- ((1E, 1' E) - ((((((((disulfide (ethane-2, 1-diyl)) bis (oxy)) bis (carbonyl)) bis (oxy)) bis (2, 3-dihydro-1H-xanthene-6, 4-diyl)) bis (ethylene-2, 1-diyl)) bis (1,3, 3-trimethyl-3H-indol-1-ium) iodide.
3. The method according to claim 2, wherein in the step (1), the molar ratio of 2-hydroxyethyl disulfide to triphosgene is 1 (3.0-3.2); the molar volume ratio of the 2-hydroxyethyl disulfide to the N, N-diisopropylethylamine is 1 mmol: (400-500) μ L.
4. The method according to claim 2, wherein the molar ratio of 2-hydroxyethyl disulfide to (E) -2- (2- (6-hydroxy-2, 3-dihydro-1H-anthracen-4-yl) vinyl) -1,3, 3-trimethyl-3H-indole-1-iodide is 1 (2.0-2.1); the molar volume ratio of the 2-hydroxyethyl disulfide to the N, N-diisopropylethylamine in the step (2) is 1 mmol: (200-300). mu.L.
5. The method according to claim 2, wherein the organic solvent in the steps (1) and (2) is anhydrous dichloromethane.
6. The method according to claim 2, wherein the temperature of the low-temperature reaction in the step (1) is 0 to 10 ℃.
7. The method according to claim 2, wherein the time of the low-temperature reaction in the step (1) is 15 to 25 minutes.
8. The method according to claim 2, wherein the room-temperature reaction time in the step (1) is 4 to 6 hours.
9. The method according to claim 2, wherein the room-temperature reaction time in the step (2) is 18 to 24 hours.
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| WO2017062364A2 (en) * | 2015-10-09 | 2017-04-13 | University Of Massachusetts | Turn-on near infrared fluorescent probes for imaging lysosomal ros in live cells at subcellular resolution |
| CN108329302A (en) * | 2018-03-22 | 2018-07-27 | 中国药科大学 | A kind of half flower cyanines class near infrared fluorescent probe compound of sulfide specificly-response and its preparation method and application |
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