CN112028797B - Dansyl derivative fluorescent probe and synthetic method and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of organic synthesis and biological mercaptan detection, and particularly relates to a dansyl derivative fluorescent probe and a synthesis method and application thereof. The synthetic method of the fluorescent probe comprises the following steps: under the conditions of inert atmosphere and room temperature, dropwise adding a trichloromethane solution of dansyl chloride into a trichloromethane solution containing bromine substituted alcohol and triethylamine, stirring at room temperature for reaction after the dropwise adding is finished, washing and drying a reaction solution after the reaction is finished, evaporating to remove a solvent, and then separating and purifying a reactant through column chromatography to obtain the dansyl derivative fluorescent probe. The fluorescent probe and the pirox Y are used as a dual-fluorescent probe, and a supramolecular proportional fluorescent sensing platform is constructed and used for H by utilizing the solubilization of a surfactant CTAB2And S, carrying out selective detection.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and biological mercaptan detection, and particularly relates to a dansyl derivative fluorescent probe and a synthesis method and application thereof.
Background
Hydrogen sulfide (H)2S) is the simplest biological thiol, yet another endogenous gaseous signaling molecule following carbon monoxide (CO) and Nitric Oxide (NO). It is widely distributed in liver, spleen and brain, and is involved in a series of physiological processes such as vasodilatation, apoptosis and nerve regulationPlays an irreplaceable role in normal physiological activities. Studies show that the abnormal level can cause Alzheimer's disease, Down syndrome, diabetes and the like. Therefore, it is very important to develop a simple, reliable, highly selective and highly sensitive method for detecting the hydrogen sulfide content in a biological sample.
At present, methods for quantitatively analyzing hydrogen sulfide include chromatography, electrochemical methods, colorimetric methods, fluorescence methods, and the like. Among many analytical methods, fluorescence methods are attracting much attention because of their characteristics such as good selectivity, high sensitivity, simple operation, and real-time on-line detection. Although a few works have been reported on the selective detection of hydrogen sulfide, the existing probe molecules for detecting hydrogen sulfide have strong dependence on the synthesis of molecules, and most probe molecules have strong hydrophobicity, so that the application of the probe molecules in aqueous solution is limited. Meanwhile, single-channel turn-on (fluorescence-enhanced) and turn-off (fluorescence-attenuated) fluorescence sensors have the defect of being easily interfered by an environmental background, and a dual-channel fluorescence sensor with a proportional (ratiometric) response signal is urgently needed to be developed to realize the sensing of the hydrogen sulfide. Thus, the construction can be used for H in biology and complex environment2Proportional fluorescent sensors for S detection still have challenges.
Disclosure of Invention
The invention aims to solve the problem of the prior H2The detection method of S has the technical problems of complex operation, low selectivity or low sensitivity and the like, and provides the dansyl derivative fluorescent probe and the synthesis method and the application thereof. Meanwhile, dansyl derivatives and commercially available piroctone Y are used as fluorescent probes, and a proportional fluorescent sensing system based on a supermolecule co-assembly strategy is constructed by solubilizing the dansyl derivatives and the commercially available piroctone Y by using a surfactant Cetyl Trimethyl Ammonium Bromide (CTAB). The fluorescence co-assembly sensing platform can detect H with high selectivity and high sensitivity2S, and the operation is simple and convenient, and the result is clear and easy to distinguish.
In order to achieve the purpose, the invention adopts the following technical scheme:
a dansyl derivative fluorescent probe has a structural formula as follows:
wherein n is 1, 2 or 3. Dansyl derivatives with different chain lengths may exhibit different properties when co-assembled with surfactants.
A method for synthesizing a dansyl derivative fluorescent probe comprises the following steps:
under the conditions of inert atmosphere and room temperature, dropwise adding a trichloromethane solution of dansyl chloride into a trichloromethane solution containing bromine substituted alcohol and triethylamine, stirring at room temperature for reaction after dropwise adding is finished, washing and drying a reaction solution after the reaction is finished, evaporating to remove a solvent, and then separating and purifying a reactant through column chromatography to obtain the dansyl derivative fluorescent probe.
Further, the inert atmosphere is nitrogen, argon or neon, and the flow rate is 0.6-0.8 mL/s. When the flow rate is within this range, not only is the waste of gas avoided, but also the reaction can be ensured to be carried out under an inert atmosphere.
Further, the molar ratio of the dansyl chloride to the bromine-substituted alcohol to the triethylamine is 1: 1-1.5: 1 to 1.5. Theoretically, the molar ratio of the reaction should be 1: 1: 1, considering that the raw material dansyl chloride is expensive, in order to ensure that the dansyl chloride reacts completely as much as possible and avoid the waste of the raw material, the reactant bromine is slightly excessive to replace alcohol and the acid-binding agent triethylamine.
Further, the bromine-substituted alcohol is one of 4-bromine-1-butanol, 6-bromine-1-hexanol or 8-bromine-1-octanol. The bromine substituted alcohols have different chain lengths, so that dansyl derivative fluorescent probes containing different chain lengths can be synthesized, and the influence of the chain lengths on the sensing performance of the dansyl derivative fluorescent probes can be further researched.
Further, the room-temperature stirring reaction time is 3-5 h. When the reaction time is increased from 0h to 3h or 5h, the yield of the target product is gradually increased; when the reaction time exceeds this range, the yield of the desired dansyl derivative is not further improved. Therefore, the optimal reaction time range in the invention is 3-5 h.
Further, the washing is carried out for 6-7 times by using saturated salt water; the drying is carried out for at least 4h by using anhydrous sodium sulfate; the eluent for column chromatography separation and purification is dichloromethane: petroleum ether is mixed according to the volume ratio of 1-2: 1, and (b) preparing a mixed solvent. And washing for 6-7 times by using saturated saline solution to remove triethylamine hydrochloride and residual triethylamine generated in the reaction process, and monitoring the pH value of a water layer to find whether the water layer is washed cleanly. Experiments show that when the water layer is neutral, the water layer needs to be washed 6-7 times by using saturated saline solution. The organic layer washed with brine may contain a small amount of water, and it was found that drying over anhydrous sodium sulfate for at least 4 hours removed the water. Through Thin Layer Chromatography (TLC) experiments, when the volume ratio of dichloromethane to petroleum ether as eluent is 1-2: 1, the separation effect of the target compound and impurities is optimal.
The application of dansyl derivative fluorescent probe is characterized in that the fluorescent probe and pyrazosine Y are used as double fluorescent probes, a supermolecular proportional fluorescent sensing platform is constructed by utilizing the solubilization of a surfactant CTAB (cetyl trimethyl ammonium bromide)2And S, carrying out selective detection. Pyrrosine Y may be substituted with H2S undergoes a michael addition reaction, quenching its fluorescence. The surfactant CTAB solubilized dansyl derivative fluorescent probe can not only promote the reaction, but also provide another fluorescent response signal, thereby realizing the reaction on H2Proportional sensing of S.
Compared with the prior art, the invention has the following advantages:
the invention discloses a dansyl derivative fluorescent probe which is simple to synthesize and sensitive to a microenvironment, and can be assembled in a surfactant aggregate together with a commercially available hydrogen sulfide receptor pyrazosine Y to construct a supermolecule fluorescent sensing system. The sensing system is simple to prepare, good in chemical stability and good in selectivity. The sensing platform constructed by the invention can be used for H2S is selectively detected, and the detection limit is 110 nM.
Drawings
FIG. 1 shows the assembly of dansyl derivative fluorescent probe/pyrazosine Y/CTAB prepared in example 1 of the present inventionDetection of H2A fluorescence intensity change curve of S;
FIG. 2 shows the detection of H by dansyl derivative fluorescent probe/pyrazosine Y/CTAB assembly prepared in example 1 of the present invention2Fluorescence intensity ratio of S (I)1/I2) A graph relating to concentration;
FIG. 3 shows the Dansulfonyl derivative fluorescent probe/pyrazosine Y/CTAB assembly prepared in example 1 of the present invention for H in 16 analytes2(S) a selective detection map;
FIG. 4 shows the detection of H in serum by dansyl derivative fluorescent probe/pyrazosin Y/CTAB assembly prepared in example 1 of the present invention2A fluorescence intensity change curve of S;
FIG. 5 shows that the dansyl derivative fluorescent probe/pyrazoxine Y/CTAB assembly prepared in example 1 detects H in serum2Fluorescence intensity ratio of S (I)1/I2) And the concentration is plotted.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention discloses a dansyl derivative fluorescent probe, which has the following structural formula:
wherein n is 1, 2 or 3.
The dansyl derivative fluorescent probe is synthesized by the following steps:
under the protection condition of nitrogen with the flow rate of 0.6-0.8 mL/s, the molar ratio of the nitrogen to the nitrogen is 1: 1.5: 1.5 dripping trichloromethane solution of dansyl chloride into the trichloromethane solution containing the bromine substituted alcohol and triethylamine, and stirring for 4 hours at room temperature after finishing dripping. After the reaction is finished, the reaction solution is washed with saturated saline for 6-7 times and then dried for 4 hours with anhydrous sodium sulfate. And (3) distilling to remove the trichloromethane, wherein the volume ratio of dichloromethane to petroleum ether is 1.5: 1 as eluent, and purifying the product by column chromatography to obtain the dansyl derivative fluorescent probe, wherein the reaction equation is as follows:
the bromine-substituted alcohol is any one of 4-bromine-1-butanol, 6-bromine-1-hexanol or 8-bromine-1-octanol.
The application of the dansyl derivative fluorescent probe in detecting biological thiol is H2S, the detection method comprises the following steps:
1. preparing solution
Adding a certain amount of 5 × 10 concentration into PBS buffer solution (10mmol/L, pH7.4)-3mol/LCTAB solution, concentration 2.5X 10-3The concentration of the mol/L dansyl derivative fluorescent probe solution is 2.5 multiplied by 10-3Adding PBS buffer solution to the volume of the solution until reaching a scale mark, and preparing the dansyl derivative/the pyrazoxine Y/CTAB (10 mu M/5 mu M/100 mu M) fluorescent probe solution. H used in the invention2S is Na2S·9H2O is substituted, so a certain mass of Na is weighed2S·9H2Dissolving O in secondary water to prepare 2.5mmol/LNa2S·9H2And (4) O solution.
2. Drawing a standard curve
2.5mL of fluorescent probe solution is measured in a cuvette, and 2.5mmol/L of Na is respectively added dropwise to the cuvette2S·9H2Mixing O solution with capillary stirring to obtain Na solution2S·9H2The concentration of O is 0 to 100 [ mu ] mol/L. The fluorescence spectra were all measured on an F-7000 fluorescence spectrometer (Hitachi, Japan) at a scanning speed of 1200nm/min and at an excitation wavelength of 345nm, with excitation and emission slits set at 10.0 and 5.0nm, respectively. After the solution is stabilized, respectively plotting fluorescence intensity along with H2Fluorescence spectrum of S concentration change, and collecting dansyl derivative (I)1) And Pyrrosine Y (I)2) Intensity of fluorescence at (b), plot I1/I2Value with H2Standard curve of S concentration change.
3. Detecting a sample to be tested
Measurement of H to be measured with a fluorometer according to the above method2(S) fluorescence intensity of the sample according to I of the biological thiol sample to be detected1/I2The value and concentration can be determined as H by combining the linear equation of the standard curve2S。
The proportional fluorescent assembly based on the dansyl derivative has good chemical stability and selectivity, can be directly used for detection, such as an F-7000 fluorescence spectrometer or other similar optical detectors, and realizes H-fluorescence detection2And (4) selective detection of S.
Example 1
Synthesizing a dansyl derivative fluorescent probe with the structural formula as follows:
the synthesis steps are as follows:
a chloroform solution containing 0.50g (1.85mmol) of dansyl chloride was added dropwise to a chloroform solution containing 253. mu.L (2.78mmol) of 4-bromo-1-butanol and 385. mu.L (2.78mmol) of triethylamine under a nitrogen atmosphere at a flow rate of 0.6mL/s at room temperature, and the reaction was stirred at room temperature for 4 hours after completion of the dropwise addition. Washing with saturated brine for 6 times, then drying with anhydrous sodium sulfate for 4h, evaporating to remove chloroform, and reacting with dichloromethane and petroleum ether at a volume ratio of 1.5: 1 as eluent, and purifying the product by column chromatography to obtain the dansyl derivative fluorescent probe, wherein the yield is 86%, and the reaction equation is as follows:
the nuclear magnetic data of the dansyl derivative fluorescent probe are as follows:1HNMR(600MHz,CDCl3)δ8.65(s,1H),8.28(d,J＝7.1Hz,2H),7.59(dt,J＝21.6,7.8Hz,2H),7.24(s,1H),4.03(t,J＝6.0Hz,2H),3.26(t,J＝6.4Hz,2H),2.92(s,6H),1.87-1.81(m,2H),1.76(dt,J＝12.0,6.0Hz,2H).
example 2
Synthesizing a dansyl derivative fluorescent probe with the structural formula as follows:
the synthesis steps are as follows:
in the synthesis procedure of example 1, 4-bromo-1-butanol used was replaced with 6-bromo-1-hexanol of equimolar mass, and the other procedure was the same as in the corresponding example 1.
Example 3
Synthesizing a dansyl derivative fluorescent probe with the structural formula as follows:
the synthesis steps are as follows:
in the synthesis procedure of example 1, 4-bromo-1-butanol used was replaced with 8-bromo-1-octanol of equimolar mass, and the other procedures were the same as in corresponding example 1.
Example 4
The dansyl derivative fluorescent probe synthesized in example 1 is assembled with commercially available piroctone Y in a surfactant CTAB aggregate to construct a supramolecular fluorescence sensing platform based on non-covalent interaction, and H is detected in a water phase2The application method of S comprises the following steps:
1. preparing solution
Adding 1mL of 5mMCTAB solution into a 50mL volumetric flask, adding PBS buffer solution (10mmol/L, pH7.4) to the flask to a position 2-3 cm away from the graduation line, and then sequentially adding 200 μ L of 2.5 × 10- 3Acetonitrile solution of mol/L dansyl derivative fluorescent probe, 100 mu L of acetonitrile solution with concentration of 2.5 multiplied by 10-3Adding PBS buffer solution into the water solution of mol/L of the pyrazoxine Y to reach the volume of a scale mark, and preparing the dansyl derivative/the pyrazoxine Y/CTAB (10 mu M/5 mu M/100 mu M) fluorescent probe solution. Weighing a certain mass of Na2S·9H2Dissolving O in secondary waterPrepared into 2.5mmol/LNa2S·9H2And (4) O solution.
2. Drawing a standard curve
Weighing 2.5mL of the fluorescent probe solution in a cuvette, and adding 2.5mmol/L of Na2S·9H2Mixing O solution with capillary stirring to obtain mixed solution H2The concentrations of S were 3, 7, 9, 10, 11, 12, 15, 20, 30, 40, 50, 70 and 100. mu. mol/L, respectively. The fluorescence spectrum measurements were performed on a fluorescence spectrometer F-7000(Hitachi, Japan) at a scanning speed of 1200nm/min, with the excitation wavelength of 345nm and excitation and emission slits of 10.0 and 5.0nm, respectively. After the solution reaches equilibrium, the fluorescence intensity is plotted against H2The fluorescence spectrum of the change in S concentration is shown in FIG. 1. And collecting dansyl derivative (I)1) And Pyrrolin Y (I)2) Intensity of fluorescence at (b), plot I1/I2Value with H2Standard curve of S concentration change, see fig. 2.
As can be seen from FIG. 1, the fluorescence intensity of the sensing platform is dependent on H in the system2The increase of S concentration shows the proportional response phenomenon that the fluorescence intensity of the pyrrosyl red Y is reduced, and the fluorescence intensity of the dansyl derivative is obviously enhanced and accompanied with blue shift. As can be seen from fig. 2, at H2When the concentration of S is 0-15 mu mol/L, I1/I2The concentration is quadratic; at 20-100 μmol/L, I1/I2The relationship is linear with concentration (each value represents the average of three replicates) and the equation is:
y1＝0.693(±0.010)+1.633E-5(±0.004)x+0.003(±0.0003)x2；
y2＝1.391(±0.043)+0.011(±0.001)x；
in the formula y1And y2Is H2When the S concentration is 0 to 15 mu mol/L and 20 to 100 mu mol/L respectively1/I2Value x is H2S concentration, correlation coefficient R20.993 and 0.963, respectively. The fluorescence sensing platform pair H is tested2The detection limit of S was 110 nmol/L.
3. Detecting a sample to be tested
To 2.5Adding biological mercaptan samples to be detected with different volumes into mL fluorescent assembly solution, monitoring the fluorescence intensity of the sensing platform by using a fluorometer, and calculating I1/I2The relation between the value and the concentration can be determined as H by combining the equation of the standard curve2S。
To demonstrate the beneficial effects of the present invention, the inventors added an equal amount of H to the dansyl derivative/pyrazosin Y/CTAB (10. mu.M/5. mu.M/100. mu.M) fluorescent assembly solution according to the method of example 42S、Cys、Hcy、GSH、Cl-、Br-、I-、HCO3 -、H2PO4 -、BrO3 -、AcO-、OH-、CO3 2-、SO4 2-、C2O4 2-And S2O3 2-Of only H2S has obvious proportional response, and the fluorescence intensity ratios of other analytes have no obvious change, which indicates that the sensing platform is used for H2S was detected with good selectivity, see figure 3 (each value represents the average of three replicates).
Example 5
Example 1 Synthesis of dansyl derivative, construction of proportional fluorescent sensing platform with Pyrrosol Y and CTAB, detection of H in serum2The application method of S comprises the following steps:
1. preparing solution
The serum solution was diluted with PBS buffer (10mmol/L, pH7.4) to a 1% volume fraction serum solution. According to the preparation of the solution in case 4, 1mL of 5mM CTAB solution (1% serum) was added to a 50mL volumetric flask, and then 1% serum solution was added thereto to a distance of 2-3 cm from the scale line, and then 200. mu.L of 2.5X 10 solutions were sequentially added thereto- 3Acetonitrile solution of mol/L dansyl derivative fluorescent probe, 100 mu L of acetonitrile solution with concentration of 2.5 multiplied by 10-3Adding 1% serum solution to a water solution of the pyrazoxine Y in mol/L, and fixing the volume to a scale mark to prepare dansyl derivative/the pyrazoxine Y/CTAB (10 mu M/5 mu M/100 mu M) fluorescent probe solution. Weighing a certain mass of Na2S·9H2O is dissolved in the secondary water, and then,the solution was prepared in an amount of 2.5mmol/LNa2S·9H2And (4) O solution.
2. Drawing a standard curve
Weighing 2.5mL of the above fluorescent probe solution in a cuvette, and adding 2.5mmol/LH respectively2Stirring the S solution by a capillary tube to uniformly mix the S solution and the S solution so as to obtain H in the mixed solution2The S concentrations were 3, 5, 7, 10, 15, 20, 30, 40, 50, 70 and 100. mu. mol/L, respectively. The fluorescence spectra were measured on a fluorescence spectrometer F-7000(Hitachi, Japan) at a scanning speed of 1200nm/min and at an excitation wavelength of 345nm, with excitation and emission slits of 10.0 and 5.0nm, respectively. After the solution reaches equilibrium, the fluorescence intensity is plotted against H2The fluorescence spectrum of the change in S concentration is shown in FIG. 4. And collecting dansyl derivative (I)1) And Pyrrosine Y (I)2) Intensity of fluorescence at (b), plot I1/I2Value with H2Standard curve of S concentration change, see fig. 5.
As can be seen from FIG. 4, the fluorescence intensity of the sensing platform is dependent on H in the system2The increase in S concentration exhibited different degrees of response. From FIG. 5, see at H2When the S concentration is 0 to 40 mu mol/L and 40 to 100 mu mol/L, I1/I2And H2The S concentrations are in different linear relationships (each value represents the average of three parallel experiments) and the linear equations are:
y1＝1.697(±0.014)+0.014(±0.0005)x；
y2＝2.034(±0.018)+0.006(±0.0003)x；
in the formula y1And y2Is I when the concentration of hydrogen sulfide is 0 to 40 mu mol/L and 40 to 100 mu mol/L1/I2The value x is the human serum protein concentration, the linear correlation coefficient R20.992 and 0.993, respectively.
3. Detecting a sample to be tested
Adding biological mercaptan samples to be detected with different volumes into 2.5mL of the fluorescent assembly solution, monitoring the fluorescence intensity of a sensing platform by using a fluorometer, and calculating I1/I2The relation between the value and the concentration can be determined as H by combining the equation of the standard curve2S。
In conclusion, the fluorescent sensing system constructed by the noncovalent co-assembly strategy can greatly reduce the dependence on organic synthesis. Meanwhile, the sensing platform can realize H in the water phase2The high selectivity detection of S can realize the potential application in serum.
Example 6
Synthesizing a dansyl derivative fluorescent probe with the structural formula as follows:
the synthesis steps are as follows:
a chloroform solution containing 0.50g (1.85mmol) of dansyl chloride was added dropwise to a chloroform solution containing 169. mu.L (1.85mmol) of 4-bromo-1-butanol and 257. mu.L (1.85mmol) of triethylamine under a nitrogen atmosphere at a flow rate of 0.7mL/s at room temperature, and the reaction was stirred at room temperature for 3 hours after completion of the dropwise addition. Washed with saturated brine 6 times, then dried over anhydrous sodium sulfate for 4h, and the chloroform evaporated. Using dichloromethane and petroleum ether with the volume ratio of 1: 1 as eluent, and purifying the product by column chromatography to obtain the dansyl derivative fluorescent probe, wherein the yield is 80%, and the reaction equation is as follows:
example 7
Synthesizing a dansyl derivative fluorescent probe with the structural formula as follows:
the synthesis steps are as follows:
a chloroform solution containing 0.50g (1.85mmol) of dansyl chloride was added dropwise to a chloroform solution containing 253. mu.L (2.78mmol) of 4-bromo-1-butanol and 385. mu.L (2.78mmol) of triethylamine under a nitrogen atmosphere at a flow rate of 0.8mL/s at room temperature, and the reaction was stirred at room temperature for 5 hours after completion of the dropwise addition. The mixture was washed with saturated brine 7 times, dried over anhydrous sodium sulfate for 4 hours, and then chloroform was distilled off. Using dichloromethane and petroleum ether with the volume ratio of 2: 1 as eluent, and purifying the product by column chromatography to obtain the dansyl derivative fluorescent probe, wherein the yield of the dansyl derivative fluorescent probe is 83%, and the reaction equation is as follows:
Claims (7)
1. a dansyl derivative fluorescent probe is characterized in that the structural formula of the fluorescent probe is as follows:
wherein n is 1 or 3.
2. The method for synthesizing the dansyl derivative fluorescent probe according to claim 1, comprising the steps of:
under the conditions of inert atmosphere and room temperature, dropwise adding trichloromethane solution of dansyl chloride into trichloromethane solution containing bromine substituted alcohol and triethylamine, stirring at room temperature for reaction, washing and drying reaction liquid after the reaction is finished, evaporating to remove the solvent, and then carrying out column chromatography separation and purification on the reactant to obtain the dansyl derivative fluorescent probe, wherein the bromine substituted alcohol is one of 4-bromine-1-butanol or 8-bromine-1-octanol.
3. The method for synthesizing the dansyl derivative fluorescent probe according to claim 2, wherein the inert atmosphere is nitrogen, argon or neon, and the flow rate is 0.6-0.8 mL/s.
4. The method for synthesizing the dansyl derivative fluorescent probe according to claim 2, wherein the molar ratio of the dansyl chloride to the bromine-substituted alcohol to the triethylamine is 1: 1-1.5: 1 to 1.5.
5. The method for synthesizing the dansyl derivative fluorescent probe according to claim 2, wherein the reaction time with stirring at room temperature is 3-5 h.
6. The method for synthesizing the dansyl derivative fluorescent probe according to claim 2, wherein the washing is 6-7 times with saturated saline; the drying is carried out for at least 4h by using anhydrous sodium sulfate; the eluent for column chromatography separation and purification is dichloromethane: petroleum ether is mixed according to the volume ratio of 1-2: 1 to prepare a mixed solvent.
7. The method for diagnosing and treating diseases of the dansyl derivative fluorescent probe according to claim 1, wherein the fluorescent probe and the piroxicam Y are used as dual fluorescent probes, and solubilization of a surfactant CTAB is utilized to construct a supermolecular proportional fluorescent sensing platform and the supramolecular proportional fluorescent sensing platform is used for H2And S, carrying out selective detection.
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| CN104151248A (en) * | 2014-07-17 | 2014-11-19 | 陕西师范大学 | Cationic fluorescent probe for dansyl biimidazole derivatives as well as synthesis method and application of cationic fluorescent probe |
| CN108822138A (en) * | 2018-04-04 | 2018-11-16 | 皖西学院 | A kind of preparation method and application for the metal complex fluorescent probe detecting hydrogen sulfide |
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| CN104151248A (en) * | 2014-07-17 | 2014-11-19 | 陕西师范大学 | Cationic fluorescent probe for dansyl biimidazole derivatives as well as synthesis method and application of cationic fluorescent probe |
| CN108822138A (en) * | 2018-04-04 | 2018-11-16 | 皖西学院 | A kind of preparation method and application for the metal complex fluorescent probe detecting hydrogen sulfide |
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| 检测硫化氢分子的荧光探针;高敏等;《化学进展》;20141231;第26卷(第6期);1065-1078 * |
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