CN108383818B - Coumarin mercaptoethylamine Schiff base Cd2+Preparation and application of fluorescent probe - Google Patents
Coumarin mercaptoethylamine Schiff base Cd2+Preparation and application of fluorescent probe Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 49
- -1 Coumarin mercaptoethylamine Chemical compound 0.000 title claims description 38
- 239000002262 Schiff base Substances 0.000 title claims description 37
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 title claims description 25
- 150000004753 Schiff bases Chemical class 0.000 title description 3
- 238000002360 preparation method Methods 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000706 filtrate Substances 0.000 claims description 20
- 229960000956 coumarin Drugs 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 claims description 5
- CJIJXIFQYOPWTF-UHFFFAOYSA-N 7-hydroxycoumarin Natural products O1C(=O)C=CC2=CC(O)=CC=C21 CJIJXIFQYOPWTF-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000004809 thin layer chromatography Methods 0.000 claims description 5
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 claims description 5
- 230000001225 therapeutic effect Effects 0.000 claims 3
- 239000000243 solution Substances 0.000 abstract description 23
- 238000001514 detection method Methods 0.000 abstract description 13
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007995 HEPES buffer Substances 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 235000016477 Taralea oppositifolia Nutrition 0.000 abstract 1
- 241001358109 Taralea oppositifolia Species 0.000 abstract 1
- 238000002189 fluorescence spectrum Methods 0.000 description 10
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 9
- 239000000523 sample Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 235000001671 coumarin Nutrition 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000003068 molecular probe Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000008085 renal dysfunction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
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Abstract
The invention relates to the field of fluorescent probes, in particular to a tonka beanThe structure of the fluorescent probe is as follows:the fluorescent probe can be in EtOH-H2Cd recognition in O (95:5, v/v, HEPES 20mmol/L) solution2+The advantages are that: exhibits excellent selectivity in competition with other ions; the fluorescent sensor has higher fluorescence sensing property; the detection limit is low; high detection sensitivity and high fluorescence quantum yield.
Description
Technical Field
The invention relates to the field of fluorescent probes, in particular to a coumarin mercaptoethylamine Schiff base fluorescent probe and application thereof.
Background
With the rapid development of the industry in China, the metal cadmium is widely applied to the production of various industrial products, such as nickel-cadmium batteries, coatings, pigments and other fields. In recent years, the threat of cadmium ions to human health is more and more emphasized, and excessive cadmium ions enriched in a human body can cause damage to bones, lungs, kidneys and nervous systems, and cause renal dysfunction, calcium dysfunction and even canceration. Therefore, the method has low cost and high response speed and can be used for detecting Cd in natural environment and biological system2+The detection method of (2) is particularly important.
Because the fluorescent molecular probe has the obvious advantages of convenient operation, low cost, high selectivity, high sensitivity and the like, the fluorescent molecular probe is generally concerned in the detection of metal ions. The coumarin compound has the advantages of high fluorescence quantum yield and capability of obtaining fluorescence of different emission bands through structural design, so that coumarin Cd is designed and developed2+Has important practical value.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims to provide a high-sensitivity high-interference-resistance Cd pairing method2+Fluorescent probe with specific identification and application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a coumarin mercaptoethylamine Schiff base fluorescent probe is characterized in that: the specific structural formula is as follows:
the application of the coumarin mercaptoethylamine Schiff base fluorescent probe is characterized in that: the coumarin mercaptoethylamine Schiff base fluorescent probe identifies Cd in a solvent2+。
Further, the coumarin mercaptoethylamine Schiff base fluorescent probe recognizes Cd2+The solvent of (A) is EtOH and H2The volume ratio of O is 95:5 EtOH-H2And (4) O solution.
Further, the coumarin mercaptoethylamine Schiff base fluorescent probe recognizes Cd2+The pH range of (1) is 3 to 13.
A preparation method of a coumarin mercaptoethylamine Schiff base fluorescent probe is characterized by comprising the following steps:
(1) synthesizing 7-hydroxy-8-coumarin aldehyde: dissolving 7-hydroxycoumarin and hexamethylenetetramine in glacial acetic acid, stirring and heating to 70-100 ℃, reacting, then adding hydrochloric acid into the system, and stirring at 50-90 ℃; cooling, adding ice water, extracting with ethyl acetate, drying the organic phase with anhydrous sodium sulfate, vacuum filtering, and rotary evaporating the filtrate under reduced pressure to remove the solvent to obtain yellow solid; then recrystallizing with absolute ethyl alcohol to obtain 7-hydroxy-8-coumarin aldehyde;
the reaction formula is as follows:
(2) synthesizing a coumarin mercaptoethylamine Schiff base fluorescent probe:
adding mercaptoethylamine hydrochloride dissolved by ethanol into a reaction vessel, adding sodium hydroxide, stirring at normal temperature, filtering to obtain a filtrate, adding an ethanol solution of 7-hydroxy-8-coumarin aldehyde into the filtrate, heating to reflux, detecting by using a thin-layer chromatography after refluxing, reacting completely, cooling to room temperature, filtering, and naturally evaporating and recrystallizing the filtrate to obtain a yellow solid;
the reaction formula is as follows:
compared with the prior art, the invention has the following beneficial effects:
(1) the fluorescent probe has coumarin fluorophore, N and O atoms and Cd in Schiff base in molecule2+Coordination and complexation realize PET blocking, fluorescent off-on signal and Cd pairing2+The fluorescence identification is carried out, and the detection sensitivity is high.
(2) The fluorescent probe pair Cd2+Has specific selectivity, basically has no change with other common ion action fluorescent signals, higher anti-interference capability, high sensitivity and low detection limit.
(3) The fluorescent probe has a wide pH application range of 3-13.
Drawings
FIG. 1 shows fluorescent probes for coumarin mercaptoethylamine Schiff base1H NMR spectrum;
FIG. 2 is a fluorescence emission spectrum of a fluorescent probe of the present invention for selective recognition of cadmium ions;
FIG. 3 is a graph showing the change of fluorescence emission spectra of the fluorescent probe of the present invention in the presence of cadmium ions at different concentrations;
FIG. 4 is a graph showing the change of fluorescence emission spectra of the fluorescent probe of the present invention in solutions of different pH values;
FIG. 5 is a graph showing the change in fluorescence emission intensity of the fluorescent probe of the present invention in the presence of cadmium ions and other metal ions;
FIG. 6 is a graph showing the calculation of the detection limit of cadmium ions by the fluorescent probe of the present invention.
Detailed Description
The following detailed description of specific embodiments of the invention is provided in connection with the accompanying drawings. These embodiments are provided for illustrative purposes only and are not intended to limit the scope or the principles of the invention, which is defined by the following claims, including obvious variations or modifications based thereon.
Example 1:
(1) the reaction formula for synthesizing the 7-hydroxy-8-coumarin aldehyde is as follows:
(2) the specific steps for synthesizing the 7-hydroxy-8-coumarin aldehyde are as follows:
10g of 7-hydroxycoumarin and 20g of hexamethylenetetramine are weighed and dissolved in 75mL of glacial acetic acid, stirred and heated to 90 ℃ for reaction for 8H, and then hydrochloric acid (150mL, conc2O84: 100, v/v) and stirred at 70 ℃ for 30 min. Cooling, adding ice water, extracting with ethyl acetate, drying the organic phase with anhydrous sodium sulfate, filtering under reduced pressure, and evaporating the filtrate under reduced pressure to remove the solvent to obtain a yellow solid. Then recrystallizing with absolute ethyl alcohol to obtain 7-hydroxy-8-coumarin aldehyde. The yield thereof was found to be 18%.
(3) And synthesizing a coumarin mercaptoethylamine Schiff base fluorescent probe according to the reaction formula:
(4) the method comprises the following specific steps of synthesizing the coumarin mercaptoethylamine Schiff base fluorescent probe:
mercaptoethylamine hydrochloride (0.57g,5.05 mmol) dissolved in 15mL of ethanol is added into a 50mL three-neck flask, sodium hydroxide (0.2g,5.05mmol) is added, the mixture is stirred for 1h at normal temperature and filtered to obtain a filtrate, an ethanol solution (15mL) of 7-hydroxy-8-coumarin aldehyde (0.8g,4.21mmol) is added into the filtrate, the mixture is heated to reflux, after the reflux is carried out for 12h, the thin layer chromatography is used for detection, the reaction is completed, the mixture is cooled to room temperature and filtered, the filtrate is naturally evaporated and recrystallized to obtain 0.2g of yellow solid, and the yield is 16%. Coumarin mercaptoethylamine Schiff base fluorescent probe1The H NMR spectrum is shown in FIG. 1.
(5) Coumarin mercaptoethylamine Schiff base fluorescent probe pair Cd2+Selective detection of：
EtOH-H of 10. mu. mol/L coumarin mercaptoethylamine Schiff base2O (95:5, v/v, HEPES 20mmol/L, pH 7.4) solution, 100. mu. mol/L of metal ion (Zn) was added thereto2+，Pb2+，Ni+，Na+， Mn2+，Mg2+，Li+，K+，Hg2+，Fe3+，Fe2+，Cu2+，Cr3+，Co2+，Cd2+，Ca2+，Ba2+， Al3+，Ag+) The fluorescence emission spectrum of the solution was measured within 15 seconds after the stirring, and the results are shown in FIG. 2. As can be seen from FIG. 2, the fluorescent probe had almost no emission peak at 458nm, and when Cd was added2+Thereafter, the fluorescent probe solution showed a strong emission peak at 458nm, however, other ions such as Zn were added2+，Pb2+，Ni+， Na+，Mn2+，Mg2+，Li+，K+，Hg2+，Fe3+，Fe2+，Cu2+，Cr3+，Co2+，Ca2+，Ba2+， Al3+，Ag+Then, the emission peak of the fluorescent probe solution at 458nm is not obviously enhanced, so the experimental result shows that only Cd is added2+Can cause the fluorescence probe solution to have obvious fluorescence enhancement at 458nm, and the coumarin mercaptoethylamine Schiff base fluorescent probe is used in EtOH-H2Cd in O (95:5, v/v, HEPES 20mmol/L, pH 7.4) solution2+Has good selectivity.
(6) Coumarin mercaptoethylamine Schiff base fluorescent probe pair Cd2+Fluorescence titration experiment of (1):
EtOH-H of 10. mu. mol/L coumarin mercaptoethylamine Schiff base2O (95:5, v/v, HEPES 20mmol/L, pH 7.4) solution, increasing Cd stepwise2+The fluorescence emission spectrum of each sample was measured within 15 seconds of stirring, and the results are shown in FIG. 3. As can be seen from FIG. 3, with Cd2+The fluorescence intensity of the probe solution at 458nm is gradually increased when the concentration is gradually increased, and when the concentration is higher than the concentration, the fluorescence intensity of the probe solution is gradually increased when the concentration is higher than the concentration of Cd2+When the concentration of (A) reaches 1.2 times of the concentration of the probe, i.e., 12. mu. mol/L, fluorescence is observedThe intensity is not increased any more, the titration is saturated, so the experimental result shows that the coumarin mercaptoethylamine Schiff base fluorescent probe is used for detecting Cd2+Has good sensing property.
(7) Coumarin mercaptoethylamine Schiff base fluorescent probe pair Cd2+pH fluorescence experiment of (2):
EtOH-H of 10. mu. mol/L coumarin mercaptoethylamine Schiff base2O (95:5, v/v, HEPES 20mmol/L,) solution, stirring uniformly for 15s, detecting fluorescence emission spectrum of each sample, and adding 100 mu mol/L Cd2+And detecting the fluorescence emission spectrum of each sample within 15s of uniform stirring. The solutions were then only changed in pH and their fluorescence emission spectra were tested sequentially. The fluorescence emission intensity at 458nm was plotted as shown in FIG. 4. As shown in FIG. 4, the fluorescent probe has a wide pH application range of 3-13.
(8) Coumarin mercaptoethylamine Schiff base fluorescent probe pair Cd2+Identified competition experiments:
EtOH-H of 10. mu. mol/L coumarin mercaptoethylamine Schiff base2O (95:5, v/v, HEPES 20mmol/L, pH 7.4) solution, 100. mu. mol/L of another metal ion (Zn) was added thereto2+，Pb2+，Ni+， Na+，Mn2+，Mg2+，Li+，K+，Hg2+，Fe3+，Fe2+，Cu2+，Cr3+，Co2+，Ca2+，Ba2+， Al3+，Ag+) Detecting the fluorescence emission spectrum of the solution within 15s after stirring uniformly, and then adding 100 mu mol/L Cd into each solution containing metal ions2+And detecting the fluorescence emission spectrum of the solution within 15s after the solution is uniformly stirred. The fluorescence emission intensity at 458nm was plotted as shown in FIG. 5. As shown in FIG. 5, other metal ion pairs Cd coexist2+Without significant interference with fluorescence recognition.
(9) Coumarin mercaptoethylamine Schiff base fluorescent probe pair Cd2+And (3) calculation of detection limit:
the limit of detection is calculated from fluorescence spectroscopy titration data. Cd with fluorescence titration intensity as ordinate2+Is rich inThe degrees are plotted as abscissa, as shown in fig. 6. In Cd2+The concentration is in the range of 1 to 12 μmol/L, using the formula DL ═ KXSb1(ii) S, wherein DL is the detection limit, K is 3, Sb1S is the slope of the calibration curve, standard deviation of the blank solution. Calculated detection limit is 7.47 multiplied by 10-8M。
Example 2:
(1) the specific steps for synthesizing the 7-hydroxy-8-coumarin aldehyde are as follows:
10g of 7-hydroxycoumarin and 20g of hexamethylenetetramine are weighed and dissolved in 75mL of glacial acetic acid, stirred and heated to 70 ℃ for reaction for 8H, and then hydrochloric acid (150mL, conc2O84: 100, v/v) and stirred at 50 ℃ for 30 min. Cooling, adding ice water, extracting with ethyl acetate, drying the organic phase with anhydrous sodium sulfate, filtering under reduced pressure, and evaporating the filtrate under reduced pressure to remove the solvent to obtain a yellow solid. Then recrystallizing with absolute ethyl alcohol to obtain 7-hydroxy-8-coumarin aldehyde. The yield thereof was found to be 13%.
(2) The method comprises the following specific steps of synthesizing the coumarin mercaptoethylamine Schiff base fluorescent probe:
adding mercaptoethylamine hydrochloride (0.57g,5.05 mmol) dissolved by 15mL of ethanol into a 50mL three-neck flask, adding sodium hydroxide (0.2g,5.05mmol), stirring at normal temperature for 1h, filtering to obtain a filtrate, adding an ethanol solution (15mL) of 7-hydroxy-8 aldehyde coumarin (0.8g,4.21mmol) into the filtrate, heating to reflux, detecting by using a thin-layer chromatography after refluxing for 12h, completely reacting, cooling to room temperature, filtering, naturally evaporating the filtrate for recrystallization to obtain a crystal yellow solid, wherein the yield is 13%.
Example 3:
(1) the specific steps for synthesizing the 7-hydroxy-8-coumarin aldehyde are as follows:
10g of 7-hydroxycoumarin and 20g of hexamethylenetetramine are weighed and dissolved in 75mL of glacial acetic acid, stirred and heated to 100 ℃ for reaction for 8H, and then hydrochloric acid (150mL, conc2O84: 100, v/v) and stirred at 90 ℃ for 30 min. Cooling, adding ice water, extracting with ethyl acetate, drying the organic phase with anhydrous sodium sulfate, filtering under reduced pressure, and evaporating the filtrate under reduced pressure to remove the solvent to obtain a yellow solid. Then recrystallizing with absolute ethyl alcoholTo obtain 7-hydroxy-8-coumarin aldehyde. The yield thereof was found to be 15%.
(2) The method comprises the following specific steps of synthesizing the coumarin mercaptoethylamine Schiff base fluorescent probe:
adding mercaptoethylamine hydrochloride (0.57g,5.05 mmol) dissolved by 15mL of ethanol into a 50mL three-neck flask, adding sodium hydroxide (0.2g,5.05mmol), stirring at normal temperature for 1h, filtering to obtain a filtrate, adding an ethanol solution (15mL) of 7-hydroxy-8 aldehyde coumarin (0.8g,4.21mmol) into the filtrate, heating to reflux, detecting by using a thin-layer chromatography after refluxing for 12h, completely reacting, cooling to room temperature, filtering, naturally evaporating the filtrate for recrystallization to obtain a crystal yellow solid with the yield of 16%.
Claims (5)
1. A coumarin mercaptoethylamine Schiff base fluorescent probe is characterized in that: the specific structural formula is as follows:
2. the non-diagnostic non-therapeutic use of a coumarin mercaptoethylamine schiff base fluorescent probe according to claim 1, characterized in that: the coumarin mercaptoethylamine Schiff base fluorescent probe identifies Cd in a solvent2+。
3. The non-diagnostic non-therapeutic use of a coumarin mercaptoethylamine schiff base fluorescent probe according to claim 2, characterized in that: coumarin mercaptoethylamine Schiff base fluorescent probe for identifying Cd2+The solvent of (A) is EtOH and H2The volume ratio of O is 95:5 EtOH-H2And (4) O solution.
4. The non-diagnostic non-therapeutic use of a coumarin mercaptoethylamine schiff base fluorescent probe according to claim 2, characterized in that: coumarin mercaptoethylamine Schiff base fluorescent probe for identifying Cd2+The pH range of (1) is 3 to 13.
5. The method for preparing coumarin mercaptoethylamine Schiff base fluorescent probe according to claim 1, which is characterized by comprising the following steps:
(1) synthesizing 7-hydroxy-8-coumarin aldehyde: dissolving 7-hydroxycoumarin and hexamethylenetetramine in glacial acetic acid, stirring and heating to 70-100 ℃, reacting, then adding hydrochloric acid into the system, and stirring at 50-90 ℃; cooling, adding ice water, extracting with ethyl acetate, drying the organic phase with anhydrous sodium sulfate, vacuum filtering, and rotary evaporating the filtrate under reduced pressure to remove the solvent to obtain yellow solid; then recrystallizing with absolute ethyl alcohol to obtain 7-hydroxy-8-coumarin aldehyde;
the reaction formula is as follows:
(2) synthesizing a coumarin mercaptoethylamine Schiff base fluorescent probe:
adding mercaptoethylamine hydrochloride dissolved by ethanol into a reaction vessel, adding sodium hydroxide, stirring at normal temperature, filtering to obtain a filtrate, adding an ethanol solution of 7-hydroxy-8-coumarin aldehyde into the filtrate, heating to reflux, detecting by using a thin-layer chromatography after refluxing, reacting completely, cooling to room temperature, filtering, and naturally evaporating and recrystallizing the filtrate to obtain a yellow solid;
the reaction formula is as follows:
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| CN201810046380.0A CN108383818B (en) | 2018-06-25 | 2018-06-25 | Coumarin mercaptoethylamine Schiff base Cd2+Preparation and application of fluorescent probe |
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