CN115420723B - A fluorescent probe for detecting Cu2+ in aqueous solution and its preparation method and application - Google Patents
A fluorescent probe for detecting Cu2+ in aqueous solution and its preparation method and application Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 22
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract 9
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000523 sample Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 12
- 238000001514 detection method Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 230000008859 change Effects 0.000 claims abstract description 9
- HWQSZPUCHJKWLS-UHFFFAOYSA-N 7-(diethylamino)-2-oxochromene-3-carbaldehyde Chemical compound C1=C(C=O)C(=O)OC2=CC(N(CC)CC)=CC=C21 HWQSZPUCHJKWLS-UHFFFAOYSA-N 0.000 claims abstract description 6
- WFJRIDQGVSJLLH-UHFFFAOYSA-N methyl n-aminocarbamate Chemical compound COC(=O)NN WFJRIDQGVSJLLH-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 12
- 229960000956 coumarin Drugs 0.000 claims description 7
- 235000001671 coumarin Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002262 Schiff base Substances 0.000 claims description 5
- -1 Schiff base compound Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
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- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 3
- 229940125782 compound 2 Drugs 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000012512 characterization method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract 4
- 125000003172 aldehyde group Chemical group 0.000 abstract 1
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 abstract 1
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 42
- 150000002500 ions Chemical class 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 231100000053 low toxicity Toxicity 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000002470 solid-phase micro-extraction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
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Abstract
本发明涉及一种用于在水溶液中检测Cu2+的荧光探针及其制备方法与应用，以肼甲酸甲酯和7‑二乙氨基香豆素‑3‑甲醛为原料，经肼甲酸甲酯上的伯胺与7‑二乙氨基香豆素‑3‑甲醛上的醛基进行亲核加成反应生成C＝N双键，通过1H NMR、13C NMR和ESI‑MS对其进行结构表征，探针在水溶液中呈现亮绿色荧光，加入铜离子后荧光淬灭，将浓度呈现梯度变化的铜离子溶液与探针SJL溶液混合后，测定荧光强度，然后以铜离子的浓度为横坐标，混合体系的荧光强度为纵坐标作图，建立铜离子溶液浓度梯度变化与荧光探针溶液荧光强度变化关系的标准线，该化合物可作为一种高灵敏、高选择性的在水溶液中检测微量Cu2+的荧光探针，络合常数为1.98×105M‑1，检测限低至0.6μM。
The invention relates to a fluorescent probe for detecting Cu2 + in an aqueous solution, and a preparation method and application thereof. Methyl hydrazinecarboxylate and 7-diethylaminocoumarin-3-formaldehyde are used as raw materials, a primary amine on the methyl hydrazinecarboxylate and an aldehyde group on the 7-diethylaminocoumarin-3-formaldehyde undergo nucleophilic addition reaction to generate a C=N double bond, and structural characterization is performed by 1 H NMR, 13 C NMR and ESI-MS. The probe exhibits bright green fluorescence in an aqueous solution, and the fluorescence is quenched after copper ions are added. A copper ion solution with a concentration gradient change is mixed with a probe SJL solution, and the fluorescence intensity is measured. A graph is then drawn with the concentration of the copper ions as the abscissa and the fluorescence intensity of the mixed system as the ordinate, and a standard line for the relationship between the concentration gradient change of the copper ion solution and the fluorescence intensity change of the fluorescent probe solution is established. The compound can be used as a highly sensitive and highly selective fluorescent probe for detecting trace amounts of Cu2 + in an aqueous solution, and the complexation constant is 1.98× 105 M -1 , and the detection limit is as low as 0.6 μM.
Description
Technical Field
The invention discloses a fluorescent probe for detecting Cu < 2+ > in an aqueous solution, and a preparation method and application thereof, and belongs to the technical field of fluorescent probes for detecting heavy metal ions.
Background
The fluorescent probe is based on the organic combination of molecular recognition and fluorescence technology, and the receptor is used for selectively combining a specific object, and the fluorescence signal is used for expressing the molecular combination information, so that the in-situ real-time detection on the molecular level is realized. The metal ion detection fluorescent probe provides a detection means with wide application value, and photophysical and photochemical problems related in the design, synthesis, identification and application processes are widely focused by researchers in different fields.
The fluorescent probe has incomparable advantages of other analysis methods, such as atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry, solid-phase microextraction combined with high performance liquid chromatography, electrochemical analysis methods and the like. Namely, the existence and concentration range of ions are visually reflected through the change of fluorescence intensity and color, and the ion-sensitive fluorescent material has high sensitivity and selectivity. Common ion-recognizing fluorescent probes recognize several general classes including photo-induced electron transfer (PET), intramolecular Charge Transfer (ICT), and Fluorescence Resonance Energy Transfer (FRET).
Coumarin derivatives are an important class of natural heterocyclic compounds widely existing in nature. The compound has unique bioactivity and excellent optical characteristic, and the benzopyran with basic structure is colorless matter without fluorescence, but if electron donating group is introduced in 7 position and electron withdrawing group is introduced in 3 or 4 position, a 'push-pull' electron system is formed, so that the strong fluorescent matter is obtained. The coumarin compound has the advantages of larger molar absorptivity, higher fluorescence quantum yield, larger Stokes shift and good light stability, can effectively reduce the background fluorescence of cell components and physiological liquid, is favored in the design of fluorescent probes, and has important significance in the design of synthesizing novel coumarin fluorescent compounds.
Copper is a common metal widely existing in the environment, and proper amount of Cu 2+ in the human body is beneficial to maintaining the normal operation of the organism, and if the metabolism of Cu 2+ in the human body is unbalanced, diseases can be brought to people. Copper is widely used in the industrial field, and causes serious pollution to the environment through the discharge of factory sewage, thereby threatening the life health of human beings. Until now, the fluorescent probe layer for detecting Cu 2+ is endless, but most of detection systems are organic solvents, which may cause harm to organisms or cause environmental pollution in the detection process, so that practical application is limited. Therefore, it is of great importance to establish a fluorescent probe recognizing Cu 2+ in aqueous solution, which has low toxicity, good biocompatibility, high selectivity, high sensitivity and easy synthesis.
Disclosure of Invention
The invention overcomes the defects existing in the prior art, provides a fluorescent probe for detecting Cu < 2+ > in aqueous solution, a preparation method and application thereof, and the designed fluorescent probe molecule takes methyl hydrazinecarboxylate as an ion receptor and coumarin as a fluorescent response group to synthesize a fluorescent probe reagent which has low toxicity, good biocompatibility, high selectivity, high sensitivity and easy synthesis, can detect trace Cu 2+ in pure water, and is used for researching a synthesis method and measuring trace Cu 2+.
In order to solve the technical problems, the technical scheme adopted by the invention is that the fluorescent probe for detecting Cu < 2+ > in an aqueous solution takes 7-diethylaminocoumarin-3-formaldehyde as a carbon source and methyl hydrazinoformate as a nitrogen source to form a Schiff base bond with strong coordination capability. The compound is named as 7-diethylamino-2-oxo-2H-chromene-3-methylenehydrazine-1-methyl formate, and the chemical structural formula of the compound is as follows:
Molecular formula C 16H19N3O4
Molecular weight 317.35
Melting point 212.3-217.2 DEG C
Solubility, namely, the water-soluble organic solvent is soluble in various organic solvents such as methanol, ethanol, methylene dichloride and the like.
Spectral properties maximum ultraviolet absorption wavelength 444nm in aqueous solution and fluorescence emission wavelength 515nm.
The structural characterization is as follows ：1H NMR(DMSO-d6,400MHz,TMS):δ(ppm)11.17(s,1H),8.23(s, 1H),8.06(s,1H),7.62(d,J＝9.2Hz,1H),6.73(dd,J1＝2.4Hz,J2＝2.4Hz,1H), 6.55(d,J＝2.0Hz,1H),3.69(s,3H),3.45(q,J＝6.8Hz,4H),1.13(t,J＝7.2 Hz,6H).13C NMR(DMSO-d6,600MHz,TMS):δ(ppm):161.22,156.78,154.29,154.27, 151.58,138.40,131.12,113.24,110.10,108.48,96.86,52.36,44.67,12.82.HRMS(ESI):m/z calcd for C16H20O4N3[(M+H)+]:318.1454,found 318.1448;C16H19O4N3Na[(M+Na)+]:340.1274,found 340.1268.
The technical route is as follows:
The preparation method comprises the following steps:
synthesis of Probe SJL
Controlling the molar ratio of methyl hydrazineformate to the compound 2 to be 1.0-1.2:1, and taking absolute ethyl alcohol as a solvent. Reflux is carried out for 5h at 85 ℃, after complete reaction, the reaction is cooled to room temperature, solid is separated out, filtration is carried out, and filter cake is washed by ice ethanol, thus obtaining yellow solid. The yellow solid is separated and purified by silica gel column chromatography by using methylene dichloride and methanol as eluent, and orange solid SJL is obtained.
Compared with the prior art, the invention has the beneficial effects that the fluorescent probe which has low toxicity, good biocompatibility, high selectivity, high sensitivity and easy synthesis and can detect trace Cu 2+ in pure water is established, the designed fluorescent probe molecule takes methyl hydrazineformate as an ion receptor and coumarin as a fluorescent response group, the fluorescent probe reagent which has low toxicity, good biocompatibility, high selectivity, high sensitivity and easy synthesis and can detect trace Cu 2+ in pure water is synthesized, and the synthesis method is researched and applied to the determination of trace Cu 2+.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 shows the chemical structure of a fluorescent probe SJL of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the fluorescent probe SJL of the invention;
FIG. 3 is a nuclear magnetic carbon spectrum of the fluorescent probe SJL of the invention;
FIG. 4 is a high-resolution mass spectrum of the fluorescent probe SJL of the present invention;
FIG. 5 is a graph showing ultraviolet spectra of the response of the fluorescent probe SJL of the present invention to different metal cations;
FIG. 6 is an ultraviolet spectrum of the titration of the fluorescent probe SJL of the invention for different Cu 2+ concentrations;
FIG. 7 is a graph showing fluorescence spectra of response of the fluorescent probe SJL of the present invention to different metal cations;
FIG. 8 is an ion competition experiment of the fluorescent probe SJL of the present invention;
FIG. 9 is a graph showing fluorescence spectra of the fluorescent probe SJL according to the present invention titrated for different Cu 2+ concentrations;
FIG. 10 shows the detection limit line of the fluorescence probe SJL to Cu 2+;
FIG. 11 is a graph showing the complexing constant of the fluorescent probe SJL versus Cu 2+;
FIG. 12 is a Job's Plot of the fluorescent probe SJL of the present invention.
Detailed Description
As shown in figures 1-12, the fluorescent probe for detecting Cu < 2+ > in an aqueous solution has the chemical structural formula of 7-diethylamino-2-oxo-2H chromene-3-methylenehydrazine-1-methyl formate:
Molecular formula C 16H19N3O4
Molecular weight 317.35
Melting point 212.3-217.2 DEG C
Solubility in water, and solubility in various organic solvents such as methanol, ethanol, dichloromethane, etc
Spectral properties maximum ultraviolet absorption wavelength 444nm in aqueous solution and fluorescence emission wavelength 515.5nm.
The fluorescent probe is coumarin Schiff base type.
A preparation method of a fluorescent probe for detecting Cu < 2+ > in an aqueous solution is implemented according to the following steps,
Firstly, synthesizing a compound 7-diethylaminocoumarin-3-formaldehyde (hereinafter referred to as a compound II);
Controlling the molar ratio of methyl hydrazineformate to the compound to be 1.0-1.2:1, taking absolute ethyl alcohol as a solvent, refluxing at 85 ℃ for 5 hours, cooling to room temperature, separating out solids, filtering, and washing a filter cake with glacial ethyl alcohol to obtain yellow solids.
And thirdly, separating and purifying the yellow solid by silica gel column chromatography by taking dichloromethane and methanol as eluent to obtain orange solid SJL, namely the fluorescent probe.
The application of the fluorescent probe for detecting Cu < 2+ > in the aqueous solution is characterized in that the Schiff base compound can be used as the fluorescent probe for detecting Cu 2+ in the aqueous solution, the concentration of Cu 2+ is used as an abscissa, the fluorescence intensity of a mixed system is used as an ordinate to be plotted, a standard line of the concentration gradient change of the Cu 2+ solution and the fluorescence intensity change value of the probe SJL solution is established, and the concentration of Cu 2+ in the solution to be detected is read out from the graph according to the fluorescence intensity when the fluorescent probe is applied, wherein the detection limit is as low as 0.6 mu M.
For further explanation of the present invention, the present invention will be described in further detail with reference to the drawings and examples, so as to enable those skilled in the art to practice the same by referring to the description.
In fig. 5, the abscissa indicates wavelength and the ordinate indicates absorbance. In the aqueous solution, the change of the ultraviolet spectrum absorbance to Cu 2+ is most obvious, and the color of the solution is changed from yellow green to brown yellow, which indicates that the probe SJL has a certain naked eye recognition capability to Cu 2+.
In fig. 6, the abscissa indicates wavelength and the ordinate indicates absorbance. In the pure water system, the concentration of Cu 2+ is 0-13.9 times of the concentration of the probe SJL in sequence. FIG. 5 shows that the absorbance of the probe SJL increases with the concentration of Cu 2+, and the maximum absorption wavelength shifts from 444nm to 473nm in red. The presence of isoconcentration spots at 363nm and 443nm, respectively, indicates that the probe SJL and the complex SJL-Cu 2+ are in dynamic equilibrium.
In fig. 7, in a pure water system, the abscissa indicates wavelength and the ordinate indicates fluorescence intensity. Compared with other ions, after Cu 2+ is added into the probe SJL, the fluorescence intensity is obviously reduced, and the quenching rate is as high as 82.3 percent.
In FIG. 8, by comparing the fluorescence intensities of the respective solutions at the same emission wavelength (444 nm), it can be seen that the selective recognition of Cu 2+ by the probe SJL is not affected by other ions.
In fig. 9, the fluorescence intensity of the probe SJL gradually decreased with an increase in the concentration of Cu 2+, and when the concentration of Cu 2+ increased up to 25.9 times, the fluorescence intensity hardly changed any more. This also indicates that the probe SJL has a higher sensitivity to Cu 2+.
In fig. 10, in the range of 0.1-0.7 times of Cu 2+ concentration, the fluorescence intensity of the probe SJL and the Cu 2+ concentration show a good linear relationship, and the linear equation is y= -978.57x+2175.64, r 2 = 0.99038. The probe can perform good quantitative detection on the concentration of Cu 2+ in the concentration range. The slope m= -978.57 × 5 can be obtained according to the equation, meanwhile, the lowest detection limit of 0.6 μm of the probe SJL is calculated by using the linear relation and the detection limit calculation formula lod=3σ/M, which shows that the sensitivity of the probe SJL is relatively high.
In fig. 11, a fitting linear equation y=4.07× -9x+8.05×10-4,R2 = 0.99241 is obtained, and a complex constant ka=1.98×10 5M-1 is obtained according to a complex constant calculation formula. This shows that the probe SJL forms a complex with better stability with Cu 2+.
In FIG. 12, the measurement of Job curve was performed by experiments, and when the total concentration was not changed, the fluorescence intensity of probe SJL at 515nm gradually decreased with the increase of the concentration ratio of Cu 2+, and when the concentration of Cu 2+ was 0.47 times, the curve showed an inflection point, indicating that the coordination ratio of probe and Cu 2+ ion was 1:1.
Synthesis of Probe SJL
Methyl hydrazinecarboxylate 90.08mg (1 mmol) was weighed into a 50mL round bottom flask, 10mL of absolute ethyl alcohol was added, and after stirring at normal temperature to dissolve it completely, 245mg (1 mmol) of 7-diethylaminocoumarin-3-carbaldehyde was added to the reaction flask, stirring was carried out at 60℃for 30min, and one drop of glacial acetic acid was added dropwise to the reaction flask. The mixture was heated to 85 ℃ and reacted at reflux for 5h. TLC monitoring, after the raw materials are completely reacted, the mixture is cooled to room temperature, solid is separated out, suction filtration and drying are carried out, and 240mg of yellow solid is obtained. The target product SJL 120mg is finally obtained by using a silica gel chromatographic column to separate and purify the target product, and CH 2Cl2/CH3 OH (300:1-200:1-100:1, v/v) is used as an eluent, and the yield is 63%.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (4)
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| CN109111434B (en) * | 2018-10-29 | 2020-07-07 | 浙江外国语学院 | Coumarin nickel ion fluorescent probe, preparation method thereof, crystal preparation method and application |
| CN111253386B (en) * | 2020-02-14 | 2024-08-27 | 中北大学 | A fluorescent probe for naked eye recognition of Cu2+ and its preparation method and application |
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| Title |
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| "A highly sensitive coumarin-based fluorescent probe for visual detection of Cu2+ in aqueous solution and its bioimaging in living cells";Junli Shi 等;《Journal of Molecular Structure》;20230201;第1281卷;第135062页 * |
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