CN114437048A - Detect Ag+Coumarin fluorescent probe, preparation method and application thereof - Google Patents
Detect Ag+Coumarin fluorescent probe, preparation method and application thereof Download PDFInfo
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229960000956 coumarin Drugs 0.000 title claims abstract description 11
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000004458 analytical method Methods 0.000 claims abstract description 5
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000523 sample Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 238000002189 fluorescence spectrum Methods 0.000 claims description 8
- 230000005284 excitation Effects 0.000 claims description 7
- 238000000862 absorption spectrum Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- GJLJILHMNBYGQT-UHFFFAOYSA-N 3-(diethylamino)-4-methylchromen-2-one Chemical compound C1=CC=C2OC(=O)C(N(CC)CC)=C(C)C2=C1 GJLJILHMNBYGQT-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910018162 SeO2 Inorganic materials 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 230000000536 complexating effect Effects 0.000 abstract description 3
- QXAMGWKESXGGNV-UHFFFAOYSA-N 7-(diethylamino)-1-benzopyran-2-one Chemical compound C1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 QXAMGWKESXGGNV-UHFFFAOYSA-N 0.000 abstract description 2
- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 0.000 abstract 1
- 230000002950 deficient Effects 0.000 abstract 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 28
- 229910021645 metal ion Inorganic materials 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- FXURYRWDOBBQLX-UHFFFAOYSA-N N1C=CC=C1.[B].[F] Chemical compound N1C=CC=C1.[B].[F] FXURYRWDOBBQLX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000008764 nerve damage Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000008816 organ damage Effects 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010040872 skin infection Diseases 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The invention relates to the field of chemical analysis, in particular to a method for detecting Ag+The coumarin fluorescent probe, and a preparation method and application thereof. The invention takes 7-diethylamino-4-methylcoumarin and benzil as raw materials to synthesize a simple coumarin fluorescent probe 7- (diethylamino) -4- (4, 5-diphenyl imidazole) -2-benzopyrone (L), wherein 7-position is a diethylamino electron donating group, 4-position is a 4, 5-diphenyl imidazole electron withdrawing group, and the fluorescent probe contains O, N electron-rich atoms and electron-deficient Ag+Complexing with Ag+Has good coordination ability and can identify Ag with high selectivity+And the method is not interfered by other coexisting ions, and has the characteristics of low detection limit, high fluorescence intensity, short response time, wide pH value range and the like.
Description
Technical Field
The invention relates to the field of chemical analysis, in particular to a method for detecting Ag+The coumarin fluorescent probe, and a preparation method and application thereof.
Background
Silver ion (Ag)+) Because of its excellent antibacterial activity, it is widely used in many commercial products and medical supplies. However, the human body is excessively ingested or exposed to Ag+It can lead to diarrhea, skin infection, nerve or organ damage to varying degrees. Even more, Ag+Can inactivate thiol enzymes, inhibit the growth and reproduction of friendly bacteria in the environment, and bring about a plurality of adverse consequences to the environment. Thus, it can treat Ag in vivo and in the environment+The quantitative detection is of great significance.
At present, for Ag+The study of detection methods is receiving increasing attention from researchers. Common detection methods include Atomic Absorption Spectroscopy (AAS), Atomic Emission Spectroscopy (AES), electrochemical methods, and mass spectrometry, but the use of these methods requires expensive equipment, complicated procedures, or long test waiting times, which limits their widespread use in ion detection. The fluorescent probe analysis method has attracted great interest due to the characteristics of good selectivity, high sensitivity, simple operation, short response time and the like, and is widely applied to biological, environmental and food detection.
Detection of Ag+The fluorescent probes with the content are usually rhodamine, pyrene, quinoline and boron fluorine pyrrole, but the reported fluorescent probes have the defects of high synthesis cost, complicated synthesis steps, large molecular weight, complex structure and the like, and are mostly reaction type or ratio type fluorescent probes.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provide a method for detecting Ag+The coumarin fluorescent probe, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
detect Ag+The coumarin fluorescent probe is named as L and has the following structural formula (I):
based on the same inventive concept, the invention also provides the Ag detection method+The preparation method of the coumarin fluorescent probe comprises the following steps:
mixing 7-N, N-diethylamino-4-methylcoumarin and SeO2Dissolving in 1, 4-dioxane, heating, refluxing, stirring, cooling to room temperature, filtering, precipitating, and purifying by column chromatography to obtain bright red solid product a; dissolving the product a, benzil and ammonium acetate in acetic acid, heating, refluxing, stirring, cooling to room temperature, adding water to quench the reaction, and adding NH with the mass percentage concentration of 20%3·H2And neutralizing the pH value to 6-7 by using O, filtering the precipitate, washing the precipitate with water, performing reduced pressure spin drying, and performing column chromatography separation and purification to obtain the probe L.
Based on the same inventive concept, the invention also provides the application of the fluorescent probe in Ag in a chemical system+The detection and analysis of (3).
Further, the chemical system comprises DMF and H2O, and the volume ratio of the two is 1: 1.
Further, the chemical system has a pH of 4 to 11.
Based on the same inventive concept, the invention also provides the Ag for detecting the application+The method comprises the following steps:
preparation of Ag in anhydrous ethanol solution+The concentration of the chloride or nitrate stock solution is 1.0-2.4 multiplied by 10-5mol/L; dissolving the probe L in DMF to prepare a detection solution, wherein the concentration of the probe L is 1.0 multiplied by 10-5mol/L; adding DMF and H2And O, stock solution and detection solution are mixed according to the volume ratio of 50: 1, and then the ultraviolet-visible absorption spectrum and the fluorescence spectrum are recorded at room temperature.
Further, the fluorescence spectrum test conditions are as follows:
slit width ExIs 3nm, EmIs 3 nm. Excitation wavelength lambdaexIs 379nmAnd testing the fluorescence within the range of 380-800 nm.
The invention has the following beneficial effects:
the probe L of the invention is used for detecting Ag+The content and the detection limit reach 4.6 multiplied by 10-9mol/L, a binding constant Ka of 2.91X 104L/mol, a complex fluorescent probe, can be quickly and simply applied to the Ag in the actual sample+And (5) carrying out quantitative detection.
Drawings
FIG. 1 shows the structural formula of probe L.
FIG. 2 shows a reaction scheme for synthesizing probe L.
FIG. 3 shows probe L in DMF: H2And (3) adding different metal ions into the solution with the ratio of O to 1: 1 to obtain the ultraviolet-visible absorption spectrum.
FIG. 4 shows the ratio of DMF to H of probe L after different metal ions are added2Fluorescence spectra in 1: 1 solution; illustration is shown: l (left) and L-Ag at 365nm excitation wavelength+(right) system fluorescence color change.
FIG. 5 shows DMF: H at probe L20-1.4 multiplied by 10 is dripped into the solution with the ratio of O to 1: 1-4mol/L Ag+Ultraviolet-visible absorption spectrum.
FIG. 6 shows DMF: H at probe L20-1.4 multiplied by 10 is dripped into the solution with the ratio of O to 1: 1-4mol/L Ag+Fluorescence emission spectrum of (a).
FIG. 7 shows the fluorescence intensity of probe L at 538nm with Ag+The linear relationship of (c).
FIG. 8 shows the ratio of DMF to H2Fluorescence intensity of L after addition of various metal ions to the 1: 1 solution.
FIG. 9 is a graph of pH vs. probes L and L-Ag+Influence of fluorescence intensity.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments, but the invention should not be construed as being limited thereto. The technical means used in the following examples are conventional means well known to those skilled in the art, and materials, reagents and the like used in the following examples can be commercially available unless otherwise specified.
Example 1: preparation method and use method of probe L
Ag of the present invention+The fluorescent probe is named as 7- (diethylamino) -4- (4, 5-diphenyl imidazole) -2-benzopyrone, and is shown in the structural formula shown in figure 1 below or simply referred to as probe L.
1) The preparation method is as follows (the preparation reaction formula is shown in figure 2):
weighing a certain amount of 7-N, N-diethylamino-4-methylcoumarin and SeO2Dissolving in 1, 4-dioxane, heating, refluxing and stirring. After 14h of reaction, the mixture was cooled to room temperature, filtered and precipitated, and subjected to column chromatography (petroleum ether: ethyl acetate: 10: 1) to obtain a bright red solid a. Dissolving the product a, benzil and ammonium acetate in a proper amount of acetic acid, heating, refluxing and stirring for 8 hours, cooling to room temperature, adding water for quenching reaction, and using NH with the mass percentage concentration of 20%3·H2And neutralizing the pH value to 6-7 by using O, filtering the precipitate, washing the precipitate for 3 times by using water, performing reduced pressure spin drying, and performing column chromatography (petroleum ether: ethyl acetate is 5: 1) to obtain a yellow solid, namely the probe L. Melting point: 278 ℃ to 279 ℃.
2) The using method comprises the following steps:
stock solutions (10.0mmol/L) of chloride or nitrate of various metal ions were prepared in anhydrous ethanol solution for further use. Compound L was dissolved in DMF to prepare a solution of 1.0mmol/L for use. Taking DMF and H each time during the experiment2O1 ml each was added to a 1cm wide quartz cuvette, 20. mu.L of the prepared L solution (1.0mmol/L) and 20. mu.L of a different metal ion (10mmol/L) were added to the cuvette respectively with a pipette gun, and then the UV-visible absorption spectrum and the fluorescence spectrum were recorded at room temperature.
Fluorescence spectrum test conditions: slit width E at room temperaturexIs 3nm, EmIs 3 nm. Excitation wavelength lambdaexIs 379nm, and the fluorescence spectrum performance is tested in the range of 380-800 nm.
Example 2: selective recognition of different metal ions by probe L
As the coumarin fluorescent probe is mainly a fluorescence quenching fluorescent probe and is easily influenced by other metal ions when complexing a specific metal ion, the method firstly researches the probe L in DMFH2Complexing ability for 19 common metal ions in 1: 1 solution. The 19 metal ions to be detected are respectively Na+、K+、Li+、Ag+、Ca2+、Mg2+、Ba2+、Co2+、Sn2+、Ni2+、Mn2 +、Cu2+、Fe2+、Pb2+、Sr2+、Hg2+、Fe3+、Al3+、Cr3+. As shown in FIG. 3, in the UV-visible absorption spectrum, 1.0X 10- 5The mol/L probe L shows an absorption peak at 388nm, and 1.0 multiplied by 10 is added-4mol/L of Ag+Then, the absorption peak at 388nm shifted red to 396nm, and an absorption peak at 301nm appeared, and it was presumed that a new complex was formed. In addition, the selectivity of the probe L to different metal ions was detected under the same experimental conditions with 379nm as the excitation wavelength, as shown in FIG. 4, only Ag was added+Then, the probe BTS showed fluorescence quenching, and the fluorescence color changed from bright yellow to colorless under 365nm excitation. The combination of the above experimental phenomena shows that the probe L can selectively react with Ag+Combine to form a new complex.
Example 3: ag of different concentrations+Ultraviolet and fluorescence titration detection of Probe L
Firstly, different concentrations of Ag are explored+Uv-vis absorption spectrum for probe L. During the test, the concentration of probe L was maintained at 1.0X 10-3mol/L，Ag+The concentration is increased from 0 to 1.4X 10-4mol/L. As shown in FIG. 5, with Ag+The addition of (3) shows that the absorption peak at 267nm gradually decreases, the absorption peaks at 296nm and 388nm gradually increase, and the absorption peak at 388nm gradually red-shifts to 399nm and appears at 300nm at an isoabsorbance point, and it is presumed that the probe L and Ag+A new complex is formed.
To further explore the probe L to Ag+In response, a fluorescence titration test was performed. During the test, different concentrations of Ag were also developed+Measurement of fluorescence titration of Probe L with the concentration of Probe L maintained at 1.0X 10-5mol/L，Ag+The concentration is increased from 0 to 1.4X 10-4mol/L. As shown in FIG. 6, 379nm is used as the excitation wavelength (slit width E)xSet to 10nm, EmSet to 5nm), with Ag in solution+The concentration is gradually increased, and the fluorescence intensity of the probe L at 538nm is gradually reduced until the fluorescence is quenched. The fluorescence titration experiment result shows that the fluorescence intensity (y) of the probe L at 538nm and Ag+The concentration (x) of (A) is 1.0 to 2.4 x 10-5Shows good linear relation in the mol/L range, as shown in FIG. 7, the linear regression equation is that y is-198.03 x +708.75, and the correlation coefficient is R20.9961, thereby realizing that the probe L is aligned with Ag+And (4) carrying out quantitative detection. Calculating the pair Ag of the probe L according to the formula LOD-3 sigma/k+Has a detection limit of 4.6 × 10-9mol/L, binding constant KaIs 2.91X 104L/mol。
Example 4: anti-interference capability of probe L on common coexisting ions
Under the same experimental conditions, the direction is 5.0X 10-5mol/L of L-Ag+DMF: H of the System2Adding 5.0X 10 to the solution of O1: 1-5And (4) establishing a bar graph of fluorescence intensity and each ion by mol/L of other metal ions. As shown in FIG. 8, Ag+When the probe is coexisted with other metal ions, the fluorescence intensity of the probe L is relatively weakened, and only five metal ions of cobalt, nickel, manganese, mercury and iron have paramagnetic action and stronger complexing ability to L-Ag in the system+Complexation creates interference, which is generally unavoidable. In general, probes L vs Ag+Has very good selectivity and certain anti-interference capability.
Example 5: different pH for probes L and Ag+Influence of response
Preparing an aqueous solution with a pH value of 1-14, and maintaining the concentration of the probe L at 1.0 x 10-5mol/L，Ag+The concentration is maintained at 1.0 × 10-4mol/L. As shown in FIG. 9, the fluorescence intensity of the probe L at 538nm remains substantially unchanged within a pH range of 4. ltoreq. pH.ltoreq.11, indicating that the probe L has excellent acid-base resistance and can be applied in a wide pH range.
It should be noted that when the following claims refer to numerical ranges, it should be understood that both ends of each numerical range and any numerical value between the two ends can be selected, and the preferred embodiments of the present invention are described for the purpose of avoiding redundancy.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. Detect Ag+The coumarin fluorescent probe is named as L and has the following structural formula (I):
2. a detecting Ag of claim 1+The preparation method of the coumarin fluorescent probe is characterized by comprising the following steps:
mixing 7-N, N-diethylamino-4-methylcoumarin and SeO2Dissolving in 1, 4-dioxane, heating, refluxing, stirring, cooling to room temperature, filtering, precipitating, and purifying by column chromatography to obtain bright red solid product a; dissolving the product a, benzil and ammonium acetate in acetic acid, heating, refluxing, stirring, cooling to room temperature, adding water to quench the reaction, and adding NH3·H2And neutralizing the pH value to 6-7 by using O, filtering the precipitate, washing the precipitate with water, performing reduced pressure spin drying, and performing column chromatography separation and purification to obtain the L.
3. The fluorescent substance of claim 1Use of an optical probe for Ag in chemical systems+The detection and analysis of (3).
4. Use according to claim 3, characterized in that the chemical system comprises DMF and H2O, and the volume ratio of the two is 1: 1.
5. Use according to claim 3, characterized in that the chemical system has a pH of 4 to 11.
6. A detection Ag for the use of claim 5+The method is characterized by comprising the following steps:
preparation of Ag in anhydrous ethanol solution+The stock solution of chloride or nitrate of 1.0-2.4 × 10-5mol/L; dissolving the probe L in DMF to prepare a detection solution, wherein the concentration of the probe L is 1.0 multiplied by 10-5mol/L; adding DMF and H2And O, stock solution and detection solution are mixed according to the volume ratio of 50: 1, and then the ultraviolet-visible absorption spectrum and the fluorescence spectrum are recorded at room temperature.
7. The method of claim 6, wherein the fluorescence spectroscopy test conditions are as follows:
slit width ExIs 3nm, EmIs 3 nm; excitation wavelength lambdaex379nm, and testing the fluorescence in the range of 380-800 nm.
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| CN105255481A (en) * | 2015-11-16 | 2016-01-20 | 齐齐哈尔大学 | Phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof |
| CN109912555A (en) * | 2019-04-11 | 2019-06-21 | 榆林学院 | A kind of aluminium ion fluorescence probe and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120288947A1 (en) * | 2010-01-15 | 2012-11-15 | Dalian Chromas Bioscience Co., Ltd | Fluorescent probe compounds, preparation method and application thereof |
| CN105255481A (en) * | 2015-11-16 | 2016-01-20 | 齐齐哈尔大学 | Phenanthrene and imidazole-coumarin double-fluorescent group ratio fluorescent molecular probe for iron ion detection and synthesis and use methods thereof |
| CN109912555A (en) * | 2019-04-11 | 2019-06-21 | 榆林学院 | A kind of aluminium ion fluorescence probe and preparation method thereof |
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