CN114437048B - Detection Ag + Coumarin fluorescent probe, preparation method and application thereof - Google Patents
Detection Ag + Coumarin fluorescent probe, preparation method and application thereof Download PDFInfo
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- CN114437048B CN114437048B CN202210147354.3A CN202210147354A CN114437048B CN 114437048 B CN114437048 B CN 114437048B CN 202210147354 A CN202210147354 A CN 202210147354A CN 114437048 B CN114437048 B CN 114437048B
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 23
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000001514 detection method Methods 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
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 8
- 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 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000002189 fluorescence spectrum Methods 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 238000000862 absorption spectrum Methods 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 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
- 238000004440 column chromatography Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000011550 stock solution 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
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000012085 test solution Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 4
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 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
- 230000007812 deficiency 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 37
- 229910021645 metal ion Inorganic materials 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 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
- 230000000171 quenching effect Effects 0.000 description 2
- 239000007787 solid Substances 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
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 1
- -1 H 2 O Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects 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
- 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 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
- 238000001228 spectrum Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- 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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- 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"
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Abstract
The invention relates to the field of chemical analysis, in particular to a method for detecting Ag + Coumarin fluorescent probe, and 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 the 7-position is diethylamino electron-donating group, the 4-position is 4, 5-diphenyl imidazole electron-withdrawing group, and the fluorescent probe contains O, N electron-rich atoms and Ag which can be in electron deficiency + Complexing with Ag + Has good coordination capability and can identify Ag with high selectivity + The fluorescent light 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 + Coumarin fluorescent probe, and preparation method and application thereof.
Background
Silver ion (Ag) + ) Has good antibacterial activity and is widely applied to a plurality of commodities and medical supplies. However, the human body excessively ingests or contacts Ag + Can lead to diarrhea, skin infections, and damage to nerves or organs to varying degrees. Even Ag + Can inactivate sulfhydryl enzymes, inhibit the growth and propagation of friendly bacteria in the environment, and cause a plurality of adverse effects to the environment. Thus, ag is treated in vivo and in the environment + The quantitative detection is of great importance.
Currently, for Ag + Detection methods are increasingly being studiedThe attention of the researchers. Common detection methods include Atomic Absorption Spectrometry (AAS), atomic Emission Spectrometry (AES), electrochemical methods, mass spectrometry, and the like, but the use of these methods requires expensive instruments, complicated procedures, long test waiting times, and the like, which limit the wide application of these methods in ion detection. The fluorescent probe analysis method has 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 content of the fluorescent probe is usually rhodamine, pyrene, quinoline and fluoroboropyrrole, but the reported fluorescent probes have the defects of high synthesis cost, complicated synthesis steps, large molecular weight, complex structure and the like, and most of the fluorescent probes are reactive or ratio type fluorescent probes.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art and provides a method for detecting Ag + Coumarin fluorescent probe, and preparation method and application thereof.
The invention adopts the technical scheme that:
detection Ag + Is designated as L, and has the following structural formula (I):
based on the same inventive concept, the invention also provides a method for detecting Ag + The preparation method of the coumarin fluorescent probe comprises the following steps:
7-N, N-diethylamino-4-methylcoumarin and SeO 2 Dissolving in 1, 4-dioxane, heating, refluxing and stirring, cooling to room temperature, filtering to precipitate, and separating and purifying by column chromatography to obtain a bright red solid product a; dissolving the product a, benzil and ammonium acetate in acetic acid, heating, refluxing and stirring, cooling to room temperature, adding water to quench reaction, and using NH with the mass percentage concentration of 20% 3 ·H 2 Neutralizing pH to 6-7, filtering to obtain precipitateAnd washing with water, drying under reduced pressure, and separating and purifying by column chromatography to obtain the probe L.
Based on the same inventive concept, the invention also provides the application of the fluorescent probe for Ag in a chemical system + Is a detection analysis of (a).
Further, the chemical system comprises DMF and H 2 O, and the volume ratio of the O to the O is 1:1.
Still further, the pH of the chemical system is from 4 to 11.
Based on the same inventive concept, the invention also provides a method for detecting Ag for realizing the application + Comprises the following steps:
preparation of Ag in absolute ethanol solution + Chloride or nitrate stock solution with the concentration of 1.0 to 2.4X10 -5 mol/L; dissolving probe L in DMF to obtain detection solution, wherein the concentration of probe L is 1.0X10 -5 mol/L; DMF, H 2 O, stock solution and detection solution were mixed in a volume ratio of 50:50:1:1, and then UV-visible absorption spectrum and fluorescence spectrum were recorded at room temperature.
Further, the fluorescence spectrum test conditions are as follows:
slit width E x At 3nm, E m Is 3nm. Excitation wavelength lambda ex Fluorescence was measured at 379nm in the range of 380 to 800 nm.
The invention has the following beneficial effects:
the probe L of the invention is used for detecting Ag + The content reaches 4.6X10 -9 mol/L, binding constant Ka reaches 2.91×10 4 L/mol is a complex fluorescent probe which can be rapidly and simply applied to an actual sample for Ag + And (5) carrying out quantitative detection.
Drawings
FIG. 1 shows the structural formula of probe L.
FIG. 2 shows the synthesis reaction scheme of probe L.
FIG. 3 shows probe L in DMF:H 2 Ultraviolet-visible absorption spectra after addition of different metal ions to o=1:1 solution.
FIG. 4 shows the addition of different goldAfter the ion, probe L is in DMF/H 2 Fluorescence spectrum in o=1:1 solution; insert: l (left) and L-Ag at 365nm excitation wavelength + (right) system fluorescence color change.
FIG. 5 shows DMF/H at probe L 2 O=1:1 solution is added with 0 to 1.4X10 by drops -4 mol/L Ag + Ultraviolet-visible absorption spectrum at that time.
FIG. 6 shows DMF/H at probe L 2 O=1:1 solution is added with 0 to 1.4X10 by drops -4 mol/L Ag + Fluorescence emission spectrum at that time.
FIG. 7 shows the fluorescence intensity of probe L at 538nm and Ag + Is a linear relationship of (c).
FIG. 8 shows the ratio of DMF to H 2 Fluorescence intensity of L after addition of various metal ions to o=1:1 solution.
FIG. 9 is a graph of pH versus probes L and L-Ag + Influence of fluorescence intensity.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific examples, which should not be construed as limiting the invention. Unless otherwise indicated, the technical means used in the following examples are conventional means well known to those skilled in the art, and the materials, reagents, etc. used in the following examples are commercially available unless otherwise indicated.
Example 1: preparation method and application method of probe L
Ag according to the invention + The fluorescent probe is named as 7- (diethylamino) -4- (4, 5-diphenyl imidazole) -2-benzopyrone, and is hereinafter or simply referred to as probe L, and the structural formula is shown in figure 1.
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 SeO 2 Dissolving in 1, 4-dioxane, heating under reflux, and stirring. The reaction was carried out for 14h, cooled to room temperature, the precipitate was filtered and column chromatographed (petroleum ether: ethyl acetate=10:1) to give a bright red solid a. Dissolving the product a, benzil and ammonium acetate in proper amount of acetic acid, heating, refluxing and stirring for 8 hours, cooling to room temperature, adding water to quench and apply the mixture with the mass percent concentration of 20 percentNH 3 ·H 2 O is neutralized to pH 6-7, the precipitate is filtered and washed 3 times with water, dried under reduced pressure, and column chromatography (petroleum ether: ethyl acetate=5:1) is performed to obtain yellow solid, namely probe L. Melting point: 278-279 deg.C.
2) The using method comprises the following steps:
chloride or nitrate stock solutions (10.0 mmol/L) of various metal ions were prepared in absolute ethanol solution for later use. Compound L was dissolved in DMF to prepare a 1.0mmol/L solution for use. Experimental procedure DMF and H were taken each time 2 O1 ml each was added to a quartz cuvette of 1cm width, and 20. Mu.L of the prepared L solution (1.0 mmol/L) and 20. Mu.L of different metal ions (10 mmol/L) were added to the cuvette, respectively, using a pipette, and then UV-visible absorption spectrum and fluorescence spectrum were recorded at room temperature.
Fluorescent spectrum test conditions: slit width E at room temperature x At 3nm, E m Is 3nm. Excitation wavelength lambda ex The fluorescence spectrum performance was measured at 379nm in the range of 380 to 800 nm.
Example 2: selective recognition of different metal ions by probe L
As coumarin fluorescent probes are mainly fluorescence quenching fluorescent probes, the coumarin fluorescent probes are easily influenced by other metal ions when complexing a specific metal ion, and probes L are firstly explored in DMF (dimethyl formamide)/H (dimethyl formamide) 2 O=1:1 complexing ability for 19 common metal ions in solution. The 19 metal ions to be measured are respectively Na + 、K + 、Li + 、Ag + 、Ca 2+ 、Mg 2+ 、Ba 2+ 、Co 2+ 、Sn 2+ 、Ni 2+ 、Mn 2 + 、Cu 2+ 、Fe 2+ 、Pb 2+ 、Sr 2+ 、Hg 2+ 、Fe 3+ 、Al 3+ 、Cr 3+ . As shown in FIG. 3, in the ultraviolet-visible absorption spectrum, 1.0X10 - 5 The mol/L probe L had an absorption peak at 388nm, and 1.0X10 was added -4 mol/L Ag + After that, the absorption peak at 388nm was red-shifted to 396nm and an absorption peak at 301nm was observed, and it was presumed that a new complex was formed. And under the same experimental conditions, 379nm is used as excitation wavelength to detect the probeSelectivity for different metal ions for needle L, as shown in FIG. 4, only Ag was added + After that, the probe BTS showed fluorescence quenching, and the fluorescence color was changed from bright yellow to colorless by naked eyes under 365nm excitation. The experimental phenomenon is combined to show that the probe L can selectively react with Ag + Combine to form new complexes.
Example 3: ag with different concentrations + Ultraviolet and fluorescence titration detection of probe L
First, the Ag with different concentrations is explored + Ultraviolet-visible absorption spectrum of probe L. During the test, the concentration of probe L was maintained at 1.0X10 -3 mol/L，Ag + The concentration was added from 0 to 1.4X10 -4 mol/L. As shown in fig. 5, with Ag + Is added, the absorption peak at 267nm is gradually decreased, the absorption peaks at 296nm and 388nm are gradually increased, the absorption peak at 388nm is gradually red shifted to 399nm, and the equal absorption point appears at 300nm, and it is presumed that the probe L and Ag are + New complexes are formed.
To further explore the probe L versus Ag + In response to the fluorescence titration, a test was performed. In the test process, the Ag with different concentrations is also developed + Testing for fluorescence titration of Probe L, the concentration of Probe L was maintained at 1.0X10 -5 mol/L，Ag + The concentration was added from 0 to 1.4X10 -4 mol/L. As shown in FIG. 6, 379nm is used as the excitation wavelength (slit width E x Set to 10nm, E m Set to 5 nm), along with Ag in solution + The concentration gradually increases and the fluorescence intensity of the probe L at 538nm gradually decreases until fluorescence is quenched. As shown by the result of fluorescence titration experiments, the fluorescence intensity (y) and Ag of the probe L at 538nm + The concentration (x) of (C) is 1.0-2.4X10 -5 As shown in FIG. 7, the linear regression equation is y= -198.03x+708.75, and the correlation coefficient is R 2 =0.9961, whereby probe L can be realized against Ag + Is a quantitative detection of (a). Calculating the probe L to Ag according to the formula lod=3σ/k + The detection limit of (2) is 4.6X10 -9 mol/L, binding constant K a Is 2.91 multiplied by 10 4 L/mol。
Example 4: anti-interference capability of probe L on common coexisting ions
Under the same experimental conditions, 5.0X10 -5 mol/L of L-Ag + DMF:H of the System 2 To the O=1:1 solution was added 5.0X10 respectively -5 mol/L of other metal ions, and establishing a histogram of fluorescence intensity and each ion. As shown in FIG. 8, ag + When the probe L coexists 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 produces interference, which is generally unavoidable. In combination, probe L versus Ag + Has very good selectivity and certain anti-interference capability.
Example 5: different pH pairs of probes L and Ag + Response influence of (a)
Preparing aqueous solution with pH value of 1-14, and maintaining the concentration of probe L at 1.0X10 -5 mol/L，Ag + The concentration was maintained at 1.0X10 -4 mol/L. As shown in FIG. 9, the fluorescence intensity of probe L at 538nm is kept substantially unchanged in the pH range of 4.ltoreq.11, indicating that probe L has excellent acid-base resistance and can be used in a wide pH range.
It should be noted that, when the claims refer to numerical ranges, it should be understood that two endpoints of each numerical range and any numerical value between the two endpoints are optional, and the present invention describes the preferred embodiments for preventing 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. It is therefore intended that the following claims be interpreted as including the 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 modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. Detection Ag + The coumarin fluorescent probe is characterized in that the probe is named L and has the following structural formula (I):
2. the method for detecting Ag according to claim 1 + The preparation method of the coumarin fluorescent probe is characterized by comprising the following steps:
7-N, N-diethylamino-4-methylcoumarin and SeO 2 Dissolving in 1, 4-dioxane, heating, refluxing and stirring, cooling to room temperature, filtering to precipitate, and separating and purifying by column chromatography to obtain a bright red solid product a; dissolving the product a, benzil and ammonium acetate in acetic acid, heating, refluxing and stirring, cooling to room temperature, adding water to quench the reaction, and using NH 3 ·H 2 And (3) neutralizing the pH value to 6-7, filtering the precipitate, washing with water, performing spin-drying under reduced pressure, and separating and purifying by column chromatography to obtain the L.
3. The use of the fluorescent probe according to claim 1, wherein the fluorescent probe is used for preparing a chemical system for detecting and analyzing Ag + Is a product of (a).
4. The use according to claim 3, wherein the chemical system comprises DMF and H 2 O, and the volume ratio of the two is 1:1.
5. Use according to claim 3, characterized in that the pH of the chemical system is 4-11.
6. Detection of Ag for achieving the use according to claim 5 + Is characterized by comprising the following steps:
preparation of Ag in absolute ethanol solution + Chloride or nitrate storage of (a)Preparing liquid with concentration of 1.0-2.4X10 –5 mol/L; dissolving probe L in DMF to obtain detection solution, wherein the concentration of probe L is 1.0X10 –5 mol/L; DMF, H 2 O, stock and test solutions according to 50:50:1:1, and then recording an ultraviolet-visible absorption spectrum and a fluorescence spectrum at room temperature.
7. The method of claim 6, wherein the fluorescence spectrum testing conditions are as follows:
slit width E x At 3nm, E m 3nm; excitation wavelength lambda ex Fluorescence was measured at 379nm in the range of 380 to 800 nm.
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