CN115490644A - 1,2, 3-triazole-4-hydrazide Schiff base fluorescent probe as well as preparation method and application thereof - Google Patents
1,2, 3-triazole-4-hydrazide Schiff base fluorescent probe as well as preparation method and application thereof Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002262 Schiff base Substances 0.000 title claims abstract description 9
- -1 1,2, 3-triazole-4-hydrazide Schiff base Chemical class 0.000 title abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- MJJMGWDMMYKRMM-UHFFFAOYSA-N 5-methyl-2-phenyltriazole-4-carbohydrazide Chemical compound N1=C(C(=O)NN)C(C)=NN1C1=CC=CC=C1 MJJMGWDMMYKRMM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 7
- XFVZSRRZZNLWBW-UHFFFAOYSA-N 4-(Diethylamino)salicylaldehyde Chemical compound CCN(CC)C1=CC=C(C=O)C(O)=C1 XFVZSRRZZNLWBW-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- ZFKBWEGNXKOUFD-UHFFFAOYSA-N ethyl 5-methyl-2-phenyltriazole-4-carboxylate Chemical compound N1=C(C)C(C(=O)OCC)=NN1C1=CC=CC=C1 ZFKBWEGNXKOUFD-UHFFFAOYSA-N 0.000 claims description 3
- AVSQIANZTCVZNC-UHFFFAOYSA-N ethyl 5-methyl-2h-triazole-4-carboxylate Chemical compound CCOC(=O)C1=NNN=C1C AVSQIANZTCVZNC-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 150000004753 Schiff bases Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 238000000799 fluorescence microscopy Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000523 sample Substances 0.000 abstract description 19
- 238000002474 experimental method Methods 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 11
- 230000004044 response Effects 0.000 abstract description 4
- 231100000263 cytotoxicity test Toxicity 0.000 abstract description 3
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000003698 anagen phase Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012930 cell culture fluid Substances 0.000 description 1
- 239000006143 cell culture medium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- FCJJZKCJURDYNF-UHFFFAOYSA-N ethyl but-2-ynoate Chemical compound CCOC(=O)C#CC FCJJZKCJURDYNF-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000009760 functional impairment Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
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- 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 a 1,2, 3-triazole-4-hydrazide Schiff base fluorescent probe and a preparation method and application thereof. In the ethanol solution test, the probe performs a response time experiment, a selectivity experiment and an ion interference experiment by using an ultraviolet absorption spectrum and a fluorescence spectrum, and can selectively detect Al 3+ Without interference from different ions. Fluorescent Probe L of the present invention 3 The cytotoxicity test shows that the composition has low toxicity and high safety.
Description
Technical Field
The invention belongs to the field of fluorescent probes, and particularly relates to a 1,2, 3-triazole-4-hydrazide Schiff base fluorescent probe as well as a preparation method and application thereof.
Background
The metallic aluminum is the metallic element with the highest content in earth crust and is widely applied in daily life and industries. However, al 3+ Is not essential metal element in living system, and is taken in excessive amountAl 3+ Can cause the functional impairment of human body, such as senile dementia, due to the intake of Al which is too high all year round 3+ The resulting health disorders of the human body; meanwhile, al in soil environment 3+ Too high a concentration will acidify the soil and inhibit the growth of plants. Therefore, rapid and highly sensitive Al is designed and developed 3+ The probe has important practical significance. The invention provides a novel fluorescent probe for detecting Al by using 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide Schiff base 3+ And applications in cell imaging.
Disclosure of Invention
The invention provides a 1,2, 3-triazole-4-hydrazide Schiff base fluorescent probe L 3 Characterized in that the fluorescent probe L 3 The structure of (A) is as follows:
another embodiment of the present invention provides the above-mentioned fluorescent probe L 3 The preparation method is characterized by comprising the following steps: reacting 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide and 4- (diethylamino) salicylaldehyde in an organic solvent to obtain the fluorescent probe L 3 . The molar ratio of the 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide to the 4- (diethylamino) salicylaldehyde is preferably 1. The organic solvent is selected from one or more of methanol, ethanol, THF, toluene and ethyl acetate. The reaction temperature is 50 ℃ to reflux temperature. The reaction time is preferably 6 to 10 hours based on TLC detection. Also comprises a step of preparing 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide by using 5-methyl-2-phenyl-1, 2, 3-triazole-4-ethyl formate and hydrazine hydrate. And further comprises the step of preparing the ethyl 5-methyl-2-phenyl-1, 2, 3-triazole-4-formate by coupling reaction of the ethyl 5-methyl-2H-1, 2, 3-triazole-4-formate and phenylboronic acid.
Another embodiment of the present invention provides the above-mentioned fluorescent probe L 3 Al in the detection Environment 3+ The use of (1). Including soil, water, atmosphere, etc.
Another embodiment of the present invention providesThe fluorescent probe L 3 Application in HeLa cell fluorescence imaging.
Compared with the prior art, the method for detecting Al based on the Schiff base fluorescent probe generated by 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide and 4- (diethylamino) salicylaldehyde 3+ The probe is used for performing a response time experiment, a selectivity experiment and an ion interference experiment by utilizing an ultraviolet absorption spectrum and a fluorescence spectrum in an ethanol solution test, and can selectively detect Al 3+ Without interference from different ions. Fluorescent Probe L of the present invention 3 The cytotoxicity test shows that the toxicity is low, namely the safety is high.
Drawings
FIG. 1 shows a fluorescent probe L 3 Nuclear magnetic hydrogen spectrum of (a);
FIG. 2 shows a fluorescent probe L 3 Nuclear magnetic carbon spectrum of (a);
FIG. 3 shows a fluorescent probe L 3 High resolution mass spectrograms of (a);
FIG. 4 shows a fluorescent probe L 3 With Al 3+ A fluorescence response time plot;
FIG. 5 shows a fluorescent probe L 3 Measurement of Al 3+ Concentration titration experiment fluorescence change chart;
FIG. 6 shows 18 types of metal ion pair probes L 3 Detection of Al 3+ A fluorescence selectivity map of (a);
FIG. 7 shows 18 types of metal ion pair probes L 3 Detection of Al 3+ A fluorescence interference immunity map of (a);
FIG. 8 Probe L 3 Toxicity test pattern on HeLa cells;
FIG. 9 Probe L 3 、L 3 +Al 3+ Images were made in HeLa cells.
Detailed Description
To facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1
(1) Synthesizing 5-methyl-2H-1, 2, 3-triazole-4-ethyl formate:
weighing 15mmol (1.0 eq) of ethyl 2-butynoate, adding 100mL of DMSO as a solvent into a 250mL round-bottom flask, stirring at room temperature for half an hour, and weighing NaN 3 30mmol (2 eq), slowly adding into a round-bottom flask, heating to 80 ℃, monitoring the reaction by TLC, and separating by column chromatography to obtain yellow solid powder. 1 H NMR(400MHz,CDCl 3 )δ9.75(s,1H),4.41(q,J＝7.1Hz,2H),2.62(s,3H),1.38(t,J＝7.1Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ160.49,141.64,134.38,60.32,13.22,9.08.
(2) Synthesizing 5-methyl-2-phenyl-1, 2, 3-triazole-4-ethyl formate:
weighing 7.50mmol of ethyl 5-methyl-2H-1, 2, 3-triazole-4-carboxylate into a 100mL round-bottom flask, adding 2mL of pyridine and 40mL of THF, stirring uniformly, weighing 0.8g of copper acetate into the round-bottom flask, slowly adding 15.0mmol of phenylboronic acid into the round-bottom flask, connecting the round-bottom flask with a condenser pipe, connecting the upper opening of the condenser pipe with a three-way valve, fixing an oxygen ball on the three-way valve by using a rubber band, vacuumizing by using a water pump to enable the whole system to be in an oxygen environment, heating to 60 ℃, reacting for 12 hours, and monitoring the end of the reaction by TLC. Performing column chromatography separation to obtain light yellow oily liquid. 1 H NMR(400MHz,CDCl 3 )δ8.12-8.06(m,2H),7.47(td,J＝7.2,1.8Hz,2H),7.41-7.34(m,1H),4.46(q,J＝7.1Hz,2H),2.61(s,3H),1.44(t,J＝7.1Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ161.52,148.80,139.29,138.11,129.27,128.23,119.37,61.31,14.34,11.63.
(3) Synthesis of 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide:
transferring the product obtained in the step (2) into a 100mL round-bottom flask, adding 40mL of absolute ethyl alcohol, dropwise adding excessive hydrazine hydrate, uniformly stirring, and heating and refluxing for 3 hours. Extracting with dichloromethane, and drying with anhydrous sodium sulfate to obtain 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide. 1 H NMR(400MHz,DMSO-d 6 )δ9.79(s,1H),8.03(dd,J＝8.7,1.1Hz,2H),7.58(t,J＝8.0Hz,2H),7.44(t,J＝7.4Hz,1H),4.55(s,2H). 13 C NMR(100MHz,DMSO-d 6 )δ160.23,146.68,140.09,139.23,130.16,128.53,118.95,11.32.
(4) 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide Schiff base probe L 3 The synthesis of (2):
weighing 500mg (2.3 mmol) of 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide, adding ethanol, stirring for dissolving, weighing 489mg (2.53 mmol) of 4- (diethylamino) salicylaldehyde, adding a small amount of ethanol for dissolving, slowly dropwise adding into the reaction, heating and refluxing for 8h, stopping heating, cooling to room temperature to precipitate a large amount of yellow solid, performing suction filtration, washing with a small amount of glacial ethanol for multiple times, and drying to obtain a yellow solid powder product. 1 H NMR(400MHz,DMSO-d 6 )δ11.95(s,1H),11.36(s,1H),8.53(s,1H),8.09(d,J＝7.7Hz,2H),7.62(t,J＝7.9Hz,2H),7.48(t,J＝7.4Hz,1H),7.19(d,J＝8.8Hz,1H),6.28(dd,J＝8.8,2.3Hz,1H),6.13(d,J＝2.2Hz,1H),3.40-3.34(m,4H),2.58(s,3H),1.11(t,J＝7.0Hz,6H). 13 C NMR(100MHz,DMSO-d 6 )δ160.21,156.35,151.09,150.74,147.85,139.68,139.19,132.12,130.23,128.80,119.19,106.88,104.21,97.98,44.29,13.01,11.49.HRMS m/z([M+H] + ):Calcd for 393.2034；found:393.2037.
Example 2
(1) Preparation of standard ion
Taking out the corresponding volume of Hg 2+ 、Ag + 、W 6+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、Pb 2+ 、Ca 2+ 、Mn 2+ 、Cd 3+ 、Co 2+ 、Fe 3+ 、Mo 6+ 、K + 、Mg 2+ 、Ni 2+ 、Na + 、Pd 2+ 、Sn 4+ Adding the metal cation standard solution into a 10mL colorimetric cylinder, adding deionized water to a constant volume to prepare the solution with the volume of 1.0 multiplied by 10 -3 mol/L standard solution.
(2) Preparation of Probe solution
39.2mg of probe L was weighed 3 In a 100mL volumetric flask, the volume of the solution was adjusted to 1.0X 10 by DMSO -3 mol/L solution.
Example 3
Ion interference experiment:
to study the probe L 3 The fluorescence spectra of various metal ions were examined in ethanol (10. Mu.M) solution. Probe L 3 The excitation wavelength of (2) is 390nm. After addition of an equal amount of ions, probe L 3 Only Al at 475nm 3+ So that the fluorescence intensity of the fluorescent material is obviously enhanced, and other ions are hardly changed, as shown in FIG. 6. No significant increase or decrease in response time occurred after 10min to plateau, as shown in fig. 4. This indicates that the probe is directed to Al 3+ Has high stable selectivity.
Example 4
Titration experiment:
investigation of Probe L by titration experiment 3 For Al 3+ The sensitivity of (2). With Al 3+ Increase in concentration, probe L 3 The fluorescence gradually increased at 475nm as shown in FIG. 5. This may be due to the probe L 3 And Al 3+ A coordination reaction occurs to generate intense fluorescence. Further, within a certain range, L 3 For Al 3+ A linear relationship exists. According to formula C L =3 σ/k, calculating L 3 For Al 3+ Detection limit of 5.84nM, which is for detecting Al 3+ Has potential application value.
Example 5
Ion coexistence experiment:
is excellent inIs one of the important factors affecting the performance of fluorescent probes. Therefore, to test the ion competition experiment, 10. Mu.M Al was added to an ethanol (10. Mu.M) solution 3+ Measuring fluorescence intensity, and adding other metal ions except W 6+ 、Sn 4+ Can quench fluorescence with certain interference; while other ions did not cause a significant change in fluorescence intensity, as shown in fig. 7. And W in the actual water sample environment 6+ 、Sn 4+ Rarely occurs or has extremely low concentration, and can not detect Al 3+ A significant interference situation occurs, so probe L 3 For Al in the actual sample 3+ The detection is also more interference-resistant.
Example 6
Cytotoxicity test:
HeLa cells in logarithmic growth phase were taken and cell concentration was adjusted to 2.5X 10 by cell counting 4 Perwell, adding DMEM cell culture medium to a 96-well plate at 100. Mu.L per well, 5% CO at 37 ℃% 2 Culturing in an incubator for 24h. Mixing L with 3 Adjusting concentration to 0, 10, 20, 40, 60, 80 μmol/L, 100 μmol/L, dividing Hela cells into blank group and experimental group, adding 100 μ L into each well according to the above concentration gradient, adding 100 μ L culture solution into blank group, setting 6 multiple wells for each concentration, and adding CO 2 After further culturing in the incubator for 24h, 20. Mu.L MTT reagent was added to each well, and CO was added to each well 2 The culture was continued for 4 hours in the incubator to reduce MTT to blue-violet crystalline formazan, the culture solution was discarded, 200. Mu.L of DMSO was added to each well and gently shaken to dissolve it sufficiently, and the absorbance at 570nm was measured by an enzyme reader. Repeat the experiment 3 times and calculate L 3 Toxicity to HeLa cells. As shown in FIG. 8, the survival rate of HeLa cells was more than 60% at a concentration of 100. Mu.M, and the probe had good low toxicity.
Cell imaging experiments:
taking HeLa cells in logarithmic growth phase, adding the cell culture fluid to a 35mm petri dish at 37 ℃ 5% CO 2 After 24h of incubation in the incubator, probe L was added 3 After incubation for 1h (10. Mu.M), al was subsequently added 3+ (10. Mu.M), after incubation for 0.5h, the cells were washed 3 times with PBS, under blue channelFluorescence imaging is performed. As shown in FIG. 9, a single probe L 3 HeLa cells (K) did not fluoresce, and Al was added 3+ Intense fluorescence was observed from HeLa cells in the blue channel.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1.1, 2, 3-triazole-4-hydrazide Schiff base fluorescent probe L 3 Characterized in that the fluorescent probe L 3 The structure of (1) is as follows:
2. the fluorescent probe L according to claim 1 3 The preparation method is characterized by comprising the following steps: reacting 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide and 4- (diethylamino) salicylaldehyde in an organic solvent to obtain the fluorescent probe L 3 。
3. The preparation method according to claim 2, wherein the molar ratio of 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide to 4- (diethylamino) salicylaldehyde is preferably 1 to 2, and more preferably 1.1 to 1.5.
4. The process according to any one of claims 2 to 3, wherein the organic solvent is selected from one or more of methanol, ethanol, THF, toluene and ethyl acetate. The reaction temperature is 50 ℃ to reflux temperature. The reaction time is preferably 6 to 10 hours.
5. The method according to any one of claims 2 to 4, further comprising the step of preparing 5-methyl-2-phenyl-1, 2, 3-triazole-4-hydrazide from ethyl 5-methyl-2-phenyl-1, 2, 3-triazole-4-carboxylate and hydrazine hydrate.
6. The preparation method according to any one of claims 2 to 5, characterized by further comprising the step of preparing ethyl 5-methyl-2-phenyl-1, 2, 3-triazole-4-carboxylate by coupling reaction of ethyl 5-methyl-2H-1, 2, 3-triazole-4-carboxylate with phenylboronic acid.
7. The fluorescent probe L as set forth in claim 1 3 Al in the detection Environment 3+ The use of (1).
8. The use as claimed in claim 7, characterized in that the environment comprises soil, water, the atmosphere or the like.
9. The fluorescent probe L as set forth in claim 1 3 The application in HeLa cell fluorescence imaging.
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