CN116375674B - Double-state fluorescent probe for picric acid detection and preparation method thereof - Google Patents
Double-state fluorescent probe for picric acid detection and preparation method thereof Download PDFInfo
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- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000001514 detection method Methods 0.000 title claims abstract description 38
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002902 bimodal effect Effects 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 12
- 101150013987 FCPB gene Proteins 0.000 claims description 50
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- -1 4-dimethylaminophenyl Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000000523 sample Substances 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- HYGLETVERPVXOS-UHFFFAOYSA-N 1-bromopyrene Chemical compound C1=C2C(Br)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 HYGLETVERPVXOS-UHFFFAOYSA-N 0.000 claims description 5
- YKVMTTIYBSVPEQ-UHFFFAOYSA-N [4-(cyanomethyl)phenyl]boronic acid Chemical compound OB(O)C1=CC=C(CC#N)C=C1 YKVMTTIYBSVPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- GBJJCODOZGPTBC-UHFFFAOYSA-N 4-fluoro-2-hydroxybenzaldehyde Chemical compound OC1=CC(F)=CC=C1C=O GBJJCODOZGPTBC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims 3
- 238000001816 cooling Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010791 quenching Methods 0.000 abstract description 11
- 230000000171 quenching effect Effects 0.000 abstract description 11
- 239000012046 mixed solvent Substances 0.000 abstract description 3
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 abstract 1
- 238000007039 two-step reaction Methods 0.000 abstract 1
- 229950002929 trinitrophenol Drugs 0.000 description 66
- 239000000243 solution Substances 0.000 description 26
- 238000001228 spectrum Methods 0.000 description 10
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 7
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 4
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 4
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000002866 fluorescence resonance energy transfer Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- VHCYLNTYLXUVLW-UHFFFAOYSA-N benzene 2-nitrophenol Chemical compound C1=CC=CC=C1.[N+](=O)([O-])C1=C(C=CC=C1)O VHCYLNTYLXUVLW-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003068 molecular probe Substances 0.000 description 2
- 239000013642 negative control Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000668 atmospheric pressure chemical ionisation mass spectrometry Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
A bimodal fluorescent probe for picric acid detection and a preparation method thereof. The fluorescent probe is obtained through two-step reaction, has strong fluorescence emission property in a dilute solution state and a solid state, can realize high-sensitivity detection of picric acid in a tetrahydrofuran-water mixed solvent system, and has a fluorescence quenching constant of 2062M ‑1 The detection limit was as low as 1.81. Mu.M. The fluorescent probe has potential for wide application in the fields of food, environment and the like.
Description
Technical Field
The invention relates to the field of fluorescent molecular probes, in particular to a bimodal fluorescent probe for picric acid detection and a preparation method thereof.
Background
Picric acid chemical name is 2,4, 6-trinitrophenol, which is an organic compound with strong toxicity and carcinogenicity, and has great harm to the environment and human health. The main sources of picric acid include picric acid-containing dyes, pesticides, medicines, chemical industry, printing and dyeing industry, waste water, waste gas, waste residue and the like. Such waste may enter the environment by means of infiltration of contaminants, wastewater treatment, etc., which threatens the health of people. Therefore, the method has important significance for detecting the picric acid, and development of a rapid, accurate and sensitive picric acid detection method is very necessary. Currently, common picric acid detection methods include high performance liquid chromatography, gas chromatography, fluorescent probe methods, and the like.
As an emerging detection method, the fluorescent probe method has the advantages of rapidness, sensitivity, high efficiency and economy, and has wide application value in picric acid detection. The fluorescent probe method adopts fluorescent molecules to react with picric acid to form a fluorescent signal, and the quantitative detection of the concentration of the picric acid is realized by detecting the intensity and spectral characteristics of the fluorescent signal. Compared with the traditional detection method, the fluorescent probe method has higher sensitivity and accuracy, simple operation and low cost, thus having wide application prospect in the fields of food, environment and the like. The fluorescent probe method has very wide advantages and application prospects in picric acid detection, and provides important support for public health and environmental protection. Although the use of fluorescent molecular probes in picric acid detection has evolved, some challenges remain. For example, finding probes with good solubility, high selectivity and high sensitivity remains a critical task. Since picric acid has a chemical structure similar to that of 2,4, 6-trinitrotoluene, 2, 4-dinitrotoluene, etc., it has been difficult to develop a fluorescent probe having high selectivity. In addition, existing fluorescent probes commonly employ single luminescent type molecules, such as solution luminescent type aggregation quenching (ACQ) molecules or solid state luminescent type Aggregation Induced Emission (AIE) molecules, and their application range is limited. Therefore, developing a novel bimodal fluorescent molecule as a picric acid probe can expand the application range of picric acid detection.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a bimodal fluorescent probe for detecting picric acid and a preparation method thereof, which are used for detecting picric acid with high sensitivity and quantification.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a bimodal fluorescent probe for picric acid detection has the following structure:
abbreviated FCPB, which has fluorescent properties in both solution and solid states.
A preparation method of a bimodal fluorescent probe for picric acid detection comprises the following synthetic routes:
the preparation method of the invention comprises the following steps:
1) Synthesis of cyano-containing intermediate CNPB: dissolving 4-cyanomethyl phenylboronic acid and 1-bromopyrene in tetrahydrofuran solutionAdding bis [ di-tert-butyl- (4-dimethylaminophenyl) phosphine]Palladium (II) dichloride (Pd-132) and potassium carbonate (K) 2 CO 3 ) Heating the solution under the protection of nitrogen for reaction, pouring the solution into saturated saline water after the reaction is finished and the solution is cooled to room temperature, extracting with an organic solvent, eluting, and purifying by column chromatography to obtain an intermediate compound CNPB;
2) Dissolving the intermediate CNPB and 4-fluoro salicylaldehyde prepared in step 1) in acetic acid and N, N-dimethylformamide, then adding piperidine, and treating under nitrogen (N) 2 ) Under the protection, heating to react, pouring the solution into ice water after the reaction is finished and the solution is cooled to room temperature, extracting with an organic solvent, eluting, and purifying by column chromatography to obtain the probe molecule FCPB.
In the step 1), the heating temperature is 60-100 ℃ and the reaction time is 12-18 h.
In the step 2), the heating temperature is 80-120 ℃ and the reaction time is 10-16 h.
In step 1) and step 2), dichloromethane extraction is used.
In step 1) and step 2), petroleum ether and methylene dichloride are used as eluent.
The mole ratio of each ingredient in the step 1) is as follows: 4-cyanomethyl phenylboronic acid, 1-bromopyrene, potassium carbonate and bis [ di-tert-butyl- (4-dimethylaminophenyl) phosphine ] palladium (II) dichloride (1:1-1.5:1-5:0.05-0.2).
The mole ratio of each ingredient in the step 2) is as follows: CNPB 4-fluoro salicylaldehyde piperidine=1:1 to 1.5:10 to 100.
The application of the FCPB is used for detecting picric acid.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) The fluorescent molecule is a two-state fluorescent molecule, has good fluorescence emission property in a solution state and a solid state, and has good applicability;
(2) The binary fluorescent probe has single selectivity for picric acid detection, hardly responds to other common aromatic nitro compounds, and has high sensitivity for picric acid detection;
(3) The fluorescence quenching curve of the bimodal fluorescent probe is a linear fitting curve, and can be used for quantitative detection of picric acid;
(4) The detection process of the bimodal fluorescent probe is simple and quick, and complex operation procedures and expensive equipment are not needed;
(5) The binary fluorescent probe has the advantages of simple synthesis route and low cost, and is beneficial to practical application and popularization.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectrum of FCPB 1 H NMR)；
FIG. 2 shows nuclear magnetic carbon spectrum of FCPB 13 C NMR)；
FIG. 3 is a Mass Spectrum (MS) of FCPB;
FIG. 4 is a normalized fluorescence spectrum of FCPB in solution and solid state;
FIG. 5 is a graph of the fluorescence response of FCPB for various aromatic nitro compounds;
FIG. 6 shows the change in fluorescence intensity of FCPB at 476nm before and after addition of different aromatic nitro compounds and picric acid;
FIG. 7 is a fluorescence titration spectrum of FCPB for picric acid;
FIG. 8 is a graph of a linear fit of FCPB maximum fluorescence intensity versus picric acid concentration;
FIG. 9 is a fluorescence spectrum of FCPB and an ultraviolet spectrum of picric acid;
fig. 10 is a LUMO orbital electron cloud distribution of HOMO, LUMO orbitals, and picric acid of FCPB.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
The preparation method of the bimodal fluorescent probe FCPB for detecting picric acid in the embodiment is as follows:
1) Synthesis of CNPB: 0.96g of 4-cyanomethylphenylboronic acid, 1.41g of 1-bromopyrene, 24mL of tetrahydrofuran, 78mg of Pd-132, and 8mL of aqueous potassium carbonate (2M) were charged to a 50mL round bottom flask. Heating under nitrogen protectionThe reaction was carried out at 80℃for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was added to 100mL of saturated brine. The organic phases were extracted three times with 50mL of dichloromethane, combined and dried over anhydrous sodium sulfate for 3 hours. After filtration, the crude product was obtained by distillation under reduced pressure. The crude product was purified by column chromatography (petroleum ether: dichloromethane=1:1) to give 1.14 g of CNPB as a white solid in 72% yield. 1 H NMR(400MHz,CDCl 3 )δ:8.00～8.23(m，8H)，7.94(d，J＝7.8Hz，1H)，7.64(d，J＝8.0Hz，2H)，7.51(d，J＝8.0Hz，2H)，3.88(s，2H)。
2) Synthesizing FCPB: 0.14g of 4-fluorosalicylaldehyde and 0.35g of CNPB are weighed, dissolved in 2mL of acetic acid and 2mL of N, N-dimethylformamide, 3mL of piperidine are added, and the mixture is reacted for 12 hours at 110 ℃ under the protection of nitrogen. After the reaction was completed, the reaction mixture was cooled and poured into 100mL of ice water. Extraction 3 times with 50mL of dichloromethane, drying over anhydrous sodium sulphate, filtration and distillation under reduced pressure give the crude product, which is finally purified by chromatography (petroleum ether: dichloromethane=1:1) to give 0.23g of FCPB as a yellowish green solid in 53% yield. 1 H NMR(400MHz,CDCl 3 )δ:7.85～8.26(m,9H),7.90(d,J＝8.0Hz,2H),7.85(s,1H),7.69(d,J＝8.0Hz,2H),6.88(d,J＝7.5Hz,1H),6.79(s,1H). 13 C NMR(101MHz,CDCl 3 ):δ161.70,155.98,140.98,140.38,137.38,134.67,131.59,131.10,130.76,130.70,128.79,128.60,128.39,127.65,127.63,127.57,127.51,126.12,125.42,125.21,125.08,125.01,124.96,124.78,112.10,100.55,49.10,34.76,27.01,25.37,24.38.HR-MS(APCI-MS):m/z＝441.2457.calcd.for[C 31 H 18 FO 2 ] + ＝441.1291。
The nuclear magnetic and mass spectrum characterization patterns of FCPB are shown in fig. 1, fig. 2 and fig. 3.
Example 2
Photophysical Properties of the two-state fluorescent Probe
Solution fluorescence spectrum test: 4.4mg FCPB was accurately weighed by a ten-thousandth scale, and dissolved in 1mL anhydrous tetrahydrofuran to prepare a mother liquor with a concentration of 0.01 mM. 10. Mu.L of the mother solution was accurately collected by a pipette, added to 1000mL of tetrahydrofuran, and diluted to a test solution having a concentration of 10. Mu.M. Pouring the solution into a cuvette, and testing the spectrum by using an LS-55 fluorescence photometer, wherein the excitation wavelength is 393nm, and the scanning range is 400-600 nm.
Solid fluorescence spectrum: 50mg FCPB is weighed and added into a 0.5mm quartz sample cell, the spectrum is tested by using an LS-55 fluorescence photometer, the excitation wavelength is 393nm, and the scanning range is 400-600 nm.
As shown in FIG. 4, the fluorescence emission wavelengths of FCPB in tetrahydrofuran solution and solid state were 476nm and 493nm, respectively. The fluorescence quantum yields in the solution and solid states were 0.60 and 0.31, respectively, indicating that FCPB has good luminescence properties in both the dilute solution and solid states, and is a typical bi-state luminescent fluorescent molecule.
Example 3
Picric acid detection application of FCPB
Selectivity test of bimodal fluorescent probes for picric acid detection: a FCPB probe solution having a concentration of 10. Mu.M was prepared using tetrahydrofuran/water (volume ratio 1/1) as a mixed solvent. Nine aromatic nitro compounds including Picric Acid (PA), dinitrotoluene (DNP), nitrobenzene (NB), o-nitrophenol benzene (o-NP), p-chloronitrobenzene (p-ClNB), p-fluoronitrobenzene (p-FNB), p-nitroaniline (p-NA), p-nitrophenol (p-NP), and p-nitrotoluene (p-NT) were dissolved in anhydrous tetrahydrofuran to prepare a mother solution having a concentration of 0.01M. To 9 parts by volume of 5mL of the FCPB probe solution, 50. Mu.L of the above aromatic nitro compound was added, and the mixture was mixed with shaking to prepare a test solution, and another 5mL of FCPB probe solution was prepared without adding any aromatic nitro compound as a reference. Pouring the test solution or the reference solution into a fluorescent cuvette, and testing the spectrum by using an LS-55 fluorescence photometer, wherein the excitation wavelength is 393nm, and the scanning range is 400-600 nm. As shown in fig. 5, only Picric Acid (PA) caused a significant quenching of FCPB fluorescence among nine aromatic nitro compounds, while the other eight aromatic nitro compounds did not have a significant effect on fluorescence intensity, indicating that FCPB has a single selectivity for picric acid recognition.
Interference immunity of binary fluorescent probes to picric acid detection: ten parts of FCPB probe solution at a concentration of 10 μm was prepared using tetrahydrofuran/water (volume ratio of 1/1) as a mixed solvent, and labeled 1,2,3,4,5,6,7,8,9, 10. Sample No. 1 was used as a blank control sample, sample No. 2 was used as a negative control sample, and the remaining samples No. 3 to 10 were used as test group samples. To sample nos. 3 to 10, dinitrotoluene (DNP), nitrobenzene (NB), o-nitrophenol benzene (o-NP), p-chloronitrobenzene (p-ClNB), p-fluoronitrobenzene (p-FNB), p-nitroaniline (p-NA), p-nitrophenol (p-NP), p-nitrotoluene (p-NT) were added in an amount equivalent to 10 equivalents of FCPB concentration, and the spectrum was measured using an LS-55 fluorescence photometer, with excitation wavelength of 393nm and scanning range of 400 to 600nm. Subsequently, after Picric Acid (PA) having a concentration of 10 equivalents of FCPB was added to sample nos. 2 to 10, fluorescence spectra were again tested under the same conditions. Then, the fluorescence intensity at 476nm was extracted and plotted to obtain the results shown in fig. 6, and the fluorescence of each group of solutions was almost the same as that of the blank group and the negative reference group before adding picric acid, further indicating that other aromatic nitro compounds had almost no effect on the fluorescence intensity of FCPB, whereas after adding picric acid, the fluorescence of the experimental group and the negative control group were significantly quenched, indicating that picric acid caused fluorescence quenching of FCPB, and that the presence of other aromatic nitro compounds did not affect detection of picric acid by FCPB. The above results indicate that nitro compounds in other directions than picric acid do not affect the fluorescence intensity of FCPB, and that the presence of these aromatic nitro compounds does not affect the detection of picric acid by FCPB.
Kinetics of bimodal fluorescent probe on picric acid detection: to 5mL of a tetrahydrofuran/water (V/V1/1) solution of FCPB at a concentration of 10. Mu.M, 5. Mu.L of picric acid solution (0.1M) was successively added and the spectra were recorded using LS-55 fluorometer. The fluorescence intensity at 476nm was plotted against the change in picric acid concentration and a linear fit was performed to obtain the results shown in fig. 7, which revealed that increasing the concentration of picric acid resulted in gradual quenching of fluorescence, and that the degree of fluorescence quenching reached 79% when picric acid equivalent to 10-fold equivalent of FCPB concentration was added. Analysis was performed using the Stern-Volmer (S-V) equation: (I) 0 /I＝1+K SV [Q]) Wherein I 0 For the initial emission intensity of the compound, I is the emission intensity after adding picric acid, K SV For quenching constant [ Q ]]Is the concentration of picric acidDegree. After fitting the linear portion (0-3 equivalent picric acid range), the quenching constant was calculated to be 2062M -1 。
Limit of detection of picric acid by the binary fluorescent probe: the limit of detection (limit of detection, loD) is a key parameter for assessing the sensitivity of picric acid fluorescent probes. To 5mL of a tetrahydrofuran/water (V/V1/1) solution of FCPB having a concentration of 10. Mu.M, 5. Mu.L of picric acid solution (0.1M) was successively added to a maximum of 3.0 equivalents, a plot of the change in fluorescence intensity at 476nm wavelength versus picric acid concentration was drawn, and a linear fit was performed to obtain the result shown in FIG. 8, wherein the response of FCPB to picric acid was nearly linear, indicating that picric acid could be quantitatively detected, and the slope K was calculated from FIG. 8. 10 parts of the above FCPB solution was prepared, and the fluorescence spectrum was tested, and the fluorescence intensity value at 476nm was taken to calculate the standard deviation σ. According to the LoD calculation formula: lod=3σ/K, and the calculated detection limit is 1.81 μm, indicating that the probe of the present invention has high sensitivity for picric acid detection.
Example 4
Picric acid detection mechanism of bimodal luminescence type fluorescent probe
FCPB and picric acid were weighed and dissolved in anhydrous tetrahydrofuran, respectively, to prepare a mother solution having a concentration of 0.01M, and 10. Mu.L of the mother solution was added to 1000. Mu.L of the anhydrous tetrahydrofuran solution using a pipette to obtain a test solution having a concentration of 10. Mu.M. The test solution was transferred to a fluorescence cuvette, the fluorescence spectrum of FCPB was measured using an LS-55 fluorescence photometer, the ultraviolet absorption spectrum of picric acid was measured using a UV-759 ultraviolet spectrophotometer, and the two spectra were normalized and compared and the spectra were overlapped to obtain the result shown in fig. 9. It can be seen that the fluorescence spectrum of FCPB and the uv absorption spectrum of picric acid overlap somewhat, indicating that Fluorescence Resonance Energy Transfer (FRET) is a possible fluorescence quenching mechanism. Based on the density functional theory, using Gaussian 09 packet and B3LYP/6-31+G (d) array, electron cloud distribution and orbital energy levels of the HOMO and LUMO orbitals of FCPB and the picric acid LUMO orbitals were calculated, resulting in the results shown in FIG. 10. It can be seen that the HOMO orbital energy level of FCPB is higher than the LUMO orbital energy level of picric acid, indicating that photo-induced electron transfer (PET) does not occur between FCPB and picric acid, and that photo-induced electron (PET) processes are not responsible for picric acid-mediated fluorescence quenching of FCPB. Thus, the picric acid detection mechanism of FCPB may be fluorescence resonance energy transfer.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and the present invention is not limited thereto, and any simple modification, equivalent substitutions and improvements made by those skilled in the art without departing from the technical scope of the present invention, are within the scope of the technical solutions of the present invention.
Claims (10)
1. A bimodal fluorescent probe for picric acid detection, characterized by the following structure:
abbreviated FCPB, which has fluorescent properties in both solution and solid states.
2. The method for preparing a bimodal fluorescent probe for picric acid detection as claimed in claim 1, wherein the synthetic route is as follows:
3. the method of manufacturing as claimed in claim 2, comprising the steps of:
1) Synthesis of cyano-containing intermediate CNPB: dissolving 4-cyanomethyl phenylboronic acid and 1-bromopyrene in tetrahydrofuran solution, adding bis [ di-tert-butyl- (4-dimethylaminophenyl) phosphine ] palladium (II) dichloride and potassium carbonate, heating the solution for reaction under the protection of nitrogen, pouring the solution into saturated saline after the reaction is finished and cooling the solution to room temperature, extracting with an organic solvent, eluting, and purifying by column chromatography to obtain an intermediate compound CNPB;
2) Dissolving the intermediates CNPB and 4-fluoro salicylaldehyde prepared in the step 1) in acetic acid and N, N-dimethylformamide, then adding piperidine, heating for reaction under the protection of nitrogen, pouring the solution into ice water after the reaction is finished and the solution is cooled to room temperature, extracting with an organic solvent, eluting, and purifying by column chromatography to obtain the probe molecule FCPB.
4. A method of preparation as claimed in claim 3, wherein: in the step 1), the heating temperature is 60-100 ℃ and the reaction time is 12-18 h.
5. A method of preparation as claimed in claim 3, wherein: in the step 2), the heating temperature is 80-120 ℃ and the reaction time is 10-16 h.
6. A method of preparation as claimed in claim 3, wherein: in step 1) and step 2), dichloromethane extraction is used.
7. A method of preparation as claimed in claim 3, wherein: in step 1) and step 2), petroleum ether and methylene dichloride are used as eluent.
8. A process according to claim 3, wherein the molar ratio of the ingredients of step 1) is as follows: 4-cyanomethyl phenylboronic acid, 1-bromopyrene, potassium carbonate and bis [ di-tert-butyl- (4-dimethylaminophenyl) phosphine ] palladium (II) dichloride (1:1-1.5:1-5:0.05-0.2).
9. A process according to claim 3, wherein the molar ratio of the ingredients of step 2) is as follows: CNPB 4-fluoro salicylaldehyde piperidine=1:1 to 1.5:10 to 100.
10. The use of a two-state fluorescent probe for picric acid detection according to claim 1 and a two-state fluorescent probe for picric acid detection prepared by the preparation method according to any one of claims 2 to 9, characterized in that: for detecting picric acid.
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