CN106085408B - A kind of 3- phenyl benzoxazine ketone benzenethiol fluorescence probe and preparation method thereof - Google Patents
A kind of 3- phenyl benzoxazine ketone benzenethiol fluorescence probe and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of 3 phenyl benzoxazine ketone benzenethiol fluorescence probes and preparation method thereof, belong to technical field of analysis and detection.The 3 phenyl benzoxazine ketone benzenethiol fluorescence probes of the present invention have good fluorescence property, benzenethiol can be selectively identified in buffer solution, it shows as responding rapid, detection limit low (being only 8nM), big Stokes displacements, Fluorescence Increasing, high selectivity, strong antijamming capability, real-time qualitative or quantitative analysis can be carried out to benzenethiol, therefore the benzenethiol fluorescence probe of the invention prepared can be applied to the benzenethiol detection in aqueous environment.
Description
Technical field
The present invention relates to technical field of analysis and detection, more particularly to a kind of 3- phenyl benzoxazine ketone benzenethiol fluorescence is visited
Pin and preparation method thereof.
Background technology
Benzenethiol is colourless liquid, has off-odor.Chemical synthesis is widely used in, particularly for medicine, pesticide, height
Molecular material and the auxiliary agent of organic synthesis etc. are also used for preparing local anesthetic.Larynx, bronchus convulsion can be caused after sucking
Contraction, oedema and chemical pneumonia, pulmonary edema, the benzenethiol in Long Term Contact water or air can cause health a series of serious
Harm is damaged including central nervous system, heart rate becomes faster, muscular atrophy, lower limb paralysis, stupor are even dead.Meet open fire, high fever
Or contacted with oxidant, there is the danger for causing combustion explosion.Therefore, it is possible to quick, highly sensitive and highly selective detection biology
In vivo and the benzenethiol in environment is increasingly valued by people.
Benzenethiol fluorescence probe based on 2,4- dinitrobenzenesulfonyls as recognition group, because its have can specific aim know
The performance of other benzenethiol, in recent years by wide coverage.Including：
Chunchang Zhao, et. al.Development of an Indole-Based Boron-
Dipyrromethene Fluorescent Probe forBenzenethiols, J. Phys. Chem. B, 2011,
115, 642-647;Dehuan Yu, et. al.Near-Infrared Fluorescent Probe for Detection
of Thiophenols inWater Samples and Living Cells,Anal. Chem., 2014, 86,8835-
8841;Xiangmin Shao, et. al. Highly Selective and Sensitive 1-Amino BODIPY-
Based RedFluorescent Probe for Thiophenols with High Off-to-On ContrastRatio,
Anal. Chem. 2015,87,399-405 etc., but since the time that these probes need the detection of benzenethiol is long, greatly
Border is applied in fact for big limitation.Therefore, a kind of fluorescence probe that can detect benzenethiol immediately is developed to have very important significance.
The content of the invention
One of the object of the invention is to provide a kind of benzenethiol fluorescence of low cost, that synthesis is simple and reaction condition is mild and visits
Pin synthetic method；The second purpose is to provide that a kind of response is rapid, the detection benzene of high sensitivity, high selectivity, strong antijamming capability
The fluorescence probe of thiophenol.
The technical scheme is that：
A kind of 3- phenyl benzoxazine ketone benzenethiol fluorescence probe is following structural formula（1）Compound represented；
。
The preparation method of the 3- phenyl benzoxazine ketone benzenethiol fluorescence probe, structural formula（2）Compound represented
Structural formula is made with the reaction of 2,4- dinitrophenyl chlorides in 7- hydroxyls -3- phenyl benzoxazinone（1）Compound represented；
。
Further, structural formula（2）Compound represented 7- hydroxyls -3- phenyl benzoxazinone and 2,4- dinitrobenzene sulphurs
Acyl chlorides reacts in organic solvent under the conditions of existing for triethylamine.
Reaction equation is as follows：
。
Preferably, the dosage of 2,4- dinitrophenyl chlorides is 7- hydroxyl -3- phenyl benzoxazinone dosages
100%-150%, the dosage of triethylamine are the 100%-600% of 7- hydroxyl -3- phenyl benzoxazinone dosages.The material ratio scope
Under, yield is high, is easily purified.
Preferably, the organic solvent is tetrahydrofuran, dichloromethane or chloroform.With tetrahydrofuran, dichloromethane
Alkane or chloroform can react at room temperature for solvent, and yield is higher.
Preferably, structural formula（2）Compound represented 7- hydroxyl -3- phenyl benzoxazinone, 2,4- dinitros
Benzene sulfonyl chloride and triethylamine are added sequentially in reaction vessel, add in organic solvent dissolving, when reaction 1-6 is small at room temperature.
The 3- phenyl benzoxazine ketone benzenethiol fluorescence probe identifies and the application in detection in benzenethiol.
Beneficial effects of the present invention are：
The 3- phenyl benzoxazine ketone benzenethiols fluorescence probe of the present invention has good fluorescence property, can buffer
Benzenethiol is selectively identified in solution, response is shown as and interrogates speed, detection limit low (being only 8nM), big Stokes displacements, fluorescence increasing
By force, selective strong, strong antijamming capability can carry out benzenethiol qualitative or quantitative analysis, therefore benzene sulphur prepared by the present invention
Phenol fluorescence probe can be applied to the benzenethiol detection in aqueous environment.
The preparation method raw material of the present invention is easy to get, and is easily monitored and controlled, and product is easily isolated purifying.
Description of the drawings
It in order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
To obtain other attached drawings according to these attached drawings.
Fig. 1 is the THF/HEPES of fluorescence probe made from embodiment 1（10 mM, pH=7.4）Solution (THF:HEPES=1:
1, concentration and probe concentration is 10 μM) and the fluorescent emission collection of illustrative plates of probe and the mixed solution of analyte（Wherein benzenethiol, p-aminophenyl
Thiophenol and be 20 μM to methoxybenzenethiol concentration；Other analyte concentrations are 100 μM, including potassium fluoride, sodium chloride, bromine
Change sodium, sodium iodide, sodium carbonate, sodium nitrite, sodium nitrate, sodium acetate, vulcanized sodium, sodium sulfocyanate, sodium sulfite, sodium sulphate, sulphur
Sodium thiosulfate, sodium dithionite, disodium hydrogen phosphate, hydrogen peroxide, ethyl mercaptan, thioacetic acid, n-amyl mercaptan, half Guang ammonia of high homotype
Acid, cysteine, glutathione, alanine, glycine and phenol）, excitation wavelength 395nm, ordinate expression fluorescence intensity,
Abscissa represents wavelength.
Fig. 2 is the THF/HEPES of fluorescence probe made from embodiment 1（10 mM, pH=7.4）Solution (THF:HEPES=1:
1, concentration and probe concentration is 10 μM) and probe and analyte（Wherein benzenethiol, p-aminophenyl thiophenol and to methoxybenzenethiol concentration
It is 20 μM；Other analyte concentrations are 100 μM, including potassium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium carbonate, nitrous acid
Sodium, sodium nitrate, sodium acetate, vulcanized sodium, sodium sulfocyanate, sodium sulfite, sodium sulphate, sodium thiosulfate, sodium dithionite, phosphoric acid
Disodium hydrogen, hydrogen peroxide, ethyl mercaptan, thioacetic acid, n-amyl mercaptan, homocysteine, cysteine, glutathione, the third ammonia
Acid, glycine and phenol）Mixed solution at 538 nm fluorescence intensity comparison diagram, excitation wavelength 395nm.Ordinate represents
Fluorescence intensity, abscissa represent different analytes；First black column expression is not added with any analyte from left to right；Below in every group of column
The black column in the left side represents the solution fluorescence intensity for there was only in the presence of the analyte, and the right gray columns represents the analyte and benzenethiol simultaneously
In the presence of solution fluorescence intensity；Last three black columns represent benzenethiol, p-aminophenyl thiophenol, methoxybenzenethiol are deposited respectively
When solution fluorescence intensity.
Fig. 3 is the THF/HEPES of fluorescence probe made from embodiment 1（10 mM, pH=7.4）Solution (THF:HEPES=1:
1, concentration and probe concentration is 10 μM) with various concentration benzenethiol（0-20µM）Change in fluorescence collection of illustrative plates after addition（λex = 395
nm）, ordinate expression fluorescence intensity, abscissa expression wavelength.
Fig. 4 is the fluorescence intensity at 538 nm in Fig. 3 with benzenethiol concentration（0-20µM）The scatter diagram of variation, ordinate
Represent fluorescence intensity, abscissa represents benzenethiol concentration.
Fig. 5 is the benzenethiol of various concentration（Wherein benzenethiol concentration is respectively 0 μM, 0.1 μM, 0.5 μM, 1 μM, 2 μ
M、4 µM、6 µM、8 µM、10 µM）It is added to the THF/HEPES of 10 μM of fluorescence probes made from embodiment 1（10mM,pH=7.4）
(THF:HEPES=1:1) after solution, solution fluorescence intensity at 538 nm changes with time figure, and ordinate represents that fluorescence is strong
Degree, abscissa represent the time.
Fig. 6 is the THF/HEPES of fluorescence probe made from embodiment 1（10mM, pH=7.4）(THF:HEPES=1:1, probe
Concentration is 10 μM) solution is before and after condition of different pH and 20 μM of benzenethiol effects, the figure of fluorescence intensity changes at 538 nm,
Ordinate represents fluorescence intensity, and abscissa represents pH.
Specific embodiment
Embodiment 1
The synthesis of 3- phenyl benzoxazine ketone benzenethiol fluorescent probe compounds
In the single-necked flask of 50mL, successively by 7- hydroxyl -3- phenyl benzoxazinone (70 mg, 0.29 mmol), 2,
4- dinitrophenyl chlorides (86 mg, 0.32 mmol) and triethylamine (81 μ L, 0.58 mmol) are dissolved in 5 mL drying tetrahydrochysenes
In furans, reaction 3h is stirred at room temperature, vacuum distillation removes solvent, gained residue with dichloromethane is dissolved, then uses 50mL
Water washing three times, with anhydrous sodium sulfate dried by organic phase, vacuum distillation remove solvent afforded crude material, with dichloromethane/ethyl acetate=
3/1, which crosses silica gel (200-300 mesh) post separation, obtains pale solid, yield 82%.
Wherein, 7- hydroxyls -3- phenyl benzoxazinone can be according to document K. Azuma, S. Suzuki, S.
Uchiyama, T.Kajiro, T. Santa and K. Imai, A study of the relationship between
the chemical structures and the fluorescence quantum yields of coumarins,
quinoxalinones and benzoxazinones for the development of sensitive
fluorescent derivatization reagents, Photochem. Photobiol. Sci., 2003,2, 443-
It is prepared by the method for 449. reports.
3- phenyl benzoxazine ketone benzenethiol fluorescent probe compounds, molecular formula are made from the present embodiment
C15H9N3O9S, nucleus magnetic hydrogen spectrum analysis are1H NMR (400 MHz, DMSO-d 6) δ9.14 (s, 1H), 8.63 (d, J =
8.4 Hz, 1H), 8.31 (d, J = 8.4 Hz, 1H), 8.14 (d, J = 7.6 Hz, 2H), 7.88 (d, J =
8.4 Hz, 1H), 7.56 (d, J = 6.9 Hz, 1H),7.53-7.49 (m, 3H), 7.45 (s, 3H), 7.24
(d, J=8.4 Hz, 1H) nuclear-magnetism carbon spectrum analysis is13C NMR (100 MHz, DMSO-d 6) δ160.61, 152.24,
147.97, 146.08, 134.64, 130.20, 130.14, 128.99, 128.73, 128.15, 127.98,
124.95,113.81,101.59. high resolution mass spectrum analysis is HRMS (ESI) calcd for [M+H]+ C20H12N3O9S:
470.0294, found: 470.0286。
Embodiment 2
The synthesis of 3- phenyl benzoxazine ketone benzenethiol fluorescent probe compounds
In the single-necked flask of 50mL, successively by 7- hydroxyl -3- phenyl benzoxazinone (70 mg, 0.29 mmol), 2,
4- dinitrophenyl chlorides (86 mg, 0.32 mmol) and triethylamine (81 μ L, 0.58 mmol) are dissolved in 5 mL drying tetrahydrochysenes
In furans, 6 h of reaction are stirred at room temperature, vacuum distillation removes solvent, gained residue 50mL dichloromethane is dissolved, Ran Houyong
50mL water washings three times, with anhydrous sodium sulfate dried by organic phase, and vacuum distillation removes solvent afforded crude material, with dichloromethane/acetic acid
Ethyl ester=3/1 crosses silica gel (200-300 mesh) post separation and obtains pale solid, yield 80%.
Embodiment 3
The synthesis of 3- phenyl benzoxazine ketone benzenethiol fluorescent probe compounds
In the single-necked flask of 50mL, successively by 7- hydroxyl -3- phenyl benzoxazinone (70 mg, 0.29 mmol), 2,
4- dinitrophenyl chlorides (86 mg, 0.32 mmol) and triethylamine (81 μ L, 0.58 mmol) are dissolved in 5 mL drying tetrahydrochysenes
In furans, reaction 1h is stirred at room temperature, vacuum distillation removes solvent, gained residue 50mL dichloromethane is dissolved, Ran Houyong
50mL water washings three times, with anhydrous sodium sulfate dried by organic phase, and vacuum distillation removes solvent afforded crude material, with dichloromethane/acetic acid
Ethyl ester=3/1 crosses silica gel (200-300 mesh) post separation and obtains pale solid, yield 70%.
Embodiment 4
The synthesis of 3- phenyl benzoxazine ketone benzenethiol fluorescent probe compounds
In the single-necked flask of 50mL, successively by 7- hydroxyl -3- phenyl benzoxazinone (90 mg, 0.6 mmol), 2,
4- dinitrophenyl chlorides (116 mg, 0.44 mmol) and triethylamine (162 μ L, 1.16 mmol) are dissolved in 5 mL dryings four
In hydrogen furans, 2 h of reaction are stirred at room temperature, vacuum distillation removes solvent, gained residue 50mL dichloromethane is dissolved, then
With 50mL water washings three times, organic phase is dried with anhydrous sodium sulfate, and vacuum distillation removes solvent afforded crude material, with dichloromethane/second
Acetoacetic ester=3/1 crosses silica gel (200-300 mesh) post separation and obtains pale solid, yield 77%.
Embodiment 5
The synthesis of 3- phenyl benzoxazine ketone benzenethiol fluorescent probe compounds
In the single-necked flask of 50mL, successively by 7- hydroxyl -3- phenyl benzoxazinone (90 mg, 0.6 mmol), 2,
4- dinitrophenyl chlorides (116 mg, 0.44 mmol) and triethylamine (162 μ L, 1.16 mmol) are dissolved in 5 mL dryings four
In hydrogen furans, 6 h of reaction are stirred at room temperature, solvent is removed under reduced pressure, gained residue 50mL dichloromethane is dissolved, Ran Houyong
50mL water washings three times, with anhydrous sodium sulfate dried by organic phase, and vacuum distillation removes solvent afforded crude material, with dichloromethane/acetic acid
Ethyl ester=3/1 crosses silica gel (200-300 mesh) post separation and obtains pale solid, yield 85%.
Embodiment 6
The synthesis of 3- phenyl benzoxazine ketone benzenethiol fluorescent probe compounds
In the single-necked flask of 50mL, successively by 7- hydroxyl -3- phenyl benzoxazinone (90 mg, 0.6 mmol), 2,
4- dinitrophenyl chlorides (116 mg, 0.44 mmol) and triethylamine (162 μ L, 1.16 mmol) are dissolved in 5 mL dryings two
In chloromethanes, reaction 2h is stirred at room temperature, vacuum distillation removes solvent, gained residue 50mL dichloromethane is dissolved, then
With 50mL water washings three times, organic phase is dried with anhydrous sodium sulfate, and vacuum distillation removes solvent afforded crude material, with dichloromethane/second
Acetoacetic ester=3/1 crosses silica gel (200-300 mesh) post separation and obtains pale solid, yield 65%.
Embodiment 7
The synthesis of 3- phenyl benzoxazine ketone benzenethiol fluorescent probe compounds
Successively by 7- hydroxyl -3- phenyl benzoxazinone (90 mg, 0.6 mmol), 2,4- dinitrophenyl chlorides (116
Mg, 0.44 mmol) and triethylamine (162 μ L, 1.16 mmol) be dissolved in 5 mL drying chloroform in, be stirred at room temperature reaction 6 h,
Vacuum distillation removes solvent, and gained residue 50mL dichloromethane is dissolved, and then with 50mL water washings three times, organic phase is used
Anhydrous sodium sulfate is dried, and vacuum distillation removes solvent afforded crude material, and silica gel (200-300 is crossed with dichloromethane/ethyl acetate=3/1
Mesh) post separation obtains pale solid, yield 55%.
Embodiment 8
3- phenyl benzoxazine ketone benzenethiol fluorescence probes detect application study to the optical physics of benzenethiol.
Benzenethiol fluorescence probe based on 3- phenyl benzoxazinones prepared by embodiment 1 is dissolved in tetrahydrofuran, is matched somebody with somebody
The storing solution that concentration is 1 mM is made.Then tetrahydrofuran/HEPES is used（10mM,pH=7.4）Solution (THF:HEPES=1:1)
Compound concentration is 10 μM of probe test solution.
3- phenyl benzoxazine ketone benzenethiol fluorescence probes have extremely weak fluorescence under 395 nm excitations at 538 nm
Transmitting, when adding in benzenethiol or p-aminophenyl thiophenol into probe solution or to methoxybenzenethiol, Fluorescence Increasing, Stokes
Displacement reaches 160 nm；When benzenethiol addition is in 0 μM -10 μM, fluorescence intensity and benzenethiol of the probe at 538 nm
Concentration is into well linearly, and it is only 8nM to detect limit；When benzenethiol addition is more than 1.2 equivalent, fluorescence intensity tends to
Stablize, and 236 times of Fluorescence Increasing；After adding in other common analytical objects, the significant changes of fluorescence probe transmitting are not caused.
As shown in Figure 1, to the THF/HEPES of 10 μM of fluorescence probes（10 mM, pH=7.4）Solution (THF:HEPES=1:
1) potassium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium carbonate, sodium nitrite, sodium nitrate, sodium acetate, vulcanized sodium, sulphur cyanogen are added in
Sour sodium, sodium sulfite, sodium sulphate, sodium thiosulfate, sodium dithionite, disodium hydrogen phosphate, hydrogen peroxide, ethyl mercaptan, sulfydryl second
After acid, n-amyl mercaptan, homocysteine, cysteine, glutathione, alanine, glycine and phenol, probe solution
Apparent enhancing does not occur for fluorescence；And add in benzenethiol or p-aminophenyl thiophenol or to methoxybenzenethiol after, probe solution
Fluorescent emission intensity be remarkably reinforced.
As shown in Figure 2, in the THF/HEPES of 10 μM of fluorescence probes（10 mM, pH=7.4）Solution (THF:HEPES=1:
1) in, when 2 equivalent benzenethiols respectively with the potassium fluoride of 10 equivalents, sodium chloride, sodium bromide, sodium iodide, sodium carbonate, nitrous acid
Sodium, sodium nitrate, sodium acetate, vulcanized sodium, sodium sulfocyanate, sodium sulfite, sodium sulphate, sodium thiosulfate, sodium dithionite, phosphoric acid
Disodium hydrogen, hydrogen peroxide, ethyl mercaptan, thioacetic acid, n-amyl mercaptan, homocysteine, cysteine, glutathione, the third ammonia
Acid, glycine and phenol and when depositing, can not disturb response of the probe to benzenethiol, probe shows good anti-interference energy
Power.
From the figure 3, it may be seen that in the THF/HEPES of 10 μM of fluorescence probes（10 mM, pH=7.4）Solution (THF:HEPES=1:
1) in, the addition of benzenethiol causes the Fluorescence Increasing of probe solution, and as benzenethiol concentration increases, fluorescence intensity by
It is cumulative big.
As shown in Figure 4, in the THF/HEPES of 10 μM of fluorescence probes（10 mM, pH=7.4）Solution (THF:HEPES=1:
1) in, when benzenethiol addition is in 0 μM -10 μM, fluorescence intensity of the probe solution at 538 nm and benzenethiol concentration
Into preferably linearly；The fluorescence probe of the present invention is very low to the detection limit of benzenethiol, is only 8nM；When benzenethiol addition is 1.2
When more than a equivalent, fluorescence intensity tends towards stability, and 236 times of Fluorescence Increasing.
As shown in Figure 5, in the THF/HEPES of 10 μM of fluorescence probes（10 mM, pH=7.4）Solution (THF:HEPES=1:
1) after adding in the benzenethiol of various concentration in, fluorescence intensity of the probe solution at 538 nm reaches balance and stabilization immediately, can
Benzenethiol is detected in real time.
It will be appreciated from fig. 6 that in the THF/HEPES of fluorescence probe（10 mM）Solution (THF:HEPES=1:1, concentration and probe concentration 10
μM) in, fluorescence probe is higher to the response of benzenethiol in the range of 6-9 in pH, shows that this probe applicability is preferable.
Claims (7)
1. a kind of 3- phenyl benzoxazine ketone benzenethiol fluorescence probe, which is characterized in that be following structural formula（1）Shown change
Close object；
。
2. the preparation method of 3- phenyl benzoxazine ketone benzenethiol fluorescence probe as described in claim 1, it is characterised in that：Knot
Structure formula（2）Structural formula is made with the reaction of 2,4- dinitrophenyl chlorides in compound represented 7- hydroxyls -3- phenyl benzoxazinone
（1）Compound represented；
。
3. the preparation method of 3- phenyl benzoxazine ketone benzenethiol fluorescence probe as claimed in claim 2, it is characterised in that：Knot
Structure formula（2）Compound represented 7- hydroxyls -3- phenyl benzoxazinone is with 2,4- dinitrophenyl chlorides existing for triethylamine
Under the conditions of react in organic solvent.
4. the preparation method of 3- phenyl benzoxazine ketone benzenethiol fluorescence probe as claimed in claim 3, it is characterised in that：2,
The dosage of 4- dinitrophenyl chlorides is the 100%-150% of 7- hydroxyl -3- phenyl benzoxazinone dosages, and the dosage of triethylamine is
The 100%-600% of 7- hydroxyl -3- phenyl benzoxazinone dosages.
5. the preparation method of 3- phenyl benzoxazine ketone benzenethiol fluorescence probe as claimed in claim 3, it is characterised in that：Institute
Organic solvent is stated as tetrahydrofuran, dichloromethane or chloroform.
6. the preparation method of 3- phenyl benzoxazine ketone benzenethiol fluorescence probe as claimed in claim 3, it is characterised in that：Knot
Structure formula（2）Compound represented 7- hydroxyl -3- phenyl benzoxazinone, 2,4- dinitrophenyl chlorides and triethylamine sequentially add
Into reaction vessel, organic solvent dissolving is added in, when reaction 1-6 is small at room temperature.
7. 3- phenyl benzoxazine ketone benzenethiol fluorescence probe as described in claim 1 identifies and answering in detection in benzenethiol
With.
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