CN110016009A - A kind of hypochlorous acid fluorescence probe and preparation method thereof - Google Patents
A kind of hypochlorous acid fluorescence probe and preparation method thereof Download PDFInfo
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- CN110016009A CN110016009A CN201910403158.6A CN201910403158A CN110016009A CN 110016009 A CN110016009 A CN 110016009A CN 201910403158 A CN201910403158 A CN 201910403158A CN 110016009 A CN110016009 A CN 110016009A
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Abstract
The present invention relates to fluorescent probe technique fields more particularly to a kind of hypochlorous acid fluorescence probe and preparation method thereof.The present invention provides a kind of hypochlorous acid fluorescence probe, molecular formula C20H19NO2S, structural formula are shown in formula I.The present invention also provides the preparation methods of above-mentioned hypochlorous acid fluorescence probe, have obtained hypochlorous acid fluorescence probe by coupling reaction, substitution reaction and addition reaction respectively.A kind of hypochlorous acid fluorescence probe provided by the invention and preparation method thereof solves the technical problem that existing fluorescence probe sensitivity is low, poor selectivity and imaging applications are limited.
Description
Technical field
The present invention relates to fluorescent probe technique fields more particularly to a kind of hypochlorous acid fluorescence probe and preparation method thereof.
Background technique
Hypochlorous acid is by Cl-And H2O2Myeloperoxidase (myeloperoxidase) effect in biosystem is lower to be generated
The important active oxygen of one kind.Although concentration is extremely low in biosystem for hypochlorous acid, crucial work is played in immune defense
With.However, excessive hypochlorous acid can cause a series of and closely related disease of inflammation due to hypochlorous high response.Cause
This, the detection method for establishing a kind of satisfaction has a very important significance for detecting natural hypochlorous acid in living cells and living body.
Compared with other conventional methods, small-molecule fluorescent probe has sensitivity outstanding and height in bio-imaging application
Spatial and temporal resolution.In recent years, the hypochlorous acid fluorescence probe based on different identification receptors is devised.However although these are glimmering
Light probe have the advantages that in many aspects its uniqueness, but its still have low sensitivity, poor selectivity, vivo biodistribution imaging answer
With limited defect.
Summary of the invention
The present invention provides a kind of hypochlorous acid fluorescence probes and preparation method thereof, solve existing fluorescence probe sensitivity
Low, poor selectivity and the limited technical problem of imaging applications.
The present invention provides a kind of hypochlorous acid fluorescence probe, molecular formula C20H19NO2S, structural formula is shown in formula I,
The present invention also provides a kind of preparation methods of hypochlorous acid fluorescence probe, comprising the following steps:
Step 1: 4- (methylamino) phenol sulfate, tert-butyl chloro-silicane and imidazoles are obtained by substitution reaction
Step 2: willIt is obtained by coupling reaction
Step 3: willIt is obtained with tetrabutyl ammonium fluoride by substitution reaction
Step 4:3-mercaptoethanol, Trimethylsilyl trifluoromethanesulfonate andIt is logical
Addition reaction is crossed to obtain
Preferably, the molar ratio of 4- (methylamino) phenol sulfate, tert-butyl chloro-silicane and imidazoles is in step 1
1:1.2:4。
It preferably, further include that cesium carbonate, palladium acetate and 1,1 '-dinaphthalene -2,2 '-bis- diphenyl phosphines are added in step 2；
In step 2The cesium carbonate, the palladium acetate, described 1,
1 '-dinaphthalene -2,2 '-bis- diphenyl phosphines molar ratio is 1:2:4:0.05:0.06.
Preferably, in step 3Molar ratio with tetrabutyl ammonium fluoride is 1:3.
Preferably, in step 43-mercaptoethanol and Trimethylsilyl trifluoromethanesulfonate
Molar ratio is 1:2:0.1.
Compared with existing fluorescence probe, the hypochlorous acid fluorescence probe that the present invention synthesizes has the advantage that (1) synthesis is simple
Convenient, yield is high, easily prepared, is suitable for amplification synthesis and production application；(2) detection means is simple, it is only necessary to by glimmering
Photothermal spectroscopic analyzer can be realized.；(3) the hypochlorous acid probe has many advantages, such as the good, high sensitivity of selectivity to response；(4) have and ring
Fast, the apparent advantage of phenomenon is answered, is had broad application prospects.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the hypochlorous acid probe of preparation of the embodiment of the present invention；
Fig. 2 is the nuclear-magnetism carbon spectrogram of the hypochlorous acid probe of preparation of the embodiment of the present invention；
Fig. 3 is the UV absorption figure that the hypochlorous acid probe of preparation of the embodiment of the present invention is added before and after hypochlorous acid；
The fluorescence spectra before and after hypochlorous acid is added in the hypochlorous acid probe of Fig. 4 embodiment of the present invention preparation.
Fig. 5 is that other bioactive molecules and hypochlorous fluorescence intensity knot are added in the hypochlorous acid probe of preparation of the embodiment of the present invention
Fruit analysis chart.
Specific embodiment
The present invention provides a kind of hypochlorous acid fluorescence probes and preparation method thereof, solve existing fluorescence probe sensitivity
Low, poor selectivity and the limited technical problem of imaging applications.
In order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below in conjunction with the present invention
Attached drawing in embodiment, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that disclosed below
Embodiment be only a part of the embodiment of the present invention, and not all embodiment.Based on the embodiments of the present invention, this field
Those of ordinary skill's all other embodiment obtained without making creative work, belongs to protection of the present invention
Range.
Embodiment 1
Step 1: respectively by 4- (methylamino) phenol sulfate 2.07g (6mmol), tert-butyl chloro-silicane 1.09g
(7.2mmol) and imidazoles 1.6g (24mmol) are added in the round-bottomed flask of 50ml, and 20ml methylene chloride are added as solvent,
It is stirred at room temperature and TLC is used to monitor.After reaction, reaction solution is washed three times with saturated common salt, and anhydrous sodium sulfate is dry
1h filters and is removed under reduced pressure solvent, obtains crude product, is then purified by silica gel column chromatography that (eluant, eluent is ethyl acetate: petroleum ether
=1:40) after, obtain 4- ((t-butyldimethylsilyl) oxygroup)-methylphenylamine, i.e. compound 4,1.28g, yield
It is 90%.
Reaction equation in step 1 are as follows:
Step 2: by the compound 4 of 950mg (4mmol), the bromo- 2 naphthaldehyde 470mg (2mmol) of 6-, 1,1 '-dinaphthalene -2,
2 '-bis- diphenyl phosphine 75mg (0.12mmol), palladium acetate 22.4mg (0.1mmol), cesium carbonate 2.6g (8mmol) are added to and are equipped with
In the bottle with two necks of reflux unit, deoxygenation is passed through dry toluene solution as solvent, back flow reaction 3h, TLC prison under the conditions of argon gas
It surveys.Partial solvent is removed under reduced pressure after the reaction was completed, mixed liquor is dissolved with methylene chloride again, is washed with saturated common salt, anhydrous slufuric acid
Sodium is dry, filters and by the way that solvent is removed under reduced pressure, and obtains crude product, is purified by silica gel column chromatography that (eluant, eluent is ethyl acetate: stone
Oily ether=1:20), 6- ((4- ((t-butyldimethylsilyi) oxygroup) phenyl) (methyl) amino) -2- naphthaldehyde is obtained, i.e.,
Compound 3,728mg, yield 93%.
The reaction equation of step 2 are as follows:
Step 3: the compound 3 of 391mg (1mmol) being added in the round-bottomed flask of 25ml, 10ml tetrahydrofuran is added
Solution adds 3ml (3mmol) TBAF (tetrabutyl ammonium fluoride), stirs 30min at room temperature, monitored by TLC as solvent,
Reaction solution adds methylene chloride dissolution, is washed with saturated common salt, anhydrous sodium sulfate is dry, filters by the way that solvent is removed under reduced pressure
And by the way that solvent is removed under reduced pressure, crude product is obtained, be then purified by silica gel column chromatography (eluant, eluent: ethyl acetate: petroleum ether: 1:
10) 6- ((4- hydroxy phenyl) (methyl) amino) -2- naphthaldehyde, i.e. compound 2,213mg, yield 59% are obtained.
The reaction equation of step 3 are as follows:
Step 4: 139mg (0.5mmol) compound 2 being added in 10ml round-bottomed flask, 8ml dichloromethane solution is added
As solvent, under the conditions of argon gas, 69ul (1mmol) 3-mercaptoethanol, 9ul (0.05mmol) trifluoromethanesulfonic acid trimethyl silicane is added
Ester stirs 1h, TLC monitoring at room temperature.After the reaction was completed, reaction solution is used and salt washing, anhydrous sodium sulfate drying filter and lead to
It crosses and solvent is removed under reduced pressure, obtain crude product, be purified by silica gel column chromatography (eluant, eluent: ethyl acetate: petroleum ether: 1:10) and obtain 4-
(((6- (1,3- tetrahydrofuran -2- base) cycloalkanes -2- base) (methyl) amino) phenol, i.e. hypochlorous acid fluorescent probe molecule 1.
The reaction equation of step 4 are as follows:
Fig. 1 and Fig. 2 is respectively the hypochlorous acid fluorescence probe of preparation of the embodiment of the present invention1H NMR figure and13C NMR figure；
1H NMR (400MHz, CDCl3): δ 7.73 (s, 1H), 7.66 (d, 1H, J=8.56Hz), 7.58 (d, 1H, J=
8.99Hz), 7.50 (d, 1H, J=6.84Hz), 7.08 (d, 2H, J=8.79Hz), 7.04 (s, 1H), 7.02 (dd, 1H, J=
2.43,8.96Hz), 6.84 (d, 1H, J=8.80Hz), 6.17 (s, 1H), 4.77 (S, 1H), 4.57 (m, 1H), 4.00 (m,
1H), 3.34 (S, 1H), 3.31 (m, 1H), 3.22 (m, 1H).
13C NMR (400MHz, CDCl3): δ 152.84,171.91,142.03,135.03,132.76,128.53,
127.05,127.00,126.94,125.75,124.93,119.27,116., 41,108.72,88.70,71.97,40.91,
34.16。
To sum up, 3 μ l fluorescent probe molecule stock solutions (1mM) are added in 3mlPBS buffer solution (0.01M, pH7.4), with
3ul ClO- stock solution (100mM) is added dropwise afterwards, fluorescence intensity change is recorded, from the figure 3, it may be seen that fluorescent probe molecule is at 311nm
There is a very strong absorption peak, ClO is added-Afterwards.Absorption peak at 311nm disappears, and occurs a new absorption peak at 378nm.
Illustrate that probe molecule can be reacted with hypochlorite ion.
For test hypochlorous acid fluorescent probe molecule fluorescence intensity change under the conditions of different hypochlorous acid concentrations research,
3ul fluorescence probe stock solution (1mM) is added in 3mlPBS buffer (0.01M, pH7.4), then is separately added into 3ul various concentration
ClO-(10,20,30,40,50,60,70,80,90,100mM) have studied its fluorescence intensity change, as shown in Figure 4, with ClO-
The increase of concentration, the fluorescence intensity at 518nm gradually increase.When being added hypochlorous final concentration of 100 μM, the hypochlorous acid is glimmering
The increased times of light probe molecule can reach 1100 times.
It is test hypochlorous acid fluorescent probe molecule to other bioactive molecules and hypochlorous selectivity, is buffered in 3ml PBS
3 μ l fluorescence probe stock solutions (1mM) are added in solution (0.01M, pH7.4), then are separately added into 3 μ l hypochlorous acid (10mM) and various
Common bioactive small molecule (50mM), as cysteine, homocysteine, glutathione, ferrous ion, potassium ion,
Sulfite ion, nitrite ion, tert-butyl alcohol hydrogen peroxide, hydroxyl radical free radical, superoxide anion, peroxinitrites from
Son measures itself and the change in fluorescence after probe reaction respectively.As shown in Figure 5, when hypochlorous acid is only added, hypochlorous acid fluorescence probe
Significant change can just occur for the fluorescence intensity of molecule.Illustrate that the probe has selectivity well.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding
Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (6)
1. a kind of hypochlorous acid fluorescence probe, which is characterized in that its molecular formula is C20H19NO2S, structural formula is shown in formula I,
2. a kind of preparation method of hypochlorous acid fluorescence probe, which comprises the following steps:
Step 1: 4- (methylamino) phenol sulfate, tert-butyl chloro-silicane and imidazoles are obtained by substitution reaction
Step 2: willIt is obtained by coupling reaction
Step 3: willIt is obtained with tetrabutyl ammonium fluoride by substitution reaction
Step 4:3-mercaptoethanol, Trimethylsilyl trifluoromethanesulfonate andBy adding
It is obtained at reaction
3. preparation method according to claim 2, which is characterized in that 4- (methylamino) phenol sulfate, tertiary fourth in step 1
The molar ratio of base dimethylchlorosilane and imidazoles is 1:1.2:4.
4. preparation method according to claim 2, which is characterized in that further include in step 2 be added cesium carbonate, palladium acetate and
1,1 '-dinaphthalenes -2,2 '-bis- diphenyl phosphines；
In step 2The cesium carbonate, the palladium acetate, described 1,1 '-
Dinaphthalene -2,2 '-bis- diphenyl phosphines molar ratio is 1:2:4:0.05:0.06.
5. preparation method according to claim 2, which is characterized in that in step 3
Molar ratio with tetrabutyl ammonium fluoride is 1:3.
6. preparation method according to claim 2, which is characterized in that in step 4Two mercaptos
The molar ratio of base ethyl alcohol and Trimethylsilyl trifluoromethanesulfonate is 1:2:0.1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880821A (en) * | 2021-10-29 | 2022-01-04 | 南京碳硅人工智能生物医药技术研究院有限公司 | Design and synthesis method of fluorescent probe for imaging epileptic intracerebral hypochlorous acid characteristics by two-photon fluorescent probe |
-
2019
- 2019-05-15 CN CN201910403158.6A patent/CN110016009B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| JINHEE PARK: "Two-photon fluorescent probe for peroxynitrite", 《TETRAHEDRON LETTERS》 * |
| LIN YUAN: "Development of Targetable Two-Photon Fluorescent Probes to Image Hypochlorous Acid in Mitochondria and Lysosome in Live Cell and Inflamed Mouse Model", 《J. AM. CHEM. SOC.》 * |
| YONG ZHOU: "Responsive mechanism of three novel hypochlorous acid fluorescent probes and solvent effect on their sensing performance", 《CHIN. PHYS. B》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880821A (en) * | 2021-10-29 | 2022-01-04 | 南京碳硅人工智能生物医药技术研究院有限公司 | Design and synthesis method of fluorescent probe for imaging epileptic intracerebral hypochlorous acid characteristics by two-photon fluorescent probe |
| CN113880821B (en) * | 2021-10-29 | 2024-03-12 | 南京碳硅人工智能生物医药技术研究院有限公司 | Fluorescent probe design for epileptic intracerebral hypochlorous acid characteristic imaging by two-photon fluorescent probe and synthetic method thereof |
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