CN103923640B - A kind of fluorescence probe and application thereof of benzothiazoles identification hydrogen sulfide - Google Patents
A kind of fluorescence probe and application thereof of benzothiazoles identification hydrogen sulfide Download PDFInfo
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Abstract
Fluorescence probe and the application thereof of benzothiazoles identification hydrogen sulfide, it belongs to field of fine chemical. This fluorescence probe is 2-(2-hydroxy phenyl) benzothiazole derivant; Proportionally, by 2-(2-hydroxy phenyl) benzothiazole and potash, 2,4-binitro bromobenzene mixes, and finally adopts silica gel chromatography to carry out purifying, obtains fluorescence probe. This fluorescence probe and corresponding hydrogen sulfide content testing process can not be subject to the interference of living things system matrix and impurity, can be used for the quantitative assay of hydrogen sulfide content in various living things systems. This should have high specific by probe, can with the cyclisation of hydrogen sulfide specificity after be hydrolyzed, i.e. the hydrolysate of ether bond rupture; Cheap and easy to get, can obtain through chemical synthesis, synthesis technique is simple; Highly sensitive, there is good fluorescence emission spectral property (450～500nm), carry out hydrogen sulfide quantitative assay by drawing standard curve.
Description
Technical field
The present invention relates to a kind of fluorescence probe and application thereof of benzothiazoles identification hydrogen sulfide, it belongs to fine chemistry industry neckTerritory.
Background technology
For centuries, hydrogen sulfide (H2S) be considered to poisonous by the one of geology activity or microbial action generationMaterial. This colourless, flammable gas has brackish rotten egg smell, and can and breathe system to mammiferous eyesSystem produces strong impulse effect. Suck excessive hydrogen sulfide gas and can cause that the loss of consciousness, respiratory failure, heartbeat stop etc.Physiological reaction, can cause death when uptake is excessive. On the other hand, more and more research is own through starting to challenge this tradition nowIdea: mammal self can produce hydrogen sulfide under controlled condition, and think sulfuration oxygen for maintaining normal lifeReason function has important function. In mammal body, hydrogen sulfide can be produced by non-enzyme effect, comprise sulphur storehouse in body release andThe metabolism of polysulfides etc. Also can be participated in catalyzing and synthesizing by plurality of enzymes, comprise cystathionie-polymerase (CBS), cystathionie-splittingSeparate enzyme (CSE), cysteine transferase and thin benzylacetone acid transsulfurase. These enzymes can be by the life of different catalytic reaction sulfur-bearingsThing molecule is as the generation such as cysteine, high cysteine hydrogen sulfide. These several enzymes appear at heart, vascular system, brain, kidney,In the tissue of the multiple organ such as lung and pancreas, illustrate that the distribution of sulfuration oxygen in mammalian body is very extensive.
In mammalian body, hydrogen sulfide can be with downstream egg white matter by the cysteine generation mercaptolation after translatingAnd be connected in the iron of ferroheme in the heart. This process will be controlled multiple physiological reaction, comprise what ischemia reperfusion causedDamage, vasodilation, cell death, Angiogenesis, nerve regulation, inflammation treatment, insulin signaling conduction and oxygen stress wait.In addition, hydrogen sulfide is also as the antioxidant of active oxygen or scavenger and play a role. But H2The concentration level of S is undesired ownBe proved relevant with a lot of diseases. The experiment of these initiatives shown hydrogen sulfide be a kind of important physiological regulating control gas andIt is not merely a kind of pollutant. It is new that the physiology role of hydrogen sulfide complexity and potential treatment application impel researcher to proposeMethod is for monitoring the generation, circulation of hydrogen sulfide and at different cells, tissue and intraorganic consumption process.
Tradition comprises that for detection of the method for hydrogen sulfide colorimetric method, polarogram sensing method and gas chromatography can draw conventionallyPlay the damage of testing sample, or can not realize the detection to sulfide in organism at all. Fluorescent molecular probe provides oneThe method of the individual note that induces one, because it has permeability of cell membrane and high selectivity, thereby can realize in living things system sulfurationThe micromolecular detection of hydrogen and other biological. XRF will provide important biology letter for the physiological function of research hydrogen sulfideBreath. If the report detecting about hydrogen sulfide light over the past two years, is subject to showing great attention to of research worker.
The invention provides a class 2-(2-hydroxy phenyl) benzothiazole derivant is for specific recognition hydrogen sulfide (H2S）Probe, after the hydrolysis of itself and hydrogen sulfide, can generate the hydrolysate with fluorescence properties. This reaction has high selectivity, highly sensitiveDegree, willing feature.
Summary of the invention
The object of the present invention is to provide a kind of specificity fluorescent probe of identifying hydrogen sulfide, this probe itself has faintFluorescence, with hydrogen sulfide (H2S) reaction afterproduct has extremely strong fluorescence properties. Utilize this probe reaction can be to multiple biological sampleHydrogen sulfide (H in this2S) content carries out quantitative assessment.
Technical scheme of the present invention is: a kind of fluorescence probe of benzothiazoles identification hydrogen sulfide, described fluorescence probe is2-(2-hydroxy phenyl) benzothiazole derivant, its structural formula is as follows:
The preparation method of described fluorescence probe comprises the steps:
(1) according to 2-(2-hydroxy phenyl) benzothiazole: 2,4-binitro bromobenzene: potash mol ratio is 1:1 ~ 2:2 ~ 3Ratio join in reaction bulb, add acetonitrile, control reaction temperature at 40 ~ 80 DEG C, stir 8-12h;
(2) by above-mentioned reactant liquor process removal of solvent under reduced pressure, residual solid adopts silica gel chromatography to carry out purifying, adoptsEthyl acetate: the eluant, eluent that n-hexane volume ratio is 1:3 carries out wash-out, obtains fluorescence probe
Described fluorescence probe is applied to the quantitative assessment of hydrogen sulfide content in biological specimen. This probe is as the spy of hydrogen sulfide, there is hydrolysis in opposite sex probe, measures the content of hydrogen sulfide in cell by the fluorescence intensity of quantitative detection hydrolysate;Concrete assay method is:
In system using 2-(2-hydroxy phenyl) benzothiazole derivant is as specific probe; Concentration and probe concentration is selected 1/ ~ 10 μM; At the conventional buffer solution such as PBS or Tris-HCl: in dimethyl sulfoxide (DMSO) mixed solution (volume ratio 7:3), reaction temperature is 20 DEG CBetween 60 DEG C, preferably 37 DEG C is the peak optimization reaction time; Reaction system pH is between 5.5 ~ 10.5, and preferably pH7.4 is optimumPH value in reaction; Reaction time is 5 ~ 120 minutes; Measure the evaluation index of hydrolysate fluorescence intensity as hydrogen sulfide content.
Probe itself has faint fluorescence, and its hydrolysate all has extremely strong fluorescence, can adopt fluorescence detector to realizeThe rapid sensitive of product and substrate detects; Fluoroscopic examination condition is: excitation wavelength 300nm, carries out fluorescence at 450 ~ 500nm and sends outPenetrate the detection of spectrum.
Beneficial effect of the present invention is: this fluorescence probe is 2-(2-hydroxy phenyl) benzothiazole derivant; According to thanExample is by 2-(2-hydroxy phenyl) benzothiazole sodium salt and potash, 2,4-binitro bromobenzene mixes, and adds N, N-dimethyl formylAmine, heating, finally adopts silica gel chromatography to carry out purifying, obtains fluorescence probe. This fluorescence probe and corresponding hydrogen sulfide content detectProcess can not be subject to the interference of living things system matrix and impurity, can be used for the quantitative assay of hydrogen sulfide content in various living things systems.This should have high specific by probe, can with the cyclisation of hydrogen sulfide specificity after be hydrolyzed, i.e. the hydrolysate of ether bond rupture;Cheap and easy to get, can obtain through chemical synthesis, synthesis technique is simple; Highly sensitive, there is good fluorescence emission spectrum spyProperty (450～500nm), carries out hydrogen sulfide quantitative assay by drawing standard curve.
Brief description of the drawings
Fig. 1 is 2-(2(2,4-dinitrophenoxy)) benzothiazole1H-NMR spectrogram.
Fig. 2 is 2-(2(2,4-dinitrophenoxy)) benzothiazole13C-NMR spectrogram.
Fig. 3 is 2-(2(2,4-dinitrophenoxy)) high resolution mass spectrum of benzothiazole.
Fig. 4 is change in fluorescence result after fluorescence probe reacts with different material.
Fig. 5 is fluorescence intensity change curve after fluorescence probe reacts with variable concentrations hydrogen sulfide.
Fig. 6 is fluorescence probe reacts fluorescence intensity change and time relation with hydrogen sulfide.
Fig. 7 is co-focusing imaging figure.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 12-(2(2,4-dinitrophenoxy)) chemical synthesis of benzothiazole
(1) by the 2-(2-hydroxy phenyl of 0.5mmol) benzothiazole and 0.625mmol potash, 0.5mmol2,4-Binitro bromobenzene is dissolved in 10mL acetonitrile, at 80 DEG C of reaction 4h;
(2) reactant liquor is carried out to decompression distillation;
(3) solid adopts silica gel chromatography to carry out purifying, adopts ethyl acetate-n-hexane (1:3v/v) to carry out wash-out,Obtain faint yellow solid, characterization result is shown in Fig. 1, Fig. 2 and Fig. 3.1HNMR(400MHz,DMSO)δ8.98(d,J=2.8Hz,1H),8.50(dd,J=7.9,1.6Hz,1H),8.42(dd,J=9.3,2.8Hz,1H),8.11(d,J=8.0Hz,1H),8.04(d,J=8.1Hz,1H),7.79–7.68(m,1H),7.66–7.51(m,2H),7.47(dd,J=14.4,7.5Hz,2H),7.24(d,J=9.3Hz,1H).13CNMR(100MHz,CDCl3)δ160.87,155.66,152.67,150.68,141.78,139.54,135.50,132.51,131.30,128.99,127.45,126.60,126.56,125.72,123.46,122.25,122.13,121.52,117.80.HRMScalcdforC16H14NO5+([M+H]+)394.0492,found394.0501。
Embodiment 22-(2(2,4-dinitrophenoxy)) benzothiazole is selective for different material
(1) prepare 99 μ l metabolic response systems in advance, comprise the PBS buffer solution (10mM) of pH7.4: dimethyl AsiaSulfone (volume ratio 7:3), fluorine ion (100 μ M), chlorion (50 μ M), bromide ion (100 μ M), iodide ion (100 μ M), sodium ion(100 μ M), potassium ion (100 μ M), calcium ion (100 μ M), magnesium ion (100 μ M), nitrate ion (100 μ M), NaHS（100μM）；
(2) be 10 μ M2-(2(2 to adding 1 μ l final concentration in reaction system, 4-dinitrophenoxy)) benzothiazoleInitial action;
(3), after 30min, carry out fluoroscopic examination (λEx=300nm，λEm=458nm); Calculate fluorescence intensity in each system(see figure 4).
Embodiment 32-(2(2,4-dinitrophenoxy)) benzothiazole and concentration of hydrogen sulfide linear relationship
(1) prepare 99 μ l metabolic response systems in advance, comprise the PBS buffer solution (10mM) of pH7.4: dimethyl AsiaSulfone (volume ratio 7:3), hydrogen sulfide (0-100 μ M) reacts 30 minutes under 37 DEG C of conditions;
(2 is 10 μ M2-(2(2 to adding 1 μ l final concentration in reaction system, 4-dinitrophenoxy)) benzothiazole risesBegin to react;
(3), after 30min, carry out fluoroscopic examination (λEx=300nm，λEm=458nm); Calculate fluorescence intensity in each system,Set up fluorescence intensity and concentration of hydrogen sulfide calibration curve (see figure 5); Calibration curve is y=3695.9x-373.09, R2=0.9931, wherein, y represents 458nm place fluorescence intensity, and x represents NaHS concentration, and (hydrazine concentration is between 0uM to 100uMLinear relationship meets).
Embodiment 42-(2(2,4-dinitrophenoxy)) benzothiazole is that probe reacts fluorescence intensity change with hydrogen sulfideRelation with the time
(1) prepare 99 μ l metabolic response systems in advance, comprise the PBS buffer solution (10mM) of pH7.4: dimethyl AsiaSulfone (volume ratio 7:3), hydrogen sulfide (200 μ M) reacts 30 minutes under 37 DEG C of conditions;
(2 is 10 μ M2-(2(2 to adding 1 μ l final concentration in reaction system, 4-dinitrophenoxy)) benzothiazole risesBegin to react;
(3), after 30min, carry out fluoroscopic examination (λEx=300nm，λEm=458nm); Calculate fluorescence intensity in each system,Set up fluorescence intensity and hydrogen sulfide reaction time linear relationship curve (see figure 6).
Hydrogen sulfide content in embodiment 5 quantitative assay human lung adenocarcinoma A549 cells
(1) human lung adenocarcinoma A549 clone is incubated on cover glass, and the culture medium of employing is that DMEM culture medium is (little containing 10%Cow's serum) and 100 μ g/ml's is dual anti-, culture environment is in 5% CO2gas incubator of 37 DEG C;
(2) before using, attached cell adopts the not DMEM culture medium containing serum to rinse 3 times, and adding final concentration is 10 μ M2-(2(2,4-dinitrophenoxy)) benzothiazole, incubate 40 minutes in 37 DEG C of temperature;
(3) afterwards, adopt PBS buffer solution to rinse 3 times. Observation of cell under laser confocal microscope, divides by fluorescenceCloth position and intensity are carried out content (see figure 7) in showed cell.
Hydrogen sulfide content in embodiment 6 quantitative assay human bloods
(1) to 380 μ l through PBS: in 10% human normal plasma of dimethyl sulphoxide solution (volume ratio 7:3) dilution, addThe final concentration of hydrogen sulfide of 20 μ l is respectively 0 μ M, 50 μ M, 100 μ M, 150 μ M, 200 μ M, 250 μ M, 300 μ M hydrogen sulfide solutions;
(2) be 10 μ M2-(2(2 to adding 1 μ l final concentration in reaction system, 4-dinitrophenoxy)) benzothiazoleInitial action;
(3) carry out fluoroscopic examination (λEx=300nm，λEm=458nm); Calculate signal to noise ratio S/N > 10, detect different hydrogen sulfideFluorescence intensity signals in content blood plasma.
Claims (2)
1. a fluorescence probe for benzothiazoles identification hydrogen sulfide, is characterized in that: described fluorescence probe is 2-(2-hydroxy benzenesBase) benzothiazole sodium salt derivative, its structural formula is as follows:
The preparation method of described fluorescence probe comprises the steps:
(1) according to 2-(2-hydroxy phenyl) benzothiazole: 2,4-binitro bromobenzene: the ratio that potash mol ratio is 1:1 ~ 2:2 ~ 3Example joins in reaction bulb, adds acetonitrile, controls reaction temperature at 40 ~ 80 DEG C, stirs 8-12h;
(2) by above-mentioned reactant liquor process removal of solvent under reduced pressure, residual solid adopts silica gel chromatography to carry out purifying, adopts acetic acidEthyl ester: the eluant, eluent that n-hexane volume ratio is 1:3 carries out wash-out, obtains fluorescence probe.
2. the fluorescence probe of a kind of benzothiazoles identification hydrogen sulfide according to claim 1, is characterized in that: described glimmeringLight probe is applied to the quantitative assessment of hydrogen sulfide content in biological specimen, and concentration of hydrogen sulfide is 0-100 μ M, sets up fluorescence intensityWith concentration of hydrogen sulfide calibration curve, calibration curve is y=3695.9x-373.09, R2=0.9931, wherein, y representative458nm place fluorescence intensity, x represents NaHS concentration.
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| CN104479669A (en) * | 2014-11-18 | 2015-04-01 | 辽宁大学 | Preparation method and applications of enhanced type fluorescent probe for detecting hydrogen sulfide |
| CN104449677B (en) * | 2014-12-29 | 2017-02-22 | 大连理工常熟研究院有限公司 | Specific fluorescent probe for recognizing fluorine ions and application of specific fluorescent probe |
| CN105086995A (en) * | 2015-05-21 | 2015-11-25 | 湖南城市学院 | Preparation and application of probe for hydrogen sulfide (H2S) based on protection-deprotection mechanism |
| CN106083760B (en) * | 2016-02-16 | 2018-09-14 | 中国科学院理化技术研究所 | Fluorescent chemical sensor capable of selectively detecting hydrogen sulfide, preparation method and application |
| CN106496217A (en) * | 2016-10-31 | 2017-03-15 | 湖南师范大学 | A kind of new detection H2The preparation method and application of S fluorescent molecular probes |
| CN107782707B (en) * | 2017-10-12 | 2020-07-17 | 华南师范大学 | Application of triphenylthiazolyl benzene in fluorescence detection of nitro aromatic explosives |
| CN111072650B (en) * | 2018-10-22 | 2021-04-06 | 北京工商大学 | Benzothiazole hydrogen sulfide fluorescent probe |
| CN111116433A (en) * | 2018-10-31 | 2020-05-08 | 北京工商大学 | Double-recognition-site hydrogen sulfide fluorescent probe |
| CN112876425B (en) * | 2021-02-06 | 2022-05-06 | 许昌学院 | Hydrogen sulfide fluorescent probe and preparation method and application thereof |
| CN115160237A (en) * | 2022-08-03 | 2022-10-11 | 王威 | Fluorescent probe for detecting hydrogen sulfide and preparation method and application thereof |
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