CN110669503B - Preparation and application of carbon monoxide near-infrared fluorescent probe - Google Patents
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Abstract
The invention relates to preparation and application of a carbon monoxide (CO) near-infrared fluorescent probe, wherein the structural formula of the probe is as follows:
the invention provides a preparation method for synthesizing the fluorescent probe by taking benzopyran nitrile-xanthene dye, triethylamine, allyl chloroformate and the like as raw materials; the fluorescent probe is a carbon monoxide fluorescent probe with near infrared emission and large Stokes displacement; firstly, the fluorescent probe shows high sensitivity to CO, and the fluorescence intensity is enhanced by 21 times; secondly, the fluorescent probe shows high selectivity to CO and is not interfered by other active oxygen, active nitrogen, various ions, biological thiol and amino acid; moreover, the fluorescent probe has rapid action with CO, and the response time is within 10 min; in addition, the fluorescent probe is applied to the detection of the content of carbon monoxide in living cells.
Description
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to preparation and application of a carbon monoxide fluorescent probe based on benzopyran nitrile-xanthene dye.
Background
Carbon monoxide (CO) is a colorless and odorless gas that competes with oxygen for binding to hemoglobin in the body, thereby preventing normal oxygen transport (l.k.weaver, n.engl.j.med.2009,360, 1217-1225). Carbon monoxide has long been recognized as a toxic and harmful substance if excessive intake of exogenous carbon monoxide can lead to carbon monoxide poisoning in living organisms. However, a great deal of scientific evidence suggests that carbon monoxide is like Nitric Oxide (NO) and hydrogen sulfide (H) 2 S), as well, play an important role in the body as gas transport agents and in various physiological and pathological processes (f.watel, r.farry, s.lancel, r.neviere, d.mathieu, fill.acad.natl.med.2006, 190,1961-1975; L.Y.Wu, R.Wang, Pharmacol. Rev.2005,57, 585-630). Furthermore, abnormal endogenous CO concentrations are closely associated with the development of various diseases, such as: alzheimer's disease, hypertension, inflammation and heart failure, etc. (D.R.Premkumar, M.A.Smith, P.L.Richey, R.B.petersen, R.Castellani, R.K.Kutty, J.Neurochem.1995,65,1399-1402, R.A.Schroeder, C.A.Ewing, J.V.Sitzmann, P.C.Kuo, dig.Dis.Sci.2000,45,2405-2410 I.T.Lee, S.F.Luo, C.W.Lee, S.W.Wang, C.C.Lin, C.C.Chang, am.J.Pathol.2009,175,519-532, V.S.Raju, N.AI, C.Liang, J.M.1.31, 1589-1589, cell 1581, 1589, U.S.W.S.W.Lee. Therefore, it is very important to develop a convenient and reliable method for real-time detection of CO in biological systems.
Conventional methods for detecting CO include electrochemical methods, gas chromatography, and colorimetric methods, which are not suitable for real-time, dynamic CO observation in living cells and living bodies. Fluorescent methods are of interest because of their many advantages, including ease of operation, good selectivity, high sensitivity, good membrane permeability, etc. (h.kobayashi, m.ogawa, r.alford, p.l.choyke, y.urano, chem.rev.2010,110,2620-2640, x.li, x.gao, w.shi, h.ma, chem.rev.2014,114, 590-659.. To date, several fluorescent probes for detecting CO have been developed for monitoring changes in CO in cells or in vivo in real time (w.feng, d.liu, q.zhai, g.feng, sens.activators b.2017,240,625-630, w.feng, d.liu, s.feng, g.feng, anal.chem.2016,88,10648-10653, s.feng, d.liu, w.feng, g.feng, anal.chem.2017,89,3754-3760, w.feng, j.hong, g.fen, sens.activators b.2017,251, 389-395.. However, these carbon monoxide fluorescent probes still have some disadvantages: the emission wavelength of the fluorescent probe is short, and the Stokes shift is small. This makes the probe susceptible to interference from self-background fluorescence and is not conducive to deep tissue and in vivo imaging detection. Therefore, it is crucial to design a near infrared fluorescent probe having a large stokes shift.
The benzopyranone-xanthene has the advantages of large Stokes shift, high fluorescence quantum yield and the like as a novel fluorescent dye. In particular, the dye has near infrared emission, so that the dye has a deeper tissue penetration depth, is not easily interfered by biological autofluorescence, and is more beneficial to biological imaging. It has been found that fluorescent probes using benzopyranonitrile-xanthene dyes have been successfully used to detect some targets, such as: cys, HNO, etc. (Y.Qi, Y.Huang, B.Li, F.Zeng, S.Z.Wu, anal.chem.2018,90,1014-1020 C.X.Zhang, M.H.Xian, X.J.Liu, F.Wang, R.Q.Yu, J.H.Jiang, talanta.2019,193, 152-160). However, CO has not been detected so far based on this dye as a fluorescent probe. Therefore, it is very necessary to design and synthesize a fluorescent probe based on benzopyran nitrile-xanthene dye to detect CO.
Disclosure of Invention
In light of the proposed requirements, the present inventors have conducted intensive studies to provide a carbon monoxide near infrared fluorescent probe based on a benzopyran nitrile-xanthene dye after a great deal of creative work.
The invention adopts the technical scheme that a carbon monoxide near-infrared fluorescent probe has the following structural formula:
a method for preparing a carbon monoxide near-infrared fluorescent probe. The method comprises the following steps:
in N 2 Under protection, 0.5 equivalent of DCX-OH,2.0 to 3.0 equivalents of allyl chloroformate and 2.0 to 3.0 equivalents of triethylamine are dissolved in 8 to 12mL of THF in a 25mL round bottom flask, then the reaction is stirred at room temperature overnight, and after the reaction is finished, water is added for dilution, CH is used for reaction 2 Cl 2 The organic layer was washed with brine and then with anhydrous Na 2 SO 4 Drying, filtering and concentrating, the crude product is treated with CH 2 Cl 2 And purifying by silica gel column chromatography as eluent to obtain a dark green solid product DCX-CO, namely the fluorescent probe.
The invention has the beneficial effect that the carbon monoxide near-infrared fluorescent probe based on the benzopyranonitrile-xanthene dye has good spectral response performance. First, the fluorescence spectrum properties of the probe were investigated. The probe itself or added Pd 2+ After that, there was no evidence at 762nmNear infrared emission peak of (a); when Pd is added to the probe 2+ And CO, a distinct near-infrared emission peak at 762nm was observed. And the near infrared fluorescence intensity of the probe is continuously enhanced along with the increase of the CO concentration. Next, the ultraviolet absorption spectrum of the probe was investigated. The probe has an absorption band at 549nm, and Pd is added 2+ After that, the absorption peak was not significantly changed. Adding Pd simultaneously 2+ And CO, the UV absorption peak at 549nm gradually decreased, and a new strong absorption peak at 598nm appeared. Then, the selectivity of the probe was investigated to examine the probe and various metal ions (Na) + ,K + ,Mg 2+ ,Ca 2+ ) And biological thiols (Cys, hcy, GSH), amino acids (Lys, glu, ala), active oxygen (ONOO) - ,H 2 O 2 ,·OH,ClO - ,O 2 - ) Active nitrogen (NO, NO) 2 - ,NO 3 - ) And the fluorescence response of the detector (CO). As a result, it was found that only CO caused the change in the fluorescence spectrum, and that the other analytes had no significant effect on the fluorescence spectrum of the probe. Finally, the effect of pH on the CO measurement by the fluorescent probe was investigated, and the CO measurement by the fluorescent probe was not affected when the pH was between 7.0 and 9.0. In addition, the fluorescent probe has a relatively quick response, and the response time is within 10 minutes.
An application of a carbon monoxide near-infrared fluorescent probe. After the cells are cultured in normal environment, the fluorescent probe and Pd are added 2+ After that, almost no fluorescence generation was observed. Then, exogenous CO cell imaging is carried out, CORM-3 (carbon monoxide releasing agent) is added into the cells for incubation, and then a fluorescent probe and Pd are added 2+ Confocal fluorescence imaging was then performed and significant fluorescence generation was observed. Then, the cells were treated with heme (which stimulates CO production) for cellular imaging of endogenous CO, and the addition of fluorescent probes and PdCl was found 2 After that, the near infrared fluorescence enhancement was clearly observed. These results indicate that the fluorescent probe can detect the CO produced in the cell, which provides a reliable means for monitoring CO changes in the relevant pathological processes in vivo.
Drawings
FIG. 1 shows a synthetic route of a fluorescent probe.
FIG. 2 is a fluorescence spectrum of a fluorescent probe after the probe is reacted with CO at different concentrations.
The abscissa is wavelength and the ordinate is fluorescence intensity. Fluorescent probe and Pd 2+ The concentrations of (A) and (B) are 10. Mu.M, and the concentrations of CO are respectively as follows: 0,1,5,10,20,30,40,50,60,70,80,90, 100. Mu.M. The emission wavelength was 762nm, corresponding to an excitation wavelength of 598nm.
FIG. 3 is a graph showing the linear response of fluorescent probe to different CO concentrations.
FIG. 4 shows a fluorescent probe and Pd 2+ And ultraviolet-visible absorption spectrogram after CO action.
The abscissa is wavelength and the ordinate is absorbance. Fluorescent probe and Pd 2+ The concentrations of (A) and (B) were all 10. Mu.M, and the CO concentration was 100. Mu.M.
FIG. 5 is a graph showing selectivity of fluorescent probes.
Fluorescent probe and Pd 2+ Concentrations of (A) were all 10. Mu.M, CO concentrations were 100. Mu.M, and other analyte concentrations were all 200. Mu.M.
FIG. 6 is a graph showing the effect of pH on fluorescent probes.
FIG. 7 is a graph showing the relationship between the fluorescence intensity of the fluorescent probe and the change with time after the CO reaction.
FIG. 8 is a graph showing cytotoxicity test. The abscissa is the concentration of the fluorescent probe and the ordinate is the survival rate of the cells.
FIG. 9 is an image of the cell image of the fluorescent probe and CO interaction. (a) cells were stained with probe for 0.5h. (b) Probe and Pd for simultaneous use in cells 2+ And dyeing for 0.5h. (c) After incubation of cells with CORM-3, the probes and Pd were used 2+ And dyeing for 0.5h. (d) Cells were treated with Heme for 4h, then with both probe and Pd 2+ And dyeing for 0.5h.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but is not limited thereto.
Example 1:
synthesis of fluorescent probes
The synthetic route is shown in figure 1. In N 2 In a 25mL round-bottom flask, under protection, DCX-OH (209mg, 0.5 mmol), chloromethylAllyl sulfate (240mg, 2.0 mmol) and triethylamine (200mg, 2.0 mmol) were dissolved in 10mL of THF, and the reaction was stirred at room temperature overnight, after completion of the reaction, diluted with water and added with CH 2 Cl 2 Extraction, washing the organic layer with brine, and then with anhydrous Na 2 SO 4 Drying, filtering and concentrating, purifying the crude product by silica gel column Chromatography (CH) 2 Cl 2 ) And obtaining a dark solid product DCX-CO (150 mg, yield 60%), namely the fluorescent probe. 1 H NMR(400MHz,CDCl 3 )δ8.91(d,J＝9.3Hz,1H),8.07(d,J＝15.6Hz,1H),7.73(t,J＝7.8Hz,1H),7.61(d,J＝7.6Hz,1H),7.43(t,J＝7.6Hz,1H),7.10(d,J＝8.3Hz,1H),7.02(s,1H),6.88(dd,J＝8.3,2.2Hz,1H),6.77(s,1H),6.49(s,1H),6.14(d,J＝15.5Hz,1H),6.08-6.00(m,1H),5.48(d,J＝17.1Hz,1H),5.39(d,J＝10.5Hz,1H),4.79(d,J＝5.9Hz,2H),2.62-2.55(m,2H),2.49(t,J＝5.9Hz,2H),1.85(dt,J＝11.8,6.1Hz,2H). 13 C NMR(100MHz,CDCl 3 )δ159.1,153.2,153.1,152.6,151.8,151.5,134.1,133.5,130.9,126.7,125.7,123.3,122.3,120.1,119.9,118.6,117.6,116.2,114.7,111.6,108.5,108.2,105.9,69.5,60.1,29.8,24.5,20.6.MS(TOF):502.2.
Example 2:
fluorescent probe and CO solution preparation
Preparation of probe solution: weighing a certain amount of probe, dissolving in dimethyl sulfoxide to prepare 1 × 10 -4 M probe solution. Simultaneously weighing a certain amount of PdCl 2 Dissolving in secondary distilled water to obtain 1 × 10 solution -4 Stock solutions of M. Preparing a CO solution: dissolving a certain amount of CORM-3 in redistilled water, transferring to a 100mL volumetric flask, adding water to the scale mark to obtain a concentration of 1.0 × 10 -3 mol·L -1 CORM-3 of (1). Will be 1.0X 10 -3 mol·L -1 The solution of CORM-3 was gradually diluted to give 1.0X 10 -3 -1.0×10 -5 mol·L -1 An aqueous solution of CORM-3. 1.0mL of a stock solution of the probe, 1.0mL of PdCl 2 Adding the solution and 1.0mL CORM-3 aqueous solution into 10mL volumetric flask, and diluting to constant volume with buffer solution to obtain a concentration of 1.0 × 10 - 5 mol·L -1 Fluorescent probe and PdCl of 2 ，1.0×10 -4 -1.0×10 -6 mol·L -1 Mixing the solution to be tested.
Example 3:
determination of fluorescence Spectroscopy of the interaction of fluorescent probes with CO
FIG. 2 shows fluorescence spectra of the interaction of fluorescent probe with CO, fluorescent probe and Pd 2+ The concentration of the carbon dioxide is 10 mu M, and the concentration of the CO is 0,1,5,10,20,30,40,50,60,70,80,90 and 100 mu M in sequence. The excitation wavelength used in the experiment is 598nm, and the emission wavelength range is 650-900 nm. The slit width was 10.0nm/10.0nm, and the fluorescence measuring instrument used was a Hitachi F4600 fluorescence spectrophotometer. As can be seen from FIG. 2, before the addition of CO, the fluorescent probe added Pd due to the quenching effect of allyl formate 2+ Thereafter, there was no significant near infrared emission peak at near infrared (762 nm); adding Pd simultaneously 2+ And CO, a distinct near-infrared emission peak at 762nm appears. This is because of Pd 2+ First reduced to Pd by CO 0 Subsequently, the Tsuji-Trost reaction is mediated, resulting in cleavage of the allyl formate, releasing the benzopyranonitrile-xanthene fluorophore, which produces near infrared fluorescence. And the near infrared fluorescence intensity of the probe molecules is continuously enhanced along with the increase of the CO concentration. FIG. 3 is a graph of the linear response of the probe to different CO concentrations. The fluorescence intensity is in linear relation with the concentration of CO, and the linear range is 1.0 multiplied by 10 -6 ～1.0×10 -4 M, the detection limit is 0.33. Mu.M. This indicates that the probe can detect CO with high sensitivity.
Example 4:
determination of ultraviolet-visible absorption spectrum of action of fluorescent probe and CO
FIG. 4 is an ultraviolet-visible absorption spectrum of the fluorescent probe after the reaction with CO, wherein the concentration of the fluorescent probe is 10 μ M and the addition amount of CO is 100 μ M. The instrument for measuring the ultraviolet visible absorption spectrum is an Agilent Cary60 ultraviolet visible spectrophotometer. As can be seen from FIG. 4, the probe itself has an absorption band at 549 nm; adding Pd 2+ After that, the absorption peak was not significantly changed; adding Pd simultaneously 2+ And CO, the absorption peak at 549nm gradually decreased, and a new strong absorption peak near 598nm appeared.
Example 5:
selectivity of fluorescent probes for CO determination
FIG. 5 is a graph of selectivity of fluorescent probes for CO determination. Examination of fluorescent Probe and Pd at a concentration of 10. Mu.M 2+ Adding CO (100 μ M) and various metal ions (Na) into the solution + ,K + ,Mg 2+ ,Ca 2+ ) And biological thiols (Cys, hcy, GSH), amino acids (Lys, glu, ala), active oxygen (ONOO) - ,H 2 O 2 ,·OH,ClO - ,O 2 - ) Active nitrogen (NO, NO) 2 - ,NO 3 - ) The fluorescent response of (c). As can be seen in FIG. 5, only CO caused a significant enhancement in the fluorescence spectrum, and the other analytes had no significant effect on the fluorescence spectrum of the probe. These results indicate that the fluorescent probe is better selective for CO.
Example 6:
influence of solution pH value on fluorescence property of fluorescent probe for determining CO
The effect of pH on the fluorescence spectrum of CO measured with the fluorescent probe was examined, and the results are shown in FIG. 6. The pH range we studied was 2.0-10.0, fluorescent probe and Pd 2+ The concentrations of (A) and (B) were all 10. Mu.M, and the concentration of CO was 100. Mu.M. As can be seen from the figure, the fluorescence intensity of the fluorescent probe is basically unchanged along with the change of pH, which shows that the pH has no great influence on the probe. However, after addition of CO, the fluorescence intensity ratio significantly increased at pH ranging from 7.0 to 9.0. In summary, when the pH value is between 7.0 and 9.0, the determination of CO by the fluorescent probe is not affected, and the pH value range is more suitable, which is very beneficial for the probe to be used for determining CO in actual samples.
Example 7:
determination of response time of fluorescent probe to CO action
We investigated the response time of fluorescent probes to CO, the results of which are shown in FIG. 7. As can be seen from the figure, the response time of the probe to CO is 10min, which can meet the requirement of real-time monitoring in actual samples. From FIG. 7, it can also be seen that the fluorescence intensity does not change any more after reaching the maximum value and in the following time, which indicates that the fluorescence probe has better light stability.
Example 8:
application of fluorescent probe in living cell
First, we performed cytotoxicity assays, as shown in fig. 8. When 0-30. Mu.M CO probe was added, the survival rate of both cells (HepG 2 cells, HCT116 cells) was above 90%. This indicates that the fluorescent probe is less toxic and can be used to detect CO in living cells. Then, we studied the application of fluorescent probe in living cells, and selected liver cancer cell HepG2 and colon cancer cell HCT116 for confocal microscopy imaging, and the results are shown in fig. 9. Only the fluorescent probe was added to the cells and little fluorescence was observed (fig. 9 a); adding fluorescent probe and Pd simultaneously into cells 2+ There was still no significant change in fluorescence (FIG. 9 b), indicating a lower CO content in the cells. Subsequently, a carbon monoxide releasing agent (CORM-3) was added to the cells, followed by the addition of the probe and Pd 2+ After 0.5h incubation, a significant fluorescence increase could be observed (fig. 9 c). Heme (Heme) is reported in the literature to stimulate the production of CO in cells. The cells were pretreated with Heme (Heme) for 4h to stimulate the production of intracellular CO, and Pd was added 2+ At the same time, the probe was used for 0.5h, and a strong fluorescent signal was detected in the cells (FIG. 9 d). These results indicate that the fluorescent probe can monitor the change of the content of CO in the cells, which provides a reliable means for monitoring the lesion related to carbon monoxide in the human body.
Claims (3)
1. A carbon monoxide near-infrared fluorescent probe, namely DCX-CO, has the following structure:
2. the method for preparing the carbon monoxide near-infrared fluorescent probe according to claim 1, which is characterized by comprising the following reaction steps:
in N 2 In a 25mL round bottom flask, 0.5 equivalent ofDCX-OH,2.0 to 3.0 equivalent of allyl chloroformate and 2.0 to 3.0 equivalent of triethylamine are dissolved in 8 to 12mL of THF, then the reaction is stirred at room temperature overnight, after the reaction is finished, water is added for dilution, and CH is used for diluting 2 Cl 2 The organic layer was washed with brine and then with anhydrous Na 2 SO 4 Drying, filtering and concentrating the crude product with CH 2 Cl 2 And purifying by silica gel column chromatography as an eluent to obtain a dark green solid product DCX-CO, namely the fluorescent probe.
3. The use of the carbon monoxide near-infrared fluorescent probe as claimed in claim 1, wherein the fluorescent probe is used for detecting the content of carbon monoxide in living cells.
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| CN108219510A (en) * | 2018-03-21 | 2018-06-29 | 湘潭大学 | The preparation and application of peroxynitrite fluorescence probe based on hemicyanine dye |
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