CN114573571B - Carbazole derivative fluorescent probe containing dicyanoisophorone group and preparation method and application thereof - Google Patents
Carbazole derivative fluorescent probe containing dicyanoisophorone group and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbazole derivative fluorescent probe containing dicyanoisophorone group, a preparation method and application thereof, wherein the carbazole derivative fluorescent probe containing dicyanoisophorone group has the structural formula:
the carbazole derivative fluorescent probe has multifunction, and ClO can be realized by ultraviolet-visible spectrophotometry and ratiometric fluorescence ‑ The visual identification and quantitative detection of the ions have good anti-interference performance, high selectivity and sensitivity under the condition that other ions exist.
Description
Technical Field
The invention relates to a carbazole derivative fluorescent probe containing dicyanoisophorone group, a preparation method and application thereof, which are particularly used for detecting ClO - Ions, which belong to the field of ion detection and fluorescent molecular probes.
Background
Reactive Oxygen Species (ROS), a by-product of oxygen metabolism, has proven to be an important intracellular signaling molecule, intimately involved in many fundamental biological processes and pathogenesis of various diseases. ClO (ClO) - As one of ROS, it has a very strong bactericidal effect in the innate immune system. ClO under physiological conditions - Can react with various biomolecules (such as amino acids, proteins, membrane lipid, DNA) rapidly, so ClO with proper concentration - Is beneficial, and abnormal ClO - Is harmful to human body, can cause oxidative damage, and can induce various human diseases such as lung injury, rheumatoid arthritis, neuron degeneration, cardiovascular diseases, cancer, etc. At the same time ClO - Has the double functions of bleaching and sterilizing, and can be widely applied to household bleaching, drinking water sterilization and other daily life. In view of the above mentioned physiological sum of HClOPathological characteristics, a specific ultra-rapid detection tool is urgently needed to visually detect ClO in living cells - Is a concentration change of (c). Thus, a method for identifying ClO rapidly, specifically and visually was developed - Fluorescent probes for ionic monitoring ClO in biological cells or in water in real time - Ions are of great importance.
Disclosure of Invention
The invention aims to provide a carbazole derivative fluorescent probe containing dicyanoisophorone group, a preparation method and application thereof, and aims to solve the technical problem that ClO can be detected and identified through molecular design synthesis - Is provided.
The carbazole derivative fluorescent probe containing dicyanoisophorone radical is a ratio fluorescent probe and can be used for preparing ClO under the condition of existence of other ions - The ion has higher selectivity and sensitivity, and the fluorescent probe and ClO of the invention - The phenomenon of obvious color change generated by ion mixing can realize naked eye identification and colorimetric analysis.
The structural formula of the carbazole derivative fluorescent probe containing dicyanoisophorone group is shown as follows:
the carbazole derivative containing dicyanoisophorone-thiophenal group has good intramolecular charge transfer effect, C=C bond contained in dicyanoisophorone group in molecule is often used as a reaction site of HClO, and under the condition of normal temperature, HClO can oxidize the dicyanoisophorone-thiophenal group into aldehyde or ketone, so that the intramolecular charge transfer effect of the whole molecular system is changed, the ultraviolet and fluorescence phenomena of an original probe compound are changed, and the probe molecule is realized to ClO - And (5) rapid detection of ions.
The preparation method of the carbazole derivative fluorescent probe containing dicyanoisophorone group comprises the following steps:
step 1: synthesis of intermediate I-DCM
3-formyl-6-iodo-N-butylcarbazole (0.7430 g,1.91 mmol) and DCM (0.4051 g,2.17 mmol) were weighed into 25mL ethanol, 0.6mL piperidine was added dropwise into a round bottom flask, and the reaction was stirred under reflux for 6 hours; after the reaction was completed, the product was separated out from the hot ethanol, filtered while it was still hot, and the filter cake was washed three times with ethanol to obtain 0.7112g of red solid.
Step 2: synthesis of SFQ
150mg of I-DCM (0.27 mg), 62.4mg of 5-aldehyde-2-thiopheneboronic acid (0.40 mg) and 31mg of Pd (PPh) were taken respectively 3 ) 4 (0.27 mmol) was poured into a three-necked flask and N was filled 2 Ensure an anaerobic environment and inject 20mL of a mixed solution of toluene and ethanol (3:1, V/V) and 3mL of saturated K with a syringe 2 CO 3 A solution, the reaction being carried out at 80 ℃ for 24 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, the product was poured into a large amount of distilled water, extracted with methylene chloride and the organic phases were combined (three times of extraction on average), and the organic phase was extracted with anhydrous MgSO 4 Drying overnight, filtering, and performing reduced pressure spin drying on the filtrate to obtain a crude product; purification by silica gel column chromatography separation technique using petroleum ether, dichloromethane and ethyl acetate (8:1:1, V/V) as eluent finally yielded 54mg of red solid.
The synthetic route of the invention is as follows:
the invention relates to the application of a carbazole derivative fluorescent probe containing dicyanoisophorone group in qualitative or quantitative detection of ClO - When used as a detection reagent.
Further, ultraviolet-visible absorption spectrometry is carried out in an organic solvent medium, and ClO is realized through the change of solution color - Qualitative or quantitative detection of (a).
Further, fluorescence spectrometry is carried out in an organic solvent medium, and ClO is realized through the change of the fluorescence intensity of the double channels - Qualitative or quantitative detection of (a).
The organic solvent medium is DMF.
The fluorescent probe of the invention can be used forClO - The ion identification and detection have strong anti-interference capability on various other ions, and the fluorescent probe and ClO of the invention - The phenomenon of obvious color change generated by ion mixing can realize naked eye identification and colorimetric analysis.
The beneficial effects of the invention are as follows:
the fluorescent probe compound has multifunction, and ClO can be respectively realized by ultraviolet-visible spectrophotometry and fluorescence spectrometry - And (5) identification of ions. The fluorescent probe of the invention can specifically recognize ClO - Ion, clO is added into DMF solution of probe - Ions, in the ultraviolet spectrum, are seen to have significantly red shifted the absorption band at 468nm by 25nm with a concomitant decrease in absorption intensity; the probe solution showed orange color under ordinary room light, and ClO was added - After the ions, the color of the solution changed to pink, while under a 365nm ultraviolet lamp, the color of the solution was seen to change from orange-red to cyan. ClO in fluorescence Spectrum - The addition of ions increases fluorescence at 473nm of the probe solution, the luminescence position is gradually red shifted to 486nm, at the same time, fluorescence at 613nm is reduced and the emission peak is disappeared, a ratiometric fluorescence phenomenon is exhibited, and the probe SFQ shows two different emission channels, which enables it to detect ClO-ions in a ratiometric manner in an ultra-short time. The probe can realize the ClO by ultraviolet-visible spectrophotometry and fluorescence spectrometry - The identification and quantitative detection of ions still have good anti-interference performance, high selectivity and sensitivity under the condition that other ions exist.
The fluorescent probe can be used for preparing the ClO in a real water sample - The ion is rapidly identified and quantitatively detected, and ClO is detected - The ion identification has higher selectivity and better anti-interference capability, and obvious color change phenomenon can realize naked eye identification and colorimetric analysis. The test of the real water sample shows that the probe has good prospect in the application of the real water sample; the practical research on the probes in the aspect of biological application shows that the probe solution can be used for exogenous ClO in cells - And detecting ions. The experimental results show that our probes are monitored in the environmentAnd has good application potential in organisms.
Drawings
FIG. 1a is an ultraviolet absorption spectrum of a fluorescent probe (SFQ) of the present invention with different ions added to DMF (insert shows ClO addition) - Color change front-to-back).
FIG. 1b shows the fluorescence spectra of a fluorescent probe (SFQ) of the invention with different ions added to DMF (insert shows ClO addition) - Color change under 365nm uv lamp illumination front and back).
FIG. 2a shows the addition of different concentrations of ClO to DMF with a fluorescent probe (SFQ) (10. Mu.M) according to the invention - (0-32.5. Mu.M) ultraviolet absorption titration spectrum.
FIG. 2b shows the addition of different concentrations of ClO to a fluorescent probe (SFQ) (10. Mu.M) according to the invention in pure DMF - (0-40. Mu.M) fluorescence titration spectrum at 370nm excitation.
FIG. 2c shows the addition of different concentrations of ClO to a fluorescent probe (SFQ) (10. Mu.M) according to the invention in pure DMF - (0-40. Mu.M) fluorescence titration spectrum under 470nm excitation.
FIG. 3a shows the intensity of ultraviolet absorption and different concentrations of ClO for fluorescent probes (SFQ) (10. Mu.M) of the present invention - (12.5-25. Mu.M).
FIG. 3b shows the fluorescence intensity ratio F of the fluorescent probe (SFQ) of the present invention 489 /F 613 With ClO - Concentration (13-27.5. Mu.M).
FIG. 4a shows a fluorescent probe (SFQ) (10. Mu.M) of the invention in ClO - Ultraviolet absorption response in the presence of other analytes.
Uv absorption of SFQ after addition of other analytes (2 equiv.); />
SFQ ultraviolet absorption in the presence of ClO-and other analytes (2 equiv.).
FIG. 4b shows the fluorescence probe SFQ (10. Mu.M) of the present invention in ClO - Fluorescence intensity ratio when other analytes are added in the presence (F 489 /F 613 )。
Represents the fluorescence intensity ratio (F) of SFQ after addition of other analytes (2 equiv.) 489 /F 613 )；
Represents the fluorescence intensity ratio (F) of SFQ in the presence of ClO-and other analytes (2 equiv.) 489 /F 613 )。
FIG. 5 shows the addition of ClO at different concentrations to the SFQ fluorescent probe of the present invention - Post-change in fluorescence intensity at 489nm with time (lambda ex ＝370nm)。
FIG. 6 shows the addition of ClO to the SFQ fluorescent probe of the present invention - Mass spectrum of the post-product.
FIG. 7 shows the fluorescence probe SFQ (10. Mu.M) and ClO of the present invention - (3.0 equiv.) in DMSO-d 6 Nuclear magnetic titration hydrogen spectrogram of (a).
FIG. 8 is a graph comparing the intensities of fluorescence captured in HepG2 cells.
Detailed Description
The invention will be further illustrated by, but is not limited to, the following examples.
Example 1: synthesis of fluorescent probe SFQ
3-formyl-6-iodo-N-butylcarbazole (0.7430 g,1.91 mmol) and DCM (0.4051 g,2.17 mmol) were weighed into 25mL ethanol and 0.6mL piperidine was added dropwise to the round bottom flask and the reaction stirred under reflux for 6 hours. At the end of the reaction, the product was precipitated from hot ethanol, filtered while hot and the filter cake was washed three times with ethanol to give 0.7112g of red solid (I-DCM). The yield was 68%.
1 H NMR(600MHz,DMSO-d 6 )δ8.68(s,1H),8.57(s,1H),7.82(d,J＝8.6Hz,1H),7.75(d, J＝8.6Hz,1H),7.67(d,J＝8.6Hz,1H),7.53(d,J＝8.6Hz,1H),7.47(d,J＝8.4Hz,2H),6.85(s, 1H),4.40(t,2H),2.64(s,2H),2.61(s,2H),2.51(s,2H),1.74(m,2H),1.29(m,2H),1.06(s,6H),0.88(t,3H).[M-H] + :545.1249.
150mg of I-DCM (0.27 mg), 62.4mg of 5-aldehyde-2-thiopheneboronic acid (0.40 mg) and 31mg of Pd (PPh) were taken respectively 3 ) 4 (0.27 mmol) was poured into a three-necked flask and filled with N 2 Ensure an anaerobic environment and inject 20mL of a mixed solution of toluene and ethanol (3:1, V/V) and 3mL of saturated K with a syringe 2 CO 3 The solution was reacted at 80℃for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the product was poured into a large amount of distilled water, extracted with methylene chloride and the organic phases were combined (three times of extraction on average), and the organic phase was extracted with anhydrous MgSO 4 Drying overnight, filtering, and drying the filtrate under reduced pressure to obtain crude product. Then petroleum ether, methylene chloride and ethyl acetate (8:1:1, V/V/V) are used as eluent, and the mixture is purified by a silica gel column chromatography technology, so that 54mg of red Solid (SFQ) is finally obtained, and the yield is 37.5%.
1 H NMR(400MHz,DMSO-d 6 )δ9.87(s,1H),8.71(s,1H),8.65(s,1H),8.04(d,J＝3.9Hz, 1H),7.90(d,J＝8.5Hz,1H),7.80(d,J＝9.7Hz,1H),7.78–7.62(m,3H),7.50–7.39(m,2H), 6.84(s,1H),4.42(t,2H),2.59(d,J＝6.8Hz,4H),1.79–1.68(m,2H),1.30–1.24(m,2H),1.02(s,6H),0.83(t,3H). 13 C NMR(101MHz,CDCl 3 )δ182.69(s),169.37(s),155.74(s),154.59(s), 142.04(s),141.61(d,J＝3.2Hz),138.19(s),137.93(s),127.68(s),127.01(s),126.10(s),125.08 (d,J＝3.6Hz),123.52-123.10(m,3C),122.72(s),120.74(s),118.65(s),113.90(s),113.19(s), 109.90(d,J＝2.9Hz),43.41(s),43.08(s),39.37(s),32.14(s),31.21(s),29.78(s),28.16(s),20.60(s),13.92(s).IR(KBr,cm -1 )2210(-CN),1384(-CH 3 ),674(C-S).[M-H] + :529.2154.
Example 2: selective spectroscopic investigation of fluorescence probe SFQ
The selectivity is one of parameters for detecting ions by the probe, and has great significance. As can be seen from FIG. 1a, in N, N-Dimethylformamide (DMF) solution, probe SFQ (10. Mu.M) showed a strong absorption peak at 468nm, which is probably due to N-pi within SFQ * And (5) transition. 2-fold equivalents of each analyte (Cl) were added to the probe SFQ - ，HSO 3 - ， SO 3 2- ，HCO 3 - ，SCN - ，CH 3 COO - ，ONOO - ，NO 2 - ，H 2 O 2 ，Cu 2+ ，Fe 3+ ，Na + ，Mg 2+ ，Co 2+ Cys, GSH and Lysine) the UV absorption is substantially unchanged, only ClO is present - At this time, the absorption band of SFQ at 468nm was significantly red shifted by 25nm with concomitant decrease in absorption intensity (FIG. 1 a). The probe SFQ solution shows orange color under the ordinary indoor light, and ClO is added - After that, the solution color became pink (inset in fig. 1 a), which coincides with the change in uv absorption. ClO in fluorescence Spectrum - The addition of (3) causes the SFQ solution to exhibit a ratiometric fluorescence, the fluorescence at 473nm is increased by a factor of about 10, the luminescence site is red shifted to 486nm, and at the same time, the fluorescence at 613nm is reduced and the emission peak is disappeared (FIG. 1 b). Under 365nm UV light, the color of the solution changed from orange-red to cyan (inset in FIG. 1 b), while the addition of the other analytes did not change significantly. The above results indicate that the probe SFQ is specific to ClO only - Has high selectivity.
Example 3: titration spectroscopic investigation of fluorescence Probe (SFQ)
Probe SFQ vs ClO - Ultraviolet and fluorescence titration spectroscopy experiments were further explored. As shown in fig. 2a, with ClO - The absorption peak of SFQ at 469nm gradually red shifts and gradually decreases at the same time as the peak at 364nm gradually shifts to 370nm. Probe SFQ (10. Mu.M) and ClO - Has a good linear relationship between the concentration of 12.5-25. Mu.M (R 2 ＝0.9919)，A 469 ＝-0.0064[ClO - ]+0.2558 (fig. 3 a). From dl=3σ/K, the probe SFQ was calculated to correspond to ClO in the uv-vis absorption spectrum - The detection limit of (2) was 1.13. Mu.M. FIGS. 2b and 2c are, respectively, probe SFQ (10. Mu.M) with different ClO concentrations - (0-40. Mu.M) fluorescence titration spectra at 470nm and 370nm excitation. As shown in FIG. 2b, the emission of the probe at 613nm gradually decreased upon 470nm excitation, while the emission of the probe at 473nm gradually increased and the emission peak position gradually shifted to 489nm upon 370nm excitation. For this purpose, we have made a fluorescence intensity ratio F 489 /F 613 With ClO - Concentration as a function of the ratio of fluorescence intensities in the range of 13-27.5. Mu.MF 489 /F 613 With ClO - The concentrations exhibit a good linear relationship (R 2 ＝0.9930)，F 489 /F 613 ＝1.5126[ClO - ]-12.1015 (fig. 3 b). From dl=3σ/K, the probe SFQ was calculated to correspond to ClO in fluorescence spectrum - The ratio detection limit of (2) was 0.14. Mu.M.
Example 4: competitive studies of fluorescent probes (SFQ)
To explore the probe SFQ vs ClO - The interference resistance of the detection is tested by performing a competitive experiment of ultraviolet-visible absorption spectrum and fluorescence spectrum. Shown in the ultraviolet absorption spectrum, only in ClO - The ultraviolet absorption of the probe SFQ is reduced in the presence of the system (FIG. 4 a), and the presence of other analytes hardly affects ClO - Is detected. Likewise, only in ClO - Fluorescence intensity ratio of probe SFQ under existing system (F 489 /F 613 ) Significantly increases by a factor of ten or more, the presence of other analytes is almost impossible for ClO - Interference caused by detection of (FIG. 4 b), probe SFQ versus ClO - Has high selectivity and anti-interference performance. Therefore, the probe is expected to be a sensor which can be developed and applied for completing ClO in complex environment - Is detected.
Example 5: time response of fluorescent probes (SFQ)
It is well known that a rapid time response is of great importance in practical applications for the detection of various analytes such as anions and cations and amino acids by fluorescent probes. As shown in FIG. 5, the addition of 12.5. Mu.M, 25. Mu.M, 50. Mu.M to the probe SFQ (10. Mu.M, DMF), respectively, all responded rapidly within 5 seconds, reached a substantial equilibrium within 20 seconds, and satisfied real-time detection of ClO as a transient metabolite - Is not limited. We look up the detection of ClO at home and abroad in recent years - By comparing the related documents of (C) and (D), it can be seen that the probe pair ClO - The response of (a) is significantly faster than that of probes reported in other documents.
Example 6: fluorescent probe SFQ pair ClO - Response mechanism study of (2)
To study the probe SFQ vs ClO - We pair the probes SFQClO - And carrying out mass spectrum and nuclear magnetic titration on the product after the reaction. As shown in fig. 6, one peak m/z= 481.2607 can be attributed to [ SFQ-o+h] + This may be that-C=c (CN) is oxidized to-c=o. To continue to verify this guess, we performed a nuclear magnetic titration test, from which it can be seen that: ha, hb, hc, and Hd all move to the high field, and chemical shifts from δ 7.46ppm,7.43ppm,6.84ppm,8.65ppm to 6.50ppm,6.42ppm,5.69ppm, and 8.52ppm, respectively (fig. 7), which may be due to the oxidation of two strong electron withdrawing groups (-CN) to a medium electron withdrawing group (-c=o). It can be demonstrated that the electron withdrawing CN group of the probe SFQ is subjected to ClO - Is thereby oxidized to a ketone group.
Example 7: clO in fluorescent probe SFQ pair water sample - Is detected by (a)
In order to examine the potential application of SFQ in real life, we selected lake water and laboratory tap water near the university of Anhui as examples to test ClO in real water sample - . Preparing SFQ (10. Mu.M) solution of probe with DMF, respectively preparing 10 with lake water and tap water -2 ClO of M - A solution. Three ClOs were added at 5. Mu.M, 10. Mu.M, 15. Mu.M, and 20. Mu.M, respectively - The fluorescence intensity of the solution was measured. As can be seen from Table 1, clO was measured - The error between the concentration and the added concentration is small, and the test recovery rate is in the range of 98.5% -103%, which shows that the probe SFQ detects ClO in a real water sample - Has high accuracy, and can be applied to ClO in a real water sample - Is detected.
TABLE 1 ClO in multiple real water samples of the fluorescent probe SFQ of the present invention - Is detected.
Example 8: fluorescent probe compound SFQ vs ClO in cells - Fluorescent development test of (2)
Using confocal microscopy, hepG2 cells stained with SFQ (10. Mu.M) for 30 min were observed, fluorescence was captured in both the red and cyan channels, and ClO was added to the cells continuously - (50Mu M) for 0.5 hours, a significant decrease in fluorescence in the red channel and a stronger fluorescence emission in the cyan channel were observed. The intensity of fluorescence captured in the cells is shown in FIG. 8, and the confocal imaging of the cells is consistent with the experimental phenomenon. From this, the probe SFQ has strong cell membrane penetrating ability and can detect the exogenous ClO in the cell through the fluorescence change of the double channels - Is a distribution of the (b).
Claims (7)
1. A carbazole derivative fluorescent probe containing dicyanoisophorone group is characterized by having the following structural formula:
2. a method for preparing a dicyanoisophorone-containing carbazole derivative fluorescent probe according to claim 1, characterized by comprising the steps of:
step 1: synthesis of intermediate I-DCM
Weighing 3-formyl-6-iodine-N-butylcarbazole and DCM, dissolving in ethanol, dripping piperidine into a round bottom flask, and stirring for reaction in a reflux state; after the reaction is finished, separating out a product from hot ethanol, filtering while the product is hot, and washing a filter cake with ethanol to obtain red solid I-DCM;
step 2: synthesis of SFQ
Respectively taking I-DCM, 5-aldehyde-2-thiopheneboronic acid and Pd (PPh) 3 ) 4 Adding into a reactor, and charging N 2 Ensuring anaerobic environment, then injecting mixed solution of toluene and ethanol and saturated K 2 CO 3 The solution is reacted at 80 ℃; cooling to room temperature after the reaction is finished, and separating and purifying to obtain a target product which is a red solid;
the reaction scheme is as follows:
3. use of a carbazole derivative fluorescent probe having a dicyanoisophorone group as claimed in claim 1, characterized in that: the carbazole derivative fluorescent probe containing dicyanoisophorone group can be used for qualitatively or quantitatively detecting ClO - When used as a detection reagent.
4. Use according to claim 3, characterized in that:
ultraviolet-visible absorption spectrometry in organic solvent medium, clO is realized by changing solution color - Qualitative or quantitative detection of (a).
5. Use according to claim 4, characterized in that:
the organic solvent medium is DMF.
6. Use according to claim 3, characterized in that:
fluorescence spectrum measurement is carried out in an organic solvent medium, and ClO is realized through the change of the fluorescence intensity of the double channels - Qualitative or quantitative detection of (a).
7. Use according to claim 6, characterized in that:
the organic solvent medium is DMF.
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