CN113444118B - Preparation and detection of coumarin-based BODIPY near-infrared fluorescent probe for HSO3-Application in probes - Google Patents
Preparation and detection of coumarin-based BODIPY near-infrared fluorescent probe for HSO3-Application in probes Download PDFInfo
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- CN113444118B CN113444118B CN202110855453.2A CN202110855453A CN113444118B CN 113444118 B CN113444118 B CN 113444118B CN 202110855453 A CN202110855453 A CN 202110855453A CN 113444118 B CN113444118 B CN 113444118B
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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Abstract
The invention relates to coumarin group BODIPY HSO3 ‑The near infrared fluorescent probe is synthesized by taking 2, 6-diiodo-1, 3, 5, 7-tetramethyl-8- (2, 4, 6-trimethylphenyl) boron dipyrrole compound and 7- (N, N diethylamino) coumarin-3-formaldehyde as raw materials and carrying out Knoevenagel condensation reaction under the catalysis of p-toluenesulfonic acid and piperidine, and the chemical structural formula of the near infrared fluorescent probe is shown as the formula (I). The strongest electron absorption wavelength of the fluorescent probe is 732nm, and the maximum fluorescence emission wavelength is 808 nm. Probe and HSO3 ‑After the action, the fluorescence intensity at 808nm in fluorescence emission spectrum and HSO3 ‑The concentration is in good linear relation, the lowest detection limit is 18.9nM, the sensitivity is high, and HSO in DMSO-water mixed solution can be realized3 ‑And (6) carrying out quantitative detection. The invention has wide potential application prospect in the fields of food and drug safety, environmental detection and the like.
Description
Technical Field
The invention belongs to the technical fields of organic compound synthesis, functional fluorescent dyes and fine chemical engineering, and particularly relates to a coumarin-based BODIPY near-infrared fluorescent probe for preparing and detecting HSO3 -Application in probes.
Background
In the food industry, sulfites are commonly used as preservatives, antioxidants. As bacteriostatic agent for food and beverage, and can be used for preventing oxidation and bacterial growth, and controlling degradation of beverage and fruit caused by enzyme or non-enzymatic reaction. Sulfites also have the efficacy of maintaining stability and are commonly used in the manufacture and storage of pharmaceuticals. At the same time, sulfites are also used as additives to the drug epinephrine, preventing its oxidative inactivation. However, high concentrations of sulfite may cause adverse reactions and acute symptoms in allergic persons, resulting in dyspnea, wheezing, urticaria, gastrointestinal distress. Indeed, even at very low levels, asthmatics may develop bronchospasm. Therefore, the method for detecting the content of the sulfite has very important significance for food and drug safety and environmental detection.
Conventional methods of sulfite analysis typically require tedious sample pretreatment, are time consuming, and have high requirements for instrumentation. Therefore, it is of great interest to develop fluorescent probes with high sensitivity, good selectivity, simple operation and sulfite sensing performance for bio-imaging. The fluorescent probe technology has the advantages of high sensitivity, rapid and convenient test process, easy modification and optimization of molecular structure and the like, shows wide application prospect in detection of medicines, foods and environments, and becomes a new research hotspot at present. However, few studies have been made on sulfite near-infrared fluorescent probes.
BODIPY (BODIPY) is a multifunctional dye, has the advantages of chemical stability, large molar extinction coefficient, high fluorescence quantum yield and the like, and attracts the close attention of researchers in the fields of fluorescent labels, fluorescent probes, organic electroluminescent devices, biotechnology, solar cells and the like. In recent years, the study of BODIPY dyes has tended to synthesize long-wavelength near-infrared fluorescent probes. The methyl groups at the 3 and 5 positions of the parent BODIPY molecule have certain chemical activity and can perform a Knoevenagel condensation reaction with aromatic aldehyde, so that different types of conjugated vinyl groups are introduced, a larger conjugated system is formed with the BODIPY host, the rigidity of the BODIPY can be maintained, the pi conjugated system can be expanded, the molecular planarity is increased, the absorption spectrum and the emission spectrum are shifted to longer wavelengths, and the further development of the research of the BODIPY near-infrared fluorescent probe is promoted. The coumarin dyes are cinnamic acid lactone compounds with suppressed double-bond rotation, have the characteristics of high fluorescence quantum yield, large Stokes displacement, bright color light, strong fluorescence intensity and the like, and have certain modifiability in structure, so that the coumarin dyes are widely concerned in the research of fluorescent probes, two-photon absorption, biological fluorescent imaging materials and the like.
Based on the excellent photophysical properties of the BODIPY fluorescent dye and the coumarin derivative, the coumarin group BODIPY HSO is synthesized in one step through Knoevenagel condensation reaction3 -A near infrared fluorescent probe. The near infrared fluorescent probe is used for HSO3 -Has excellent sensitivity with HSO3 -The fluorescence intensity at the maximum emission wavelength after the action can be compared with the HSO3 -The concentration is in good linear relation, and can realize HSO in dimethyl sulfoxide (DMSO) -water mixed solution3 -And (5) quantitatively detecting the concentration. Thus, it is possible to provideThe probe has wide application prospect in the fields of food and drug safety, environmental detection and the like.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide coumarin group BODIPY HSO3 -A near-infrared fluorescent probe and a preparation method and application thereof.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the coumarin group BODIPY HSO3 -The near-infrared fluorescent probe and the preparation method and the application thereof are characterized in that the fluorescent probe has a structural formula shown as the following formula (I):
coumarin group BODIPY HSO3 -The near infrared fluorescent probe and its preparation process and application includes the following steps:
under the anhydrous condition, adding a 2, 6-diiodo-1, 3, 5, 7-tetramethyl-8- (2, 4, 6-trimethylphenyl) boron dipyrrole compound and 7- (N, N diethylamino) coumarin-3-formaldehyde into dry toluene according to the molar ratio of 1: 2-3, adding p-toluenesulfonic acid and piperidine, stirring and heating, controlling the temperature at 125-140 ℃, reacting for 6-8 hours, cooling to room temperature after the reaction is finished, diluting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, and separating; removing organic solvent under reduced pressure, separating and purifying the residue by silica gel column chromatography to obtain coumarin group BODIPY HSO3 -And (3) a near infrared fluorescent probe (I).
The specific chemical reaction formula is as follows:
in the above step, the molar ratio of the 2, 6-diiodo-1, 3, 5, 7-tetramethyl-8- (2, 4, 6-trimethylphenyl) boron dipyrrole compound, the p-toluenesulfonic acid and the 7- (N, N-diethylamino) coumarin-3-formaldehyde is 1: 0.5-1: 2-3, and the ratio of the volume of the toluene, the piperidine and the 2, 6-diiodo-1, 3, 5, 7-tetramethyl-8- (2, 4, 6-trimethylphenyl) boron dipyrrole compound to the amount of the substance is 25 mL: 1 mmol.
In the above step, the eluent for silica gel column chromatography was 100% dichloromethane.
The invention has the advantages of
Compared with the prior art, the coumarin group BODIPY HSO3 -The near-infrared fluorescent probe and the preparation method and the application thereof have the advantages that: (1) the preparation method is simple and easy to implement, has good selectivity, and avoids the problems of multiple steps, high difficulty and the like of the BODIPY near-infrared fluorescent probe; (2) the fluorescent probe has the strongest electron absorption wavelength of 732nm and the maximum emission wavelength of 808nm, and has high molar extinction coefficient (more than 2.0 × 10)5cm-1mol-1L), large stokes shift (76nm), and the like; (3) the fluorescent probe and HSO3 -After the action, the fluorescence intensity at 808nm in fluorescence emission spectrum and HSO3 -The concentration is in a good linear relationship (Y-946.78-4.93X, R20.96), the lowest detection limit is 18.9nM, the sensitivity is high, and the swallow can realize the HSO in DMOS-water mixed solution3 -And (5) quantitatively detecting the concentration.
Drawings
FIG. 1 shows coumarin group BODIPY HSO3 -Ultraviolet-visible absorption spectrum of near infrared fluorescent probe (I);
FIG. 2 shows coumarin group BODIPY HSO3 -Fluorescence emission spectrum of the near-infrared fluorescent probe (I);
FIG. 3 shows coumarin-based BODIPY HSO3 -Near infrared fluorescent probe (I) solutions in different HSOs3 -Fluorescence emission at concentrations (0-120. mu.M).
FIG. 4 is coumarin based BODIPY HSO3 -Fluorescence intensity of near-infrared fluorescence probe (I) solution at 808nm and system HSO3 -Linear dependence of concentration.
Detailed Description
The invention is further described below with reference to the specific drawings.
By using1H-NMR and UV-Vis spectra characterization and confirmation of coumarin group BODIPY HSO3 -Structure and properties of the near infrared fluorescent probe (I). The detection instrument is as follows: bruker ARX600 NMR Spectrometer (deuterated chloroform as solvent), Shimadzu UV-3100 UV-visible spectrophotometer (scanning range 300-900 nm, optical path slit 2nm), fluorescence spectrum was measured with American Amico Bowman Series 2 Luminescence Spectrometer.
Example 1 coumarin based BODIPY class HSO3 -Preparation of near-infrared fluorescent Probe (I)
A dry round bottom flask was equipped with a Dean-Stark apparatus in the absence of water, and 2, 6-diiodo-1, 3, 5, 7-tetramethyl-8- (2, 4, 6-trimethylphenyl) fluoroborodipyrrole compound (618mg, 1mmol), 7- (N, N diethylamino) coumarin-3-carbaldehyde (735mg, 3mmol) and p-toluenesulfonic acid (172mg, 1mmol) were dissolved in 25mL of toluene and 1mL of piperidine and heated to 140 deg.C under reflux. And (3) detecting the reaction by TLC, and stopping the reaction after the 2, 6-diiodo-1, 3, 5, 7-tetramethyl-8- (2, 4, 6-trimethylphenyl) boron dipyrrole compound completely disappears after the reaction is carried out for 8 hours. Cooling to room temperature, diluting with dichloromethane, washing with water, separating, drying with anhydrous sodium sulfate, evaporating under reduced pressure to remove organic solvent, separating and purifying the residue by silica gel column chromatography with eluent of 100% dichloromethane to obtain gray brown solid product coumarin group BODIPY HSO3 -Near-infrared fluorescent probe (I) (375mg, 35%).1H NMR(600MHz， CDCl3)：δ8.38-8.03(m，2H)，8.00-7.86(m，2H)，7.85-7.50(m，2H)，7.41(t，J＝8.4Hz，2H)，6.99(d， J＝9.0Hz，2H)，6.69(d，J＝55.8Hz，2H)，6.54(dd，J＝19.8，2.4Hz，2H)，3.46(s，8H)，2.37(d，J＝ 6.0Hz，3H)，2.14-2.08(m，6H)，1.48(d，J＝3.6Hz，3H)，1.46(d，J＝24.6Hz，3H)，1.24(t，J＝6.0 Hz，12H)。
UV-vis: 490nm, 732nm (FIG. 1); emission wavelet: 808nm (FIG. 2).
Example 2 coumarin based BODIPY class HSO3 -Preparation of near-infrared fluorescent Probe (I)
In analogy to example 1, except that in this example 2, 6-diiodo-1, 3, 5, 7-tetramethyl-8- (2, 4, 6-trimethylphenyl) fluorodipyrrole is reacted with 7- (N, N-diethylamino) -3-carboxaldehyde-coumarin in a molar ratio of 1: 2; the reaction temperature was controlled at 125 ℃ and the reaction time was 6 hours. Yield: 25 percent.
Example 3 coumarin based BODIPY class HSO3 -Preparation of near-infrared fluorescent Probe (I)
In analogy to example 1, except that in this example 2, 6-diiodo-1, 3, 5, 7-tetramethyl-8- (2, 4, 6-trimethylphenyl) fluoroborodipyr is reacted with p-toluenesulfonic acid in a molar ratio of 1: 0.5; the reaction temperature was controlled at 125 ℃ and the reaction time was 6 hours. Yield: 20 percent.
Example 4 coumarin based BODIPY class HSO3 -Near infrared fluorescent probe (I) solution ultraviolet-visible absorption spectrum
Coumarin radical BODIPY HSO3 -The near-infrared fluorescent probe (I) was dissolved in methylene chloride and was set to a concentration of 1X 10-5The ultraviolet-visible absorption spectrum of the methylene chloride solution was measured. FIG. 1 shows coumarin group BODIPY HSO3 -Ultraviolet-visible absorption spectrum of the near infrared fluorescent probe (I) solution.
Example 5 coumarin based BODIPY class HSO3 -Fluorescence spectrum of near infrared fluorescence probe (I) solution
The coumarin group BODIPY HSO3 -The near-infrared fluorescent probe (I) was dissolved in methylene chloride and was set to a concentration of 1X 10-5And measuring the fluorescence emission spectrum of the dichloromethane solution with mol/L. FIG. 2 shows coumarin group BODIPY HSO3 -Fluorescence spectrum of near infrared fluorescence probe (I) solution.
Example 6 coumarin based BODIPY class HSO3 -Near infrared fluorescent probe (I) with different HSO3 -Fluorescence emission change at concentration (0-120. mu.M)
The coumarin radical BODIPY HSO prepared in the example 1 is taken3 -Near infrared fluorescent probe (I) was dissolved in a PBS (10mM, pH 7.4) solution containing DMSO as a co-solvent (PBS/DMSO 3: 1, v/v) to prepare a 1mmol/L stock solution. 10.4g of sodium hydrogensulfite was added to 100mL of deionized water to prepare a 1mol/L aqueous solution of sodium hydrogensulfite. 3mL of the solution was taken out of the PBS stock solution and added to a cuvette, 10. mu.L of a 1mol/L aqueous solution of sodium hydrogen sulfite was added each time, stirred well, and the fluorescence emission spectrum was measured at an excitation wavelength of 730 nm. With HSO3 -The fluorescence intensity at 808nm gradually becomes weaker with the increase of the concentration. FIG. 3 shows coumarin-based BODIPY HSO3 -Near infrared fluorescent probe (I) solutions in different HSOs3 -Graph of fluorescence emission at concentrations (0-120. mu.M).
Example 7 coumarin based BODIPY class HSO3 -Fluorescence linear range determination of near infrared fluorescent probe (I)
By analysing different HSOs3 -Concentration (0-120. mu.M) (lambda.)ex730nm) coumarin group BODIPY HSO3 -Fluorescence intensity and system HSO of near-infrared fluorescent probe (I) at 808nm3 -Relationship of concentration, evaluation probe against HSO3 -The responsiveness of (c). Shows probe HSO3 -The concentration is in good linear relation in the range of 0-120 mu M, and the linear correlation coefficient is R2The linear relationship is Y946.78-4.93X, 0.96. And calculating to obtain the fluorescent probe molecule pair HSO3 -The detection limit of (a) was 18.94 nM. FIG. 4 is coumarin based BODIPY HSO3 -Fluorescence intensity of near-infrared fluorescence probe (I) solution at 808nm and system HSO3 -Linear dependence of concentration.
Claims (2)
1. Preparation and detection of coumarin-based BODIPY near-infrared fluorescent probe for HSO3 -The probe has a structural formula shown as a formula (I):
2. the coumarin-based BODIPY near-infrared fluorescent probe of claim 1 in preparation of HSO (high-speed oligonucleotide) detection3 -The use of the fluorescent probe in a probe, characterized in that the fluorescent probe is used with HSO3 -After the action, the fluorescence intensity at 808nm in fluorescence emission spectrum and HSO3 -The concentration is in good linear relation, and the lowest detection limit is 18.9nM, thereby realizing HSO in DMSO-water mixed solution3 -And (4) carrying out quantitative detection.
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