CN111925383A - BODIPY-based Cu2+Fluorescent probe and its preparation method and use - Google Patents
BODIPY-based Cu2+Fluorescent probe and its preparation method and use Download PDFInfo
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007850 fluorescent dye Substances 0.000 title abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000000523 sample Substances 0.000 claims abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- OVTCUIZCVUGJHS-UHFFFAOYSA-N dipyrrin Chemical compound C=1C=CNC=1C=C1C=CC=N1 OVTCUIZCVUGJHS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- NHJRXMJGDMOERY-UHFFFAOYSA-N 2,4-dimethylpyrrole Chemical compound CC1=CN=C(C)[CH]1 NHJRXMJGDMOERY-UHFFFAOYSA-N 0.000 claims description 3
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 claims description 3
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 238000012984 biological imaging Methods 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 210000005056 cell body Anatomy 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- -1 atomicAbsorption Chemical compound 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012921 fluorescence analysis Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- GEGSMLCAXKIGQP-UHFFFAOYSA-N n,n-bis(pyridin-2-ylmethyl)aniline Chemical group C=1C=CC=NC=1CN(C=1C=CC=CC=1)CC1=CC=CC=N1 GEGSMLCAXKIGQP-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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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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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
BODIPY-based cu (ii) fluorescent probes having the following structure:
the invention synthesizes the BODIPY probe based on pyridine-2-formic acid phenol ester group for the first time, and introduces the pyridine-2-formic acid phenol ester group to the meso position of the BODIPY. The synthesized probe has large molar absorption coefficient, high fluorescence quantum efficiency, high selectivity and low detection limit on copper ions, has low toxicity to organisms, and can be applied to cell bodies to detect the copper ions. Therefore, the research has attractive application prospect in the aspect of detecting copper ions in a biological system. The invention discloses a preparation method of the compound.
Description
Technical Field
The invention relates to a BODIPY fluorescent probe containing functional groups and application thereof in detection of copper ions in biological cells.
Background
Copper element exists in nature and human body, and is vital to normal operation and metabolism of human organs. Copper is an important component of enzymes in the human body, and excessive or insufficient copper ion content in the human body can cause diseases and even death. Therefore, it is very significant to accurately and timely detect the content of copper ions in the human body. [ see: burdo J R, Connor J R. BioMetals,2003,16:63-75]There are many methods for detecting copper ions, such as atomicAbsorption, coupled plasma mass spectrometry, electrochemical methods, fluorescence analysis methods. [ see: (a) soylak M, unol Y E.food Chem Toxicol,2010,48: 1511-.]As a novel developed detection method, the fluorescence analysis method has the advantages of simple and convenient operation, high detection speed, no destructiveness and the like, and becomes a very practical detection method. [ see: qu X Y, Li C J, Chen H C, et al. chem. Commun.,2013,49:7510-7512.]One of the problems to be solved urgently in the fluorescence analysis method is to synthesize a fluorescent probe with high sensitivity, good selectivity and good solubility. The boron fluorine dipyrromethene (BODIPY) fluorescent dye has a plurality of excellent photophysical properties, such as high molar absorptivity, high fluorescence quantum yield, easily modified structure and the like, and is widely applied to design and synthesis of Cu2+A fluorescent probe.
BODIPY fluorescence enhanced Cu is reported for the first time in 20062+Fluorescent probe for detecting Cu by hydrolysis of acetyl2+The purpose of (1). [ see: qi, x.; jun, e.j.; xu, l.; kim, s.j.; hong, j.s.j.; yoon, y.j.; yoon, j.y.j.org.chem.2006,71,2881.]Subsequently, the literature reports two successive reports of the ability to detect Cu2+The BODIPY fluorescent probe detects ions by introducing N- (2-phenol group) aniline group and N, N-di (2-picolyl) aniline group into the meso position of the BODIPY mother nucleus and utilizing a light-induced electron transfer (PET) mechanism to achieve the purpose of changing fluorescence intensity. [ see: (a) wang, d.p.; shiraishi, y.; hirai, t.chem.commu.2011, 47,2673.(b) l.zhou, C-c.zhu, Y-s.xue, W-j.he, H-b.du, X-z.you, Y-z.li, inorg.chem.commu, 2013,35,355]
According to the invention, a BODIPY compound with high fluorescence quantum yield is used as a fluorescent group, 4- (pyridine-2-formic acid) phenol ester group and p-hydroxyphenyl are used as functional groups, and the functional groups are reasonably modified to the middle position of a BODIPY mother nucleus to obtain the fluorescent probe Q1-Q3.
Disclosure of Invention
The invention relates to a series of boron-fluorine dipyrromethene (BODIPY) fluorescent probes containing functional groups of 4- (pyridine-2-formic acid) phenol ester group or p-hydroxyphenyl group, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a BODIPY fluorescent probe has the following structure: the substituent R corresponds to the compound
A process for preparing the boron-dipyrromethene (BODIPY) -based compound Q1-Q3 as described above, which can be prepared by the following reaction,
it comprises the following steps:
1. preparation of BODIPY-type compound Q1:
adding (0.4540g, 2mmol) corresponding aldehyde, (0.3800g, 4mmol)2, 4-dimethylpyrrole, 0.01mL trifluoroacetic acid and 100mL anhydrous dichloromethane into a 250mL round bottom flask, stirring at room temperature overnight, then adding (0.4500g, 2mmol)2, 3-dichloro-5, 6-dicyan p-benzoquinone, oxidizing for 1h, sequentially adding 3mL triethylamine and 3mL boron trifluoride diethyl etherate solution, reacting for 5h, adding water for quenching, after the reaction is finished, extracting with dichloromethane, performing reduced pressure spin drying, performing column chromatography, and passing through a column with a developing agent with a dichloromethane to petroleum ether ratio of 1:2 to obtain the corresponding Q1 product.
The nuclear magnetic data for compound Q1 are as follows,1H NMR(CDCl3,600MHZ):8.87(d,1H,J＝6Hz),8.31(d,1H,J＝12Hz),7.96(t,1H,J＝12Hz),7.59(t,1H,J＝6Hz),7.44(d,2H,J＝6Hz),7.42(d,2H,J＝6Hz),6.00(s,2H),2.57(s,6H),1.46(s,6H).
2. preparation of BODIPY compounds Q2 and Q3:
in a 100mL two-necked flask, was charged (0.0710g, 0.16mmol) of the BODIPY compound Q1, (0.0430g, 0.32mmol) p-methoxybenzaldehyde, 0.4mL anhydrous piperidine, 0.4mL glacial acetic acid and 50mL anhydrous acetonitrile, heated to 90 ℃ using a water trap under argon, and the reaction was monitored by TLC until all of the Q1 starting material spots disappeared. After the reaction is finished, cooling to room temperature, performing reduced pressure spin drying, performing column chromatography, and passing through a column by using a developing agent with the ratio of dichloromethane to petroleum ether being 1:2 to obtain corresponding products Q2 and Q3.
The nuclear magnetic data for compound Q2 are as follows,1H NMR(CDCl3,600MHZ):7.55(m,4H),7.21(d,1H,J＝18Hz),7.16(d,2H,J＝12Hz),6.96(t,2H,J＝6Hz),6.91(d,1H,J＝12Hz),6.59(s,1H),5.99(s,1H),3.84(s,3H),2.59(s,3H),1.49(s,3H),1.45(s,3H).
the nuclear magnetic data for compound Q3 are as follows,1H NMR(CDCl3,600MHZ):7.65(d,2H,J＝18Hz),7.61(d,4H,J＝6Hz),7.24(d,2H,J＝12Hz),7.21(d,2H,J＝12Hz),6.99(d,2H,J＝6Hz),6.96(d,2H,J＝12Hz),6.63(s,2H),3.88(s,6H),1.53(s,6H).
the detection instrument is as follows: bruker ARX600 MHz NMR spectrometer (TMS as internal standard, deuterated CDCl)3Solvent), rayleigh TU-1901 uv-visible spectrophotometer (scanning range 350-700 nm, light path slit 1nm), Cary Eclips type fluorescence spectrometer.
The invention has the advantages of
Compared with the prior art, the invention has the following remarkable advantages: the 4- (pyridine-2-formic acid) phenol ester group is selected as a functional group for the first time and is connected to the meso position of the BODIPY mother nucleus, so that the purpose of detecting copper ions in a biological system is achieved. The absorption peak and the fluorescence peak of the compound Q1-Q3 are both positioned in a visible light region, the compound Q1 has excellent photophysical properties, and the compound Q1-Q3 can efficiently and selectively identify Cu2+. Probe Q1 is a meso-position pyridine-2-formic acid phenol ester BODIPY probe, and has many favorable properties such as large visible absorption spectrum, high fluorescence quantum yield and Cu2+High ion selectivity, low biological toxicity and high efficiency of detecting Cu in biological cells2+Ions. The research has important significance for designing and synthesizing the fluorescent probe with high efficiency and high selectivity.
Drawings
The crystal structure of probe Q1 of FIG. 1;
FIG. 2 Probe Q1 with Cu in DMSO aqueous solution2+Absorption spectrum obtained by different concentrations
FIG. 3 shows the absorption spectrum of probe Q1 obtained by adding common metal ions into DMSO aqueous solution.
FIG. 4 Probe Q1 confocal fluorescence imaging pictures, bright field pictures, and overlay pictures in RAW cells. (a) Is a picture of probe Q1 incubated in cells at 37 ℃ for 30 min; (d) the cells were supplemented with 100. mu.M Cu at 37 ℃2+Incubating the pictures for 1 h; (b) and (e) are pictures of the cells in bright field, respectively; (c) and (f) are pictures of cells under overlap, respectively.
Detailed Description
Example 1 synthesis of compound Q1:
a250 mL round bottom flask was charged with the corresponding aldehyde (2mmol), (4mmol)2, 4-dimethylpyrrole, 0.01mL trifluoroacetic acid and 100mL dry dichloromethane and stirred at room temperature overnight. Then 2, 3-dichloro-5, 6-dicyan p-benzoquinone (2mmol) is added for oxidation reaction for 1h, 3mL of triethylamine and boron trifluoride diethyl etherate solution are sequentially added for reaction for 5h, and water is added for quenching reaction. After the reaction is finished, extracting by using dichloromethane, decompressing and spin-drying, carrying out column chromatography, and passing through a column by using a developing agent with the dichloromethane to petroleum ether ratio of 1:2 to obtain a corresponding BODIPY product. The single crystal spectrum of compound Q1 is shown in FIG. 1.
Example 2 synthesis of compound Q2, Q3:
a100 mL two-necked flask was charged with (0.16mmol) of a simple BODIPY compound, (0.32mmol) of the corresponding aldehyde, 0.4mL of anhydrous piperidine, 0.4mL of glacial acetic acid and 50mL of anhydrous acetonitrile, heated to 90 ℃ using a water trap under argon, and the reaction was monitored by TLC until all the starting material spots disappeared. After the reaction is finished, cooling to room temperature, precipitating a large amount of solid after the reaction, and directly filtering to obtain the solid as a product. Extracting the filtrate with water and saturated salt solution, drying with anhydrous sodium sulfate, vacuum concentrating to obtain crude product, performing column chromatography, and purifying with developing agent containing dichloromethane and petroleum ether at a ratio of 1:2 to obtain the corresponding product.
EXAMPLE 3 Probe Q1 As a Probe for Metal ions
Probe Q1 can selectively identify Cu2+The probe Q1 was dissolved in a mixed solution of DMSO and water (V/V, 4:1) at a concentration of 10. mu.M, and Cu of different concentrations was gradually added dropwise2+Into this solution, the corresponding fluorescence emission spectra were then obtained, which were found to follow Cu2+The increase in concentration produces a regular change in the fluorescence spectrum of the probe (FIG. 2). Under the same conditions, adding common metal ion (Al) into another part of the solution3+、Ca2+、Cd2+、Hg2+、K+、Mg2+、Na+、Fe3+、Ni2+、Zn2+、Co2+) The results showed that the fluorescence spectrum of the probe was substantially unchanged (FIG. 3).
Example 4. Probe Q1 was used in bioimaging.
Probe Q1 can be successfully applied to cell imaging and detection of Cu in cells2+Is present. The temperature is controlled at 37 ℃, the probe Q1 is incubated in RAW cells for 30min, and the cells can be seen to have green fluorescence (a) by excitation with 460nm light; cu addition of 100. mu.M2+Cells were incubated for 1 hour and excited with 460nm light, and no fluorescence was observed (d). From the bright field at the same time [ (b) and (e)]And overlapping fields [ (c) and (f)]It was further demonstrated that probe Q1 can detect copper ions in cells (FIG. 4).
Claims (3)
1. A boron fluorine dipyrromethene BODIPY compound is characterized in that: it has the following structure: the compounds corresponding to the substituents R are as follows
2. A process for the preparation of boron-dipyrromethene (BODIPY) -based compounds Q1-Q3 according to claim 1, comprising the steps of:
1. preparation of BODIPY compound Q1:
adding corresponding aldehyde (2mmol), (4mmol)2, 4-dimethylpyrrole, 0.01mL trifluoroacetic acid and 100mL anhydrous dichloromethane into a 250mL round-bottom flask, stirring overnight at room temperature, then adding (0.4500g, 2mmol)2, 3-dichloro-5, 6-dicyan p-benzoquinone, carrying out oxidation reaction for 1h, sequentially adding 3mL triethylamine and 3mL boron trifluoride diethyl etherate solution, reacting for 5h, adding water to quench the reaction, after the reaction is finished, extracting with dichloromethane, carrying out reduced pressure spin drying, carrying out column chromatography, and using a mixed solution of dichloromethane and petroleum ether as a developing agent to obtain a corresponding product.
2. Preparation of BODIPY compounds Q2 and Q3:
in a 100mL two-necked flask, was charged (0.0710g, 0.16mmol) of the BODIPY compound Q1, (0.0430g, 0.32mmol) p-methoxybenzaldehyde, 0.4mL anhydrous piperidine, 0.4mL glacial acetic acid and 50mL anhydrous acetonitrile, heated to 90 ℃ using a water trap under argon, and the reaction was monitored by TLC until all of the Q1 starting material spots disappeared. After the reaction is finished, cooling to room temperature, performing reduced pressure spin drying, performing column chromatography, and passing through a column by using a developing agent with the ratio of dichloromethane to petroleum ether being 1:2 to obtain corresponding products Q2 and Q3.
3. The boron dipyrromethene-based compound of claim 1 in detecting Cu2+Metal ion and biological imaging probe.
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