CN102206235A - Phosphorescent iridium complex capable of dissolving in water system, and preparation method thereof - Google Patents
Phosphorescent iridium complex capable of dissolving in water system, and preparation method thereof Download PDFInfo
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 27
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
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- 238000010992 reflux Methods 0.000 claims description 9
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- 238000000034 method Methods 0.000 claims description 8
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- 238000003756 stirring Methods 0.000 claims description 6
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 claims description 5
- NMLYGLCBSFKJFI-UHFFFAOYSA-N 4-pyridin-2-ylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=CC=N1 NMLYGLCBSFKJFI-UHFFFAOYSA-N 0.000 claims description 5
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- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
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- 238000007363 ring formation reaction Methods 0.000 abstract description 2
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- 125000003277 amino group Chemical group 0.000 abstract 1
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- 230000002708 enhancing effect Effects 0.000 abstract 1
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- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 28
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
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- DKPSSMOJHLISJI-UHFFFAOYSA-N 1,10-phenanthrolin-5-amine Chemical compound C1=CC=C2C(N)=CC3=CC=CN=C3C2=N1 DKPSSMOJHLISJI-UHFFFAOYSA-N 0.000 description 2
- PDDBTWXLNJNICS-UHFFFAOYSA-N 5-nitro-1,10-phenanthroline Chemical compound C1=CC=C2C([N+](=O)[O-])=CC3=CC=CN=C3C2=N1 PDDBTWXLNJNICS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 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
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- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention relates to a phosphorescent iridium complex capable of dissolving in a water system, and a preparation method thereof, and specifically relates to a preparation method for water-soluble cysteine and high-cysteine phosphorescent probes based on an iridium complex, and application thereof in the fields of cell marking and imaging, belonging to the technical field of chemical/biological sensors. By the complex material, an aldehyde group in a C^N complex and an amino group and a sulfydryl group in cysteine and high-cysteine generate cyclization reaction to produce a thiazole ring, thus enhancing the phosphorescent emission of the iridium complex; and water solubility is realized by an N^N complex containing a quaternary ammonium salt, a phosphate, a sulfonate and a carboxylate, thus realizing the detection of cysteine and high-cysteine in an aqueous solution.
Description
Technical Field
The invention belongs to the technical field of chemical/biological sensors, and particularly relates to a preparation method of a water-soluble cysteine and homocysteine phospho-optical probe based on an iridium complex and application of the water-soluble cysteine and homocysteine phospho-optical probe in the fields of cell marking and imaging.
Background
Sulfhydryl-containing amino acids such as cysteine and homocysteine (FIG. 1) play a key role in maintaining physiological balance in human body. For example, cysteine and homocysteine are essential for the growth of cells and tissues and organs in the organism. The lack of cysteine causes serious health problems in humans, such as slow growth, hair loss, skin damage, muscle and fat loss, and liver damage. The lack of homocysteine is more dangerous, and can cause diseases such as senile dementia, cardiovascular diseases, osteoporosis and the like. Therefore, it is important to detect cysteine and homocysteine.
Molecular structures of cysteine and homocysteine
Among the existing techniques for detecting biological thiols, the fluorescence chemical sensor is widely used because of its simplicity and versatility. Having d in contrast to organic fluorescence6、d8And d10The phosphorescent heavy metal complex with the electronic structure has excellent photophysical properties, such as large Stokes shift, easy distinguishing of excitation and emission peaks, capability of being excited by visible light, long emission life, and contribution to effectively distinguishing from background fluorescence signals by using a time resolution technology so as to improve the signal-to-noise ratio and sensitivity of detection.
However, most metal complex phosphorescent probes are limited to detecting cysteine and homocysteine in organic solutions. To date, only a few probes are able to detect cysteine and homocysteine in cells by fluorescence confocal microscopy. The key problem is that the water solubility of the metal complex phosphorescent probe reported at present is poor, and the mixed solvent of water and an organic solvent, such as dimethyl sulfoxide, is necessary for realizing the detection of cysteine and homocysteine in cells, and the organic solvent has toxicity to the cells. Therefore, there is a need to develop new, completely water-soluble metal complex cysteine and homocysteine phosphorescent probes as well as living cell phosphorescent probes.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a phosphorescent iridium complex soluble in a water system, a preparation method thereof, and applications of the complex in detecting cysteine and homocysteine and in cell marking and imaging. And detecting the response performance of the complex to cysteine and homocysteine by using an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum.
The technical scheme is as follows: the phosphorescent iridium complex soluble in a water system has the following structural formula:
wherein,
BF4 -、Cl-or Br-And R represents:
wherein,
Br-or I-And Z is H or Na. The preparation method comprises the following steps:
in particular to 4- (2-pyridyl) -benzaldehyde and IrCl3·3H2And carrying out reflux reaction on the O in a solvent with the mixing ratio of 2-ethoxyethanol to water being 3: 1/v: v for 24 hours to obtain a dichloro bridge intermediate and the phenanthroline derivative, refluxing the dichloro bridge intermediate and the phenanthroline derivative in a solvent with the mixing ratio of dichloromethane to methanol being 2: 1/v: v for 4 hours, adding an ionic salt to be exchanged, stirring the mixture at room temperature for 1 hour, then, spinning out the solvent, and separating the obtained solid by using a column chromatography method to obtain the iridium complex.
Has the advantages that: the structures of the iridium complex material and the intermediate are characterized by Nuclear Magnetic Resonance (NMR), chromaticness-mass spectrometry (GCMS), matrix assisted laser analysis time-of-flight mass spectrometry (MALDI-TOF-MS) and the like, and the influence of the addition of cysteine and homocysteine on photophysical properties and an energy transfer process is detected by using an ultraviolet absorption spectrum and a fluorescence emission spectrum.
According to the invention, the aldehyde group in the C ^ N ligand and the amino and sulfydryl of cysteine and homocysteine generate cyclization reaction to generate thiazole ring, so that the phosphorescence emission of the iridium complex is enhanced; the water solubility is realized by using the N ^ N ligand containing quaternary ammonium salt, phosphate, sulfonate and carboxylate, so that the detection of cysteine and homocysteine in a water system is realized.
Drawings
FIG. 1 is a graph showing changes of UV-visible spectrum of synthesized complex of the present invention for cysteine and homocysteine. FIG. 1a shows cysteine and FIG. 1b shows homocysteine.
FIG. 2 is a graph showing the change of fluorescence emission spectra of the complex synthesized in the present invention for cysteine and homocysteine. FIG. 2a shows cysteine and FIG. 2b shows homocysteine.
FIG. 3 shows selectivity test of the complex synthesized in the present invention.
Detailed Description
The invention provides a phosphorescent iridium complex for detecting cysteine and homocysteine in a water system, which has a specific structural formula as follows:
wherein,BF4 -、Cl-or Br-And R can respectively represent:
wherein,Br-or I-And Z is H or Na.
The preparation and synthesis route of the water-soluble phosphorescent iridium complex provided by the invention is as follows:
in particular to 4- (2-pyridyl) -benzaldehyde and IrCl3·3H2And carrying out reflux reaction on the O in a mixed solvent (3: 1/v: v) of 2-ethoxyethanol and water for 24 hours, refluxing the obtained dichloro bridge intermediate and the phenanthroline derivative in the mixed solvent (2: 1/v: v) of dichloromethane and methanol for 4 hours, adding ionic salt to be exchanged, stirring at room temperature for 1 hour, then, spinning out the solvent, and separating the obtained solid by using a column chromatography method to obtain the iridium complex.
The application of the iridium complex with water-soluble phosphorescence is as follows: detection of cysteine and homocysteine, cell labeling and imaging.
In order to better understand the contents of the present patent, the following further illustrates the technical solution of the present invention by specific examples. The method specifically comprises synthesis, property determination and titration experiments. These examples do not limit the invention.
Example 1 preparation of water-soluble iridium complex:
compound 1: preparation of 5-nitro-1, 10-phenanthroline
Adding 5g of 1, 10-o-phenanthroline hydrate into a round-bottom flask, adding 30mL of concentrated sulfuric acid for dissolution, then dropwise adding 15mL of fuming nitric acid, heating the solution to keep the temperature at 160-170 ℃, and carrying out reaction reflux for 2 hours. After the reaction was completed, it was allowed to cool to room temperature, and then the solution was poured into ice water. The pH was adjusted to 3 by adding 10% strength sodium hydroxide solution. The yellow precipitate which separated out was the product, filtered off with suction, washed with clear water and dried in vacuo. 5g (88%) of a pale yellow solid are obtained. GC-MS (EI-m/z): 225 (M)+)
Compound 2: preparation of 5-amino-1, 10-phenanthroline
1.889g of 5-nitro-1, 10-phenanthroline is dissolved in 150mL of anhydrous ethanol, 0.378g of 5% Pd/C catalyst is added, the mixture is heated to 70 ℃ under the protection of nitrogen, and then 150mL of anhydrous ethanol and 1.3g of hydrazine hydrate mixed solution are added dropwise for reflux reaction for 5 hours. After the reaction was completed, it was allowed to cool to room temperature, and the Pd/C catalyst was filtered off while it was hot, and washed with ethanol several times. Most of ethanol in the filtrate is evaporated, cooled, yellow solid is separated out, filtered, dried and recrystallized by ethanol to obtain yellow needle-shaped solid (1.42g, 76%).1HNMR(400MHz，CDCl3)9.21(d，1H)，8.95(d，1H)，8.28(d，1H)，7.99(d，1H)，7.66(dd，1H)，7.52(dd，1H)，6.9(s，1H)，4.3(s，2H).
Compound 3: preparation of N ^ N ligand (cpa)
0.3g of 5-amino-1, 10-phenanthroline is dissolved in 55mL of anhydrous tetrahydrofuran, 0.22mL of triethylamine is added, and the mixture is stirred for 30min under the protection of nitrogen. The mixture was then cooled to 0 deg.C, and a mixture of 5mL tetrahydrofuran and 0.22mL chloroacetyl chloride was added dropwise and stirred overnight at room temperature. After completion of the reaction, it was washed with 5% aqueous sodium bicarbonate, and the organic layer was collected, spin-dried, washed with water and ether to give a brown solid (0.241 g; 59%).1HNMR(400MHz，CDCl3)9.26(d，1H)，9.18(d，1H)，8.95(s，1H)，8.38(s，1H)，8.33(d，1H)，8.26(d，1H)，7.72-7.75(dd，1H)，7.66-7.69(dd，1H)，4.43(s，2H).
Compound 4: preparation of 4- (2-pyridyl) -benzaldehyde dichloro-bridge
Weighing IrCl3·3H2O (1mmol) and 4- (2-pyridyl) -benzaldehyde (2.5mmol) are added into a three-neck flask, and the three-neck flask is vacuumized, filled with nitrogen and vacuumized on a double-row pipe, circulated for three times, and finally protected by nitrogen. Injecting a mixture (3: 1/v: v) of 2-ethoxyethanol and water into a reaction system by using an injector, stirring, heating the reaction system to 110 ℃, and reacting for about 24 hours, wherein a precipitate is generated in the reaction process. The reaction system is cooled to room temperature, and then the precipitate is filtered and washed with water and ethanol to obtain a solid product, namely. Yield: 68 percent of
Compound 5: iridium complex [ Ir (bpa)2cpa]+PF6 -Preparation of
Weighing 121mg of iridium dichlorobridge compound and 68mg of N ^ N ligand (cpa) into a double-neck bottle, and adding15mL CH2Cl2And a mixed solvent of methanol (2: 1/v: v) under magnetic stirring. After 4 hours, cool to room temperature and add 5 equivalents of potassium hexafluorophosphate (KPF)6) After stirring for about 1 hour, the solvent was removed by rotary evaporation under reduced pressure, and the resulting solid mixture was redissolved in about 10mL of CH2Cl2Filtering to remove insoluble substances, removing solvent from the filtrate by rotary evaporation under reduced pressure, and separating the obtained solid by column chromatography (dichloromethane/acetone) to obtain pure product. Yield: 69 percent1H NMR(400MHz，CDCl3)9.76(d，2H)，9.24(s，1H)，8.80(d，1H)，8.52-8.55(d，2H)，8.23(d，1H)，8.19(d，1H)，8.04-8.09(dd，2H)，7.84-7.91(m，4H)，7.74-7.77(dd，1H)，7.58-7.61(t，2H)，7.43-7.46(t，2H)，7.11-7.13(t，1H)，7.11-7.13(t，1H)，7.05-7.07(t，1H)，6.80-6.83(d，2H)，4.40(d，2H).
Compound 6: iridium complex [ Ir (bpa)2pto]PF6 -Is prepared under N2Under the protection condition, 1 equivalent of iridium complex is dissolved in a dimethylformamide solution, 10 equivalents of triethylamine is dropwise added, and the temperature is raised to 110 ℃ for reflux stirring reaction for 3 hours; cooling to room temperature, spinning out a dimethylformamide solution, dissolving the obtained solid in a small amount of dichloromethane, separating by using a column chromatography method, spinning out a developing agent, and drying in vacuum to obtain the water-soluble iridium complex. Yield: 37 percent of1H NMR(400MHz，CDCl3)9.76(s，2H)，8.75(s，1H)，8.55(d，1H)，8.19(d，1H)，8.06-8.09(t，3H)，7.84-7.91(m，5H)，7.68-7.72(dd，1H)，7.58-7.60(m，2H)，7.42(d，1H)，7.38(d，1H)，7.03-7.07(t，2H)，7.02-7.10(m，2H)，6.81-6.84(dd，2H)，3.66-3.72(dd，6H)，1.46-1.49(t，9H).m/e 893.7(M-PF6).
Example 2: uv-vis spectroscopy of the complex response to cysteine and homocysteine: preparing 20 mu M of complex solution (pure water is used as a solvent), transferring 2mL of complex solution into a fluorescence cuvette, gradually dropwise adding 0-200eq of cysteine and homocysteine solution which are used as the solvent, until the balance is reached (namely the spectrum does not obviously change any more), and respectively measuring the ultraviolet-visible emission spectrogram without adding or dropwise adding different contents of cysteine and homocysteine, as shown in figure 1. The test data shows that: with the addition of cysteine and homocysteine, the absorption peaks near 320nm and 430nm decrease.
Example 3: fluorescence emission spectroscopy test of the complexes in response to cysteine and homocysteine: preparing 20 mu M of complex solution (pure water is used as a solvent), transferring 2mL of complex solution into a fluorescence cuvette, gradually dropwise adding 0-200eq of cysteine and homocysteine solution which are used as the solvent, until the balance is reached (namely the spectrum does not obviously change any more), and respectively measuring fluorescence emission spectrograms of cysteine and homocysteine with different contents without adding or dropwise adding, as shown in figure 2. The test data shows that: with the addition of cysteine and homocysteine, the emission intensity gradually increased.
Example 4: selective experiments: prepare 20 μ M complex solution (pure water as solvent), remove 2mL complex solution in the fluorescence cuvette, add 200eq pure water as solvent for different amino acids, reach equilibrium, and then test, as shown in FIG. 3. The test data shows that: the complex has no response to other amino acids except cysteine and homocysteine.
Example 5: live cell imaging experiments:
the iridium complex was prepared as a 10mmol solution, and 20uL of the solution was transferred to 2000uL of PBS buffer solution to dilute the solution to a concentration of 10. mu.M. After incubating the cells for 30 minutes by taking 2mL of solution, the cells are washed 3-5 times by PBS buffer solution, confocal imaging of the cells is excited by 405nm wavelength, and Z scanning is carried out. The test data shows that: the water-soluble iridium complex has good cell penetrability and is distributed in a cytoplasmic region.
Claims (2)
1. A phosphorescent iridium complex soluble in a water system, characterized in that the iridium complex has the following structural formula:
wherein,
BF4 -、Cl-or Br-And R represents:
wherein,
Br-or I-And Z is H or Na.
2. A process for the preparation of a phosphorescent iridium complex soluble in aqueous systems according to claim 1, characterized in that the route of the preparation is as follows:
in particular to 4- (2-pyridyl) -benzaldehyde and IrCl3·3H2And carrying out reflux reaction on the O in a solvent with the mixing ratio of 2-ethoxyethanol to water being 3: 1/v: v for 24 hours to obtain a dichloro bridge intermediate and the phenanthroline derivative, refluxing the dichloro bridge intermediate and the phenanthroline derivative in a solvent with the mixing ratio of dichloromethane to methanol being 2: 1/v: v for 4 hours, adding an ionic salt to be exchanged, stirring the mixture at room temperature for 1 hour, then, spinning out the solvent, and separating the obtained solid by using a column chromatography method to obtain the iridium complex.
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