CN115466292A - Ruthenium complex probe and preparation method and application thereof - Google Patents
Ruthenium complex probe and preparation method and application thereof Download PDFInfo
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- CN115466292A CN115466292A CN202211136376.6A CN202211136376A CN115466292A CN 115466292 A CN115466292 A CN 115466292A CN 202211136376 A CN202211136376 A CN 202211136376A CN 115466292 A CN115466292 A CN 115466292A
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- hypochlorous acid
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- 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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention discloses a ruthenium complex probe and a preparation method and application thereof, and belongs to the technical field of phosphorescent probes. The ruthenium complex probe has the following structure:
the invention has the advantages that: (1) The ruthenium complex probe provided by the invention has the advantages of large Stokes displacement, good selectivity, high sensitivity and short response time, can quickly, real-timely and specifically detect hypochlorous acid in an environment, and is an excellent 'turn-on' type phosphorescent probe; (2) The ruthenium complex probe provided by the invention has lower cytotoxicity and excellent mitochondrial targeting capability, can target mitochondria of living cells, and detects hypochlorous acid in the mitochondria of the living cells; (3) The ruthenium complex provided by the inventionThe preparation method of the compound probe has the advantages of mild reaction conditions and simple preparation process.
Description
Technical Field
The invention relates to a phosphorescent probe, a preparation method and application thereof, in particular to a ruthenium complex probe, a preparation method thereof and application thereof in hypochlorous acid detection, and belongs to the technical field of phosphorescent probes.
Background
Under the global abuse and repeated large environment of new crown blight, a plurality of places in the environment need to be subjected to simple disinfection operation, wherein the hypochlorous acid disinfectant has a good effect in epidemic prevention and disinfection in recent years, and the oxidation effect of the hypochlorous acid can oxidize bacteria and the drug potency of the hypochlorous acid. However, the corrosivity and strong oxidizing property of hypochlorous acid have certain potential harm to the environment, and when excessive hypochlorous acid is left in the water treatment process, the residual chlorine ions in a circulating water system are excessive, the pH balance is influenced, and the pollution and the damage to underground water, soil and air are caused.
In addition, under normal physiological conditions, intracellular oxidative and reductive substances are in dynamic equilibrium, and if this equilibrium is broken, it will cause imbalance of internal environment, damage to biological tissues, and even induce cancer. Reactive Oxygen Species (ROS) are a general term for a series of oxygen-containing compounds that are produced by metabolism in the living body, and are one of oxidative substances, which play important roles in various physiological processes, such as cell information transduction, cell differentiation, migration, cellular immunity, and the like. Therefore, monitoring ROS in organisms will help to study their pathogenesis and realize specific diagnosis and treatment. Among many ROS, protonated hypochlorous acid, which is generated by chloride ions and hydrogen peroxide in the catalytic reaction of myelocatalase, has higher oxidation and shorter lifespan, mainly in neutrophils, macrophages and monocytes in the organism. The abnormal change of hypochlorous acid may cause various diseases such as rheumatoid, lung injury, arthritis, cardiovascular diseases, etc., and has attracted much attention. Therefore, it is crucial to resolve the physiological role of hypochlorous acid in immune and pathological processes, and to design highly selective and sensitive detection strategies.
At this stage, phosphorescence and fluorescence are widely spotlighted as one of the most convenient and sensitive methods in the imaging technology, which reflect the content of hypochlorous acid by a change in luminous intensity. The phosphorescence molecular probe enhances intersystem crossing of electrons from an excited singlet state to an excited triplet state due to a strong spin-orbit coupling effect caused by d electrons of metal, and causes the complex molecules to generate phosphorescence with longer emission life than small molecules. Compared with fluorescent organic small molecules, the phosphorescent complex molecules also have the properties of good light stability, photobleaching resistance, larger Stokes shift and the like. The method has great advantages for monitoring and imaging in complicated micro-environments, and combines a time resolution technology to improve the sensitivity of detecting the target object in the complicated micro-environments, so that the method becomes a novel biological imaging material with development prospect.
To date, organic small molecule probes for hypochlorous acid have been extensively studied, while phosphorescent probes have also been partially studied, for example:
(1) In environmental analysis, a test strip for detecting hypochlorous acid is prepared by combining a phosphorescent probe with the test strip, the hypochlorous acid is rapidly and visually detected in the environment and a water body, and the concentration of the hypochlorous acid is judged by the aid of the shade of color (Hou LX, shangguanan M Q, lu Z, et al. A cyclomethylated iridium (III) complex-based fluorescence detection and application by test strips [ J ],2019, 566, 27-31);
(2) In bioassays, phosphorescent probes achieve targeted detection of different organelles in cells by their own properties or introduction of different organelle targeting groups, and imaging hypochlorous acid in cells and organisms with the aid of imaging microscopy for analyzing their physiological role in immune and pathological processes (Li GY, lin Q, sun L, et al. Phosphorescent targeted to wo-phototon Iridium (III) for selective detection of hypochrous in live cells and in vivo, biomaterials,2015, 53, 285-295 Wu W J, guan R L, liao X, et al. Bimodal Visualization of endogenesis Nitric Oxide in solutions with a Two-Photon Iridium (III) phosphor reagent, analysis, 2019, 10272, et al.
However, the application of the ruthenium-based complex probe to the specificity, quick response and real-time monitoring of hypochlorous acid still remains a problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide a ruthenium complex probe capable of quickly, timely and specifically detecting hypochlorous acid in environment and mitochondria of living cells, and a preparation method of the ruthenium complex probe.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a ruthenium complex probe is characterized by having a structure shown as follows:
a method for preparing the ruthenium complex probe is characterized by comprising the following steps:
(1) Preparation of Compound 1
Mixing 5-methyl phenanthroline and SeO 2 Placing in o-dichlorobenzene, refluxing at 180 deg.C for 4h, cooling the mixture to room temperature and filtering with diatomaceous earth, extracting the filtrate with hydrochloric acid solution, collecting the water phase, adjusting pH of the water phase to neutrality, and extracting the water phase with dichloromethaneCollecting the organic layer, and collecting anhydrous MgSO 4 Adding into organic layer, shaking and drying at room temperature for 20min, filtering and collecting solution, and finally removing solvent by vacuum evaporation to obtain compound 1;
(2) Preparation of Compound 2
Placing the compound 1 and diaminobenzonitrile in ethanol, refluxing for 6h at 75 ℃, cooling to room temperature, filtering the mixture, washing with ethanol, and drying to obtain a compound 2;
(3) Preparation of Compound 3
Adding RuCl 3 ·3H 2 Placing O, phenanthroline and LiCl in N, N-dimethylformamide, refluxing for 8h at 150 ℃ under the protection of nitrogen, cooling to room temperature, adding acetone, cooling the obtained solution at 0 ℃ overnight, filtering the precipitate, washing with cold distilled water and acetone, and drying to obtain a compound 3;
(4) Synthesis of ruthenium Complex probes
Adding the compound 2 and the compound 3 into a flask, adding dichloromethane and methanol, refluxing at 65 ℃ for 24h under the protection of nitrogen, after the reaction is finished, evaporating the dichloromethane under reduced pressure, and then adding the mixture containing NH 4 PF 6 The aqueous solution of (a) was added to the flask, stirred for 1 hour, and the resulting residue was filtered, dried and then the crude product was purified by silica gel column chromatography to obtain a ruthenium complex probe.
Preferably, in step (1), 5-methylphenanthroline and SeO 2 The molar ratio of (a) to (b) is 52.
Preferably, in step (2), the molar ratio of compound 1 to diaminobenzonitrile is 5.
Preferably, in step (3), ruCl 3 ·3H 2 The molar ratio of O, phenanthroline and LiCl is 5.
Preferably, in step (4), compound 2, compound 3 and NH 4 PF 6 1; the volume ratio of dichloromethane to methanol is 1.
The invention has the advantages that:
(1) The ruthenium complex probe provided by the invention has the advantages of large Stokes displacement, good selectivity, high sensitivity and short response time, can quickly and specifically detect hypochlorous acid in an environment in real time, has the luminous intensity increased along with the increase of the hypochlorous acid concentration, shows a good linear relation in a certain concentration range, and is an excellent 'turn-on' type phosphorescent probe;
(2) Cell experiments prove that the ruthenium complex probe provided by the invention has lower cytotoxicity and excellent mitochondrial targeting capability, can target mitochondria of living cells and detect hypochlorous acid in the mitochondria of the living cells, and has important significance for deeply researching the physiological process of the hypochlorous acid in organisms;
(3) The preparation method of the ruthenium complex probe provided by the invention has the advantages of mild reaction conditions and simple preparation process.
Drawings
FIG. 1 shows a ruthenium complex probe prepared according to the present invention 1 H NMR spectrum;
FIG. 2 is a graph showing the UV titration absorption spectrum of a ruthenium complex probe prepared according to the present invention in response to hypochlorous acid;
FIG. 3 is a graph of phosphorescence titration emission spectra of ruthenium complex probes prepared according to the present invention in response to hypochlorous acid;
FIG. 4 is a linear fit of phosphorescence intensity for different hypochlorous acid concentration responses for ruthenium complex probes prepared in accordance with the present invention;
FIG. 5 is a graph showing the response of the ruthenium complex probe prepared according to the present invention to hypochlorous acid at various pH values;
FIG. 6 is a graph showing the time response of a ruthenium complex probe prepared according to the present invention;
FIG. 7 is a graph showing the selective recognition of different ions by the ruthenium complex probe prepared according to the present invention;
FIG. 8 is a graph showing the results of the toxicity test of cells (Hela) using the ruthenium complex probe according to the present invention;
FIG. 9 is a diagram showing the co-localization of cells (Hela) and mitochondria of the ruthenium complex probe prepared according to the present invention, wherein (a) is an image of cells after the ruthenium complex probe responded to hypochlorous acid, (b) is an image of cells of a mitochondrial localization agent (Mito-Tracker Green), (c) is an image of Merge of (a) and (b), and (d) is a Pearson correlation coefficient diagram;
FIG. 10 is a graph showing the intensity of cell (Hela) mitochondrial co-localization of the ruthenium complex probe prepared according to the present invention and the co-localization agent.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
1. Structure of ruthenium complex probe
The ruthenium complex probe provided by the invention has the following structure:
the ruthenium-based complex is specifically a phenanthroline complex of ruthenium.
2. Preparation method of ruthenium complex probe
The invention provides a method for preparing a ruthenium complex probe with the structure, which comprises the following steps:
(1) Preparation of Compound 1
1.00g (5.20 mmol) of 5-methylphenanthroline and 1.38g (12.30 mmol) of SeO 2 Placed in 80mL of o-dichlorobenzene at 180 ℃ under reflux for 4h, then the mixture was cooled to room temperature and filtered through celite, followed by 200mL of hydrochloric acidSolution (1.0 mol/L) the filtrate was extracted in four portions, the aqueous phase was collected and the pH of the aqueous phase was adjusted to neutral, then the aqueous phase was extracted five times with 250mL of dichloromethane, the organic layer was collected and 0.5g of anhydrous MgSO (MgSO) was added 4 Added to the organic layer, dried at room temperature for 20min with shaking, filtered and the solution collected, and finally the solvent was removed by evaporation in vacuo to yield 0.75g (3.60 mmol) of compound 1. The yield was 69%.
The hydrogen nuclear magnetic resonance spectrum of compound 1 is as follows:
1 H NMR(400MHz，DMSO-d 6 )δ10.43(s，1H)，9.60(dd，J＝8.5，1.6Hz，1H)，9.26(dd，J＝4.2，1.8Hz，1H)，9.18(dd，J＝4.2，1.8Hz，1H)，8.80(s，1H)，8.73(dd，J＝8.2，1.8Hz，1H)，7.93-7.87(m，2H)。
(2) Preparation of Compound 2
208mg (1 mmol) of compound 1 and 129.6mg (1.2 mmol) of diaminobenzonitrile are placed in 40mL of ethanol and refluxed at 75 ℃ for 6h, after cooling to room temperature, the mixture is filtered, washed with 20mL of ethanol and dried to yield 207mg (0.69 mmol) of compound 2. The yield was 69%.
The hydrogen nuclear magnetic resonance spectrum of compound 2 is as follows:
1 H NMR(400MHz，DMSO-d 6 )δ9.57(dd，J＝8.6，1.7Hz，1H)，9.16(dd，J＝4.5，1.7Hz，2H)，8.88(s，1H)，8.78(s，1H)，8.53(dd，J＝8.2，1.8Hz，1H)，8.13(s，2H)，7.85(td，J＝7.7，4.2Hz，2H)。
(3) Preparation of Compound 3
261.5mg (1 mmol) of RuCl 3 ·3H 2 O, 396mg (2 mmol) of phenanthroline and 195mg (4.6 mmol) of LiCl are placed in 5mL of N, N-dimethylformamide and refluxed at 150 ℃ for 8h under the protection of nitrogen, and then cooled to room temperatureThereafter, 10mL of acetone was added, the resulting solution was cooled at 0 ℃ overnight, and the precipitate was filtered and washed three times with cold distilled water and acetone (for the purpose of removing impurities before drying), and dried to obtain 435.0mg (765.8 mmol) of compound 3. The yield was 76.58%.
Compound 3 was used directly in the next reaction without further purification.
(4) Synthesis of ruthenium Complex probes
59.6mg (0.2 mmol) of Compound 2 and 113.6mg (0.2 mmol) of Compound 3 are introduced into a 50mL round-bottomed flask, 10mL of dichloromethane and 10mL of methanol are then added, and the mixture is refluxed at 65 ℃ for 24 hours under nitrogen, after the reaction is completed, dichloromethane in the solution is removed by evaporation under reduced pressure, and then a solution containing 326mg (2 mmol) of NH is obtained 4 PF 6 Was added to a round bottom flask, stirred for 1h, the resulting residue was filtered, dried and the crude product was purified by silica gel column chromatography (DCM/MeOH = 50/1) to give 105.0g (0.1 mmol) of ruthenium complex probe. The yield was 50%.
The hydrogen nuclear magnetic resonance spectrum of the ruthenium complex probe is as follows:
1 H NMR(400MHz，DMSO-d 6 )δ9.70(dd，J＝8.7，1.2Hz，1H)，9.05(s，1H)，8.97(s，1H)，8.69(ddd，J＝8.3，3.4，1.7Hz，5H)，8.32(s，4H)，8.19-8.12(m，5H)，8.10(dt，J＝5.3，1.8Hz，2H)，7.79(dd，J＝8.7，5.3Hz，1H)，7.73(dtd，J＝7.9，6.0，5.5，2.7Hz，6H)。
of the ruthenium Complex Probe 1 The H NMR spectrum is shown in FIG. 1.
The prepared ruthenium complex probe was dissolved in DMSO to prepare a 10mM stock solution. Unless otherwise specified, the samples used in the following experiments were obtained by stock dilution.
3. Ultraviolet titration absorption spectrum for detecting ruthenium complex probe
The absorption spectrum of a ruthenium complex probe (10 μ M) was measured, and the test solvent was a mixed solution of DMSO/PBS =1/1 (V/V), and the uv spectrum was collected at a spectral window of 300 to 650nm for every 50 μ M of hypochlorous acid added.
The ultraviolet titration absorption spectrum of the ruthenium complex probe in response to hypochlorous acid is shown in fig. 2.
As can be seen from FIG. 2, as the hypochlorous acid concentration in the system increases (0 to 500. Mu.M), the ruthenium complex probe shows a red-shift characteristic in the ultraviolet spectrum in the visible light region, its peak at 400nm gradually disappears, new peaks appear at 425nm and 460nm, and the peak intensity decreases as a whole.
This indicates that the molecular structure of the ruthenium complex probe is changed after hypochlorous acid is added, which results in a change in the ultraviolet absorption spectrum, and at the same time, the change enables the detection of the hypochlorous acid concentration.
4. Phosphorescence titration emission spectrum for detecting ruthenium complex probe
The emission spectrum of the ruthenium complex probe (10 μ M) was measured using a mixed solution of DMSO/PBS =1/1 (V/V) as a test solvent, an excitation wavelength of 460nm, a spectrum window of 500 to 750nm, and a phosphorescence spectrum at every 50 μ M hypochlorous acid addition.
The resulting phosphorescence titration emission spectrum of the ruthenium complex probe in response to hypochlorous acid is shown in FIG. 3.
As can be seen from FIG. 3, the maximum emission wavelength was 590nm, and the phosphorescence intensity of the ruthenium complex probe solution gradually increased as the hypochlorous acid concentration (0 to 600. Mu.M) in the system increased.
Therefore, the ruthenium complex probe can realize the detection of the concentration of hypochlorous acid.
5. Linear relationship of detection ruthenium complex probe to response of different hypochlorous acid concentrations
The phosphorescence intensity of the ruthenium complex probe response for different concentrations of hypochlorous acid was linearly fitted.
The linear fit plot of the phosphorescence intensity of the resulting ruthenium complex probe in response to different hypochlorous acid concentrations is shown in fig. 4.
As can be seen from FIG. 4, the ruthenium complex probe showed a good linear relationship in the concentration range of 75 to 450. Mu.M.
This indicates that the ruthenium complex probe has the ability to quantitatively detect hypochlorous acid.
6. Detecting the response condition of the ruthenium complex probe to hypochlorous acid under different pH values
Emission spectra of ruthenium complex probe (10 μ M) were measured under different pH conditions without and with hypochlorous acid added, and the test solvent was a mixed solution of DMSO/PBS =1/1 (V/V), excitation wavelength was 460nm, and phosphorescence intensity at 590nm was collected.
The response graph of the resulting ruthenium complex probe to hypochlorous acid at different pH's is shown in FIG. 5.
As can be seen from FIG. 5, the ruthenium complex probe shows better stability in the pH range of 7-11, and the phosphorescence signal is enhanced after hypochlorous acid is added, wherein the phenomenon of the ruthenium complex probe is more obvious in a weak alkaline environment, which lays a good foundation for the application of the ruthenium complex probe in organisms.
7. Detection of time response of ruthenium complex probes
The time for which phosphorescence of a ruthenium complex probe (10. Mu.M) stabilized after hypochlorous acid was added was measured, and the test solvent was a mixed solution of DMSO/PBS =1/1 (V/V), the excitation wavelength was 460nm, and the phosphorescence intensity at 590nm was collected.
The time response of the resulting ruthenium complex probe is shown in FIG. 6.
As can be seen from FIG. 6, the phosphorescence at 590nm of the ruthenium complex probe solution rapidly increased to be stable after the addition of hypochlorous acid, and the change process was completed within 15 s.
This indicates that the ruthenium complex probe has a fast response speed, which is advantageous for increasing the speed and efficiency of detecting hypochlorous acid.
8. Detecting the selectivity of a ruthenium complex probe for different ions
Measuring the phosphorescence spectral response of the ruthenium complex probe (10 mu M) and different objects to be measured, wherein the objects to be measured are respectively ClO - 、ONOO - 、NO、 1 O 2 、O 2 ·- 、·OH、H 2 O 2 、TBHP、SO 4 2+ 、CO 3 2+ 、K + 、Ca 2+ 、Na + 、Mg 2+ 、Cu 2+ Cys, hcy and GSH, wherein a test solvent is a mixed solution of DMSO/PBS =1/1 (V/V), the concentration of a substance to be tested is 300 mu M, the excitation wavelength is 460nm, and the phosphorescence intensity at 590nm is collected.
The resulting selective recognition pattern of the ruthenium complex probe for different ions is shown in fig. 7.
As can be seen from FIG. 7, other active oxygen species and common interfering ions, in addition to hypochlorous acid, did not produce a significant change in phosphorescence intensity for the ruthenium complex probe.
This shows that the ruthenium complex probe has excellent selectivity for hypochlorous acid, and can effectively avoid the interference of other ions on the detection result.
9. Detection of cell (Hela) toxicity of ruthenium Complex probes
Digesting the cells at 5X 10 4 Density of/well into 96-well cell culture plates, setting 3 multiple wells, and accounting for 5% CO at 37 ℃% 2 Culturing in an incubator for 24h. After the cells grew into a monolayer, the culture solution was discarded, ruthenium complex probe solutions (0. Mu.M, 3.125. Mu.M, 6.25. Mu.M, 12.5. Mu.M, 25. Mu.M, 50. Mu.M) having different concentration gradients were added thereto, the mixture was charged at 37 ℃ and 5% CO 2 And (3) incubating the culture box for 4 hours, adding 20 mu of LMTT solution into each hole, continuing to culture for 4 hours, stopping culturing, carefully absorbing the culture solution in each hole, adding 150 mu of LDMSO into each hole, oscillating the microplate reader for 10min to fully dissolve crystals, and measuring the OD value by the microplate reader.
The cell (Hela) toxicity profile of the resulting ruthenium complex probe is shown in FIG. 8.
As can be seen from FIG. 8, the ruthenium conjugate probe was very weak in toxicity to Hela cells and had an even proliferative effect on Hela cells; the survival rate of Hela cells gradually decreased with the increase of the concentration of the ruthenium complex probe, but the survival rate of Hela cells was about 100% even at a concentration of 50. Mu.M, as compared with the control group.
This indicates that the ruthenium complex probe has very low cytotoxicity and has little toxic harm to cells.
10. Detection of cell mitochondrial co-localization of ruthenium complex probes
HeLa cells were grown adherent to a six-well plate at 37 ℃ overnight, and the cells were incubated with a ruthenium complex probe solution (30. Mu.M) and Mito-Tracker Green (1. Mu.M) for 30min, followed by addition of a hypochlorous acid solution (100. Mu.M), incubation for 10min, and cell imaging using a confocal microscope. For the ruthenium complex probe, the excitation wavelength is 488nm, and the emission wavelength is 550-700 nm. For MTG, the excitation wavelength is 488nm, and the emission wavelength is 500-530 nm.
The obtained image of the co-localization of the cell mitochondria is shown in FIG. 9, and the obtained graph of the intensity of the co-localization of the cell mitochondria is shown in FIG. 10.
As can be seen from FIG. 9, the Pearson correlation coefficient (Pr) of the ruthenium complex probe with Mito-Tracker Green was 0.92.
As can be seen from FIG. 10, the ruthenium complex probe coincided well with the intensity curve of Mito-Tracker Green.
This indicates that the ruthenium complex probe targets mainly mitochondria after entering cells.
Mitochondria serve as a major site of energy conversion in cells, and play an important role in metabolism of living bodies. The ruthenium complex probe provided by the invention mainly targets mitochondria after entering cells, so the ruthenium complex probe can monitor the change of hypochlorous acid in mitochondria, which is important for analyzing the physiological action of the hypochlorous acid in the immune and pathological processes.
In conclusion, the ruthenium complex probe provided by the invention has the advantages of good hypochlorous acid selectivity, high sensitivity, short response time, lower cytotoxicity and excellent mitochondrial targeting capability, so that the probe can be used for quickly, specifically detecting hypochlorous acid in an environment in real time and also can be used for targeting mitochondria of living cells to detect hypochlorous acid in the mitochondria of the living cells.
It should be noted that the above-mentioned embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious and belong to the technical scheme of the invention are still in the protection scope of the invention.
Claims (9)
1. A ruthenium complex probe is characterized by having the following structure:
2. a method of preparing the ruthenium complex probe of claim 1, comprising the steps of:
(1) Preparation of Compound 1
Mixing 5-methyl phenanthroline and SeO 2 Placing in o-dichlorobenzene, refluxing at 180 deg.C for 4 hr, cooling the mixture to room temperature and filtering with diatomaceous earth, extracting the filtrate with hydrochloric acid solution, collecting the water phase, adjusting pH of the water phase to neutrality, extracting the water phase with dichloromethane, collecting the organic layer, and collecting anhydrous MgSO 4 Adding into organic layer, shaking and drying at room temperature for 20min, filtering and collecting solution, and removing solvent by vacuum evaporation to obtain compound 1;
(2) Preparation of Compound 2
Placing the compound 1 and diaminobenzonitrile in ethanol, refluxing at 75 ℃ for 6h, cooling to room temperature, filtering the mixture, washing with ethanol, and drying to obtain a compound 2;
(3) Preparation of Compound 3
Adding RuCl 3 ·3H 2 Placing O, phenanthroline and LiCl in N, N-dimethylformamide, refluxing for 8h at 150 ℃ under the protection of nitrogen, cooling to room temperature, adding acetone, cooling the obtained solution at 0 ℃ overnight, filtering the precipitate, washing with cold distilled water and acetone, and drying to obtain a compound 3;
(4) Synthesis of ruthenium Complex probes
Adding the compound 2 and the compound 3 into a flask, adding dichloromethane and methanol, refluxing at 65 ℃ for 24h under the protection of nitrogen, evaporating dichloromethane under reduced pressure after the reaction is finished, and adding NH 4 PF 6 The obtained aqueous solution was added to a flask, stirred for 1 hour, and the obtained residue was filtered, dried and then purified by silica gel column chromatography to obtain a ruthenium complex probe.
3. The method according to claim 2, wherein, in step (1), 5-methylphenanthrene and SeO 2 The molar ratio of (a) to (b) is 52.
4. The process according to claim 2, wherein in step (2), the molar ratio of compound 1 to diaminobenzonitrile is 5.
5. The method of claim 2, wherein in step (3), ruCl 3 ·3H 2 The molar ratio of O, phenanthroline and LiCl is 5.
6. The method according to claim 2, wherein in step (4), compound 2, compound 3 and NH 4 PF 6 1.
7. The method according to claim 2, wherein in step (4), the volume ratio of dichloromethane to methanol is 1.
8. Use of the ruthenium complex probe of claim 1 to detect hypochlorous acid in an environment.
9. Use of the ruthenium complex probe according to claim 1 for detecting hypochlorous acid in a living cell mitochondria.
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