CN115466292B - 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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- CN115466292B CN115466292B CN202211136376.6A CN202211136376A CN115466292B CN 115466292 B CN115466292 B CN 115466292B CN 202211136376 A CN202211136376 A CN 202211136376A CN 115466292 B CN115466292 B CN 115466292B
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- 239000000523 sample Substances 0.000 title claims abstract description 103
- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229940125782 compound 2 Drugs 0.000 claims description 12
- 229940126214 compound 3 Drugs 0.000 claims description 12
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- 238000000034 method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
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- UJAQYOZROIFQHO-UHFFFAOYSA-N 5-methyl-1,10-phenanthroline Chemical compound C1=CC=C2C(C)=CC3=CC=CN=C3C2=N1 UJAQYOZROIFQHO-UHFFFAOYSA-N 0.000 claims description 2
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- 238000006073 displacement reaction Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
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- 238000012360 testing method Methods 0.000 description 10
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- RUVJFMSQTCEAAB-UHFFFAOYSA-M 2-[3-[5,6-dichloro-1,3-bis[[4-(chloromethyl)phenyl]methyl]benzimidazol-2-ylidene]prop-1-enyl]-3-methyl-1,3-benzoxazol-3-ium;chloride Chemical compound [Cl-].O1C2=CC=CC=C2[N+](C)=C1C=CC=C(N(C1=CC(Cl)=C(Cl)C=C11)CC=2C=CC(CCl)=CC=2)N1CC1=CC=C(CCl)C=C1 RUVJFMSQTCEAAB-UHFFFAOYSA-M 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
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- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 208000037273 Pathologic Processes Diseases 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 3
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- 229910052707 ruthenium Inorganic materials 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
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- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- 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"
- 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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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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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 phosphorescence probes. The ruthenium complex probe structure is shown as follows: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 rapidly, real-time and specifically detect hypochlorous acid in the environment, and is an excellent turn-on phosphorescent probe; (2) The ruthenium complex probe provided by the invention has low cytotoxicity and excellent mitochondrial targeting capability, and can target mitochondria of living cells and detect hypochlorous acid in the mitochondria of the living cells; (3) The preparation method of the ruthenium complex probe provided by the invention has the advantages of mild reaction conditions and simple preparation process.
Description
Technical Field
The invention relates to a phosphorescence probe and a preparation method and application thereof, in particular to a ruthenium complex probe and a preparation method thereof and application thereof in hypochlorous acid detection, and belongs to the technical field of phosphorescence probes.
Background
Under the global and repeated large environment of new coronary epidemic situation, a plurality of places in the environment need to be subjected to simple disinfection operation, wherein hypochlorous acid disinfectant shows good effect in epidemic prevention disinfection work in recent years, and bacteria and self-potency can be oxidized by oxidation action of hypochlorous acid. However, the corrosiveness and the strong oxidizing property of hypochlorous acid have certain potential harm to the environment, and when the hypochlorous acid is reserved for many times in the water treatment process, excessive chloride ions of a circulating water system can be remained, the pH balance is affected, and the pollution and the damage of underground water, soil and air are caused.
In addition, in normal physiological environments, oxidative and reductive substances in cells are in dynamic balance, and if this balance is broken, it may cause an imbalance in internal environment, damage biological tissues, and even induce cancer. Reactive Oxygen Species (ROS), which is a generic term for a series of oxygen-containing compounds produced by metabolism in living organisms, is one of oxidizing substances, and plays an important role in various physiological processes such as cell information transduction, cell differentiation, migration, cellular immunity, and the like. Thus, monitoring ROS in organisms will help to study their pathogenesis and to achieve specific diagnostics. Among the various ROS, protonated hypochlorous acid produced by the catalytic reaction of chloride ions and hydrogen peroxide with myelocatalase has a higher oxidizing property and a shorter lifetime, mainly in neutrophils, macrophages and monocytes in organisms. Abnormal changes in hypochlorous acid can lead to various diseases such as rheumatoid, lung injury, arthritis and cardiovascular diseases, and the like, and have attracted considerable attention. Therefore, it is important to analyze the physiological roles of hypochlorous acid in immune and pathological processes, as well as to design highly selective and sensitive detection strategies.
At present, phosphorescence and fluorescence are one of the most convenient and sensitive methods in the imaging technology, which react to the content of hypochlorous acid by a change in luminous intensity, and have been widely paid attention to. The phosphorescent molecular probe enhances intersystem leap 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 a metal, and causes a complex molecule to generate phosphorescence with longer emission lifetime than a small molecule. Compared with fluorescent small organic molecules, the phosphorescent complex molecules also have the properties of good photostability, photobleaching resistance, larger Stokes shift and the like. The method has great advantages for monitoring and imaging in a complicated microenvironment, and combines a time resolution technology to improve the sensitivity of target object detection in the complicated microenvironment, thereby becoming a novel biological imaging material with development prospect.
Organic small molecule probes for hypochlorous acid have been widely studied so far, and 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 test paper, the hypochlorous acid is rapidly and visually detected in the environment and water, and the concentration of the hypochlorous acid is judged by assistance of the shade of the color (HouLX, shangguan M Q, lu Z, et al A cyclometalated iridium (III) complex-based fluorescence probe for hypochlorite detection and its application by test strips [ J ],2019, 566, 27-31);
(2) In bioassays, phosphorescent probes effect targeted detection of different organelles in cells by their own identity or by the introduction of different organelle targeting groups, and hypochlorous acid imaging in cells and organisms by means of imaging microscopy for resolving their physiological roles in immune and pathological processes (Li GY, lin Q, sun L, et al, amplified targeting two-Photon Iridium (III) phosphorescent probe for selective detection of hypochlorite in live cells and in vivo, biomaterials,2015, 53, 285-295;Wu W J,Guan R L,Liao X X,et al.Bimodal Visualization of Endogenous Nitric Oxide in Lysosomes with a Two-Photon Iridium (III) Phosphorescent Probe, analytical Chemistry,2019, 91 (15), 10266-10272).
However, the specificity, rapid response and real-time monitoring of the application of ruthenium-based complex probes to hypochlorous acid remains a need for a solution to the problem of those skilled in the art.
Disclosure of Invention
The invention aims to provide a ruthenium complex probe capable of rapidly and specifically detecting hypochlorous acid in environment and living cell mitochondria in real time and a preparation method of the ruthenium complex probe.
In order to achieve the above object, the present invention adopts the following technical scheme:
a ruthenium complex probe characterized by the structure shown below:
a method for preparing the ruthenium complex probe, which is characterized by comprising the following steps:
(1) Preparation of Compound 1
5-Methylphenanthroline and SeO 2 Reflux-extracting with o-dichlorobenzene at 180deg.C for 4 hr, cooling the mixture to room temperature, filtering with diatomite, extracting the filtrate with hydrochloric acid solution, collecting the aqueous phase, adjusting pH of the aqueous phase to neutrality, extracting the aqueous phase with dichloromethane, collecting the organic layer, concentrating the aqueous phase, concentrating the organic layer, and concentrating the organic layer to obtain the final product 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 6 hours at 75 ℃, cooling to room temperature, filtering the mixture, washing with ethanol, and drying to obtain a compound 2;
(3) Preparation of Compound 3
RuCl is to be processed 3 ·3H 2 Placing O, phenanthroline and LiCl in N, N-dimethylformamide, refluxing at 150 ℃ for 8 hours 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, drying, and obtaining a compound 3;
(4) Synthetic ruthenium complex probes
Compound 2 and compound 3 were added to a flask, then dichloromethane and methanol were added, reflux was performed at 65 ℃ for 24 hours under nitrogen protection, after the reaction was completed, dichloromethane was evaporated under reduced pressure, and then NH was contained 4 PF 6 Adding the aqueous solution of (2) into a flask, stirring for 1h, filtering the obtained residue, drying, and purifying the crude product by silica gel column chromatography to obtain the ruthenium complex probe.
Preferably, in step (1), 5-methylparaben and SeO 2 The molar ratio of (2) to (123).
Preferably, in step (2), the molar ratio of compound 1 to diaminobenzonitrile is 5:6.
Preferably, in step (3), ruCl 3 ·3H 2 The molar ratio of O, phenanthroline and LiCl is 5:10:23.
Preferably, in step (4), compound 2, compound 3 and NH 4 PF 6 The molar ratio of (2) is 1:1:10; the volume ratio of dichloromethane to methanol was 1:1.
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 rapidly, real-time and specifically detect hypochlorous acid in the environment, has luminous intensity increased along with the increase of hypochlorous acid concentration, shows good linear relation in a certain concentration range, and is an excellent turn-on 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 detect hypochlorous acid in the mitochondria of the living cells, and has important significance for deeply researching the physiological process of 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 an ultraviolet titration absorption spectrum of the response of the ruthenium complex probe prepared by the invention to hypochlorous acid;
FIG. 3 is a graph of phosphorescence titration emission spectrum of the ruthenium complex probe prepared by the invention in response to hypochlorous acid;
FIG. 4 is a graph of a linear fit of the phosphorescence intensities of ruthenium complex probes prepared according to the invention in response to different hypochlorous acid concentrations;
FIG. 5 is a graph showing the response of the ruthenium complex probe prepared according to the present invention to hypochlorous acid at different pH values;
FIG. 6 is a graph showing the time response of the ruthenium complex probe prepared according to the present invention;
FIG. 7 is a graph showing 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 cell (Hela) toxicity detection of the ruthenium complex probe prepared according to the present invention;
FIG. 9 is a graph of the co-localization of the mitochondria of the cells (Hela) of the ruthenium complex probe prepared according to the present invention, wherein (a) is a graph of the cell imaging of the ruthenium complex probe in response to hypochlorous acid, (b) is a graph of the cell imaging of the mitochondrial localization agent (Mito-Tracker Green), (c) is a graph of the Merge of (a) and (b), and (d) is a graph of the Pearson correlation coefficient;
FIG. 10 is a graph of the co-localization intensity of cell (Hela) mitochondria of the ruthenium complex probe prepared according to the present invention with a co-localization reagent.
Detailed Description
The invention is described in detail below with reference to the drawings and the specific 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 method for preparing the ruthenium complex probe with the structure comprises the following steps:
(1) Preparation of Compound 1
1.00g (5.20 mmol) of 5-methylparaben and 1.38g (12.30 mmol) of SeO are combined 2 Placing in 80mL o-dichlorobenzene, refluxing at 180 ℃ for 4 hours, then cooling the mixture to room temperature and filtering with diatomite, then extracting filtrate with 200mL hydrochloric acid solution (1.0 mol/L) 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 methylene chloride, the organic layer was collected, and 0.5g of anhydrous MgSO 4 Added to the organic layer, dried with shaking at room temperature for 20min, filtered and the solution was collected and finally the solvent was removed by vacuum evaporation to give 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, refluxed at 75℃for 6h, cooled to room temperature, and the mixture is filtered, washed with 20mL of ethanol and dried to give 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 were placed in 5mL of N, N-dimethylformamide under nitrogen protection, refluxed at 150℃for 8h, cooled to room temperature, 10mL of acetone was added, the resulting solution was cooled at 0℃overnight, the precipitate was filtered and washed three times with cold distilled water and acetone (purpose: remove impurities before drying), and dried to give 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) Synthetic ruthenium complex probes
59.6mg (0.2 mmol) of Compound 2 and 113.6mg (0.2 mmol) of Compound 3 were added to a 50mL round bottom flask, followed by the addition of10mL of methylene chloride and 10mL of methanol were added, refluxed at 65℃for 24 hours under nitrogen protection, and after completion of the reaction, the methylene chloride in the solution was removed by evaporation under reduced pressure, and then 326mg (2 mmol) of NH was contained 4 PF 6 To a round bottom flask, stirring for 1h, filtering the resulting residue, drying and purifying the crude product 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)。
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 all obtained by dilution of stock solutions.
3. Ultraviolet titration absorption spectrum for detecting ruthenium complex probe
The absorption spectrum of the ruthenium complex probe (10. Mu.M) was measured, the test solvent was a mixed solution of DMSO/PBS=1/1 (V/V), a spectral window of 300-650 nm was collected, and an ultraviolet spectrum was collected every 50. Mu.M hypochlorous acid was added.
The ultraviolet titration absorption spectrum of the obtained ruthenium complex probe responding to hypochlorous acid is shown in figure 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 exhibits a red shift characteristic in ultraviolet spectrum in the visible region, its peak gradually disappears at 400nm, new peaks appear at 425nm and 460nm, and the peak intensity decreases as a whole.
This shows 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 can realize the detection of hypochlorous acid concentration.
4. Phosphorescence titration emission spectrum for detecting ruthenium complex probe
The emission spectrum of the ruthenium complex probe (10 mu M) is measured, the test solvent is a mixed solution of DMSO/PBS=1/1 (V/V), the excitation wavelength is 460nm, a spectrum window of 500-750 nm is collected, and a phosphorescence spectrum is collected every 50 mu M hypochlorous acid is added.
The phosphorescence titration emission spectrum of the obtained ruthenium complex probe responding to hypochlorous acid is shown in figure 3.
As can be seen from FIG. 3, the maximum emission wavelength was 590nm, and the phosphorescence intensity of the ruthenium complex probe solution was gradually increased as the hypochlorous acid concentration (0 to 600. Mu.M) in the system was increased.
Therefore, the ruthenium complex probe can realize the detection of hypochlorous acid concentration.
5. Detection of the linear relationship of the response of the ruthenium Complex probe to different hypochlorous acid concentrations
The phosphorescence intensities of the ruthenium complex probe in response to varying concentrations of hypochlorous acid were linearly fitted.
The resulting linear fit of the phosphorescence intensities of the ruthenium complex probe responses to different hypochlorous acid concentrations is shown in FIG. 4.
As can be seen from FIG. 4, the ruthenium complex probe shows 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. Detection of response of ruthenium Complex probes to hypochlorous acid at different pH
The emission spectrum of the ruthenium complex probe (10. Mu.M) without hypochlorous acid and after hypochlorous acid addition was measured at different pH conditions, 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 response of the obtained ruthenium complex probe to hypochlorous acid at different pH 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 to 11, and the phosphorescence signal is enhanced after hypochlorous acid is added, wherein the phenomenon of the ruthenium complex probe is more remarkable 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 phosphorescence to reach stability after hypochlorous acid addition was measured for the ruthenium complex probe (10. Mu.M), 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 ruthenium complex probe solution was stabilized by rapid increase of phosphorescence at 590nm after hypochlorous acid was added, and the change was completed within 15 s.
This demonstrates that the ruthenium complex probe has a rapid response speed, which is advantageous for improving the speed and efficiency of detecting hypochlorous acid.
8. Detection of selectivity of ruthenium Complex probes for different ions
Determination of the phosphorescent Spectrum response of the ruthenium Complex Probe (10. Mu.M) and different test substances, clO for the test substances respectively - 、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, GSH the test solvent is a mixed solution of DMSO/PBS=1/1 (V/V), the concentration of the analyte is 300 mu M, the excitation wavelength is 460nm, and the phosphorescence intensity at 590nm is collected.
The obtained selective recognition graph of the ruthenium complex probe for different ions is shown in fig. 7.
As can be seen from fig. 7, other active oxygen and common interfering ions, in addition to hypochlorous acid, do not produce a significant change in the phosphorescence intensity of the ruthenium complex probe.
This shows that the ruthenium complex probe has excellent selectivity to hypochlorous acid, and can effectively avoid interference of other ions to detection results.
9. Detection of cellular (Hela) toxicity of ruthenium Complex probes
The digested cells were treated at 5X 10 4 Density of wells/density of wells was inoculated into 96 well cell culture plates with 3 multiplex wells at 37℃and 5% CO 2 Culturing in an incubator for 24 hours. After the cells grow into a monolayer, the culture solution is 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) with different concentration gradients are added, and the mixture is put into a medium of 37 ℃ and 5% CO 2 Incubating in an incubator for 4 hours, adding 20 mu LMTT solution into each hole, continuing to cultivate for 4 hours, stopping culturing, carefully sucking out the culture solution in the holes, adding 150 mu LDMSO into each hole, oscillating for 10 minutes by using a microplate reader, fully dissolving the crystals, and measuring the OD value by using 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 complex probe has weak toxicity to Hela cells and even has proliferation effect on Hela cells; as the ruthenium complex probe concentration increased, hela cell viability gradually decreased, but compared to the control group, hela cell viability was around 100% even at a concentration of 50 μm.
This demonstrates that the ruthenium complex probe has very low cytotoxicity and little toxic damage to cells.
10. Detection of Co-localization of cellular mitochondria of ruthenium Complex probes
HeLa cells were grown on six well plates at 37℃overnight with incubation of cells for 30min with ruthenium complex probe solution (30. Mu.M) and Mito-Tracker Green (1. Mu.M), followed by addition of hypochlorous acid solution (100. Mu.M), incubation for 10min, and cell imaging using confocal microscopy. For ruthenium complex probes, 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 cell mitochondria co-localization is shown in fig. 9, and the obtained image of cell mitochondria co-localization intensity 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 coincides well with the Mito-Tracker Green's intensity curve.
This suggests that the ruthenium complex probe primarily targets mitochondria after entering the cell.
Mitochondria serve as the primary energy conversion sites within cells, which play an important role in the metabolism of living beings. The ruthenium complex probe provided by the invention mainly targets mitochondria after entering cells, so that the ruthenium complex probe can monitor the change of hypochlorous acid in the mitochondria, which is important for analyzing the physiological effect of hypochlorous acid in 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 rapidly, real-time and specifically detecting hypochlorous acid in the environment, targeting mitochondria of living cells and detecting hypochlorous acid in mitochondria of the living cells.
It should be noted that the above-mentioned examples of the present invention are only examples for clearly illustrating the present invention, and are not limiting to the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. Not all embodiments are exhaustive. All obvious changes or modifications which come within the spirit of the invention are desired to be protected.
Claims (9)
1. A ruthenium complex probe characterized by the structure shown below:
。
2. a method of preparing the ruthenium complex probe according to claim 1, comprising the steps of:
(1) Preparation of Compound 1
；
5-Methylphenanthroline and SeO 2 Reflux-extracting with o-dichlorobenzene at 180deg.C for 4 hr, cooling the mixture to room temperature, filtering with diatomite, extracting the filtrate with hydrochloric acid solution, collecting the aqueous phase, adjusting pH of the aqueous phase to neutrality, extracting the aqueous phase with dichloromethane, collecting the organic layer, concentrating the aqueous phase, concentrating the organic layer, and concentrating the organic layer to obtain the final product 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 6 hours at 75 ℃, cooling to room temperature, filtering the mixture, washing with ethanol, and drying to obtain a compound 2;
(3) Preparation of Compound 3
；
RuCl is to be processed 3 ·3H 2 Placing O, phenanthroline and LiCl in N, N-dimethylformamide, refluxing at 150 ℃ for 8 hours 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, drying, and obtaining a compound 3;
(4) Synthetic ruthenium complex probes
；
Compound 2 and compound 3 were added to the flask, then dichloromethane and methanol were added, and the mixture was refluxed at 65 ℃ for 24 hours under nitrogen protection, and the reaction was completedAfter evaporation of the dichloromethane under reduced pressure, the mixture then contains NH 4 PF 6 Adding the aqueous solution of (2) into a flask, stirring for 1h, filtering the obtained residue, drying, and purifying the crude product by silica gel column chromatography to obtain the ruthenium complex probe.
3. The process according to claim 2, wherein in step (1), 5-methylparaben and SeO 2 The molar ratio of (2) to (123).
4. The process according to claim 2, wherein in step (2), the molar ratio of compound 1 to diaminobenzonitrile is 5:6.
5. The method according to claim 2, wherein in step (3), ruCl 3 ·3H 2 The molar ratio of O, phenanthroline and LiCl is 5:10:23.
6. The method according to claim 2, wherein in step (4), compound 2, compound 3 and NH 4 PF 6 The molar ratio of (2) is 1:1:10.
7. The process according to claim 2, wherein in step (4), the volume ratio of dichloromethane to methanol is 1:1.
8. Use of the ruthenium complex probe according to claim 1 for detecting hypochlorous acid in an environment for the purpose of non-disease diagnosis and treatment.
9. Use of the ruthenium complex probe according to claim 1 for detecting hypochlorous acid in live cell line particles for the purpose of non-disease diagnosis and treatment.
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