CN111233754B - Phosphorescent probe based on platinum complex and application thereof in hypochlorous acid detection - Google Patents

Phosphorescent probe based on platinum complex and application thereof in hypochlorous acid detection Download PDF

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CN111233754B
CN111233754B CN202010061292.5A CN202010061292A CN111233754B CN 111233754 B CN111233754 B CN 111233754B CN 202010061292 A CN202010061292 A CN 202010061292A CN 111233754 B CN111233754 B CN 111233754B
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hypochlorous acid
probe
platinum complex
compound
phosphorescent
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CN111233754A (en
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汤静洁
黄俊生
黎鹏
孟飞
黄东婷
聂梅
刘泽槟
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Guangdong Institute of Bioengineering Guangzhou Cane Sugar Industry Research Institute
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Guangdong Institute of Bioengineering Guangzhou Cane Sugar Industry Research Institute
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • G01N21/64—Fluorescence; Phosphorescence
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The invention discloses a transition metal platinum complex phosphorescence probe and application thereof in hypochlorous acid detection. The luminous intensity of the fluorescent probe is reduced along with the increase of hypochlorous acid concentration, and the fluorescent probe is in linear correlation in a certain concentration range, is an excellent Turn-off phosphorescent probe, has good selectivity, can respond specifically to hypochlorous acid, does not respond to other cations, anions, partial sulfur-containing amino acids and other active oxygen species, has the advantages of high sensitivity, short response time (less than 5 s) and good pH stability, can realize specific and real-time detection of hypochlorous acid, and is a good phosphorescent probe for detecting hypochlorous acid.

Description

Phosphorescent probe based on platinum complex and application thereof in hypochlorous acid detection
Technical Field
The invention belongs to the technical field of molecular probes, and particularly relates to a phosphorescence probe based on a platinum complex and application thereof in hypochlorous acid detection.
Background
In recent years, reactive oxygen species (Reactive oxygen species, ROS) have become increasingly the heat of research in the field of life sciencesThe active oxygen is an active substance generated by single electron reduction of oxygen molecules, and comprises superoxide radical (O 2 – ) Hydrogen peroxide (H) 2 O 2 ) Singlet oxygen 1 O 2 ) Hydroxyl radical (. OH), hypochlorous acid (HClO) and hypochlorite (ClO) – ) Among them, hypochlorous acid is a relatively common active oxygen species, endogenous HClO of organisms is mediated by Myeloperoxidase (MPO), has high reactivity and short life span, is an important oxidant, plays an antimicrobial effect in physiological state, plays a role in protecting organisms, and plays a role in regulating a plurality of physiological and pathological activity processes as signal molecules in cells and among cells, and abnormal hypochlorous acid levels are closely related to injury, aging, inflammation, cancer and the like.
At present, chemiluminescence is one of the most convenient and sensitive methods for detecting hypochlorous acid in a biological system, and the principle is that after a specific reaction occurs between a probe molecule and hypochlorous acid, the optical property of the probe molecule is obviously changed, and the optical property is usually represented by the change of luminous intensity or the change of emission wavelength, so that the hypochlorous acid distribution is reflected by monitoring the luminous condition.
The currently reported method for detecting hypochlorous acid mostly utilizes a small molecular fluorescent probe, is widely researched due to the advantages of high sensitivity, good selectivity, low detection limit and the like, achieves a great achievement in hypochlorous acid detection and cell imaging, and has a relatively perfect and deep theoretical basis in mechanism research, but in a biological system, the organic fluorescent probe also faces the problems of obvious background interference, insufficient stability, low accuracy and the like, so that more and more scientific researchers turn the eyes to a phosphorescent molecular probe, compared with the organic fluorescent molecular probe capable of emitting light in a singlet state, the phosphorescent molecular probe based on a transition metal complex mostly belongs to the luminescence of the triplet state, and the singlet state-triplet state mixing is caused due to the spin-orbit coupling effect caused by a heavy atom effect, so that the quantum efficiency is improved. In particular having d 6 、d 8 And d 10 Ru (II) -, os (II) -, re (I) -, ir (III) -, cu (I) -, pt (II) -and Au (I) -complex with electronic configuration not only has no weaknessThe fluorescent probe has the advantages of high stability, high luminous efficiency, long luminous life, large Stokes displacement, easy adjustment of excitation and emission spectrum and the like, and is widely focused in the fields of biosensing and cell imaging, thereby becoming a novel biological imaging material with development prospect.
Literature search results show that currently phosphorescent probes are mainly focused on Ru (II) or Ir (III) complexes, and related researches on platinum complex probes are few and still in a starting stage. Regarding the preparation and application of the platinum complex molecular probe, although scholars at home and abroad carry out some researches, the platinum complex molecular probe is directly used for cell imaging or detecting oxygen molecules in cells by utilizing the long-luminescence lifetime characteristic of the platinum complex; the study of "Turn-off" type platinum complex phosphorescent probes for hypochlorous acid detection has been recently published.
Disclosure of Invention
Based on the above, it is necessary to provide a phosphorescence probe based on platinum complex and its application in hypochlorous acid detection, the probe provides more available detection means for diagnosis, treatment effect evaluation and other aspects of HClO related diseases, the probe also has the advantages of high sensitivity, short response time (< 5 s) and good pH stability, can realize specific and real-time detection of hypochlorous acid, and meanwhile, the detection performance of the probe has higher detection efficiency, more accurate detection result, high selectivity for hypochlorous acid, and no response to other cations, anions, partial sulfur-containing amino acids and other active oxygen species, and has important practical significance and value for improving the health level of residents in China.
The technical scheme is as follows:
the technical scheme adopted by the invention is as follows:
Figure BDA0002374583290000031
r is H, -CH 3 ，-C 2 H 5 One or more of Ar, -OH and-CHO.
Preparation method of phosphorescence probe based on platinum complexThe method comprises the steps of (1) reacting a compound
Figure BDA0002374583290000032
Dissolving in diethyl ether and cooling to-78deg.C, slowly dropwise adding n-butyllithium solution (1.1 eq,2.5M in n-hexane) under nitrogen protection, stirring for 5 min, slowly dropwise adding the compound containing ∈10->
Figure BDA0002374583290000033
Is reacted at-78 ℃ for 1h under the protection of nitrogen, then saturated ammonium acetate is added to the reacted solution after the temperature is raised to room temperature to quench the excess n-butyllithium, then the ethyl acetate is used for extraction, the organic phase 1 is collected and passed through MgSO 4 Drying the organic phase 1, filtering, and removing the solvent to obtain the compound
Figure BDA0002374583290000034
(2) The compound is prepared
Figure BDA0002374583290000035
Dissolving in acetic acid, adding 5% (v/v) concentrated sulfuric acid and 5% (v/v) acetic anhydride, reflux-reacting for 6 hr, dissolving in water, extracting with ethyl acetate, and MgSO 4 Drying, filtering, concentrating to obtain crude product 1, and subjecting crude product 1 to column chromatography to obtain white solid compound
Figure BDA0002374583290000036
(3) The compound is pressed
Figure BDA0002374583290000037
Dissolving in mixed solvent of 1, 4-dioxane and water (4:1), adding Pd (PPh) 3 ) 4 (10％)、K 2 CO 3 (2.0 eq) and R group-substituted phenylboronic acid (1.1 eq) were refluxed under nitrogen protection for 14 to 18 hours, and after the reaction was completed, the solvent was removed, and then CH was used 2 Cl 2 Extraction and collection of organic phase 2 over MgSO 4 For organic mattersDrying, filtering and concentrating the phase 2 to obtain a crude product 2, and subjecting the crude product 2 to column chromatography to obtain a white solid compound +.>
Figure BDA0002374583290000041
(4) The compound is prepared
Figure BDA0002374583290000042
And K 2 PtCl 4 (1.2 eq) and TBAB (0.2 eq) are dissolved in acetic acid and reflux reacted for 16-22 h under the protection of nitrogen, pure water is added after the reaction is finished, yellow solid is separated out, and the yellow solid compound is obtained by filtration and collection and column chromatography>
Figure BDA0002374583290000043
The platinum complex-based phosphorescent probe is applied to hypochlorous acid detection.
The beneficial effects of the invention are as follows: the fluorescent probe based on the platinum complex is easy to prepare, the luminous intensity of the fluorescent probe is reduced along with the increase of the hypochlorous acid concentration and is linearly related in a certain concentration range, the fluorescent probe is an excellent Turn-off type fluorescent probe, the fluorescent probe has good selectivity, can only respond specifically to hypochlorous acid, has high selectivity to hypochlorous acid, does not respond to other cations, anions, part of sulfur-containing amino acids and other active oxygen species, has the advantages of high sensitivity, short response time (less than 5 s) and good pH stability, can realize the specificity and real-time detection of hypochlorous acid, and is a good fluorescent probe for detecting hypochlorous acid.
Drawings
FIG. 1 is an ultraviolet absorbance spectrum of a platinum complex-based phosphorescent probe in response to hypochlorous acid;
FIG. 2 is a phosphorescent emission spectrum of a platinum complex-based phosphorescent probe in response to hypochlorous acid;
FIG. 3 is a graph of a linear fit of phosphorescence intensities of a platinum complex-based phosphorescence probe responsive to different hypochlorous acid concentrations;
FIG. 4 is a graph of experimental data for ion competition for a phosphorescent probe based on a platinum complex;
FIG. 5 is a graph of experimental data on pH stability of a phosphorescent probe based on a platinum complex; a1, a platinum complex phosphorescence probe.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
The preparation method of the phosphorescence probe based on the platinum complex comprises the following preparation steps:
(1) The compound is prepared
Figure BDA0002374583290000051
Dissolving in diethyl ether and cooling to-78deg.C, slowly dropwise adding n-butyllithium solution (1.1 eq,2.5M in n-hexane) under nitrogen protection, stirring for 5 min, slowly dropwise adding the compound containing ∈10->
Figure BDA0002374583290000052
Is reacted at-78 ℃ for 1h under the protection of nitrogen, then saturated ammonium acetate is added to the reacted solution after the temperature is raised to room temperature to quench the excess n-butyllithium, then the ethyl acetate is used for extraction, the organic phase 1 is collected and passed through MgSO 4 Drying the organic phase 1, filtering, removing the solvent to obtain the compound +.>
Figure BDA0002374583290000061
(2) The compound is prepared
Figure BDA0002374583290000062
Dissolving in acetic acid, adding 5% (v/v) concentrated sulfuric acid and 5% (v/v) acetic anhydride, reflux-reacting for 6 hr, dissolving in water, extracting with ethyl acetate, and MgSO 4 Drying, filtering, concentrating to obtain crude product 1, and subjecting crude product 1 to column chromatography to obtain white solid compound
Figure BDA0002374583290000063
Yield 62%;
(3) The compound is pressed
Figure BDA0002374583290000064
Dissolving in mixed solvent of 1, 4-dioxane and water (4:1), adding Pd (PPh) 3 ) 4 (10％)、K 2 CO 3 (2.0 eq) and 4-formylphenylboronic acid (1.1 eq) were reacted under reflux under nitrogen for 14-18 h, after which the solvent was removed after the reaction was completed, and then CH was used 2 Cl 2 Extraction and collection of organic phase 2 over MgSO 4 Drying, filtering and concentrating the organic phase 2 to obtain a crude product 2, and subjecting the crude product 2 to column chromatography to obtain a white solid compound +.>
Figure BDA0002374583290000065
Yield 82%; />
(4) The compound is prepared
Figure BDA0002374583290000066
And K 2 PtCl 4 (1.2 eq) and TBAB (0.2 eq) are dissolved in acetic acid and reflux reacted for 16-22 h under the protection of nitrogen, pure water is added after the reaction is finished, yellow solid is separated out, and the yellow solid compound is obtained by filtration and collection and column chromatography>
Figure BDA0002374583290000071
The yield was 71%.
Example 2 ultraviolet absorbance spectroscopy test of platinum Complex-based phosphorescent probes for hypochlorous acid response
The ultraviolet absorption spectrum test concentration is 15 μm, the test solvent is a mixed solution of THF/pb=1/1, fig. 1 is an ultraviolet absorption spectrum diagram of a phosphorescent probe of a platinum complex after hypochlorous acid with different concentrations is added, as shown in fig. 1, with the increase of hypochlorite concentration, the absorption peak of the phosphorescent probe of the platinum complex at 237nm is slightly increased, the absorption peak at 260nm is gradually reduced and moves to 272nm, the absorption peak at 306nm is obviously reduced, the absorption in the range of 320-366 nm is slightly enhanced, and the absorption peak at 428nm is completely disappeared. The results show to some extent that the structure of the phosphorescent probe of the platinum complex is changed after the reaction with hypochlorous acid, resulting in a change in the ultraviolet absorption.
Example 3 phosphorescent emission spectroscopy test of a platinum complex-based phosphorescent probe response to hypochlorous acid.
The test concentration of the phosphorescence emission spectrum is 50 mu M, the test solvent is a mixed solution of THF/PB=1/1, fig. 2 shows the phosphorescence emission spectrum of the phosphorescence probe of the platinum complex after hypochlorous acid with different concentrations is added, as shown in fig. 2, the maximum emission wavelength is 563nm, and the phosphorescence intensity of the phosphorescence probe of the platinum complex is gradually weakened along with the increase of the hypochlorous acid concentration (0-75 mu M), so that the phosphorescence response detection of hypochlorous acid can be realized.
Example 4 phosphorescent probes based on platinum complexes phosphorescent intensity linear fit curve experiments for different hypochlorous acid concentrations.
The curve obtained by linearly fitting the phosphorescence intensities of the platinum complex to the response of different hypochlorous acid concentrations is shown in figure 3, and the phosphorescence probe of the platinum complex has good linear phosphorescence response to hypochlorous acid in the concentration range of 5-55 mu M, so that the quantitative detection of hypochlorous acid can be realized.
Example 5 ion competition experiments with phosphorescent probes based on platinum complexes.
This example examined the phosphorescent spectral response of a phosphorescent probe of a platinum complex to hypochlorous acid and to different test objects, each of test objects 1-25 being Cys, hcy, GSH, H 2 O 2 、·OH、 1 O 2 、·OtBu、TBHP、ClO - 、Mn 2+ 、Al 3+ 、Fe 2+ 、Mg 2 + 、Zn 2+ 、Cu 2+ 、NO 2 - 、NO 3 - 、Cl - 、SO 4 2- 、SO 3 2- 、HSO 3 - 、S 2 O 3 2- 、S 2 O 8 2- 、CO 3 2- And HCO 3 - The concentration of the phosphorescence probe of the prepared platinum complex is 20 mu M, the concentration of the hypochlorous acid added is 50 mu M, the concentration of other analytes is 200 mu M, and the result of fig. 4 shows that other active oxygen species and common interfering ions can not cause obvious phosphorescence change of the phosphorescence probe of the platinum complex except hypochlorous acid, thus proving that the phosphorescence probe of the platinum complex has high selectivity to hypochlorous acid.
Example 6 pH stability experiment of phosphorescent probes based on platinum complexes.
This example compares the phosphorescence intensity of the phosphorescent probe of the platinum complex without hypochlorous acid and after hypochlorous acid addition at different pH conditions, the concentration of the phosphorescent probe of the formulated platinum complex was 20 μm and the test solvent was a mixed solution of THF/pb=1/1. As shown in FIG. 5, the phosphorescence probe of the platinum complex has better stability and insignificant change of phosphorescence intensity in the pH range of 5-9; after addition of 50. Mu.M hypochlorous acid, phosphorescence at all pH conditions was essentially lost. The phosphorescence probe of the platinum complex has better stability in the pH range of 5-9, which lays a good foundation for the further application in organisms.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (3)

1. A phosphorescent probe based on a platinum complex, characterized by the following structure:
Figure FDA0004188715270000011
2. the method for preparing a phosphorescent probe based on a platinum complex according to claim 1, comprising the steps of (1) reacting a compound
Figure FDA0004188715270000012
Dissolving in diethyl ether, cooling to-78deg.C, slowly dropwise adding n-butyllithium solution under nitrogen protection, stirring for 5 min, and slowly dropwise adding +.>
Figure FDA0004188715270000013
Under the protection of nitrogen, at the temperature of-78 ℃ for 1h, then adding saturated ammonium acetate to quench the excess n-butyllithium after the reaction, extracting with ethyl acetate, collecting the organic phase 1, passing through MgSO 4 Drying the organic phase 1, filtering, and removing the solvent to obtain the compound
Figure FDA0004188715270000014
(2) The compound is prepared
Figure FDA0004188715270000015
Dissolving in acetic acid, adding 5% v/v concentrated sulfuric acid and 5% v/v acetic anhydride, and refluxing the mixed solutionAfter the reaction was completed for 6 hours, the mixture was dissolved in water, extracted with ethyl acetate, and MgSO 4 Drying, filtering, concentrating to obtain crude product 1, and subjecting crude product 1 to column chromatography to obtain white solid compound
Figure FDA0004188715270000016
(3) The compound is pressed
Figure FDA0004188715270000021
Dissolving in a mixed solvent of 1, 4-dioxane and water, adding Pd (PPh) 3 ) 4 、K 2 CO 3 And R group substituted phenylboronic acid, reflux-reacting for 14-18 h under nitrogen protection, removing solvent after reaction, and then using CH 2 Cl 2 Extraction and collection of organic phase 2 over MgSO 4 Drying, filtering and concentrating the organic phase 2 to obtain a crude product 2, and subjecting the crude product 2 to column chromatography to obtain a white solid compound +.>
Figure FDA0004188715270000022
(4) The compound is prepared
Figure FDA0004188715270000023
And K 2 PtCl 4 And TBAB is dissolved in acetic acid, reflux reaction is carried out for 16 to 22 hours under the protection of nitrogen, pure water is added after the reaction is finished, yellow solid is separated out, and the yellow solid compound is obtained by filtration and collection and column chromatography
Figure FDA0004188715270000024
3. Use of a platinum complex-based phosphorescent probe according to claim 1 for the preparation of a probe for detecting hypochlorous acid.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108535233A (en) * 2018-05-17 2018-09-14 南京邮电大学 One kind is for hypochlorous water-soluble phosphorescence nano-particle of ratio method detection and the preparation method and application thereof
CN110003286A (en) * 2019-05-08 2019-07-12 兰州大学 A kind of platinum complex and preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108535233A (en) * 2018-05-17 2018-09-14 南京邮电大学 One kind is for hypochlorous water-soluble phosphorescence nano-particle of ratio method detection and the preparation method and application thereof
CN110003286A (en) * 2019-05-08 2019-07-12 兰州大学 A kind of platinum complex and preparation method and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Novel Platinum(II) Complex-based Luminescent Probe for Detection of Hypochlorite in Cancer Cells";JIngjie Tang et al.;《Photochemistry and Photobiology》;第97卷;第317-326页 *
"Novel recognition mechanism based on oxidative addition of Pt(II) complex-based luminescent probes for hypochlorite ion detection†";Jingjie Tang et al.;《Analyst》;第146卷;第5691-5703页 *
"Selective Hypochlorous Acid Detection by Electronic Tuning of Platinum-4,5-bis(diphenylphosphino)acridine-Thiolate Complexes";Yifei Gao et al.;《Inorg. Chem.》;第58卷;第9290-9302 *

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