CN109336815B - Two-photon fluorescent probe for detecting hypochlorous acid in intracellular endoplasmic reticulum - Google Patents
Two-photon fluorescent probe for detecting hypochlorous acid in intracellular endoplasmic reticulum Download PDFInfo
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- CN109336815B CN109336815B CN201811080077.9A CN201811080077A CN109336815B CN 109336815 B CN109336815 B CN 109336815B CN 201811080077 A CN201811080077 A CN 201811080077A CN 109336815 B CN109336815 B CN 109336815B
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- 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"
- G01N2021/6432—Quenching
Abstract
The invention provides a method for detecting hypochlorous acid in endoplasmic reticulum of cellsTwo-photon fluorescent probe:
. Can be obtained by three-step reaction by using 4-methylthio-1, 8-naphthalic anhydride, trifluoroacetic acid and p-toluenesulfonyl chloride as raw materials. The two-photon fluorescent probe can be used for detecting hypochlorous acid in a solution or a cell endoplasmic reticulum. The fluorescent probe can be obtained by chemical synthesis, has simple and feasible synthesis process, cheap and easily obtained raw materials, low preparation cost, easy popularization and high specificity, is not interfered by other components, can be used for real-time determination of hypochlorous acid in endoplasmic reticulum of living cells, and has wide application prospect.
Description
Technical Field
The invention relates to a two-photon fluorescent probe for detecting hypochlorous acid in a cell endoplasmic reticulum and application thereof, belonging to the field of small molecule fluorescent materials.
Background
As an important organelle in the cell, Endoplasmic Reticulum (ER) plays a very important role in the whole cell. It is intracellular protein synthesis, folding, Ca2+Reserve and Ca2+Important sites involved in intracellular signal transduction are also sites of synthesis for steroids, cholesterol and other lipids. The main physiological functions of the endoplasmic reticulum include regulation of protein synthesis, folding and localization, and maintenance of intracellular Ca2+And (4) balancing. The change of the environment in the endoplasmic reticulum is highly sensitive, so that the normal physiological functions of the endoplasmic reticulum are damaged when cells are stimulated by chemotoxic substances, and the endoplasmic reticulum stress occursAnd (4) exciting. Too strong or prolonged endoplasmic reticulum stress can cause apoptosis. Therefore, endoplasmic reticulum stress is closely related to the occurrence and development of various human diseases such as cancer, inflammatory diseases, metabolic diseases, osteoporosis, neurodegenerative diseases, and the like.
Endogenous hypochlorous acid in a living body is an important active oxygen species (ROS), has important physiological functions in the living body, participates in a plurality of physiological processes, and plays an extremely important role in bacteria of an immune system for resisting external invasion. Endogenous hypochlorous acid is generated by the reaction of hydrogen peroxide and chloride ions under the catalysis of Myeloperoxidase (MPO), and has important antibacterial property. Due to the high reactivity and non-specificity of hypochlorous acid, once living organisms drink or contact water with high hypochlorous acid content, the hypochlorous acid content in the living organisms cannot be maintained in a normal physiological level range, and host tissues are damaged, so that a series of diseases are caused, such as: inflammatory diseases, neurasthenia, kidney diseases, cardiovascular diseases, certain cancers and the like.
Compared with the traditional analysis methods such as an ultraviolet absorption method, an electrochemical method, a chromatography method and the like, the fluorescence analysis method has the characteristics of good selectivity, high sensitivity, simplicity and convenience in operation and the like, and can detect and image bioactive molecules in real time under the condition of not damaging biological samples. Due to these advantages of fluorescence assays, a large number of fluorescent probes for detecting biologically active molecules have been reported in recent years. The endoplasmic reticulum is an important organelle and is a main site for generating Reactive Oxygen Species (ROS) and Reactive Sulfur Species (RSS) in cells, hypochlorous acid is generated by reaction of hydrogen peroxide and chloride ions under the catalysis of myeloperoxidase, and the detection and analysis of the hypochlorous acid in the endoplasmic reticulum have important research values and are helpful for researching the endoplasmic reticulum-induced apoptosis process. Some fluorescent probes have been reported in the literature for targeting endoplasmic reticulum, but their application is limited due to their disadvantages such as poor water solubility, poor selectivity, narrow detection interval, and poor linearity. Therefore, the design of the endoplasmic reticulum targeted hypochlorous acid fluorescent probe has important significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a two-photon fluorescent probe for detecting hypochlorous acid in a cell endoplasmic reticulum targeting manner, which has high specificity and is not interfered.
The invention also aims to provide a synthesis method of the two-photon fluorescent probe, which has the advantages of cheap and easily obtained raw materials and low preparation cost.
In order to achieve the purpose, the invention adopts the following technical scheme.
A two-photon fluorescent probe for detecting hypochlorous acid in a cell endoplasmic reticulum has a structural formula shown in formula (I):
formula (I).
The two-photon fluorescent probe can be synthesized by the following method:
(1) heating and refluxing 4-methylthio-1, 8-naphthalic anhydride and BOC-hexamethylene diamine in ethanol, and separating and purifying a product to obtain a compound 1:
(2) and (3) stirring the compound 1 and trifluoroacetic acid in dichloromethane for reaction at room temperature, and separating and purifying a product to obtain a compound 2:
(3) reacting the compound 2 with p-toluenesulfonyl chloride in dichloromethane in the presence of triethylamine, and separating and purifying the product to obtain a final product, namely a fluorescent probe:
in the step (1), the molar ratio of the 4-methylthio-1, 8-naphthalic anhydride to the BOC-hexamethylene diamine is 1-1.2: 1.
In the step (1), the reaction temperature is 90 ℃; the reaction time is 4-6 hours.
In the step (1), the separation and purification operations are performed by using ethyl acetate: petroleum ether =3:1 (v/v) as eluent through a silica gel column.
In the step (2), the molar ratio of the compound 1 to trifluoroacetic acid is 1: 1-1.2.
In the step (2), the reaction time is 2 to 6 hours.
In the step (2), the separation and purification operation is to separate methanol: dichloromethane: triethylamine =15:1:0.05 (v/v) as eluent was passed through a silica gel column.
In the step (3), the molar ratio of the compound 2 to the p-toluenesulfonyl chloride is 1: 1-1.5.
In the step (3), the reaction temperature is 0-5 ℃; the reaction time is 2-5 hours.
In the step (3), the separation and purification operation is carried out by mixing dichloromethane: methanol =100:1 (v/v) as eluent over a silica gel column.
The application of the two-photon fluorescent probe in detecting hypochlorous acid in solution or endoplasmic reticulum of cells.
The mechanism of fluorescence of the probe is as follows: under the condition of hypochlorous acid, the methylthio in the probe molecule is subjected to oxidation reaction, and the fluorescence is quenched. Meanwhile, because the p-toluenesulfonamide has endoplasmic reticulum targeting property, the endoplasmic reticulum can be distinguished from other organelles, so that the fluorescent probe can be used for detecting hypochlorous acid in the intracellular reticulum.
The invention has the following advantages:
the fluorescent probe can be obtained by chemical synthesis, the synthesis process is simple and easy to implement, the raw materials are cheap and easy to obtain, the preparation cost is low, and the popularization is easy. The fluorescent probe has high specificity, is not interfered by other components in the corresponding hypochlorous acid detection process, can be used for real-time determination of hypochlorous acid in endoplasmic reticulum of living cells, and has wide application prospect. The fluorescent probe provided by the invention has high sensitivity and good fluorescence emission spectrum characteristics, and can be used for measuring hypochlorous acid in the endoplasmic reticulum of the cell by drawing a standard curve, so that the aim of quickly and accurately detecting the hypochlorous acid in the endoplasmic reticulum of the cell can be fulfilled.
Drawings
FIG. 1 shows a fluorescent probe1H NMR spectrum;
FIG. 2 is a fluorescence spectrum of a fluorescent probe under different concentrations of hypochlorous acid;
FIG. 3 is data of a linear relationship between fluorescent probe and hypochlorous acid concentration;
FIG. 4 shows the selectivity of fluorescent probes for different substances;
FIG. 5 is a photograph of co-located bio-imaging of fluorescent probes with commercial probes;
FIG. 6 is a biological image of the fluorescent probe detecting hypochlorous acid in living cells.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
EXAMPLE 1 Synthesis of fluorescent Probe
(1) Dissolving 120mg of 4-methylthio-1, 8-naphthalic anhydride in about 150mL of ethanol, heating to 90 ℃ under reflux for 20min, dissolving BOC-hexamethylenediamine in 2mL of ethanol, adding dropwise to the reaction solution, stirring under reflux for 4 hours, cooling, filtering, spin-drying the filtrate, adding ethyl acetate: petroleum ether =3:1 (v/v) by silica gel column chromatography to give a yellow product (compound 1);
(2) the product obtained in step (1) was dissolved with about 20mL of dichloromethane at room temperature, and 2.5mL of trifluoroacetic acid dissolved with about 1.2mL of dichloromethane was added dropwise to the reaction solution, stirred at room temperature for 3 hours, and then the product was spin-dried with methanol: dichloromethane: triethylamine =15:1:0.05 (v/v) as eluent was passed through a silica gel column to obtain a yellow product (compound 2);
(3) dissolving 225mg of the yellow solid obtained in the step (2) and 90mg of triethylamine in about 25mL of dichloromethane, dissolving 120mg of p-toluenesulfonyl chloride in 2mL of dichloromethane, slowly dropwise adding the dissolved p-toluenesulfonyl chloride into the reaction solution under the condition of ice salt bath, continuously stirring for 3 hours, and carrying out column chromatography to obtain a yellow solid with the yield of 85 percent, namely, the yield of the fluorescent probeNeedles, abbreviated NHS-ER; it is composed of1The H NMR spectrum is shown in FIG. 1. The reaction formula of each step is as follows:
EXAMPLE 2 response of fluorescent probes to varying concentrations of hypochlorous acid
The probe obtained in example 1 was dissolved in ethanol, and then prepared into a 10. mu.M probe buffer solution (containing 10% ethanol) with a PBS buffer solution having a pH of 7.4. 26 parts of the probe solution are respectively added with water or a sodium hypochlorite solution with the same volume, so that the concentration of hypochlorite is 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380 and 400 mu M in sequence. Then, fluorescence scanning (lambda) is performedEx=405 nm); the relative fluorescence intensity in each system was calculated. The response of probe NHS-ER to different concentrations of hypochlorous acid is shown in FIG. 2: the peak value of the maximum fluorescence intensity is 502 nm. Corresponding light intensity (I) at 502nm502nm) The ordinate and hypochlorite concentration were plotted on the abscissa to obtain FIG. 3, which shows that I502nmThe fluorescence intensity of the fluorescent dye is linearly related to the hypochlorite concentration, and the fluorescence intensity decreases with the increase of the hypochlorite concentration.
EXAMPLE 3 selectivity of fluorescent probes
The probe obtained in example 1 was dissolved in ethanol, and then prepared into a 10. mu.M probe buffer solution (containing 10% ethanol) with a PBS buffer solution having a pH of 7.4. 20 parts of the above probe solution were added to 400. mu.L of 40mM Hcys and Na, respectively2S、Na2SO3、H2O2、Cys、NaNO2And metal ions, etc., and then fluorescence scanning (lambda)Ex=405 nm); calculating the relative fluorescence intensity in each system; the response of probe NHS-ER to different concentrations of hypochlorous acid is shown in FIG. 4 (a); corresponding light intensity (I) at 502nm502nm) As an ordinate, a histogram of the response of the probe to different substances was obtained, as shown in fig. 4 (b): wherein 1-20 respectively represent 1, blank, 2, KI, 3, CaCl2; 4, FeSO4; 5, Cys; 6, CoCl2; 7, MgCl2;8, NaBr; 9, NaF; 10, CuSO4; 11, GSH; 12, H2O2; 13, TBHP; 14, DBTP; 15, Hcy;16, ZnCl2; 17, Na2SO3; 18, NaNO2; 19, Na2S, 20, NaClO. As can be seen from FIG. 4, the relative fluorescence intensity of NHS-ER of the probe could not be reduced by other substances than hypochlorite, indicating that the probe could specifically recognize hypochlorite against various interfering substances.
Example 4 Co-localization of fluorescent probes with endoplasmic reticulum commercial probes
Hela cells were placed in a culture medium (DMEM medium containing 10% fetal calf serum) at 37 deg.C under 5% CO2And 20% of O2The culture box is used for culturing for 48 hours. The fluorescent probe solution obtained in example 1 was aspirated at a concentration of 20. mu.M by a microsyringe, added to the medium containing Hela cells, and cultured in the incubator for further 30 min. The above HeLa cells were then treated with ER-Tracker Red (1. mu.M) for 5 minutes. The cultured cells were then washed 3 times with PBS buffer and fluorescence imaging was performed (probe: Lambda em = 488-538 nm; ER-Tracker Red: Lambda em = 561-611 nm). The results are shown in FIG. 5: the cells to which the probe was added emitted intense green fluorescence; cells added with ER-Tracker Red emit Red fluorescence, and the superposition image of the cells and the cells shows that the probe can well locate endoplasmic reticulum.
Example 5 biological imaging of cellular exogenous hypochlorous acid by fluorescent probes
Placing 3 parts of Hela cells in culture medium (DMEM culture solution containing 10% fetal calf serum) at 37 deg.C and 5% CO2And 20% of O2The culture box is used for culturing for 48 hours. The fluorescent probe solution obtained in example 1 was aspirated at a concentration of 10. mu.M by a microsyringe, added to the medium containing Hela cells, and cultured in the incubator for further 30 min. Adding water and 50 μ M or 100 μ M sodium hypochlorite solution with the same volume, and culturing for 30 min. The cultured cells were then washed 3 times with PBS buffer and fluorescence imaging was performed (λ em = 488-538 nm). The results are shown in FIG. 6: cells without the addition of sodium hypochlorite solution emit intense green fluorescence;the fluorescence of cells added with 50. mu.M or 100. mu.M sodium hypochlorite solution decreased, and the decrease intensity of 100. mu.M was more.
Claims (6)
1. A two-photon fluorescent probe for detecting hypochlorous acid in a cell endoplasmic reticulum has a structural formula shown in formula (I):
formula (I).
2. A method for synthesizing the two-photon fluorescent probe according to claim 1, comprising the steps of:
(1) heating and refluxing 4-methylthio-1, 8-naphthalic anhydride and BOC-hexamethylene diamine in ethanol, and separating and purifying a product to obtain a compound 1:
(2) and (3) stirring the compound 1 and trifluoroacetic acid in dichloromethane for reaction at room temperature, and separating and purifying a product to obtain a compound 2:
(3) reacting the compound 2 with p-toluenesulfonyl chloride in dichloromethane in the presence of triethylamine, and separating and purifying the product to obtain a final product, namely a fluorescent probe:
3. the method of synthesis of claim 2, wherein the molar ratio of 4-methylthio-1, 8-naphthalic anhydride to BOC-hexanediamine is 1-1.2: 1; the molar ratio of the compound 1 to the trifluoroacetic acid is 1: 1-1.2; the molar ratio of the compound 2 to the p-toluenesulfonyl chloride is 1: 1-1.5.
4. The synthesis method according to claim 2, wherein in the step (1), the reaction temperature is 90 ℃, and the reaction time is 4-6 hours; in the step (2), the reaction time is 2-6 hours; in the step (3), the reaction temperature is 0-5 ℃; the reaction time is 2-5 hours.
5. The synthesis method according to claim 2, wherein in the step (1), the separation and purification operation is carried out by mixing ethyl acetate: petroleum ether =3:1 (v/v) as eluent, passing through a silica gel chromatographic column;
in the step (2), the separation and purification operation is to separate methanol: dichloromethane: triethylamine =15:1:0.05 (v/v) as eluent was passed through a silica gel column;
in the step (3), the separation and purification operation is carried out by mixing dichloromethane: methanol =100:1 (v/v) as eluent over a silica gel column.
6. Use of the two-photon fluorescent probe of claim 1 in the preparation of a hypochlorous acid reagent in a detection solution or the endoplasmic reticulum of a cell.
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| CN110078665A (en) * | 2019-05-16 | 2019-08-02 | 济南大学 | A kind of hypochlorous fluorescence probe of detection of endoplasmic reticulum targeting and application |
| CN110156688B (en) * | 2019-05-22 | 2021-08-24 | 济南大学 | Fluorescent probe for detecting polarity of targeted endoplasmic reticulum and application thereof |
| CN110357869B (en) * | 2019-08-08 | 2022-05-10 | 山东省医学科学院药物研究所（山东省抗衰老研究中心、山东省新技术制药研究所） | HClO fluorescent probe designed based on ICT mechanism, and synthetic method and application thereof |
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| CN107446571A (en) * | 2017-08-01 | 2017-12-08 | 济南大学 | A kind of two-photon nitroreductase fluorescence probe of endoplasmic reticulum targeting and its synthetic method and application |
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