CN110563702A - Near-infrared fluorescent compound, preparation method and application thereof in detecting ferrous ions - Google Patents
Near-infrared fluorescent compound, preparation method and application thereof in detecting ferrous ions Download PDFInfo
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Abstract
The present disclosure provides a near-infrared fluorescent compound, a preparation method thereof and an application thereof in detecting ferrous ions, wherein the chemical structural formula is as follows:The present disclosure provides near infrared fluorescent compounds capable of imparting Fe2+the fluorescent probe has the maximum excitation emission wavelength reaching the near infrared region and is used for Fe2+the selectivity of (A) is better.
Description
Technical Field
The disclosure relates to a near-infrared fluorescent compound, a preparation method and application thereof in detecting ferrous ions.
background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
iron is an essential metal element for maintaining normal life activities of human bodies, and plays an important role in oxygen transfer, DNA synthesis and other cell functions. However, excessive iron increases the production of reactive oxygen species ROS, damages cell membranes, proteins and DNA, and leads to apoptosis, and iron overload is directly related to the induction of thalassemia, Friedel-crafts ataxia, and other diseases. In addition, since transferrin and ferritin, which are involved in iron metabolism, are synthesized in the liver, the liver becomes the primary organ of iron overload damage, and a great deal of research shows that iron overload is closely related to occurrence and development of many liver diseases. Monitoring iron homeostasis is therefore essential to maintaining normal vital activities.
As known to the inventor, the existing methods for detecting ferrous ions include a spectroscopic method, an electrochemical method, a fluorescence method and the like, wherein the fluorescence method has the advantages of high selectivity, low toxicity, convenience in use and the like and is widely applied to biological analysis; however, the inventors of the present disclosure found in their studies that Fe was detected at present2+The fluorescent probe has the problems that the maximum excitation emission wavelength can rarely reach a near infrared region, and the fluorescent probe is easily interfered by other metal ions.
Disclosure of Invention
In order to overcome the defects of the prior art, the present disclosure aims to provide a near-infrared fluorescent compound, a preparation method and an application thereof in detecting ferrous ions, which can enable Fe2+The fluorescent probe has the maximum excitation emission wavelength reaching the near infrared region and is used for Fe2+The selectivity of (A) is better.
In order to achieve the purpose, the technical scheme of the disclosure is as follows:
In one aspect, the present disclosure provides a near-infrared fluorescent compound having a chemical structural formula as follows:
On the other hand, the present disclosure provides a preparation method of the near-infrared fluorescent compound, which comprises the following reaction routes:
In a third aspect, the present disclosure provides an application of the near-infrared fluorescent compound in detecting ferrous ions.
In a fourth aspect, the present disclosure provides a fluorescent probe for detecting ferrous ions, including the above near-infrared fluorescent compound.
In a fifth aspect, the disclosure provides an application of the near-infrared fluorescent compound or the fluorescent probe in preparing a drug-induced liver injury detection reagent.
The principle of detecting ferrous ions by adopting the near-infrared fluorescent compound is as follows: with the pentadentate N4O ligand as the recognition group and QCy7 as the fluorophore, the probe itself did not fluoresce because the conjugated structure of the fluorophore QCy7 was masked by the recognition group; when Fe2+After coordination with a recognition group, at O2C-O bond is broken under the action of the trigger, and the masked near infrared fluorescence of QCy7 is triggered, so that Fe is generated2+The specific detection of (2) becomes possible.
The beneficial effect of this disclosure does:
1. The near infrared fluorescent compounds provided by the present disclosure are capable of being Fe2+The fluorescent probe has the maximum excitation emission wavelength reaching the near infrared region and is used for Fe2+The selectivity of (A) is better.
2. The near-infrared fluorescent compound provided by the disclosure has the advantages of simple preparation, accurate positioning and the like.
3. the near infrared fluorescent compound provided by the present disclosure is to Fe2+After specific binding, near-infrared fluorescence can be generated, and the interference of the autofluorescence of biological tissues can be avoided.
Drawings
the accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to limit the disclosure.
FIG. 1 is a fluorescence detection graph of probe LCy7 prepared in example 1 of the present disclosure, where A is an absorption spectrum, B is a fluorescence spectrum, C is a graph showing the relationship between fluorescence intensity and pH change, and D is a histogram of probe LCy7 for detecting different metal ions;
FIG. 2 is a mass spectrum of probe LCy7 prepared in example 1 of the present disclosure;
Fig. 3 is a confocal imaging diagram of the probe LCy7 prepared in example 1 of the present disclosure, where a is a control group, B is a cell incubated for 6H with 100 μ M of added ammonium ferrous sulfate (FAS), C is a cell incubated for 6H with 100 μ M of added ammonium ferrous sulfate, then 50 μ M of desferrioxamine, which is an iron chelator, is added for 40min, D is a field diagram with only 50 μ M of desferrioxamine added for 40min, E is a field diagram with a, F is a field diagram with B, G is a field diagram with C, H is a field diagram with D, and I is a fluorescence intensity output diagram.
FIG. 4 is a representation of the in vivo imaging of probe LCy7 prepared according to example 1 of the present disclosure on a mouse model with drug-induced liver injury, the left image showing the left hand mouse in the imaging graph as a control group, the right hand mouse as a model group, and the right hand image showing a histogram of fluorescence intensity;
FIG. 5 is a fluorescent spectrum before and after detecting ferrous ions by the fluorescent probe prepared by the comparative example of the present disclosure.
Detailed Description
it should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to solve the existing detection of Fe2+the fluorescent probe has the problems that the maximum excitation emission wavelength can rarely reach a near infrared region, and is easily interfered by other metal ions, and the like.
In one exemplary embodiment of the present disclosure, a near-infrared fluorescent compound is provided, which has a chemical structural formula as follows:
In another embodiment of the present disclosure, a method for preparing the near-infrared fluorescent compound is provided, which includes the following reaction scheme:
In one or more embodiments of the embodiment, compound 1 and tert-butyl bromoacetate undergo a substitution reaction to obtain compound 2, compound 2 and 2, 6-dibromomethylpyridine undergo a substitution reaction to obtain compound 3, 4-hydroxyisophthalaldehyde and compound 3 undergo an etherification reaction to obtain compound 4, compound 4 and 2 equivalents of 1,2,3, 3-tetramethyl-3H-indole iodide undergo a condensation reaction to obtain compound 5, and tert-butyl protecting groups are removed from compound 5 to obtain a near-infrared fluorescent compound.
in this series of examples, the conditions of the etherification reaction were: adding cesium carbonate, and heating to 75-85 ℃ under an inert atmosphere for reaction.
In the series of embodiments, in the etherification reaction, the molar ratio of 4-hydroxyisophthalaldehyde to the compound 3 is 1-1.5: 1.
In this series of examples, the conditions of the condensation reaction were: adding sodium acetate, and heating to 55-65 ℃ under an inert atmosphere for reaction.
In this series of examples, the process for removing the t-butyl protecting group from compound 5 is: after mixing compound 5 with trifluoroacetic acid, the reaction was carried out under an inert atmosphere.
In a third embodiment of the present disclosure, an application of the near-infrared fluorescent compound in detecting ferrous ions is provided.
In a fourth embodiment of the present disclosure, a fluorescent probe for detecting ferrous ions is provided, which includes the near-infrared fluorescent compound.
the fifth embodiment of the disclosure provides an application of the near-infrared fluorescent compound or the fluorescent probe in preparing a drug-induced liver injury detection reagent.
The principle of detecting ferrous ions by adopting the near-infrared fluorescent compound disclosed by the invention is as follows: with the pentadentate N4O ligand as the recognition group and QCy7 as the fluorophore, the probe itself did not fluoresce because the conjugated structure of the fluorophore QCy7 was masked by the recognition group; when Fe2+After coordination with a recognition group, at O2C-O bond is broken under the action of the trigger, and the masked near infrared fluorescence of QCy7 is triggered, so that Fe is generated2+The specific detection of (2) becomes possible.
QCy7 as a fluorophore enabling Fe2+The fluorescent probe has the advantage that the maximum excitation emission wavelength reaches a near infrared region, and has the advantages of low fluorescent background and high tissue penetrating power in the probe research process. After research, not all fluorophores are combined with the pentadentate N4O ligand and can specifically combine with ferrous ions to generate fluorescence signals, for example, fluorophores such as naphthalic anhydride, and further research shows that the fluorescence signals can be generated after the fluorescence probes are combined with the ferrous ions by adopting QCy7 as the fluorophore, and the maximum excitation emission wavelength of the fluorescence signals reaches the near infrared region.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.
example 1
Synthesis of fluorescent probe:
Di-2-pyridinone (0.744,3.9mmol) and hydroxylamine hydrochloride (0.39,6.06mmol) were dissolved in 9mL of anhydrous ethanol, stirred at room temperature for 90min, sodium hydroxide (0.78g,19.98mmol) was slowly added and heated to 80 deg.C under reflux for 10min, during which time the solution turned dark orange and a white precipitate formed. The reaction mixture was treated with water (60mL) and concentrated hydrochloric acid (30mL) and the ethanol was removed by rotary evaporation to give a dark red solution. The product was precipitated by the addition of saturated aqueous sodium carbonate (60mL) and isolated by vacuum filtration, washed with water and dried under vacuum at room temperature to give the product di-2-pyridylketoxime as a white solid.
The chemical route is as follows:
In 8.5mL ethanol, 5mL water and 7.5mL 23% ammonia water, add bis-2-pyridylketoxime (0.5g,2.5mmol) and ammonium acetate (0.33g,4.28mmol), dissolve and heat to 80 deg.C, 30min later add zinc powder (0.74g,11.3mmol) and heat reflux for 4.5h, filter to remove solids, filtrate rotary evaporation concentration, the resulting aqueous solution with sodium hydroxide solution alkalized and extracted with dichloromethane. The organic phase was washed with brine and dried over anhydrous magnesium sulfate, and the solvent was evaporated to give di-2-pyridylmethylamine (compound 1) as a colorless oil.
The chemical route is as follows:
To a solution of di-2-pyridylmethylamine (2.4g,13mmol) in tetrahydrofuran (50mL) cooled in an ice-water bath was added dropwise tert-butyl bromoacetate (2.5g,12.8mmol) and DIPEA (2.3mL,13.2mmol), the mixture was stirred in an ice bath overnight, the tetrahydrofuran was removed by rotary evaporation, the residue was dissolved in dichloromethane and extracted with a saturated sodium bicarbonate solution, water and brine, the organic phase was dried over anhydrous magnesium sulfate, and the residue obtained after rotary evaporation was purified with a basic alumina column (ethyl acetate: n-hexane 4:1) to give compound 2.
The chemical route is as follows:
Compound 2(0.99g,3.3mmol) obtained in the previous step, 2, 6-dibromomethylpyridine (1.1g,4.0mmol) and cesium carbonate (1.3g,4.0mmol) were heated to 40 ℃ in 50ml acetonitrile and stirred overnight. After filtration, insoluble matter was removed, and the filtrate was concentrated and purified by a basic alumina column (ethyl acetate: n-hexane ═ 4:1) to obtain compound 3.
the chemical route is as follows:
Compound 3(0.24mmol,0.1156g) and 4-hydroxyisophthalaldehyde (0.24mmol,0.036g) were dissolved in 5mL acetonitrile, cesium carbonate (0.36mmol,0.117g) was added, and the mixture was stirred in N2Reflux overnight at 80 ℃ under protection. And (3) after the reaction is finished, performing rotary evaporation and concentration, and performing reaction by using dichloromethane: methanol 15:1 column chromatography gave compound 4 as a yellow oil in 37.5% yield.
The chemical route is as follows:
compound 4(0.3mmol, 0.1843g) was dissolved in 5mL of acetic anhydride, and 1,2,3, 3-tetramethyl-3H-indolium iodide (1.2mmol, 0.37g) and anhydrous sodium acetate (0.9mmol, 0.074g) were added to the mixture at 60 ℃ N2And reacting for 1h under protection. After the reaction is finished, spin-drying, reacting with dichloromethane: methanol 20: 1 as eluent, and purification on a neutral alumina column gave cyan compound 5 in 10% yield.
The chemical route is as follows:
compound 5(20mg) was dissolved in 2mL of dichloromethane, 1mL of trifluoroacetic acid was added, and the mixture was stirred under N2Stirring overnight under protection. The reaction was spin dried, extracted with saturated sodium bicarbonate and deionized water, dried over anhydrous sodium sulfate, and spin evaporated to give probe LCy715 mg.1H NMR(400MHz,DMSO-d6):δ14.32(s,1H),8.66(d,J＝4.8Hz,1H),8.56(m,1H),8.11-8.08(t,J＝7.6Hz,1H),7.97(t,J＝3.2Hz,1H),7.92-7.89(m,6H),7.83-7.81(m,4H),7.66(d,J＝2Hz,1H),7.65(d,J＝1.6Hz,1H),7.64(d,J＝2Hz,2H),7.62(s,2H),7.61(s,2H),4.22(s,2H),4.12-4.07(m,3H),3.46(s,1H),2.77(s,12H),1.85-1.83(t,J＝4.4Hz,4H),1.80-1.77(t,J＝6.4Hz,2H),1.73(s,2H),1.26-1.24(d,J＝9.6Hz,3H).13C NMR(101MHz,DMSO-d6):δ196.49,182.26,182.05,172.58,161.95,159.39,159.02,158.66,158.30,157.16,154.97,149.23,147.18,142.58,142.32,142.04,140.56,129.75,129.24,123.67,120.44,117.55,115.53,114.65,111.76,69.87,54.36,52.62,34.96,25.97,25.86,22.11,14.32.13C NMR(101MHz,DMSO-d6):δ196.49,182.26,182.05,172.58,161.95,159.39,159.02,158.66,158.30,157.16,154.97,149.23,147.18,142.58,142.32,142.04,140.56,129.75,129.24,125.88,123.67,120.44,117.55,115.53,114.65,111.76,54.36,52.62,34.96,25.97,25.86,22.11,14.32.HRMS(ESI):calcd for C52H52N6O3 2+[M]2+M/z 404.2045, found 404.2033 (see FIG. 2).
The chemical route is as follows:
The synthesized probe LCy7 was dissolved in Tris buffer (pH 7.4) for fluorescence detection, as shown in fig. 1, indicating a maximum absorption wavelength of 560nm (fig. 1A). The excitation wavelength was 560nm and the emission wavelength was 690nm (FIG. 1B). FIG. 1C depicts the relationship between the fluorescence intensity of the probe and the change in pH. It can be seen that the probe is not affected by pH. FIG. 1D depicts the selectivity of the probe. It can be seen that the probe is not interfered by other metal ions (A: Fe)2+(20μM),B:Al3+(1mM),C:Ca2+(1mM),D:Cu+(20μM),E:Cu2+(20μM),F:Fe3+(20μM),G:K+(1mM),H:Mg2+(1mM),I:Mn2+(20μM),J:Na+(1mM),K:Zn2+(20μM),L:Ni2+(20μM),M:Ba2+(20μM),N:Cd2+(20μM),O:Pd2+(20μM),P:Sn2+(20μM),Q:Sr2+(20. mu.M), R: Blank.). FIG. 2 is a mass spectrum and a hydrogen carbon spectrum of probe LCy 7.
FIG. 3 shows probe LCy7 for Fe in cells2+Confocal imaging was performed. Exogenous Fe to HL-7702 cells with probe LCy7(10 μm)2+Visualization is performed. Cells were directly incubated with 100. mu.M Ferrous Ammonium Sulfate (FAS) and the intracellular fluorescence intensity was found to be increased 2-fold compared to the control. Indicating that probe LCy7 can be directed to exogenous Fe at the cellular level2+And performing visual imaging. To demonstrate the change in fluorescenceIs made of Fe2+Induced, incubation of high Fe with 50 μ M deferiprone (an iron chelator) (DFP)2+The cells were kept for 40min to reduce the amount of free iron in the cells. The fluorescence intensity in cells treated with DFP is obviously reduced by 2 times, which proves that the increase of the fluorescence intensity of cells is really caused by the addition of Fe2+The result is. In addition, after the cells are treated by 50 mu M DFP for 40min, the cells are stained by the probe, and the fluorescence is obviously reduced by 2 times compared with the fluorescence intensity of the cells of a control group which is not treated by the DFP, which indicates that the probe can image endogenous Fe of the cells2+. The above results indicate that probe LCy7 has good membrane permeability and can be used to observe Fe in cells2+The variation of (2).
fig. 4 is a live image of probe LCy7 on a mouse model of drug-induced liver injury. Firstly, acetaminophen (APAP)450mg/Kg is used for intraperitoneal injection of mice to establish a drug liver injury model, and a control group is injected with normal saline with the same volume. Surgery was performed 6 hours later and fluorescence imaging of the liver site was performed in a small animal live imager. As can be seen from the imaging results, the fluorescence intensity of the model group mice is enhanced by 1.3 times compared with that of the control group.
Comparative example
Compound 3(0.24mmol,0.1156g) and compound 6(0.26mmol,0.1066g) were dissolved in 5mL acetonitrile, cesium carbonate (0.24mmol,0.078g) was added and the mixture was stirred under N2Reflux overnight at 80 ℃ under protection. And (3) after the reaction is finished, performing rotary evaporation and concentration, and performing reaction by using dichloromethane: methanol 15:1 column chromatography gave compound 7 as a yellow oil. Compound 7(20mg) was dissolved in 2mL of dichloromethane, 1mL of trifluoroacetic acid was added, and the mixture was stirred under N2Stirring overnight under protection. And (3) spin-drying the reactant, extracting with saturated sodium bicarbonate and deionized water, drying with anhydrous sodium sulfate, and spin-steaming to obtain the fluorescent probe.
As shown in FIG. 5, the detection of ferrous ions by using the fluorescent probe is almost unchanged, which indicates that the fluorescent probe cannot detect ferrous ions.
The above description is only a preferred embodiment of the present disclosure and is not intended to limit the present disclosure, and various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (10)
1. A near-infrared fluorescent compound is characterized by having a chemical structural formula as follows:
2. A method for preparing the near-infrared fluorescent compound of claim 1, which comprises the following reaction routes:
3. the method according to claim 2, wherein the compound 1 is substituted with t-butyl bromoacetate to obtain a compound 2, the compound 2 is substituted with 2, 6-dibromomethylpyridine to obtain a compound 3, 4-hydroxyisophthalaldehyde, the compound 3 is etherified to obtain a compound 4, the compound 4 is condensed with 2 equivalents of 1,2,3, 3-tetramethyl-3H-indolium iodide to obtain a compound 5, and the compound 5 is subjected to removal of a t-butyl protecting group to obtain the near-infrared fluorescent compound.
4. The method for preparing a near-infrared fluorescent compound according to claim 3, wherein the etherification reaction conditions are as follows: adding cesium carbonate, and heating to 75-85 ℃ under an inert atmosphere for reaction.
5. the method according to claim 3, wherein the molar ratio of 4-hydroxyisophthalaldehyde to the compound 3 in the etherification reaction is 1 to 1.5: 1.
6. the method for preparing a near-infrared fluorescent compound according to claim 3, wherein the conditions of the condensation reaction are: adding sodium acetate, and heating to 55-65 ℃ under an inert atmosphere for reaction.
7. the method of claim 3, wherein the removal of the t-butyl protecting group from compound 5 comprises: after mixing compound 5 with trifluoroacetic acid, the reaction was carried out under an inert atmosphere.
8. Use of the near-infrared fluorescent compound of claim 1 in the detection of ferrous ions.
9. A fluorescent probe for detecting ferrous ions, comprising the near-infrared fluorescent compound according to claim 1.
10. Use of the near-infrared fluorescent compound of claim 1 or the fluorescent probe of claim 9 in the preparation of a drug-induced liver injury detection reagent.
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| DEBABRATA MAITY等: "A switch-on near-infrared fluorescence-ready probe for Cu(I): live cell imaging", 《SUPRAMOLECULAR CHEMISTRY》 * |
| HO YU AU-YEUNG等: "Molecular Imaging of Labile Iron(II) Pools in Living Cells with a Turn-On Fluorescent Probe", 《J. AM. CHEM. SOC.》 * |
| NAAMA KARTON-LIFSHIN等: "A Unique Paradigm for a Turn-ON Near-Infrared Cyanine-Based Probe Noninvasive Intravital Optical Imaging of Hydrogen Peroxide", 《J. AM. CHEM. SOC.》 * |
| 王栩 等: "细胞内活性小分子近红外荧光成像探针", 《化学进展》 * |
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