CN111892643A - Diglycine copper ion gel fluorescent probe compound and preparation method and application thereof - Google Patents

Diglycine copper ion gel fluorescent probe compound and preparation method and application thereof Download PDF

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CN111892643A
CN111892643A CN202010665468.8A CN202010665468A CN111892643A CN 111892643 A CN111892643 A CN 111892643A CN 202010665468 A CN202010665468 A CN 202010665468A CN 111892643 A CN111892643 A CN 111892643A
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高文霞
冯欣
吴华悦
刘妙昌
周云兵
黄小波
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Wenzhou University
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Abstract

The invention discloses a diglycine copper ion gel fluorescent probe compound and a preparation method and application thereof, the compound related to the invention is shown in the specification formula (1), and the compound is used as a gel for preparing gel with Cu2+Sensitive advantage, the gel has specific Cu2+Sensitive advantage, only adding Cu2+Quenching of the fluorescence occurs.

Description

Diglycine copper ion gel fluorescent probe compound and preparation method and application thereof
Technical Field
The invention belongs to the field of organic chemistry and chemical detection and analysis, and particularly relates to a diglycine copper ion gel fluorescent probe compound and a preparation method and application thereof.
Background
Copper is known to be one of the most abundant transition metals in the living system, second only to iron and zinc, and is an important trace element in animals and plants (z.aydin, b.yan, y.wei, et al.a novel near-induced turn-on and ratio metric fluorescent probe card of coupler (II) ion determination in cells, chem.comm.2020, 56,6043), copper ion, although playing a key role in many physiological processes such as signal transduction, redox reaction, central nervous system and energy generation, has also high toxicity to the living system (p.vertically, k.sun wood, j.s.kim., et al.the role of coupler in physiological sensors for diseases of the heart, 51,5556, for example parkinson's disease. This is because Copper not only catalyzes the production of free radicals, which can destroy lipids, proteins, DNA and other biomolecules, but also interfere with proteins containing iron-sulfur clusters, and can replace other metals such as zinc from metalloproteins, inhibiting their activity (d.denoyer, s.massdan, s.la Fontaine, m.a.filter, Targeting Copper in Cancer therapy: 'Copper at Cancer'. metalomics, 2015,7, 1459). Copper therefore cannot exist freely in the cytoplasm and must be complexed at any time.
In view of the above characteristics of copper ions, in modern medical detection, it is often necessary to detect the content of copper ions in human body to prevent excessive copper ions from causing related diseases. Therefore, the development of a high-efficiency and sensitive copper ion detection probe has very important significance. The invention of the present application is provided based on this.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the invention aims to provide a diglycine copper ion gel fluorescent probe compound and a preparation method and application thereof. The copper ion gel prepared by the compound hasWith Cu2+And the method is sensitive and can be used for realizing the detection of copper ions.
In order to achieve the above object, a first object of the present invention is to provide a compound represented by the following formula (1):
Figure BDA0002580224730000021
the compound of formula (1) of the present application is named
4,4', 4 "-nitrile (N- (2- ((2- ((2- ((2- ((3- (5, 5-dimethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amino) -2-oxoethyl) benzamide).
The second purpose of the invention is to provide a preparation method of the diglycine copper ion gel fluorescent probe compound, which comprises the following steps:
mixing 2-amino-N- (2- (((3- (5, 5-dimethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amino) -2-oxyethyl) acetamide shown in formula (2), and (tert-butoxycarbonyl) glycylglycine, DCC and DMAP shown in formula (3) in a DMF solvent, stirring for reaction at room temperature, and carrying out aftertreatment on the obtained reaction liquid a to obtain a compound C shown in formula (4)24H36BN5O8；
Figure BDA0002580224730000031
Dissolving the compound shown in the formula (4) prepared in the step I in a dichloromethane solvent, adding trifluoroacetic acid, reacting for 15-30h, and performing aftertreatment on the reaction liquid b obtained after the reaction is finished to prepare the compound shown in the formula (5);
Figure BDA0002580224730000032
dissolving the compound shown in the formula (5) prepared in the step (II) in a DMF solvent, dissolving the compound shown in the formula (6) in the DMF solvent, mixing, adding DCC and DMAP, reacting, and carrying out aftertreatment on the obtained reaction liquid c to obtain a compound shown in the formula (1), namely the diglycine type copper ion gel fluorescent probe compound;
Figure BDA0002580224730000033
further, the amount ratio of the compounds represented by the formulae (2) and (3) to DCC and DMAP in the step (i) is set to 1.0:1.0:1.2: 1.2.
The amount ratio of the compound represented by the formula (5) or (6) to the DCC and DMAP in the third step is 3.5:1.0:3.5: 3.5.
In the step (i), the post-treatment method of the reaction solution a comprises: and (2) carrying out vacuum filtration on the reaction liquid a, evaporating the solvent from the filtrate, adding ethyl acetate for ultrasonic treatment, carrying out vacuum filtration, washing and drying the filter cake for multiple times by using ethanol and ethyl acetate to obtain a compound shown as a formula (4), wherein in the step (II), the post-treatment method of the reaction liquid b comprises the following steps: evaporating the solvents trifluoroacetic acid and chloroform from the reaction liquid b, adding a small amount of acetonitrile, performing ultrasonic treatment, performing reduced pressure suction filtration, washing a filter cake with ethyl acetate for multiple times, and drying to obtain a compound shown as a formula (5), wherein in the step III, the post-treatment method of the reaction liquid c comprises the following steps: and (3) carrying out vacuum filtration on the reaction liquid c, evaporating the solvent from the filtrate, adding ethyl acetate, carrying out ultrasonic filtration, carrying out vacuum filtration, and washing and drying the filter cake for multiple times by using ethanol and ethyl acetate to obtain the compound shown in the formula (1).
Further setting that in the step I, the volume dosage of the DMF solvent is 75-80 mL/g based on the mass of the compound shown in the formula (2);
in the step II, the volume consumption of the dichloromethane and the solvent is 20-30 mL/g based on the mass of the compound shown in the formula (4); the volume usage amount of the trifluoroacetic acid and the solvent is 24-36 mL/g based on the mass of the compound shown in the formula (4);
in the step (c), the volume usage amount of the DMF solvent is usually 55 to 60mL/g based on the mass of the compound represented by formula (5).
In addition, the invention also provides an application method of the compound shown in the formula (1), and the compound shown in the formula (1) is used for preparing specific Cu2+Coagulation of sensitive organogelsAnd (3) glue.
Further setting the method to add the compound shown in the formula (1) into an organic solvent, sealing and heating to 90 ℃ for complete dissolution, then standing and cooling to room temperature to prepare the specific Cu2+A sensitive organogel.
In addition, the invention also provides specific Cu obtained by the application method2+Sensitive organogel, Cu of said organogel2+The sensitivity and specificity make the probe become a copper ion gel fluorescent probe.
The invention mainly designs and synthesizes a small molecular gel factor containing the diglycine group, the gel realizes the complexing sensitivity of specific copper ions, and the novel diglycine copper ion gel type fluorescent probe can be used for detecting the copper ions in the human body and has important application value.
The compound (1) is used as a gelling agent to prepare gel with Cu2+And (4) sensitivity. The compound (1) is a good gel, and self-assembles into a three-dimensional network structure in solvents such as ethanol, methanol and the like through non-covalent bond acting forces such as Van der Waals force, hydrogen bonds, pi-pi superposition and the like among gel factor molecules, so that the solvent molecules lose fluidity to form gel, as shown in figure 1. The gel has specific Cu2+Sensitive advantage, only adding Cu2+Quenching of the fluorescence occurs as shown in figure 2. Because amide bonds contained in the molecular structure of the compound (1) have hydrogen bonding effects, the compound can be bonded with Cu2+The complexation occurs, the interaction force among gel factors is destroyed, so that the gel is converted into sol to realize the effect of Cu2+Is sensitive to the response.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a schematic diagram of gel of compound (1) in ethanol, wherein FIG. 1A is a picture of gel under natural illumination and FIG. 1B is a picture of gel under fluorescent illumination;
FIG. 2 fluorescence plot of gelator versus common cation response.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Some of the compound names in this example are illustrated below:
DCC is short for dicyclohexylcarbodiimide, and DMAP is short for 4-dimethylaminopyridine; DMF is dimethylformamide for short. DMSO is dimethyl sulfoxide for short.
Specific Synthesis examples of Compound (1) include example 1 to example 3
Example 1
80mL of DMF, 2-amino-N- (2- (((3- (5, 5-dimethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amino) -2-oxyethyl) acetamide (1g,3.13mmol), (tert-butoxycarbonyl) glycylglycine (0.73g,3.13mmol), DCC (0.77g,3.756mmol), DMAP (0.46g,3.756mmol) were added to a 250mL round-bottomed flask, and the mixture was stirred at room temperature for 12 hours, then the reaction solution a was suction-filtered under reduced pressure, after evaporation of the solvent from the filtrate, ethyl acetate was added thereto, followed by sonication, suction-filtering under reduced pressure, the filter cake was washed once with ethanol, then washed 2 times with ethyl acetate, and dried to obtain a compound represented by the formula (4) (C)24H36BN5O8Tert-butyl (2- ((2- ((2- ((2- ((3- (1,3, 2-dioxaborane-2-yl) phenyl) amino) -2-oxoethyl) carbamate), yield 83.1%.
Example 2
Compound (4) (1.38g,2.6mmol) was added to a mixed solvent of 30ml of chloroform and 36ml of trifluoroacetic acid and stirred at room temperature for 12 hours. Evaporating the reaction liquid b to remove the solvents trifluoroacetic acid and chloroform, adding 5ml of acetonitrile, performing ultrasonic treatment, performing reduced pressure suction filtration, washing the filter cake with ethyl acetate for 3 times, and drying to obtain the compound (C) shown in the formula (5)19H28BN5O62-amino-N- (2- ((2) ((b)2- ((3- (5, 5-dimethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) amino) -2-oxoethyl) acetamide), yield 77.6%.
Example 3
A100 mL round bottom flask was charged with 50mL of DMF, 2-amino-N- (2- ((2- ((2- ((3- (5, 5-dimethyl-1, 3, 2-dioxaborocan-2-yl) phenyl) amino) -2-oxoethyl) acetamide (1.52g,3.5mmol), tris (4-carboxyphenyl) amine (0.38g,1mmol), DCC (1.46g,7mmol), DMAP (0.85g,7mmol) and stirred at room temperature for 12 h. And (3) carrying out vacuum filtration on the reaction liquid c, evaporating the solvent from the filtrate, adding 48ml of ethyl acetate, carrying out ultrasonic filtration, carrying out vacuum filtration, washing the filter cake once with ethanol, then washing 3 times with ethyl acetate, and drying to obtain the compound shown in the formula (1), wherein the yield is 79%.
The specific preparation of the Compound (1) gel is as in examples 4 to 10
Example 4
16.23mg of gelator was dissolved in 10ml DMSO to prepare 10-3mol/L gelator solution, taking out 1ml gelator solution to be diluted to the scale mark in a 100ml volumetric flask to prepare 10-5mol/L gelator solution; are separately prepared 10- 2The total number of the common cations in the water solution is 19. Taking 20 gel factor solutions in 4ml of centrifuge tubes, wherein one gel factor solution is not added with ions to serve as a blank control, and the other gel factor solution is added with 20 mu l of different cation solutions respectively to be shaken uniformly, and then transferred to a fluorescence cuvette to measure the fluorescence intensity.
Example 5
16.23mg of gelator was dissolved in 10ml DMSO to prepare 10-3mol/L gelator solution, taking out 1ml gelator solution to be diluted to the scale mark in a 100ml volumetric flask to prepare 10-5mol/L gelator solution; 159mgCuSO4Dissolving in 10ml of distilled water to prepare 0.1mol/L Cu2+The solution is prepared into 30ml, 1ml of 0.1mol/L Cu is taken2+The solution is put into a 10ml volumetric flask, and the constant volume is obtained to be 0.01mol/L Cu2+And (3) solution. 4ml of gelator solution is put into a 5ml centrifuge tube, and 20 mu L of 0.01mol/L Cu is added2+Shaking the solution, and mixing the solutionTransferring to a fluorescence cuvette to measure the fluorescence intensity.
Example 6
16.23mg of gelator was dissolved in 10ml DMSO to prepare 10-3mol/L gelator solution, taking out 1ml gelator solution to be diluted to the scale mark in a 100ml volumetric flask to prepare 10-5mol/L gelator solution; 2ml of 0.1mol/L Cu is taken2+The solution is put into a 10ml volumetric flask, and the constant volume is obtained to be 0.02mol/L Cu2+And (3) solution. 4ml of gelator solution is put into a 5ml centrifuge tube, and 20 mu.l of 0.02mol/L Cu is added2+Shaking the solution evenly, transferring the solution to a fluorescence cuvette, and measuring the fluorescence intensity of the solution.
Example 7
16.23mg of gelator was dissolved in 10ml DMSO to prepare 10-3mol/L gelator solution, taking out 1ml gelator solution to be diluted to the scale mark in a 100ml volumetric flask to prepare 10-5mol/L gelator solution; taking 4ml of 0.1mol/L Cu2+The solution is put into a 10ml volumetric flask to obtain 0.04mol/L Cu2+And (3) solution. 4ml of gelator solution is put into a 5ml centrifuge tube, and 20 mu.l of 0.04mol/L Cu is added2+Shaking the solution evenly, transferring the solution to a fluorescence cuvette, and measuring the fluorescence intensity of the solution.
Example 8
16.23mg of gelator was dissolved in 10ml DMSO to prepare 10-3mol/L gelator solution, taking out 1ml gelator solution to be diluted to the scale mark in a 100ml volumetric flask to prepare 10-5mol/L gelator solution; 6ml of 0.1mol/L Cu are taken2+The solution is put into a 10ml volumetric flask, and the constant volume is obtained to be 0.06mol/L Cu2+And (3) solution. 4ml of gelator solution is put into a 5ml centrifuge tube, and 20 mu.l of 0.06mol/L Cu is added2+Shaking the solution evenly, transferring the solution to a fluorescence cuvette, and measuring the fluorescence intensity of the solution.
Example 9
16.23mg of gelator was dissolved in 10ml DMSO to prepare 10-3mol/L gelator solution, taking out 1ml gelator solution to be diluted to the scale mark in a 100ml volumetric flask to prepare 10-5mol/L gelator solution; taking 8ml of 0.1mol/L Cu2+Putting the solution into a 10ml volumetric flask, and fixing the volume to obtain0.08mol/L Cu2+And (3) solution. 4ml of gelator solution is put into a 5ml centrifuge tube, 20 mu L of 0.08mol/L Cu is added2+Shaking the solution evenly, transferring the solution to a fluorescence cuvette, and measuring the fluorescence intensity of the solution.
Example 10
16.23mg of gelator was dissolved in 10ml DMSO to prepare 10-3mol/L gelator solution, taking out 1ml gelator solution to be diluted to the scale mark in a 100ml volumetric flask to prepare 10-5mol/L gelator solution; 159mgCuSO4Dissolving in 10ml of distilled water to prepare 0.1mol/L Cu2+To the solution, 20. mu.l of 0.1mol/L Cu was added2+Shaking the solution evenly, transferring the solution to a fluorescence cuvette, and measuring the fluorescence intensity of the solution.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.

Claims (9)

1. A diglycine copper ion gel fluorescent probe compound is characterized in that the chemical structural formula is shown as formula (1):
Figure FDA0002580224720000011
2. the preparation method of the diglycine copper ion gel fluorescent probe compound as claimed in claim 1, characterized by comprising the following steps:
mixing 2-amino-N- (2- (((3- (5, 5-dimethyl-1, 3, 2-dioxaborane-2-yl) phenyl) amino) -2-oxyethyl) acetamide shown in formula (2), and (tert-butoxycarbonyl) glycylglycine, DCC and DMAP shown in formula (3) in a DMF solvent, stirring for reaction at room temperature, and carrying out aftertreatment on the obtained reaction liquid a to obtain a compound C shown in formula (4)24H36BN5O8；
Figure FDA0002580224720000012
Dissolving the compound shown in the formula (4) prepared in the step I in a dichloromethane solvent, adding trifluoroacetic acid, reacting for 15-30h, and performing aftertreatment on the reaction liquid b obtained after the reaction is finished to prepare the compound shown in the formula (5);
Figure FDA0002580224720000021
dissolving the compound shown in the formula (5) prepared in the step (II) in a DMF solvent, dissolving the compound shown in the formula (6) in the DMF solvent, mixing, adding DCC and DMAP, reacting, and carrying out aftertreatment on the obtained reaction liquid c to obtain a compound shown in the formula (1), namely the diglycine type copper ion gel fluorescent probe compound;
Figure FDA0002580224720000022
3. the method of claim 2, wherein: in the step (i), the ratio of the amounts of the compounds represented by the formulae (2) and (3) to the amounts of the DCC and DMAP is 1.0:1.0:1.2: 1.2.
4. The production method according to claim 3, characterized in that: the amount ratio of the compounds represented by the formulas (5) and (6) to the DCC and DMAP is 3.5:1.0:3.5: 3.5.
5. The method of claim 1, wherein: in the step (i), the post-treatment method of the reaction solution a comprises: and (2) carrying out vacuum filtration on the reaction liquid a, evaporating the solvent from the filtrate, adding ethyl acetate for ultrasonic treatment, carrying out vacuum filtration, washing and drying the filter cake for multiple times by using ethanol and ethyl acetate to obtain a compound shown as a formula (4), wherein in the step (II), the post-treatment method of the reaction liquid b comprises the following steps: evaporating the solvents trifluoroacetic acid and chloroform from the reaction liquid b, adding a small amount of acetonitrile, performing ultrasonic treatment, performing reduced pressure suction filtration, washing a filter cake with ethyl acetate for multiple times, and drying to obtain a compound shown as a formula (5), wherein in the step III, the post-treatment method of the reaction liquid c comprises the following steps: and (3) carrying out vacuum filtration on the reaction liquid c, evaporating the solvent from the filtrate, adding ethyl acetate, carrying out ultrasonic filtration, carrying out vacuum filtration, and washing and drying the filter cake for multiple times by using ethanol and ethyl acetate to obtain the compound shown in the formula (1).
6. The method of claim 1, wherein:
in the step I, the volume consumption of the DMF solvent is 75-80 mL/g based on the mass of the compound shown in the formula (2);
in the step II, the volume consumption of the dichloromethane and the solvent is 20-30 mL/g based on the mass of the compound shown in the formula (4); the volume usage amount of the trifluoroacetic acid and the solvent is 24-36 mL/g based on the mass of the compound shown in the formula (4);
in the step (c), the volume usage amount of the DMF solvent is usually 55 to 60mL/g based on the mass of the compound represented by formula (5).
7. A method of using the compound of claim 1, wherein: the compound represented by the formula (1) is used for preparing specific Cu2+A gelling agent for a sensitive organogel.
8. The method of use according to claim 7, wherein: adding a compound shown as a formula (1) into an organic solvent, sealing and heating to 90 ℃ for complete dissolution, standing and cooling to room temperature to prepare the specific Cu2+A sensitive organogel.
9. Specific Cu obtained by the application method of claim 72+A sensitive organogel.
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