CN114163634A - Preparation method and application of imidazole-containing fused heterocyclic polymer and polyelectrolyte - Google Patents
Preparation method and application of imidazole-containing fused heterocyclic polymer and polyelectrolyte Download PDFInfo
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Abstract
The invention discloses a preparation method and application of imidazole-containing fused heterocyclic polymer and polyelectrolyte, wherein the method comprises the following steps: under the protection of inert gas, dissolving an internal alkyne monomer, a phenylimidazole monomer, a rhodium catalyst and an additive into a solvent, fully reacting, cooling, adding Sodium Diethyldithiocarbamate Trihydrate (SDT) to generate a metal complex, filtering to remove the metal complex, and adding an organic phase into a precipitator for precipitation to obtain the imidazole-containing fused heterocyclic polymer. The obtained imidazole-containing fused heterocyclic polymer can be converted into polyelectrolyte by modification. The imidazole-containing fused heterocyclic polymer has good solubility, high thermal and morphological stability, high refractive index, low dispersibility, pH response characteristics and interesting optical properties, has unique potential application value in optoelectronic materials and intracellular pH fluorescence sensors, and has potential advantages in cancer treatment.
Description
Technical Field
The invention belongs to the technical field of preparation of fused heterocyclic polymers, and particularly relates to a preparation method and application of a fused heterocyclic polymer containing imidazole and polyelectrolyte.
Background
In the past few decades, a variety of fused heterocyclic polymers have been developed and synthesized, such as benzodipyrrole, isoquinoline, benzimidazole, and the like. Among them, polymers having a benzimidazole or imidazopyridine skeleton have been widely studied. The fused heterocyclic skeleton has amphoteric property and can be used for fluorescence sensing and biological imaging. In addition, they have a wide range of biological activities, such as anticancer, antibacterial, antitumor activity, antiviral, antifungal, antiulcer, antiinflammatory, antidiabetic, etc. The incorporation of such frameworks into polymer backbones can impart many interesting properties and applications to them. For example, the conjugated structure of these fused heterocycles imparts excellent thermal and mechanical properties, making them particularly well suited for a variety of demanding high temperature applications, such as firefighter protective clothing. The amphoteric nature of benzimidazoles in the building blocks has led to their widespread use in electrolyte systems and separators for electrochemical devices. In addition, the imidazole-containing hetero-fused heterocyclic polymers also have great potential in the aspects of cancer resistance, drug/gene delivery, metal ion detection, nano composite materials and the like.
Therefore, attracted by the above structural advantages, it is still necessary to synthesize and develop such polymers and explore their potential applications.
Disclosure of Invention
In order to further improve the defects of the existing synthetic method, the invention aims to provide a preparation method of the imidazole-containing fused heterocyclic polymer.
The invention also aims to provide a fused heterocyclic polymer containing imidazole and aza cationic polyelectrolyte prepared by the method.
It is a further object of the present invention to provide the use of the above-mentioned polymers and polyelectrolytes. The imidazole-containing fused heterocyclic polymer has potential application in optoelectronic materials and intracellular pH fluorescence sensors. The azacationic polyelectrolytes have potential applications in cancer therapy.
The purpose of the invention is realized by the following technical scheme:
a preparation method of imidazole-containing fused heterocyclic polymer comprises the following steps:
dissolving an internal alkyne monomer, a phenylimidazole monomer, a rhodium catalyst and an additive into an organic solvent, and reacting under preset conditions to obtain reaction mother liquor;
adding the reaction mother liquor into an SDT aqueous solution, and separating to obtain an organic phase;
and filtering the organic phase, and removing the metal complex in the organic phase to obtain the imidazole-containing fused heterocyclic polymer.
Optionally, the preparation method, wherein the structural general formula of the imidazole-containing fused heterocyclic polymer is shown in formula (1):
the structural general formula of the internal alkyne monomer is shown as formula (2):
the structural general formula of the phenylimidazole monomer is shown as formula (3):
in the formulas (1) to (3), x, y, z and w are integers of 1 to 200 respectively, Ar is an aryl or aryl derivative substituent, and R is an electron donating substituent or an electron withdrawing substituent.
The general formula of the reaction involved in formula (1) is shown below:
alternatively, the method of manufacturing, wherein the organic solvent is selected from one or more of toluene, 1, 2-dichloroethane, 1, 4-dioxane, o-xylene, and N, N-dimethylformamide;
the rhodium catalyst is dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, and the dosage of the rhodium catalyst is 10-40% of the molar dosage of the internal alkyne monomer;
the additive is copper (II) acetate hydrate, and the dosage of the additive is 2-8 equivalent of the dosage of the internal alkyne monomer;
the molar ratio of the phenylimidazole monomer to the internal alkyne monomer is (0.5-3) to 1;
the concentration of the internal alkyne monomer is 0.2 mol/L;
the preset conditions include: the reaction temperature is 100-120 ℃ under the inert gas atmosphere, and the reaction time is 1-24 h.
Optionally, the preparation method, wherein the step of filtering the organic phase to remove the metal complex in the organic phase to obtain the imidazole-containing fused heterocyclic polymer specifically includes:
adsorbing the organic phase in a neutral alumina column, and cleaning with petroleum ether to remove the metal complex;
after the metal complex is removed, cleaning with tetrahydrofuran to obtain a cleaning solution;
and adding the cleaning solution into a precipitator to obtain the imidazole-containing fused heterocyclic polymer.
Alternatively, the method of preparation, wherein: ar is selected from any one of the following structural formulas 1-23; r is selected from any one of the following structural formulas 24-26;
is a joint; wherein m and n are integers of 11-20, R1、R2The same or different, independently hydrogen, halogen atom, alkylamine, alkyl or alkoxy, and X is selected from oxygen, sulfur or selenium element.
An imidazole-containing fused heterocyclic polymer, wherein the imidazole-containing fused heterocyclic polymer is prepared by the preparation method.
A method for preparing polyelectrolyte, which comprises the following steps:
dissolving the imidazole-containing fused heterocyclic polymer and methyl iodide into chloroform, and reacting at room temperature to obtain a mixed solution;
and adding the mixed solution into petroleum ether for precipitation to obtain the polyelectrolyte.
Optionally, in the method for preparing polyelectrolyte, a general structural formula of the polyelectrolyte is shown as formula (4):
in the formula (4), x, y, z and w are integers of 1-200, Ar is selected from any one of the structural formulas 1-23 in claim 5; r is selected from any one of the structural formulas 24-26 as defined in claim 5; is a junction; wherein m and n are integers of 1-20, R1、R2The same or different, independently hydrogen, halogen atom, alkylamine, alkyl or alkoxy, and X is selected from oxygen, sulfur or selenium element.
The general formula of the reaction involved in formula (4) is shown below:
a polyelectrolyte, wherein the polyelectrolyte is prepared by the method.
The imidazole-containing fused heterocyclic polymer has good solubility, and can be dissolved in dichloromethane, trichloromethane, tetrahydrofuran, toluene, N, N-dimethylformamide, 1, 2-dichloroethane and the like. Meanwhile, the imidazole-containing fused heterocyclic polymer has high thermal and morphological stability, high refractive index and low dispersion, has pH response characteristics, and has unique application value in quantitative detection of intracellular pH.
The application of the imidazole-containing fused heterocyclic polymer is to serve as an optoelectronic material and an intracellular pH fluorescence sensor.
The polyelectrolyte has potential advantages in cancer treatment.
Has the advantages that: the monomers used in the polymerization method are cheap and easy to obtain, the weight-average molecular weight of the obtained polymer is as high as 30900, the yield is as high as 99.6%, and the atom economy is high. The polymerization method can efficiently obtain the imidazole-containing fused heterocyclic polymer with high molecular weight within the reaction time of not more than 2 hours.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of imidazole-containing fused heterocyclic polymer P1 in deuterated dichloromethane obtained in example 1;
FIG. 2 is a graph showing the photoluminescence of the imidazole-containing fused heterocyclic polymer P1 obtained in example 1 in tetrahydrofuran solutions with different water contents;
FIG. 3A is a graph showing the photoluminescence of the imidazole-containing fused heterocyclic polymer P2 obtained in example 2 in tetrahydrofuran solutions with different water contents; FIG. 3B is a graph showing the acid-base response spectrum of the polymer P2 in its aggregated state after the addition of a certain amount of trifluoroacetic acid or sodium hydroxide solution; FIG. 3C is a graph of the reversible cycle of acid-base response of the polymeric P2 in its aggregated state.
FIG. 4A is a spectrum diagram showing the change of the aggregation state of imidazole-containing fused heterocyclic polymer P2 according to the pH of the solution obtained in example 2; FIG. 4B is a graph of the fluorescence intensity ratio of polymer P2 at 510nm and 616nm as a function of pH; FIG. 4C is an imaging diagram of nanoparticles of Polymer P2 in 4T1 cells in different pH environments; FIG. 4D is a graph of the ratio of fluorescence intensity for the two channels of FIG. 4C versus different intracellular pH; fig. 4E is pH thermography of 4T1 cells with added polymer P2 nanoparticles.
FIG. 5 is a graph of the photoluminescence of the aza cationic polyelectrolyte P3 obtained in example 3 in dimethyl sulfoxide solutions with different water contents.
FIG. 6A is a Reactive Oxygen Species (ROS) indicator Dichlorofluorescein (DCFH) used to evaluate the ROS production efficiency of the aza cationic polyelectrolyte P3 obtained in example 3; FIG. 6B is a study of the killing effect of P3 on 3T3 and 4T1 cells by 3- (4, 5-dimethyl-2-thiazolyl) -2, 5-diphenyl-2H-bromotetrazole (MTT); FIG. 6C is a graph of the phototherapeutic effect of polyelectrolyte P3 on 4T1 cells.
Detailed Description
The present invention will be described in further detail with reference to specific examples and drawings, but the embodiments of the present invention are not limited thereto, and may be performed with reference to conventional techniques for process parameters not particularly noted.
Example 1
A preparation method of a fused heterocyclic polymer containing imidazole comprises the following steps:
(1) under the protection of inert gas, 34.8mg of 1- (4-methoxyphenyl) -1H-imidazole, 94.1mg of 4, 4' - (1, 4-hexenedioxy) bis (tolane), 50.3mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer and 320mg of copper (II) acetate hydrate are added into 2mL of dry o-xylene for dissolution, and the reaction is stirred at 110 ℃ for 2 hours;
(2) after completion of the reaction, the reaction mother liquor was diluted with 7mL of dichloromethane. 756mg of SDT were dissolved directly in 50mL of deionized water. The diluted reaction mother liquor was added to the aqueous SDT solution and stirred for 2 hours. Then removing the water phase, finally passing the remaining organic phase through a small neutral alumina column with the thickness of 8cm, after the organic phase is completely permeated into the column, firstly using petroleum ether to pass through the column, so that the ferrous metal complex in the column is firstly removed, when the color of the column is lightened or the dripped solvent is light and transparent, using THF to pass through the column, dripping into 200mL of petroleum ether for precipitation, collecting the precipitate, and drying in vacuum (the drying temperature is 55 ℃) to constant weight to obtain the imidazole-containing fused heterocyclic polymer.
The product yield of this example was 99.6%, the weight average molecular weight was 14700g/mol, and the PDI was 1.2. Of these, 1- (4-methoxyphenyl) -1H-imidazole is available as such, and 4, 4' - (1, 6-hexanedioxy) bis (tolane) is prepared according to the method disclosed in the literature (Gao, m.; Lam, j.w.y.; Liu, y.; Li, j.; Tang, b.z. polymer Chemistry 2013,4(9), 2841-2849.).
The imidazole-containing fused heterocyclic polymer obtained in this example has the structural formula shown in P1:
the reaction equation involved in this example is as follows:
the hydrogen nuclear magnetic spectrum of the imidazole-containing fused heterocyclic polymer P1 in deuterated dichloromethane in the example is shown in FIG. 1. As can be seen from fig. 1, the solvent peak and the water peak of deuterated dichloromethane are located at 5.36 and 1.46ppm, respectively. Besides, the signals of the hydrogen atoms in P1 are all the signals of the hydrogen atoms, and the signals of the hydrogen atoms with characteristics can be correspondingly assigned. Wherein, the peak at 3.65-3.77ppm is the characteristic peak of methoxy hydrogen atom on the condensed ring in P1, and the peak at 1.59ppm, 1.86ppm and 4.0ppm are the characteristic peak of dioxy hexylene hydrogen atom in P1.
The photoluminescence profile of P1 in tetrahydrofuran solutions with different water contents of this example is shown in fig. 2. As can be seen from FIG. 2, the polymer emits well in the tetrahydrofuran solution, and as the water content is increased to 30%, the emission intensity gradually increases, and further increase in the water content results in a decrease in the emission intensity.
Example 2
A preparation method of a fused heterocyclic polymer containing imidazole comprises the following steps:
(1) under the protection of inert gas, 34.8mg of 1- (4-methoxyphenyl) -1H-imidazole, 89.0mg of 4,4 '- (4, 4' -triphenylaminyl) bis (tolane), 50.3mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer and 320mg of copper (II) acetate hydrate are added into 2mL of dry o-xylene to be dissolved, and the reaction is stirred at 110 ℃ for 2 hours;
(2) after completion of the reaction, the reaction mother liquor was diluted with 7mL of dichloromethane. 756mg of SDT were dissolved directly in 50mL of deionized water. The diluted reaction mother liquor was added to the aqueous SDT solution and stirred for 2 hours. Then removing the water phase, finally passing the remaining organic phase through a small neutral alumina column with the thickness of 8cm, after the organic phase is completely permeated into the column, firstly using petroleum ether to pass through the column, so that the ferrous metal complex in the column is firstly removed, when the color of the column is lightened or the dripped solvent is light and transparent, using THF to pass through the column, dripping into 200mL of petroleum ether for precipitation, collecting the precipitate, and drying in vacuum (the drying temperature is 55 ℃) to constant weight to obtain the imidazole-containing fused heterocyclic polymer. The product yield of this example was 86.7%, the weight average molecular weight was 10300g/mol, and the PDI was 1.2.
The 1- (4-methoxyphenyl) -1H-imidazole of this example was purchased directly and 4,4 '- (4, 4' -triphenylaminyl) bis (tolane) was prepared according to the method disclosed in the literature (Gao, M.; Lam, J.W.Y.; Liu, Y.; Li, J.; Tang, B.Z.Polymer Chemistry 2013,4(9), 2841-2849.).
The imidazole-containing fused heterocyclic polymer obtained in this example has the structural formula shown in P2:
the reaction equation involved in this example is as follows:
the photoluminescence profile of the imidazole-containing fused heterocyclic polymer P2 in tetrahydrofuran solutions with different water contents in this example is shown in fig. 3A. As can be seen from FIG. 3A, the polymer fluoresces well in both solution and in the aggregate state. However, as shown in FIG. 3B, when a certain amount of trifluoroacetic acid was added to the mixed system, the fluorescence of the polymer was significantly reduced and the maximum emission wavelength was significantly red-shifted. Then, after adding sodium hydroxide solution, the fluorescence of the polymer returns to the original state. Therefore, the polymer shows obvious acid-base response characteristics. It can be seen from fig. 3C that these two states can be cycled back and forth many times in succession, showing high reversibility and repeatability.
The change of fluorescence of the imidazole-containing fused heterocyclic polymer P2 in this example with the change of solution pH is shown in FIG. 4A. FIG. 4A shows that as the pH of the solution becomes lower, the fluorescence of P2 gradually decreases and a red shift occurs. FIG. 4B shows the fluorescence intensity ratio of the polymer at 510nm and 616nm as a function of pH, with the inset being a photograph of the irradiation at 365nm excitation. The polymer has obvious response to pH and can be used for intracellular pH change.
The imaging of the nanoparticles containing imidazole fused heterocycle polymer P2 in 4T1 cells in different pH environments of this example is shown in fig. 4C. Fluorescence from the green channel in the cellular image of fig. 4C increased dramatically with decreasing pH, while fluorescence from the blue channel did not change significantly. FIG. 4D is a graph of the ratio of fluorescence intensities of the two channels of FIG. 4C as a function of different intracellular pH. From this curve, the mean pH of the organelles within the 4T1 cell can be estimated. The pH values at points 1 and 2 in FIG. 4E were calculated from the curves as 4.9. + -. 0.2 and 5.3. + -. 0.2, respectively, which is expected for acidic organelles (endosomes and lysosomes) having a pH between 4.7 and 6.3.
Example 3
The method for generating the aza cationic polyelectrolyte by simply post-modifying the imidazole-containing fused heterocyclic polymer comprises the following steps:
(1) 25mg of imidazole-containing fused heterocyclic polymer P2 and 1mL of methyl iodide were dissolved in 1mL of chloroform, and the reaction was stirred at room temperature for 12 hours.
(2) After the reaction is completed, the reaction solution is dropped into 100mL of petroleum ether for precipitation, the precipitate is collected and dried in vacuum (the drying temperature is 55 ℃) to constant weight, and the aza cationic polyelectrolyte is obtained. The product yield of this example was 99.7%.
The aza cationic polyelectrolyte obtained in this example has the structural formula shown in P3:
the reaction equation involved in this example is as follows:
the graph of the photoluminescence of the aza cationic polyelectrolyte P3 of this example in dimethyl sulfoxide solutions with different water contents is shown in fig. 5. As can be seen from fig. 5, the polymer fluoresces well red in both solution and in the aggregate state.
FIG. 6A is a graph of the ROS production efficiency of the aza cationic polyelectrolyte P3 obtained in example 3 evaluated using the ROS indicator DCFH. As can be seen from fig. 6A, only DCFH hardly emits under white light illumination. After addition of P3, the emission intensity of DCFH reached nearly 730-fold within 150s under white light illumination, indicating that P3 has extraordinary ROS-generating ability. Fig. 6B is a graph investigating the killing effect of P3 on 3T3 and 4T1 cells by the MTT method. As can be seen from fig. 6B, P3 showed weak dark cytotoxicity to normal 3T3 cells even at high concentration, while the inhibitory ability to 4T1 cells was significantly stronger, showing its extraordinary recognition ability to normal and cancer cells. And after white light irradiation, the killing capacity of the P3 to 4T1 cells is further enhanced. Fig. 6C is a graph of the phototherapy effect of P3 on 4T1 cells. As can be seen from FIG. 6C, P3 still has strong ROS-producing ability in living cells, and has strong killing effect on 4T1 cells under white light irradiation.
Claims (11)
1. A method for preparing imidazole-containing fused heterocyclic polymer is characterized by comprising the following steps:
dissolving an internal alkyne monomer, a phenylimidazole monomer, a rhodium catalyst and an additive into an organic solvent, and reacting under preset conditions to obtain reaction mother liquor;
adding the reaction mother liquor into sodium diethyldithiocarbamate trihydrate aqueous solution, and separating to obtain an organic phase;
and filtering the organic phase, and removing the metal complex in the organic phase to obtain the imidazole-containing fused heterocyclic polymer.
2. The preparation method according to claim 1, wherein the imidazole-containing fused heterocyclic polymer has a general structural formula shown in formula (1):
the structural general formula of the internal alkyne monomer is shown as formula (2):
the structural general formula of the phenylimidazole monomer is shown as formula (3):
in the formulas (1) to (3), x, y, z and w are integers of 1 to 200 respectively, Ar is an aryl or aryl derivative substituent, and R is an electron donating substituent or an electron withdrawing substituent.
3. The method according to claim 1, wherein the organic solvent is one or more selected from the group consisting of toluene, 1, 2-dichloroethane, 1, 4-dioxane, o-xylene, and N, N-dimethylformamide;
the rhodium catalyst is dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, and the dosage of the rhodium catalyst is 10-40% of the molar dosage of the internal alkyne monomer;
the additive is copper (II) acetate hydrate, and the dosage of the additive is 2-8 equivalent of the dosage of the internal alkyne monomer;
the molar ratio of the phenylimidazole monomer to the internal alkyne monomer is (0.5-3) to 1;
the concentration of the internal alkyne monomer is 0.2 mol/L;
the preset conditions include: the reaction temperature is 100-120 ℃ under the inert gas atmosphere, and the reaction time is 1-24 h.
4. The preparation method according to claim 1, wherein the step of filtering the organic phase to remove the metal complex in the organic phase to obtain the imidazole-containing fused heterocyclic polymer specifically comprises:
adsorbing the organic phase in a neutral alumina column, and cleaning with petroleum ether to remove the metal complex;
after the metal complex is removed, cleaning with tetrahydrofuran to obtain a cleaning solution;
and adding the cleaning solution into a precipitator to obtain the imidazole-containing fused heterocyclic polymer.
5. The method of claim 2, wherein: ar is selected from any one of the following structural formulas 1-23; r is selected from any one of the following structural formulas 24-26;
is a junction; wherein m and n are integers of 1-20, R1、R2The same or different, independently hydrogen, halogen atom, alkylamine, alkyl or alkoxy, and X is selected from oxygen, sulfur or selenium element.
6. An imidazole-containing fused heterocyclic polymer characterized by being produced by the production method according to any one of claims 1 to 5.
7. A method for preparing polyelectrolyte, which is characterized by comprising the following steps:
dissolving the imidazole-containing fused heterocyclic polymer of claim 6 and methyl iodide in chloroform, and reacting at room temperature to obtain a mixed solution;
and adding the mixed solution into petroleum ether for precipitation to obtain the polyelectrolyte.
8. The method of claim 7, wherein the general structural formula of the polyelectrolyte is represented by formula (4):
in the formula (4), x, y, z and w are integers of 1-200, Ar is selected from any one of the structural formulas 1-23 in claim 5; r is selected from any one of the structural formulas 24-26 as defined in claim 5; is a junction; wherein m and n are integers of 1-20, R1、R2The same or different, independently hydrogen, halogen atom, alkylamine, alkyl or alkoxy, and X is selected from oxygen, sulfur or selenium element.
9. A polyelectrolyte obtained by the method of any one of claims 7 and 8.
10. The use of the imidazole-containing fused heterocyclic polymer according to claim 6 as an optoelectronic material and an intracellular pH fluorescence sensor.
11. Use of a polyelectrolyte according to claim 9, characterized in that the polyelectrolyte is used as a medicament for the treatment of cancer.
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Citations (3)
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|---|---|---|---|---|
| CN102282150A (en) * | 2009-02-02 | 2011-12-14 | 默克专利有限公司 | Metal complexes |
| CN106967217A (en) * | 2016-01-14 | 2017-07-21 | 华南理工大学 | Polyimidazole class compound and its in-situ preparation method and application |
| CN111961201A (en) * | 2019-05-03 | 2020-11-20 | 香港科技大学 | Polyelectrolyte capable of generating nitrogen-containing cations in situ by one-pot method and application thereof |
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Patent Citations (3)
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| CN102282150A (en) * | 2009-02-02 | 2011-12-14 | 默克专利有限公司 | Metal complexes |
| CN106967217A (en) * | 2016-01-14 | 2017-07-21 | 华南理工大学 | Polyimidazole class compound and its in-situ preparation method and application |
| CN111961201A (en) * | 2019-05-03 | 2020-11-20 | 香港科技大学 | Polyelectrolyte capable of generating nitrogen-containing cations in situ by one-pot method and application thereof |
Non-Patent Citations (3)
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| ALEXANDER RISS ET AL.,: "Rhodium(III)-catalyzed cascade oxidative annulation reactions of aryl imidazolium salts with alkynes involving multiple C–H bond activation" * |
| DEBASISH GHORAI ET AL.,: "Rhodium(III)−N-Heterocyclic Carbene-Driven Cascade C−H Activation Catalysis" * |
| QINGMEI GE ET AL.,: "Synthesis of substituted benzo[ij]imidazo[2,1,5-de]- quinolizine by rhodium(III)-catalyzed multiple C–H activation and annulations" * |
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