CN110003488B - Amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide and synthesis method thereof - Google Patents
Amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide and synthesis method thereof Download PDFInfo
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- CN110003488B CN110003488B CN201910301881.3A CN201910301881A CN110003488B CN 110003488 B CN110003488 B CN 110003488B CN 201910301881 A CN201910301881 A CN 201910301881A CN 110003488 B CN110003488 B CN 110003488B
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Abstract
The invention relates to amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide and a synthesis method thereof. The synthesized hyperbranched polyphosphoric acid amide does not contain benzene rings, only contains amino and P ═ O bonds, has good biocompatibility and biodegradability, and can emit bright blue fluorescence and has aggregation-induced luminescence characteristics. The hyperbranched polyphosphoric acid amide reported in the patent has the advantages of simple and convenient synthesis and purification process, controllable process, less three-waste pollution, good stability of the product, low toxicity, good biodegradability, environmental friendliness and high fluorescence intensity. Easy modification and realization of functionalization, high fluorescence intensity, wide application range and the like.
Description
Technical Field
The invention belongs to the field of high-molecular luminescent materials, and relates to amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide and a synthesis method thereof.
Background
In recent years, with the increasing awareness of environmental protection, the non-traditional fluorescent polymers without benzene ring and other large-pi conjugated structures have received much attention from academia and industry because they have good biocompatibility, biodegradability and environmental friendliness. The polymers can emit fluorescence under certain conditions, and have wide application prospects in the fields of cell fluorescence imaging, gene vectors, drug controlled release and the like. The polyphosphazene amide as a novel polymer has good biocompatibility, biodegradability, modifiability and thermal stability, and is widely applied to the fields of DNA/RNA delivery, flame-retardant materials and the like. The hyperbranched polyphosphazene amide has a definite three-dimensional structure and a large number of active groups with modifiable tail ends, and is a very good gene delivery tool.
Xu et al [ Royal Society of Chemistry,2015,5:50425] A dendritic polyphosphamide was synthesized by click Chemistry using ethyl dichlorophosphate and N- (2-aminoethyl) -N- (1-methyl) -1, 2-ethylenediamine as starting materials and used for gene and siRNA delivery. Ye et al (Polymer Degradation and Stability,2017,142: 29) use phenyl dichlorophosphate and melamine as raw materials to synthesize a hyperbranched polyphosphoric acid amide. In the existing synthesis method of the polyphosphoric acid amide, phosphorus oxychloride or polychlorinated phosphate ester is used as a raw material and reacts with polyamine to prepare the polyphosphoric acid amide. HCl generated in the synthesis process reacts with triethylamine to generate salt, and the salt is removed through suction filtration. In the reaction process, acetonitrile and other solvents are added to ensure that the reaction is smoothly carried out. The synthetic method has the disadvantages that the purification of the product is complicated after the reaction, and the phosphorus oxychloride or the polychlorinated phosphate is toxic or corrosive, so that the industrial production of the polyphosphoric acid amide is limited. Therefore, the simple and environment-friendly synthesis process of the polyphosphoric acid amide has great application prospect. In addition, no report on the fluorescence property of the polyphosphazene amide exists at present, so that the characterization means after the gene loading of the polyphosphazene amide is complicated. If a polyphosphoric amide carrier with aggregation-induced emission performance can be developed, simple visualization of characterization can be realized, so that the technical means of gene therapy by using polyphosphoric amide as a carrier is greatly improved.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides an amphiphilic aggregation-induced emission hyperbranched polyphosphazene and a synthesis method thereof, and develops a plurality of amphiphilic hyperbranched polyphosphazenes with aggregation-induced emission characteristics, and the synthesized hyperbranched polyphosphazene can emit bright blue fluorescence.
Technical scheme
An amphiphilic aggregation-induced emission hyperbranched polyphosphazene amide is characterized in that: triethyl phosphate and diamine are used as raw materials, the molar ratio is 2: 1-4, the triethyl phosphate and the diamine are obtained through an ester aminolysis reaction, and the structural formula of the obtained amphiphilic aggregation-induced luminescence hyperbranched polyphosphoric acid amide is as follows:
the diamines include, but are not limited to, ethylenediamine, 1, 6-hexanediamine, propylenediamine, urea, 1, 5-diaminopentane, 1, 7-diaminoheptane.
A synthetic method of the amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide is characterized by comprising the following steps:
step 1: mixing triethyl phosphate and diamine in a molar ratio of 2: 1-4;
step 2: under the protection of nitrogen, heating to 70-180 ℃, and stirring for reaction for 9-18 h;
and step 3: dissolving the product in ethanol, dialyzing, rotary evaporating and vacuum drying to obtain the amphiphilic aggregation-induced luminescent hyperbranched polyphosphoric acid amide.
A use method of the amphiphilic aggregation-induced emission hyperbranched polyphosphazene is characterized by comprising the following steps: dissolving amphiphilic aggregation-induced emission hyperbranched polyphosphazene in water, and emitting bright blue fluorescence under the irradiation of ultraviolet light; increasing the wavelength of the ultraviolet light causes a red shift.
A use method of the amphiphilic aggregation-induced emission hyperbranched polyphosphazene is characterized by comprising the following steps: dissolving amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide in an organic solvent, and emitting bright blue fluorescence under ultraviolet irradiation; increasing the wavelength of the ultraviolet light causes a red shift.
Advantageous effects
The invention provides amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide and a synthesis method thereof. The synthesized hyperbranched polyphosphoric acid amide does not contain benzene rings, only contains amino and P ═ O bonds, has good biocompatibility and biodegradability, and can emit bright blue fluorescence and has aggregation-induced luminescence characteristics. The hyperbranched polyphosphoric acid amide reported in the patent has the advantages of simple and convenient synthesis and purification process, controllable process, less three-waste pollution, good stability of the product, low toxicity, good biodegradability, environmental friendliness and high fluorescence intensity. Easy modification and realization of functionalization, high fluorescence intensity, wide application range and the like.
The hyperbranched polyphosphoric acid amide synthesized by the invention can be dissolved in water or an organic reagent, and can emit bright blue fluorescence under the irradiation of ultraviolet light. The synthesis method has the characteristics of simple process, controllable structure, no need of catalyst solvent, environmental friendliness and the like. The synthesized hyperbranched polyphosphoric acid amide has good biocompatibility, biodegradability and easy modification, and has aggregation-induced emission characteristics, so that the hyperbranched polyphosphoric acid amide has wide application prospects in the aspects of DNA/RNA (deoxyribonucleic acid/ribonucleic acid) transportation, cell imaging, drug delivery and the like.
Drawings
FIG. 1 shows the excitation spectrum and the emission spectrum of a pure amino-terminated hyperbranched polyphosphazene. As can be seen, the maximum excitation wavelength is 397nm, at which the fluorescence intensity is strongest, and the corresponding emission wavelength is 442 nm.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1
The preparation method of the amino-terminated hyperbranched polyphosphoric acid amide comprises the following steps: reacting triethyl phosphate (27.32g) and ethylenediamine (14.42g) in a molar ratio of 1:1.6 under the protection of nitrogen, mixing, slowly heating to 80 ℃, stirring at the temperature, reacting for 10 hours, dissolving the product in ethanol, dialyzing, rotary evaporating, and vacuum drying to obtain the amino-terminated hyperbranched polyphosphoric acid amide.
Example 2
The preparation method of the amino-terminated hyperbranched polyphosphoric acid amide comprises the following steps: reacting triethyl phosphate (27.32g) and ethylenediamine (16.23g) in a molar ratio of 1:1.8 under the protection of nitrogen, mixing, slowly heating to 80 ℃, stirring at the temperature, reacting for 10 hours, dissolving the product in ethanol, dialyzing, rotary evaporating, and vacuum drying to obtain the amino-terminated hyperbranched polyphosphoric acid amide.
Example 3
The preparation method of the amino-terminated hyperbranched polyphosphoric acid amide comprises the following steps: reacting triethyl phosphate (27.32g) and ethylenediamine (18.03g) in a molar ratio of 1:2 under the protection of nitrogen, mixing, slowly heating to 80 ℃, stirring at the temperature, reacting for 10 hours, dissolving the product in ethanol, dialyzing, performing rotary evaporation, and performing vacuum drying to obtain the amino-terminated hyperbranched polyphosphoric acid amide.
Example 4
The preparation method of the terminal ethoxy hyperbranched polyamino ester comprises the following steps: reacting triethyl phosphate (27.32g) and ethylenediamine (12.62g) in a molar ratio of 1:1.4 under the protection of nitrogen, mixing, slowly heating to 80 ℃, stirring at the temperature, reacting for 10 hours, dissolving the product in ethanol, dialyzing, rotary evaporating, and vacuum drying to obtain the amino-terminated hyperbranched polyphosphoric acid amide.
Example 5
The preparation method of the amino-terminated hyperbranched polyphosphoric acid amide comprises the following steps: reacting triethyl phosphate (27.32g) and 1, 6-hexamethylene diamine (27.89g) in a molar ratio of 1:1.6 under the protection of nitrogen, mixing, slowly heating to 120 ℃, stirring at the temperature, reacting for 12 hours, dissolving the product in ethanol, dialyzing, rotary evaporating, and vacuum drying to obtain the amino-terminated hyperbranched polyphosphoric acid amide.
Example 6
The preparation method of the amino-terminated hyperbranched polyphosphoric acid amide comprises the following steps: reacting triethyl phosphate (27.32g) and 1, 3-propane diamine (17.31g) in a molar ratio of 1:1.6 under the protection of nitrogen, mixing, slowly heating to 110 ℃, stirring at the temperature, reacting for 11 hours, dissolving the product in ethanol, dialyzing, rotary evaporating, and vacuum drying to obtain the amino-terminated hyperbranched polyphosphoric acid amide.
Example 7
The preparation method of the amino-terminated hyperbranched polyphosphoric acid amide comprises the following steps: reacting triethyl phosphate (27.32g) and urea (14.41g) in a molar ratio of 1:1.6 under the protection of nitrogen, mixing, slowly heating to 110 ℃, stirring at the temperature, reacting for 11h, dissolving the product in ethanol, dialyzing, rotary evaporating, and vacuum drying to obtain the amino-terminated hyperbranched polyphosphoric acid amide.
Example 8
The preparation method of the amino-terminated hyperbranched polyphosphoric acid amide comprises the following steps: reacting triethyl phosphate (27.32g) and 1, 5-diaminopentane (24.52g) in a molar ratio of 1:1.6 under the protection of nitrogen, mixing, slowly heating to 130 ℃, stirring at the temperature, reacting for 14h, dissolving the product in ethanol, dialyzing, rotary evaporating, and vacuum drying to obtain the amino-terminated hyperbranched polyphosphoric acid amide.
Example 9
The preparation method of the amino-terminated hyperbranched polyphosphoric acid amide comprises the following steps: reacting triethyl phosphate (27.32g) and 1, 7-diaminoheptane (31.26g) in a molar ratio of 1:1.6 under the protection of nitrogen, mixing, slowly heating to 150 ℃, stirring at the temperature, reacting for 16h, dissolving the product in ethanol, dialyzing, rotary evaporating, and vacuum drying to obtain the amino-terminated hyperbranched polyphosphoric acid amide.
Claims (2)
1. A synthetic method of amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide is characterized by comprising the following steps: the amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide is prepared from triethyl phosphate and diamine serving as raw materials in a molar ratio of 2: 1-4 through an ester aminolysis reaction, and the structural formula of the amphiphilic aggregation-induced emission hyperbranched polyphosphoric acid amide is as follows:
the synthesis method comprises the following steps:
step 1: mixing triethyl phosphate and diamine in a molar ratio of 2: 1-4;
step 2: under the protection of nitrogen, heating to 70-180 ℃, and stirring for reaction for 9-18 h;
and step 3: and (3) dissolving the product obtained by the reaction in the step (2) in ethanol, dialyzing, performing rotary evaporation, and performing vacuum drying to obtain the amphiphilic aggregation-induced luminescent hyperbranched polyphosphazene.
2. The method for synthesizing amphiphilic aggregation-induced emission hyperbranched polyphosphazene according to claim 1, wherein the amphiphilic aggregation-induced emission hyperbranched polyphosphazene comprises the following steps: the diamine comprises ethylenediamine, 1, 6-hexamethylenediamine, propylenediamine, urea, 1, 5-diaminopentane and 1, 7-diaminoheptane.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102295778A (en) * | 2011-06-30 | 2011-12-28 | 西安交通大学 | Hyperbranched polyphosphoramidate and preparation method thereof |
| CN107151316A (en) * | 2017-06-20 | 2017-09-12 | 西北工业大学 | The hyperbranched polycarbonates and preparation method of the carbonyl end-blocking of energy emitting bright fluorescence |
| CN108727576A (en) * | 2018-05-29 | 2018-11-02 | 西北工业大学 | A kind of hyperbranched poly amino ester and preparation method that can emit multicolor fluorescence |
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| HUP0700792A2 (en) * | 2007-12-07 | 2010-04-28 | Peter Dr Anna | Process for the preparation of amine functional phosphoric amides and their use as flame retardant and curing agent for epoxy resing |
| EP2675618B1 (en) * | 2011-02-17 | 2018-07-04 | Vanderbilt University | Enhancement of light emission quantum yield in treated broad spectrum nanocrystals |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295778A (en) * | 2011-06-30 | 2011-12-28 | 西安交通大学 | Hyperbranched polyphosphoramidate and preparation method thereof |
| CN107151316A (en) * | 2017-06-20 | 2017-09-12 | 西北工业大学 | The hyperbranched polycarbonates and preparation method of the carbonyl end-blocking of energy emitting bright fluorescence |
| CN108727576A (en) * | 2018-05-29 | 2018-11-02 | 西北工业大学 | A kind of hyperbranched poly amino ester and preparation method that can emit multicolor fluorescence |
Non-Patent Citations (2)
| Title |
|---|
| Fluorescence emission from hyperbranched polycarbonate without conventional chromohpores;Yuqun Du, et al;《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY》;20180618;第364卷;第415-423页 * |
| Synthesis and properties of a novel hyperbranched polyphosphoramidate using an A2+CB2 approach;Yuhong Liu, et al;《POLYMER INTERNATIONAL》;20120803;第62卷(第3期);第390-396页 * |
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