CN110003488A - A kind of amphiphilic aggregation-induced emission hyperbranched poly phosphamide and synthetic method - Google Patents
A kind of amphiphilic aggregation-induced emission hyperbranched poly phosphamide and synthetic method Download PDFInfo
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- CN110003488A CN110003488A CN201910301881.3A CN201910301881A CN110003488A CN 110003488 A CN110003488 A CN 110003488A CN 201910301881 A CN201910301881 A CN 201910301881A CN 110003488 A CN110003488 A CN 110003488A
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Abstract
The present invention relates to a kind of amphiphilic aggregation-induced emission hyperbranched poly phosphamide and synthetic methods, pass through the poly- phosphamide of amine-decomposing method synthesis of super branched of simple controllable ester using triethyl phosphate and diamine as raw material.In synthesized hyperbranched poly phosphamide be free of phenyl ring, contain only amido and P=O key, have good biocompatibility and biological degradability, and this kind of hyperbranched poly phosphamide can emitting bright blue-fluorescence, and have aggregation-induced emission characteristic.The hyperbranched poly phosphamide of this patent report has synthesis and purifying technique simplicity, process control, three-waste pollution few, and the stability of product is good, toxicity is low, biological degradability is good, environment friendly and fluorescence intensity are high.It is easy to carry out modification and realizes the features such as functionalization, fluorescence intensity are high, have a wide range of application.
Description
Technical field
The invention belongs to high-molecular luminous material field, it is related to a kind of amphiphilic aggregation-induced emission hyperbranched poly phosphinylidyne
Amine and synthetic method.
Background technique
In recent years, as people's awareness of environmental protection continues to increase, and the non-traditional fluorescence without the big pi-conjugated structure such as phenyl ring is poly-
Object is closed, due to being free of the structures such as phenyl ring, with good biocompatibility, biological degradability and environment friendly, and by
The extensive concern of academia and industry.These polymer can issue fluorescence under certain conditions, cell fluorescence be imaged,
The fields such as genophore and medicine controlled releasing have a wide range of applications.Poly- phosphamide is as a kind of new polymers, because having
Good biocompatibility, biological degradability, modifiability and thermal stability, in DNA/RNA delivery and fire proofing etc.
Field is widely used.Hyperbranched poly phosphamide has the modifiable work of specific three-dimensional structure and a large amount of end
Property group, be a kind of very good gene delivery tool.
Xu etc. [Royal Society of Chemistry, 2015,5:50425] is with dichloro etherophosphoric acid and N- (2- ammonia
Ethyl)-N- (1- methyl) -1,2- ethylenediamine is raw material, a kind of poly- phosphamide of dendroid has been synthesized simultaneously by click chemistry reaction
It is used for gene and the transhipment of siRNA.Ye etc. [Polymer Degradation and Stability, 2017,142:29]
Using dichloro-phenyl phosphate and melamine as raw material, a kind of hyperbranched poly phosphamide has been synthesized.In the synthesis of current poly- phosphamide
In method, being mostly used phosphoryl chloride phosphorus oxychloride or more chlorine phosphate esters is raw material, react being prepared with polyamine.It is generated in synthesis process
HCl reacted with triethylamine generate salt again through filter remove.Acetonitrile equal solvent can be added during the reaction is able to reaction
It goes on smoothly.The shortcomings that this kind of synthesis mode, is after reacting that purification of products is complicated, and phosphoryl chloride phosphorus oxychloride or more chlorine phosphate esters are toxic
Or be corrosive, so that the industrialized production of poly- phosphamide is restricted.Therefore simple environmental-friendly poly- phosphamide synthesizes work
Skill has great application prospect.In addition, there has been no the reports in terms of poly- phosphamide fluorescence property at present, so that poly- phosphinylidyne
Characterization method after amine loaded gene is complicated.As can a kind of poly- phosphamide carrier with aggregation-induced emission performance is developed,
The Simple visual of characterization can be realized, so that the technological means for making poly- phosphamide carry out gene therapy as carrier obtains pole
Big progress.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of amphiphilic aggregation-induced emission hyperbranched poly phosphorus
Amide and synthetic method, develop a variety of Ambident hyperbranched poly- phosphamides with aggregation-induced emission characteristic, and synthesis surpasses
The poly- phosphamide of branching can issue bright blue-fluorescence.
Technical solution
A kind of amphiphilic aggregation-induced emission hyperbranched poly phosphamide, it is characterised in that: with triethyl phosphate and diamine
For raw material, molar ratio is 2:1~4, is obtained by the aminolysis reaction of ester, the amphiphilic aggregation-induced emission hyperbranched poly phosphorus of gained
The structural formula of amide are as follows:
The diamine includes but is not limited to ethylenediamine, 1,6- hexamethylene diamine, propane diamine, urea, 1,5- 1,5-DAP, and 1,
7- diaminoheptane.
A kind of synthetic method of the amphiphilic aggregation-induced emission hyperbranched poly phosphamide, it is characterised in that step is such as
Under:
Step 1: being mixed triethyl phosphate with diamine for 2:1~4 with molar ratio；
Step 2: under nitrogen protection, being warming up to 70 DEG C~180 DEG C, be stirred to react 9~18h；
Step 3: product being dissolved in ethyl alcohol, is dialysed, is rotated, vacuum drying has obtained amphiphilic aggregation-induced emission
Hyperbranched poly phosphamide.
A kind of application method of the amphiphilic aggregation-induced emission hyperbranched poly phosphamide, it is characterised in that: by parents
Property aggregation-induced emission hyperbranched poly phosphamide is dissolved in water, and bright blue-fluorescence is issued under ultraviolet light；Increase ultraviolet
Red Shift Phenomena occurs for the wavelength of light.
A kind of application method of the amphiphilic aggregation-induced emission hyperbranched poly phosphamide, it is characterised in that: by parents
Property aggregation-induced emission hyperbranched poly phosphamide is dissolved in organic solvent, and bright blue-fluorescence is issued under ultraviolet light；Increase
Add the wavelength of ultraviolet light, Red Shift Phenomena occurs.
Beneficial effect
A kind of amphiphilic aggregation-induced emission hyperbranched poly phosphamide proposed by the present invention and synthetic method, with tricresyl phosphate second
Ester and diamine are amine-decomposing method synthesis of super branched poly- phosphamide of the raw material by simple controllable ester.Synthesized hyperbranched poly phosphorus
Phenyl ring is free of in amide, contains only amido and P=O key, and there is good biocompatibility and biological degradability, and this kind of over-expense
Change poly- phosphamide can emitting bright blue-fluorescence, and have aggregation-induced emission characteristic.The hyperbranched poly phosphorus of this patent report
Amide has synthesis and purifying technique simplicity, process control, three-waste pollution few, and the stability of product is good, toxicity is low, biological drop
The good, environment friendly of solution property and fluorescence intensity are high.It is easy to carry out modification to realize that functionalization, fluorescence intensity are high, have a wide range of application
Etc. features.
Hyperbranched poly phosphamide synthesized by the present invention was both water-soluble, can also be dissolved in organic reagent, and ultraviolet
Light irradiation is lower can to issue bright blue-fluorescence.This synthetic method, have simple process, structure-controllable, without catalyst it is molten
Agent and it is environmental-friendly the features such as.The hyperbranched poly phosphamide of synthesis has good biocompatibility, biological degradability, Yi Xiu
Decorations property and the aggregation-induced emission characteristic itself having make it in the side such as DNA/RNA transhipment, cell imaging, drug delivery
Mask has wide practical use.
Detailed description of the invention
Fig. 1 is the excitation spectrum and emission spectra of pure amino-terminated hyperbranched poly phosphamide.As it can be seen that its maximum excitation wavelength
For 397nm, at this point, fluorescence intensity is most strong, corresponding launch wavelength is 442nm.
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
Example 1
The preparation method of the poly- phosphamide of amine-terminated hyperbrancedization: under nitrogen protection, triethyl phosphate (27.32g) and second two
Amine (14.42g) is 1:1.6 reaction with molar ratio, after mixing, is to slowly warm up to 80 DEG C, and be stirred at this temperature, is reacted
Product is dissolved in ethyl alcohol, dialysed by 10h, is rotated, and vacuum drying has obtained amino-terminated hyperbranched poly phosphamide.
Example 2
The preparation method of the poly- phosphamide of amine-terminated hyperbrancedization: under nitrogen protection, triethyl phosphate (27.32g) and second two
Amine (16.23g) is 1:1.8 reaction with molar ratio, after mixing, is to slowly warm up to 80 DEG C, and be stirred at this temperature, is reacted
Product is dissolved in ethyl alcohol, dialysed by 10h, is rotated, and vacuum drying has obtained amino-terminated hyperbranched poly phosphamide.
Example 3
The preparation method of the poly- phosphamide of amine-terminated hyperbrancedization: under nitrogen protection, triethyl phosphate (27.32g) and second two
Amine (18.03g) is 1:2 reaction with molar ratio, after mixing, is to slowly warm up to 80 DEG C, and be stirred at this temperature, is reacted
Product is dissolved in ethyl alcohol, dialysed by 10h, is rotated, and vacuum drying has obtained amino-terminated hyperbranched poly phosphamide.
Example 4
Hold the preparation method of ethyoxyl hyperbranched poly amino ester: under nitrogen protection, triethyl phosphate (27.32g) and second
Diamines (12.62g) is 1:1.4 reaction with molar ratio, after mixing, is to slowly warm up to 80 DEG C, and be stirred at this temperature, instead
10h is answered, product is dissolved in ethyl alcohol, is dialysed, is rotated, vacuum drying has obtained amino-terminated hyperbranched poly phosphamide.
Example 5
The preparation method of the poly- phosphamide of amine-terminated hyperbrancedization: under nitrogen protection, triethyl phosphate (27.32g) and 1,6-
Hexamethylene diamine (27.89g) is 1:1.6 reaction with molar ratio, after mixing, is to slowly warm up to 120 DEG C, and stirred at this temperature
It mixes, reacts 12h, product is dissolved in ethyl alcohol, is dialysed, rotate, vacuum drying has obtained amino-terminated hyperbranched poly phosphinylidyne
Amine.
Example 6
The preparation method of the poly- phosphamide of amine-terminated hyperbrancedization: under nitrogen protection, triethyl phosphate (27.32g) and 1,3-
Propane diamine (17.31g) is 1:1.6 reaction with molar ratio, after mixing, is to slowly warm up to 110 DEG C, and stirred at this temperature
It mixes, reacts 11h, product is dissolved in ethyl alcohol, is dialysed, rotate, vacuum drying has obtained amino-terminated hyperbranched poly phosphinylidyne
Amine.
Example 7
The preparation method of the poly- phosphamide of amine-terminated hyperbrancedization: under nitrogen protection, triethyl phosphate (27.32g) and urea
(14.41g) is 1:1.6 reaction with molar ratio, after mixing, is to slowly warm up to 110 DEG C, and be stirred at this temperature, is reacted
Product is dissolved in ethyl alcohol, dialysed by 11h, is rotated, and vacuum drying has obtained amino-terminated hyperbranched poly phosphamide.
Example 8
The preparation method of the poly- phosphamide of amine-terminated hyperbrancedization: under nitrogen protection, triethyl phosphate (27.32g) and 1,5-
1,5-DAP (24.52g) is 1:1.6 reaction with molar ratio, after mixing, is to slowly warm up to 130 DEG C, and carry out at this temperature
Stirring reacts 14h, product is dissolved in ethyl alcohol, is dialysed, and rotates, and vacuum drying has obtained amino-terminated hyperbranched poly phosphorus
Amide.
Example 9
The preparation method of the poly- phosphamide of amine-terminated hyperbrancedization: under nitrogen protection, triethyl phosphate (27.32g) and 1,7-
Diaminoheptane (31.26g) is 1:1.6 reaction with molar ratio, after mixing, is to slowly warm up to 150 DEG C, and carry out at this temperature
Stirring reacts 16h, product is dissolved in ethyl alcohol, is dialysed, and rotates, and vacuum drying has obtained amino-terminated hyperbranched poly phosphorus
Amide.
Claims (5)
1. a kind of amphiphilic aggregation-induced emission hyperbranched poly phosphamide, it is characterised in that: be with triethyl phosphate and diamine
Raw material, molar ratio are 2:1~4, are obtained by the aminolysis reaction of ester, the amphiphilic aggregation-induced emission hyperbranched poly phosphinylidyne of gained
The structural formula of amine are as follows:
2. amphiphilic aggregation-induced emission hyperbranched poly phosphamide according to claim 1, it is characterised in that: the diamine
Including but not limited to ethylenediamine, 1,6- hexamethylene diamine, propane diamine, urea, 1,5- 1,5-DAP, 1,7- diaminoheptane.
3. a kind of synthetic method of amphiphilic aggregation-induced emission hyperbranched poly phosphamide as claimed in claim 1 or 2, feature exist
In steps are as follows:
Step 1: being mixed triethyl phosphate with diamine for 2:1~4 with molar ratio；
Step 2: under nitrogen protection, being warming up to 70 DEG C~180 DEG C, be stirred to react 9~18h；
Step 3: product being dissolved in ethyl alcohol, is dialysed, is rotated, vacuum drying has obtained amphiphilic aggregation-induced emission over-expense
Change poly- phosphamide.
4. a kind of application method of amphiphilic aggregation-induced emission hyperbranched poly phosphamide as claimed in claim 1 or 2, feature exist
In: amphiphilic aggregation-induced emission hyperbranched poly phosphamide is dissolved in water, bright blue-fluorescence is issued under ultraviolet light；
Increase the wavelength of ultraviolet light, Red Shift Phenomena occurs.
5. a kind of application method of amphiphilic aggregation-induced emission hyperbranched poly phosphamide as claimed in claim 1 or 2, feature exist
In: amphiphilic aggregation-induced emission hyperbranched poly phosphamide is dissolved in organic solvent, bright indigo plant is issued under ultraviolet light
Color fluorescence；Increase the wavelength of ultraviolet light, Red Shift Phenomena occurs.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009077796A2 (en) * | 2007-12-07 | 2009-06-25 | Anna Peter | Process for the preparation of amine functional phosphoric amides |
| CN102295778A (en) * | 2011-06-30 | 2011-12-28 | 西安交通大学 | Hyperbranched polyphosphoramidate and preparation method thereof |
| US20140046083A1 (en) * | 2011-02-17 | 2014-02-13 | Vanderbilt University | Enhancement of Light Emission Quantum Yield in Treated Broad Spectrum Nanocrystals |
| 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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2019
- 2019-04-16 CN CN201910301881.3A patent/CN110003488B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009077796A2 (en) * | 2007-12-07 | 2009-06-25 | Anna Peter | Process for the preparation of amine functional phosphoric amides |
| US20140046083A1 (en) * | 2011-02-17 | 2014-02-13 | Vanderbilt University | Enhancement of Light Emission Quantum Yield in Treated Broad Spectrum Nanocrystals |
| 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 (3)
| Title |
|---|
| FAN-XIN ZENG, ET AL: "Design, Preparation, and Characterization of a Novel Hyper-Cross-Linked Polyphosphamide Polymer and Its Adsorption for Phenol", 《IND. ENG. CHEM. RES.》 * |
| YUHONG LIU, ET AL: "Synthesis and properties of a novel hyperbranched polyphosphoramidate using an A2+CB2 approach", 《POLYMER INTERNATIONAL》 * |
| YUQUN DU, ET AL: "Fluorescence emission from hyperbranched polycarbonate without conventional chromohpores", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY》 * |
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