CN103626804B - Polyphosphazene microspheres containing trans-resveratrol unit and preparation method thereof - Google Patents
Polyphosphazene microspheres containing trans-resveratrol unit and preparation method thereof Download PDFInfo
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- CN103626804B CN103626804B CN201310606089.1A CN201310606089A CN103626804B CN 103626804 B CN103626804 B CN 103626804B CN 201310606089 A CN201310606089 A CN 201310606089A CN 103626804 B CN103626804 B CN 103626804B
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Abstract
Poly (organophosphazenes) microsphere containing trans-resveratrol unit of a kind of organic field of micro-nano material technology and preparation method thereof, the microsphere diameter prepared is 600-1000nm, and microsphere surface is smooth is solid construction.The present invention adopts the crosslinking condensation reaction under the effect of acid binding agent of hexachlorocyclotriphosphazene and trans-resveratrol to form, and preparation method is simple, can prepare in a large number in the industry.Its two kinds of monomers all human body are friendly, can be applicable to load and the controlled release of medicine; Surface poly-hydroxy and double bond functional group, be easy to modification and modification, can be applicable to the fields such as support of the catalyst.
Description
Technical field
What the present invention relates to is a kind of method of organic field of micro-nano material technology, specifically a kind of polyphosphazene microspheres containing trans-resveratrol unit and preparation method thereof.
Background technology
Polyphosphonitrile micro Nano material based on ring cross-linking type structure is the micro Nano material of the organic inorganic hybridization of a class novelty.Polyphosphonitrile micro Nano material has different patterns, and its component units is mainly organic composition, has good consistency and avidity with various macromolecular material, has a lot of superiority relative to inorganic nano material.And polyphosphonitrile micro Nano material also possesses the advantage of the easy chemical modification of polyphosphonitrile material, micro-nanometer structural material (the document 1.T.Zhangetal. with different chemical character surface can be obtained by simple nucleophilic substitution reaction, J.Appl.Polym.Sci.95,880, (2005)).
Polymer microballoon is strong because of the designability of its structure composition, the controllability of particle diameter and form, and specific surface area is large, the advantages such as surface adsorption is strong, at sorbent material, support of the catalyst, microreactor, Dou You important place, the field such as drug carrier and controlled release position (document 1.J.Mater.Chem.A, 2013,1,112-116,2.J.Mater.Chem.A, 2013,1,930-937,3.NanoLett.2013,13,207-212).A large amount of inorganic materials is as carbon ball, and silica spheres, metal or metal oxide, the microballoon of macromolecular material etc. is synthesized (small2010,6, No.22,2546 – 2552, Angew.Chem.Int.Ed.2011,50,6799 – 6802).And along with nanotechnology research deepen continuously and to the continuous expansion of every field, and the excellent properties of polyphosphonitrile material, the polyphosphazene microspheres material with micro nano structure obtains the concern of scientific research personnel day by day.The high-ratio surface sum that polyphosphonitrile micro Nano material integrates micro Nano material is easy to the character of chemically modified, is a kind of micro Nano material of excellent performance.Wherein, because polyphosphonitrile material has excellent biocompatibility and biodegradability, therefore, bio-medical material based on polyphosphonitrile receives much concern always and achieves greater advance (document 4.Adv.Funct.Mater.2011,21,2641 – 2651,5.Adv.Funct.Mater.2010,20,2794 – 2806,6.T.Kimetal., Langmuir2013,29,9156-9163).
Polymer materials one of most distinct issues in biological medicine application are that general polymerization thing material discharges small molecules polymerization single polymerization monomer gradually in degradation process, wherein most harmful.Trans-resveratrol is the natural chemical substance extracted from plant, is the degeneration-resistant material phytoalexin of one as vitis spp at first and is found.(BaurJAetal.，NatureReviewDrugDiscovery.2006；5；493-506)。Now confirm that trans-resveratrol has anti-inflammatory, anti-oxidant, the vital role such as anticancer.Shortcomings such as but trans-resveratrol is because of its poorly water-soluble, and bioavailability is low and apply limited.
In sum, at present existing a large amount of linear, grafting and crosslinked polyphosphonitrile material are synthesized, and crosslinked polyphosphazene microspheres is in progress slower in medicinal application, the defect that prior art is larger has: one, and the synthesis of target product is complicated, and operation is loaded down with trivial details; Two, the monomer selected in the synthesis of polyphosphazene microspheres etc. are most harmful, cause it in medicinal application, have very large defect; Three, drug loading complex steps.
Through finding the retrieval of prior art, Chinese patent literature publication number CN103113410A, publication date 2013-05-22, disclose the high temperature resistant polyphosphazene microspheres in a kind of organic micro-nano field and preparation method thereof, this technology obtains after being washed by the product be obtained by reacting under hexachlorocyclotriphosphazene, Phloroglucinol and triethylamine ultrasonic water bath environment.But the defect of the prior art compared with the present invention and deficiency are that in prior art, monomer is Phloroglucinol, its toxicity is larger, to allergic, acute poisoning can cause stupor etc., Long Term Contact more can cause anaemia, jaundice, and has genotoxicity and mutagenicity, hydrolysis in human body can cause adverse consequences, limits its application in medical.
Summary of the invention
The present invention is directed to prior art above shortcomings, propose a kind of polyphosphazene microspheres containing trans-resveratrol unit and preparation method thereof, select trans-resveratrol to do monomer, itself not only have multiple medical effect, and having hydroxyl and double bond, easier modification is to be applicable to the selection of different pharmaceutical; Microsphere diameter is 600-1000nm, and microsphere surface is smooth is solid construction, and adopt the crosslinking condensation reaction under the effect of acid binding agent of hexachlorocyclotriphosphazene and trans-resveratrol to form, preparation method is simple, can prepare in a large number in the industry.Its two kinds of monomers all human body are friendly, can be applicable to load and the controlled release of medicine; Surface poly-hydroxy and double bond functional group, be easy to modification and modification, can be applicable to the fields such as support of the catalyst.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of polyphosphazene microspheres containing trans-resveratrol unit, its structural formula is:
Described microsphere diameter is 600-1000nm, and microsphere surface is smooth is solid construction,
The present invention relates to the preparation method of above-mentioned crosslinked polyphosphazene microspheres, react by hexachlorocyclotriphosphazene, trans-resveratrol and acid binding agent are dissolved in organic solvent, wherein: the mol ratio of hexachlorocyclotriphosphazene and trans-resveratrol is 1:3, the mol ratio of hexachlorocyclotriphosphazene and acid binding agent is 1:6 ~ 1:16; After reaction terminates, solid product centrifugation is also washed and be drying to obtain crosslinked polyphosphazene microspheres.
Described hexachlorocyclotriphosphazene and the ratio of organic solvent are 0.1 ~ 5g/L;
Described temperature of reaction is 10 ~ 60 DEG C, and the reaction times is 2 to 6 hours.
Described reaction is preferably carry out in the ultrasonic water bath of 50 ~ 190W at power.
Described washing refers to: by crude product organic solvent washing three times, then use deionized water wash three times.
Described organic solvent is acetonitrile, acetone, tetrahydrofuran (THF) or its mixing.
Described acid binding agent is the alkoxy pyridines of triethylamine, pyridine or C1 ~ C3.
The present invention relates to the application of the above-mentioned polyphosphazene microspheres containing trans-resveratrol unit, be specially the polyphosphazene microspheres that this is contained trans-resveratrol unit and be used for making pharmaceutical carrier or support of the catalyst.
Technique effect
Compared with prior art, the prepared crosslinked polyphosphazene microspheres of the present invention has the cross-linking chemistry structure formed by hexachlorocyclotriphosphazene and trans-resveratrol condensation, two kinds of monomers are all friendly to human body, at water, good dispersing property is had in phosphate buffered saline buffer and organic solvent, and there are great amount of hydroxy group and double bond functional group in surface, be easy to modify and modification.The prepared crosslinked polyphosphazene microspheres of the present invention is that single stage method completes, and do not add tensio-active agent or stablizer, convenient post-treatment, the washing of by product triethylamine hydrochloride can remove.
Accompanying drawing explanation
Fig. 1 is the low power stereoscan photograph of the polyphosphazene microspheres that embodiment 1 obtains.
Fig. 2 is the high power stereoscan photograph of the polyphosphazene microspheres that embodiment 1 obtains.
Fig. 3 is the high power transmission electron microscope photo (particle of microsphere surface is institute's metal spraying particle before scanning shoot) of the polyphosphazene microspheres that embodiment 1 obtains.
Fig. 4 is the fourier infrared photo of the target polyphosphazene microspheres that embodiment 1 obtains.
Fig. 5 is the low power stereoscan photograph of the polyphosphazene microspheres that embodiment 2 obtains.
Fig. 6 is the low power stereoscan photograph of the polyphosphazene microspheres that embodiment 3 obtains.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
0.06 gram of (0.18mmol) hexachlorocyclotriphosphazene is added in 100mL flask, 0.08 gram of (0.36mmol) trans-resveratrol, add 50mL acetonitrile dispersing and dissolving, 2mL (1.44mmol) triethylamine is added when bath temperature reaches 30 DEG C, 3h is reacted in ultrasonic (190W) water bath with thermostatic control, after reaction terminates, solid is through centrifugation, by crude product washing with alcohol three times, then use deionized water wash three times, finally in vacuum drying oven, namely dry 24h obtains crosslinked polyphosphazene microspheres.
Fig. 1 is the low power stereoscan photograph that gained is cross-linked polyphosphazene microspheres, Fig. 2 is the high power stereoscan photograph that gained is cross-linked polyphosphazene microspheres, Fig. 3 is the projection electromicroscopic photograph of crosslinked polyphosphazene microspheres, and be 600 ~ 1000nm by the diameter of photo this microballoon visible, microsphere surface is smooth is solid construction.
Fig. 4 is the Fourier transform infrared spectrogram of crosslinked polyphosphazene microspheres, in figure 1600 and 1505
-1the resonance absorption of phenyl ring, 1185 and 875cm
- 1the resonance absorption of P=N and P-N key, 960cm
-1it is the resonance absorption of P-O-Ar key.The two kinds of monomers in infrared spectrum surface successfully there occurs reaction, and it is the crosslinked polycondensation structure of trans-resveratrol and phosphonitrile.
Embodiment 2
Adopt the equipment described in embodiment 1 and preparation process, hexachlorocyclotriphosphazene is wherein 0.06 gram (0.18mmol), and trans-resveratrol is 0.12 gram (0.54mmol).Interpretation shows, the diameter of microballoon is about 800nm, and microsphere surface is smooth is solid construction (see Fig. 5), and its structure is the crosslinking condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Embodiment 3
The equipment described in embodiment 1 of employing and preparation process, ultrasonic power is wherein 190W, and water bath with thermostatic control temperature is 30 DEG C, and reaction solvent is acetone, takes out sample segment after 3h, through ethanol and deionized water wash repeatedly after sample preparation.SEM interpretation shows, the diameter of microballoon is 800nm ~ 900nm, and microsphere surface is smooth is solid construction (see Fig. 6), and its structure is the crosslinking condensation structure of hexachlorocyclotriphosphazene and trans-resveratrol.
Claims (1)
1. a preparation method for the polyphosphazene microspheres containing trans-resveratrol unit, it is characterized in that, its structural formula is:
Described microsphere diameter is 600-1000nm, microsphere surface is smooth is solid construction, described preparation method, react by hexachlorocyclotriphosphazene, trans-resveratrol and acid binding agent are dissolved in organic solvent, wherein: the mol ratio of hexachlorocyclotriphosphazene and trans-resveratrol is 1:3, the mol ratio of hexachlorocyclotriphosphazene and acid binding agent is 1:6 ~ 1:16; After reaction terminates, solid product centrifugation is also washed and be drying to obtain crosslinked polyphosphazene microspheres;
Described hexachlorocyclotriphosphazene and the ratio of organic solvent are 0.1 ~ 5g/L;
Described temperature of reaction is 10 ~ 60 DEG C, and the reaction times is 2 to 6 hours;
Described reaction is carry out in the ultrasonic water bath of 50 ~ 190W at power;
Described washing refers to: by crude product organic solvent washing three times, then use deionized water wash three times;
Described organic solvent is acetonitrile, acetone, tetrahydrofuran (THF) or its mixing;
Described acid binding agent is the alkoxy pyridines of triethylamine, pyridine or C1 ~ C3.
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| CN104497316A (en) * | 2014-12-10 | 2015-04-08 | 上海交通大学 | High-nitrogen-content polymeric microsphere and preparation method thereof |
| US9878039B1 (en) | 2016-09-01 | 2018-01-30 | International Business Machines Corporation | Microcapsule having a microcapsule shell material that is rupturable via a retro-dimerization reaction |
| CN106519240A (en) * | 2016-11-04 | 2017-03-22 | 江南大学 | PH responding type polyphosphazene particle emulsifier and preparation method thereof |
| US10328535B2 (en) | 2016-11-07 | 2019-06-25 | International Business Machines Corporation | Self-heating solder flux material |
| CN111248195A (en) * | 2020-02-24 | 2020-06-09 | 暨南大学 | Nano-silver-loaded polyphosphazene composite antibacterial agent and preparation method and application thereof |
| CN111484531A (en) * | 2020-03-09 | 2020-08-04 | 南华大学上虞高等研究院有限公司 | Polyphosphazene microsphere containing phloretin unit, preparation method and application thereof |
| CN112841221A (en) * | 2021-01-27 | 2021-05-28 | 浙江工业大学 | Silver-loaded polyphosphazene microsphere with mesoporous core-shell structure as well as preparation method and application thereof |
| CN113143785A (en) * | 2021-04-02 | 2021-07-23 | 西安交通大学 | Natural polyphenol functionalized antioxidant compound sunscreen agent and preparation method thereof |
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| CN101018793A (en) * | 2004-09-14 | 2007-08-15 | 味之素欧姆尼凯姆股份有限公司 | Phosphorylated polyphenols as colour-stable agents |
| CN103113410A (en) * | 2013-03-05 | 2013-05-22 | 上海交通大学 | High-temperature resistant polyphosphazene microsphere and preparation method thereof |
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| US4727175A (en) * | 1986-09-29 | 1988-02-23 | The Dow Chemical Company | Hydroxyphenoxyphosphazenes and a process for producing same |
| CN101018793A (en) * | 2004-09-14 | 2007-08-15 | 味之素欧姆尼凯姆股份有限公司 | Phosphorylated polyphenols as colour-stable agents |
| CN103113410A (en) * | 2013-03-05 | 2013-05-22 | 上海交通大学 | High-temperature resistant polyphosphazene microsphere and preparation method thereof |
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| SYNTHESIS OF CYCLOTRIPHOSPHAZENES CONTAINING CYANOSTILBENES WITH DIFFERENT TERMINAL SUBSTITUENTS;Bao, R et al;《SYNTHETIC COMMUNICATIONS》;20120203;第42卷(第11期);第1661-1668页 * |
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