CN103739852B - MPEG grafting α-zein polymkeric substance and preparation method thereof - Google Patents
MPEG grafting α-zein polymkeric substance and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of mPEG grafting α-zein polymkeric substance and preparation method thereof, solve the lapping of existing zein as medicine and nutrient substance, be unfavorable for controlling the release of medicine and the homogeneous technical problem of size distribution.First this polymkeric substance is reacted by mPEG and Succinic anhydried and prepares mPEG-COOH; Reacted by mPEG-COOH and α-zein again and prepare mPEG grafting α-zein polymkeric substance.After mPEG grafting α-zein polymkeric substance that the inventive method prepares is water-soluble, stable existence can be formed and the microballoon of size uniformity (particle diameter is at 80-100nm), less than the particle diameter of zein of mixing, hydrophobic class medicine, the controllable release of nutrient substance and bioavailability can be improved.
Description
Technical field
The present invention relates to a kind of polymkeric substance, be specifically related to a kind of mPEG grafting α-zein polymkeric substance and preparation method thereof.
Background technology
Zein (zein) is present in corn embryosperm, is a kind of natural mixing prolamine (comprising alpha, beta, gamma, delta tetra-kinds of components).It has good biocompatibility, low water absorbable, is widely used in the fields such as the parcel of medicine, transport.Current people are directly using the coating material of zein as medicine and nutrient substance, and the microspherulite diameter distribution that the prolamine of this mixing is formed in aqueous is comparatively large, is unfavorable for the controllable release controlling size distribution and medicine.In addition, the solvability of this zein microballoon and stability comparatively limited.
In mixing prolamine, α-zein (α-zein) component accounts for 60%, and it has enriches self-assembly behavior, and is the macromole that component is single, is suitable as very much the package shipment material of medicine, nutrient substance etc.α-zein is hydrophobic, and in grafting, hydroaropic substance makes it become amphipathic prolamine, and so this amphipathic α-zein just can be water-soluble, for improving hydrophobic class medicine, the controllable release of nutrient substance and bioavailability.In addition, very important meaning is also had to the deep processing of better utilised corn resources and agricultural-food with conversion.
Summary of the invention
The present invention solves the lapping of existing zein as medicine and nutrient substance, is unfavorable for controlling the release of medicine and the homogeneous technical problem of size distribution, provides a kind of mPEG grafting α-zein polymkeric substance and preparation method thereof.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A kind of mPEG grafting α-zein polymkeric substance, first this polymkeric substance is reacted by mPEG and Succinic anhydried and prepares mPEG-COOH; Reacted by mPEG-COOH and α-zein again and prepare mPEG grafting α-zein polymkeric substance;
The weight-average molecular weight of described mPEG is 1KDa ~ 50KDa;
The weight-average molecular weight of described α-zein is 22KDa ~ 26KDa;
Described α-zein is prepared by following method: first zein is dissolved in N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO); Repeatedly extract in methylene dichloride or ether again; Finally the throw out after extraction is dissolved in more than 90% methyl alcohol or ethanolic soln, centrifuging and taking supernatant liquor, and is diluted with water to concentration less than 80%, the solid normal hexane after filtration or petroleum ether, obtain after vacuum-drying;
The weight-average molecular weight of described polymkeric substance is 23KDa ~ 76KDa, and its concrete structure is shown below:
A preparation method for mPEG grafting α-zein polymkeric substance, this preparation method comprises the following steps:
(1) be dissolved in methylene dichloride by mPEG, add excessive Succinic anhydried, 45 ~ 65 DEG C of water-baths, stir 3 ~ 7h, repeated precipitation in ether and methylene dichloride, vacuum is spent the night, will obtain white powder water-soluble after, dialysis also obtains mPEG-COOH after freeze-drying;
(2) mPEG-COOH is dissolved in N-Methyl pyrrolidone, add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) and N-hydroxy-succinamide (NHS), mPEG-COOH, the mol ratio 1:1.2:1.2 of EDCHCl and NHS, stir 3 ~ 6h, above-mentioned mixed solution is slowly dropped in the dimethyl sulphoxide solution of α-zein, the mol ratio of mPEG-COOH and α-zein is 5:1, stirring at room temperature 24 ~ 28h, after completion of the reaction, repeated precipitation in ether and N-Methyl pyrrolidone, dry, by water-soluble for the product obtained, dialysis also obtains white mPEG grafting α-zein polymkeric substance after freeze-drying.
In technique scheme, the stirring velocity described in step (1) is 300 ~ 700rpm, and churning time is 5h.
In technique scheme, the number of times of the repeated precipitation described in step (1) is 2 ~ 6 times.
In technique scheme, the dialysis time described in step (1) is two days.
In technique scheme, the number of times of the repeated precipitation described in step (2) is 2 ~ 6 times.
In technique scheme, the dialysis time described in step (2) is 1 ~ 4 day.
The present invention has following beneficial effect:
The present invention obtains pure α-zein component after carrying out purifying to zein, more successful grafting hydroaropic substance mPEG becomes amphipathic prolamine (accompanying drawing 1,2 is provable) thereon.MPEG has well water-soluble and biocompatibility, be the food of U.S. FDA authentication security, drug material, it and α-zein albumen are reacted, can by good for mPEG water-soluble, transfer on binding substances, enable α-zein water-soluble and wrap up hydrophobic class medicine and nutrient substance etc.
And, after mPEG grafting α-zein polymkeric substance that the inventive method prepares is water-soluble, stable existence can be formed and the microballoon of size uniformity (particle diameter is at 80 ~ 100nm), less than the particle diameter of zein of mixing, hydrophobic class medicine, the solubleness of nutrient substance and bioavailability can be improved.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Fig. 1 is the infrared spectrogram of mPEG grafting α-zein polymkeric substance prepared by embodiment 1.
Fig. 2 is mPEG grafting α-zein polymkeric substance 1HNMR spectrogram prepared by embodiment 1.
Fig. 3 is the grain size distribution of mPEG grafting α-zein polymkeric substance prepared by embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of mPEG grafting α-zein polymkeric substance prepared by embodiment 1.
Embodiment
A kind of mPEG grafting α-zein polymkeric substance, first this polymkeric substance is reacted by mPEG and Succinic anhydried and prepares mPEG-COOH; Reacted by mPEG-COOH and α-zein again and prepare mPEG grafting α-zein polymkeric substance; The weight-average molecular weight of described mPEG is 1KDa ~ 50KDa; The weight-average molecular weight of described α-zein is 22KDa ~ 26KDa;
Described α-zein is prepared by following method: first zein is dissolved in N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO); Repeatedly extract in methylene dichloride or ether again; Finally the throw out after extraction is dissolved in more than 90% methyl alcohol or ethanolic soln, centrifuging and taking supernatant liquor, and is diluted with water to concentration less than 80%, after filtering, solid normal hexane or petroleum ether, obtain after vacuum-drying; The weight-average molecular weight of resulting polymers is 23KDa ~ 76KDa.
The concrete structure of described α-zein refers to (Momany, F.A., etal. (2006). " Structuralcharacterizationofalpha-zein. " JournalofAgriculturalandFoodChemistry54 (2): 543-547.).
MPEG grafting α-zein polymkeric substance is specifically prepared by following method:
(1) mPEG is dissolved in methylene dichloride, add excessive Succinic anhydried, 45 ~ 65 DEG C of water-baths, 300 ~ 700rpm stirs 3 ~ 7h, repeated precipitation 2 ~ 6 times in ether and methylene dichloride, and vacuum is spent the night, to obtain white powder water-soluble after, be injected in dialysis tubing, dialyse two days, after freeze-drying, obtain mPEG-COOH; Preferred churning time is 5h;
(2) mPEG-COOH is dissolved in N-Methyl pyrrolidone, add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) and N-hydroxy-succinamide (NHS), mPEG-COOH, the mol ratio 1:1.2:1.2 of EDCHCl and NHS, stir 3 ~ 6h, above-mentioned mixed solution is slowly dropped in the dimethyl sulphoxide solution of α-zein, the mol ratio of mPEG-COOH and α-zein is 5:1, stirring at room temperature 24 ~ 28h, after completion of the reaction, Precipitation in ether, be dissolved in again in N-Methyl pyrrolidone, repeated precipitation 2 ~ 6 times, dry, the product obtained is water-soluble, inject dialysis tubing, dialyse 1 ~ 4 day, freeze-drying again, obtain white mPEG grafting α-zein polymkeric substance (mPEG-α-zein).Synthetic route is as follows:
The preparation embodiment of α-zein
1 portion of Semen Maydis powder is dissolved in 5 part of 50 ~ 75% ethanol, centrifuging and taking supernatant liquor.Thin up, until no longer include albumen precipitation, dries after filtration, obtains zein.Remove the grease in zein with normal hexane equal solvent, get 1 part of degreasing zein and be dissolved in 30 parts of N-Methyl pyrrolidone, repeatedly extract 3 times at the methylene dichloride of 90 parts and remove riboflavin.Finally with more than 90% ethanolic soln washing, centrifuging and taking supernatant liquor, is diluted with water to concentration less than 80%, filters; By the solid n-hexane filtered, vacuum-drying obtains white α-zein powder.
Embodiment 1
1gmPEG (Mz=1KDa) is dissolved in methylene dichloride, adds excessive Succinic anhydried.45 DEG C of water-baths, 300rpm stirs 5h.Repeated precipitation 2 times in ether and methylene dichloride, suction filtration final vacuum spends the night.To obtain white powder water-soluble after, inject relative molecular weight be the dialysis tubing of 3500, dialyse two days.MPEG-COOH is obtained after freeze-drying.Above-mentioned product is dissolved in 10mlN-methyl-2-pyrrolidone, adds 0.018gEDCHCl(activator) and 0.027gNHS, stir-activating 3h.Above-mentioned mixed solution is slowly dropped to 1g α-zein(Mz=26KDa) dimethyl sulphoxide solution in, stir 28h, after completion of the reaction, Precipitation in ether, then be dissolved in N-Methyl pyrrolidone, 2 times repeatedly.The product that drying obtains is water-soluble, and injecting molecular weight cut-off is the dialysis tubing of 30000, and dialyse 1 day in water, obtain mPEG grafting α-zein polymkeric substance after freeze-drying, weigh, productive rate is 64%.
The infared spectrum of the polymkeric substance that accompanying drawing 1 is prepared for this embodiment, this collection of illustrative plates shows: a.850cm
-1two CH
2cH
2o characteristic peak, these two peaks upper of the α-zein after grafting first have without male offspring.B.2800cm
-1α-the zein of purifying does not have methyl peak, after grafting, occurs the vibration peak of methyl.Illustrate that mPEG is successfully grafted to α-zein.Also confirm further at accompanying drawing 21HNMR spectrogram.
Accompanying drawing 3 and 4 is respectively grain size distribution and the scanning electron microscope (SEM) photograph of polymkeric substance prepared by this embodiment, by soluble in water for the mPEG grafting α-zein polymkeric substance of preparation, form micella, detect its size distribution, dynamic light scattering (DLS) result display about 80nm, can find out that the particle diameter of microballoon ratio the mixing zein formed with α-zein is little, and even size distribution (PDI=0.180.2), the time of releasing of effective controlling functions Summing Factor medicine after absorption human body and speed.
Embodiment 2
10gmPEG (Mz=25KDa) is dissolved in methylene dichloride, adds excessive Succinic anhydried.65 DEG C of water-baths, 700rpm stirs 3h.Repeated precipitation 4 times in ether, suction filtration final vacuum spends the night.To obtain white powder water-soluble after, inject relative molecular weight be the dialysis tubing of 35000, dialyse two days.MPEG-COOH is obtained after freeze-drying.Above-mentioned product is dissolved in 100mlN-methyl-2-pyrrolidone, adds 0.036gEDCHCl(activator) and 0.054gNHS, stir-activating 4h.Above-mentioned mixed solution is slowly dropped to 1.2g α-zein(Mz=22KDa) dimethyl sulphoxide solution in, stir 24h, after completion of the reaction, Precipitation in ether, then be dissolved in N-Methyl pyrrolidone, 4 times repeatedly.The product that drying obtains is water-soluble, and injecting molecular weight cut-off is the dialysis tubing of 35000, and dialyse 4 days in water, obtain mPEG grafting α-zein polymkeric substance after freeze-drying, weigh, productive rate is 62%.
Embodiment 3
100gmPEG (Mz=50KDa) is dissolved in methylene dichloride, adds excessive Succinic anhydried.55 DEG C of water-baths, 500rpm stirs 7h.Repeated precipitation 6 times in ether, suction filtration final vacuum spends the night.To obtain white powder water-soluble after, inject molecular weight cut-off be 60000 ultra-filtration membrane dialyse, dialyse two days.MPEG-COOH is obtained after freeze-drying.10gmPEG-COOH, 0.0297gDCC and 0.01657gNHS are mixed and drips a small amount of triethylamine, stir-activating 6h.Above-mentioned mixed solution is slowly dropped to 0.6g α-zein(Mz=22KDa) dimethyl sulphoxide solution in, stirring at room temperature 26h.After completion of the reaction, Precipitation in ether, then be dissolved in N-Methyl pyrrolidone, 6 times repeatedly.Product is dialyse 3 days in the dialysis tubing of 60000 at molecular weight cut-off, and obtain mPEG grafting α-zein polymkeric substance after freeze-drying, weigh, productive rate is 63%.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (7)
1. mPEG grafting α-zein polymkeric substance, is characterized in that, first this polymkeric substance is reacted by mPEG and Succinic anhydried and prepare mPEG-COOH; Reacted by mPEG-COOH and α-zein again and prepare mPEG grafting α-zein polymkeric substance;
The weight-average molecular weight of described mPEG is 1KDa ~ 50KDa;
The weight-average molecular weight of described α-zein is 22KDa ~ 26KDa;
Described α-zein is prepared by following method: first zein is dissolved in N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO); Repeatedly extract in methylene dichloride or ether again; Finally the throw out after extraction is dissolved in more than 90% methyl alcohol or ethanolic soln, centrifuging and taking supernatant liquor, and is diluted with water to concentration less than 80%, the solid normal hexane after filtration or petroleum ether, obtain after vacuum-drying;
The weight-average molecular weight of described polymkeric substance is 23KDa ~ 76KDa, and its concrete structure is shown below:
2. the preparation method of mPEG grafting α-zein polymkeric substance according to claim 1, it is characterized in that, this preparation method comprises the following steps:
(1) mPEG is dissolved in methylene dichloride, adds excessive Succinic anhydried, 45 ~ 65 DEG C of water-baths, stir 3 ~ 7h, repeated precipitation in ether and methylene dichloride, suction filtration final vacuum spends the night, to obtain white powder water-soluble after, dialysis and freeze-drying after obtain mPEG-COOH;
(2) mPEG-COOH is dissolved in N-Methyl pyrrolidone, add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) and N-hydroxy-succinamide (NHS), mPEG-COOH, the mol ratio 1:1.2:1.2 of EDCHCl and NHS, stir 3 ~ 6h, above-mentioned mixed solution is slowly dropped in the dimethyl sulphoxide solution of α-zein, the mol ratio of mPEG-COOH and α-zein is 5:1, stirring at room temperature 24 ~ 28h, after completion of the reaction, repeated precipitation in ether and N-Methyl pyrrolidone, dry, by water-soluble for the product obtained, dialysis also obtains white mPEG grafting α-zein polymkeric substance after freeze-drying.
3. the preparation method of mPEG grafting α-zein polymkeric substance according to claim 2, is characterized in that, the stirring velocity described in step (1) is 300 ~ 700rpm, and churning time is 5h.
4. the preparation method of mPEG grafting α-zein polymkeric substance according to claim 2, is characterized in that, the number of times of the repeated precipitation described in step (1) is 2 ~ 6 times.
5. the preparation method of mPEG grafting α-zein polymkeric substance according to claim 2, is characterized in that, the dialysis time described in step (1) is two days.
6. the preparation method of mPEG grafting α-zein polymkeric substance according to claim 2, is characterized in that, the number of times of the repeated precipitation described in step (2) is 2 ~ 6 times.
7. the preparation method of mPEG grafting α-zein polymkeric substance according to claim 2, is characterized in that, the dialysis time described in step (2) is 1 ~ 4 day.
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| CN108403662B (en) * | 2018-05-08 | 2020-05-22 | 华南理工大学 | Trihydroxymethyl aminomethane modified zein functional drug-loaded microsphere and preparation method thereof |
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| CN1326732A (en) * | 2000-03-14 | 2001-12-19 | Basf公司 | Soft capsule containing vinyl ester and poly ether polymer, its use and producing method |
| CN101679021A (en) * | 2007-03-02 | 2010-03-24 | 伊利诺伊大学评议会 | Particulate drug delivery |
| CN102120823A (en) * | 2011-01-06 | 2011-07-13 | 鲁传华 | Synthesis of water soluble zein and application thereof in pharmaceutical preparation |
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| CN1326732A (en) * | 2000-03-14 | 2001-12-19 | Basf公司 | Soft capsule containing vinyl ester and poly ether polymer, its use and producing method |
| CN101679021A (en) * | 2007-03-02 | 2010-03-24 | 伊利诺伊大学评议会 | Particulate drug delivery |
| CN102120823A (en) * | 2011-01-06 | 2011-07-13 | 鲁传华 | Synthesis of water soluble zein and application thereof in pharmaceutical preparation |
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