CN104857560A - Injectable hydrogel prepared from carboxylated pullulan and preparation method of injectable hydrogel - Google Patents
Injectable hydrogel prepared from carboxylated pullulan and preparation method of injectable hydrogel Download PDFInfo
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- CN104857560A CN104857560A CN201510269825.8A CN201510269825A CN104857560A CN 104857560 A CN104857560 A CN 104857560A CN 201510269825 A CN201510269825 A CN 201510269825A CN 104857560 A CN104857560 A CN 104857560A
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Abstract
The invention relates to Injectable hydrogel prepared from carboxylated pullulan and a preparation method of the injectable hydrogel. According to the preparation method, carboxylated pullulan is dissolved in deionized water, and a cross-linking agent solution is added and stirred for a reaction; a reaction liquid is heated in water bath to prepare hydrogel, and the hydrogel is dipped and cleaned and prepared to form injectable granules by a granulator. The hydrogel is prepared from the carboxylated pullulan and the cross-linking agent with a chemical cross-linking method, has excellent injectability, can be molded into stent models in different shapes, and has high stability, mechanical strength, biological efficiency and biodegradability.
Description
Technical field
The present invention relates to a kind of hydrogel, be specifically related to a kind of carboxylated pulullan polysaccharide injection aquagel and preparation method thereof.
Background technology
The characteristics such as the biocompatibility that nontoxic, transfection efficiency is high, good and anti-degradation property are the key factors that skin injury reparation builds.Recently, the physicochemical characteristics that the polymer that the polysaccharide having bacterial fermentation to produce is mixed with is favourable and simple biological degradability, construction unit is that regular straight or branched forms, and therefore receives the concern of people gradually.Pulullan polysaccharide is produced by short stalk mold fermentation, and construction unit connects maltotriose by α (1 → 4) glycosidic bond, connected between maltotriose by α (1 → 6) glycosidic bond.Current pulullan polysaccharide is mainly used in food, medicine and some industrial circles.Carboxylated pulullan polysaccharide be by fermentation mode to pulullan polysaccharide modification, same structure unit connects maltotriose by α (1 → 4) glycosidic bond, connected by α (1 → 6) glycosidic bond between maltotriose, connect a carboxymethyl in the C6 position of maltotriose, this structure has pliability, adds dissolubility and adhesiveness.Someone studies report: hyaluronic acid and BDDE are cross-linked the hydrogel of preparation very by the concern of people, but the degrees of expansion of this hydrogel is larger, the aperture of hydrogel is large, cell adhesion is difficult.
Summary of the invention
The object of this invention is to provide a kind of carboxylated pulullan polysaccharide injection aquagel and preparation method thereof, adopt Chemical Crosslinking Methods preparation to have more the higher skin packing material of degradability, biocompatibility, safety and implant frame material.
Inventor selects carboxylated pulullan polysaccharide to replace hyaluronic acid, carboxylated pulullan polysaccharide is by fermenting and producing, cost ratio hyaluronic acid is cheap a lot, the hydrogel swelling degree prepared is little, aperture relatively evenly, degradation time and adhesion characteristics etc. all express well.A lot of cross-linking agent also has report, such as, and dimethyl-suberimidate, Biformyl, genipin and carbodiimides hydrochloride etc., but BDDE enjoys the favor of people always, also by the certification of FDA/EMEA regulations.Therefore, the present invention selects that the carboxylated pulullan polysaccharide of pulullan polysaccharide modification and crosslinking agent B DDE are crosslinked prepares injectable hydrogel, analyzes the evaluation of the physical chemistry of novel hydrogel, biology and cytology aspect.
Implementation procedure of the present invention is as follows:
A preparation method for carboxylated pulullan polysaccharide injection aquagel, comprises the following steps:
(1) be dissolved in deionized water by carboxylated pulullan polysaccharide, obtain the carboxylated pulullan polysaccharide solution that quality volume fraction is 100 ~ 500mg/mL, it is 20 ~ 27 DEG C that temperature controls;
(2) add mass fraction be 5 ~ 15% cross-linking agent BDDE stir, control temperature is 25 ~ 30 DEG C, and wherein the mass ratio of carboxylated pulullan polysaccharide and cross-linking agent is 100 ~ 1000:1 ~ 20;
(3) reactant liquor is obtained hydrogel at 45 ~ 55 DEG C of reaction 3 ~ 6h;
(4) obtained hydrogel embathes 2 ~ 6 days by apirogen water and phosphate buffered solution in succession, makes injectable granule with granulator.
Above-mentioned carboxylated pulullan polysaccharide is the outer neutral polysaccharide of water solublity born of the same parents of Aureobasidium pullulans secretion, and its molecular weight is 530000g/mol.
The pH of above-mentioned phosphate buffered solution is 7.4.
The preparation method of above-mentioned carboxylated pulullan polysaccharide injection aquagel, concrete preparation process is:
(1) be dissolved in deionized water by carboxylated pulullan polysaccharide powder, obtain the carboxylated pulullan polysaccharide solution 5mL that quality volume fraction is 100 ~ 500mg/mL, it is 20 ~ 27 DEG C that reaction temperature controls, and reacts 0.5 ~ 1h under agitation;
(2) add 0.05 ~ 0.3mL, mass fraction is the cross-linking agent solution of 5 ~ 15%, it is 25 ~ 30 DEG C that reaction temperature controls, and reacts 0.1 ~ 0.6h under agitation;
(3) reactant liquor is put in 3h ~ 6h in 50 DEG C of thermostat water baths, obtained hydrogel;
(4) obtained hydrogel embathes 2 ~ 6 days by apirogen water and phosphate buffered solution in succession, makes injectable granule with granulator.
The present invention has the following advantages:
The carboxylated pulullan polysaccharide injection aquagel of one involved in the present invention is that carboxylated pulullan polysaccharide and BDDE (BDDE) are combined the skin packing material made.Carboxylated pulullan polysaccharide is the outer neutral polysaccharide of water solublity born of the same parents secreted by Aureobasidium pullulans (Aureobasidium pullulans), employing Chemical Crosslinking Methods is made, in carboxylated pulullan polysaccharide, two adjacent hydroxyls dock with the epoxy radicals at the two ends of BDDE, form one to graft (co) polymers.Polymer reacts the hydrogel being formed and be similar to g., jelly-like at 50 DEG C; the millimetre-sized granule of different-grain diameter is made by granulator; the advantage use for syringeability hydrogel, have that stability is high, biology performance is good, operating wound can avoided.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of carboxylated pulullan polysaccharide hydrogel (PCB);
Fig. 2 is the sample drawing of carboxylated pulullan polysaccharide hydrogel;
Fig. 3 is the scanning electron microscope (SEM) photograph of carboxylated pulullan polysaccharide hydrogel, and in figure, No. 1 is the scanning electron microscope (SEM) photograph (amplifying 100 times) of hydrogel, and No. 2 is the scanning electron microscope (SEM) photograph (amplifying 250 times) of hydrogel;
Fig. 4 is the residual quantity of BDDE in carboxylated pulullan polysaccharide hydrogel;
Fig. 5 is the crush test of carboxylated pulullan polysaccharide hydrogel;
Fig. 6 be carboxylated pulullan polysaccharide be injected in mice subcutaneous after, tissue and the inflammatory reaction of material, with transmission electron microscope observing, in figure, blank is injecting normal saline; PCB is the transmission electron microscope picture that carboxylated pulullan polysaccharide is injected in subcutaneous 1 week of mice and 24 weeks.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention will be described in detail.
A kind of carboxylated pulullan polysaccharide hydrogel involved in the present invention, the outer neutral pulullan polysaccharide of the water solublity born of the same parents secreted with Aureobasidium pullulans (Aureobasidium pullulans) is for raw material, adopt 1,4-butanediol diglycidyl ether (BDDE) cross-linking agent carries out chemical crosslinking, at reactant liquor being put into 50 DEG C, static placement 3 ~ 6h, prepares hydrogel.The thick product prepared, through purification process, namely adopts BDDE residual in apirogen water and phosphate buffered solution replacing water gel and impurity.
What the carboxylated pulullan polysaccharide in raw material adopted is the outer neutral polysaccharide of water solublity born of the same parents secreted by Aureobasidium pullulans (Aureobasidium pullulans), compared with hyaluronic acid, it has, and good water solubility, reaction condition are gentle, the remarkable advantage such as have good stability.In addition, carboxylated pulullan polysaccharide itself has good biocompatibility and degradability, can be applicable to field of tissue engineering technology.
The preparation method of the carboxylated pulullan polysaccharide injection aquagel that the present invention relates to, is realized by following steps:
Step one: be dissolved in deionized water by carboxylated pulullan polysaccharide powder, obtains the carboxylated pulullan polysaccharide solution 5mL that quality volume fraction is 100 ~ 500mg/mL, and it is 20 ~ 27 DEG C that reaction temperature controls, and reacts 0.5 ~ 1h under agitation;
Step 2: add 0.05 ~ 0.3mL, mass fraction is the cross-linking agent solution of 5 ~ 15%, it is 25 ~ 30 DEG C that reaction temperature controls, and reacts 0.1 ~ 0.6h under agitation;
Step 3: reactant liquor is put in 3h ~ 6h in 50 DEG C of thermostat water baths, obtained hydrogel;
Step 4: obtained hydrogel embathes 2 ~ 6 days by apirogen water and phosphate buffered solution in succession, makes the injectable granule of different-grain diameter with granulator.
In step one, carboxylated pulullan polysaccharide refers to the outer neutral polysaccharide of water solublity born of the same parents secreted by Aureobasidium pullulans, and its molecular weight is 530000g/mol.
In step 2, cross-linking agent is BDDE.
In step 4, the pH of phosphate buffered solution is 7.4.
1, the strand of 4-butanediol diglycidyl ether and carboxylated pulullan polysaccharide reacts and defines graft (co) polymers, the hydrogel being similar to g., jelly-like is formed at 50 DEG C of temperature, impurity residual in apirogen water and phosphate buffered solution wash water gel and some unreacted BDDEs.Scavenging period is 2 ~ 6 days.The grade granule of different-grain diameter made by hydrogel granulation machine after purification, then can load in syringe for injection.
Embodiment 1
Step one: be dissolved in deionized water by carboxylated pulullan polysaccharide powder, obtains the carboxylated pulullan polysaccharide solution 5mL that quality volume fraction is 100mg/mL, and it is 27 DEG C that reaction temperature controls, and reacts 0.5h under agitation;
Step 2: add 0.3mL, mass fraction is the cross-linking agent solution of 5%, it is 30 DEG C that reaction temperature controls, and reacts 0.1h under agitation;
Step 3: reactant liquor is put in 6h in 50 DEG C of thermostat water baths, obtained hydrogel;
Step 4: obtained hydrogel embathes 2 days by apirogen water and phosphate buffered solution in succession, makes the injectable granule of different-grain diameter with granulator.
In step one, carboxylated pulullan polysaccharide refers to the outer neutral polysaccharide of water solublity born of the same parents secreted by Aureobasidium pullulans, and its molecular weight is 530000g/mol.
In step 2, cross-linking agent is BDDE.
In step 4, the pH of phosphate buffered solution is 7.4.
Embodiment 2
Step one: be dissolved in deionized water by carboxylated pulullan polysaccharide powder, obtains the carboxylated pulullan polysaccharide solution 5mL that quality volume fraction is 300mg/mL, and it is 24 DEG C that reaction temperature controls, and reacts 0.7h under agitation;
Step 2: add 0.18mL, mass fraction is the cross-linking agent solution of 10%, it is 27 DEG C that reaction temperature controls, and reacts 0.3h under agitation;
Step 3: reactant liquor is put in 4.5h in 50 DEG C of thermostat water baths, obtained hydrogel;
Step 4: obtained hydrogel embathes 4 days by apirogen water and phosphate buffered solution in succession, makes the injectable granule of different-grain diameter with granulator.
In step one, carboxylated pulullan polysaccharide refers to the outer neutral polysaccharide of water solublity born of the same parents secreted by Aureobasidium pullulans, and its molecular weight is 530000g/mol.
In step 2, cross-linking agent is BDDE.
In step 4, the pH of phosphate buffered solution is 7.4.
Embodiment 3
Step one: be dissolved in deionized water by carboxylated pulullan polysaccharide powder, obtains the carboxylated pulullan polysaccharide solution 5mL that quality volume fraction is 500mg/mL, and it is 20 DEG C that reaction temperature controls, and reacts 1h under agitation;
Step 2: add 0.05mL, mass fraction is the cross-linking agent solution of 15%, it is 25 DEG C that reaction temperature controls, and reacts 0.6h under agitation;
Step 3: reactant liquor is put in 3h in 50 DEG C of thermostat water baths, obtained hydrogel;
Step 4: obtained hydrogel embathes 6 days by apirogen water and phosphate buffered solution in succession, makes the injectable granule of different-grain diameter with granulator.
In step one, carboxylated pulullan polysaccharide refers to the outer neutral polysaccharide of water solublity born of the same parents secreted by Aureobasidium pullulans, and its molecular weight is 530000g/mol.
In step 2, cross-linking agent is BDDE.
In step 4, the pH of phosphate buffered solution is 7.4.
Carry out INFRARED ABSORPTION, scanning electron microscope analysis, sample observation, BDDE residual quantity and Compressive Strength Analysis to the product of above embodiment, its analysis result is as follows:
1, the infrared absorption peak of the characteristic group of hydrogel as shown in Figure 1, at 1646 cm
-1, 1373 cm
-1and 1157cm
-1there is absworption peak at place.
2, the sample of hydrogel packing material as shown in Figure 2, and Hydrogels is similar to the milk white gel of g., jelly-like, is creamy white.
3, the scanning electron microscope analysis of hydrogel packing material as shown in Figure 3, and hydrogel is the loose structure of three-dimensional network shape, arranges more regular.
4, the residual quantity of the BDDE of hydrogel as shown in Figure 4, and the BDDE content that hydrogel remains after different time cleaning is lower, conformance with standard.
5, the comprcssive strength of hydrogel as shown in Figure 5, the relation between compression displacement and compressive load.Compressive load reaches 0.1MPa.
6, hydrogel be injected in mice subcutaneous after, the inflammatory reaction around transmission electron microscope observing tissue is carried out to skin histology, as shown in Figure 6, within first week, can be observed material, macrophage, fibroblast and cavity; Tissue has the endoplasmic reticulum of fibroblast, collagen fiber and some diffusions around after 24th week.Compared with blank, the cavity after 24 weeks significantly reduces, and inflammatory reaction reduces, and histocompatibility is good.
The hydrogel packing material that the present invention obtains shows for the zoopery of Adult female ICR mice: the hydrogel prepared with chemical crosslink technique, has good mechanical strength and biocompatibility, is suitable for tissue filling.
Content of the present invention is not limited to cited by embodiment, and the conversion of those of ordinary skill in the art by reading description of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Claims (5)
1. a preparation method for carboxylated pulullan polysaccharide injection aquagel, is characterized in that comprising the following steps:
(1) be dissolved in deionized water by carboxylated pulullan polysaccharide and obtain the carboxylated pulullan polysaccharide solution that quality volume fraction is 100 ~ 500mg/mL, it is 20 ~ 27 DEG C that temperature controls;
(2) add mass fraction be 5 ~ 15% cross-linking agent BDDE stir, control temperature is 25 ~ 30 DEG C, and wherein the mass ratio of carboxylated pulullan polysaccharide and cross-linking agent is 100 ~ 1000:1 ~ 20;
(3) reactant liquor is obtained hydrogels 45 ~ 55 DEG C of reactions;
(4) obtained hydrogel embathes 2 ~ 6 days by apirogen water and phosphate buffered solution in succession, makes injectable granule with granulator.
2. the preparation method of carboxylated pulullan polysaccharide injection aquagel according to claim 1, is characterized in that: carboxylated pulullan polysaccharide is the outer neutral polysaccharide of water solublity born of the same parents of Aureobasidium pullulans secretion, and its molecular weight is 530000g/mol.
3. the preparation method of carboxylated pulullan polysaccharide injection aquagel according to claim 1, is characterized in that: the pH of phosphate buffered solution is 7.4.
4. the preparation method of carboxylated pulullan polysaccharide injection aquagel according to claim 1, is characterized in that:
(1) be dissolved in deionized water by carboxylated pulullan polysaccharide powder, obtain the carboxylated pulullan polysaccharide solution 5mL that quality volume fraction is 100 ~ 500mg/mL, it is 20 ~ 27 DEG C that reaction temperature controls, and reacts 0.5 ~ 1h under agitation;
(2) add 0.05 ~ 0.3mL, mass fraction is the cross-linking agent solution of 5 ~ 15%, it is 25 ~ 30 DEG C that reaction temperature controls, and reacts 0.1 ~ 0.6h under agitation;
(3) reactant liquor is put in 3h ~ 6h in 50 DEG C of thermostat water baths, obtained hydrogel;
(4) obtained hydrogel embathes 2 ~ 6 days by apirogen water and phosphate buffered solution in succession, makes injectable granule with granulator.
5. the carboxylated pulullan polysaccharide injection aquagel that preparation method according to claim 1 is obtained.
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| CN105820267A (en) * | 2016-04-27 | 2016-08-03 | 河北大学 | Skin wound repairing preparation as well as preparation method and application thereof |
| CN107022091A (en) * | 2017-03-31 | 2017-08-08 | 福州大学 | A kind of preparation method of multiple response self-healing hydrogel |
| CN112280061A (en) * | 2020-11-19 | 2021-01-29 | 南京瑞贝西生物科技有限公司 | Preparation method of magnetic polysaccharide-based hydrogel |
| US11319566B2 (en) | 2017-04-14 | 2022-05-03 | Capsugel Belgium Nv | Process for making pullulan |
| US11576870B2 (en) | 2017-04-14 | 2023-02-14 | Capsugel Belgium Nv | Pullulan capsules |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107022091B (en) * | 2017-03-31 | 2019-05-07 | 福州大学 | A kind of preparation method of multiple response self-healing hydrogel |
| US11319566B2 (en) | 2017-04-14 | 2022-05-03 | Capsugel Belgium Nv | Process for making pullulan |
| US11576870B2 (en) | 2017-04-14 | 2023-02-14 | Capsugel Belgium Nv | Pullulan capsules |
| US11878079B2 (en) | 2017-04-14 | 2024-01-23 | Capsugel Belgium Nv | Pullulan capsules |
| CN112280061A (en) * | 2020-11-19 | 2021-01-29 | 南京瑞贝西生物科技有限公司 | Preparation method of magnetic polysaccharide-based hydrogel |
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Application publication date: 20150826 |