CN100582145C - Preparation method of pH sensitive carboxymethyl chitosan hydrogel - Google Patents
Preparation method of pH sensitive carboxymethyl chitosan hydrogel Download PDFInfo
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- CN100582145C CN100582145C CN200610125192A CN200610125192A CN100582145C CN 100582145 C CN100582145 C CN 100582145C CN 200610125192 A CN200610125192 A CN 200610125192A CN 200610125192 A CN200610125192 A CN 200610125192A CN 100582145 C CN100582145 C CN 100582145C
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Abstract
The invention discloses a preparing method of pH value sensitive dialdehyde starch crosslinking carboxymethyl chitosan aquagel, which comprises the following steps: blending carboxymethyl chitosan solution with density at 1-4% and dialdehyde starch solution with density at 1-6% according to the weight rate at 1:0.5-5.0; stirring evenly under 30-60 Deg C; defoaming in the vacuum; stewing at indoor temperature for 6-36h to form gel; washing through deionized water; drying in the vacuum to obtain constant weight material as the product.
Description
Technical field
The invention belongs to resource and pharmaceutical chemistry technical field, the preparation method of the responsive dialdehyde starch crosslinked carboxymethyl chitosan hydrogel of particularly a kind of pH.
Background technology
The pH sensitive aquagel is meant that hydrogel can absorb moisture content generation swelling with the variation of environment pH value or discharge moisture content contraction sudden change.The macromolecular pH susceptibility of this class hydrogel principle is to have in self network to be dissociated into ionic acidity or basic group (as: carboxyl, amino).They can capture or discharge proton according to the variation of the pH of environment, produce ionization in various degree, thereby cause the electric density of gel network and network structure to change, and then swelling takes place or shrink sudden change (FloryP J.J Chemical Physics, 1977,66:5720; Zhang Kan, Zhang Liming. the Guangzhou chemistry, 2000,26:46).Utilize this specific character of pH sensitive aquagel to prepare diffusion and rate of release (Nicole J E, Kelly R S, Kao W J.Biomaterials, 2002,24:509 that medicine could be regulated and control to preparation easily; Li F, Liu W G, YaoK D.Biomaterials, 2002,23:343; Aiedeh K, Taha M O.Arch Pharm, 1999,332:103).So the pH sensitive aquagel is oral pharmaceutical sustained release preparation and controlled release preparation carrier (Lee W F, Shieh C H.J ApplPol Sci, 1999,73:195 commonly used; Semde R, Amighi K, Devleeschouwer M J, et al.Int J Pharm, 2000,197:181; Yin Y H, Yang Y J, Xu H B, 2002,38:2305).
But because it is bad much to be used at present to prepare the biocompatibility of synthesized polymer material of gel, linking agent is to human body toxic side effect (Park Y K, Park Y H, Shi B A.J Contr Rel, 2000,69:97), limited of the widespread use of pH sensitive aquagel in the drug delivery field.Therefore, seek that exploitation has the gelatinous material of excellent biological compatibility and be problem demanding prompt solution the linking agent that human body has no side effect.
Cm-chitosan is a chitosan derivatives.It has excellent biological compatibility, wetting ability, biodegradable.The introducing of carboxyl has improved the water-soluble of chitosan on the one hand greatly in the chitosan, and on the other hand, carboxyl is the environmental sensitivity group, and its introducing makes cm-chitosan become the splendid raw material of preparation environment sensitive material.In addition, also have a large amount of hydroxyls and amino in the carboxymethyl chitosan glycan molecule, can be cross-linked to form network structure (Shu X Z, Zhu K J, Song W H.In J Pharm, 2001,212:192 with linking agent with adsorptive power; Shin M N, Kang H S, ParkT G, et al.Pol Bull, 2002,47:451; Khalid M N, Agnely F, Yagoubi N.Eur J PharmSci, 2002,15:425).So select raw material (Chen S C, Wu Y C, Mi F L, et al.J Control Res, 2004, the 96:285 of cm-chitosan as the pH sensitive aquagel; Chen L Y, Tian Z G, Du Y M.Biomaterials, 2004,25:3725).
In the preparation process of hydrogel, the kind of linking agent also is a key factor.According to report, adopt at present extensively glutaraldehyde, epoxy chloropropane, dibasic acid anhydride etc. as linking agent to cm-chitosan carry out crosslinked preparation hydrogel (Sun Liping, Du Yumin, Chen Lingyun, etc. polymer journal, 2004, (2): 191; Yang Xudong, Wu Guojie, woods plays gold. New Chemical Materials, 2005,33:48).But, because these linking agents itself are exactly the stronger material of toxicity, human body there is very big toxic side effect, there is not actual medicament using value.Dialdehyde starch is the oxidation of starch product, is a kind of natural polymer dialdehyde linking agent, and human body is had no side effect, and has been widely used in weaving, medicine, field of food.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who human body is had no side effect, has the pH sensitive carboxymethyl chitosan hydrogel of good biocompatibility.
To achieve these goals, technical scheme provided by the invention is: the preparation method of pH sensitive carboxymethyl chitosan hydrogel, it is characterized in that comprising the steps: with concentration is that carboxymethyl chitosan sugar aqueous solution and the concentration of 1-4% (weight ratio) is 1-6% (weight ratio) the dialdehyde starch aqueous solution according to weight ratio 1: 0.5-5.0 mixes, mixed solution stirs under 30-60 ℃, after vacuum defoamation, room temperature leaves standstill and became glue in 6-36 hour, with deionized water wash, vacuum-drying is to constant weight, and the gained xerogel is the pH sensitive carboxymethyl chitosan hydrogel.
Described concentration is the preparation of the carboxymethyl chitosan sugar aqueous solution of 1-4% (weight ratio): with the degree of substitution by carboxymethyl of cm-chitosan is that 0.4-1.8, viscosity-average molecular weight are 3.0 * 10
5-6.0 * 10
5Cm-chitosan be added to the water, wherein the weight ratio of cm-chitosan and water is 1-4%, stirs down in 40-100 ℃, filters, and discards filter residue, concentration be the carboxymethyl chitosan sugar aqueous solution of 1-4% (weight ratio).
Described concentration is the preparation of 1-6% (weight ratio) the dialdehyde starch aqueous solution: with oxidisability is that the dialdehyde starch of 30-80% is added to the water, wherein the weight ratio of dialdehyde starch and water is=1-6%, stir down in 30-100 ℃, filter, discard filter residue, getting concentration is 1-6% (weight ratio) the dialdehyde starch aqueous solution.
Described dialdehyde starch is W-Gum, yam starch or tapioca (flour).
Measure the swelling ratio (SR) of pH sensitive carboxymethyl chitosan hydrogel in different pH value buffered soln that the present invention obtains swelling kinetics with weighting method with the investigation hydrogel: drying completely hydrogel place the molten damping fluid of a series of different pH values (1.0,3.0,5.0,7.4,9.0,11.0,13.0), after for some time, take out, blot hydrogel surface moisture with filter paper, this process proceed to weigh continuously for three times by the weight of swollen hydrogel constant till.Be calculated as follows its equilibrium swelling rate: SR=100 (W-W
0)/W
0Wherein, W
0Be the xerogel quality (g) before the swelling; The total mass of hydrogel (g) when W is swelling equilibrium.The result shows that prepared a series of hydrogels all have tangible pH responsiveness, near swelling capacity minimum iso-electric point, and when departing from iso-electric point, swelling capacity obviously increases.
Because still exist in this hydrogel molecular structure a large amount of facile hydrolysiss or protonated COOH ,-NH
2,-OH etc., dissociating of these groups is subjected to the influence of extraneous pH, its ionization difference in different pH value liquid: carboxyl ionization during at higher pH, amino ionization when the low pH of pH; The wetting ability of formed group is also different: when extraneous pH changed, the corresponding change of the dissociation degree of these groups caused inside and outside ionic concn to change; In addition, dissociating of these groups also can destroy corresponding hydrogen bond in the gel, and the cross-linking set of gel network is reduced, and causes gel network structure to change, and causes gel swelling.Thereby its swelling behavior has special pH susceptibility.
The invention has the beneficial effects as follows: being to adopt dialdehyde starch to make linking agent, because dialdehyde starch is the oxidation of starch product, is a kind of natural polymer dialdehyde linking agent, and human body is had no side effect; And cm-chitosan is a chitosan derivatives, and it has excellent biological compatibility, wetting ability, biodegradable.Therefore the product of the present invention's preparation is except having no side effect, have human body the good biocompatibility, and test finds that its swelling property also has good pH susceptibility through swelling behavior, can be used for the slow control delivery of oral pharmaceutical.
Description of drawings
Fig. 1 is the infrared spectrogram of the prepared pH sensitive carboxymethyl chitosan hydrogel of the present invention
Fig. 2 is the pH-swelling ratio graphic representation of the prepared pH sensitive carboxymethyl chitosan hydrogel of embodiment 1
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
With degree of substitution by carboxymethyl is 0.6, and viscosity-average molecular weight is 3.5 * 10
5Cm-chitosan 5.0 gram join in 125 ml distilled waters, 70 ℃ are stirred down until whole dissolvings, the clarification carboxymethyl chitosan sugar aqueous solution of 4% (weight ratio); With oxidisability is that 60% dialdehyde starch, 10.0 grams join in 200 milliliters of (i.e. 200 grams) water, and 60 ℃ are stirred down and make its dissolving as far as possible, filter, and get 5% (weight ratio) dialdehyde starch aqueous solution.Is 50 ℃ under to mix reaction 5 hour at 1: 0.5 with above-mentioned carboxymethyl chitosan sugar aqueous solution and the dialdehyde starch aqueous solution according to weight ratio, after vacuum defoamation, transfers in the test tube, and room temperature leaves standstill and became glue in 15 hours; Hydrogel with preparation takes out from test tube then, uses the deionized water thorough washing, puts into vacuum drying oven and is dried to constant weight, obtains pH sensitive carboxymethyl chitosan hydrogel (being called for short hydrogel CMCD-1).Described dialdehyde starch is a W-Gum.
Drying completely hydrogel CMCD-1 place the molten damping fluid of a series of different pH values (1.0,3.0,5.0,7.4,9.0,11.0,13.0), after for some time, take out, blot hydrogel surface moisture with filter paper, this process proceed to weigh continuously for three times by the weight of swollen hydrogel constant till.Be calculated as follows its equilibrium swelling rate: SR=100 (W-W
0)/W
0Wherein, W
0Be the xerogel quality (g) before the swelling; The total mass of hydrogel (g) when W is swelling equilibrium.The result shows that prepared hydrogel CMCD-1 has tangible pH responsiveness, near swelling capacity minimum iso-electric point, and when departing from iso-electric point, swelling capacity obviously increases.
Embodiment 2:
With degree of substitution by carboxymethyl is 0.9, and viscosity-average molecular weight is 4.5 * 10
5Cm-chitosan 3.0 gram join in 100 ml waters, 60 ℃ are stirred down until whole dissolvings, the clarification carboxymethyl chitosan sugar aqueous solution of 3% (weight ratio); With oxidisability is that 66.8% dialdehyde starch, 10.0 grams join in 250 ml waters, and 50 ℃ are stirred down and make its dissolving as far as possible, filter, 4% (weight ratio) dialdehyde starch aqueous solution.Above-mentioned carboxymethyl chitosan sugar aqueous solution and the dialdehyde starch aqueous solution ratio according to 1: 1.5 (weight ratio) is fully mixed under 30 ℃, transfer in the test tube, vacuum defoamation, room temperature left standstill 18 hours; Hydrogel with preparation takes out from test tube then, uses the deionized water thorough washing, and vacuum-drying to constant weight obtains pH sensitive carboxymethyl chitosan hydrogel (being hydrogel CMCD-2).Described dialdehyde starch is a yam starch.
Measure and calculate equilibrium swelling rate under its different pH values according to the described method of embodiment 1.The result shows that prepared hydrogel CMCD-2 has tangible pH responsiveness, near swelling capacity minimum iso-electric point, and when departing from iso-electric point, swelling capacity obviously increases.
Embodiment 3:
With degree of substitution by carboxymethyl is 1.2, and viscosity-average molecular weight is 5.0 * 10
5Cm-chitosan 1.0 gram join in 100 ml waters, 40 ℃ are stirred down until whole dissolvings, the clarification carboxymethyl chitosan sugar aqueous solution of 1% (weight ratio); With oxidisability is that 50% dialdehyde starch, 15.0 grams join in 250 ml waters, and 80 ℃ are stirred down and make its dissolving as far as possible, filter, 6% (weight ratio) dialdehyde starch aqueous solution.Above-mentioned carboxymethyl chitosan sugar aqueous solution and the dialdehyde starch aqueous solution ratio according to 1: 3.0 (weight ratio) is fully mixed under 60 ℃, transfer in the test tube, vacuum defoamation, room temperature left standstill 24 hours; Hydrogel with preparation takes out from test tube then, uses the deionized water thorough washing, removes impurity, and vacuum-drying to constant weight gets pH sensitive carboxymethyl chitosan hydrogel (being hydrogel CMCD-3).Described dialdehyde starch is a tapioca (flour).
Measure and calculate equilibrium swelling rate under its different pH values according to the described method of embodiment 1.The result shows that prepared hydrogel CMCD-3 has tangible pH responsiveness, near swelling capacity minimum iso-electric point, and when departing from iso-electric point, swelling capacity obviously increases.
Embodiment 4:
With degree of substitution by carboxymethyl is 1.5, and viscosity-average molecular weight is 4.0 * 10
5Cm-chitosan 3.0 gram join in 150 ml waters, 40 ℃ are stirred down until whole dissolvings, the clarification carboxymethyl chitosan sugar aqueous solution of 2% (weight ratio); With oxidisability is that 40% dialdehyde starch, 6.0 grams join in 200 ml waters, and 50 ℃ are stirred down and make its dissolving as far as possible, filter, 3% (weight ratio) dialdehyde starch aqueous solution.Above-mentioned carboxymethyl chitosan sugar aqueous solution and the dialdehyde starch aqueous solution ratio according to 1: 5.0 (weight ratio) is fully mixed under 30 ℃, pour in the test tube, vacuum defoamation, room temperature left standstill 30 hours; Hydrogel with preparation takes out from test tube then, uses the deionized water thorough washing, and vacuum-drying to constant weight obtains pH sensitive carboxymethyl chitosan hydrogel (being hydrogel CMCD-4).Described dialdehyde starch is a W-Gum.
Measure and calculate equilibrium swelling rate under its different pH values according to the described method of embodiment 1.The result shows that prepared hydrogel CMCD-4 has tangible pH responsiveness, near swelling capacity minimum iso-electric point, and when departing from iso-electric point, swelling capacity obviously increases.
The bound value and the interval value of the processing parameter of the preparation of the preparation of carboxymethyl chitosan sugar aqueous solution of the present invention, the dialdehyde starch aqueous solution can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (4)
1.pH the preparation method of sensitive carboxymethyl chitosan hydrogel, it is characterized in that comprising the steps: with concentration is that carboxymethyl chitosan sugar aqueous solution and the concentration of 1-4% (weight ratio) is 1-6% (weight ratio) the dialdehyde starch aqueous solution according to weight ratio 1: 0.5-5.0 mixes, mixed solution stirs under 30-60 ℃, after vacuum defoamation, room temperature leaves standstill and became glue in 6-36 hour, with deionized water wash, vacuum-drying gets the pH sensitive carboxymethyl chitosan hydrogel to constant weight.
2. the preparation method of pH sensitive carboxymethyl chitosan hydrogel according to claim 1 is characterized in that: described concentration is the preparation of the carboxymethyl chitosan sugar aqueous solution of 1-4% (weight ratio): with the degree of substitution by carboxymethyl of cm-chitosan is that 0.4-1.8, viscosity-average molecular weight are 3.0 * 10
5-6.0 * 10
5Cm-chitosan be added to the water, wherein the weight ratio of cm-chitosan and water is 1-4%, stirs down in 40-100 ℃, filters, and discards filter residue, concentration be the carboxymethyl chitosan sugar aqueous solution of 1-4% (weight ratio).
3. the preparation method of pH sensitive carboxymethyl chitosan hydrogel according to claim 1, it is characterized in that: described concentration is the preparation of 1-6% (weight ratio) the dialdehyde starch aqueous solution: with oxidisability is that the dialdehyde starch of 30-80% is added to the water, wherein the weight ratio of dialdehyde starch and water is=1-6%, stir down in 30-100 ℃, filter, discard filter residue, getting concentration is 1-6% (weight ratio) the dialdehyde starch aqueous solution.
4. the preparation method of pH sensitive carboxymethyl chitosan hydrogel according to claim 3 is characterized in that: described dialdehyde starch is W-Gum, yam starch or tapioca (flour).
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| CN101209354B (en) * | 2007-12-25 | 2010-06-02 | 青岛博益特生物材料有限公司 | Medical blood-stopping healing agent for wound-surface and uses thereof |
| CN101830992B (en) * | 2010-04-03 | 2012-01-25 | 大连理工大学 | PH-/temperature dual-sensitive starch derivative and preparation method thereof |
| CN101831005B (en) * | 2010-04-27 | 2012-08-15 | 中国药科大学 | PH sensitive type chitosan derivant and application thereof in pharmaceutics |
| CN103450364B (en) * | 2013-09-03 | 2016-03-16 | 华中农业大学 | Carboxymethyl starch with high substitution degree and composite aquogel, preparation method and application |
| CN105011343B (en) * | 2015-05-27 | 2018-01-19 | 青岛农业大学 | A kind of intestinal-specific pH sensitiveness condenses microcapsule delivery system and preparation method and application again |
| CN106046397A (en) * | 2016-06-28 | 2016-10-26 | 深圳市阳光之路生物材料科技有限公司 | Joint lubricating material and preparation method thereof |
| CN106109400A (en) * | 2016-07-22 | 2016-11-16 | 金陵科技学院 | A kind of oral drugs hydrogel slow-released carrier and preparation method and applications |
| CN106220325B (en) * | 2016-07-25 | 2019-04-05 | 合肥工业大学 | A kind of water-fast degradable plant nutrition slow-release material and preparation method thereof |
| CN106430395A (en) * | 2016-08-27 | 2017-02-22 | 武汉理工大学 | Method of using hydrogel to adsorb heavy metals in water |
| CN106860871A (en) * | 2017-01-09 | 2017-06-20 | 安徽大学 | Preparation method of carboxymethyl chitosan pH sensitive hydrogel drug carrier |
| CN109957118B (en) * | 2019-04-11 | 2022-05-13 | 闽江学院 | Construction method of pH response type biomass nano composite hydrogel |
| CN110754651A (en) * | 2019-10-30 | 2020-02-07 | 武汉轻工大学 | Preparation method of starch gel food additive |
| CN110917123A (en) * | 2019-11-19 | 2020-03-27 | 南京大学射阳高新技术研究院 | Preparation and application of medical biodegradable isolation adhesive |
| CN113248800A (en) * | 2021-05-24 | 2021-08-13 | 广州市尚信净化工程有限公司 | Carboxymethylated carrageenan gel and preparation method thereof |
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