CN110183687A - A kind of compound hydrogel material and the preparation method and application thereof - Google Patents
A kind of compound hydrogel material and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110183687A CN110183687A CN201910347712.3A CN201910347712A CN110183687A CN 110183687 A CN110183687 A CN 110183687A CN 201910347712 A CN201910347712 A CN 201910347712A CN 110183687 A CN110183687 A CN 110183687A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- hydrogel
- hydrogel material
- ionic liquid
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0052—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/0066—Medicaments; Biocides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/009—Materials resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/602—Type of release, e.g. controlled, sustained, slow
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
Abstract
The invention discloses a kind of compound hydrogel materials and the preparation method and application thereof.Composite hydrogel prepared by the present invention has accurate and suitable swollen performance, it can keep the stabilization of structure for a long time in water, and the absorption of methylene blue is tested and is shown: its equilibrium adsorption capacities is up to 6.9mg/g, this illustrates that compound hydrogel material of the invention has very excellent Drug loading capacity, and there is good slow release effect to methylene blue, different drugs can be embedded in composite hydrogel as needed simultaneously, drug is slowly constantly discharged by diffusion and the degradation of hydrogel, acting on diseased region can promote the healing of wound or weakens the feeling of pain of wound, and hydrogel will not have an effect with wound, the diffusate of wound can be discharged by hydrogel, and its transparent characteristic at any time observes the healing state of wound through gel convenient for patient and doctor.
Description
Technical field
The invention belongs to field of compound material more particularly to a kind of compound hydrogel material and the preparation method and application thereof.
Background technique
Medical dressing is a kind of medical material that provisional covering is carried out to various wounds, wound surface, most important
Function is to provide the environment for being conducive to wound healing: protection wound controls the diffusate of wound, avoids bacterium and dust pollution.
Ideal medical dressing need to have following functions: (1) good biocompatibility, and moisture and the excessive of body fluid can be prevented to scatter and disappear；
(2) with surface of a wound good fit, and dressing will not stick together with wound when removing, and be avoided that the replacement secondary damage of dressing bring
Wound；(3) invasion for resisting bacterium and particulates emission prevents from infecting；(4) there is suitable swollen performance, moisture-inhibiting, ventilative, absorption
Contact surface is able to maintain certain humidity while extra exudate, mitigates wound pain；(5) good mechanical performance, can be to increasing
Cell colonization provides support.Above-mentioned requirements can be fully achieved there is presently no dressing, traditional dressing is inertia dressing, mainly by
Medical absorbent cotton gauze is mostly process by cotton, lint and linen, is made to the healing of the surface of a wound without significantly promotion
With.
Aerogel dressing is a kind of novel wound dressing developed in recent years.The characteristics of hydrogel be have it is good
Biocompatibility and water-retaining property cause vast concern in the past few decades.Since hydrogel has and extracellular base
The ability of the similitude of matter and the interaction of intrinsic cell, they have been widely studied for biomedical applications.Therefore, water
Gel has certain prospect as wound healing material.The material for preparing hydrogel at present mainly has synthesis macromolecule and natural
Macromolecule, synthesis high molecular material have the shortcomings that it is some obvious, such as: poor biocompatibility, chronic toxicity be high, immune resistance
By force, mechanical strength and toughness are insufficient, and natural polymer has source abundant, high degradability and good biology
The properties such as compatibility are the primary raw materials for preparing hydrogel.Cellulose is as active natural polymer using wide in hydrogel
The drugloading rate of general but current cellulose aquagel material is too low, and since there are very excellent water absorbing properties to cause for it
Its application with when medical dressing due to its swollen performance is excessively good and the problem of squeeze normal surrounding tissue so that its application is limited.
Have the advantages of existing medical aquogel therefore, it is necessary to develop one kind while there is more high drug load and suitable
Swollen performance hydrogel material to be pushed further into application of the hydrogel in medical material.
Summary of the invention
The purpose of the present invention is to provide a kind of compound hydrogel materials and the preparation method and application thereof.
The technical solution used in the present invention is:
One of the objects of the present invention is to provide a kind of compound hydrogel material, which includes cellulose and calabash
Lubrajel.
Preferably, the mass ratio of above-mentioned cellulose and trigonella bean gum is (1~5): 1；More preferably (1.5~2.5): 1.
Preferably, above-mentioned cellulose is selected from microcrystalline cellulose.
Microcrystalline cellulose is the knot formed by making cellulosic degree of polymerization reach capacity the degree of polymerization after dilute acid hydrolysis cellulose
Crystalline flour end, large specific surface area also have unique rheological behavior, excellent mechanical property.
It is highly preferred that above-mentioned microcrystalline cellulose is selected from tealeaves microcrystalline cellulose, corn microcrystalline cellulose, oat microcrystalline cellulose
At least one of element, soybean microcrystalline cellulose, apple microcrystalline cellulose.
Another object of the present invention is to provide the preparation methods of above-mentioned compound hydrogel material, include the following steps:
1) by cellulose dissolution in ionic liquid, cellulose solution is obtained；
2) trigonella bean gum is added in cellulose solution, obtains mixed solution A；
3) it will be washed after mixed solution A cooling, be freeze-dried to obtain compound hydrogel material afterwards.
Preferably, the mass ratio of cellulose described in step 1) and ionic liquid is 1:(15~30)；Preferably 1:(15~
25)；More preferably 1:20.
Preferably, the solution temperature of cellulose is 90~120 DEG C in step 1)；More preferably 95~105 DEG C.
Preferably, the dissolution time of step 1) is 0.5~8h；Preferably 1~5h；More preferably 2~3h.
Preferably, step 1) further includes the steps that being stirred；Preferably, mixing speed is 100~200rpm/min.
Preferably, step 2) also includes the steps that being stirred；Preferably, the same step 1) of mixing speed in step 2).
Preferably, the mixing time in step 2) is 1~8h；More preferably 3~5h.
Preferably, the same step 1) of temperature of trigonella bean gum is added in step 2).
Preferably, mixed solution A is cooled to room temperature by step 3).
Preferably, step 3) is washed using polar solvent or its aqueous solution.
Preferably, step 3) carries out washing by soaking using polar solvent or its aqueous solution, washs to hydrogel volume no longer
Variation, it is preferable that the time for carrying out washing by soaking every time is 0.5~15 day.
Preferably, the freeze-drying temperature in step 3) is -30~-50 DEG C；It is highly preferred that freeze-drying temperature is -40
℃。
Preferably, the time of the freeze-drying in step 3) is 0.5~5 day；Preferably 1~3 day；More preferably 2 days.
Preferably, above-mentioned polar solvent is in water, alcohols, nitrile, amides, sulfoxide type, sulfone class, water-soluble alcohol ethers
At least one.
Preferably, the volume ratio of polar solvent and aqueous solution is (1~5): (5~1) in the aqueous solution of polar solvent；It is more excellent
It is selected as 1:1.
Preferably, above-mentioned polar solvent is selected from water or alcohols；Preferably, above-mentioned alcohols is in isopropanol, methanol, ethyl alcohol
At least one；It is highly preferred that above-mentioned alcohols is selected from isopropanol.
Preferably, above-mentioned ionic liquid is selected from [AMIm] Cl ionic liquid, [Bdmim] Cl ionic liquid, [R1R2mim]Cl
Ionic liquid, [C2Mim] Br ionic liquid, at least one of [Hemim] Br ionic liquid.
Since [AMIm] Cl ionic liquid has aggregate velocity fast, reaction condition is mild, high conversion rate, stable excellent of property
Point, therefore above-mentioned ionic liquid is more preferably [AMIm] Cl ionic liquid.
The present invention also provides application of the above-mentioned compound hydrogel material in medical material.
Preferably, above-mentioned medical material is medical dressing material.
The beneficial effects of the present invention are:
1, the present invention prepares compound hydrogel material using cellulose and trigonella bean gum, and cellulose and trigonella bean gum have very
Compatibility between good substance, while the two is with good chemical combination stability and biological degradability, so that compound water congealing glue material
Material has hypotoxicity, meanwhile, the addition of trigonella bean gum also can in raising system polymer concentration, reduce water loss, and
The intensity of hydrogel backbone is enhanced, to enhance the slow release effect of drug.
2, composite hydrogel prepared by the present invention has accurate and suitable swollen performance, can keep for a long time in water
The stabilization of structure, and the absorption of methylene blue is tested and is shown: for its equilibrium adsorption capacities up to 6.9mg/g, this illustrates this
The compound hydrogel material of invention has very excellent Drug loading capacity, and has good slow release effect to methylene blue, together
When different drugs can be embedded in composite hydrogel as needed, drug is slowly held by diffusion and the degradation of hydrogel
It discharges continuously, acting on diseased region can promote the healing of wound or weaken the feeling of pain of wound, and hydrogel will not be with wound
Have an effect, the diffusate of wound can be discharged by hydrogel, while its transparent characteristic convenient for patient and doctor through gel with
When the healing state of wound is observed.
Detailed description of the invention
Fig. 1: a compound hydrogel material outside drawing prepared for embodiment 1；B is outside hydrogel material prepared by comparative example 1
See figure；
The SEM that Fig. 2: a is tealeaves microcrystalline cellulose, b is trigonella bean gum, c is compound hydrogel material prepared by embodiment 1
Figure；
The compound hydrogel material that Fig. 3: a is tealeaves microcrystalline cellulose, b is trigonella bean gum, c is the preparation of embodiment 1
FTIR figure；
The XRD that Fig. 4: a is tealeaves microcrystalline cellulose, b is trigonella bean gum, c is compound hydrogel material prepared by embodiment 1
Figure；
The heat that Fig. 5: a is tealeaves microcrystalline cellulose, b is trigonella bean gum, c is compound hydrogel material prepared by embodiment 1
Weight curve graph and differential hot weight curve；
The moisture expansivity of the hydrogel material of compound hydrogel material and the preparation of comparative example 1 that Fig. 6 is prepared for embodiment 1 is at any time
Between change curve；
The hydrogel material of compound hydrogel material and the preparation of comparative example 1 that Fig. 7 is prepared for embodiment 1 is to methylene blue
Adsorption capacity versus time curve figure；
The hydrogel material of compound hydrogel material and the preparation of comparative example 1 that Fig. 8 is prepared for embodiment 1 is to methylene blue
Release rate (release drug rate) versus time curve figure；
The cell growth state figure of Fig. 9: a composite hydrogel prepared for embodiment 1；B is hydrogel prepared by comparative example 1
Cell growth state figure.
Specific embodiment
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art are according to the present invention
Some nonessential modifications and adaptations that the principle of elaboration is made all belong to the scope of protection of the present invention.Following specific works of example
Skill parameter etc. is also only an example in OK range, i.e. those skilled in the art can do suitable model by the explanation of this paper
Interior selection is enclosed, and does not really want to be defined in hereafter exemplary specific data.
Embodiment 1
A kind of compound hydrogel material is made of tealeaves microcrystalline cellulose and trigonella bean gum.
A kind of preparation method of compound hydrogel material, comprising the following steps:
1) weigh 0.50g tealeaves cellulose in test tube, be added 10.0g [AMIm] Cl ionic liquid, after in constant temperature magnetic force
3h is stirred persistently with the mixing speed of 200rpm/min at 100 DEG C in stirring oil bath pan, obtains tealeaves microcrystalline cellulose solution；
2) 0.3g trigonella bean gum is added in tealeaves microcrystalline cellulose solution, continues stirring with 200rpm/min at 100 DEG C
It mixes speed and persistently stirs 5h, obtain mixed solution A；
3) test tube is taken out and is cooled to room temperature from oil bath pan, isopropanol water solution (isopropanol is added in backward test tube
It is 1:1 with the volume ratio of water), 10d is impregnated, when the volume for observing composite hydrogel becomes smaller, by composite hydrogel from test tube
In be transferred to beaker, continue to impregnate 8d with new isopropanol water solution, after with the abundant washing by soaking of deionized water completely in -40 DEG C
Compound hydrogel material is obtained after freeze-drying 2d.
Embodiment 2
A kind of compound hydrogel material is made of corn microcrystalline cellulose and trigonella bean gum.
A kind of preparation method of compound hydrogel material, comprising the following steps:
1) 0.50g corn microcrystalline cellulose is weighed in test tube, and 10.0g [AMIm] Cl ionic liquid, rear Yu Hengwen is added
2h is stirred persistently with the mixing speed of 180rpm/min at 95 DEG C in magnetic agitation oil bath pan, it is molten to obtain corn microcrystalline cellulose
Liquid；
2) 0.1g trigonella bean gum is added in corn microcrystalline cellulose solution, continues stirring with 180rpm/min at 100 DEG C
It mixes speed and persistently stirs 4h, obtain mixed solution A；
3) test tube is taken out and is cooled to room temperature from oil bath pan, isopropanol water solution (isopropanol is added in backward test tube
It is 1:1 with the volume ratio of water), 10d is impregnated, when the volume for observing composite hydrogel becomes smaller, by composite hydrogel from test tube
In be transferred to beaker, continue to impregnate 6d with new isopropanol water solution, after with the abundant washing by soaking of deionized water completely in -40 DEG C
Compound hydrogel material is obtained after freeze-drying 2d.
Embodiment 3
A kind of compound hydrogel material is made of oat microcrystalline cellulose and trigonella bean gum.
A kind of preparation method of compound hydrogel material, comprising the following steps:
1) weigh 0.50 oat microcrystalline cellulose in test tube, be added 10.0g [AMIm] Cl ionic liquid, after in constant temperature magnetic
2h is stirred persistently with the mixing speed of 100rpm/min at 102 DEG C in power stirring oil bath pan, obtains oat microcrystalline cellulose solution；
2) 0.4g trigonella bean gum is added in oat microcrystalline cellulose solution, continues stirring with 100rpm/min at 100 DEG C
It mixes speed and persistently stirs 4h, obtain mixed solution A；
3) test tube is taken out and is cooled to room temperature from oil bath pan, isopropanol water solution (isopropanol is added in backward test tube
It is 1:1 with the volume ratio of water), 14d is impregnated, when the volume for observing composite hydrogel becomes smaller, by composite hydrogel from test tube
In be transferred to beaker, continue to impregnate 10d with new isopropanol water solution, after with the abundant washing by soaking of deionized water completely in -40
DEG C freeze-drying 2d after obtain compound hydrogel material.
Comparative example 1
A kind of hydrogel material is made of tealeaves microcrystalline cellulose.
The preparation method is the same as that of Example 1 for hydrogel material in comparative example 1, the difference is that: do not include in comparative example 1
Trigonella bean gum.
1, the form and pattern of compound hydrogel material:
Compound hydrogel material that embodiment 1 is prepared, cellulose aquagel carry out macroscopic observation, the result is shown in Figure 1,
Simultaneously it is prepared by embodiment 1 compound hydrogel material, tealeaves microcrystalline cellulose, trigonella bean gum milling metal spraying after, in scanning electricity
Observation comparison is carried out to its microscopic appearance under mirror (SEM), as a result sees Fig. 2；
From Fig. 1 (a): transparent characteristic, water prepared by comparative example 1 is presented in compound hydrogel material prepared by the present invention
Gel is slightly in yellow (Fig. 1 b).
As shown in Figure 2: tealeaves microcrystalline cellulose surface is smooth (Fig. 2 a), and trigonella bean gum is then in a strip shape, and there are biggish skies
Gap (Fig. 2 b), and compound hydrogel material be then in it is streak, have apparent protrusion and less hole (Fig. 2 c).
Meanwhile the composite hydrogel that implementation 2-3 is prepared also has above-mentioned form and pattern.
2, infrared (FTIR) spectrum test of Fourier:
Compound hydrogel material prepared by embodiment 1, tealeaves microcrystalline cellulose, trigonella bean gum carry out Fourier's infrared light
Spectrum test, is measured, 4000~400cm of scanning range using KBr pressed disc method-1, resolution ratio 2cm-1, as a result see Fig. 3；
From Fig. 3 a: tealeaves microcrystalline cellulose is in 3423cm-1There is the stretching vibration peak of intramolecular hydroxyl O-H in place,
2922cm-1Be then methyl, in methylene and methine C-H stretching vibration peak, 1654cm-1For C=O stretching vibration peak,
1401cm-1It is nearby-CH2Scissoring vibration absorption peak, be the characteristic peak of cellulosic structure, 1159cm-1The peak at place is cellulose
Characteristic absorption peak caused by the vibration of upper C-O, 1069cm-1Place is the absorption peak of C-O, 897cm-1Place is C-1 group vibrational frequency
Place, the above results are consistent with document report；
From Fig. 3 b: trigonella bean gum is in 500~4000cm-1With the characteristic absorption peak of carbohydrate in range.3425cm-1
The absorption peak that place occurs is the stretching vibration peak of intramolecular or intermolecular O-H, in 2923cm-1And 2852cm-1Neighbouring absorption peak
It is to be caused by C-H stretching vibration, but this absorption peak usually cover by the broad peak caused by O-H stretching vibration, 1629cm-1Place
Strong absworption peak is then the asymmetric stretching vibration of carboxylate (- COO), while being also the absorption peak of the hyrate sample of sugar.1300
~1000cm-1Between absorption peak be as caused by C-O stretching vibration, one of which belongs to C-O-H and glucosides in saccharide ring
Key C-O-C, C-O-H and C-O-R another then that belong to GalA carboxyl；
From Fig. 3 c: composite hydrogel presents the characteristic peak of cellulose and trigonella bean gum, this illustrates ionic liquid pair
There is no derivative reaction occurs during the heating for dissolving of cellulose and trigonella bean gum, dissolution, and cellulose are only played
Also there is no chemical reactions with trigonella bean gum.
3, X-ray diffraction (XRD) is tested:
Compound hydrogel material prepared by embodiment 1, tealeaves microcrystalline cellulose, trigonella bean gum carry out XRD analysis, specifically
Condition are as follows: copper target, incident ray wavelength 0.15418nm, Ni filter plate, pipe press 40kV, Guan Liu 40mA, 5~60 ° of scanning angle range
0.04 ° of scanning step, scanning speed 38.4s/step, DS=0.5 ° of slit, RS=8mm (corresponding LynxExe detector array),
As a result see Fig. 4；
It is generally acknowledged that the crystal form of cellulose is broadly divided into: the crystallization of cellulose type I type and cellulose II type crystallize, wherein fiber
For the characteristic diffraction peak of plain I type crystallization near 2 θ=22.6 °, the characteristic diffraction peak of cellulose II type crystallization is attached in 2 θ=20.8 °
Closely.From Fig. 4 a: being 13.8 °, 22.1 ° in 2 θ of the angle of diffraction and obvious diffraction maximum, the diffraction maximum pair of 2 θ=13.8 ° nearby occur
(101) crystal face is answered, corresponding (002) crystal face of the main peak of 2 θ=22.1 ° is almost the same with the characteristic peak positions of cellulose crystal form I,
There are many small peaks in position in him, illustrates to contain amorphous component in cellulose.
From Fig. 4 b: nearby there is diffusing scattering peak in 2 θ=20.1 ° in trigonella bean gum, indicates that there are certain crystalline substances in structure
Body region, but the regularity of molecules align is poor.
From Fig. 4 c: when cellulose dissolution is in ionic liquid [AMIm] Cl, and being blended with trigonella bean gum, prepare Compound Water
After gel, diffraction maximum and cellulose are closer to, this illustrates the property of composite hydrogel closer to fine to a certain extent
Dimension element, meanwhile, nearby there is the stronger peak crystallization of relative narrower in 2 θ=14.1 ° in product, this explanation is blended compound in the two
Crystalline order in object is higher, this also illustrates it with stronger stability, intensity, hardness and rigidity.
4, thermogravimetric analysis (TG):
Thermogravimetric analysis refers to that the quality that sample is measured under program control temperature to the dependence of temperature, can be used for judging material
The thermal stability and purity of material weigh compound hydrogel material, tealeaves crystallite prepared by the dry embodiment 1 of 7~10mg respectively
Cellulose, trigonella bean gum are in thermogravimetric analyzer, thermogravimetric analysis condition are as follows: nitrogen flow 25mL/min, heating rate 20
DEG C/min, temperature range is 30~600 DEG C, as a result sees Fig. 5；
From Fig. 5 a and 5b: tealeaves microcrystalline cellulose and trigonella bean gum have obviously weightless platform, and first loses
Galassing platform appears in the position less than 200 DEG C, be by the low-boiling point materials such as water volatilization caused by as the temperature rises,
200~400 DEG C have a weightless slope sharply, this is mainly caused by material itself is thermally decomposed, from Fig. 5 c: Compound Water
Just there is apparent weightlessness effect within the temperature range of being greater than 200 DEG C in gel rubber material, and weight-loss ratio is lower than tea when final balance
Leaf microcrystalline cellulose and trigonella bean gum, this illustrates that compound hydrogel material has apparent water lock effect, the partial heat of Cong Tuzhong
Weight curve is it is found that the thermal stability of composite hydrogel is higher than cellulose and trigonella bean gum.
5, swollen performance and water conservation are tested:
Using the moisture expansivity of conventional gravimetry measurement compound hydrogel material.Precise has been dried in beaker
Hydrogel in the embodiment 1 of weight in compound hydrogel material and comparative example 1, is added a large amount of deionized waters, impregnates at room temperature,
At interval of certain time (t) from the hydrogel in the compound hydrogel material or comparative example 1 taken out in water in embodiment 1, it is used in combination
Filter paper wipes dry colloid surface moisture and weighs, according to formula: moisture expansivity (%)=(ms-md)/md* 100%, wherein msFor
Balance the quality (g) of hydrogel under swollen state；mdFor the quality (g) of dried hydrogel before swollen, compound water congealing glue material is calculated
The moisture expansivity of material, and curve is drawn, as a result see Fig. 6；
As shown in Figure 6: either compound hydrogel material or hydrogel material are shown fast in initial 5min
The phenomenon that speed water suction swollen, but the hydrogel material in comparative example 1 is rapidly reached equilibrium state after 5min, and balance moisture expansivity is about
It is 400%, its weight is initial 3~4 times at this time, and the compound hydrogel material in embodiment 1 is after impregnating 30min,
The trend slowly risen is presented in moisture expansivity, equilibrium state is reached after 100min, balance moisture expansivity is about 180%, its is heavy at this time
Amount is initial 1.45 times, it can be seen that, the compound hydrogel material of embodiment 1 can significantly reduce the moisture expansivity of hydrogel,
Medical dressing field has a good application prospect, and just reaches constant-quality after placing 14d, shows good water conservation effect
Fruit is conducive to keep the surface of a wound wet, and 1 dehydration of comparative example is very fast, and in 10d, weight just remains unchanged substantially, percentage of water loss compared with
Greatly, it is detailed in the following table 1:
The water retention property of table 1 embodiment 1 and comparative example 1
6, medicine and Drug Releasing Test are carried:
(1) it draws methylene blue standard curve: accurately weighing 0.0500g methylene blue and be dissolved in deionized water and determine
Hold to 100mL and obtains concentration as 500mg/L methylene blue standard solution.Then by above-mentioned solution be diluted to concentration gradient be 1mg/L,
The standard solution of 2mg/L, 3mg/L, 4mg/L, 5mg/L.Its light absorption value at 665nm is measured with visible spectrophotometer, with
The concentration of methylene blue solution is abscissa, and corresponding light absorption value is ordinate, and the regression equation for obtaining standard curve is y=
0.0117x+0.1406, R2=0.9949.
(2) hydrogel sample in the composite hydrogel and comparative example 1 in sample 0.050g embodiment 1 is accurately weighed respectively
In 50mL centrifuge tube, 100.0mg/L methylene blue solution 25.0mL is added.It places, samples at regular intervals at room temperature, survey
Determine light absorption value of the solution at 665nm, the remaining content of Methylene Blue in Solution is calculated by methylene blue standard curve.Sample
Product are to the adsorption capacity of methylene blue according to formula: adsorption capacity=(C0-Ct) V/m, in formula, C0For the first of methylene blue solution
Beginning concentration (mg/L)；CtThe concentration (mg/L) for being methylene blue solution in t moment；V is the volume (mL) of methylene blue solution；
M is that the quality (g) of hydrogel before carrying medicine calculates sample to the adsorption capacity of methylene blue, and draws curve, as a result sees Fig. 7:
As shown in Figure 7: the composite hydrogel of this implementation 1 is higher to the adsorption capacity of methylene blue, and adsorption capacity may be up to
6.90 ± 0.36mg/g, and it is higher than comparative example 1, this illustrates that composite hydrogel of the invention can be improved the absorption to methylene blue
Capacity, that is to say, that composite hydrogel of the invention has superior drugloading rate.
After carrying medicine, sample is taken out, flushed three times with deionized water and is weighed after drying to constant weight, conical flask is put into
In, 200mL deionized water is added as dissolution medium.5mL dissolution medium, measurement light absorption value and basis are drawn at regular intervals
Methylene blue solution standard curve calculates the concentration of methylene blue solution, discharges drug rate according to formula: release drug rate
(%)=(Wt/W0) × 100% calculates, in formula, WtMethylene blue total burst size (g) when for moment t；W0Before drug release
The quality (g) that methylene blue always loads, and corresponding curve is drawn, as a result see Fig. 8:
As shown in Figure 8: the rate of release of preceding 30min, the composite hydrogel Methylene Blue of the present embodiment 1 are very fast, then,
Release rate is in a basic balance, and the drug release ability of the composite hydrogel of embodiment 1 is better than comparative example 1.
7, biocompatibility test:
The composite hydrogel that embodiment 1 is prepared and hydrogel (control group) material prepared by comparative example 1 are laid on 6 holes
In plate, then for 24 hours, then with phosphate buffer rinsed repeatedly, until the ethanol solution on surface is washed with the molten leaching sterilization of 75% ethanol
Only, 3T3 cell is diluted to required cell number (about 10 with culture solution after5/ mL), it adds it in 6 orifice plates, after culture for 24 hours
Cellular morphology is observed under the microscope, as a result sees Fig. 9；
As shown in Figure 9: compound hydrogel material (Fig. 9 a) and the cell growth state of control group (Fig. 9 b) are close, form rule
Then, intracellular granular it is few, without vacuole, cell membrane is clear, this illustrate the compound hydrogel material in embodiment 1 have good life
Object compatibility.
Embodiment 2~3 is also with the said effect of embodiment 1.
Claims (10)
1. a kind of compound hydrogel material, it is characterised in that: the hydrogel material includes cellulose and trigonella bean gum.
2. compound hydrogel material according to claim 1, it is characterised in that: the quality of the cellulose and trigonella bean gum
Than for 1~5:1.
3. compound hydrogel material according to claim 1, it is characterised in that: the cellulose is selected from microcrystalline cellulose.
4. the preparation method of compound hydrogel material described in claims 1 to 3 any one, it is characterised in that: including as follows
Step:
1) by cellulose dissolution in ionic liquid, cellulose solution is obtained；
2) trigonella bean gum is added in cellulose solution, obtains mixed solution A；
3) it will be washed after mixed solution A cooling, be freeze-dried to obtain compound hydrogel material afterwards.
5. the preparation method according to claim 4, it is characterised in that: the matter of cellulose described in step 1) and ionic liquid
Amount is than being 1:15~30；Preferably, the solution temperature of cellulose is 90~120 DEG C in step 1)；Preferably, dissolution time is
0.5~8h.
6. the preparation method according to claim 4, it is characterised in that: mixed solution A is cooled to room temperature by step 3)；It is preferred that
Ground, step 3) are washed using polar solvent or its aqueous solution；Preferably, the freeze-drying temperature in step 3) be -30~-
50℃；Preferably, the time of freeze-drying is 0.5~5 day.
7. preparation method according to claim 6, it is characterised in that: the polar solvent is selected from water, alcohols, nitrile, acyl
At least one of amine, sulfoxide type, sulfone class, water-soluble alcohol ethers；Preferably, polar solvent and water in polar solvent aqueous solution
The volume ratio of solution is 1~5:5~1.
8. the preparation method according to claim 4, it is characterised in that: the ionic liquid is selected from [AMIm] Cl ionic liquid
Body, [Bdmim] Cl ionic liquid, [R1R2Mim] Cl ionic liquid, [C2Mim] Br ionic liquid, in [Hemim] Br ionic liquid
At least one.
9. application of the compound hydrogel material described in claims 1 to 3 any one in medical material.
10. application according to claim 9, it is characterised in that: the medical material is medical dressing material.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910347712.3A CN110183687A (en) | 2019-04-28 | 2019-04-28 | A kind of compound hydrogel material and the preparation method and application thereof |
| CN201911318303.7A CN110903497B (en) | 2019-04-28 | 2019-12-19 | Composite hydrogel material for stopping bleeding and promoting healing and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910347712.3A CN110183687A (en) | 2019-04-28 | 2019-04-28 | A kind of compound hydrogel material and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110183687A true CN110183687A (en) | 2019-08-30 |
Family
ID=67715231
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910347712.3A Pending CN110183687A (en) | 2019-04-28 | 2019-04-28 | A kind of compound hydrogel material and the preparation method and application thereof |
| CN201911318303.7A Active CN110903497B (en) | 2019-04-28 | 2019-12-19 | Composite hydrogel material for stopping bleeding and promoting healing and preparation method and application thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911318303.7A Active CN110903497B (en) | 2019-04-28 | 2019-12-19 | Composite hydrogel material for stopping bleeding and promoting healing and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN110183687A (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009132229A2 (en) * | 2008-04-24 | 2009-10-29 | Medtronic, Inc. | Cold ionizing radiation sterilization |
| CN103480033B (en) * | 2013-10-08 | 2015-10-28 | 江苏昌吉永生物科技有限公司 | A kind of medical bio polysaccharide hemostasia and healing sponge and preparation method thereof |
| CN105131317B (en) * | 2015-09-17 | 2018-06-29 | 华南理工大学 | Compound water congealing glued membrane and bamboo shoots leftover bits and pieces prepare method and the application of the aquagel membrane |
| ES2950114T3 (en) * | 2015-11-06 | 2023-10-05 | Ethicon Inc | Compacted hemostatic cellulosic aggregates |
| CN106390187A (en) * | 2016-09-26 | 2017-02-15 | 沈阳尚贤微创医疗器械股份有限公司 | Composite hemostatic sponge of microcrystalline cellulose and collagen and preparation method thereof |
| CN109224124B (en) * | 2018-11-21 | 2021-05-25 | 广州润虹医药科技股份有限公司 | Liquid dressing for stopping bleeding and promoting healing |
| CN110016160A (en) * | 2019-04-10 | 2019-07-16 | 南方医科大学 | A kind of preparation method of polysaccharide based aquagel |
-
2019
- 2019-04-28 CN CN201910347712.3A patent/CN110183687A/en active Pending
- 2019-12-19 CN CN201911318303.7A patent/CN110903497B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110903497B (en) | 2022-03-25 |
| CN110903497A (en) | 2020-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Biological properties of dialdehyde carboxymethyl cellulose crosslinked gelatin–PEG composite hydrogel fibers for wound dressings | |
| US11130823B2 (en) | Method for producing hydrogels | |
| DK2463308T3 (en) | Polymer hydrogels and their medical use | |
| US9162007B2 (en) | Superabsorbent polymer composite comprising a superabsorbent polymer and cellulosic nanofibrils | |
| CN103665439B (en) | With environmental response Nano bacteria cellulose composite material and preparation method and application | |
| CN111019162A (en) | Preparation method and application of chitosan polypeptide derivative self-crosslinking hydrogel taking oxidized hyaluronic acid as crosslinking agent | |
| CN109225077A (en) | A kind of nano-cellulose/gelatin-compounded aeroge and its application | |
| US11020421B2 (en) | Superabsorbent materials and methods of production thereof | |
| CN108409988B (en) | Preparation method of spongy macroporous polyvinyl alcohol hydrogel | |
| Yiğitoğlu et al. | Microwave-assisted synthesis of alginate-g-polyvinylpyrrolidone copolymer and its application in controlled drug release | |
| Zhang et al. | A novel candidate for wound dressing: Transparent porous maghemite/cellulose nanocomposite membranes with controlled release of doxorubicin from a simple approach | |
| CN107383397A (en) | To aoxidize hydroxyethyl cellulose as derivatives of hyaluronic acids self-crosslinking hydrogel of crosslinking agent and preparation method thereof | |
| CN106084302B (en) | Self-crosslinking hydroformylation nanometer bacteria cellulose functional porous material and preparation method | |
| Mondal et al. | Cellulosic hydrogels: a greener solution of sustainability | |
| KR101486224B1 (en) | Water absorbent resin containing the biopolymer useful for components of disposable diapers and preparation method thereof | |
| CN110016160A (en) | A kind of preparation method of polysaccharide based aquagel | |
| CN105295075A (en) | Preparation method of polyvinyl alcohol composite hydrogel with fast hydroscopicity, high swellbility and adjustable aperture sizes | |
| Li et al. | Construction of porous structure-based carboxymethyl chitosan/sodium alginate/tea polyphenols for wound dressing | |
| CN110183687A (en) | A kind of compound hydrogel material and the preparation method and application thereof | |
| Zhang et al. | Immobilization of derivatized dextran nanoparticles on konjac glucomannan/chitosan film as a novel wound dressing | |
| JP7352428B2 (en) | Absorbent resin particles and their manufacturing method | |
| CN114702704A (en) | Functional polymer film/hydrogel film based on one-way nanopore dehydration, and preparation method and device thereof | |
| CN106614649B (en) | A kind of preparation of the cyclodextrin inclusion compound and its wettable powder of cycloxaprid | |
| Fang et al. | Preparation and characterization of N-phthaloyl-chitosan-g-(PEO–PLA–PEO) as a potential drug carrier | |
| TW202037629A (en) | Crosslinking agent, preparation process and uses thereof, and hydrogel comprising crosslinking agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190830 |