CN103845757B - A kind of artificial articular cartilage material and preparation method thereof - Google Patents
A kind of artificial articular cartilage material and preparation method thereof Download PDFInfo
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- CN103845757B CN103845757B CN201310694865.8A CN201310694865A CN103845757B CN 103845757 B CN103845757 B CN 103845757B CN 201310694865 A CN201310694865 A CN 201310694865A CN 103845757 B CN103845757 B CN 103845757B
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Abstract
The invention discloses a kind of artificial articular cartilage material, relate to hydrogel soft materials chemistry and modify field, modify polyacrylamide-Sodium Alginate Hydrogel Films with graphene oxide and hydroxyapatite, and the PAM-ALG-GO-HA composite aquogel adopting Raolical polymerizable to prepare.Its preparation is: in homodisperse GO solution in advance, add acicular nanometer HA granule gradually form mixed aqueous solution, and add the correlated response agent of acrylamide monomer, ALG monomer and synthesis PAM-ALG hydrogel, adopt Raolical polymerizable to prepare PAM-ALG-GO-HA composite aquogel.The biological activity of two-dimensional structure and the functional group that has of surface and HA excellence that the present invention makes full use of GO nanometer sheet itself carries out chemical modification to PAM-ALG hydrogel, effectively improve mechanical property and the biological activity of PAM-ALG hydrogel, expand the range of application of PAM-ALG hydrogel, there is clear and definite scientific meaning and huge using value.
Description
Technical field
The present invention relates to a kind of hydrogel soft materials chemistry method of modifying, particularly relate to the preparation method of a kind of novel artificial articular cartilage material PAM-ALG-GO-HA.
Background technology
Along with the cross development of bionics and field of new, the new material research of bionical organization of human body processability excellence comes into one's own day by day.Smooth, resilient tissue-articular cartilage that one deck 2 ~ 7mm of human body knee joint surface coverage is thick; the pressure of the various high load capacities that energy grantee goes round and begins again in life and impact; natural life-span can up to 70 ~ 80 years; and joint can be made freely movable; vibrate produced energy when can absorb physical activity simultaneously, play the effect of buffering and Saving cortilage.And " goldstandard " of artificial knee joint replacement material is cobalt-base alloys and ultra-high molecular weight polyethylene at present, this standard only uses hard ultra-high molecular weight polyethylene as the material between prosthetic joint contact surface, the stress that can not effectively disperse joint to produce at the volley on the one hand, can cause implanting prosthetic to loosen and dislocation; On the other hand, Long-term Clinical Observation shows, and superhigh molecular weight polyethylene material meeting and surrounding metal alloy in long service process rub thus produce abrasive dust, and the wearing and tearing in late period of final artificial joint can be very serious.These failure phenomenons and current manual's joint designs do not have the natural structure of bionical human synovial, and not designing the defects such as articular cartilage has very large relation, so prepare novel artificial articular cartilage material to seem particularly necessary and urgent.
PAM-ALG novel hydrogels material is expected to obtain application in fields such as artificial cartilage, artificial-muscle and flexible robot's manufactures himself to be similar to the characteristics such as the micro-cavernous structure of natural cartilage, high water absorption and elasticity, good biocompatibility and certain self-regeneration function.But according to measuring and calculating, walk in motion the daily of people, the stress of knee joint place cartilage carrying is 1.2 ~ 7.2 times of body weight, the stress of hip joint place cartilage carrying is 2.5 ~ 5.8 times of body weight.Bearing under so high stress, this soft material is as artificial articular cartilage replacing material, and its mechanical property can't meet bears heavily stressed requirement to articular cartilage in human normal motor activity.Secondly, this soft material as other artificial soft tissue replacement materials such as artificial-muscles, although itself have strong biocompatibility because of its biological activity poor, can not integrate with surrounding tissue.So, be necessary to be improved further PAM-ALG hydrogel according to its concrete applied environment.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of artificial articular cartilage material and preparation method thereof, graphene oxide and hydroxyapatite is adopted to carry out chemical modification to polyacrylamide-Sodium Alginate Hydrogel Films, give full play to the feature that Hydrogels is similar to native articular cartilage, with the HA of the GO nanometer sheet and good biological activity with excellent mechanical performance, chemical modification is carried out to PAM-ALG hydrogel, effectively improve mechanical property and the biological activity of PAM-ALG hydrogel.
In order to solve the problems of the technologies described above, a kind of artificial articular cartilage material of the present invention, it is characterized in that, polyacrylamide-Sodium Alginate Hydrogel Films is modified with graphene oxide and hydroxyapatite, and the polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel adopting Raolical polymerizable to prepare.
The preparation method of a kind of artificial articular cartilage material of the present invention, comprises the following steps:
Preparation stannic oxide/graphene nano sheet aqueous solution, supersound process, makes stannic oxide/graphene nano sheet solution temperature remain on 10-50 DEG C of scope;
Be that the needle nano-hydroxy apatite even particulate dispersion of 10-1000nm is in stannic oxide/graphene nano sheet aqueous solution by granularity, in mixed process, aqueous temperature scope control, at 10-80 DEG C, after Homogeneous phase mixing, obtains hydroxyapatite and the stable mixed aqueous solution of graphene oxide;
Under anaerobic protection of the environment; the raw material of Raolical polymerizable synthesis polyacrylamide and Sodium Alginate Hydrogel Films is added successively in above-mentioned mixed aqueous solution; through 20-90min; by Raolical polymerizable at 30 ~ 70 DEG C of temperature, thus obtain polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel.
Further, in the present invention, acrylamide monomer in polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel: sodium alginate monomer: graphene oxide: the mass ratio of hydroxyapatite is 500:(40-70): (1-5): (5-35).
Compared with prior art, the invention has the beneficial effects as follows:
The biological activity that the present invention makes full use of the two-dimensional structure of graphene oxide (GO) nanometer sheet itself and the functional group that has of surface and hydroxyapatite (HA) excellent carries out chemical modification to polyacrylamide-sodium alginate (PAM-ALG) hydrogel, effectively improve mechanical property and the biological activity of PAM-ALG hydrogel, expand the range of application of PAM-ALG hydrogel, there is clear and definite scientific meaning and huge using value.
Accompanying drawing explanation
Fig. 1 is PAM-ALG hydrogel and PAM-ALG-GO-HA composite aquogel (c and microstructure figure d) in the embodiment of the present invention 1; The wherein microstructure figure of a and b to be the microstructure figure of PAM-ALG hydrogel, c and d be PAM-ALG-GO-HA composite aquogel;
Fig. 2 is GO, HA, PAM-ALG hydrogel in the embodiment of the present invention 1, the infrared spectrogram of PAM-ALG-HA and PAM-ALG-GO-HA composite aquogel;
Fig. 3 is the compression test stress-strain diagram of PAM-ALG hydrogel and PAM-ALG-GO-HA composite aquogel in the embodiment of the present invention 1.
Detailed description of the invention
A kind of artificial articular cartilage material of the present invention, modify polyacrylamide-Sodium Alginate Hydrogel Films with graphene oxide and hydroxyapatite, and the polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel adopting Raolical polymerizable to prepare, wherein, acrylamide monomer: sodium alginate monomer: graphene oxide: the mass ratio of hydroxyapatite is 500:(40-70): (1-5): (5-35).Having huge specific surface area according to GO two-dimensional structure is the feature that the synthesis of hydrogel provides a lot of grafting site, utilize the carboxyl functional group on GO and the amido functional group generation dehydration condensation in hydrogel, the cross-linking reaction realizing GO and hydrogel improves its mechanical property.And in hydrogel, introduce the biological activity of the composite modified further raising hydrogel of HA.
The preparation method of a kind of artificial articular cartilage material of the present invention, comprises the following steps:
Preparation stannic oxide/graphene nano sheet aqueous solution,
The needle nano-hydroxy apatite even particulate dispersion by granularity being 10-1000nm, in stannic oxide/graphene nano sheet aqueous solution, obtains hydroxyapatite and the stable mixed aqueous solution of graphene oxide;
Under anaerobic protection of the environment; the raw material of Raolical polymerizable synthesis polyacrylamide and Sodium Alginate Hydrogel Films is added successively in above-mentioned mixed aqueous solution; through 20-90min; by Raolical polymerizable at 30 ~ 70 DEG C of temperature, thus obtain polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel.
The anaerobic protective gas that described anaerobic protection of the environment adopts, to be as the criterion with colloid solution is reactionless, can select the conventional protective gas such as nitrogen, argon; Add the raw material of synthesis PAM and ALG hydrogel successively, comprising: monomer 1: acrylamide; Initiator: Ammonium persulfate.; Covalently cross-linked dose: methylene diacrylamide; Catalyst: N, N, N ', N ' ,-tetramethyl diacetayl amide; Ionic crosslinking agent: anhydrous calcium chloride; Monomer 2: sodium alginate; Dehydrant: carbodiimides and N-hydroxy-succinamide.Wherein, acrylamide is under anaerobic protection of the environment, and initiator ammonium persulfate produces the acrylamide triggered and covalent crosslinking agent generation cross-linking reaction of primary group of free radicals.Meanwhile, sodium alginate ALG and bivalent cation Ca
2+ionomer reaction can be formed.When two kinds of monomers exist simultaneously, the grid generation dehydration condensation that the grid that PAM chain is formed also can be formed with ALG chain is formed covalently cross-linked and closely combines.Meanwhile, on the one hand because GO itself has two-dimensional structure, namely longitudinal thickness is between several to dozens of nanometers, lateral length is between nanoscale to micron order, and this huge specific surface area is that the synthesis of hydrogel provides a lot of grafting sites.On the other hand, the amido functional group generation dehydration condensation on the upper carboxyl functional group of GO and PAM, increases the grid degree of cross linking of PAM-ALG hydrogel thus strengthens the mechanical property of composite aquogel further.
Below logical specific embodiment tells about concrete preparation process of the present invention.The invention provides embodiment is in order to accurate understanding, is never restriction the present invention.Those skilled in the art is under the present invention's enlightenment, and the various replacements made under the prerequisite not departing from present inventive concept, change and amendment etc., all belong to scope.
Embodiment 1:
1) by fully ultrasonic 1 hour of standby for Hummers legal system graphene oxide GO nanometer sheet aqueous solution.
2) in above-mentioned concentration be 2mg/ml 15mlGO nanometer sheet aqueous solution in the HA of mechanical blending 5%, and sonic oscillation 30min, ensure that HA is dispersed in GO nanometer sheet aqueous solution.
3) in above-mentioned GO and HA mixed solution, under the protection of the environment of high pure nitrogen, the raw material of Raolical polymerizable synthesis PAM-ALG hydrogel is added successively, i.e. monomer 1: acrylamide 5g; Initiator: Ammonium persulfate. 0.015g; Covalently cross-linked dose: methylene diacrylamide 0.0031g; Catalyst: N, N, N ', N ' ,-tetramethyl diacetayl amide 16 μ L; Ionic crosslinking agent: anhydrous calcium chloride 0.0661g; Monomer 2: sodium alginate 0.5g; Dehydrant: carbodiimides 0.04g and N-hydroxy-succinamide 0.02g.Through 60min, by Raolical polymerizable at 50 DEG C of temperature, prepare PAM-ALG-GO-HA composite aquogel.
The microstructure figure of hydrogel and PAM-ALG-GO-HA composite aquogel as shown in Figure 1.Can find from Fig. 1 (a) and (b), the microstructure of hydrogel presents angioid three-dimensional porous network structure, and aperture is at several microns.This structure is similar to the microstructure of native human's articular cartilage, the grid of porous makes interstitial fluid free-flow between the hole that it is mutually through, will disperse the pressure that extraneous motion produces joint like this, this microstructure is most important for the lubrication of articular cartilage, damping and expansion function.Shown in the microstructure (Fig. 1 c and Fig. 1 d) of PAM-ALG-GO-HA composite aquogel, by introducing inorganic reinforcement phase GO and HA in PAM-ALG hydrogel, hydrogel hardens, be frozen in dry process at PAM-ALG-GO-HA composite aquogel, hard hydrogel grid prevents the growth of HA crystal, therefore clearly can see the grid edge having the thin layer of one deck Semen Salicis babylonicae cum pilus shape to be closely attached to macromolecule hydrogel matrix in figure 1 c.In sum, the microstructure of hydrogel and PAM-ALG-GO-HA composite aquogel presents micro-porous web trellis, and grid distribution uniform.
Fig. 2 is GO, HA, hydrogel, the infrared spectrogram of PAM-ALG-HA and PAM-ALG-GO-HA composite aquogel.Can find from figure, GO and HA be feature peak position as corresponding in map logo respectively, wherein 1263.10cm in the infrared spectrum spectrogram of hydrogel
-1the stretching vibration peak of the C-N key in the corresponding secondary amine key of peak position, this shows that two kinds of simplex mesh PAM and ALG in hydrogel combine with the form of chemical bond.1418.59cm in the infrared spectrogram of PAM-ALG-GO-HA composite aquogel
-1the stretching vibration peak of C-N key in the corresponding amido link of peak position, this shows that the monomer PAM in GO and hydrogel grid creates chemical crosslink reaction.
Fig. 3 is the compression test stress-strain diagram of hydrogel before and after PAM-ALG compound GO and HA.Upper as can be seen from figure, after adding GO and HA, slope of a curve and modulus of elasticity in comperssion raise greatly, so composite aquogel has stronger mechanical property.
Embodiment 2:
1) by fully ultrasonic 1.5 hours of standby for Brodie legal system graphene oxide GO nanometer sheet aqueous solution.
2) in above-mentioned concentration be 0.5mg/ml 20mlGO nanometer sheet aqueous solution in the HA of mechanical blending 3%, and sonic oscillation 40min, ensure that HA is dispersed in GO nanometer sheet aqueous solution.
3) in above-mentioned GO and HA mixed solution, under the protection of the environment of high-purity argon gas, the raw material of Raolical polymerizable synthesis PAM-ALG hydrogel is added successively, i.e. monomer 1: acrylamide; Initiator: Ammonium persulfate. 0.015g; Covalently cross-linked dose: methylene diacrylamide 0.0031g; Catalyst: N, N, N ', N ' ,-tetramethyl diacetayl amide 16 μ L; Ionic crosslinking agent: anhydrous calcium chloride 0.0661g; Monomer 2: sodium alginate 0.6g; Dehydrant: carbodiimides 0.04g and N-hydroxy-succinamide 0.02g.Through 40min, by Raolical polymerizable at 60 DEG C of temperature, prepare PAM-ALG-GO-HA composite aquogel.
Embodiment 3:
1) by fully ultrasonic 2 hours of standby for Staudenmaier legal system graphene oxide GO nanometer sheet aqueous solution.
2) in above-mentioned concentration be 2mg/ml 25mlGO nanometer sheet aqueous solution in the HA of mechanical blending 5%, and sonic oscillation 30min, ensure that HA is dispersed in GO nanometer sheet aqueous solution.
3) in above-mentioned GO and HA mixed solution, under the protection of the environment of high pure nitrogen, the raw material of Raolical polymerizable synthesis PAM-ALG hydrogel is added successively, i.e. monomer 1: acrylamide; Initiator: Ammonium persulfate. 0.015g; Covalently cross-linked dose: methylene diacrylamide 0.0031g; Catalyst: N, N, N ', N ' ,-tetramethyl diacetayl amide 16 μ L; Ionic crosslinking agent: anhydrous calcium chloride 0.0661g; Monomer 2: sodium alginate 0.5g; Dehydrant: carbodiimides 0.04g and N-hydroxy-succinamide 0.02g.Through 80min, by Raolical polymerizable at 40 DEG C of temperature, prepare PAM-ALG-GO-HA composite aquogel.
Embodiment 4:
1) by graphene oxide GO nanometer sheet aqueous solution standby for Hummers legal system fully ultrasonic 1 time.
2) in above-mentioned concentration be 2mg/ml 15mlGO nanometer sheet aqueous solution in the HA of mechanical blending 7%, and sonic oscillation 40min, ensure that HA is dispersed in GO nanometer sheet aqueous solution.
3) in above-mentioned GO and HA mixed solution, under the protection of the environment of high-purity argon gas, the raw material of Raolical polymerizable synthesis PAM-ALG hydrogel is added successively, i.e. monomer 1: acrylamide; Initiator: Ammonium persulfate. 0.015g; Covalently cross-linked dose: methylene diacrylamide 0.0031g; Catalyst: N, N, N ', N ' ,-tetramethyl diacetayl amide 16 μ L; Ionic crosslinking agent: anhydrous calcium chloride 0.0661g; Monomer 2: sodium alginate 0.6g; Dehydrant: carbodiimides 0.04g and N-hydroxy-succinamide 0.02g.Through 60min, by Raolical polymerizable at 50 DEG C of temperature, prepare PAM-ALG-GO-HA composite aquogel.
Although invention has been described for composition graphs above; but the present invention is not limited to above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is only schematic; instead of it is restrictive; those of ordinary skill in the art is under enlightenment of the present invention; when not departing from present inventive concept, can also make a lot of distortion, these all belong within protection of the present invention.
Claims (2)
1. an artificial articular cartilage material, it is characterized in that, polyacrylamide-Sodium Alginate Hydrogel Films is modified with graphene oxide and hydroxyapatite, and the polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel adopting Raolical polymerizable to prepare; Acrylamide monomer in polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel: sodium alginate monomer: graphene oxide: the mass ratio of hydroxyapatite is 500:(40-70): (1-5): (5-35).
2. the preparation method of a kind of artificial articular cartilage material as claimed in claim 1, is characterized in that: comprise the following steps:
Preparation stannic oxide/graphene nano sheet aqueous solution, supersound process, makes stannic oxide/graphene nano sheet solution temperature remain on 10-50 DEG C of scope;
Be that the needle nano-hydroxy apatite even particulate dispersion of 10-1000nm is in stannic oxide/graphene nano sheet aqueous solution by granularity, in mixed process, aqueous temperature scope control, at 10-80 DEG C, after Homogeneous phase mixing, obtains hydroxyapatite and the stable mixed aqueous solution of graphene oxide;
Under anaerobic protection of the environment, the raw material of Raolical polymerizable synthesis polyacrylamide and Sodium Alginate Hydrogel Films is added successively in above-mentioned mixed aqueous solution, wherein, the raw material of Raolical polymerizable synthesis polyacrylamide and Sodium Alginate Hydrogel Films comprises: monomer 1: acrylamide; Initiator: Ammonium persulfate.; Covalently cross-linked dose: methylene diacrylamide; Catalyst: N, N, N ', N ' ,-tetramethyl diacetayl amide; Ionic crosslinking agent: anhydrous calcium chloride; Monomer 2: sodium alginate; Dehydrant: carbodiimides and N-hydroxy-succinamide; Through 20-90min, by Raolical polymerizable at 30 ~ 70 DEG C of temperature, thus obtain polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel; Acrylamide monomer in described polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel: sodium alginate monomer: graphene oxide: the mass ratio of hydroxyapatite is 500:(40-70): (1-5): (5-35).
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