CN103845757A - Artificial articular cartilage material and preparation method thereof - Google Patents
Artificial articular cartilage material and preparation method thereof Download PDFInfo
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- CN103845757A CN103845757A CN201310694865.8A CN201310694865A CN103845757A CN 103845757 A CN103845757 A CN 103845757A CN 201310694865 A CN201310694865 A CN 201310694865A CN 103845757 A CN103845757 A CN 103845757A
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Abstract
The invention discloses an artificial articular cartilage material, which relates to the field of chemical modification of hydrogel soft materials. Polyacrylamide-sodium alginate hydrogel is modified with graphene oxide and hydroxyapatite, and PAM-ALG-GO-HA composite hydrogel is prepared by a free radical polymerization reaction. The preparation method comprises the following steps: gradually adding needle-like nano HA particles into a GO solution which is uniformly dispersed in advance to form a mixed aqueous solution, adding an acrylamide monomer, an ALG monomer and related reactants for synthesizing PAM-ALG hydrogel, and performing the free radical polymerization reaction to prepare the PAM-ALG-GO-HA composite hydrogel. According to the artificial articular cartilage material disclosed by the invention, chemical modification is performed on the PAM-ALG hydrogel by fully using the two-dimensional structure of a GO nano chip and the functional groups on the surface and the excellent biological activity of HA, the mechanical property and biological activity of the PAM-ALG hydrogel are effectively improved, the application range of the PAM-ALG hydrogel is expanded, and the artificial articular cartilage material has clear scientific significance and a huge application value.
Description
Technical field
The present invention relates to a kind of hydrogel soft materials chemistry method of modifying, relate in particular 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.Thick smooth, the resilient tissue-articular cartilage of one deck 2～7mm of human body knee joint surface coverage; pressure and the impact of the various high load capacities that energy grantee goes round and begins again in life; natural life-span can be up to 70～80 years; and can make joint freely movable; can absorb physical activity time, vibrate produced energy, play the effect of buffering and Saving cortilage simultaneously.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 become flexible and dislocation; On the other hand, Long-term Clinical Observation shows, thus superhigh molecular weight polyethylene material in long service process can and around metal alloy friction produce abrasive dust, the wearing and tearing in late period of final artificial joint can be very serious.These failure phenomenons and current Artificial Joint Design do not have the natural structure of bionical human synovial, and not designing the defects such as articular cartilage has very large relation, seem particularly necessary and urgent so prepare novel artificial articular cartilage material.
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 micro-cavernous structure of natural cartilage, high water absorption and elasticity, the good characteristic such as 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, and 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 in human normal motor activity bears heavily stressed requirement to articular cartilage.Secondly, this soft material, as other artificial soft tissue replacement materials such as artificial-muscles, although it is poor because of its biological activity itself to have strong biocompatibility, can not be integrated with surrounding tissue.So, be necessary according to its concrete applied environment, PAM-ALG hydrogel to be improved further.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of artificial articular cartilage material and preparation method thereof, adopt graphene oxide and hydroxyapatite to carry out chemical modification to polyacrylamide-Sodium Alginate Hydrogel Films, give full play to the feature that Hydrogels is similar to natural joint cartilage, with thering is the GO nanometer sheet of excellent mechanical property and the HA of good biological activity carries out chemical modification 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, with graphene oxide and hydroxyapatite modification polyacrylamide-Sodium Alginate Hydrogel Films, and the polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel that adopts 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 ℃ of scope;
The needle nano-hydroxy apatite uniform particles that is 10-1000nm by granularity is scattered in stannic oxide/graphene nano sheet aqueous solution, in mixed process, aqueous temperature scope control, at 10-80 ℃, after evenly mixing, obtains the stable mixed aqueous solution of hydroxyapatite and graphene oxide;
Under anaerobic protection of the environment; in above-mentioned mixed aqueous solution, add successively the raw material of the synthetic polyacrylamide of Raolical polymerizable and Sodium Alginate Hydrogel Films; through 20-90min; at 30～70 ℃ of temperature, pass through Raolical polymerizable, thereby 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 present invention makes full use of the two-dimensional structure of graphene oxide (GO) nanometer sheet itself and the biological activity of the surperficial functional group having and hydroxyapatite (HA) excellence carries out chemical modification to polyacrylamide-sodium alginate (PAM-ALG) hydrogel, mechanical property and the biological activity of PAM-ALG hydrogel are effectively improved, 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; Wherein a and b are the microstructure figure of PAM-ALG hydrogel, and c and d are the microstructure figure of PAM-ALG-GO-HA composite aquogel;
Fig. 2 is GO in the embodiment of the present invention 1, HA, PAM-ALG hydrogel, 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.
The specific embodiment
A kind of artificial articular cartilage material of the present invention, to modify polyacrylamide-Sodium Alginate Hydrogel Films with graphene oxide and hydroxyapatite, and the polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel that adopts 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).According to the GO two-dimensional structure synthetic feature that a lot of grafting sites are provided that to have huge specific surface area be hydrogel, utilize the amido functional group generation dehydration condensation in carboxyl functional group and the hydrogel on GO, the cross-linking reaction that realizes 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 uniform particles that is 10-1000nm by granularity is scattered in stannic oxide/graphene nano sheet aqueous solution, obtains the stable mixed aqueous solution of hydroxyapatite and graphene oxide;
Under anaerobic protection of the environment; in above-mentioned mixed aqueous solution, add successively the raw material of the synthetic polyacrylamide of Raolical polymerizable and Sodium Alginate Hydrogel Films; through 20-90min; at 30～70 ℃ of temperature, pass through Raolical polymerizable, thereby 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 be selected the conventional protective gas such as nitrogen, argon; The raw material that adds successively synthetic PAM and ALG hydrogel, 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 elementary free radical.Meanwhile, sodium alginate ALG and bivalent cation Ca
2+can form ionomer reaction.In the time that two kinds of monomers exist simultaneously, the grid that PAM chain forms also can form covalently cross-linked and closely combine with the grid generation dehydration condensation that ALG chain forms.Meanwhile, on the one hand because GO itself has two-dimensional structure, longitudinal thickness for lateral length between several to dozens of nanometers be nanoscale between micron order, this huge specific surface area is hydrogel syntheticly 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, thus the grid degree of cross linking of increase PAM-ALG hydrogel further strengthens the mechanical property of composite aquogel.
Below logical specific embodiment is told about concrete preparation process of the present invention.The invention provides embodiment is for accurate understanding, is never restriction the present invention.Those skilled in the art is under the present invention's enlightenment, and various replacements, variation and the modification etc. under the prerequisite that does not depart from aim of the present invention, made, all belong to protection domain of the present invention.
Embodiment 1:
1) by graphene oxide GO nanometer sheet aqueous solution standby Hummers legal system fully ultrasonic 1 hour.
2) HA of mechanical blending 5% in the 15ml GO nanometer sheet aqueous solution that is 2mg/ml in above-mentioned concentration, and sonic oscillation 30min, guarantee 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, add successively the raw material of the synthetic PAM-ALG hydrogel of Raolical polymerizable,, 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, at 50 ℃ of temperature, by Raolical polymerizable, 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) with (b), the microstructure of hydrogel presents angioid three-dimensional porous network structure, and aperture is several microns of left and right.This structure is similar to the microstructure of natural human articular cartilage, the grid of porous makes free-flow between hole that interstitial fluid connects mutually at it, the pressure that will disperse so extraneous motion to produce joint, this microstructure is most important for lubricated, damping and the expansion function of articular cartilage.The microstructure of PAM-ALG-GO-HA composite aquogel (Fig. 1 c and Fig. 1 d) shown in, by introduce inorganic wild phase GO and HA in PAM-ALG hydrogel, hydrogel sclerosis, be frozen in dry process at PAM-ALG-GO-HA composite aquogel, hard hydrogel grid has stoped the growth of HA crystal, therefore in Fig. 1 c, can clearly see the grid edge that has the thin layer of one deck Semen Salicis babylonicae cum pilus shape to be closely attached to macromolecule hydrogel matrix.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.From scheming, can find, 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 two kinds of simplex mesh PAM in hydrogel and the ALG form combination with 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 has produced chemical crosslink reaction.
Fig. 3 is the compression test stress-strain diagram of hydrogel before and after the compound GO of PAM-ALG and HA.From scheming, can find out, add after GO and HA, slope of a curve is that modulus of elasticity in comperssion raises greatly, so composite aquogel has stronger mechanical property.
Embodiment 2:
1) by graphene oxide GO nanometer sheet aqueous solution standby Brodie legal system fully ultrasonic 1.5 hours.
2) HA of mechanical blending 3% in the 20ml GO nanometer sheet aqueous solution that is 0.5mg/ml in above-mentioned concentration, and sonic oscillation 40min, guarantee 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, add successively the raw material of the synthetic PAM-ALG hydrogel of Raolical polymerizable,, 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, at 60 ℃ of temperature, by Raolical polymerizable, prepare PAM-ALG-GO-HA composite aquogel.
Embodiment 3:
1) by graphene oxide GO nanometer sheet aqueous solution standby Staudenmaier legal system fully ultrasonic 2 hours.
2) HA of mechanical blending 5% in the 25ml GO nanometer sheet aqueous solution that is 2mg/ml in above-mentioned concentration, and sonic oscillation 30min, guarantee 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, add successively the raw material of the synthetic PAM-ALG hydrogel of Raolical polymerizable,, 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, at 40 ℃ of temperature, by Raolical polymerizable, prepare PAM-ALG-GO-HA composite aquogel.
Embodiment 4:
1) by graphene oxide GO nanometer sheet aqueous solution standby Hummers legal system fully ultrasonic 1 o'clock.
2) HA of mechanical blending 7% in the 15ml GO nanometer sheet aqueous solution that is 2mg/ml in above-mentioned concentration, and sonic oscillation 40min, guarantee 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, add successively the raw material of the synthetic PAM-ALG hydrogel of Raolical polymerizable,, 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, at 50 ℃ of temperature, by Raolical polymerizable, prepare PAM-ALG-GO-HA composite aquogel.
Although in conjunction with figure, invention has been described above; but the present invention is not limited to the above-mentioned specific embodiment; the above-mentioned specific embodiment is only schematic; rather than restrictive; those of ordinary skill in the art is under enlightenment of the present invention; in the situation that not departing from aim of the present invention, can also make a lot of distortion, within these all belong to protection of the present invention.
Claims (4)
1. an artificial articular cartilage material, it is characterized in that, with graphene oxide and hydroxyapatite modification polyacrylamide-Sodium Alginate Hydrogel Films, and the polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel that adopts Raolical polymerizable to prepare.
2. a kind of artificial articular cartilage material as claimed in claim 1, is characterized in that: 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).
3. a kind of preparation method 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 ℃ of scope;
The needle nano-hydroxy apatite uniform particles that is 10-1000nm by granularity is scattered in stannic oxide/graphene nano sheet aqueous solution, in mixed process, aqueous temperature scope control, at 10-80 ℃, after evenly mixing, obtains the stable mixed aqueous solution of hydroxyapatite and graphene oxide;
Under anaerobic protection of the environment; in above-mentioned mixed aqueous solution, add successively the raw material of the synthetic polyacrylamide of Raolical polymerizable and Sodium Alginate Hydrogel Films; through 20-90min; at 30～70 ℃ of temperature, pass through Raolical polymerizable, thereby obtain polyacrylamide-sodium alginate-graphene oxide-hydroxyapatite composite aquogel.
4. a kind of preparation method of artificial articular cartilage material described in claim 3, is characterized in that: 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).
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