CN102698316A - Rapid-curing adhesive bone repair material and preparation method thereof - Google Patents
Rapid-curing adhesive bone repair material and preparation method thereof Download PDFInfo
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- CN102698316A CN102698316A CN2012101549708A CN201210154970A CN102698316A CN 102698316 A CN102698316 A CN 102698316A CN 2012101549708 A CN2012101549708 A CN 2012101549708A CN 201210154970 A CN201210154970 A CN 201210154970A CN 102698316 A CN102698316 A CN 102698316A
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Abstract
The invention discloses a rapid-curing adhesive bone repair material and a preparation method of the repair material. The material is prepared by blending solid powder and curing solution, wherein the solid powder is phosphate bone cement powder, and the curing solution is prepared by dissolving natural polysaccharides or derivatives of the natural polysaccharides or combination of the natural polysaccharides or the derivatives in organic acid solution. The solid powder can be rapidly cured when being mixed with the curing solution, to obtain repair material with excellent collapse resistance, high mechanical strength and good biocompatibility and degradability. The material can be used for preparing bonding resetting material of bone fragments in case of comminuted fracture and intra-articular fracture, preparing bonding fixing material of artificial joint and internal fixation device, and also preparing filling material of fracture gap and bone defect.
Description
Technical field
The invention belongs to field of medical materials, relate to a kind of viscosity bone renovating material.
Background technology
Development along with the Modern High-Speed traffic; And the increasing the weight of of social population's aging, fracture becomes more and more common clinically, and the comminuted fracture that high-energy causes is also more and more sees; It is bigger to treat the comminuted fracture difficulty clinically, the comminuted fracture of especially near joint.Treatment can be fixed through screw, draw point, steel wire, nylon suture etc. for comminuted fracture at present.Traditional clinical treatment advocates part can't be removed or spacious putting by fixed ossiculum fragment; But to non-intra-articular fracture; Having under the strong fixed situation, can cause bone damaged after the ossiculum fragment is removed, obviously influencing speed of fracture union; And be unfavorable for keeping the fracture para-position and, the probability of malunion of fracture and disunion increased line; The spacious ossiculum piece of putting tends to be shifted after surgery and gets into surrounding soft tissue, forms ectopic ossification, thereby influences function.
Adopting medical bone bonding agent to carry out bonding to broken bone piece is present more promising a kind of Therapeutic Method.But all there are some problems in the adhesive of medical that uses at present.Traditional orthopaedics binding agent polymethyl methacrylate bone cement quick solidifying, bonding strength is higher, but because monomer whose has cytotoxicity, can cause the rapid drawdown of patient's blood pressure in the operation; Strong heat release meeting in the polymerization process causes that surrounding tissue is downright bad.Alpha-cyanacrylate adhesive is a kind of one-package adhesive, and is solvent-free, need not when bonding to overstock to add; Normal temperature solidified, under wet environment also can with tissue combine good, but heat release is woven with the burn effect to adjacent set on every side in its polymerization process; And really up to the mark surrounding tissue is worn and torn repeatedly of solidfied material can be caused mechanical damage; Its catabolite polyformaldehyde has toxicity, and the too fast operating difficulty of polymerization speed increases (Cai Ping, Liu Gonghan; China's clear spring etc., the medical glue of a-cyanoacrylate is repaired the application in the rabbit temporal bone inner face neurologic defect in the chitin chamber.China's reconstruction surgical magazine, 2002,16 (3): 158-160; Li Zhenlin, Yang Bei, model peace, the new development of esters of acrylic acid Study on Adhesive.The Henan chemical industry, 2004 (7): 4-7.).The adhesive strength of fibrin class binding agent is lower, is again Blood Preparations, possibly cause irritated and immunoreation or infective virus (Chen Keming, the development of adhesive fibrin and application.Foreign medical science surgery fascicle, 1995, (1): 22; Ding Fengquan, adhesive fibrin clinical practice overview.Binding agent, 1986; 2:21).
Develop calcium phosphate bone cement in recent years, good biocompatibility, heat release is low, can be used for clinical bone reparation.But also exist intensity low, solidify slow, shortcoming such as water-resistance is relatively poor, (Wang Wenbo, Chen Tongyi, the artificial diaphysis of self-curable calcium phosphates such as Chen Zhongwei are implanted into long-term experiment research, Chinese orthopedics, 2002,9 (5): 460 to have influenced its clinical practice; Mohamed Habib, Gamal Baroud waits Mechanisms underlying the limited injectability of hydraulic calcium phosphate paste, Acta Biomaterialia, 2008,4:1465).It is the inorganic bone binding agent of main component that Liu Changsheng etc. have prepared with ammonium magnesium phosphate and hydroxyapatite, implants and can be absorbed gradually, has a good application prospect.But the water-resistance of this material is undesirable, defeated and dispersed easily (CN1307908 in the oozing of blood environment; Wu Zizheng, Zhang Jian etc., the experimentation of the bonding fracture of magnesium phosphate bone cementum, Chinese reconstruction surgical magazine, 2006,20 (9): 912).
Natural polysaccharide has excellent biological compatibility, and has certain viscosity, in tissue repair, is widely used.In the phosphate bone cement, adding natural polysaccharides such as chitosan, alginic acid can increase the bonding force of bone cement slurry, improves anti-collapsibility performance (Wang Ying, Wei Jie; Guo Han, Liu Changsheng, Journal of Inorganic Materials; The research of water-resistant type calcium phosphorus cement biological activity bone renovating material, 2006,21 (6); Hua Liu, Hong Li, etc.; Novel injectable calcium phosphate/chitosan composites for bone substitute materials; Acta Biomaterialia, 2006,2:557); But also prolonged hardening time simultaneously, thereby can't meet clinical needs fully.
Therefore, the present invention press for the development a kind of can quick-setting viscosity degradable bone renovating material.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of viscosity bone renovating material is provided, but fast setting.
Another object of the present invention is to provide the method for preparing of this bone renovating material.
First aspect of the present invention provides a kind of bone renovating material, has following one or more characteristic:
(b1) setting time≤20min;
(b2) adhesive strength>=25Ncm
-2
(b3) comprcssive strength >=15MPa;
(b4) anti-collapsibility performance: in simulated body fluid, behind 100r/min vibration 24h, weight-loss ratio≤10wt%.
In another preference, said bone renovating material has following one or more characteristic:
(b1) be 1.5 ~ 10min setting time;
(b2) adhesive strength is 25 ~ 85Ncm
-2
(b3) comprcssive strength is 15 ~ 85MPa;
(b4) anti-collapsibility performance: in simulated body fluid, behind 100r/min vibration 24h, weight-loss ratio≤10wt%.
In another preference, said bone renovating material has following one or more characteristic:
(b1) be 1.5 ~ 5min setting time;
(b2) adhesive strength is 25 ~ 85Ncm
-2
(b3) comprcssive strength is 15 ~ 85MPa;
(b4) anti-collapsibility performance: in simulated body fluid, behind 100r/min vibration 24h, weight-loss ratio≤1wt%.
In another preference, said bone renovating material is a phosphoric acid salt bone cement repair materials.
Second aspect of the present invention provides the method for preparing of the said bone renovating material of first aspect, comprises step:
Is 0.8: 1 ~ 4 with pressed powder and consolidation liquid by solid-to-liquid ratio: 1g/mL is in harmonious proportion, and obtains said bone renovating material; Wherein, said pressed powder is a phosphate bone cement powder; Said consolidation liquid is formulated in aqueous solutions of organic acids by natural polysaccharide, natural polysaccharide derivant or its composition dissolves.
In another preference, said pressed powder is selected from: calcium hydrogen phosphate, a kind of or its mixture in dalcium biphosphate, tricalcium phosphate, tetracalcium phosphate, OCP, magnesium phosphate, hydroxyapatite, the fluor-apatite; And/or
Said natural polysaccharide is selected from: a kind of or its mixture in chitosan, sodium alginate, cellulose, the starch; And/or
Said natural polysaccharide derivant is selected from: a kind of or its mixture in carboxymethyl chitosan, quaternary ammonium salt chitosan, sulfated chitosan, the phosphonized chitosan; And/or
Described organic acid is selected from: a kind of or its mixture in citric acid, malic acid, tartaric acid or the ascorbic acid.
In another preference, the mass percent concentration of said aqueous solutions of organic acids is 1% ~ 50%.
In another preference, the mass percent concentration of said aqueous solutions of organic acids is 5% ~ 40%.
In another preference, in the said consolidation liquid, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its compositions is 0.1% ~ 6%.
In another preference, in the said consolidation liquid, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its compositions is 1% ~ 5%.
In another preference, said solid-to-liquid ratio is 1.2: 1 ~ 3: 1g/mL.
In another preference, said solid-to-liquid ratio is 1.6: 1 ~ 2.5: 1g/mL.
The third aspect of the invention provides a kind of test kit that is used to form the described bone renovating material of first aspect, comprises following component:
(a) pressed powder, said pressed powder are phosphate bone cement powder;
(b) natural polysaccharide, natural polysaccharide derivant or its compositions;
(c) aqueous solutions of organic acids;
Or comprise following component:
(a ') pressed powder, said pressed powder are phosphate bone cement powder;
(b ') consolidation liquid: said consolidation liquid contains: natural polysaccharide, natural polysaccharide derivant or its compositions; And aqueous solutions of organic acids.
In another preference, said pressed powder is selected from: calcium hydrogen phosphate, a kind of or its mixture in dalcium biphosphate, tricalcium phosphate, tetracalcium phosphate, OCP, magnesium phosphate, hydroxyapatite, the fluor-apatite; And/or
Said natural polysaccharide is selected from: a kind of or its mixture in chitosan, sodium alginate, cellulose, the starch; And/or
Said natural polysaccharide derivant is selected from: a kind of or its mixture in carboxymethyl chitosan, quaternary ammonium salt chitosan, sulfated chitosan, the phosphonized chitosan; And/or
Described organic acid is selected from: a kind of or its mixture in citric acid, malic acid, tartaric acid or the ascorbic acid.
In another preference, the mass percent concentration of said aqueous solutions of organic acids is 5% ~ 40%;
Said component (b) is dissolved in said component (c) and forms consolidation liquid, and the mass percent concentration of said component (b) is 1% ~ 5%; Or in said component (b ') consolidation liquid, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its compositions is 1% ~ 5%.
In another preference, said component (b) is dissolved in said component (c) and forms consolidation liquid, and the solid-to-liquid ratio of said component (a) pressed powder and said consolidation liquid is 0.8: 1 ~ 4: 1g/mL;
Or the solid-to-liquid ratio of said component (a ') pressed powder and said component (b ') consolidation liquid is 0.8: 1 ~ 4: 1g/mL.
Fourth aspect of the present invention provides the purposes of described bone renovating material of first aspect or the described test kit of the third aspect, and said purposes is selected from down group:
(a1) be used to prepare the jointing material of bonding bone;
(a2) be used to prepare the jointing material of bonding artificial joint;
(a3) be used to prepare the jointing material of bonding internal fixation device; Or
(a4) be used to prepare the packing material of filling fracture gap or bone defect.
The present invention utilizes organic acid to improve the rheological characteristic of bone cement, makes it can accomplish curing fast, and has higher early strength, has improved anti-collapsibility property simultaneously.The present invention simultaneously utilizes the chelation of natural polysaccharide or derivatives thereof and metal ion to make it have viscosity, can with firm bonding of other interface generation.By both combineds effect; Make bone renovating material of the present invention have viscosity; Have good anti-collapsibility performance and quick-setting characteristics simultaneously, high compression strength and adhesive strength are arranged, and have excellent biological compatibility; Solved the water-resistance that traditional bone adhesives exists not enough, solidify defectives such as slow, cells in vivo toxicity and degradability, be a kind of bone renovating material with clinical practice potentiality.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and hereinafter can mutual combination between specifically described each technical characterictic in (like embodiment), thus constitute new or optimized technical scheme.As space is limited, this tired no longer one by one stating.
Description of drawings
Fig. 1 is adhesive strength test sketch map.
Fig. 2 is that traditional calcium phosphate bone cement and the anti-collapsibility property of viscosity bone renovating material in water compare, and wherein, a left side is traditional phosphate bone cement; The right side is the viscosity bone renovating material.
Fig. 3 is anti-collapsibility property quantitative test figure as a result.
Fig. 4 is that hardening time is with liquid phase component citric acid content variation diagram.
Fig. 5 is that adhesive strength is with liquid phase component citric acid content variation diagram.
Fig. 6 is for solidifying the sem photograph of back material.
Fig. 7 is the adhesion form Electronic Speculum figure of the material surface of osteoblast after curing.
The specific embodiment
The present inventor is through extensively and in depth research; Unexpected employing natural polysaccharide and the organic acid found is to the common modification of phosphate bone cement, and organic acid has improved the rheological characteristic of bone cement, makes it can accomplish curing fast; And have higher early strength, improved anti-collapsibility property simultaneously; The chelation of natural polysaccharide or derivatives thereof and metal ion makes it have viscosity, can bonding bone cips or internal fixation device.On this basis, accomplished the present invention.
Term
As used herein, said " pressed powder " is phosphate bone cement powder, is selected from: calcium hydrogen phosphate, a kind of or its mixture in dalcium biphosphate, tricalcium phosphate, tetracalcium phosphate, OCP, magnesium phosphate, hydroxyapatite, the fluor-apatite.
As used herein, said " natural polysaccharide " is selected from: a kind of or its mixture in chitosan, sodium alginate, cellulose, the starch.
As used herein, said " natural polysaccharide derivant " is selected from: a kind of or its mixture in carboxymethyl chitosan, quaternary ammonium salt chitosan, sulfated chitosan, the phosphonized chitosan.
As used herein, said " organic acid " is selected from: a kind of or its mixture in citric acid, malic acid, tartaric acid or the ascorbic acid.
The mass percent concentration of said aqueous solutions of organic acids is 1% ~ 50%, preferably, is 5% ~ 40%, more preferably, is 20% ~ 40%.
Bone renovating material
Bone renovating material of the present invention is the phosphate bone cement, has following one or more characteristic:
(b1) setting time≤20min;
(b2) adhesive strength>=25Ncm
-2
(b3) comprcssive strength >=14MPa;
(b4) anti-collapsibility performance: in simulated body fluid, behind 100r/min vibration 24h, weight-loss ratio≤10wt%.
In another preference, said bone renovating material has following one or more characteristic:
(b1) be 1.5 ~ 10min setting time;
(b2) adhesive strength is 25 ~ 85Ncm
-2
(b3) comprcssive strength is 15 ~ 85MPa;
(b4) anti-collapsibility performance: in simulated body fluid, behind 100r/min vibration 24h, weight-loss ratio≤10wt%.
In another preference, said bone renovating material has following one or more characteristic:
(b1) be 1.5 ~ 5min setting time;
(b2) adhesive strength is 25 ~ 85Ncm
-2
(b3) comprcssive strength is 15 ~ 85MPa;
(b4) anti-collapsibility performance: in simulated body fluid, behind 100r/min vibration 24h, weight-loss ratio≤1wt%.
Test kit
The test kit that is used to form bone renovating material of the present invention comprises following component:
(a) pressed powder, said pressed powder are phosphate bone cement powder;
(b) natural polysaccharide, natural polysaccharide derivant or its combination;
(c) aqueous solutions of organic acids.
Said component (b) is dissolved in said component (c) aqueous solutions of organic acids and forms consolidation liquid, and the mass percent concentration of said component (b) is 0.1wt% ~ 6wt%.
In another preference, the mass percent concentration of said component (b) is 1wt% ~ 5wt%.
In another preference, the mass percent concentration of said component (b) is 1.5wt% ~ 2.5wt%.
Said component (b) is dissolved in said component (c) and forms consolidation liquid, and the solid-to-liquid ratio of said component (a) pressed powder and said consolidation liquid is 0.8: 1 ~ 4: 1g/mL, preferably, solid-to-liquid ratio is 1.2: 1 ~ 3: 1g/mL, more preferably, solid-to-liquid ratio is 1.6: 1 ~ 2.5: 1g/mL.
In another preference, solid-to-liquid ratio is 2: 1g/ml.
Another kind provided by the invention is used to form the test kit of bone renovating material, comprises following component:
(a ') pressed powder, said pressed powder are phosphate bone cement powder;
(b ') consolidation liquid: said consolidation liquid contains: natural polysaccharide, natural polysaccharide derivant or its combination; And aqueous solutions of organic acids.
In said component (b ') consolidation liquid, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its combination is 0.1wt% ~ 6wt%.
In another preference, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its combination is 1wt% ~ 5wt%.
In another preference, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its combination is 1.5wt% ~ 2.5wt%.
The solid-to-liquid ratio of said component (a ') pressed powder and said component (b ') consolidation liquid is 0.8: 1 ~ 4: 1g/mL, preferably, solid-to-liquid ratio is 1.2: 1 ~ 3: 1g/mL, more preferably, solid-to-liquid ratio is 1.6: 1 ~ 2.5: 1g/mL.
In another preference, solid-to-liquid ratio is 2: 1g/mL.
Method for preparing
The method for preparing of bone renovating material provided by the invention comprises step:
Is 0.8: 1 ~ 4 with pressed powder and consolidation liquid by solid-to-liquid ratio: 1g/mL is in harmonious proportion, and obtains said bone renovating material.
In another preference, solid-to-liquid ratio is 1.2: 1 ~ 3: 1g/mL, preferably, solid-to-liquid ratio is 1.6: 1 ~ 2.5: 1g/mL.
In another preference, solid-to-liquid ratio is 2: 1g/mL.
Wherein, the compound method of consolidation liquid is following:
(i) preparation aqueous solutions of organic acids, mass percent concentration is 5% ~ 40%;
(ii) natural polysaccharide, natural polysaccharide derivant or its combination are dissolved in aqueous solutions of organic acids and form consolidation liquid, wherein, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its combination is 1wt% ~ 5wt%.
In another preference, the mass percent concentration of the aqueous solutions of organic acids of step (i) preparation is 10% ~ 40%, and preferably, mass percent concentration is 20% ~ 40%.
In another preference, the consolidation liquid that step (ii) obtains, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its combination is 1.2wt% ~ 3wt%, preferably is 1.5wt% ~ 2wt%.
The present invention utilizes organic acid to improve the rheological characteristic of bone cement, makes it can accomplish curing fast, and has higher early strength, has improved anti-collapsibility property simultaneously.The present invention simultaneously utilizes the chelation of natural polysaccharide or derivatives thereof and metal ion to make it have viscosity, can with firm bonding of other interface generation.
By both combineds effect; Make bone renovating material of the present invention have viscosity; Have good anti-collapsibility performance and quick-setting characteristics simultaneously, high compression strength and adhesive strength are arranged, and have excellent biological compatibility; Solved the water-resistance that traditional bone adhesives exists not enough, solidify defectives such as slow, cells in vivo toxicity and degradability, be a kind of bone renovating material with clinical practice potentiality.
Bone renovating material of the present invention can be used for preparing bone cips in comminuted fracture, the unstable fracture the bonding material or be used to prepare the material that is adhesively fixed of artificial joint and internal fixation device of resetting, or be used to prepare fracture gap and the damaged packing material of bone.
The above-mentioned characteristic that the present invention mentions, or the characteristic that embodiment mentions can combination in any.All characteristics that this case description is disclosed can with any composition forms and usefulness, each characteristic that is disclosed in the description, the alternative characteristics that can anyly be provided identical, impartial or similar purpose replaces.Therefore removing has special instruction, the characteristic that is disclosed to be merely the general example of equalization or similar features.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example is usually according to the normal condition or the condition of advising according to manufacturer.
Only if definition separately, the same meaning that employed all specialties and scientific words and one skilled in the art are familiar with in the literary composition.In addition, any with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
General experiment
(1) anti-water experiment
Bone renovating material after the modulation solidified (W that weighs
0), put into simulated body fluid, place the vibration case to vibrate then in 100r/min.
Behind the vibration 24h sample is taken out, dry 24h in 60 ℃ of baking ovens, (W weighs
1).
Calculate weight-loss ratio by following formula:
Weight-loss ratio=(W
0-W
1)/W
0* 100%
Weigh the water repelling property of material with weightless situation.
Wherein, simulated body fluid can adopt the conventional method in this area to prepare, as according to Kukubo T, and J Biomed Mater Res, 1990, the disclosed ion concentration prescription of 24:721-734 is prepared.
(2) test hardening time (setting time)
Mediation pressed powder and consolidation liquid are inserted high 10mm, (tamp) in the cuvette of diameter 6mm as far as possible; One floating; Then plastic membrane sealing is used at two ends, put in 100% relative humidity, the 37 ℃ of environment (climatic chamber, Shanghai one permanent experimental facilities company limited); Adopt cement consistency and analyzer setting time (being Vicat apparatus, Wuxi construction material instrument machinery plant) to measure setting time.
When measuring setting time, load onto the test point of diameter 1.1mm in the lower end of round metal bars, the slipper gross weight is 300 ± 2 grams.During mensuration sample placed test point and slurry surface contact, unclamp parbuckle screw suddenly, test point freely sinks to slurry, observes pointer and indicates numerical value.
From adding consolidation liquid, when test point sank to slurry and is no more than 1mm, required time was setting time.The group data repeat 3 times.
(3) adhesive strength test
Adopt shear strength to characterize bond properties.Shear strength is the leading indicator of reflection glue-joint strength (adhesive strength), in order to the intensity of opposing stress on sign and the glue-line plane parallel direction.
Get fresh Os Sus domestica, process 40mm * 25mm * 5mm osteocomma batten.Test shear strength method is as shown in Figure 1, and an end of the first osteocomma batten 1 is fixed on the afterburning frame 5 with finer wire, and an end of the second osteocomma batten 2 is lain on the ergometer 6 with finer wire.The slurry 7 that is in harmonious proportion is spread upon the other end of the first osteocomma batten 1; Account for 1/3 place of length overall; The other end of pressing the second osteocomma batten 2 is ridden on the first osteocomma batten 1, push material unnecessary between the osteocomma batten is overflowed, two osteocomma battens are fully fitted to a pair of.Bonding force was tested in bonding back 6 hours record stretching resistance size (F).Every experimental group comprises 5 pairs of parallel samples.
Record the length and the width of every osteocomma stick portion in each group respectively with micrometer, calculate bond area (S).σ=F/S calculates bonding strength according to formula.
(4) intensity test
With pressed powder and consolidation liquid liquid-solid ratio mix homogeneously, insert diameter 6mm, in the stainless steel mould of high 20mm by 0.8 ~ 4mL/g.Batten is promptly put into 100% relative humidity, 37 ℃ of environment after taking out, and solidifies after 3 days to take out, and both ends of the surface polish with fine sandpaper, measures compressive strength by universal testing machine.Load speed is 1mm/min, and maximum pressure is 2000N, and every group of data comprise 5 parallel samples.
Embodiment 1
Preparation 5wt% aqueous citric acid solution adds chitosan, sodium alginate, makes consolidation liquid, wherein contains 1wt% chitosan, 1wt% sodium alginate.Take by weighing 0.4g calcium phosphate bone cement powder, add the 0.5mL consolidation liquid, bone cement powder and consolidation liquid mix homogeneously.
Pastel is put into simulated body fluid, place vibration case (100r/min) vibration 24h then, observe water repelling property, the result sees Fig. 2, by Fig. 2 it is thus clear that, added citric acid in the consolidation liquid after, bone adhesives water-resistance is improved preferably.
Through test, be 19min setting time, and comprcssive strength is 15MPa, and adhesive strength is 26Ncm
-2
Embodiment 2
Preparation 40wt% aqueous citric acid solution adds chitosan, sodium alginate, makes consolidation liquid, wherein contains 1wt% chitosan, 5wt% sodium alginate.Take by weighing 0.4g calcium phosphate bone cement powder, add the 0.2mL consolidation liquid, and with bone cement powder and consolidation liquid mix homogeneously.Be 8min setting time, and its comprcssive strength is 52MPa behind the bone dry, and adhesive strength is 43Ncm
-2
Embodiment 3
Preparation 5wt% aqueous citric acid solution adds chitosan, sodium alginate, makes consolidation liquid, wherein contains 5wt% chitosan, 1wt% sodium alginate.Take by weighing 0.4g calcium phosphate bone cement powder, add the 0.4mL consolidation liquid, and with bone cement powder and consolidation liquid mix homogeneously.Be 13min setting time, and its comprcssive strength is 29MPa behind the bone dry, and adhesive strength is 68Ncm
-2
Embodiment 4
Preparation 40wt% aqueous citric acid solution adds carboxymethyl chitosan, starch, makes consolidation liquid, wherein contains 5wt% carboxymethyl chitosan, 5wt% starch.Take by weighing 0.4g calcium phosphate bone cement powder, add the 0.1mL consolidation liquid, and with bone cement powder and consolidation liquid mix homogeneously.Be 6.5min setting time, and its comprcssive strength is 45MPa behind the bone dry, and adhesive strength is 32Ncm
-2
Embodiment 5
Preparation 30wt% aqueous citric acid solution adds sulfated chitosan, sodium alginate, makes consolidation liquid, wherein contains 1wt% sulfated chitosan, 5wt% sodium alginate.Take by weighing the 0.4g hydroxyapatite powder, add the 0.4mL consolidation liquid, and with bone cement powder and consolidation liquid mix homogeneously.Be 9.5min setting time, and its comprcssive strength is 61MPa behind the bone dry, and adhesive strength is 49Ncm
-2
Embodiment 6
Preparation 40wt% aqueous solution of malic acid adds chitosan, starch, makes consolidation liquid, wherein contains 3wt% chitosan, 5wt% starch.Take by weighing the beta-calcium phosphate bone cement powder of 0.4g, add the 0.1mL consolidation liquid, and with bone cement powder and consolidation liquid mix homogeneously.Be 10.5min setting time, and its comprcssive strength is 55MPa behind the bone dry, and adhesive strength is 31Ncm
-2
Embodiment 7
Preparation 40wt% aqueous tartaric acid solution adds chitosan, sodium alginate, makes consolidation liquid, wherein contains 5wt% chitosan, 5wt% sodium alginate.Take by weighing 0.4g calcium phosphate bone cement powder, add the 0.2mL consolidation liquid, and with bone cement powder and consolidation liquid mix homogeneously.Be 7.5min setting time, and its comprcssive strength is 71MPa behind the bone dry, and adhesive strength is 69Ncm
-2
Embodiment 8
Preparation 30wt% aqueous solution of malic acid adds phosphonized chitosan and makes consolidation liquid, wherein contains the 4wt% phosphonized chitosan.Take by weighing 0.4g tetracalcium phosphate bone cement powder, add the 0.2mL consolidation liquid, and with bone cement powder and consolidation liquid mix homogeneously.Be 9.5min setting time, and its comprcssive strength is 43MPa behind the bone dry, and adhesive strength is 26Ncm
-2
Embodiment 9
(0,10wt%, 20wt%, 40wt%) aqueous citric acid solution of preparation variable concentrations adds chitosan and makes consolidation liquid, wherein contains the 2wt% chitosan.Take by weighing 0.4g calcium phosphate bone cement powder, add the 0.2mL consolidation liquid, and with bone cement powder and consolidation liquid mix homogeneously.
Sample takes out sample behind 100r/min vibration 24h as in the simulated body fluid, and dry 24h in 60 ℃ of baking ovens weighs, and weighs the water repelling property of material with the weightless situation of bone cementum firming body.The result is as shown in Figure 3, and the weight-loss ratio of firming body is respectively under each concentration: 14.5%, 8.6%, 0.44% and 0.37%.Adding the weightless of citric acid after fixing body obviously reduces.The bone adhesives weight-loss ratio that does not add citric acid reaches 14.5%, and the citric acid weight-loss ratio of interpolation 10% reduces to 8.6%, and the citric acid weight-loss ratio of interpolation 20% and 40% drops to 0.44% and 0.37% respectively, does not almost have defeated and dispersed.
Adopt cement consistency and setting time analyzer measure setting time.The result is as shown in Figure 4, and each concentration is respectively following hardening time: 22 minutes, 16 minutes, 12 minutes and 5.2 minutes.Organic acid can shorten hardening time.Be 22 minutes hardening time when not containing citric acid, adds 40% citric acid rear curing time and shorten to 5.2 minutes.This shows, add organic acid and can reduce the time of operation so that during the actual operation operation.
The adhesive strength test result is as shown in Figure 5, and the adhesive strength under each concentration is respectively: 24.56Ncm
-2, 35.72Ncm
-2, 59.95Ncm
-2And 72Ncm
-2Adhesive strength strengthens along with the raising of citric acid content.
Firming body among the embodiment 2 is put into 100% relative humidity, 37 ℃ of environment, solidify after 3 days and take out drying.Sample is cut off, get the microstructure of adopting the sem observation material behind the fresh section metal spraying.As shown in Figure 6, the visible a large amount of needle-like hydroxyapatite crystal of section part.
Embodiment 11
Firming body among the embodiment 2 is put into 100% relative humidity, 37 ℃ of environment, solidify and take out drying after 3 days.Put into the culture tube that the DMEM culture fluid is housed with after the curable binder precursor sterilization, place 37 ℃, 100% relative humidity, 5%CO
2In the incubator 24 hours, after the taking-up, it was subsequent use to blot the material surface culture fluid.
Get the 4th generation the exponential phase osteoblast, after trypsinization, the centrifugal collection, be prepared into 1 * 10
6The cell suspension of/mL concentration drips in material to saturated.The material of absorptive cell suspension is placed 37 ℃, 100% relative humidity, 5%CO
2Cultivated in the incubator 4 hours, and again the culture fluid in the culture dish was added to the normal cultured consumption, continue to place 37 ℃, 100% relative humidity, 5%CO
2Cultivated respectively in the incubator 8 hours.Complex with material and cell takes out then, washs gently 3 times with PBS, places fixedly 30min of 2% paraformaldehyde-2.5% glutaraldehyde, after 50%, 70%, 90%, 100% ethanol dewaters step by step then, adopts the cell pattern of scanning electron microscopic observation material surface.The result is as shown in Figure 7, shows: cell is at material surface full extension, and in the material surface adhesion well, illustrative material has the good cell compatibility.
All documents in that the present invention mentions are all quoted as a reference in this application, are just quoted such as a reference separately as each piece document.Should be understood that in addition after having read above-mentioned teachings of the present invention, those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. a bone renovating material is characterized in that, has following one or more characteristic:
(b1) setting time≤20min;
(b2) adhesive strength>=25Ncm
-2
(b3) comprcssive strength >=15MPa;
(b4) anti-collapsibility performance: in simulated body fluid, behind 100r/min vibration 24h, weight-loss ratio≤10wt%.
2. the method for preparing of a bone renovating material as claimed in claim 1 is characterized in that, comprises step:
Is 0.8: 1 ~ 4 with pressed powder and consolidation liquid by solid-to-liquid ratio: 1g/mL is in harmonious proportion, and obtains said bone renovating material; Wherein, said pressed powder is a phosphate bone cement powder; Said consolidation liquid is formulated in aqueous solutions of organic acids by natural polysaccharide, natural polysaccharide derivant or its composition dissolves.
3. method as claimed in claim 2 is characterized in that, said pressed powder is selected from: calcium hydrogen phosphate, a kind of or its mixture in dalcium biphosphate, tricalcium phosphate, tetracalcium phosphate, OCP, magnesium phosphate, hydroxyapatite, the fluor-apatite; And/or
Said natural polysaccharide is selected from: a kind of or its mixture in chitosan, sodium alginate, cellulose, the starch; And/or
Said natural polysaccharide derivant is selected from: a kind of or its mixture in carboxymethyl chitosan, quaternary ammonium salt chitosan, sulfated chitosan, the phosphonized chitosan; And/or
Described organic acid is selected from: a kind of or its mixture in citric acid, malic acid, tartaric acid or the ascorbic acid.
4. method as claimed in claim 2 is characterized in that, the mass percent concentration of said aqueous solutions of organic acids is 1% ~ 50%.
5. method as claimed in claim 2 is characterized in that, in the said consolidation liquid, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its compositions is 0.1% ~ 6%.
6. a test kit that is used to form the described bone renovating material of claim 1 is characterized in that, comprises following component:
(a) pressed powder, said pressed powder are phosphate bone cement powder;
(b) natural polysaccharide, natural polysaccharide derivant or its compositions;
(c) aqueous solutions of organic acids;
Or comprise following component:
(a ') pressed powder, said pressed powder are phosphate bone cement powder;
(b ') consolidation liquid: said consolidation liquid contains: natural polysaccharide, natural polysaccharide derivant or its compositions; And aqueous solutions of organic acids.
7. test kit as claimed in claim 6 is characterized in that, said pressed powder is selected from: calcium hydrogen phosphate, a kind of or its mixture in dalcium biphosphate, tricalcium phosphate, tetracalcium phosphate, OCP, magnesium phosphate, hydroxyapatite, the fluor-apatite; And/or
Said natural polysaccharide is selected from: a kind of or its mixture in chitosan, sodium alginate, cellulose, the starch; And/or
Said natural polysaccharide derivant is selected from: a kind of or its mixture in carboxymethyl chitosan, quaternary ammonium salt chitosan, sulfated chitosan, the phosphonized chitosan; And/or
Described organic acid is selected from: a kind of or its mixture in citric acid, malic acid, tartaric acid or the ascorbic acid.
8. test kit as claimed in claim 6 is characterized in that, the mass percent concentration of said aqueous solutions of organic acids is 5% ~ 40%;
Said component (b) is dissolved in said component (c) and forms consolidation liquid, and the mass percent concentration of said component (b) is 1% ~ 5%; Or in said component (b ') consolidation liquid, the mass percent concentration of said natural polysaccharide, natural polysaccharide derivant or its compositions is 1% ~ 5%.
9. test kit as claimed in claim 6 is characterized in that, said component (b) is dissolved in said component (c) and forms consolidation liquid, and the solid-to-liquid ratio of said component (a) pressed powder and said consolidation liquid is 0.8: 1 ~ 4: 1g/mL;
Or the solid-to-liquid ratio of said component (a ') pressed powder and said component (b ') consolidation liquid is 0.8: 1 ~ 4: 1g/mL.
10. the purposes of bone renovating material as claimed in claim 1 or each described test kit of claim 6 ~ 9 is characterized in that, said purposes is selected from down group:
(a1) be used to prepare the jointing material of bonding bone;
(a2) be used to prepare the jointing material of bonding artificial joint;
(a3) be used to prepare the jointing material of bonding internal fixation device; Or
(a4) be used to prepare the packing material of filling fracture gap or bone defect.
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