CN107198795B - One kind bone cement containing rubidium and the preparation method and application thereof - Google Patents
One kind bone cement containing rubidium and the preparation method and application thereof Download PDFInfo
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- CN107198795B CN107198795B CN201710416623.0A CN201710416623A CN107198795B CN 107198795 B CN107198795 B CN 107198795B CN 201710416623 A CN201710416623 A CN 201710416623A CN 107198795 B CN107198795 B CN 107198795B
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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Abstract
The invention belongs to bone injuries to repair field of medical materials, and in particular to one kind bone cement containing rubidium and the preparation method and application thereof.The present invention provides a kind of bone cement containing rubidium, bone cement described in the bone cement is made of ribidium salt solution and calcium aluminate, the concentration of rubidium salt is that 0.01~1mol/L bone cement containing rubidium provided by the present invention has setting time short in the ribidium salt solution, setting temperature is low, good plasticity, bio-compatible performance, suitable for orthopaedics, cranial surgery, the Plastic renovation in the fields such as dentistry and cranium field.
Description
Technical field
The invention belongs to bone injuries to repair field of medical materials, and in particular to a kind of bone cement and preparation method thereof with answer
With.
Background technique
Bone cement is a kind of medical material for bone surgery, due to it part physical property and solidification after appearance
With character quite as building, white cement for decoration, so popular title there has been.In fact, its rectification of name is bone cement, main
It is used for prosthetic replacement's operation and artificial prosthesis is fixed.The filling of bone defect cavity is irreplaceable, can be with according to chemical component
It is divided into organic and inorganic two major classes.Organic bone cement is mainly acrylic polymer, and inorganic-bone cement is mainly calcium phosphate,
Novel inorganic-bone cements many in recent years are continuously developed out, such as calcium silicates bone cement, calcium aluminate bone cement, calcium sulfate
Bone cement, magnesium phosphate cement etc..Currently, mainly using polymethyl methacrylate (PMMA) bone cement in operation, but study
It was found that PMMA bone cement there is elasticity modulus excessively high, polymerization process sharply many defects such as heat release, nonabsorable, polymerize
Cheng Zhonghui generates the volume contraction of 3-7%, causes interface to generate microfissure, and then influence stability and mechanical property.Common
Side effect further include: centrum closes on segment refracture, and nerve is burnt, osteonecrosis etc..
Inorganic-bone cement is made of solid phase and liquid phase, and can voluntarily be solidified into after two-phase mixtures by certain time has centainly
The hard material of intensity can fill irregular bone defect, be ideal bone renovating material.Compared with organic bone cement, nothing
Machine bone cement is few in solidification process releasing heat, or not heat release；Without toxic products (such as monomer)；With good bio-compatible
Property and bioactivity.Calcium aluminate bone (CAC) has more than 100 years history in the application of building field.CAC has than calcium phosphate bone cement
There is higher intensity, but hydration time is short.2000, market is introduced as a kind of new dental prosthetic material in Sweden CAC,
Trade name DoxaDent.The report of In vivo study shows to form between CAC repair materials and tooth and combine closely, and aluminium
Sour calcium in the curing process can in-situ preparation hydroxyapatite.Calcium aluminate bone cement setting time is long, and internal mineralization ability needs
Reinforce, rubidium salt and CAC is compound, setting time can be shortened, improve compression strength to a certain extent, preparation comprehensive performance is more
Excellent bone cement material.
Summary of the invention
A kind of function admirable is provided it is an object of the invention to overcome above-mentioned the deficiencies in the prior art place, bio-compatible
The good bone cement and the preparation method and application thereof of property.
To achieve the above object, the technical scheme adopted by the invention is as follows: a kind of bone cement containing rubidium, by ribidium salt solution and aluminium
Sour calcium is made, and the concentration of rubidium salt is 0.01~1mol/L in the ribidium salt solution.
Rubidium ion ionization potential with higher, therefore be easier to ionize, so that rubidium be made to have in chemical reaction
Very high activity and electropositive, so rubidium salt can accelerate hydration in CAC, rubidium ion accelerated release in vitro can give bone cement table
More bigger holes are brought in face, so that calcium ion is accelerated to discharge, safe pH value, the bio-compatible that calcium aluminate bone cement has
The good feature of property.
As the preferred embodiment of the bone cement of the present invention containing rubidium, the concentration of rubidium salt is in the ribidium salt solution
0.01~0.1mol/L.This is because cell activity has begun reduction, compression strength drop when concentration is greater than 0.1mol/L
It is low, and cause the waste of rubidium element.
As the preferred embodiment of the bone cement of the present invention containing rubidium, the ribidium salt solution be rubidium nitrate solution,
Rubidium chloride solution or rubidium carbonate solution it is one or more.
It is furthermore preferred that the ribidium salt solution is rubidium chloride solution.
As the preferred embodiment of the bone cement of the present invention containing rubidium, the quality of the ribidium salt solution and the calcium aluminate
Than for 0.3-0.7 ︰ 1.
It is furthermore preferred that the mass ratio for stating ribidium salt solution and the calcium aluminate is 0.7 ︰ 1.
As the preferred embodiment of the bone cement of the present invention containing rubidium, the ribidium salt solution is to be prepared via a method which
It obtaining: under agitation, rubidium salt solid being dissolved as 1mol/L, rear gradient dilution is 0.1mol/L, 0.05mol/L,
0.01mol/L uses gradient dilution to be more time saving and energy saving, reduces the brought error that solid dissolution remains in inner wall,
Reduce repeatedly weigh it is cumbersome.
As the preferred embodiment of the bone cement of the present invention containing rubidium, the preparation method of the calcium aluminate be by calcium salt and
After aluminium salt dissolves respectively, the ratio that the molar ratio according to calcium in aluminium in aluminium salt and calcium salt is 2:1 is mixed, and adds lemon
Lemon acid solution is mixed, and the molar ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1:1 in aluminium salt；To
After mixing acquired solution clarification, ethylene glycol stirring is added, the molar ratio (1-3) of ethylene glycol and citric acid: 1, in 100-150 DEG C
It is heated to gel state；Then it in 120-150 DEG C of drying, then grinds, is put into sintering furnace in 1000-1300 DEG C of heating 3-5h,
Obtain calcium aluminate powder.According to the method, the available higher calcium aluminate powder of purity.
As the preferred embodiment of the bone cement of the present invention containing rubidium, the calcium salt is calcium nitrate, and the aluminium salt is nitre
Sour aluminium.
As the preferred embodiment of the bone cement of the present invention containing rubidium, the average particle size of the calcium aluminate is 0.5~15 μ
m.The partial size of calcium aluminate collagen material reduces to a certain extent, is conducive to the promotion of compression strength and the change of mobility
As the preferred embodiment of the bone cement of the present invention containing rubidium, the calcium aluminate the preparation method comprises the following steps: by aluminic acid
Calcium powder carries out ball milling according to the ratio that ratio of grinding media to material is 1:5-15, and alcohol or acetone is added, and the revolving speed of ball milling is 300-400r/
Min, time 2-36h；It is dried in vacuo after ball milling, sieves powder, obtain the calcium aluminate that average particle size is 0.5-15 μm.
As the preferred embodiment of the bone cement of the present invention containing rubidium, the ball grinder is using zirconium oxide or oxidation aluminum
It is yttria coating toughened zirconium oxide ball at, the ball, diameter is divided into tri- kinds of 1mm.2mm.3mm, different scale ball weight when ball milling
Amount proportion 1:3.
As the preferred embodiment of the bone cement of the present invention containing rubidium, ball milling is arranged revolving speed 300-400r/min, and every 10
Minute rest 1 minute starts to reversely rotate ball milling.
As the preferred embodiment of the bone cement of the present invention containing rubidium, ball-milling medium selects acetone, alcohol etc..
As the preferred embodiment of the bone cement of the present invention containing rubidium, Ball-milling Time 4-30h, by ball grinder after ball milling
After rapid vacuum is dry, by sieve sieving 200-400 mesh.
The present invention also provides the preparation methods of the above-mentioned bone cement containing rubidium comprising following steps: is added into calcium aluminate
Ribidium salt solution obtains slurry, and gained slurry is stood 1-21 days under 37 DEG C of constant temperatures, 100% water bath；Wherein, institute
The concentration for stating rubidium salt in ribidium salt solution is 0.01~1mol/L.
The application in medical material is repaired in preparation bone injury finally, the present invention also provides above-mentioned bone cements containing rubidium.
Compared with the prior art, the advantages of the present invention are as follows:
1. the material of bone cement containing rubidium of the present invention, purity is higher, and partial size can be changed by ball milling parameter, due to rubidium
Ion ionization potential with higher, therefore be easier to ionize, to make rubidium that there is very high activity in chemical reaction
And electropositive, so rubidium salt can accelerate hydration in CAC, rubidium ion accelerated release in vitro can be brought more to bone cement surface
Bigger hole, so that calcium ion is accelerated to discharge, safe pH value, the spy for the good biocompatibility that calcium aluminate bone cement has
Point.
2. biology bone renovating material of the present invention has good setting time at room temperature, have fine
Biocompatibility and stability, the compression strength of calcium aluminate can be improved in a certain range.It is specifically for example of the present invention
Bone cement repair materials add 0.1mol/L rubidium salt presetting period 9 minutes into calcium aluminate bone cement, eventually according to liquid-solid ratio 0.7
Solidifying 27 minutes time, compression strength maximum temperature only have 30-32 DEG C, and compression strength is better than blank control group, cell Proliferation energy within 1 day
Power is significantly better than the calcium aluminate bone cement of blank control group.
3. using solution chemical processes in the preparation process of Bone Defect Repari containing rubidium of the invention, 800-1200 DEG C of heating temperature, add
As long as 3 hours of hot time, plasticity is good after preparing slurry, and operating method is simple, and proportion of raw material is adjustable, and low energy consumption.
Detailed description of the invention:
Fig. 1 is the setting time maximum temperature figure for the composite bone cement being prepared using embodiment 1-5 the method.
Fig. 2 is the maximum temperature figure for the composite bone cement being prepared using embodiment 1-5 the method.
Fig. 3 is the scanning electron microscope (SEM) photograph for the composite bone cement being prepared using embodiment 1-5 the method
Fig. 4 is the power spectrum test chart for the composite bone cement being prepared using embodiment 1-5 the method.
Fig. 5 is that the composite bone cement that embodiment 1 and 5 the method for embodiment are prepared is respectively adopted to be immersed in analogue body
X-ray diffraction analysis spectrogram in liquid (SBF) after 21 days.
Fig. 6 is 1 day compression test figure of the composite bone cement being prepared using embodiment 1-5 the method.
Fig. 7 is at 37 degrees Celsius, and using the bone cement containing rubidium of embodiment 4, in simulated body fluid (SBF), 14 days and 21 days in vitro
Mineralising scanning electron microscope (SEM) photograph
Fig. 8 is at 37 degrees Celsius, and using the bone cement containing rubidium of embodiment 4, in simulated body fluid (SBF), 14 days and 21 days in vitro
Mineralising power spectrum test chart
Fig. 9 is at room temperature, for bone cement containing rubidium 1.3.5 days for using embodiment 1-5, MTT test chart
Figure 10 is at room temperature, for 1 day cell adhesion experiments of bone cement containing rubidium of 1.3.5 of embodiment of the present invention preparation.
Specific embodiment:
Purposes, technical schemes and advantages in order to better illustrate the present invention, below in conjunction with drawings and examples to this
Invention is described further.
Embodiment 1
The preparation method of the bone cement containing rubidium described in the present embodiment, includes the following steps:
The bone cement powder that will be sieved after ball milling is placed again into agate mortar grinding, calcareous with aluminic acid according to ribidium salt solution
Amount is added 0mol/L ribidium salt solution (ultra-pure deionized water) than being 0.7:1, after being thoroughly mixed, is packed into clean mold
In, mold is put into 37 degree of 100% water baths of constant temperature, bone cement cylinder is stood in 37 DEG C of insulating boxs, stands 1-21
It is demoulded after it up to institute's art bone cement repair materials.
Embodiment 2
The preparation method of bone cement described in the present embodiment, includes the following steps:
The bone cement powder that will be sieved after ball milling is placed again into agate mortar grinding, calcareous with aluminic acid according to ribidium salt solution
Amount is added 0.01mol/L ribidium salt solution (ultra-pure deionized water) than being 0.7:1, after being thoroughly mixed, is packed into clean mould
In tool, mold is put into 37 DEG C of 100% water baths of constant temperature, bone cement cylinder is stood in 37 DEG C of insulating boxs, stands 1-
It is demoulded after 21 days up to institute's art bone cement repair materials.
Embodiment 3
The preparation method of bone cement described in the present embodiment, includes the following steps:
The bone cement powder that will be sieved after ball milling is placed again into agate mortar grinding, calcareous with aluminic acid according to ribidium salt solution
Amount is added 0.05mol/L ribidium salt solution (ultra-pure deionized water) than being 0.7:1, after being thoroughly mixed, is packed into clean mould
In tool, mold is put into 37 DEG C of 100% water baths of constant temperature, bone cement cylinder is stood in 37 DEG C of insulating boxs, stands 1-
It is demoulded after 21 days up to institute's art bone cement repair materials.
Embodiment 4
The preparation method of bone cement described in the present embodiment, includes the following steps:
The bone cement powder that will be sieved after ball milling is placed again into agate mortar grinding, calcareous with aluminic acid according to ribidium salt solution
Amount is added 0.1mol/L ribidium salt solution (ultra-pure deionized water) than being 0.7:1, after being thoroughly mixed, is packed into clean mould
In tool, mold is put into 37 DEG C of 100% water baths of constant temperature, bone cement cylinder is stood in 37 DEG C of insulating boxs, stands 1-
It is demoulded after 21 days up to art institute bone cement repair materials.
Embodiment 5
The preparation method of bone cement described in the present embodiment, includes the following steps:
The bone cement powder that will be sieved after ball milling is placed again into agate mortar grinding, calcareous with aluminic acid according to ribidium salt solution
Amount is added 1mol/L ribidium salt solution (ultra-pure deionized water) than being 0.7:1, after being thoroughly mixed, is packed into clean mold
In, mold is put into 37 DEG C of 100% water baths of constant temperature, bone cement cylinder is stood in 37 DEG C of insulating boxs, stands 1-21
It is demoulded after it up to institute's art bone cement repair materials.
Embodiment 6
The preparation method of calcium aluminate bone cement, includes the following steps: described in the present embodiment
By calcium nitrate, aluminum nitrate mixes after dissolving respectively, rear that citric acid solution mixing is added, and ethylene glycol is finally added dropwise
Stirring, heating 80-150 degree are heated to gel state, are put into drying box 120-150 degree heating overnight and put solidification foam grinding
Enter sintering furnace 800-1200 degree heating 3-5h, the higher calcium aluminate powder of purity can be obtained, the calcium aluminate powder that sintering is finished
Wet-milling 3-20h, vacuum drying are passed through in end, and sieving is put into the storage of electronic dry case.
Embodiment 7
Bone cement ball grinding method described in the present embodiment, includes the following steps:
(1) according to ratio of grinding media to material 15-10:1, suitable alcohols are added as ball-milling medium.
It (2) is respectively the yttria coating of 1mm.2mm.3mm with diameter using ball grinder made of zirconium oxide or aluminium oxide
Toughened zirconium oxide ball carries out ball milling, and different scale ball weight matches 1:3:6 when ball milling
(3) revolving speed 300-400r/min is arranged in ball milling, rests 1 minute within every 10 minutes, starts to reversely rotate ball milling.
(4) after drying ball grinder rapid vacuum after 4~30h of ball milling, by sieve sieving 200-400 mesh.
Embodiment 8
A kind of bone cement of the embodiment of the present invention, bone cement described in the present embodiment are made of ribidium salt solution and calcium aluminate, institute
Stating ribidium salt solution is rubidium nitrate solution, and the concentration of rubidium salt is 0.5mol/L, the ribidium salt solution and the aluminic acid in ribidium salt solution
The mass ratio of calcium is 0.3 ︰ 1.
In the present embodiment, the average particle size of the calcium aluminate is 0.5 μm, preparation method are as follows: distinguishes calcium salt and aluminium salt
After dissolution, the ratio that the molar ratio according to calcium in aluminium in aluminium salt and calcium salt is 2:1 is mixed, and adds citric acid solution
It is mixed, the molar ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1:1 in aluminium salt；Gained to be mixed
After solution clarification, ethylene glycol stirring is added, the molar ratio (1-3) of ethylene glycol and citric acid: 1, it is heated to coagulating in 100-150 DEG C
Gluey state；Then it in 120-150 DEG C of drying, then grinds, is put into sintering furnace in 1000-1300 DEG C of heating 3-5h, obtains aluminic acid
Calcium powder；Wherein, the calcium salt is calcium nitrate, and the aluminium salt is aluminum nitrate.
Bone cement described in the present embodiment the preparation method comprises the following steps: ribidium salt solution is added into calcium aluminate, slurry is obtained, by gained
Slurry stands 1-21 days under 37 DEG C of constant temperatures, 100% water bath；Wherein, the calcium salt is calcium nitrate, and the aluminium salt is
Aluminum nitrate.
Embodiment 9
A kind of bone cement of the embodiment of the present invention, bone cement described in the present embodiment are made of ribidium salt solution and calcium aluminate, institute
Stating ribidium salt solution is rubidium chloride solution, and the concentration of rubidium salt is 1mol/L, the ribidium salt solution and the calcium aluminate in ribidium salt solution
Mass ratio be 0.5 ︰ 1.
In the present embodiment, the average particle size of the calcium aluminate is 10 μm, preparation method are as follows: calcium salt and aluminium salt difference is molten
Xie Hou, according to calcium in aluminium in aluminium salt and calcium salt molar ratio be 2:1 ratio be mixed, add citric acid solution into
Row mixes, and the molar ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1:1 in aluminium salt；Gained to be mixed is molten
After liquid clarification, ethylene glycol stirring is added, the molar ratio (1-3) of ethylene glycol and citric acid: 1, gel is heated in 100-150 DEG C
State；Then it in 120-150 DEG C of drying, then grinds, is put into sintering furnace in 1000-1300 DEG C of heating 3-5h, obtains calcium aluminate
Powder；Wherein, the calcium salt is calcium nitrate, and the aluminium salt is aluminum nitrate.
Bone cement described in the present embodiment the preparation method comprises the following steps: ribidium salt solution is added into calcium aluminate, slurry is obtained, by gained
Slurry stands 1-21 days under 37 DEG C of constant temperatures, 100% water bath.
Embodiment 10
A kind of bone cement of the embodiment of the present invention, bone cement described in the present embodiment are made of ribidium salt solution and calcium aluminate, institute
Stating ribidium salt solution is rubidium carbonate solution, and the concentration of rubidium salt is 0.01mol/L, the ribidium salt solution and the aluminic acid in ribidium salt solution
The mass ratio of calcium is 0.7 ︰ 1.
In the present embodiment, the average particle size of the calcium aluminate is 15 μm, preparation method are as follows: calcium salt and aluminium salt difference is molten
Xie Hou, according to calcium in aluminium in aluminium salt and calcium salt molar ratio be 2:1 ratio be mixed, add citric acid solution into
Row mixes, and the molar ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1:1 in aluminium salt；Gained to be mixed is molten
After liquid clarification, ethylene glycol stirring is added, the molar ratio (1-3) of ethylene glycol and citric acid: 1, gel is heated in 100-150 DEG C
State；Then it in 120-150 DEG C of drying, then grinds, is put into sintering furnace in 1000-1300 DEG C of heating 3-5h, obtains calcium aluminate
Powder；Wherein, the calcium salt is calcium nitrate, and the aluminium salt is aluminum nitrate.
Bone cement described in the present embodiment the preparation method comprises the following steps: ribidium salt solution is added into calcium aluminate, slurry is obtained, by gained
Slurry stands 1-21 days under 37 DEG C of constant temperatures, 100% water bath.
Embodiment 11
The preparation method of the bone cement containing rubidium described in the present embodiment, includes the following steps:
Rubidium salt is dissolved in ultra-pure deionized water, is configured to 1mol/L, 0.1mol/L, 0.05mol/L, 0.01mol/L, blank
Control is ultra-pure deionized water group, mixes, regrinds for 0.7:1 with calcium aluminate mass ratio according to ribidium salt solution, dense with difference
Degree rubidium salt is mixed into slurry, and obtained slurry is injected in designed, designed mold, is put into 37 degree of 100% water baths of constant temperature.
Fig. 1 is to obtain the setting time of bone cement using above embodiments 1-5 the method, and wherein CAC is indicated to bone water
The ribidium salt solution concentration added in mud is 0mol/L；CAC1 indicates that the ribidium salt solution concentration added into bone cement is 0.01mol/
L；CAC2 indicates that the ribidium salt solution concentration added into bone cement is 0.05mol/L；CAC3 indicates the rubidium added into bone cement
Concentration of salt solution is 0.1mol/L；CAC4 indicates that the ribidium salt solution concentration added into bone cement is 1mol/L.It can be with according to Fig. 1
Find out, as rubidium chloride concentration is from 0mol/L to 1mol/L, the presetting period is reduced to 5min from 58min, and final setting time is from 214min
It is reduced to 14min
Fig. 2 is the solidification maximum temperature obtained using above embodiments 1-5 the method, and maximum temperature is taken the photograph 30.8 to 32
Between family name's degree, without because rubidium salt is added to have significant change.
Fig. 3 is under 37 DEG C of water bath with thermostatic control environmental conditions, using embodiment 1, embodiment 2, embodiment 3, embodiment 4, reality
Apply bone cement described in example 5.It can be clearly seen that from Fig. 3, the calcium aluminate on bone cement surface of the invention is sheet, recessed
Convex injustice is more advantageous to cell Proliferation.A1-3 is pattern after pure CAC is hydrated 1 day, and there are hole, inner surface hole and control group in surface
(control group is that ribidium salt solution is not added, and has only added the bone cement of ultrapure water, rubidium is not added in CAC, that is, blank control group herein) ratio is wanted
It is few；B1-3 is pattern after 0.1mol/L RbCl is mixed CAC 1 day, and inner surface gap is increased, and surface is more irregular, in pit
There are many attachments；C1-3 is pattern after 1mol/L RbCl is mixed CAC 1 day, and internal surface of column relative clearance is few, but circle
The obvious mostly many bedded substances of column exocuticle, the calcium aluminate on bone cement surface of the invention is sheet, uneven more to have
Conducive to cell Proliferation.It can be clearly seen that from energy spectrum diagram, the rubidium element on bone cement surface of the invention is than in bone cement
Portion is more, it may be speculated that rubidium ion is more advantageous to hair with the extension of time, gradually from cement internal migration to outside in this way
Wave the biological effect of rubidium ion.
Under the conditions of 37 DEG C, using bone cement described in embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5
Test is discharged in SBF intermediate ion and pH test shows that the calcium ion burst size more than bone cement amount containing rubidium of the invention is more, thus it is speculated that rubidium
It is easier to discharge compared to calcium, causes bigger porosity, lead to the accelerated release in vitro of calcium ion, wherein 0.1mol/L experimental group phosphorus member
Plain downward trend is maximum, and side demonstrates surface mineralization ability, and pH value is between 7.45-7.85, between human normal pH.
It is the calcium aluminate bone cement that rests in water vapor after 7 days is inside and outside that Fig. 4, which is power spectrum test, is passed through
Power spectrum Elemental redistribution can be seen that internal rubidium constituent content is more without outside, illustrate that rubidium element can gradually ooze out bone cement cylinder
Outside, it is advantageous for rubidium in this way and acts on cell.
If Fig. 5 is the X-ray for obtaining calcium aluminate bone cement using above embodiments 1-5 the method and impregnating 21 days in SBF
Diffraction analysis spectrogram produces hydroxyapatite and aluminium hydroxide as can be seen from the figure on matrix calcium aluminate surface.
Fig. 6 is embodiment 1-5 initial stage compression test, it can be seen that the bone cement of the RbCl containing 0.1mol/L and blank control
Group is compared, and initial stage improves compression strength, and 1mol/LRbCl group bone cement compression strength is decreased obviously.
Fig. 7InaWithB is that CAC is statically placed in 21 days test charts, c in SBFWithD is that CAC1 is statically placed in 21 days test charts in SBF,
In a large amount of ball shaped hydroxy-apatites of the Surface Creation of bone cement, by amplification factor we have found that hydroxyapatite diameter 3-5um,
There is a large amount of hole on surface, is conducive to cell and grows into, and tests its surface bead power spectrum, and Ca/P is respectively 1.64 and 1.72, very
Chemical formula close to hydroxyapatite forms 1.67, illustrates that the mineralising energy for keeping sound calcium aluminate bone cement excellent after rubidium is added
Power.
Fig. 8 is to solidify later bone cement to steep in SBF for power spectrum test, and surface has grown many little particles, we
Element determination is carried out to little particle, verifying is hydroxyapatite, and in biomaterial, material surface energy grows hydroxyl in SBF
Apatite, side illustration it have good biocompatibility.
Fig. 9 is the leaching liquor for selecting the bone cement containing rubidium, and bone marrow stromal cells (abbreviation BMMC cell) are tested using MTT
Method test cell vegetative map tests 1.3.5 days cell activity, shows the breeding ratio sky for adding rubidium chloride bone cement for cell
White control group (not adding rubidium bone cement) has more facilitation, and the 0.1mol/L advantage of bone cement containing rubidium is most obvious, with the time
Extend, addition rubidium chloride bone cement effect is also more preferable.
Figure 10 is to select 3 days adherency test charts of bone marrow stromal cells (abbreviation BMMC cell) cell,
Abcd respectively represents CAC CAC1 CAC2 CAC4, compares from figure, it can be seen that cell is in the table of bone cement containing rubidium
Face growing way is fine, uropodium occurs, and surface bone cement containing rubidium is suitble to the proliferation of cell.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of bone cement containing rubidium, which is characterized in that the bone cement is made of ribidium salt solution and calcium aluminate, the ribidium salt solution
The concentration of middle rubidium salt is 0.01~1mol/L.
2. bone cement containing rubidium according to claim 1, which is characterized in that the concentration of rubidium salt is 0.01 in the ribidium salt solution
~0.1mol/L.
3. bone cement containing rubidium according to claim 1 or 2, which is characterized in that the ribidium salt solution is rubidium nitrate solution, chlorine
Change at least one of rubidium solution, rubidium carbonate solution.
4. bone cement containing rubidium according to claim 1, which is characterized in that the quality of the ribidium salt solution and the calcium aluminate
Than for 0.3-0.7 ︰ 1.
5. bone cement containing rubidium according to claim 1, which is characterized in that the calcium aluminate the preparation method comprises the following steps: by calcium salt
After dissolving respectively with aluminium salt, the ratio that the molar ratio according to calcium in aluminium in aluminium salt and calcium salt is 2:1 is mixed, and is added
Citric acid solution is mixed, and the molar ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1:1 in aluminium salt；
After acquired solution clarification to be mixed, ethylene glycol stirring is added, the molar ratio (1-3) of ethylene glycol and citric acid: 1, in 100-150
DEG C it is heated to gel state；Then it in 120-150 DEG C of drying, then grinds, is put into sintering furnace in 1000-1300 DEG C of heating 3-
5h obtains calcium aluminate powder.
6. bone cement containing rubidium according to claim 1 or 5, which is characterized in that the average particle size of the calcium aluminate be 0.5~
15μm。
7. bone cement containing rubidium according to claim 6, which is characterized in that the calcium aluminate the preparation method comprises the following steps: by aluminic acid
Calcium powder carries out ball milling according to the ratio that ratio of grinding media to material is 1:5-15, and alcohol or acetone is added, and the revolving speed of ball milling is 300-400r/
Min, time 2-36h；It is dried in vacuo after ball milling, sieves powder, obtain the calcium aluminate that average particle size is 0.5-15 μm.
8. bone cement containing rubidium according to claim 5, which is characterized in that the calcium salt is calcium nitrate, and the aluminium salt is nitre
Sour aluminium.
9. a kind of preparation method of the bone cement containing rubidium as described in any one of claim 1~8, which is characterized in that including walking as follows
It is rapid: ribidium salt solution is added into calcium aluminate, obtains slurry, gained slurry is quiet under 37 DEG C of constant temperatures, 100% water bath
It sets 1-21 days.
10. bone cement containing rubidium described in claim 1 repairs the application in medical material in preparation bone injury.
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| JP2014223260A (en) * | 2013-05-17 | 2014-12-04 | サンメディカル株式会社 | Bone formation material for bone defect part, and kit thereof |
| CN105828742A (en) * | 2013-11-21 | 2016-08-03 | 托莱多大学 | Macroporous granules of alkaline earth phosphates using cement technology and gas evolving porogen |
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| JP2014223260A (en) * | 2013-05-17 | 2014-12-04 | サンメディカル株式会社 | Bone formation material for bone defect part, and kit thereof |
| CN105828742A (en) * | 2013-11-21 | 2016-08-03 | 托莱多大学 | Macroporous granules of alkaline earth phosphates using cement technology and gas evolving porogen |
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| Title |
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| 整形外科填充材料的制备及性能研究;谭彦妮;《中国博士学位论文全文数据库 医药卫生科技辑》;20111215(第12期);论文第25页第1段至第28页第2段 |
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