CN107198795A - A kind of bone cement containing rubidium and preparation method and application - Google Patents
A kind of bone cement containing rubidium and preparation method and application Download PDFInfo
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- CN107198795A CN107198795A CN201710416623.0A CN201710416623A CN107198795A CN 107198795 A CN107198795 A CN 107198795A CN 201710416623 A CN201710416623 A CN 201710416623A CN 107198795 A CN107198795 A CN 107198795A
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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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
Field of medical materials is repaired the invention belongs to bone injury, and in particular to a kind of bone cement containing rubidium and preparation method and application.The present invention provides a kind of bone cement containing rubidium, bone cement described in the bone cement is made up of ribidium salt solution with calcium aluminate, the concentration of rubidium salt is that 0.01~1mol/L bone cements containing rubidium provided by the present invention have 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 field such as dentistry and cranium field.
Description
Technical field
Field of medical materials is repaired the invention belongs to bone injury, and in particular to a kind of bone cement and preparation method thereof is with answering
With.
Background technology
Bone cement is a kind of medical material for bone surgery, due to outward appearance after its part physical property and solidification
With character quite as building, the white cement of finishing, 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 Cranial defect cavity is irreplaceable, can be with according to chemical composition
It is divided into organic and inorganic two major class.Organic bone cement is mainly acrylic polymer, and inorganic-bone cement is mainly calcium phosphate,
New 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..At present, it is main in operation to use polymethyl methacrylate (PMMA) bone cement, but research
It was found that, PMMA bone cements have that modulus of elasticity is too high, polymerization process drastically many defects such as heat release, nonabsorable, polymerize
Cheng Zhonghui produces 3-7% volume contraction, causes interface to produce microfissure, and then influence stability and mechanical property.Common
Side effect also includes：Centrum closes on section refracture, and nerve is burnt, osteonecrosis etc..
Inorganic-bone cement is made up of solid phase and liquid phase, can be voluntarily solidified into certain by certain time after two-phase mixtures
The hard material of intensity, can fill irregular Cranial defect, be preferable 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 the history of more than 100 years 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.Form and combine closely between the report display CAC repair materials and tooth of In vivo study, and
Calcium aluminate in the curing process can in-situ preparation hydroxyapatite.Calcium aluminate bone cement setting time is long, and internal mineralization ability has
It is to be strengthened, rubidium salt is combined with CAC, setting time can be shortened, compression strength is improved to a certain extent, combination property is prepared more
Plus excellent bone cement material.
The content 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 part, bio-compatible
Good bone cement of property and preparation method and application.
To achieve the above object, the technical scheme taken of the present invention is：A kind of bone cement containing rubidium, it is 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 has higher ionization potential, therefore is easier ionization, so that rubidium has 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 accelerate calcium ion to discharge, safe pH values, the biofacies that calcium aluminate bone cement has
The characteristics of capacitive is good.
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.Because, when concentration is more than 0.1mol/L, cytoactive has begun to reduction, compression strength drop
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,
The one or more of rubidium chloride solution or rubidium carbonate solution.
It is furthermore preferred that the ribidium salt solution is rubidium chloride solution.
It is used 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
Obtain：Under agitation, it is 1mol/L by rubidium salt solid dissolving, rear gradient dilution is 0.1 mol/L, 0.05mol/L,
0.01mol/L, uses gradient dilution to be more time saving and energy saving, reduces the error brought that solid dissolving remains in inwall,
Reduce repeatedly weigh 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
It is 2 according to the mol ratio of calcium in aluminium in aluminium salt and calcium salt after aluminium salt dissolves respectively：1 ratio is mixed, and adds lemon
Lemon acid solution is mixed, and the mol ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1 in aluminium salt:1；Treat
Mix after resulting solution clarification, add the mol ratio (1-3) of ethylene glycol stirring, ethylene glycol and citric acid：1, in 100-150 DEG C
It is heated to gel state；Then in 120-150 DEG C of drying, then grind, be put into sintering furnace and heat 3-5h in 1000-1300 DEG C,
Obtain calcium aluminate powder.According to methods described, the higher calcium aluminate powder of purity can be obtained.
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 particle mean size of the calcium aluminate is 0.5~15
μm.The particle diameter of calcium aluminate collagen material is reduced to a certain extent, is conducive to the lifting of compression strength and the change of mobility
As the preferred embodiment of the bone cement of the present invention containing rubidium, the preparation method of the calcium aluminate is：By aluminic acid
Calcium powder is 1 according to ratio of grinding media to material:5-15 ratio carries out ball milling, adds alcohol or acetone, the rotating speed of ball milling is 300-400r/
Min, the time is 2-36h；It is dried in vacuo after ball milling, sieves powder, obtains the calcium aluminate that particle mean 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
Into the ball is yttria coating toughened zirconium oxide ball, and diameter is divided into tri- kinds of 1mm.2mm.3mm, different scale ball weight during ball milling
Amount proportioning 1：3.
As the preferred embodiment of the bone cement of the present invention containing rubidium, ball milling sets rotating speed 300-400r/min, 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 is by ball grinder after 4-30h, ball milling
After rapid vacuum is dried, by screen cloth sieving 200-400 mesh.
Present invention also offers the preparation method of the above-mentioned bone cement containing rubidium, it comprises the following steps：Added into calcium aluminate
Ribidium salt solution, obtains slurry, and gained slurry is stood into 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.
Finally, the application during bone injury repairs medical material is being prepared present invention also offers above-mentioned bone cement containing rubidium.
Compared with prior art, the advantage of the invention is that：
1. the material of bone cement containing rubidium of the present invention, purity is higher, particle diameter can be changed by ball milling parameter, due to rubidium
Ion has higher ionization potential, therefore is easier ionization, so that rubidium has very high activity in chemical reaction
And electropositive, so rubidium salt can accelerate hydration in CAC, rubidium ion accelerated release in vitro can bring more to bone cement surface
Bigger hole, so that accelerate calcium ion to discharge, safe pH values, the spy for the good biocompatibility that calcium aluminate bone cement has
Point.
2. biological bone renovating material of the present invention, at ambient temperature, with good setting time, with fine
Biocompatibility and stability, the compression strength of calcium aluminate can be improved in certain limit.It is specifically for example of the present invention
Bone cement repair materials, according to liquid-solid ratio 0.7, addition 0.1mol/L rubidiums salt presetting period 9 minutes into calcium aluminate bone cement are whole
Solidifying 27 minutes time, compression strength maximum temperature only has 30-32 DEG C, and 1 day compression strength is better than blank control group, cell propagation
Ability is significantly better than the calcium aluminate bone cement of blank control group.
3. solution chemical processes are used in the preparation process of Bone Defect Repari containing rubidium of the present invention, 800-1200 DEG C of heating-up temperature, plus
As long as hot 3 hours of time, it is good to prepare plasticity after slurry, and operating method is simple, and proportion of raw material is adjustable, and energy consumption is low.
Brief description of the drawings：
Fig. 1 is the setting time maximum temperature figure of the composite bone cement prepared using embodiment 1-5 methods describeds.
Fig. 2 is the maximum temperature figure of the composite bone cement prepared using embodiment 1-5 methods describeds.
Fig. 3 is the scanning electron microscope (SEM) photograph of the composite bone cement prepared using embodiment 1-5 methods describeds
Fig. 4 is the power spectrum test chart of the composite bone cement prepared using embodiment 1-5 methods describeds.
Fig. 5 is that the composite bone cement that embodiment 1 and the methods described of embodiment 5 prepare 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 prepared using embodiment 1-5 methods describeds.
Fig. 7 be at 37 degrees Celsius, using the bone cement containing rubidium of embodiment 4,14 days and 21 days bodies in simulated body fluid (SBF)
Outer mineralising scanning electron microscope (SEM) photograph
Fig. 8 be at 37 degrees Celsius, using the bone cement containing rubidium of embodiment 4,14 days and 21 days bodies in simulated body fluid (SBF)
Outer mineralising power spectrum test chart
Fig. 9 is at room temperature, for using embodiment 1-5 bone cement containing rubidium 1.3.5 days, MTT test charts
It is 1 day cell adhesion experiments of bone cement containing rubidium prepared by 1.3.5 of the embodiment of the present invention at room temperature that Figure 10, which is,.
Embodiment：
In order to which the object, technical solutions and advantages of the present invention are better described, 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, comprises the following steps：
By the bone cement powder sieved after ball milling, agate mortar grinding is placed again into, it is calcareous with aluminic acid according to ribidium salt solution
Amount is than being 0.7：1,0mol/L ribidium salt solutions (ultra-pure deionized water) are added, after being thoroughly mixed, load clean mould
In, mould is put into 37 degree of water baths of constant temperature 100%, bone cement cylinder is stood in 37 DEG C of insulating boxs, 1-21 is stood
Demoulding produces institute's art bone cement repair materials after it.
Embodiment 2
The preparation method of bone cement described in the present embodiment, comprises the following steps：
By the bone cement powder sieved after ball milling, agate mortar grinding is placed again into, it is calcareous with aluminic acid according to ribidium salt solution
Amount is than being 0.7：1,0.01mol/L ribidium salt solutions (ultra-pure deionized water) are added, after being thoroughly mixed, load clean mould
In tool, mould is put into 37 DEG C of water baths of constant temperature 100%, bone cement cylinder is stood in 37 DEG C of insulating boxs, 1- is stood
The demoulding produces institute's art bone cement repair materials after 21 days.
Embodiment 3
The preparation method of bone cement described in the present embodiment, comprises the following steps：
By the bone cement powder sieved after ball milling, agate mortar grinding is placed again into, it is calcareous with aluminic acid according to ribidium salt solution
Amount is than being 0.7：1,0.05mol/L ribidium salt solutions (ultra-pure deionized water) are added, after being thoroughly mixed, load clean mould
In tool, mould is put into 37 DEG C of water baths of constant temperature 100%, bone cement cylinder is stood in 37 DEG C of insulating boxs, 1- is stood
The demoulding produces institute's art bone cement repair materials after 21 days.
Embodiment 4
The preparation method of bone cement described in the present embodiment, comprises the following steps：
By the bone cement powder sieved after ball milling, agate mortar grinding is placed again into, it is calcareous with aluminic acid according to ribidium salt solution
Amount is than being 0.7：1,0.1mol/L ribidium salt solutions (ultra-pure deionized water) are added, after being thoroughly mixed, load clean mould
In tool, mould is put into 37 DEG C of water baths of constant temperature 100%, bone cement cylinder is stood in 37 DEG C of insulating boxs, 1- is stood
The demoulding produces art institute bone cement repair materials after 21 days.
Embodiment 5
The preparation method of bone cement described in the present embodiment, comprises the following steps：
By the bone cement powder sieved after ball milling, agate mortar grinding is placed again into, it is calcareous with aluminic acid according to ribidium salt solution
Amount is than being 0.7：1,1mol/L ribidium salt solutions (ultra-pure deionized water) are added, after being thoroughly mixed, load clean mould
In, mould is put into 37 DEG C of water baths of constant temperature 100%, bone cement cylinder is stood in 37 DEG C of insulating boxs, 1-21 is stood
Demoulding produces institute's art bone cement repair materials after it.
Embodiment 6
The preparation method of calcium aluminate bone cement, comprises the following steps described in the present embodiment：
By calcium nitrate, aluminum nitrate is mixed after dissolving respectively, rear to add citric acid solution mixing, and ethylene glycol is finally added dropwise
Stirring, heating 80-150 degree is heated to gel state, is put into drying box 120-150 degree heating overnight, solidification foam grinding is put
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, comprises the following steps：
(1) according to ratio of grinding media to material 15-10：1, add suitable alcohols and be used as ball-milling medium.
(2) ball grinder being made of zirconium oxide or aluminum oxide, is respectively 1mm.2mm.3mm yttria coating with diameter
Toughened zirconium oxide ball carries out ball milling, different scale ball weight proportioning 1 during ball milling：3：6
(3) ball milling sets rotating speed 300-400r/min, rests 1 minute within every 10 minutes, starts to reversely rotate ball milling.
(4) after ball grinder rapid vacuum is dried after 4~30h of ball milling, by screen cloth 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 is made up of ribidium salt solution with calcium aluminate, institute
Ribidium salt solution is stated for rubidium nitrate solution, 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 particle mean size of the calcium aluminate is 0.5 μm, and its preparation method is：Calcium salt and aluminium salt are distinguished
It is 2 according to the mol ratio of calcium in aluminium in aluminium salt and calcium salt after dissolving：1 ratio is mixed, and adds citric acid solution
Mixed, the mol ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1 in aluminium salt:1；Gained to be mixed
After solution clarification, the mol ratio (1-3) of ethylene glycol stirring, ethylene glycol and citric acid is added：1, it is heated to coagulating in 100-150 DEG C
Gluey state；Then in 120-150 DEG C of drying, then grind, be put into sintering furnace and heat 3-5h in 1000-1300 DEG C, obtain aluminic acid
Calcium powder；Wherein, the calcium salt is calcium nitrate, and the aluminium salt is aluminum nitrate.
The preparation method of bone cement described in the present embodiment is：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 is made up of ribidium salt solution with calcium aluminate, institute
Ribidium salt solution is stated for rubidium chloride solution, 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 particle mean size of the calcium aluminate is 10 μm, and its preparation method is：Calcium salt and aluminium salt difference is molten
Xie Hou, is 2 according to the mol ratio of calcium in aluminium in aluminium salt and calcium salt：1 ratio is mixed, and is added citric acid solution and is entered
The mol ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1 in row mixing, aluminium salt:1；Gained to be mixed is molten
After liquid clarification, the mol ratio (1-3) of ethylene glycol stirring, ethylene glycol and citric acid is added：1, it is heated to gel in 100-150 DEG C
State；Then in 120-150 DEG C of drying, then grind, be put into sintering furnace and heat 3-5h in 1000-1300 DEG C, obtain calcium aluminate
Powder；Wherein, the calcium salt is calcium nitrate, and the aluminium salt is aluminum nitrate.
The preparation method of bone cement described in the present embodiment is：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 is made up of ribidium salt solution with calcium aluminate, institute
Ribidium salt solution is stated for rubidium carbonate solution, 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 particle mean size of the calcium aluminate is 15 μm, and its preparation method is：Calcium salt and aluminium salt difference is molten
Xie Hou, is 2 according to the mol ratio of calcium in aluminium in aluminium salt and calcium salt：1 ratio is mixed, and is added citric acid solution and is entered
The mol ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1 in row mixing, aluminium salt:1；Gained to be mixed is molten
After liquid clarification, the mol ratio (1-3) of ethylene glycol stirring, ethylene glycol and citric acid is added：1, it is heated to gel in 100-150 DEG C
State；Then in 120-150 DEG C of drying, then grind, be put into sintering furnace and heat 3-5h in 1000-1300 DEG C, obtain calcium aluminate
Powder；Wherein, the calcium salt is calcium nitrate, and the aluminium salt is aluminum nitrate.
The preparation method of bone cement described in the present embodiment is：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, comprises the following steps：
Rubidium salt is dissolved in ultra-pure deionized water, 1mol/L, 0.1mol/L, 0.05mol/L, 0.01mol/L, blank is configured to
Compare as ultra-pure deionized water group, be 0.7 according to ribidium salt solution and calcium aluminate mass ratio：1 mixing, regrinding is dense with difference
Degree rubidium salt is mixed into slurry, and obtained slurry is injected in designed, designed mould, is put into 37 degree of water baths of constant temperature 100%.
Fig. 1 is the setting time that bone cement is obtained using above example 1-5 methods describeds, and wherein CAC is represented to bone water
The ribidium salt solution concentration added in mud is 0mol/L；CAC1 represents that the ribidium salt solution concentration added into bone cement is 0.01mol/
L；CAC2 represents that the ribidium salt solution concentration added into bone cement is 0.05mol/L；CAC3 represents the rubidium added into bone cement
Concentration of salt solution is 0.1mol/L；CAC4 represents that the ribidium salt solution concentration added into bone cement is 1mol/L.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, final setting time is from 214min
It is reduced to 14min
Fig. 2 is the solidification maximum temperature obtained using above example 1-5 methods describeds, and maximum temperature is 30.8 to 32
Between degree Celsius, without because adding rubidium salt 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 the 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 beneficial for cell propagation.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 has only added the bone cement of ultra-pure water, CAC herein is blank control group, is not added with rubidium to be not added with ribidium salt solution) is than wanting
It is few；B1-3 is that 0.1mol/L RbCl mix CAC patterns after 1 day, and inner surface space is increased, and surface is more irregular, in pit
There are many attachments；C1-3 is that 1mol/L RbCl mix CAC patterns after 1 day, and internal surface of column relative clearance is few, but circle
The obvious many bedded substances more of post exocuticle, the calcium aluminate on bone cement surface of the invention is sheet, uneven more to have
Beneficial to cell propagation.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 with the extension of time, gradually from cement internal migration to outside, be so more beneficial for hair
Wave the biological effect of rubidium ion.
Under the conditions of 37 DEG C, using the bone cement described in embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5
Test is discharged in SBF intermediate ions and pH tests show that the calcium ion burst size more than bone cement amount containing rubidium of the invention is more, thus it is speculated that rubidium
Release is easier compared to calcium, bigger porosity is caused, causes the accelerated release in vitro of calcium ion, wherein 0.1mol/L experimental groups phosphorus member
Plain downward trend is maximum, surface mineralization ability is demonstrated sideways, pH value is between 7.45-7.85, between human normal pH.
Fig. 4 is that the calcium aluminate bone cement rested in water vapor after 7 days is inside and outside for power spectrum test, is passed through
Power spectrum Elemental redistribution can be seen that internal rubidium constituent content, without outside many, illustrates that rubidium element can gradually ooze out bone cement cylinder
Outside, so it is advantageous for rubidium and acts on cell.
If Fig. 5 is to obtain the X-ray that calcium aluminate bone cement soaks 21 days in SBF using above example 1-5 methods describeds
Diffraction analysis spectrogram, as can be seen from the figure on matrix calcium aluminate surface, generates hydroxyapatite and aluminium hydroxide.
Fig. 6 is embodiment 1-5 compression tests at initial stage, it can be seen that the bone cement of the RbCl containing 0.1mol/L and blank control
Group is compared, and improves compression strength initial stage, 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 multiplication factor we have found that hydroxyapatite diameter 3-5um,
There is substantial amounts of hole on surface, is conducive to cell to grow into, and its surface bead power spectrum is tested, and Ca/P is respectively 1.64 and 1.72, very
Chemical formula close to hydroxyapatite constitutes 1.67, illustrates that holding rings the excellent mineralising energy of calcium aluminate bone cement after adding rubidium
Power.
Fig. 8 is that the later bone cement of solidification is steeped in SBF for power spectrum test, and surface has grown many little particles, we
Element determination is carried out to little particle, checking is hydroxyapatite, and in biomaterial, material surface energy grows hydroxyl in SBF
Apatite, side illustration it there is good biocompatibility.
Fig. 9 is the leaching liquor from the bone cement containing rubidium, and bone marrow stromal cells (abbreviation BMMC cells) are tested using MTT
Method test cell vegetative map, tests 1.3.5 days cytoactives, shows to add breeding ratio sky of the rubidium chloride bone cement for cell
White control group (without rubidium bone cement) has more facilitation, and 0.1mol/L bone cements containing rubidium advantage is most obvious, over time
Extension, addition rubidium chloride bone cement effect is also more preferable.
Figure 10 is to adhere to test chart within 3 days from bone marrow stromal cells (abbreviation BMMC cells) cell,
Abcd represents CAC CAC1 CAC2 CAC4 respectively, is contrasted from figure, it can be seen that cell is in the table of bone cement containing rubidium
Face growing way very well, occurs in that uropodium, and surface bone cement containing rubidium is adapted to the propagation of cell.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent substitution, without departing from the essence of technical solution of the present invention
And scope.
Claims (10)
1. a kind of bone cement containing rubidium, it is characterised in that the bone cement is made up of ribidium salt solution with 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, it is characterised 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, it is characterised 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, it is characterised 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, it is characterised in that the preparation method of the calcium aluminate is：By calcium salt
It is 2 according to the mol ratio of calcium in aluminium in aluminium salt and calcium salt after being dissolved respectively with aluminium salt：1 ratio is mixed, and is added
Citric acid solution is mixed, and the mol ratio of aluminium and citric acid in the total amount and citric acid solution of calcium in calcium salt is 1 in aluminium salt:1；
After resulting solution clarification to be mixed, the mol ratio (1-3) of ethylene glycol stirring, ethylene glycol and citric acid is added：1, in 100-150
DEG C it is heated to gel state；Then in 120-150 DEG C of drying, then grind, be put into sintering furnace and heat 3- in 1000-1300 DEG C
5h, obtains calcium aluminate powder.
6. bone cement containing rubidium according to claim 1 or 5, it is characterised in that the particle mean size of the calcium aluminate is 0.5~
15μm。
7. bone cement containing rubidium according to claim 6, it is characterised in that the preparation method of the calcium aluminate is：By aluminic acid
Calcium powder is 1 according to ratio of grinding media to material:5-15 ratio carries out ball milling, adds alcohol or acetone, the rotating speed of ball milling is 300-400r/
Min, the time is 2-36h；It is dried in vacuo after ball milling, sieves powder, obtains the calcium aluminate that particle mean size is 0.5-15 μm.
8. the preparation method of the bone cement according to claim 5 containing rubidium, it is characterised in that the calcium salt is calcium nitrate, the aluminium
Salt is aluminum nitrate.
9. a kind of preparation method of the bone cement containing rubidium as described in any one of claim 1~8, it is characterised in that including following step
Suddenly：Ribidium salt solution is added into calcium aluminate, slurry is obtained, by gained slurry under 37 DEG C of constant temperatures, 100% water bath it is quiet
Put 1-21 days；Wherein, the concentration of rubidium salt is 0.01~1mol/L in the ribidium salt solution.
10. the bone cement containing rubidium described in claim 1 is preparing the application during bone injury repairs medical material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107823718A (en) * | 2017-11-22 | 2018-03-23 | 广州光鼎科技有限公司 | A kind of mesopore bioactive glass of multistage containing rubidium and its preparation method and application |
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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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|---|---|---|---|---|
| CN107823718A (en) * | 2017-11-22 | 2018-03-23 | 广州光鼎科技有限公司 | A kind of mesopore bioactive glass of multistage containing rubidium and its preparation method and application |
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