CN106267330A - A kind of bone cement with the high yield thermal efficiency - Google Patents
A kind of bone cement with the high yield thermal efficiency Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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Abstract
The present embodiment relates to a kind of bone cement with the high yield thermal efficiency, and the raw material of preparing of described bone cement includes that mass percent is 0.2 1.0% magnetic nanoparticle MxFe3‑xO4；Described magnetic nanoparticle MxFe3‑xO4In, M is the mixture of one or more materials in cobalt manganese/zinc, and the span of X is 0.1～1.Bone cement of the present invention adds the magnetic nanoparticle with the high yield thermal efficiency wherein, less at addition, and the product of the frequency (f) in magnetic field and intensity (H) is less than 5 × 109Am‑1s‑1In the case of just there is the higher efficiency of heating surface, both can play the effect killing tumor cell, also in the safety range that human body can bear.
Description
Technical field
The invention belongs to biomedicine technical field, be specifically related to a kind of bone cement with the high yield thermal efficiency.
Background technology
Bone is the third-largest Malignant tumor of bonal metastasis predilection site [1] being only second to lungs and liver, the carcinoma of prostate of about 70%
Patient with breast cancer, easily there is Bone tumour [2] in the patients with gastrointestinal carcinoma of the renal carcinoma of 30%-40%, thyroid cancer patients and 10%.
Bone tumor often causes and has an intense pain, and its modal complication is pathologisch Bruch, makes patient activity limited, has a strong impact on life
Quality [3].Traditional expectant treatment requires that patient fixes suffering limb and lies up the several months, but bed can be to patient for a long time
Life bring great inconvenience, greatly reduce the quality of life of patient, also considerably increase old people simultaneously and suffer from old silly
Slow-witted risk [4] .1938 PMMA bone cement (PMMA) is applied to the filling of monkey defect of skull first,
Go through since then and improve polymethyl methacrylate (PMMA) for many years and finally change in quality to become orthopaedics repair materials is widely used clinically,
The therapy of Cement fixation substantially reduces the treatment cycle [5] of the concurrent pathologisch Bruch of bone tumor.But, traditional poly-methyl
Acrylic acid methyl ester. bone cement only has Bone Defect Repari effect, can not treat bone metastaes.Existing bone tumour therapy scheme is many
Being aided with Radiotherapy chemotherapy for striking off bone grafting, the major defect that the method exists is: one is that relapse rate is high, and two is easily to adjacent healthy group
It is woven into damage.Therefore find and a kind of not only locally can kill tumor cell but also can the very spine that just becomes of the material of repairing bone defect
Hands.
Nineteen fifty-seven Glichrist et al. first proposed the concept [6] of magnetic thermotherapy.Magnetic thermotherapy is to utilize magnetisable material handing over
The loss produced in varying magnetic field, converts electromagnetic energy into heat energy, and then realizes target hyperthermia in tissue.The survival temperature of tumor cell
Spend lower 2-3 DEG C than normal cell, when tumor cell temperature rises to more than 42-45 DEG C, intracellular many structures and protein
Function irreversible damage will occur, thus there is death in tumor tissues.Magnetic thermotherapy targeting is high, and side effect is little, and magnetic
Medium can repeatedly use after once implanting as required, is particularly suitable for treating the bone tumor [7] being in health depths.In the recent period
Research display, thermotherapy also can collaborative with chemotherapy and radiation be carried out improving curative effect, more can resist by activating autoimmune ability
Tumor [8] (the method treatment muscle skeleton that it is medium local magnetic thermotherapy with ferromagnetic ceramic material that Kokubo etc. propose first
The tumor [9] of system, Portela A etc. with the biological active glass ceramic powder of SiO2-Al2O3-Fe2O3-MgO-CaO system is
Solid phase, with water as liquid phase, is prepared for magnetic bone cement [10] that heat production value is 2.11W g-1, and its heat production performance is far from reaching
Clinical treatment requirement.These bioactive glass material are chronically at research and development state, can't apply to clinic.Matsumine
In the calcium phosphate bone water (CPC) [11] made first containing micron order Fe3O4, but the mechanics of calcium phosphate bone cement (CPC) is strong
Degree will be generally less than the PMMA bone cement (PMMA) extensively used clinically, and the bone not being suitable for load-bearing bone lacks
Damage packing material.Fe3O4 powder mixing polymethyl methacrylate is made magnetic bone water by Kenji Takegami et al. first
Mud, but its magnetic-particle content to reach to can be only achieved when 60%～80% treatment temperature required.) but some researchs show, receive
After rice grain enters human body by blood circulation, it is eventually build up at liver and kidney, the nano-particle long-term impact on human body
It is currently not and will be apparent from [10].Human body is a blood circulation, when magnetic nanoparticle is after tumor locus heat production, its heat meeting
Quickly being taken away by the blood circulation around tumor tissues, cause tissue temperature not reach thermotherapy requirement, this is to magnetic nanoparticle
Thermogenesis in alternating magnetic field proposes extremely harsh requirement.Simultaneously according to recommendation human body limiting safe model medically
Enclosing [12], the product of the frequency (f) in magnetic field residing for human body and intensity (H) is not higher than 6 × 107Oe/s.Therefore at magnetic hyperthermia process
In, in order to reduce potential side effect, meeting the magnetic field condition of the human-body safety limit simultaneously, clinical treatment is expected to improve nanometer
While granule heating properties, dosage reduces as far as possible.
Summary of the invention
There is the efficiency of heating surface for bone cement of the prior art low, magnetic nanoparticle consumption is big, magnetic during use
The frequency (f) of field is higher with the product of intensity (H) and human body exists the defect of potential side effect, it is proposed that one has height
The bone cement of heat production efficiency.
In bone cement raw material of the present invention, including the magnetic nanoparticle that mass percent is 0.2～1.0%
MxFe3-xO4；
Described magnetic nanoparticle MxFe3-xO4In, M is the mixture of one or more materials in cobalt manganese/zinc, the value of X
Scope is 0.1～1.
Preferably, described M is zinc.
The most preferably, magnetic nanoparticle is Zn0.7Fe2.3O4。
Preferably, described M is the mixture of zinc and manganese, and the amount percent of the material of described zinc is 5%-90%.
The most preferably, described magnetic nanoparticle MxFe3-xO4For Zn0.5Mn0.5Fe2O4。
Preferably, described M is the mixture of manganese, zinc and cobalt, and the amount percent of the material of manganese is 10%～89%, the thing of zinc
The amount percent of matter is 10%～89%, the amount percent of the material of cobalt is 1%～30%.
Preferably, described magnetic nanoparticle MxFe3-xO4Preparation method comprise the steps:
Ferrum predecessor is mixed with M predecessor, obtains mixture, by described mixture and 1,2～hexadecane diol add together
It is added in the mixed liquor of Bian ether, oleic acid and oleic acid amine, and stirs；Under argon or nitrogen atmosphere, described mixed liquor is existed
20～40min it are incubated at 110～130 DEG C；Then it is warmed up to 190～210 DEG C, is incubated 20～40min；Finally be warmed up to 290～
310 DEG C, it is incubated 20～40min, after being cooled to room temperature, isolated magnetic nanoparticle MxFe3-xO4；
Described M predecessor is the mixed of one or more materials in zinc acetylacetonate, acetylacetone cobalt or manganese acetylacetonate
Compound；
During described ferrum predecessor mixes with M predecessor, by ferrum element and the material of metallic element in M predecessor
Amount total amount calculates, and in the metallic element of every 3.0 moles, in M predecessor, the amount of the material of metallic element is 0.1～1.0 mole；
Preferably, the raw material of described bone cement is polymethyl methacrylate (PMMA) or calcium phosphate (CPC).
It is a further object of the present invention to provide the preparation method of bone cement of the present invention, comprise the steps:
1) by bone cement raw material and magnetic nanoparticle all in temperature 22～25 DEG C, the condition of relative humidity 40%-50%
Lower standing 2～4h；
2) magnetic nanoparticle is dissolved in bone cement solution, ultrasonic makes institute's magnetic nanoparticle at described bone cement solution
In dispersed, then the solution being dispersed with magnetic nanoparticle is mixed homogeneously with bone cement raw material, obtains bone cement compound；
3) described bone cement compound is placed in mould moulding, obtains bone cement.
Described bone cement raw material is polymethyl methacrylate or calcium phosphate；Preferably polymethyl methacrylate.
Bone cement solution of the present invention is the solution dissolving corresponding bone cement raw material, such as polymethyl methacrylate
Solution be PMMA, the solution of calcium phosphate is water.
The bone cement of the high yield thermal efficiency of the present invention, has the advantages that
1) in bone cement raw material, the magnetic nanoparticle M with the high yield thermal efficiency of the present invention is addedxFe3-xO4,
Just there is in the case of addition only about 1% the higher efficiency of heating surface, greatly reduce addition；
2) bone cement of the present invention is during application, and the product of the frequency (f) in magnetic field and intensity (H) is only
4.68×109Am-1s-1, human body will not be brought potential side effect.
Accompanying drawing explanation
Fig. 1 be bone cement raw material be the Zn that PMMA adds 0.5%0.7Fe2.3O4Under the externally-applied magnetic field of 390KHz, 12KA/m
Heating curve；
Fig. 2 be bone cement raw material be the Zn that PMMA adds 0.5%0.5Mn0.5Fe2O4Externally-applied magnetic field at 390KHz, 12KA/m
Under heating curve；
Fig. 3 be bone cement raw material be the Zn that PMMA adds 1%0.7Fe2.3O4Under the externally-applied magnetic field of 390KHz, 12KA/m
Heating curve；
Fig. 4 be bone cement raw material be the Zn that CPC adds 0.5%0.7Fe2.3O4Under the externally-applied magnetic field of 390KHz, 12KA/m
Heating curve；
Fig. 5 be bone cement raw material be the Fe that PMMA adds 0.5%3O4Intensification under the externally-applied magnetic field of 390KHz, 12KA/m
Bent.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Magnetic nanoparticle involved in embodiment is prepared from by the following method:
Ferrum predecessor is mixed with M predecessor, obtains mixture, by described mixture and 1,2～hexadecane diol add together
It is added in the mixed liquor of Bian ether, oleic acid and oleic acid amine, and stirs；Under argon or nitrogen atmosphere, described mixed liquor is existed
30min it is incubated at 120 DEG C；Then it is warmed up to 200 DEG C, is incubated 30min；Finally it is warmed up to 300 DEG C, is incubated 30min, is cooled to room
Wen Hou, isolated magnetic nanoparticle MxFe3-xO4；
Described M predecessor is the mixed of one or more materials in zinc acetylacetonate, acetylacetone cobalt or manganese acetylacetonate
Compound.
Embodiment 1
The present embodiment relates to a kind of bone cement with the high yield thermal efficiency, and its bone cement raw material is PMMA, adds wherein
The magnetic nanoparticle Zn of 0.5%0.7Fe2.3O4；
The present embodiment further relates to the preparation method of this magnetic bone cement, comprises the steps:
1) by PMMA, MMA and magnetic nanoparticle in 23 DEG C, more than 2h under relative humidity 40%-50% environment, is placed,
2) weigh PMMA powder 1.99g to be placed in crucible, weigh magnetic nanoparticle 0.01g, and magnetic nano particle is molten
In the MMA solution of 1ml, ultrasonic make granule the most dispersed, then the mixed solution containing magnetic nanoparticle is noted
It is mapped to fill mix homogeneously in the crucible of PMMA powder.
3) mixture of mixing being transferred to a diameter of 6mm, in the cylindrical die of a height of 12mm, about 10min treats that it is complete
After polymerization, the demoulding.
The present embodiment further relates to the concrete application of this magnetic Nano bone cement, as follows:
Bone cement after the demoulding is put in coil, under the externally-applied magnetic field of 390KHz, 12KA/m, uses optical fiber sensing
Its ramp case in time monitored by device, using 37 DEG C as initial temperature, can rise 13 DEG C and reach 50 DEG C of (its temperature after 150s
Change is such as Fig. 1), and time more than 46 DEG C, the function of the many structures in tumor cell and protein will occur irreversible damage
Wound, thus tumor tissues occur death, therefore this example magnetic bone cement be fully achieved under alternating magnetic field treatment temperature required, for
Locally magnetic thermotherapy treatment tumor provides possibility.In the present embodiment the product of the frequency (f) in magnetic field and intensity (H) be 4.68 ×
109Am-1s-1, human body will not be brought side effect.
Embodiment 2
Compared with Example 1, its difference is, described magnetic nanoparticle is Zn0.5Mn0.5Fe2O4, its addition is
0.5%.
The present embodiment further relates to the preparation method of this bone cement, comprises the steps:
1) by PMMA, MMA and magnetic nanoparticle in 23 DEG C, more than 2h under relative humidity 40%-50% environment, is placed,
2) weigh PMMA powder 1.99g to be placed in crucible, weigh magnetic nanoparticle 0.01g, and magnetic nano particle is dissolved in
In the MMA solution of 1ml, ultrasonic make granule the most dispersed, then the mixed solution containing magnetic nanoparticle is injected
Mix homogeneously in the crucible fill PMMA powder.
3) mixture of mixing being transferred to a diameter of 6mm, in the cylindrical die of a height of 12mm, about 10min treats that it is complete
After polymerization, the demoulding.
The present embodiment further relates to the concrete application of this elastic nano bone cement, as follows:
Bone cement after the demoulding is put in coil, under the externally-applied magnetic field of 390KHz, 12KA/m, uses optical fiber sensing
Its ramp case in time monitored by device, using 37 DEG C as initial temperature, can rise 13 DEG C and reach 50 DEG C of (its temperature after 200s
Change is such as Fig. 2), and time more than 46 DEG C, the function of the many structures in tumor cell and protein will occur irreversible damage
Wound, thus tumor tissues occur death, therefore this example magnetic bone cement be fully achieved under alternating magnetic field treatment temperature required, for
Locally magnetic thermotherapy treatment tumor provides possibility.In the present embodiment the product of the frequency (f) in magnetic field and intensity (H) be 4.68 ×
109Am-1s-1, human body will not be brought side effect.
Embodiment 3
Compared with Example 1, its difference is, described magnetic nanoparticle is Zn0.7Fe2.3O4, its addition is 1%.
The present embodiment further relates to the preparation method of this bone cement, comprises the steps:
1) by PMMA, MMA and magnetic nanoparticle in 23 DEG C, more than 2h under relative humidity 40%-50% environment, is placed,
2) weigh PMMA powder 1.99g to be placed in crucible, weigh magnetic nanoparticle 0.02g, and magnetic nano particle is dissolved in
In the MMA solution of 1ml, ultrasonic make granule the most dispersed, then the mixed solution containing magnetic nanoparticle is injected
Mix homogeneously in the crucible fill PMMA powder.
3) mixture of mixing being transferred to a diameter of 6mm, in the cylindrical die of a height of 12mm, about 10min treats that it is complete
After polymerization, the demoulding.
The present embodiment further relates to the concrete application of this elastic nano bone cement, as follows:
Bone cement after the demoulding is put in coil, under the externally-applied magnetic field of 390KHz, 12KA/m, uses optical fiber sensing
Its ramp case in time monitored by device, using 37 DEG C as initial temperature, can rise 13 DEG C after 100s, and central temperature reaches 50
DEG C (its variations in temperature such as Fig. 3), and time more than 46 DEG C, the function of the many structures in tumor cell and protein will occur
Irreversible damage, thus there is death in tumor tissues, therefore this example magnetic bone cement is fully achieved treatment under alternating magnetic field
Temperature required, provide possibility for local magnetic thermotherapy treatment tumor.In the present embodiment, the frequency (f) in magnetic field and intensity (H's) takes advantage of
Amass is 4.68 × 109Am-1s-1, human body will not be brought side effect.
Embodiment 4
The present embodiment relates to a kind of bone cement with the high yield thermal efficiency, and its bone cement raw material is calcium phosphate (CPC), magnetic
Nano-particle is Zn0.7Fe2.3O4, its addition is 0.5%.
The present embodiment further relates to the preparation method of this bone cement, comprises the steps:
1) by CPC and magnetic nanoparticle in 23 DEG C, more than 2h under relative humidity 40%-50% environment, is placed,
2) weigh CPC powder 1.99g to be placed in crucible, weigh magnetic nanoparticle 0.01g, and magnetic nano particle is dissolved in
Sterile water for injection (the H of 0.32ml2O), in, ultrasonic make granule the most dispersed, then by containing magnetic nanoparticle
Mixed solution is expelled to fill mix homogeneously in the crucible of CPC powder.
The present embodiment further relates to the concrete application of this magnetic Nano bone cement, as follows:
Above-mentioned mixing put into mould after about 5min after it is polymerized completely, the demoulding, put it in coil, at 390KHz,
Under the externally-applied magnetic field of 12KA/m, with its ramp case in time of optical fiber temperature sensor monitors, using 37 DEG C as initial temperature,
13 DEG C can be risen after 200s, reach 50 DEG C (its variations in temperature such as Fig. 4), and the many knots in tumor cell time more than 46 DEG C
The function of structure and protein will occur irreversible damage, thus death, therefore this example magnetic bone cement occurs in tumor tissues
Under alternating magnetic field, it is fully achieved treatment temperature required, provides possibility for local magnetic thermotherapy treatment tumor.Magnetic in the present embodiment
The frequency (f) of field and the product of intensity (H) are 4.68 × 109Am-1s-1, human body will not be brought side effect.
Comparative example 1
Compared with Example 1, difference is, adds the Fe of 0.5% in PMMA3O4, additional at 390KHz, 12KA/m
Under magnetic field, with its ramp case in time of optical fiber temperature sensor monitors, using 37 DEG C as initial temperature, after 600s on
Rise 10 DEG C, central temperature reaches 47 DEG C (its variations in temperature such as Fig. 5), and time more than 46 DEG C the many structures in tumor cell with
The function of protein will occur irreversible damage, thus death occurs in tumor tissues, and therefore this example magnetic bone cement is being handed over
It is fully achieved treatment under varying magnetic field temperature required, provides possibility for local magnetic thermotherapy treatment tumor.Magnetic field in the present embodiment
The product of frequency (f) and intensity (H) is 4.68 × 109Am-1s-1, human body will not be brought side effect.
Although, used general explanation, detailed description of the invention and test, the present invention made detailed retouching
Stating, but on the basis of the present invention, can make some modifications or improvements it, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (8)
1. a bone cement with the high yield thermal efficiency, it is characterised in that the raw material of preparing of bone cement includes mass percent
It is 0.2～1.0% magnetic nanoparticle MxFe3-xO4；
Described magnetic nanoparticle MxFe3-xO4In, M is the mixture of one or more materials in cobalt manganese/zinc, the span of X
It is 0.1～1.
Bone cement the most according to claim 1, it is characterised in that described M is zinc.
Bone cement the most according to claim 1, it is characterised in that described M is the mixture of zinc and manganese, the material of described zinc
Amount percent be 5%-90%.
Bone cement the most according to claim 1, it is characterised in that described M is the mixture of manganese, zinc and cobalt, the material of manganese
Amount percent be 10%～89%, the amount percent of the material of zinc be 10%～89%, the amount percent of the material of cobalt be 1%
～30%.
5. according to the bone cement described in any one of Claims 1 to 4, it is characterised in that described magnetic nanoparticle MxFe3-xO4's
Preparation method comprises the steps:
Ferrum predecessor is mixed with M predecessor, obtains mixture, by described mixture and 1,2～hexadecane diol add to together
In the mixed liquor of Bian ether, oleic acid and oleic acid amine, and stir；Under argon or nitrogen atmosphere, by described mixed liquor 110～
20～40min it are incubated at 130 DEG C；Then it is warmed up to 190～210 DEG C, is incubated 20～40min；Finally it is warmed up to 290～310 DEG C,
Insulation 20～40min, after being cooled to room temperature, isolated magnetic nanoparticle MxFe3-xO4；
Described M predecessor is the mixture of one or more materials in zinc acetylacetonate, acetylacetone cobalt or manganese acetylacetonate；
During described ferrum predecessor mixes with M predecessor, total with the amount of the material of metallic element in M predecessor by ferrum element
Amount calculates, and in the metallic element of every 3.0 moles, in M predecessor, the amount of the material of metallic element is 0.1～1.0 mole.
6. according to the bone cement described in any one of Claims 1 to 5, it is characterised in that the raw material of preparing of described bone cement is poly-
Methyl methacrylate or calcium phosphate；Preferably polymethyl methacrylate.
7. the preparation method of the bone cement described in any one of claim 1～6, it is characterised in that comprise the steps:
1) by bone cement raw material and magnetic nanoparticle all temperature 22～25 DEG C, quiet under conditions of relative humidity 40%-50%
Put 2～4h；
2) magnetic nanoparticle is dissolved in bone cement solution, ultrasonic make institute's magnetic nanoparticle in described bone cement solution all
Even dispersion, then the solution being dispersed with magnetic nanoparticle is mixed homogeneously with bone cement raw material, obtain bone cement compound；
3) described bone cement compound is placed in mould moulding, obtains bone cement.
Preparation method the most according to claim 7, it is characterised in that described bone cement raw material is polymethyl methacrylate
Or calcium phosphate；Preferably polymethyl methacrylate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110251724A (en) * | 2019-06-28 | 2019-09-20 | 重庆医科大学附属第二医院 | A kind of magnetic PMMA bone cement and its preparation method and application carrying adriamycin |
| WO2022028035A1 (en) * | 2020-08-03 | 2022-02-10 | 首都医科大学附属北京朝阳医院 | Anti-myeloma nano-bone cement, preparation method therefor and use thereof |
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