CN102557527B - Temperature control magnetic bone cement and preparation method thereof - Google Patents
Temperature control magnetic bone cement and preparation method thereof Download PDFInfo
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- CN102557527B CN102557527B CN 201210000742 CN201210000742A CN102557527B CN 102557527 B CN102557527 B CN 102557527B CN 201210000742 CN201210000742 CN 201210000742 CN 201210000742 A CN201210000742 A CN 201210000742A CN 102557527 B CN102557527 B CN 102557527B
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Abstract
The invention relates to temperature control magnetic bone cement and a preparation method thereof. The preparation method comprises the following steps: weighing FeCl3 6H2O, ZnCl2 and MnCl2 4H2O, mixing the materials according to the stoichiometric ratio of Mn0.15Zn0.85Fe2O4, adding ultra-pure water for preparing a solution, reacting, then getting a precursor of a manganese-zinc ferrite, calcining the precursor of the manganese-zinc ferrite to get manganese-zinc ferrite powder, adding a spherical poly(methyl methacrylate) particle powder agent containing benzoyl peroxide into the manganese-zinc ferrite powder, uniformly mixing, further adding methyl methacrylate containing dimethyl mercaptopropionic acid, and blending to prepare a product. The Curie temperature of the bone cement prepared by the preparation method disclosed by the invention is about 50 DEG C, the magnetic bone cement containing the manganese-zinc ferrite in the different proportions can raise the temperature from 37 DEG C to 50 DEG C and be constant at the temperature under an external alternating magnetic field, and the temperature control performance is realized.
Description
Technical field
The present invention relates to a kind of bio-medical material, specifically a kind of temperature control magnetic bone cement and preparation method.
Background technology
The postoperative recurrence problem of bone tumor is a great problem of puzzlement medical circle.Bone tumor recurrence not only makes the patient stand more misery, but life-threatening very.Because the Problems Concerning Their Recurrence of bone tumor, people have proposed the requirement of oncotherapy function to the bone renovating material that originally only has bone repair and reconstruction function.Bone cement is a kind of by clinical widely used orthopaedics repair materials, and it is generally by solid phase and liquid-phase mixing, and having can clinical any figuration, handiness, the advantage such as performance is good.
The magnetic thermotherapy utilizes magnetisable material the externally-applied magnetic field power conversion can be become the characteristics of heat energy under alternating magnetic field, the suitable shape of magnetic induction dielectric material is implanted or is imported to patient's tumor locus, add suitable alternating magnetic field, can heat tumor area, (cancerous cell is will be dead more than 42 ℃ than normal cell and tissue characteristics more responsive to heat to utilize tumor cell and tissue, but and about normal cell heat resistanceheat resistant to 48 ℃), reach the purpose of high magnetic target therapy.Characteristics such as the magnetic induction thermotherapy has simple to operate, and is with low cost, safe, and side effect is little, and the magnetic induction medium is once implantation, thermotherapy repeatedly is so be particularly suitable for treating the bone tumor that is in the health depths.And the magnetic bone cement of exploitation tool is a hot research direction of bone material.
In magnetic thermotherapy process, the control of the temperature of area for treatment is most important.If heating-up temperature is crossed the low purpose that can not have thermotherapy, and if excess Temperature will be heated to normal tissue, cause the normal muscle in next door or neural etc. organize overheated necrosis.So when thermotherapy, realize the control of thermotherapy temperature, could be safety and the effectiveness of guaranteeing to treat.Wherein overheated is a phenomenon that must prevent.But the present magnetic bone cement material of studying does not nearly all design function of temperature control.In the reality use, just need to use other attemperating unit that temperature is carried out measurement and control, complex operation.
For magnetic material, can there be the Curie temperature characteristic, the magnetic of material disappears when temperature is higher than Curie temperature, and no longer can the magnetic induction heating.But the material that plays at present magnetic induction in the magnetic bone cement of exploitation almost is ferroso-ferric oxide entirely, although ferroso-ferric oxide has higher magnetic heat generation ability, but its Curie temperature is very high, has reached about 590 ℃, and the bone cement take ferroso-ferric oxide as the magnetic crystalline phase is very easy to superheated.
Summary of the invention
The present invention is for solving the existing easy superheated problem of magnetic bone cement, a kind of temperature control magnetic bone cement and preparation method thereof is provided, this bone cement has good cell compatibility, about 50 ℃ of Curie temperature, when temperature reached 50 ℃, material was stopped heating, and temperature can realize heating once again when being lower than this temperature, guarantee preference temperature, prevent from simultaneously in the thermotherapy process superheating phenomenon occuring, improve the safety of magnetic thermotherapy.
The present invention solves the problems of the technologies described above the technical scheme of employing to be: a kind of temperature control magnetic bone cement and preparation method comprise following steps:
One) preparation of manganese-zinc ferrite
1) takes by weighing respectively FeCl
36H
2O, ZnCl
2And MnCl
24H
2O also presses Mn
0.15Zn
0.85Fe
2O
4Stoichiometric proportion batching, add ultra-pure water, be made into the solution that concentration of metal ions is 0.3mol/L, under 90 ℃ constant temperature, react 4h;
In the course of reaction, the NaOH solution that drips concentration in the solution and be 1mol/L under the mixing speed of 3000rpm is take the pH value of control reaction solution as 10;
2) precipitation that produces after the reaction in the step 1 is washed and centrifugalize under the 6000rpm rotating speed with ultra-pure water, dry under the condition that is deposited in temperature 60 C, pressure 0.09-0.093MPa after the separation, obtain the manganese-zinc ferrite presoma, for subsequent use;
3) the manganese-zinc ferrite presoma that obtains is calcined 1h under the condition of 450 ℃ of temperature, pressure 0.09-0.093MPa, namely obtain manganese-zinc-ferrite powder;
Two) preparation of temperature control magnetic bone cement
4) preparation of bone cement substrate:
Get spherical poly methyl methacrylate particle powder, after screening, choose granularity less than the spherical poly methyl methacrylate particle powder of 200 purposes, then add therein benzoyl peroxide, mix homogeneously makes solid phase bone cement substrate, and is for subsequent use;
The mean molecule quantity of described spherical polymethyl methacrylate is 270kDa;
The addition of described benzoyl peroxide is 4 % of solid phase bone cement substrate gross weight;
Other gets methyl methacrylate monomer, makes liquid phase bone cement substrate after adding therein the dimethyl sulphoniopropionate mix homogeneously;
The addition of described dimethyl sulphoniopropionate is 2 % of liquid phase bone cement substrate gross weight;
5) get the manganese-zinc-ferrite powder that makes in the step 3 and join mix homogeneously in the bone cement solid-phase matrix in the step 4, make the bone cement compound; Then be that the ratio of 1:1 adds the bone cement liquid-phase substrate in the step 4 in the bone cement compound according to weight ratio, then use stainless steel knife to be in harmonious proportion 3min and namely make product;
Wherein, the addition of manganese-zinc-ferrite powder is the 40%-60% of final products gross weight.
Among the present invention, FeCl
36H
2O, ZnCl
2And MnCl
24H
2When O reacts, can cause the variation of pH in solution, therefore need to drip sodium hydroxide solution and make its pH value be stabilized in 10.
Among the present invention, the programming rate when the manganese-zinc ferrite presoma that makes is calcined is 5 ℃/min.
Beneficial effect: polymethyl methacrylate is present widely used bone cement clinically, and molecular formula is mixed in this research in polymethyl methacrylate be Mn
0.15Zn
0.85Fe
2O
4Manganese-zinc ferrite, but the preparation temperature control the magnetic bone cement.Studies show that this bone cement hardening time about 10-25min, meet clinically the requirement to bone cement curing operation time 8-30min; Comprcssive strength is about 83.6-98Mpa, and is approaching with the comprcssive strength of cortical bone; The MTT experiment shows that material has good cell compatibility; The Curie temperature test shows the about 50 ° of C of Curie temperature of material, all can realize being warmed up to 50 ° of C from 37 ° of C adding the magnetic bone cement that contains the different proportion manganese-zinc ferrite under the alternating magnetic field, and in time increase continue not to heat up, but constant in this temperature, has realized temperature-control performance.The experimentation of Akihiko Matsumine etc. shows, when the magnetic material temperature reaches 50 ° of C, can make the temperature on osseous tissue surface to reach about the effective 43 ° of C of thermotherapy, and organizing around can not making again simultaneously is influenced.It is similar to it that the material magnetic heat generation of this research detects magnetic field intensity, and the Curie temperature of material is about 50 ° of C, can have beneficial effect so the reply of the material of this research design realizes temperature-controlled heat treatment treatment bone tumor.
The specific embodiment
The present invention is further elaborated below in conjunction with specific embodiment.
Embodiment 1
A kind of temperature control magnetic bone cement, its preparation process is as follows:
One) preparation of manganese-zinc ferrite
1) takes by weighing respectively FeCl
36H
2O, ZnCl
2And MnCl
24H
2O also presses Mn
0.15Zn
0.85Fe
2O
4Stoichiometric proportion batching, add ultra-pure water, be made into the solution that concentration of metal ions is 0.3mol/L, under 90 ℃ constant temperature, react 4h;
In the course of reaction, the NaOH solution that drips concentration in the solution and be 1mol/L under the mixing speed of 3000rpm is take the pH value of control reaction solution as 10;
2) precipitation that produces after the reaction in the step 1 is washed and centrifugalize under the 6000rpm rotating speed with ultra-pure water, dry under the condition that is deposited in temperature 60 C, pressure 0.09-0.093MPa after the separation, obtain the manganese-zinc ferrite presoma, for subsequent use;
3) the manganese-zinc ferrite presoma that obtains is calcined 1h under the condition of 450 ℃ of temperature, pressure 0.09-0.093MPa, namely obtain manganese-zinc-ferrite powder;
Two) preparation of temperature control magnetic bone cement
4) preparation of bone cement substrate:
Get spherical poly methyl methacrylate particle powder, after screening, choose granularity less than the spherical poly methyl methacrylate particle powder of 200 purposes, then add therein benzoyl peroxide, mix homogeneously makes solid phase bone cement substrate, and is for subsequent use;
The mean molecule quantity of described spherical polymethyl methacrylate is 270kDa;
The addition of described benzoyl peroxide is 4 % of solid phase bone cement substrate gross weight;
Other gets methyl methacrylate monomer, makes liquid phase bone cement substrate after adding therein the dimethyl sulphoniopropionate mix homogeneously;
The addition of described dimethyl sulphoniopropionate is 2 % of liquid phase bone cement substrate gross weight;
5) get the manganese-zinc-ferrite powder that makes in the step 3 and join mix homogeneously in the bone cement solid-phase matrix in the step 4, make the bone cement compound; Then be that the ratio of 1:1 adds the bone cement liquid-phase substrate in the step 4 in the bone cement compound according to weight ratio, then use stainless steel knife to be in harmonious proportion 3min and namely make product;
Wherein, the addition of manganese-zinc-ferrite powder is 50% of final products gross weight.
Get the temperature control magnetic bone cement that makes, check its indices method as follows:
One, hardening time;
After getting solid phase powder and liquid phase stirring 3min, move in Ф 9 * 5mm mould, flatten, place relative humidity 100%, in 37 ℃ of calorstats, the 400N load is lower, with the needle point diameter rustless steel pinprick concrete column face that is 1mm, stop to move down to load and be the cement solidification time.Get 5 samples, average.
Two, comprcssive strength;
After getting solid phase powder and liquid phase stirring 3min, sample is made the smooth cylindric sample of Ф 4 * 8mm in two ends, until after the sample solidifies with its 37 ℃ of calorstats at relative humidity 100% in maintenance 72h, use SHIMADZU SES-1000 to test its comprcssive strength, load 900N, pressing speed 1mm/min.Choose 5 harmless samples, test its meansigma methods for every group.
Three, crystalline phase forms;
Material is worn into fine powder, adopt X crystalline phase diffractometer (X'Pert Pro MPD X, Philips) to detect its crystalline phase and form 0.06 °/s of scanning step.
Four, magnetic test and magnetic heating performance detect;
Material is worn into the pillar of 3 millimeters of long 6 millimeters, diameters, use vibrating specimen magnetometer (Lake shore7410) to detect its magnetic; Material is made the cylinder of Ф 9 * 9mm, before curing, insert glass-stem thermometer, after cured material is placed radio-frequency induction coil, frequency 100kHz, magnetic field size 25K Am
-1, temperature of every 5min record is tested its in time heating curve under alternating magnetic field, observes its intensification ability.
Five, the mensuration of material Curie temperature;
Adopt falling temperature method to measure the Curie temperature of material.Sample is placed even cooling system, allow it respectively at the situation borehole cooling that adds magnetic field and do not add magnetic field, record the cooling curve of sample, 2 corresponding temperature-visualizeds of curve burble point are sample Curie temperature roughly.
Six, cytotoxicity test;
With material with 37 ° of C oxirane disinfections, again the mass volume ratio (mg/mL) of material with 200:1 added in the culture fluid of LG-DMEM, 37 ° of C are hatched 24 h, with above-mentioned suspension high speed centrifugation, supernatant is with the filter paper filtering sterilization of 0.22 um, hydrochloric acid solution with 0.1 M is adjusted pH value to 7.4 ± 0.5, and the lixiviating solution that obtains adds 10% FBS as initial lixiviating solution, the cell experiment after initial lixiviating solution is used for afterwards by 2 times of GM culture fluid dilutions; Get the most vigorous third generation cell ROS17/2.8(rat osteosarcoma cells of growth after the recovery) (density is 5 * 10 in the cell inoculation
4Individual/ml) in 24 well culture plates, the original culture fluid of sucking-off behind the 24 h cell attachments, lixiviating solution 200 uL that add corresponding dilution number replace, organize in contrast with the GM culture fluid, cell culture ld, behind 3d and the 5d, 1,3,5d respectively gets a culture plate and adds MTT solution (5mg/ml) 40 μ l, continues to cultivate 4h under 37 ° of C, stops cultivating, the careful suction abandoned culture supernatant in the hole, every hole adds 420 μ l DMSO, and vibration 10min fully dissolves crystal, draw in every hole liquid 200 μ l in 96 hole flat undersides, then select the 570nm wavelength, measure each hole absorbance at enzyme-linked immunosorbent assay instrument, the record result.Do 3 Duplicate Samples (P＜0.05).
Adopt said method to detect its performance to the temperature control magnetic bone cement that makes, the result is: be 12 ± 2min its hardening time, and mechanical strength is 98.1 ± 5.3Mpa, is expected to for weight bearing area bone repairing and treating; XRD studies show that the main component of material is polymethyl methacrylate and manganese-zinc ferrite; Use vibrating specimen magnetometer to record material 1.59 * 10
6Am
-1Saturation magnetization be 2.96Am
2Kg
-1The Curie temperature that falling temperature method records material is about 50 ° of C; At 100kHz, 25K Am
-1Alternating magnetic field under can see that material has good intensification ability, on 37 ° of C basal temperatures, through about 25min, material can be realized the intensification of 13 ° of C, reaches about 50 ° of C, reach this temperature after, the temperature constant of material has embodied function of temperature control about 50 ° of C.Cell experiment shows that material has good cell compatibility.
Embodiment 2
The preparation of the preparation of manganese-zinc ferrite and bone cement substrate all as described in Example 1.
Get manganese-zinc-ferrite powder and join mix homogeneously in the bone cement solid-phase matrix, make the bone cement compound; Then be that the ratio of 1:1 adds the bone cement liquid-phase substrate in the bone cement compound according to weight ratio, then use stainless steel knife to be in harmonious proportion 3min and namely make product;
Wherein, the addition of manganese-zinc-ferrite powder is 40% of final products gross weight.
Adopt the experimental technique among the embodiment 1 to detect its performance to the temperature control magnetic bone cement that makes, the result is: recording its hardening time is 10 ± 1min, mechanics comprcssive strength 91.1 ± 3.7Mpa; Use vibrating specimen magnetometer to record material 1.59 * 10
6Am
-1Saturation magnetization be 1.97Am
2Kg
-1Under the basal temperature of 37 ° of C, under alternating magnetic field, can realize heating up, be stabilized at last about 50 ° of C; The MTT experiment shows that material has good cell compatibility.
Embodiment 3
The preparation of the preparation of manganese-zinc ferrite and bone cement substrate all as described in Example 1.
Get manganese-zinc-ferrite powder and join mix homogeneously in the bone cement solid-phase matrix, make the bone cement compound; Then be that the ratio of 1:1 adds the bone cement liquid-phase substrate in the bone cement compound according to weight ratio, then use stainless steel knife to be in harmonious proportion 3min and namely make product;
Wherein, the addition of manganese-zinc-ferrite powder is 60% of final products gross weight.
Adopt the experimental technique among the embodiment 1 to detect its performance to the temperature control magnetic bone cement that makes, the result is: recording its hardening time is 25 ± 2.5min, comprcssive strength 83.6 ± 4.2Mpa; Use vibrating specimen magnetometer to record material 1.59 * 10
6Am
-1Saturation magnetization be 3.15Am
2Kg
-1Under the basal temperature of 37 ° of C, under alternating magnetic field, can realize heating up, be stabilized at last about 50 ° of C; The MTT experiment shows that material has good cell compatibility.
Claims (1)
1. the preparation method of a temperature control magnetic bone cement is characterized in that, comprises following steps:
One) preparation of manganese-zinc ferrite
1) takes by weighing respectively FeCl
36H
2O, ZnCl
2And MnCl
24H
2O also presses Mn
0.15Zn
0.85Fe
2O
4Stoichiometric proportion batching, add ultra-pure water, be made into the solution that concentration of metal ions is 0.3mol/L, under 90 ℃ constant temperature, react 4h;
In the course of reaction, the NaOH solution that drips concentration in the solution and be 1mol/L under the mixing speed of 3000rpm is take the pH value of control reaction solution as 10;
2) precipitation that produces after the reaction in the step 1 is washed and centrifugalize under the 6000rpm rotating speed with ultra-pure water, dry under the condition that is deposited in temperature 60 C, pressure 0.09-0.093MPa after the separation, obtain the manganese-zinc ferrite presoma, for subsequent use;
3) the manganese-zinc ferrite presoma that obtains is calcined 1h under the condition of 450 ℃ of temperature, pressure 0.09-0.093MPa, namely obtain manganese-zinc-ferrite powder;
Two) preparation of temperature control magnetic bone cement
4) preparation of bone cement substrate:
Get spherical poly methyl methacrylate particle powder, after screening, choose granularity less than the spherical poly methyl methacrylate particle powder of 200 purposes, then add therein benzoyl peroxide, mix homogeneously makes solid phase bone cement substrate, and is for subsequent use;
The mean molecule quantity of described spherical polymethyl methacrylate is 270kDa;
The addition of described benzoyl peroxide is 4 % of solid phase bone cement substrate gross weight;
Other gets methyl methacrylate monomer, makes liquid phase bone cement substrate after adding therein the dimethyl sulphoniopropionate mix homogeneously;
The addition of described dimethyl sulphoniopropionate is 2 % of liquid phase bone cement substrate gross weight;
5) get the manganese-zinc-ferrite powder that makes in the step 3 and join mix homogeneously in the bone cement solid-phase matrix in the step 4, make bone cement solid phase mixing material; Then be that the ratio of 1:1 adds the bone cement liquid-phase substrate in the step 4 in bone cement solid phase mixing material according to weight ratio, then use stainless steel knife to be in harmonious proportion 3min and namely make product;
Wherein, the addition of manganese-zinc-ferrite powder is the 40%-60% of final products gross weight.
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| CN104591293A (en) * | 2014-12-24 | 2015-05-06 | 合肥协知行信息***工程有限公司 | Preparation method of manganese zinc ferrite nanoparticles |
| CN106267330A (en) * | 2016-08-29 | 2017-01-04 | 首都师范大学 | A kind of bone cement with the high yield thermal efficiency |
| CN108129048B (en) * | 2018-02-09 | 2020-06-23 | 河南科技大学 | Temperature-controlled magnetic-thermal bone cement capable of rapidly increasing temperature and preparation method thereof |
| 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 |
| CN110776266B (en) * | 2019-11-07 | 2021-10-08 | 郑州大学 | Preparation method of building material with electromagnetic wave absorption function |
| CN114053477B (en) * | 2020-08-03 | 2023-06-06 | 首都医科大学附属北京朝阳医院 | Anti-myeloma nano bone cement and preparation method and application thereof |
| CN114404655B (en) * | 2022-01-28 | 2022-12-20 | 洛阳市中医院 | Porous scaffold with photo-thermal effect and preparation method thereof |
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| FR2870129A1 (en) * | 2004-05-14 | 2005-11-18 | Ceravic Sas Soc Par Actions Si | POLYMERIC CEMENT FOR PERCUTANEOUS VERTEBROPLASTY |
| CN101125219A (en) * | 2007-09-04 | 2008-02-20 | 山东大学 | Rapidly solidified calcium phosphate cement composite material and its preparation method |
| CN101530635B (en) * | 2009-04-21 | 2012-09-12 | 上海交通大学医学院附属第九人民医院 | Bioactive bone-repairing cement material |
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