CN113772981A - Novel black phosphorus/calcium phosphate bone cement and preparation method thereof - Google Patents
Novel black phosphorus/calcium phosphate bone cement and preparation method thereof Download PDFInfo
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/02—Phosphate cements
- C04B12/025—Phosphates of ammonium or of the alkali or alkaline earth metals
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- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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Abstract
A novel black phosphorus/calcium phosphate bone cement and a preparation method thereof. The form of the black phosphorus is a nano sheet or a quantum dot; the calcium phosphate includes anhydrous calcium hydrogen phosphate, tricalcium phosphate or tetracalcium phosphate. The anhydrous calcium hydrophosphate is obtained by taking anhydrous ethanol as a ball milling medium and performing ball milling and drying by a wet ball milling method. Mixing tetracalcium phosphate or tricalcium phosphate and anhydrous calcium hydrophosphate in a mass ratio of 1: 1, mixing to obtain the calcium phosphate cement powder. The solidifying liquid of the bone cement adopts 20 wt% citric acid aqueous solution, and the pH value of the citric acid is adjusted to 4 by 0.1 mol/L sodium hydroxide solution. The solid-liquid ratio of the hydrated bone cement is 0.5 ml/g. And (3) dispersing the black phosphorus nanosheet and the black phosphorus quantum dot prepared by a liquid phase stripping method and an ultrasonic dispersion method in the curing liquid or doping the non-stripped black phosphorus powder into the bone cement powder to obtain the black phosphorus-doped calcium phosphate bone cement. The method has the characteristics of simple and easy operation, environmental friendliness and the like.
Description
Technical Field
The invention belongs to the field of biomedical materials, and particularly relates to novel black phosphorus/calcium phosphate bone cement and a preparation method thereof.
Background
Among the bone repair materials, bone cement is one of the major bright spots. The main basic characteristics of the injection are injectability and self-curing, and in addition, the characteristics of good biocompatibility, bone induction, antibiosis and antiphlogosis are required.
At present, the bone cement which is commonly used clinically mainly comprises polymethyl methacrylate (PMMA) bone cement and bioceramic bone cement. The bioceramic bone cement mainly comprises magnesium phosphate bone cement, calcium sulfate bone cement, calcium silicate bone cement and calcium phosphate bone cement. Some of the first three types of bone cements have no osteoinductivity, and can release a large amount of reaction heat in the preparation process, so that the setting time is too short; some of them have poor mechanical properties, low compressive strength, no biological activity and too fast degradation speed in vivo, resulting in the generation of sterile inflammatory reaction of surrounding tissues. The calcium phosphate cement can not completely meet the clinical requirements, the composition of the calcium phosphate cement is the same as that of human bones, the cured product is similar to the inorganic component of natural bones, and the calcium phosphate cement has good biocompatibility, osteoconductivity and osteoinductivity, and the degraded product can stimulate the growth of surrounding bone tissues, so the calcium phosphate cement is a novel bone tissue repairing and filling material.
The common calcium phosphate cement comprises two or more calcium phosphate salts (solid phase) and a curing liquid (liquid phase, water or water solution), which form a plastic mixed slurry once mixed, and can be gradually cured after being implanted into a living body to form a substitute material of bone tissue. The most commonly used solid phase phosphate is alpha-tricalcium phosphate (alpha-TCP) or tetracalcium phosphate, can generate hydration reaction to generate calcium-deficient hydroxyapatite (CDHA), has high solubility in a solution, has more common solid phase components of alpha-TCP bone cement, and has the defects of complex and fussy preparation and mixing process flows. On the other hand, after being implanted into a body, phosphate radicals are reduced along with the degradation of hydroxyapatite, the generated apatite components are reduced, and incomplete repair may be caused.
Black Phosphorus (BP), an allotrope of phosphorus element, is converted from white phosphorus at high temperature and high pressure, is a novel two-dimensional photoelectric material, and shows great application potential in the fields of photoelectricity and nano biophotonic science due to excellent photoelectric characteristics, ultrahigh photothermal conversion efficiency, good biocompatibility and degradability; firstly, especially under the action of light, oxygen and water, the black phosphorus is very easy to degrade to generate phosphate radicals, and the characteristic can just compensate the phosphate radicals lost due to the generation of hydroxyapatite in the bone cement, so that continuous output is realized, and sustainable repair is realized. Secondly, as the black phosphorus can absorb near infrared light, the curing time of the bone cement is controllable while heat is generated, and the degradation of the black phosphorus can be promoted and the bone repair can be accelerated; if the near-infrared heat treatment is applied to the later-stage repair process of osteosarcoma or osteocarcinoma, cells of osteosarcoma or osteocarcinoma can be killed by the near-infrared heat treatment, and additional bone repair can be provided, so that the integration of treatment and repair is achieved; thirdly, the black phosphorus has huge specific surface area and can adsorb a large amount of drugs (anticancer drugs, antibiotics and bone repair growth factors), thereby achieving the purpose of integration of treatment and repair.
Disclosure of Invention
The invention provides a novel black phosphorus-calcium phosphate bone cement with antibacterial treatment, controllable curing time, good biocompatibility and excellent mechanical property and a preparation method thereof. The bone cement has the advantages of adjustable curing time, drug loading, antibacterial property, good mechanical property and better biocompatibility, and can meet the requirements of clinical treatment of various bone defects.
According to the invention, tricalcium phosphate or tetracalcium phosphate is obtained by a heat treatment method, good-form components are selected as solid-phase components of bone cement, and black phosphorus nanosheets and black phosphorus quantum dots with the consistent particle size and shape are prepared by a liquid-phase stripping method; preparing solid-phase components of the bone cement by a physical mixing method; the black phosphorus-calcium phosphate cement with good biocompatibility, high mechanical strength and controllable curing time is prepared under the optimal process by controlling the proportion of the black phosphorus, the calcium phosphate and the calcium hydrophosphate and comparing process parameters of variables such as the type of the curing liquid, the mechanical strength, the near infrared light power, the irradiation time, the injector propulsion speed and the like.
A novel black phosphorus/calcium phosphate cement is characterized in that the form of the black phosphorus is a nano sheet or a quantum dot; calcium phosphates include anhydrous calcium hydrogen phosphate, alpha tricalcium phosphate (alpha-TCP), amorphous tricalcium phosphate (TCCP), and tetracalcium phosphate.
Under the irradiation of near infrared light of 808 nm, the curing time is reduced along with the increase of the proportion of the black phosphorus, wherein the black phosphorus can be solidified within 3 s at the shortest time; the mechanical strength of the black phosphorus accounting for 15 percent can reach 50 MPa.
The novel black phosphorus/calcium phosphate bone cement has the performance of resisting escherichia coli and staphylococcus aureus and has the functions of bone repair and bone induction.
A method for preparing novel black phosphorus-calcium phosphate bone cement comprises the following steps:
(1) preparation of solid phase component of calcium phosphate cement: the method comprises the steps of ball-milling commercially available calcium hydrophosphate dihydrate in a planetary ball mill for 2 hours at 450 rpm by using absolute ethyl alcohol as a ball milling medium through a wet ball milling method, and then drying for 12 hours at 120 ℃ to obtain the anhydrous calcium hydrophosphate. Mixing commercially available tetracalcium phosphate or tricalcium phosphate and anhydrous calcium hydrophosphate in a mass ratio of 1: 1, mixing to obtain the calcium phosphate cement powder.
(2) Preparing black phosphorus nanosheets or black phosphorus quantum dots: 700 mg of blocky black phosphorus crystals are taken and ground into black phosphorus powder in N, N-Dimethylformamide (DMF), the black phosphorus powder is placed in 35ml of DMF, and ultrasonic treatment is carried out for 16 h by using an ultrasonic cell disruptor probe in ice bath to obtain black phosphorus dispersion liquid. And centrifuging the dispersion liquid at the rotating speed of 4000 rpm for 15 min to obtain un-stripped black phosphorus, and centrifuging the supernatant at the rotating speed of 20000 rpm for 20 min to obtain stripped black phosphorus nanosheets and black phosphorus quantum dots. Washing the obtained black phosphorus with isopropanol and deoxygenated water for 2-3 times, and freeze-drying to obtain a sample.
(3) Preparation of black phosphorus-calcium phosphate bone cement: and dispersing the black phosphorus nanosheets or the black phosphorus quantum dots in the curing liquid or doping the unstripped black phosphorus powder into the bone cement powder to obtain the black phosphorus-doped calcium phosphate bone cement. The proportion of the black phosphorus is 0.1-0.5%, and the specific proportion is adjusted according to the requirement. The solidifying liquid of the bone cement adopts 20 wt% citric acid aqueous solution, and the pH value of the citric acid is adjusted to 4 by 0.1 mol/L sodium hydroxide solution. The solid-liquid ratio of the hydrated bone cement is 0.5 ml/g.
In the method of the present invention, the ultrasonication apparatus used was a BILON-R1200 model, manufactured by Shanghai Bilang instruments, with a horn gauge of 10 mm and a maximum power of 1000W.
In the method of the present invention, the black phosphorus concentration is 0.1% to 0.5%, preferably 0.3%. When the concentration of the black phosphorus is too low, the effect is not obvious when the near infrared light is irradiated, and the curing time is a little longer; when the concentration of the polylactic acid reaches 0.3 percent or more, the temperature is higher after near-infrared irradiation, the curing time is shortened and controllable, and when the concentration is too high, the temperature is too high to damage normal cells too much.
The invention has the beneficial effects that: the bone cement has the advantages of adjustable curing time, drug loading, antibacterial property, good mechanical property and better biocompatibility, and can meet the requirements of clinical treatment of various bone defects.
The black phosphorus/calcium phosphate bone cement has the properties of rapid molding and solidification (3 s-30 s) under the irradiation of near infrared light, high mechanical strength (0.1-0.5 percent of black phosphorus), good antibacterial and biocompatibility, bone regeneration and repair and the like. The method has the characteristics of simple and easy operation, environmental friendliness and the like.
Drawings
FIG. 1 is the scanning electron microscope image of the new type black phosphorus-calcium phosphate cement.
Detailed Description
The invention will be further described with reference to the following examples, which are intended only for a better understanding of the invention and in no way should be construed as limiting the scope of the invention, which is defined in the appended claims. The following are exemplary embodiments of the invention from which the above advantages of the invention may be more fully understood.
Preparation of black phosphorus nanosheet or black phosphorus quantum dot
Taking 700 mg of blocky black phosphorus crystals, grinding the blocky black phosphorus crystals into black phosphorus powder with the particle size of 1-5 microns in N, N-Dimethylformamide (DMF), placing the black phosphorus powder into 35ml of DMF, and carrying out ice bath ultrasound for 16 h by using an ultrasonic cell disruptor probe to obtain the black phosphorus dispersion liquid. And centrifuging the black phosphorus dispersion liquid at the rotating speed of 4000 rpm for 15 min to obtain the non-stripped black phosphorus, and centrifuging the supernatant at the rotating speed of 20000 rpm for 20 min to obtain the stripped black phosphorus nanosheet or black phosphorus quantum dot. Washing the obtained black phosphorus with isopropanol and deoxygenated water for 2-3 times, and freeze-drying to obtain a black phosphorus nanosheet sample.
Preparation of solid phase component of calcium phosphate cement
The method comprises the steps of ball-milling commercially available calcium hydrophosphate dihydrate in a planetary ball mill for 2 hours at 450 rpm by using absolute ethyl alcohol as a ball milling medium through a wet ball milling method, and then drying for 12 hours at 120 ℃ to obtain the anhydrous calcium hydrophosphate. Mixing commercially available tetracalcium phosphate or tricalcium phosphate and anhydrous calcium hydrophosphate in a mass ratio of 1: 1, mixing to obtain the calcium phosphate cement powder.
Preparation of black phosphorus-calcium phosphate bone cement
And dispersing the black phosphorus nanosheet or the black phosphorus quantum dot in the curing liquid or doping the unstripped black phosphorus powder into the bone cement powder to obtain the black phosphorus doped calcium phosphate bone cement with the black phosphorus content of 0.1-0.5%. The curing liquid of the calcium phosphate cement doped with the black phosphorus adopts 20 wt% citric acid aqueous solution, and the pH value of the citric acid is adjusted to 4 by using 0.1 mol/L sodium hydroxide solution. The solid-liquid ratio of the hydrated bone cement is 0.5 mL/g.
Research on antibacterial performance of black phosphorus-calcium phosphate bone cement
The antibacterial property of the black phosphorus-calcium phosphate bone cement is detected by adopting a bacteriostatic ring method:
firstly, activating, separating and purifying gram-negative escherichia coli and gram-positive staphylococcus aureus for later use, and then tabletting the black phosphorus-calcium phosphate cement.
Diluting the purified Escherichia coli and Staphylococcus aureus liquid to 106cfu/mL, pouring solid culture medium into a flat plate, sucking 100 mu L of bacterial liquid after the solid culture medium is solidified, injecting the bacterial liquid, uniformly coating the bacterial liquid by using a coater,the sample pieces are respectively placed in the center of a culture dish and marked with marks, the sample pieces are placed in a constant temperature incubator (37 ℃) for 24 hours and then taken out for observation, the diameter of the antibacterial ring is measured by a vernier caliper and recorded, and each group of samples is subjected to 3 parallel tests. The results show that the experimental group has obvious inhibition ring formation on two bacteria, while the control group does not generate the inhibition ring, which indicates that the black phosphorus-calcium phosphate bone cement has certain antibacterial effect and has antibacterial effect on gram-negative bacteria (escherichia coli) and gram-positive bacteria (staphylococcus aureus). Meanwhile, after the control group is irradiated by near infrared laser with the wavelength of 808 nm for 1-5 minutes, the temperature and the size of an antibacterial ring of the control group are detected.
Cytotoxicity study of black phosphorus-calcium phosphate bone cement
To a concentration of 105 the/mL MC3T3 cells were plated in three sterile 96-well plates, 100. mu.L per well, 5 rows and 6 columns per plate, sealed with PBS buffer water to reduce evaporation, and incubated at 37 deg.C with 5% CO2The culture is carried out in an incubator for 24 hours and is reserved for standby. Preparing the black phosphorus-calcium phosphate bone cement into 3 cylindrical slices with phi 10 mm multiplied by 1 mm, carrying out ultraviolet sterilization for 24 h, preparing leaching liquor by a serum-free culture medium, and diluting the leaching liquor of 3 groups of samples into five concentrations of 20 mg/mL, 10 mg/mL, 5 mg/mL, 2.5 mg/mL and 1.25 mg/mL. Taking pure serum-free culture medium as a control group, taking pure culture medium without cells as a blank group, adding five concentrations of leaching liquor, making five parallel controls for each sample, totaling 5 rows and 7 columns, and arranging 3 well plates in the same way. Adding 100 mu L of leaching liquor and serum-free culture medium with corresponding concentrations into each hole, respectively, incubating in an incubator for 24 h, 72 h and 120 h, then taking out 1 hole plate, adding 10 mu L of CCK-8 solution into each hole, incubating in the incubator for 2h, taking out when the color of the culture medium is changed from pink to orange, measuring the absorbance of each hole at 450 nm by using a microplate reader, and calculating the survival rate of cells in each hole.
The calculation formula is as follows:
and the mean and standard deviation were calculated, respectively.
Claims (4)
1. A novel black phosphorus/calcium phosphate cement is characterized in that the form of the black phosphorus is a nano sheet or a quantum dot; the calcium phosphate includes anhydrous calcium hydrogen phosphate, tricalcium phosphate or tetracalcium phosphate.
2. The novel black phosphorus/calcium phosphate cement as claimed in claim 1, wherein the tricalcium phosphate comprises alpha tricalcium phosphate, amorphous tricalcium phosphate.
3. The novel black phosphorus/calcium phosphate cement as claimed in claim 1, wherein the curing time of the black phosphorus under 808 nm near infrared light irradiation is reduced with the increase of the proportion of the black phosphorus, and the black phosphorus/calcium phosphate cement can be cured within 3 s at the shortest time; the mechanical strength of the black phosphorus accounting for 15 percent can reach 50 MPa; the novel black phosphorus/calcium phosphate bone cement has the performance of resisting escherichia coli and staphylococcus aureus and has the functions of bone repair and bone induction.
4. The novel black phosphorus/calcium phosphate cement according to claim 1, characterized by the fact that it is prepared by the following steps:
(1) preparation of solid phase component of calcium phosphate cement: carrying out ball milling on calcium hydrogen phosphate dihydrate in a planetary ball mill for 2h at 450 rpm by using absolute ethyl alcohol as a ball milling medium through a wet ball milling method, and then drying for 12 h at 120 ℃ to obtain anhydrous calcium hydrogen phosphate; mixing tetracalcium phosphate or tricalcium phosphate and anhydrous calcium hydrophosphate in a mass ratio of 1: 1, mixing to obtain calcium phosphate cement powder;
(2) preparing black phosphorus nanosheets or black phosphorus quantum dots: grinding 700 mg of blocky black phosphorus crystals in N, N-dimethylformamide into black phosphorus powder, placing the black phosphorus powder in 35ml of N, N-dimethylformamide, and performing ice-bath ultrasound for 16 h by using a probe of an ultrasonic cell disruptor to obtain black phosphorus dispersion liquid; centrifuging the black phosphorus dispersion liquid at the rotating speed of 4000 rpm for 15 min to obtain un-stripped black phosphorus, and centrifuging the supernatant at the rotating speed of 20000 rpm for 20 min to obtain stripped black phosphorus nanosheets or black phosphorus quantum dots; washing the obtained black phosphorus nanosheet or black phosphorus quantum dot for 2-3 times by using isopropanol and deoxygenated water, and freeze-drying;
(3) preparation of black phosphorus-calcium phosphate bone cement: dispersing black phosphorus nanosheets or black phosphorus quantum dots in a curing liquid or doping unpeeled black phosphorus powder into solid-phase cement powder to obtain black phosphorus-doped calcium phosphate cement with the black phosphorus content of 0.1-0.5%; the solidifying liquid of the bone cement adopts 20 wt% citric acid aqueous solution, and the pH value of the citric acid is adjusted to 4 by 0.1 mol/L sodium hydroxide solution; the solid-liquid ratio of the hydrated bone cement is 0.5 ml/g.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106668951A (en) * | 2016-11-23 | 2017-05-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Doped black phosphorus quantum dot thermal treatment syringeability bone cement as well as preparation and application thereof |
| CN108815580A (en) * | 2018-07-23 | 2018-11-16 | 吴容思 | A kind of calcium phosphate bone cement and preparation method thereof of controllable degradation |
| US20200174288A1 (en) * | 2018-11-29 | 2020-06-04 | Samsung Electronics Co., Ltd. | Quantum dots and devices including the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106668951A (en) * | 2016-11-23 | 2017-05-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Doped black phosphorus quantum dot thermal treatment syringeability bone cement as well as preparation and application thereof |
| CN108815580A (en) * | 2018-07-23 | 2018-11-16 | 吴容思 | A kind of calcium phosphate bone cement and preparation method thereof of controllable degradation |
| US20200174288A1 (en) * | 2018-11-29 | 2020-06-04 | Samsung Electronics Co., Ltd. | Quantum dots and devices including the same |
Non-Patent Citations (1)
| Title |
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| 赵益涛: ""基于黑磷的多功能TCP/PLGA支架体系应用性初探"", 《中国优秀博硕士学位论文全文数据库(硕士) 医药卫生科技辑(月刊)》, no. 01, 15 January 2021 (2021-01-15), pages 7 * |
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