CN111298199B - Temporary implant for orthopedics department and preparation method thereof - Google Patents
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Abstract
The invention provides an orthopedic temporary implant and a preparation method thereof, belonging to the technical field of medical materials. The orthopedic temporary implant is an injectable composite temperature-sensitive hydrogel composed of chitosan quaternary ammonium salt, quaternary ammonium salt modified nano hydroxyapatite and an amphoteric surfactant. After the injectable composite temperature-sensitive hydrogel is injected into a human body, the quaternary ammonium salt on the surface of the chitosan quaternary ammonium salt and the phosphate radical on the surface of the quaternary ammonium salt modified nano hydroxyapatite form electrostatic interaction through anions and cations of the amphoteric surfactant, and the hydrogel with the porous three-dimensional cross-linked network structure is obtained. According to the invention, the temperature-sensitive hydrogel is formed by quaternary ammonium salt modification and mainly utilizing electrostatic action, so that the mechanical property of the hydrogel is improved, and meanwhile, the hydrogel is endowed with good antibacterial property; the amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and relates to an orthopedic temporary implant and a preparation method thereof.
Background
The number of patients with bone defects caused by improper treatment of fracture and fracture after treatment, severe trauma, infection, bone tumor and the like is as many as ten million all the year around the world. Bone defect is a common disease, mainly is local bone loss caused by trauma and diseases (such as infection, tumor and the like), and is still one of the problems facing orthopedics due to high clinical morbidity and lack of an ideal treatment method. Although bone grafting (autologous bone grafting and allogeneic bone grafting) is a traditional treatment means for repairing bone defects and has good curative effect, the method still has obvious defects and limitations. Therefore, the search for ideal bone graft substitute materials is highly unpredictably needed.
Some temperature-sensitive hydrogels are receiving increasing attention because they can form gels in situ at conditions close to physiological pH and temperature. Without any other chemical or environmental stimulus, temperature is the only stimulus for its gelation. In general, hydrogels with temperature sensitive properties can be injected into tissue or organ cavities in a minimally invasive surgical manner and formed with solid fillers of specific shapes to match the cavity, which makes them desirable for a variety of biomedical applications. Chitosan is used as a biodegradable natural polymer material with excellent performance, and the hydrogel prepared by the chitosan is widely applied, in particular, the temperature-sensitive hydrogel prepared by chitosan/GP (beta-sodium glycerophosphate) is used as an in-situ gel scaffold to repair or reconstruct defects of cartilage, bones, nerves and skin, and is used as a carrier for conveying drugs or bioactive molecules. However, chitosan/GP hydrogels have limited applications due to their lower mechanical properties and faster in vivo degradation rates.
The Chinese patent with application number 201510252453.8 discloses an injectable porous-drug-loaded polymethyl methacrylate-based composite scaffold bone graft material and a preparation method thereof, wherein polymethyl methacrylate is used as a scaffold for providing mechanical support, and chitosan-based temperature-sensitive glue is used as a pore-forming agent and a carrier of a bone guiding material and a drug to form an injectable porous three-dimensional structure bone cement composite, which has good biocompatibility and mechanical properties, but poor biodegradability of polymethyl methacrylate.
Therefore, it is urgently needed to prepare a bone grafting material which has good biocompatibility, high mechanical property and matched degradation rate in vivo with a bone defect repair mechanism.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an orthopedic temporary implant and a preparation method thereof, wherein the injectable hydrogel is formed by quaternary ammonium salt modification and mainly utilizing electrostatic action, so that the mechanical property of the hydrogel is improved, and meanwhile, the hydrogel is endowed with good antibacterial property; the amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing an orthopedic temporary implant, comprising the steps of:
s1, dissolving chitosan quaternary ammonium salt in deionized water to obtain a chitosan quaternary ammonium salt water solution;
s2, respectivelyPreparation of calcium in aqueous inorganic salt solution and (NH)4)2HPO4Adjusting pH of the two solutions to 10-11 with ammonia water, and adding (NH) at molar ratio of calcium to phosphorus of 1.674)2HPO4Adding the water solution into an inorganic salt water solution of calcium, adding organosilicon quaternary ammonium salt, uniformly mixing, performing hydrothermal treatment for 4-16h at 90-180 ℃ in a high-pressure reaction kettle, and then performing centrifugal separation, washing and drying to obtain quaternary ammonium salt modified nano hydroxyapatite;
s3, adding the quaternary ammonium salt modified nano hydroxyapatite obtained in the step S2 and the amphoteric surfactant into the chitosan quaternary ammonium salt aqueous solution obtained in the step S1 according to the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant of 100 (10-15) to (5-10), and uniformly stirring to obtain the orthopedic temporary implant.
As a further improvement of the invention, in step S2, the molar ratio of the organosilicon quaternary ammonium salt to the calcium atoms is 1 (5-10).
As a further improvement of the present invention, in step S2, the modified inorganic salt is anhydrous calcium chloride.
As a further improvement of the invention, in step S1, the concentration of the chitosan quaternary ammonium salt aqueous solution is 20-45 mg/mL.
Advantageous effects
Compared with the prior art, the orthopedic temporary implant and the preparation method thereof provided by the invention have the following beneficial effects:
(1) the invention provides an orthopedic temporary implant, which is an injectable composite hydrogel composed of chitosan quaternary ammonium salt, quaternary ammonium salt modified nano hydroxyapatite and an amphoteric surfactant. After the injectable composite hydrogel is injected into a human body, the quaternary ammonium salt on the surface of the chitosan quaternary ammonium salt and the phosphate radical on the surface of the quaternary ammonium salt modified nano hydroxyapatite form electrostatic interaction through anions and cations of the amphoteric surfactant, and the hydrogel with the porous three-dimensional cross-linked network structure is obtained. According to the invention, the injectable hydrogel is modified by quaternary ammonium salt, and the electrostatic effect is mainly utilized to form the injectable hydrogel, so that the mechanical property of the hydrogel is improved, and meanwhile, the hydrogel is endowed with good antibacterial property; the amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
(2) The invention takes chitosan quaternary ammonium salt as a main body of the injectable hydrogel, and the surface of the chitosan quaternary ammonium salt is rich in amino, hydroxyl and quaternary ammonium salt cations; the specific surface area of the quaternary ammonium salt modified nano hydroxyapatite is large, the quaternary ammonium salt is not easy to agglomerate after being adsorbed on the surface, and the number of active points of electrostatic action is increased; the amphoteric surfactant contains cations and anions at the same time, can be used as a bridge for electrostatic action, and connects the chitosan quaternary ammonium salt and the quaternary ammonium salt modified nano hydroxyapatite to form a porous three-dimensional network structure, so that the mechanical strength of the hydrogel is remarkably improved.
(3) The invention adopts a hydrothermal method to prepare nano hydroxyapatite, and in the preparation process, organosilicon quaternary ammonium salt is added, and in the hydrothermal process, the organosilicon quaternary ammonium salt is a cationic surfactant, the molecule is in a long rod-shaped micelle structure in an aqueous solution, one end of the molecule is a positively charged hydrophilic head which has stronger affinity with water molecules, and the other end of the molecule is a hydrophobic tail which has weaker affinity with the water molecules. The organosilicon quaternary ammonium salt molecules are separated into cations and anions in an aqueous solution system, in the reaction process, the positively charged cations can be selectively adsorbed on the hydrophilic crystal face of the nano hydroxyapatite, and the formed hydroxyapatite precursor can continuously carry out chemical reaction, so that the hydroxyapatite is generated by being attached to the surface of the organosilicon quaternary ammonium salt micelle in a certain direction, and the prepared quaternary ammonium salt modified nano hydroxyapatite has large specific surface area, more active points and good antibacterial property.
Drawings
Fig. 1 is a graph showing the in vitro degradation rate of the orthopedic temporary implants prepared in example 1 and comparative examples 1 and 2.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
A method for preparing an orthopedic temporary implant, comprising the steps of:
s1, dissolving chitosan quaternary ammonium salt in deionized water to obtain a chitosan quaternary ammonium salt water solution with the concentration of 20-45 mg/mL;
s2, respectively preparing inorganic salt aqueous solution of calcium and (NH)4)2HPO4Adjusting pH of the two solutions to 10-11 with ammonia water, and adding (NH) at molar ratio of calcium to phosphorus of 1.674)2HPO4Adding the water solution into an inorganic salt water solution of calcium, adding organosilicon quaternary ammonium salt, uniformly mixing, performing hydrothermal treatment for 4-16h at 90-180 ℃ in a high-pressure reaction kettle, and then performing centrifugal separation, washing and drying to obtain quaternary ammonium salt modified nano hydroxyapatite;
in the hydrothermal process, the organosilicon quaternary ammonium salt is a cationic surfactant, the molecule is in a long rod-shaped micelle structure in an aqueous solution, one end of the molecule is a positively charged hydrophilic head which has strong affinity with water molecules, and the other end of the molecule is a hydrophobic tail which has weak affinity with the water molecules. The organosilicon quaternary ammonium salt molecules are separated into cations and anions in an aqueous solution system, in the reaction process, the positively charged cations can be selectively adsorbed on the hydrophilic crystal face of the nano hydroxyapatite, and the formed hydroxyapatite precursor can continuously carry out chemical reaction, so that the hydroxyapatite is attached to the surface of the organosilicon quaternary ammonium salt micelle to be generated according to a certain direction.
S3, adding the quaternary ammonium salt modified nano hydroxyapatite obtained in the step S2 and the amphoteric surfactant into the chitosan quaternary ammonium salt aqueous solution obtained in the step S1 according to the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant of 100 (10-15) to (5-10), and uniformly stirring to obtain the orthopedic temporary implant.
In step S2, the molar ratio of the organosilicon quaternary ammonium salt to the calcium atoms is 1 (5-10). The quaternary ammonium salt is added in the preparation process of the nano hydroxyapatite and is adsorbed on the surface of the nano hydroxyapatite along with the growth process of the nano hydroxyapatite, so that the surface activity and the antibacterial property are improved.
As a further improvement of the present invention, in step S2, the modified inorganic salt is anhydrous calcium chloride.
After the injectable composite hydrogel is injected into a human body, under the stimulation of the pH environment of the human body, the quaternary ammonium salt on the surface of the chitosan quaternary ammonium salt and the phosphate radical on the surface of the quaternary ammonium salt modified nano hydroxyapatite form electrostatic interaction through anions and cations of an amphoteric surfactant, and the hydrogel with a porous three-dimensional cross-linked network structure is obtained. According to the invention, the injectable hydrogel is formed by quaternary ammonium salt modification and mainly utilizing electrostatic interaction, so that the mechanical property of the hydrogel is improved, and meanwhile, the hydrogel is endowed with good antibacterial property.
The chitosan quaternary ammonium salt is used as a main body of the injectable hydrogel, and the surface of the chitosan quaternary ammonium salt is rich in amino, hydroxyl and quaternary ammonium salt cations; the specific surface area of the quaternary ammonium salt modified nano hydroxyapatite is large, the quaternary ammonium salt is not easy to agglomerate after being adsorbed on the surface, and the number of active points of electrostatic action is increased; the amphoteric surfactant contains cations and anions at the same time, can be used as a bridge for electrostatic action, and connects the chitosan quaternary ammonium salt and the quaternary ammonium salt modified nano hydroxyapatite to form a porous three-dimensional network structure, so that the mechanical strength of the hydrogel is remarkably improved.
The amphoteric surfactant is amino acid type amphoteric surfactant. The amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
The quaternary ammonium salt is organosilicon quaternary ammonium salt. The organosilicon quaternary ammonium salt is any one or more of organosilicon quaternary ammonium salt of trimethoxy silane containing C10-C18 alkyl and organosilicon quaternary ammonium salt of triethoxy silane containing C10-C18 alkyl. The organosilicon quaternary ammonium salt has good antibacterial property and biocompatibility.
The embodiment of the present invention will be described in detail below with reference to specific examples.
Example 1
An orthopedic temporary implant prepared by the steps of:
s1, dissolving chitosan quaternary ammonium salt in deionized water to obtain a chitosan quaternary ammonium salt water solution with the concentration of 30 mg/mL;
s2, respectively preparing an anhydrous calcium chloride aqueous solution with the concentration of 45mg/mL and (NH) with the concentration of 30mg/mL4)2HPO4Adjusting pH of the two aqueous solutions to 10 with ammonia water, and adding (NH) at molar ratio of calcium to phosphorus of 1.674)2HPO4Adding the aqueous solution into an anhydrous calcium chloride aqueous solution, adding hexadecyl trimethoxy silane quaternary ammonium salt according to the molar ratio of organosilicon quaternary ammonium salt to calcium atoms of 1:8, stirring and mixing uniformly, pouring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 12h, then carrying out centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain quaternary ammonium salt modified nano hydroxyapatite;
s3, adding the quaternary ammonium salt modified nano hydroxyapatite obtained in the step S2 and glutamic acid into the chitosan quaternary ammonium salt aqueous solution obtained in the step S1 according to the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant of 100:12:8, and uniformly stirring to obtain the orthopedic temporary implant.
Comparative example 1
An orthopedic temporary implant was prepared in a manner similar to that of example 1, except that in step S3, the amphoteric surfactant glutamic acid was not added, but the rest was substantially the same as in example 1 and thus will not be described herein.
Comparative example 2
An orthopedic temporary implant was fabricated by a method similar to that of example 1, except that, in step S2, the hexadecyl trimethoxy silane quaternary ammonium salt was not added, but the method was substantially the same as that of example 1 and thus will not be repeated herein.
The compressive strength and the elastic modulus of the orthopedic temporary implant are respectively tested by using an Instron 5697 model universal testing machine under the environment of room temperature and 47% humidity according to the standard GB/T1041 and 1992. The test results are shown in table 1, and it can be seen that the compressive strength and the elastic modulus of the orthopedic temporary implant prepared in example 1 are respectively as high as 18.98 ± 0.43MPa and 17.67 ± 0.36MPa, while the compressive strength and the elastic modulus of comparative example 1 and comparative example 2 are both significantly reduced, which indicates that the quaternary ammonium salt modification of nano-hydroxyapatite and the addition of amphoteric surfactant in hydrogel have significant effect on improving the mechanical strength of hydrogel, and further proves that the invention can improve the electrostatic effect by introducing a substance with cation or anion into each hydrogel component, thereby improving the crosslinking degree of hydrogel and further improving the mechanical strength.
Table 1 results of mechanical strength test of example 1 and comparative examples 1 and 2
| Test specimen | Compressive strength (MPa) | Modulus of elasticity (MPa) |
| Example 1 | 18.98±0.43 | 17.67±0.36 |
| Comparative example 1 | 12.23±0.65 | 13.63±0.55 |
| Comparative example 2 | 13.68±0.52 | 14.87±0.64 |
And soaking the prepared orthopedic temporary implant in simulated body fluid, taking out samples every 24 hours, drying, weighing the weight of the orthopedic temporary implant, and calculating the accumulated degradation rate of the orthopedic temporary implant.
The in vitro degradation rates of example 1 and comparative examples 1 and 2 are shown in fig. 1, and it can be seen that the degradation rate of the orthopaedic temporary implant prepared in example 1 in simulated body fluid is significantly lower than that of comparative examples 1 and 2, because the quaternary ammonium salt modification of nano-hydroxyapatite and the addition of amphoteric surfactant to hydrogel can increase the degree of cross-linking of hydrogel, thereby reducing the degradation rate, and thus prolonging the bone defect repair time and repair effect.
Examples 2 to 3
Examples 2-3 provide orthopedic temporary implants, which are prepared according to a method different from that of example 1 in that, in step S2, the molar ratio of the silicone quaternary ammonium salt to the calcium atom is shown in table 2, and the rest is substantially the same as example 1, and thus, the description thereof is omitted.
Table 2 results of mechanical strength test of examples 2 to 3
As can be seen from table 2, as the molar ratio of the organosilicon quaternary ammonium salt to the calcium atoms increases and as the content of the organosilicon quaternary ammonium salt increases, the mechanical strength of the orthopaedic temporary implant tends to increase gradually, because during the growth process of hydroxyapatite, the organosilicon quaternary ammonium salt can be selectively adsorbed on the hydrophilic crystal face of the nano hydroxyapatite, reducing the agglomeration property thereof, increasing the surface active sites, and thus increasing the degree of crosslinking. However, the content of the organosilicon quaternary ammonium salt is too much, which is not beneficial to the growth of the nano hydroxyapatite.
Examples 4 to 5
Examples 4 to 5 provide orthopedic temporary implants, which are different from example 1 in that, in step S3, the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant is shown in table 3, and the rest is substantially the same as example 1, and thus, the description thereof is omitted.
Table 3 results of mechanical strength test of examples 4 to 5
As can be seen from table 3, the mechanical strength of the orthopaedic temporary implant shows a tendency to increase gradually with the increase of the content of the amphoteric surfactant, because the amphoteric surfactant, which serves as a bridge of the hydrogel cross-linked body, can cross-link the chitosan quaternary ammonium salt and the quaternary ammonium salt-modified hydroxyapatite into a three-dimensional network structure by electrostatic interaction, thereby improving the mechanical strength.
In conclusion, the invention takes the chitosan quaternary ammonium salt as the main body of the injectable hydrogel, and the surface of the chitosan quaternary ammonium salt is rich in amino, hydroxyl and quaternary ammonium salt cations; the specific surface area of the quaternary ammonium salt modified nano hydroxyapatite is large, the quaternary ammonium salt is not easy to agglomerate after being adsorbed on the surface, and the number of active points of electrostatic action is increased; the amphoteric surfactant contains cations and anions at the same time, can be used as a bridge for electrostatic action, and connects the chitosan quaternary ammonium salt and the quaternary ammonium salt modified nano hydroxyapatite to form a porous three-dimensional network structure, so that the mechanical strength of the hydrogel is remarkably improved. The quaternary ammonium salt is modified, and the injectable hydrogel is mainly formed by utilizing the electrostatic effect, so that the mechanical property of the hydrogel is improved, and the hydrogel is endowed with good antibacterial property; the amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. A method for preparing an orthopedic temporary implant, comprising the steps of:
s1, dissolving chitosan quaternary ammonium salt in deionized water to obtain a chitosan quaternary ammonium salt water solution;
s2, respectively preparing inorganic salt aqueous solution of calcium and (NH)4)2HPO4Adjusting pH of the two solutions to 10-11 with ammonia water, and adding (NH) at molar ratio of calcium to phosphorus of 1.674)2HPO4Adding the water solution into an inorganic salt water solution of calcium, adding organosilicon quaternary ammonium salt, uniformly mixing, performing hydrothermal treatment for 4-16h at 90-180 ℃ in a high-pressure reaction kettle, and then performing centrifugal separation, washing and drying to obtain quaternary ammonium salt modified nano hydroxyapatite;
s3, adding the quaternary ammonium salt modified nano hydroxyapatite obtained in the step S2 and the amphoteric surfactant into the chitosan quaternary ammonium salt aqueous solution obtained in the step S1 according to the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant of 100 (10-15) to (5-10), and uniformly stirring to obtain the orthopedic temporary implant.
2. The method for producing an orthopedic temporary implant according to claim 1, wherein in step S2, the molar ratio of said quaternary ammonium silicone salt to calcium atoms is 1 (5-10).
3. The method for preparing an orthopedic temporary implant according to claim 1, wherein in step S2, the inorganic salt of calcium is anhydrous calcium chloride.
4. The method of claim 1, wherein the concentration of the aqueous solution of chitosan quaternary ammonium salt in step S1 is 20-45 mg/mL.
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| EP1127581A1 (en) * | 1998-02-27 | 2001-08-29 | Musculoskeletal Transplant Foundation | Malleable paste for filling bone defects |
| WO2007064304A1 (en) * | 2005-12-01 | 2007-06-07 | National University Of Singapore | Biocompatible composition and uses thereof |
| CN103191459A (en) * | 2013-04-06 | 2013-07-10 | 广东泰宝医疗科技股份有限公司 | Composite silica gel protective dressing and preparation method thereof |
| CN104324419A (en) * | 2014-10-28 | 2015-02-04 | 暨南大学 | Injectable nano-hydroxyapatite/chitosan composite hydrogel as well as preparation method and application thereof |
| CN104909347A (en) * | 2015-07-03 | 2015-09-16 | 厦门大学 | Preparation method for hydroxylapatite |
| CN106178125A (en) * | 2016-07-20 | 2016-12-07 | 太原理工大学 | A kind of preparation method of nanometer hydroxyapatite chitosan compound microsphere |
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2020
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1127581A1 (en) * | 1998-02-27 | 2001-08-29 | Musculoskeletal Transplant Foundation | Malleable paste for filling bone defects |
| WO2007064304A1 (en) * | 2005-12-01 | 2007-06-07 | National University Of Singapore | Biocompatible composition and uses thereof |
| CN103191459A (en) * | 2013-04-06 | 2013-07-10 | 广东泰宝医疗科技股份有限公司 | Composite silica gel protective dressing and preparation method thereof |
| CN104324419A (en) * | 2014-10-28 | 2015-02-04 | 暨南大学 | Injectable nano-hydroxyapatite/chitosan composite hydrogel as well as preparation method and application thereof |
| CN104909347A (en) * | 2015-07-03 | 2015-09-16 | 厦门大学 | Preparation method for hydroxylapatite |
| CN106178125A (en) * | 2016-07-20 | 2016-12-07 | 太原理工大学 | A kind of preparation method of nanometer hydroxyapatite chitosan compound microsphere |
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