CN115770320A - Preparation method of magnesium phosphate/phytic acid/gelatin/calcined dolomite bone adhesive - Google Patents

Preparation method of magnesium phosphate/phytic acid/gelatin/calcined dolomite bone adhesive Download PDF

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CN115770320A
CN115770320A CN202211596110.XA CN202211596110A CN115770320A CN 115770320 A CN115770320 A CN 115770320A CN 202211596110 A CN202211596110 A CN 202211596110A CN 115770320 A CN115770320 A CN 115770320A
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gelatin
phytic acid
magnesium phosphate
calcined
dolomite
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周春晖
屈雪静
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a preparation method of magnesium phosphate/phytic acid/gelatin/calcined dolomite bone adhesive, which is prepared by dissolving gelatin in phytic acid solution, and rapidly and completely mixing and reacting magnesium phosphate/calcined dolomite with the phytic acid/gelatin solution at room temperature; the bone adhesive prepared by using the chelation of calcium and magnesium ions in the calcined dolomite and the phytic acid and the stable crosslinking of gelatin and the phytic acid based on ionic bonds can achieve stronger bonding strength, excellent compressive strength and tensile strength, has short bonding time, good biocompatibility and biodegradability, simple preparation method and low price.

Description

Preparation method of magnesium phosphate/phytic acid/gelatin/calcined dolomite bone adhesive
Technical Field
The invention relates to a preparation method of a bone adhesive, in particular to a preparation method of a magnesium phosphate/phytic acid/gelatin/calcined dolomite bone adhesive.
Background
The incidence of large-area bone defects caused by trauma, tumors, bone defects, arthritis and infection is high worldwide, especially the number of highly comminuted fractures due to large external forces is increasing every year. At present, the fracture is clinically treated mainly by a conservative treatment mode or an operation, and besides a few fractures are suitable for functional reduction, the fracture still needs to be treated by the operation in most cases. At present, the method for treating the comminuted fracture is a combined mode of internal fixation and external fixation, mainly uses plates, pins, screws and other firm internal fixators at the fracture part, and places metal nails at the tail ends of the plates to fix the fracture fragments, and the mode is also always the golden standard of surgical treatment. However, the surrounding joints, such as most comminuted fractures, require anatomical reduction to meet the needs of movement to prevent osteoarthritis from occurring; the internal fixator is difficult to accurately fix broken fragments together, especially highly comminuted fractures; osteoporotic bone cannot secure the screws firmly; the internal fixator serving as an in vitro implant is easy to cause bone tissue infection at an implantation part and needs to be removed after bone healing; the problems that the metal surface often forms a false film which promotes the growth of bacteria in vivo and the like still remain to be solved. Therefore, the problem of fixation of highly comminuted fractures is an urgent problem to be solved. Clinicians operating on comminuted fracture patients find it necessary to bond comminuted fracture fragments together to secure the fragments and promote bone healing.
The dolomite after high-temperature calcination releases carbon dioxide and is converted into a mixture containing CaO and MgO. Ca provided by dolomite 2+ And Mg 2+ Is physiologically involved in bone metabolism and can stimulate osteoblast regeneration and self-repair when released from bone adhesion bioactive materials. Dolomite is used as a calcium source and a magnesium source, and has great application potential when participating in the preparation of biological materials. The phytic acid is polyhydroxy compound extracted from edible beans, has strong chelating ability to various metal ions, and has biocompatibility proved, and can be used for simultaneously calcining dolomite and Mg in skeleton 2+ 、Ca 2+ Chelation was performed. The gelatin is a natural protein with high biocompatibility extracted from collagen with high richness, and has good biocompatibility. In addition, the amino groups contained in the gelatin can generate the cross-linking effect based on ionic bonds with the hydroxyl groups in the phytic acid.
Currently, the universal glue cyanoacrylate (Qiuton, a bone adhesive and its preparation method: chinese patent, CN107343965, 2020) has been developed to provide biocompatibility and adhesive strength, but its chemical integrity results in a dense adhesive layer that does not allow ingrowth of new bone tissue and limits bone growth and bone repair to some extent. Biological bone adhesives such as hydrogel (Zhang ice goose, an organic-inorganic hybrid hydrogel bone adhesive and a preparation method thereof: chinese patent, CN113577371A, 2019.) have adhesive performance and mechanical performance, but problems of low adhesive strength, excessive expansion of the adhesive and the like can occur. According to the invention, the bone adhesive prepared by adding gelatin on the basis of magnesium phosphate/phytic acid/calcined dolomite can bond broken bones in a short time, and has strong viscosity. The prepared novel bone adhesive has good adhesive property and mechanical property, and has important significance for fixing broken bones.
Disclosure of Invention
Aiming at the defects of the prior bone adhesive, the invention provides a preparation method of magnesium phosphate/phytic acid/gelatin/calcined dolomite bone adhesive, which is prepared by adding gelatin into phytic acid solution, and rapidly and completely mixing and reacting calcined dolomite with the phytic acid/gelatin solution at room temperature.
The technical scheme of the invention is as follows:
a preparation method of magnesium phosphate/phytic acid/gelatin/calcined dolomite bone cement comprises the following steps:
(1) Grinding natural dolomite, sieving (200 mesh sieve), placing in a muffle furnace, heating to 800-1000 ℃, and calcining for 5h to obtain calcined dolomite;
the rate of temperature rise is 5 ℃/min;
the obtained calcined dolomite contains MgO and CaO;
(2) Placing magnesium phosphate in a muffle furnace, heating to 800-1000 ℃, and calcining for 4h to obtain calcined magnesium phosphate;
the rate of temperature rise is 5 ℃/min;
(3) Preparing phytic acid solution at 0-10 ℃, adding gelatin into the phytic acid solution, and stirring and dissolving to obtain phytic acid/gelatin solution; mixing the calcined dolomite obtained in the step (1) and the calcined magnesium phosphate obtained in the step (2), then adding the mixture into a phytic acid/gelatin solution, and uniformly mixing to obtain a bone adhesive;
the mass fraction of the phytic acid solution is 15-25%;
the mass fraction of the gelatin in the phytic acid/gelatin solution is 5-13%;
the mass ratio of the calcined dolomite to the calcined magnesium phosphate is 1: 4-20, wherein the mass ratio of the total of calcined dolomite and calcined magnesium phosphate to the phytic acid/gelatin solution is 1:45 to 55.
Compared with the existing bone adhesive, the invention has the following beneficial effects:
the bone adhesive prepared by using the chelation of calcium and magnesium ions in the calcined dolomite and the phytic acid and the ionic bond-based crosslinking of gelatin and the phytic acid can achieve stronger bonding strength, excellent compressive strength and tensile strength, has short bonding time, good biocompatibility and biodegradability, simple preparation method and low price.
Drawings
Fig. 1 is a bone of example 1.
Fig. 2 is a graph of the bond strength of bone cement at different gelatin addition levels.
Detailed Description
The invention is further described below in conjunction with specific embodiments, the advantages and features of which will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
In the following examples, natural dolomite is from Qingyang county, anhui province.
Example 1
Weighing 6.25g of 70% phytic acid solution, 1.25g of gelatin and 17.5g of deionized water, adding the gelatin and the deionized water into the 70% phytic acid solution, and stirring on a magnetic stirrer until the gelatin is completely dissolved to obtain a liquid phase substance. And (3) putting 0.025g of natural dolomite into a muffle furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, and calcining for 5 hours to obtain calcined dolomite. The calcined dolomite was ground into powder with an agate mortar, and the powder was thoroughly ground and sieved through a 200 mesh sieve. 0.475g of magnesium phosphate was placed in a muffle furnace and heated to 800 ℃ at a rate of 5 ℃/min and calcined for 4h. And fully grinding the calcined natural dolomite/magnesium phosphate in an agate mortar to obtain a solid-phase substance. And mixing the solid phase and the liquid phase, quickly stirring, curing for 15s, transferring the bone adhesive to the section of a fresh pig rib by using a glass rod, uniformly spreading the bone adhesive on the section by using the glass rod, and continuously pressing the pig rib for 1min along the axis to obtain the bonded pig rib.
It can be seen from fig. 1 that the broken pig ribs are cemented.
Example 2
Weighing 6.25g of phytic acid solution with the mass fraction of 70%, 1.25g of gelatin and 17.5g of deionized water, adding the gelatin and the deionized water into the phytic acid solution with the mass fraction of 70%, and stirring on a magnetic stirrer until the gelatin is completely dissolved to obtain a liquid phase substance. And (3) putting 0.025g of natural dolomite into a muffle furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, and calcining for 5 hours to obtain the calcined dolomite. The calcined dolomite was ground into powder with an agate mortar and thoroughly ground and sieved through a 200 mesh sieve. 0.475g of magnesium phosphate was placed in a muffle furnace and heated to 900 ℃ at a heating rate of 5 ℃/min and calcined for 4h. And fully grinding the calcined natural dolomite/magnesium phosphate in an agate mortar to obtain a solid-phase substance. And mixing the solid phase and the liquid phase, quickly stirring, curing for 15s, transferring the bone adhesive to the section of a fresh pig rib by using a glass rod, uniformly spreading the bone adhesive on the section by using the glass rod, and continuously pressing the pig rib along the axis for 1min to obtain the bonded pig rib.
Example 3
Weighing 6.25g of 70% phytic acid solution, 1.25g of gelatin and 17.5g of deionized water, adding the gelatin and the deionized water into the 70% phytic acid solution, and stirring on a magnetic stirrer until the gelatin is completely dissolved to obtain a liquid phase substance. And (3) putting 0.025g of natural dolomite into a muffle furnace, heating to 1000 ℃ at the heating rate of 5 ℃/min, and calcining for 5 hours to obtain calcined dolomite. The calcined dolomite was ground into powder with an agate mortar and thoroughly ground and sieved through a 200 mesh sieve. 0.475g of magnesium phosphate was placed in a muffle furnace and heated to 1000 ℃ at a heating rate of 5 ℃/min and calcined for 4h. And fully grinding the calcined natural dolomite/magnesium phosphate in an agate mortar to obtain a solid-phase substance. And mixing the solid phase and the liquid phase, quickly stirring, curing for 15s, transferring the bone adhesive to the section of a fresh pig rib by using a glass rod, uniformly spreading the bone adhesive on the section by using the glass rod, and continuously pressing the pig rib along the axis for 1min to obtain the bonded pig rib.
Example 4
Weighing 6.25g of phytic acid solution with the mass fraction of 70%, 1.75g of gelatin and 17g of deionized water, adding the gelatin and the deionized water into the phytic acid solution with the mass fraction of 70%, and stirring on a magnetic stirrer until the gelatin is completely dissolved to obtain a liquid phase substance. And (3) putting 0.04g of natural dolomite into a muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and calcining for 5 hours to obtain calcined dolomite. The calcined dolomite was ground into powder with an agate mortar and thoroughly ground and sieved through a 200 mesh sieve. 0.46g of magnesium phosphate was put into a muffle furnace and heated to 900 ℃ at a heating rate of 5 ℃/min and calcined for 4 hours. And fully grinding the calcined natural dolomite/magnesium phosphate in an agate mortar to obtain a solid-phase substance. And mixing the solid phase and the liquid phase, quickly stirring, curing for 15s, transferring the bone adhesive to the section of a fresh pig rib by using a glass rod, uniformly spreading the bone adhesive on the section by using the glass rod, and continuously pressing the pig rib along the axis for 1min to obtain the bonded pig rib.
Example 5
Weighing 6.25g of 70% phytic acid solution, 2.25g of gelatin and 16.5g of deionized water, adding the gelatin and the deionized water into the 70% phytic acid solution, and stirring on a magnetic stirrer until the gelatin is completely dissolved to obtain a liquid phase substance. And (3) putting 0.055g of natural dolomite into a muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and calcining for 5 hours to obtain calcined dolomite. The calcined dolomite was ground into powder with an agate mortar and thoroughly ground and sieved through a 200 mesh sieve. 0.445g of magnesium phosphate was placed in a muffle furnace and heated to 900 ℃ at a heating rate of 5 ℃/min and calcined for 4h. And fully grinding the calcined natural dolomite/magnesium phosphate in an agate mortar to obtain a solid-phase substance. And mixing the solid phase and the liquid phase, quickly stirring, curing for 15s, transferring the bone adhesive to the section of a fresh pig rib by using a glass rod, uniformly spreading the bone adhesive on the section by using the glass rod, and continuously pressing the pig rib for 1min along the axis to obtain the bonded pig rib.
Example 6
Weighing 6.25g of 70% phytic acid solution, 2.75g of gelatin and 16g of deionized water, adding the gelatin and the deionized water into the 70% phytic acid solution, and stirring on a magnetic stirrer until the gelatin is completely dissolved to obtain a liquid phase substance. And (3) putting 0.07g of natural dolomite into a muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and calcining for 5 hours to obtain the calcined dolomite. The calcined dolomite was ground into powder with an agate mortar and thoroughly ground and sieved through a 200 mesh sieve. 0.43g of magnesium phosphate was put into a muffle furnace and heated to 900 ℃ at a heating rate of 5 ℃/min and calcined for 4 hours. And fully grinding the calcined natural dolomite/magnesium phosphate in an agate mortar to obtain a solid-phase substance. And mixing the solid phase and the liquid phase, quickly stirring, curing for 15s, transferring the bone adhesive to the section of a fresh pig rib by using a glass rod, uniformly spreading the bone adhesive on the section by using the glass rod, and continuously pressing the pig rib for 1min along the axis to obtain the bonded pig rib.
Example 7
Weighing 6.25g of 70% phytic acid solution, 3.25g of gelatin and 15.5g of deionized water, adding the gelatin and the deionized water into the 70% phytic acid solution, and stirring on a magnetic stirrer until the gelatin is completely dissolved to obtain a liquid phase substance. And (3) putting 0.085g of natural dolomite into a muffle furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and calcining for 5 hours to obtain calcined dolomite. The calcined dolomite was ground into powder with an agate mortar and thoroughly ground and sieved through a 200 mesh sieve. 0.415g of magnesium phosphate is placed in a muffle furnace and heated to 900 ℃ at a heating rate of 5 ℃/min and calcined for 4h. And fully grinding the calcined natural dolomite/magnesium phosphate in an agate mortar to obtain a solid-phase substance. And mixing the solid phase and the liquid phase, quickly stirring, curing for 15s, transferring the bone adhesive to the section of a fresh pig rib by using a glass rod, uniformly spreading the bone adhesive on the section by using the glass rod, and continuously pressing the pig rib for 1min along the axis to obtain the bonded pig rib.

Claims (5)

1. The preparation method of the magnesium phosphate/phytic acid/gelatin/calcined dolomite bone adhesive is characterized by comprising the following steps of:
(1) Grinding natural dolomite, sieving, placing in a muffle furnace, heating to 800-1000 ℃, and calcining for 5h to obtain calcined dolomite;
(2) Placing magnesium phosphate in a muffle furnace, heating to 800-1000 ℃, and calcining for 4h to obtain calcined magnesium phosphate;
(3) Preparing phytic acid solution at 0-10 ℃, adding gelatin into the phytic acid solution, and stirring and dissolving to obtain phytic acid/gelatin solution; and (3) mixing the calcined dolomite obtained in the step (1) and the calcined magnesium phosphate obtained in the step (2), then adding the mixture into a phytic acid/gelatin solution, and uniformly mixing to obtain the bone cement.
2. The method for preparing magnesium phosphate/phytic acid/gelatin/doloma bone cement according to claim 1, wherein the temperature increase rate in step (1) or step (2) is 5 ℃/min.
3. The method for preparing magnesium phosphate/phytic acid/gelatin/dolime bone cement according to claim 1, wherein the phytic acid solution is 15 to 25% by mass in the step (3).
4. The method for preparing magnesium phosphate/phytic acid/gelatin/doloma bone cement according to claim 1, wherein in the step (3), the mass fraction of the gelatin in the phytic acid/gelatin solution is 5 to 13%.
5. The method for preparing magnesium phosphate/phytic acid/gelatin/calcined dolomite bone cement according to claim 1, wherein, in the step (3), the mass ratio of the calcined dolomite to the calcined magnesium phosphate is 1: 4-20, wherein the mass ratio of the total of calcined dolomite and calcined magnesium phosphate to the phytic acid/gelatin solution is 1:45 to 55.
CN202211596110.XA 2022-12-12 2022-12-12 Preparation method of magnesium phosphate/phytic acid/gelatin/calcined dolomite bone adhesive Pending CN115770320A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA499761A (en) * 1954-02-02 P. Grettie Donald Gelatin
US20160175481A1 (en) * 2013-08-09 2016-06-23 Gunze Limited Bone regeneration material kit, paste-like bone regeneration material, bone regeneration material, and bone bonding material
CN106496601A (en) * 2016-10-26 2017-03-15 华南理工大学 A kind of can be from the high intensity hydrogel and preparation method thereof into tubulose or cup-shaped
CN107303397A (en) * 2016-04-20 2017-10-31 中国科学院化学研究所 A kind of Injectable compound bone cement with bioactivity and its production and use
CN110354305A (en) * 2019-07-23 2019-10-22 山东大学 The application and the bone cement based on sodium phytate that sodium phytate prepares bone cement solidify liquid
CN111870738A (en) * 2020-06-11 2020-11-03 上海蕴邦生物科技有限公司 Bone repair material and preparation method and application thereof
CN112516378A (en) * 2020-12-02 2021-03-19 浙江工业大学 Preparation method of phytic acid/silk fibroin/calcined dolomite bone adhesive

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA499761A (en) * 1954-02-02 P. Grettie Donald Gelatin
US20160175481A1 (en) * 2013-08-09 2016-06-23 Gunze Limited Bone regeneration material kit, paste-like bone regeneration material, bone regeneration material, and bone bonding material
CN107303397A (en) * 2016-04-20 2017-10-31 中国科学院化学研究所 A kind of Injectable compound bone cement with bioactivity and its production and use
CN106496601A (en) * 2016-10-26 2017-03-15 华南理工大学 A kind of can be from the high intensity hydrogel and preparation method thereof into tubulose or cup-shaped
CN110354305A (en) * 2019-07-23 2019-10-22 山东大学 The application and the bone cement based on sodium phytate that sodium phytate prepares bone cement solidify liquid
CN111870738A (en) * 2020-06-11 2020-11-03 上海蕴邦生物科技有限公司 Bone repair material and preparation method and application thereof
CN112516378A (en) * 2020-12-02 2021-03-19 浙江工业大学 Preparation method of phytic acid/silk fibroin/calcined dolomite bone adhesive

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MANNA HU: "Fabrication of a novel bone adhesive(crosslinked phytic acid-gelatin coordinated with magnesium phosphate and calcined dolomite, and montmorillonite) for enhancing adhesion strength and biocompatibility", JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY, vol. 104, 24 April 2024 (2024-04-24), pages 317 - 334 *
MEININGER SUSANNE: "Phytic acid as alternative setting retarder enhanced biological performance of dicalcium phosphate cement in vitro", SCIENTIFIC REPORTS, vol. 7, pages 558 *
祁燕: "植酸螯合型羟基磷灰石骨水泥的研究", 中国优秀硕士学位论文全文数据库, pages 080 - 106 *

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