CN108569717B - Preparation method of silver-doped nano calcium sulfate nanospheres for 3D printing of tissue scaffold - Google Patents

Preparation method of silver-doped nano calcium sulfate nanospheres for 3D printing of tissue scaffold Download PDF

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CN108569717B
CN108569717B CN201810690748.7A CN201810690748A CN108569717B CN 108569717 B CN108569717 B CN 108569717B CN 201810690748 A CN201810690748 A CN 201810690748A CN 108569717 B CN108569717 B CN 108569717B
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苏英
徐焰
陈顺
贺行洋
杨进
王迎斌
陈威
李颜娟
黄健翔
蒋健
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Abstract

The invention discloses a preparation method of silver-doped nano calcium sulfate nanospheres for 3D printing of a tissue scaffold, which solves the problems of small specific surface area, uneven particle size distribution, printability, biocompatibility, degradability, structure and mechanical properties of the existing material to be further improved. The technical scheme includes that ammonium sulfate and calcium chloride are added into a water-alcohol system containing polyalcohol amine, the mixture reacts under stirring, and after the reaction, the calcium sulfate nano particles are prepared by centrifugal drying; adding calcium sulfate nano particles into a polylactic acid aqueous solution, reacting under stirring, centrifuging after reaction, ultrasonically cleaning, and drying to obtain calcium sulfate/polylactic acid nanospheres; and adding the calcium sulfate/polylactic acid nanospheres into deionized water to prepare a dispersion, adding silver nitrate and glucose, reacting under stirring, and drying after reaction to prepare the calcium sulfate/silver/polylactic acid nanospheres. The method is simple, and has loose and breathable structure, printability, biocompatibility, degradability, structure and good mechanical property.

Description

Preparation method of silver-doped nano calcium sulfate nanospheres for 3D printing of tissue scaffold
Technical Field
The invention relates to a 3D printing tissue material, in particular to a preparation method of silver-doped nano calcium sulfate nanospheres for a 3D printing tissue scaffold.
Background
Many of the developed scaffold preparation methods include solution casting/particle filtration, gas foaming, fiber weaving, etc., but these methods have the common problem of difficulty in effectively and accurately controlling the shape, size, connection form, spatial distribution, etc. of the scaffold pores, failing to meet the complex structural requirements of the scaffold in tissue engineering, failing to accurately position different cells in the spatial structure of the scaffold, etc. The 3D printing technology is an advanced manufacturing method which is different from the traditional material reduction manufacturing and is based on the discrete-stacking principle and forms a three-dimensional entity by stacking layer by layer under the assistance of a computer. The method has unique and remarkable advantages in high precision, personalized manufacture and complex shape construction. In the field of biomedicine, a complex biological three-dimensional structure such as a personalized implant, a reproducible artificial bone, an in-vitro cell three-dimensional structure body, an artificial organ and the like can be constructed by 3D printing of biological materials or living cells, so that the unique advantages of personalized customization and complex structure regulation and control manufacturing based on biological 3D printing are achieved. The preparation material used as the 3D tissue scaffold must have the characteristics of printability, biocompatibility, degradability, structure, mechanical property and the like. At present, calcium sulfate has good biocompatibility and can be used as an excellent biological material. Compared with the traditional calcium sulfate material, the nano calcium sulfate has more excellent chemical and physical properties, such as high specific surface area, mechanical strength and the like. However, as a 3D tissue scaffold material, it is also desired to have a more excellent loose structure to further improve the air permeability compatibility and avoid the problems of infection of an implant caused by the growth of bacteria inside the material.
The invention patent of application No. CN200610030350.8 introduces a preparation method of calcium sulfate nanometer material (nanoparticle/tube/rod/wire), which adopts n-amyl alcohol micellar solution of calcium salt and cyclohexane micellar solution of sulfate to mix by reversed phase micellar solution to respectively obtain calcium sulfate nanometer materials of nanoparticle, nanotube, nanorod and nanowire. However, the nano material obtained by the method has low printability, small specific surface area and limited biocompatibility.
The invention patent of application No. CN201310162070.2 introduces a calcium sulfate-based composite particle for biomedical slow-release metal ions and a preparation method thereof, adopts a wet chemical method, obtains calcium sulfate powder containing metal ions and nano-structured calcium phosphate powder containing metal ions by heat treatment, can be widely used in the field of biomedical materials such as bone filling materials, bone cement and the like, but the materials after heat treatment have poor mechanical strength and printability and have larger defects of biocompatibility and are not beneficial to degradation.
Disclosure of Invention
The invention aims to solve the technical problems and provides a preparation method of silver-doped nano calcium sulfate nanospheres for 3D printing tissue scaffolds, which is simple in method, loose in structure, air-permeable, printable, biocompatible, degradable, good in structure and mechanical properties.
The technical scheme comprises the following steps:
step 1: adding ammonium sulfate and calcium chloride into a water-alcohol system containing polyalcohol amine, reacting under stirring, and centrifugally drying after reaction to obtain calcium sulfate nanoparticles;
step 2: adding calcium sulfate nano particles into a polylactic acid aqueous solution, reacting under stirring, centrifuging after reaction, ultrasonically cleaning, and drying to obtain calcium sulfate/polylactic acid nanospheres;
and step 3: and adding the calcium sulfate/polylactic acid nanospheres into deionized water to prepare a dispersion, adding silver nitrate and glucose, reacting under stirring, and drying after reaction to prepare the calcium sulfate/silver/polylactic acid nanospheres.
In the step 1, the adding amount of ammonium sulfate is 100-150 parts by weight, and the adding amount of calcium chloride is 80-100 parts by weight; in the water-alcohol system containing polyalcohol amine, the adding amount of the polyalcohol amine is 10-20 parts by weight, the adding amount of the deionized water is 100-150 parts by weight, and the adding amount of the ethanol is 50-100 parts by weight.
And (2) adding a surfactant in the step (1), wherein the addition amount of the surfactant is 10-20 parts by weight.
The surfactant is sodium succinate and/or sodium citrate.
In the step 2, the adding amount of the calcium sulfate nano particles is 100 parts by weight; in the aqueous solution of the polylactic acid, the adding amount of the polylactic acid is 10-15 parts by weight, and the adding amount of the aqueous solution is 200-250 parts by weight.
In the step 3, the dispersion liquid is prepared by adding 100 parts by weight of calcium sulfate/polylactic acid nanospheres into 150 parts by weight of ionized water 100-; the silver nitrate is added in 5-10 parts by weight, and the glucose is added in 20-30 parts by weight.
The stirring speed in the steps 1, 2 and 3 is controlled to be 2200 and 2800 r/min.
The reaction temperature in the steps 1 and 2 is controlled to be 25-30 ℃, and the reaction temperature in the step 3 is controlled to be 50-80 ℃.
The calcium sulfate/silver/polylactic acid nanospheres prepared in the step 3 have uniform particle size distribution, the particle size is 100-150nm, and the specific surface area is 230-300m2/g。
Aiming at the problems in the background art, in the step 1, the size of calcium sulfate is regulated by adopting polyalcohol amine in a hydroalcoholic system, the subsequent in-situ growth of silver doping is facilitated, and the size of the calcium sulfate is further regulated by adding a surfactant sodium succinate or sodium citrate to limit the surface by utilizing a coprecipitation method; in the step 2, polylactic acid is used as a structural polymer, has excellent biocompatibility and can be adsorbed on the surface of particles, so that the dispersing performance of the nano particles is improved, the agglomeration phenomenon possibly occurring in the preparation process is reduced, the degradability is strong, the molecular weight is easy to regulate and control, and the calcium sulfate/polylactic acid nanospheres are prepared by an in-situ growth method in an ultrasonic construction mode; in the step 3, silver is doped on the calcium sulfate in an in-situ growth mode to prepare the calcium sulfate/silver/polylactic acid nanosphere, so that the prepared calcium sulfate/silver/polylactic acid nanosphere has high specific surface area and pore channels, good mechanical properties and biocompatibility, and is easy for 3D printing and forming.
Further, in the step 1, on the basis that the addition amount of ammonium sulfate is 100-150 parts by weight, calcium chloride is added to react to generate calcium sulfate, the addition amount is preferably 80-100 parts by weight, so that the waste of calcium chloride raw materials is caused if the addition amount is too large, and the size and the morphology of the calcium sulfate are influenced if the addition amount is too small due to insufficient calcium sources; adding a surfactant to further regulate the size of the calcium sulfate, wherein the addition amount of the surfactant is preferably 10-20 parts by weight, too much can limit the formation and growth of calcium sulfate particles, and too little can increase the size of the calcium sulfate too much; in a water-alcohol system containing the polyalcohol amine, the polyalcohol amine regulates and controls the size of calcium sulfate based on a surface induction principle, so the addition amount is preferably 10-20 parts by weight, too much polyalcohol amine causes uneven appearance of the calcium sulfate, and too little polyalcohol amine has an unobvious calcium sulfate induction effect.
Further, in the step 2, on the basis that the addition amount of the calcium sulfate nanoparticles is 100 parts by weight, the calcium sulfate nanospheres can be constructed by adding the polylactic acid, the addition amount is preferably 10-15 parts by weight, so that calcium sulfate agglomeration and polylactic acid waste can be caused if the addition amount is too large, and stable calcium sulfate nanospheres cannot be obtained if the addition amount is too small due to insufficient polylactic acid.
The reactions in steps 1, 2 and 3 are preferably performed under high-speed stirring to ensure uniform mixing of raw materials and stable size of generated calcium sulfate, and the rotation speed is preferably 2200-.
In the step 3, on the basis of 100 parts by weight of the calcium sulfate/polylactic acid nanospheres, silver nitrate is added to realize in-situ growth of silver nanoparticles on the calcium sulfate/polylactic acid nanospheres, glucose is added to reduce the silver nitrate, the adding amount of the silver nitrate is preferably 5-10 parts by weight, the adding amount of the glucose is 20-30 parts by weight, the reaction temperature is preferably controlled at 50-80 ℃, the structure of the calcium sulfate/polylactic acid nanospheres can be damaged when the reaction temperature is too high, the reduction efficiency of the silver nitrate is low or even the silver nitrate is not reduced when the reaction temperature is too low, and the in-situ growth of the silver nanoparticles cannot be guaranteed.
The invention takes the ammonium sulfate solution and the calcium chloride solution as raw materials, adds the polylactic acid solution, and prepares the calcium sulfate/silver/polylactic acid nanosphere by reducing the silver nitrate, the production process is green, environment-friendly, economic and rapid,the prepared calcium sulfate/silver/polylactic acid nanosphere spherical particles have uniform particle size distribution, loose and breathable structure, the size of 100-150nm and the specific surface area of 230-300m2The ink has good dispersibility, printability, biocompatibility, degradability, structure and mechanical property; the used raw materials are commercially available, the preparation process is simple and economical, and the method has great potential in the aspect of 3D printing of the tissue scaffold.
Detailed Description
The present invention will be described in further detail with reference to examples, in which ammonium sulfate and calcium chloride are used as raw materials, and polyalcohol amine, polylactic acid, sodium succinate and/or sodium citrate, silver nitrate and glucose are commercially available products.
Example 1:
step 1: adding 20 parts by weight of polyalcohol amine into a mixed solution of 100 parts by weight of deionized water and 50 parts by weight of ethanol to form a water-alcohol system containing the polyalcohol amine, adding 100 parts by weight of ammonium sulfate and 90 parts by weight of calcium chloride into the water-alcohol system containing the polyalcohol amine, then adding 10 parts by weight of sodium succinate, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the pressure of 2200-;
step 2: adding 100 parts by weight of calcium sulfate nanoparticles and 10 parts by weight of polylactic acid into 200 parts by weight of aqueous solution, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the temperature of 2200-.
And step 3: 100 parts by weight of calcium sulfate/polylactic acid nanospheres are taken, 100 parts by weight of deionized water is added to prepare dispersion liquid, 5 parts by weight of silver nitrate and 30 parts by weight of glucose are added to react for 10 minutes at 50 ℃, then numerical control machinery with the temperature of 25 ℃, 2200 and 2800r/min is used for stirring for 5 minutes, standing for 10 minutes is carried out, and drying treatment is carried out at the temperature of 25 ℃ and 15Mpa, thus obtaining the calcium sulfate/silver/polylactic acid nanospheres.
The average median particle diameter of the calcium sulfate/silver/polylactic acid nanospheres prepared by the method is 120nm, and the specific surface area is 240m2(ii) in terms of/g. The dispersion is good, the viscosity of the dispersion can reach 3000CPS, the material has no biotoxicity, the material can be degraded in 5 months, and the elastic modulus of a test piece can reach 6 MPa.
Example 2:
step 1: adding 10 parts by weight of polyalcohol amine into 100 parts by weight of deionized water and 100 parts by weight of ethanol mixed solution to form a water-alcohol system containing the polyalcohol amine, adding 150 parts by weight of ammonium sulfate and 80 parts by weight of calcium chloride into the water-alcohol system containing the polyalcohol amine, then adding 10 parts by weight of sodium succinate, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the pressure of 2200-;
step 2: adding 100 parts by weight of calcium sulfate nanoparticles and 12 parts by weight of polylactic acid into 250 parts by weight of aqueous solution, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the temperature of 2200-.
And step 3: 100 parts by weight of calcium sulfate/polylactic acid nanospheres are taken, 100 parts by weight of deionized water is added to prepare dispersion liquid, 10 parts by weight of silver nitrate and 20 parts by weight of glucose are added to react for 10 minutes at 50 ℃, then numerical control machinery with the temperature of 25 ℃, 2200 and 2800r/min is used for stirring for 5 minutes, standing for 10 minutes is carried out, and drying treatment is carried out at the temperature of 25 ℃ and 15Mpa, thus obtaining the calcium sulfate/silver/polylactic acid nanospheres.
The average median particle diameter of the calcium sulfate/silver/polylactic acid nanospheres prepared by the method is 100nm, and the specific surface area is 250m2(ii) in terms of/g. The dispersion is good, the viscosity of the dispersion can reach 5000CPS, the material has no biotoxicity and can be degraded in 6 months, and the elastic modulus of a test piece can reach 8 MPa.
Example 3:
step 1: adding 20 parts by weight of polyalcohol amine into a mixed solution of 150 parts by weight of deionized water and 50 parts by weight of ethanol to form a water-alcohol system containing the polyalcohol amine, adding 150 parts by weight of ammonium sulfate and 100 parts by weight of calcium chloride into the water-alcohol system containing the polyalcohol amine, adding 20 parts by weight of sodium succinate, stirring for 5min by using a numerical control machine at 25 ℃ and 2200-;
step 2: adding 100 parts by weight of calcium sulfate nanoparticles and 15 parts by weight of polylactic acid into 250 parts by weight of aqueous solution, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the temperature of 2200-.
And step 3: 100 parts by weight of calcium sulfate/polylactic acid nanospheres are taken, 150 parts by weight of deionized water is added to prepare dispersion liquid, 8 parts by weight of silver nitrate and 30 parts by weight of glucose are added to react for 10 minutes at 50 ℃, then numerical control machinery with the temperature of 25 ℃, 2200 and 2800r/min is used for stirring for 5 minutes, standing for 10 minutes is carried out, and drying treatment is carried out at the temperature of 25 ℃ and 15Mpa, thus obtaining the calcium sulfate/silver/polylactic acid nanospheres.
The average median particle diameter of the calcium sulfate/silver/polylactic acid nanospheres prepared by the method is 150nm, and the specific surface area is 230m2(ii) in terms of/g. The dispersibility is good, the viscosity of dispersion can reach 4000CPS, the material has no biotoxicity, and 5The film can be degraded in months, and the elastic modulus of a test piece can reach 6.5 MPa.
Example 4:
step 1: adding 15 parts by weight of polyalcohol amine into 100 parts by weight of deionized water and 80 parts by weight of ethanol mixed solution to form a water-alcohol system containing the polyalcohol amine, adding 100 parts by weight of ammonium sulfate and 100 parts by weight of calcium chloride into the water-alcohol system containing the polyalcohol amine, then adding 10 parts by weight of sodium succinate, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the pressure of 2200-;
step 2: adding 200 parts by weight of aqueous solution into 100 parts by weight of calcium sulfate nanoparticles and 13 parts by weight of polylactic acid, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the temperature of 2200-.
And step 3: taking 100 parts by weight of calcium sulfate/polylactic acid nanospheres, adding 120 parts by weight of deionized water to prepare dispersion, adding 10 parts by weight of silver nitrate and 25 parts by weight of glucose, reacting at 50 ℃ for 10 minutes, stirring for 5 minutes by using a numerical control machine at 25 ℃, 2200 and 2800r/min, standing for 10 minutes, and drying at 25 ℃ and 15Mpa to obtain the calcium sulfate/silver/polylactic acid nanospheres.
The average median particle diameter of the calcium sulfate/silver/polylactic acid nanospheres prepared by the method is 140nm, and the specific surface area is 280m2(ii) in terms of/g. The dispersibility is good, the viscosity of the dispersion can reach 6500CPS, the material has no biotoxicity, the material can be degraded in 6.5 months, and the elastic modulus of a test piece can reach 5.5 MPa.
Example 5:
step 1: adding 20 parts by weight of polyalcohol amine into 100 parts by weight of deionized water and 50 parts by weight of ethanol mixed solution to form a water-alcohol system containing polyalcohol amine, adding 150 parts by weight of ammonium sulfate and 80 parts by weight of calcium chloride into the water-alcohol system containing polyalcohol amine, adding 15 parts by weight of sodium succinate, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the pressure of 2200-;
step 2: 100 parts by weight of calcium sulfate nanoparticles and 10 parts by weight of polylactic acid are taken, 230 parts by weight of aqueous solution is added, the mixture is stirred for 5min by a numerical control machine with the temperature of 25 ℃ and the temperature of 2200-.
And step 3: 100 parts by weight of calcium sulfate/polylactic acid nanospheres are taken, 150 parts by weight of deionized water is added to prepare dispersion liquid, 10 parts by weight of silver nitrate and 20 parts by weight of glucose are added to react for 10 minutes at 50 ℃, then numerical control machinery with the temperature of 25 ℃, 2200 and 2800r/min is used for stirring for 5 minutes, standing for 10 minutes is carried out, and drying treatment is carried out at the temperature of 25 ℃ and 15Mpa, thus obtaining the calcium sulfate/silver/polylactic acid nanospheres.
The average median particle diameter of the calcium sulfate/silver/polylactic acid nanospheres prepared by the method is 125nm, and the specific surface area is 300m2(ii) in terms of/g. The dispersibility is good, the viscosity of the dispersion can reach 6000CPS, the material has no biotoxicity and can be degraded in 8 months, and the elastic modulus of a test piece can reach 8 MPa.
Example 6:
step 1: adding 15 parts by weight of polyalcohol amine into 100 parts by weight of deionized water and 80 parts by weight of ethanol mixed solution to form a water-alcohol system containing the polyalcohol amine, adding 150 parts by weight of ammonium sulfate and 100 parts by weight of calcium chloride into the water-alcohol system containing the polyalcohol amine, then adding 10 parts by weight of sodium succinate, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the pressure of 2200-;
step 2: adding 100 parts by weight of calcium sulfate nanoparticles and 15 parts by weight of polylactic acid into 250 parts by weight of aqueous solution, stirring for 5min by using a numerical control machine with the temperature of 25 ℃ and the temperature of 2200-.
And step 3: 100 parts by weight of calcium sulfate/polylactic acid nanospheres are taken, 100 parts by weight of deionized water is added to prepare dispersion liquid, 5 parts by weight of silver nitrate and 30 parts by weight of glucose are added to react for 10 minutes at 50 ℃, then numerical control machinery with the temperature of 25 ℃, 2200 and 2800r/min is used for stirring for 5 minutes, standing for 10 minutes is carried out, and drying treatment is carried out at the temperature of 25 ℃ and 15Mpa, thus obtaining the calcium sulfate/silver/polylactic acid nanospheres.
The average median particle diameter of the calcium sulfate/silver/polylactic acid nanospheres prepared by the method is 110nm, and the specific surface area is 270m2(ii) in terms of/g. The dispersibility is good, the viscosity of the dispersion can reach 5000CPS, the material has no biotoxicity, the material can be degraded in 5.5 months, and the elastic modulus of a test piece can reach 5.5 MPa.
Comparative example 1
Compared with the example 1, the hexadecyl sodium sulfonate is used for replacing the polyalcohol amine, and other steps are the same. In this comparative example, calcium sulfate/polylactic acid nanospheres and calcium sulfate/silver/polylactic acid nanospheres were not finally obtained. The viscosity of the dispersion is 2000CPS, and printing and forming are not easy.
Comparative example 2
The other steps were the same as in example 1 except that polyethylene glycol was used instead of polylactic acid. In this comparative example, calcium sulfate/polylactic acid nanospheres and calcium sulfate/silver/polylactic acid nanospheres were not finally obtained. The viscosity of the dispersion is 2200CPS, and the printing and molding are not easy.

Claims (9)

1. A preparation method of silver-doped nano calcium sulfate nanospheres for 3D printing of tissue scaffolds is characterized by comprising the following steps of: the method comprises the following steps:
step 1: adding ammonium sulfate and calcium chloride into a water-alcohol system containing polyalcohol amine, reacting under stirring, and centrifugally drying after reaction to obtain calcium sulfate nanoparticles;
step 2: adding calcium sulfate nano particles into a polylactic acid aqueous solution, reacting under stirring, centrifuging after reaction, ultrasonically cleaning, and drying to obtain calcium sulfate/polylactic acid nanospheres;
and step 3: and adding the calcium sulfate/polylactic acid nanospheres into deionized water to prepare a dispersion, adding silver nitrate and glucose, reacting under stirring, and drying after reaction to prepare the calcium sulfate/silver/polylactic acid nanospheres.
2. The method for preparing silver-doped nano calcium sulfate nanospheres for 3D printing tissue scaffolds as claimed in claim 1, wherein in the step 1, the addition amount of ammonium sulfate is 100-150 parts by weight, and the addition amount of calcium chloride is 80-100 parts by weight; in the water-alcohol system containing polyalcohol amine, the adding amount of the polyalcohol amine is 10-20 parts by weight, the adding amount of the deionized water is 100-150 parts by weight, and the adding amount of the ethanol is 50-100 parts by weight.
3. The preparation method of the silver-doped nano calcium sulfate nanospheres for 3D printing of the tissue scaffold according to claim 1 or 2, wherein a surfactant is further added in the step 1, and the addition amount of the surfactant is 10-20 parts by weight.
4. The preparation method of the silver-doped nano calcium sulfate nanosphere for 3D printing tissue scaffold according to claim 3, wherein the surfactant is sodium succinate and/or sodium citrate.
5. The preparation method of the silver-doped nano calcium sulfate nanospheres for 3D printing the tissue scaffold according to claim 1 or 2, wherein in the step 2, the addition amount of the calcium sulfate nanoparticles is 100 parts by weight; in the aqueous solution of the polylactic acid, the adding amount of the polylactic acid is 10-15 parts by weight, and the adding amount of the aqueous solution is 200-250 parts by weight.
6. The method for preparing silver-doped nanometer calcium sulfate nanospheres for 3D printing tissue scaffolds as claimed in claim 1 or 2, wherein in the step 3, the dispersion liquid is prepared by adding 100 parts by weight of calcium sulfate/polylactic acid nanospheres into 150 parts by weight of deionized water; the silver nitrate is added in 5-10 parts by weight, and the glucose is added in 20-30 parts by weight.
7. The method for preparing silver-doped nano calcium sulfate nanospheres for 3D printing tissue scaffolds as claimed in claim 1, wherein the stirring speed in steps 1, 2 and 3 is controlled to be 2200-.
8. The preparation method of the silver doped nanometer calcium sulfate nanosphere for 3D printing of the tissue scaffold as claimed in claim 1 or 7, wherein the reaction temperature in step 1 or 2 is controlled at 25-30 ℃ and the reaction temperature in step 3 is controlled at 50-80 ℃.
9. The method for preparing silver-doped nanometer calcium sulfate nanospheres for 3D printing tissue scaffolds as claimed in claim 1, wherein the calcium sulfate/silver/polylactic acid nanospheres prepared in step 3 have uniform particle size distribution, particle size of 100-150nm and specific surface area of 230-300m2/g。
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