Magnesium alloy material with heparin loaded at surface as well as preparation method and application thereof

Abstract

The invention discloses a magnesium alloy material with heparin loaded at the surface. The magnesium alloy material with the heparin loaded at the surface is prepared from a magnesium alloy material,a chitosan functionalized graphene oxide coating and a heparin coating from bottom to top, wherein (3-chloropropyl)triethoxy silane is fixed at the surface of the magnesium alloy material. The invention also discloses a preparation method and application of the magnesium alloy material with the heparin loaded at the surface. A magnesium alloy surface modification method is used, so that the corrosion resisting performance of magnesium alloy can be improved; the biocompatibility of the magnesium alloy can be obviously improved; particularly, a large amount of heparin is loaded at the surface; the blood compatibility of the material can be obviously improved; the functionalized graphene oxide is used for loading the heparin, so that the heparin loading quantity is greatly improved; a built surface modifying layer has the characteristic of multifunction and bioactivity.

Description

technical field

[0001] The invention relates to the technical field of biomaterials, in particular to a magnesium alloy material with heparin on the surface and its preparation method and application. The surface modification of the magnesium alloy by the method can endow the magnesium alloy with good corrosion resistance and blood phase Capacitance. Background technique

[0002] Magnesium and its alloys have become a research hotspot in biomaterials due to their good mechanical properties and biodegradability. Magnesium alloys can be absorbed by the human body after implantation, avoiding the problem of secondary surgery, and have been extensively studied in orthopedic medical devices and cardiovascular stents. However, the chemical properties of magnesium alloys are lively, and they degrade quickly under the complex physiological conditions of the human body. They are prone to generate excessive hydrogen gas in the surrounding tissues to form bubbles, thereby delaying tis...

Examples

Embodiment 1

[0032] Example 1 Preparation of magnesium alloy material with heparin on its surface

[0033] 1. Modification of carboxylated graphene oxide with chitosan to obtain GOCS:

[0034] 1) Ultrasonic disperse graphene oxide in 0.01mol / L sodium hydroxide solution to obtain a 5mg / ml graphene oxide solution, add 0.01mol chloroacetic acid, stir and react for 2-4 hours, and repeatedly centrifuge and wash the solution to neutral To remove impurities to obtain carboxylated graphene oxide (GO-COOH); GO-COOH is dissolved in water to obtain a GO-COOH solution, and the prepared GO-COOH solution has a concentration of 1 mg / ml;

[0035]2) Ultrasonic disperse 1 mg / ml GO-COOH solution and chitosan (CS, 5 mg / ml) in MES buffer solution (2-morpholineethanesulfonic acid buffer, adjust the pH of the solution to about 6), add 1 -(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC, 10mM) and N-hydroxysuccinimide (NHS, 10mM) solution, shaking reaction for 2-4 hours, the solution The unreacted substances we...

Embodiment 2

[0043] Example 2 Preparation of magnesium alloy material with heparin on its surface

[0044] 1. Modification of carboxylated graphene oxide with chitosan to obtain GOCS solution:

[0045] 1) Ultrasonic disperse graphene oxide in 0.1mol / L sodium hydroxide solution to obtain a 5mg / ml graphene oxide solution, add 0.03mol chloroacetic acid, stir and react for 2-4 hours, and repeatedly centrifuge and wash the solution to neutral To remove impurities to obtain carboxylated graphene oxide (GO-COOH); GO-COOH is dissolved in water to obtain a GO-COOH solution; the prepared GO-COOH solution has a concentration of 5 mg / ml;

[0046] 2) Ultrasonic disperse 5 mg / ml GO-COOH solution and chitosan (CS, 10 mg / ml) in MES buffer solution (adjust the pH of the solution to about 6), add 1-(3-dimethylaminopropyl )-3-ethylcarbodiimide (EDC, 10mM) and N-hydroxysuccinimide (NHS, 10mM) solution, shaking reaction for 2-4 hours, the solution was repeatedly centrifuged and washed to remove unreacted subs...

Embodiment 3

[0054] Example 3 Preparation of magnesium alloy material with heparin on its surface

[0055] 1. Modification of carboxylated graphene oxide with chitosan to obtain GOCS:

[0056] 1) Ultrasonic disperse graphene oxide in 0.05mol / L sodium hydroxide solution to obtain 5mg / ml graphene oxide solution, add 0.05mol chloroacetic acid, stir and react for 2-4 hours, and repeatedly centrifuge and wash the solution to neutral To remove impurities to obtain carboxylated graphene oxide (GO-COOH), GO-COOH is dissolved in water to obtain GO-COOH solution; the concentration of the prepared GO-COOH solution is 3mg / ml;

[0057] 2) Ultrasonic disperse 3mg / ml GO-COOH solution and chitosan (CS, 7.5mg / ml) in MES buffer solution (adjust the pH of the solution to about 6), add 1-(3-dimethylaminopropyl Base)-3-ethylcarbodiimide (EDC, 10mM) and N-hydroxysuccinimide (NHS, 10mM) solution, shaking reaction for 2-4 hours, the solution was repeatedly centrifuged and washed to remove unreacted substances, a...

technical field

[0001] The invention relates to the technical field of biomaterials, in particular to a magnesium alloy material with heparin on the surface and its preparation method and application. The surface modification of the magnesium alloy by the method can endow the magnesium alloy with good corrosion resistance and blood phase Capacitance. Background technique

[0002] Magnesium and its alloys have become a research hotspot in biomaterials due to their good mechanical properties and biodegradability. Magnesium alloys can be absorbed by the human body after implantation, avoiding the problem of secondary surgery, and have been extensively studied in orthopedic medical devices and cardiovascular stents. However, the chemical properties of magnesium alloys are lively, and they degrade quickly under the complex physiological conditions of the human body. They are prone to generate excessive hydrogen gas in the surrounding tissues to form bubbles, thereby delaying tis...

Examples

Embodiment 1

[0032] Example 1 Preparation of magnesium alloy material with heparin on its surface

[0033] 1. Modification of carboxylated graphene oxide with chitosan to obtain GOCS:

[0034] 1) Ultrasonic disperse graphene oxide in 0.01mol / L sodium hydroxide solution to obtain a 5mg / ml graphene oxide solution, add 0.01mol chloroacetic acid, stir and react for 2-4 hours, and repeatedly centrifuge and wash the solution to neutral To remove impurities to obtain carboxylated graphene oxide (GO-COOH); GO-COOH is dissolved in water to obtain a GO-COOH solution, and the prepared GO-COOH solution has a concentration of 1 mg / ml;

[0035]2) Ultrasonic disperse 1 mg / ml GO-COOH solution and chitosan (CS, 5 mg / ml) in MES buffer solution (2-morpholineethanesulfonic acid buffer, adjust the pH of the solution to about 6), add 1 -(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC, 10mM) and N-hydroxysuccinimide (NHS, 10mM) solution, shaking reaction for 2-4 hours, the solution The unreacted substances we...

Embodiment 2

[0043] Example 2 Preparation of magnesium alloy material with heparin on its surface

[0044] 1. Modification of carboxylated graphene oxide with chitosan to obtain GOCS solution:

[0045] 1) Ultrasonic disperse graphene oxide in 0.1mol / L sodium hydroxide solution to obtain a 5mg / ml graphene oxide solution, add 0.03mol chloroacetic acid, stir and react for 2-4 hours, and repeatedly centrifuge and wash the solution to neutral To remove impurities to obtain carboxylated graphene oxide (GO-COOH); GO-COOH is dissolved in water to obtain a GO-COOH solution; the prepared GO-COOH solution has a concentration of 5 mg / ml;

[0046] 2) Ultrasonic disperse 5 mg / ml GO-COOH solution and chitosan (CS, 10 mg / ml) in MES buffer solution (adjust the pH of the solution to about 6), add 1-(3-dimethylaminopropyl )-3-ethylcarbodiimide (EDC, 10mM) and N-hydroxysuccinimide (NHS, 10mM) solution, shaking reaction for 2-4 hours, the solution was repeatedly centrifuged and washed to remove unreacted subs...

Embodiment 3

[0054] Example 3 Preparation of magnesium alloy material with heparin on its surface

[0055] 1. Modification of carboxylated graphene oxide with chitosan to obtain GOCS:

[0056] 1) Ultrasonic disperse graphene oxide in 0.05mol / L sodium hydroxide solution to obtain 5mg / ml graphene oxide solution, add 0.05mol chloroacetic acid, stir and react for 2-4 hours, and repeatedly centrifuge and wash the solution to neutral To remove impurities to obtain carboxylated graphene oxide (GO-COOH), GO-COOH is dissolved in water to obtain GO-COOH solution; the concentration of the prepared GO-COOH solution is 3mg / ml;

[0057] 2) Ultrasonic disperse 3mg / ml GO-COOH solution and chitosan (CS, 7.5mg / ml) in MES buffer solution (adjust the pH of the solution to about 6), add 1-(3-dimethylaminopropyl Base)-3-ethylcarbodiimide (EDC, 10mM) and N-hydroxysuccinimide (NHS, 10mM) solution, shaking reaction for 2-4 hours, the solution was repeatedly centrifuged and washed to remove unreacted substances, a...

Images