CN110585475A - Light-operated antibacterial degradable zinc alloy suture material and preparation method thereof - Google Patents

Light-operated antibacterial degradable zinc alloy suture material and preparation method thereof Download PDF

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Publication number
CN110585475A
CN110585475A CN201910880513.9A CN201910880513A CN110585475A CN 110585475 A CN110585475 A CN 110585475A CN 201910880513 A CN201910880513 A CN 201910880513A CN 110585475 A CN110585475 A CN 110585475A
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China
Prior art keywords
zinc alloy
suture
light
alcohol
suture material
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CN201910880513.9A
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Chinese (zh)
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饶席
赵俊杰
方亚星
张永平
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Southwest University
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Southwest University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L17/00Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06At least partially resorbable materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L17/00Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/14Post-treatment to improve physical properties
    • A61L17/145Coating
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/12Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/02Methods for coating medical devices

Abstract

The invention relates to a light-operated antibacterial degradable zinc alloy suture material and a preparation method thereof, wherein the material takes zinc alloy (Zn-2 ~ 4at% Li) as a substrate, the surface of the zinc alloy is covered with a zinc oxide nanorod array coating, the light-operated antibacterial function is realized by a zinc oxide nanostructure, and the material is prepared by in-situ growth on the surface of the substrate by an alcohol hot alkali liquor oxidation method.

Description

Light-operated antibacterial degradable zinc alloy suture material and preparation method thereof
Technical Field
The invention relates to a light-operated antibacterial degradable zinc alloy suture material and a preparation method thereof, in particular to a method for constructing a coating with a rod-shaped micro-nano zinc oxide array on the surface of a substrate made of zinc alloy (Zn-2 ~ 4at% Li) by an alcohol-thermal reaction method and having antibacterial and anti-inflammatory capabilities, belonging to the field of biomedical materials.
Background
The suture is a special thread used for ligation of wounds and suture hemostasis in surgical operations. The current clinical application is mainly artificial synthetic polymer suture.
The synthetic suture has low mechanical property and high price, and the application development of the synthetic suture is greatly limited by the post-implantation reaction and complications.
The magnesium alloy is used as a degradable medical material, and can realize gradual degradation in vivo until final absorption by utilizing the characteristic of easy corrosion in human body environment, thereby realizing the aim of clinical application. Compared with synthetic polymer materials, the magnesium alloy has higher rigidity and better processing performance, thereby being more suitable for surgical sutures. Due to the fact that the corrosion potential of the material is too high, the life cycle of the material in a human body is too short, and the material is degraded and collapsed before the reconstruction of human tissues is completed. In addition, hydrogen is often released during the degradation process of the magnesium alloy, thereby inducing inflammation and inhibiting the adhesion and growth of cells on the surface of the implant.
The absorbable and degradable zinc is a new biomedical material, has the advantages of corrosion potential lower than magnesium, degradation rate matching with human tissue cell recovery and reconstruction rate, excellent mechanical property, capability of being absorbed and degraded biologically and the like, and can avoid secondary operation so as to reduce the body burden of a patient and the risk of secondary infection.
The zinc element has various important physiological functions and wide pharmacological actions, and can participate in energy metabolism of organisms and control emotion; zinc is an indispensable trace element. For humans, it plays a crucial role in regulating cellular metabolism and homeostasis. Zinc is readily biodegradable and absorbed in the body and is therefore classified as a recognized substance. Zinc is a safe material provided by the Food and Drug Administration (FDA).
ZnO has unique optical, semiconductor and piezoelectric properties, and can easily absorb ultraviolet light as a semiconductor with wide band gap energy. Several studies have shown that zinc oxide nanoparticles can be used as photosensitizers due to their potential photosensitivity. A unique photocatalytic effect under light irradiation. Aqueous suspensions of ZnO can generate Reactive Oxygen Species (ROS) such as hydroxyl and hydrogen upon irradiation with light. Peroxides are effective in decomposing organic compounds. The zinc oxide nanoparticles destroy the structure of bacterial cell membranes and inhibit the activity of certain membrane enzymes through the production of active oxygen, thereby leading to the production of lead. ZnO is an effective antibacterial and anticancer drug (Journal Of Materials Chemistry B, 2018, 6(30): 4852-4871.).
The micro-nano coating is constructed on the surface of the zinc alloy, so that the biocompatibility of the zinc alloy can be improved, and the corrosion rate of the zinc alloy can be controlled. The alcohol-thermal reaction can construct a zinc oxide nano-rod coating on the metal surface, and is widely applied to the construction of medical metal surface coatings of titanium, magnesium and the like at present. Therefore, the technology has wide prospect in the related field of constructing the high-bioactivity coating on the surface of the medical zinc alloy.
Disclosure of Invention
Technical problem
The invention aims to provide a zinc alloy suture material which has a rod-shaped micro-nano structure on the surface, has a compact coating with controllable degradation rate, can control antibiosis under the catalysis of light energy, has the functions of antibiosis and antiphlogosis and helps to restore and reconstruct damaged skin tissues and an alcohol thermal oxidation preparation method thereof aiming at the defects of the existing surgical suture material.
Technical scheme
The light-operated antibacterial zinc alloy suture line material with controllable degradation rate is a zinc oxide micro-nano rod array coating which is uniform and compact, has an antibacterial and anti-inflammatory effect and controllable degradation rate and is obtained on the surface of a zinc alloy substrate by adopting alkali liquor alcohol heat treatment. The uniform and compact coating is generated in the alcohol-thermal reaction process of the alkali liquor, and the thickness, the density and the micro-morphology of the coating can be adjusted by adjusting the alcohol-thermal reaction parameters of the alkali liquor, so that the degradation rate of the coating is further controlled. The zinc element can participate in the energy metabolism of the body to regulate the cell metabolism and homeostasis, the zinc oxide has potential photosensitivity and unique photocatalytic effect under the irradiation of light, and the generated active oxygen substances such as hydroxyl and hydrogen destroy the structure of bacterial cell membranes to inhibit the activity of certain membrane enzymes, relieve inflammatory reaction and prevent further aggravation of the damage to tissues.
The invention is realized by the following technical scheme:
a light-operated antibacterial degradable zinc alloy suture material is characterized in that a matrix of the suture material is Zn-2 ~ 4at% Li-zinc alloy, a zinc oxide micro-nano rod array coating is arranged on the surface of the suture material, the coating is obtained by in-situ growth on the surface of the zinc alloy matrix by adopting an alkali liquor alcohol thermal synthesis method, and the light-operated antibacterial degradable zinc alloy suture material has the characteristics of uniformity, compactness, antibacterial and anti-inflammatory effects and controllable degradation rate.
The preparation method of the light-operated antibacterial degradable zinc alloy suture material comprises the following steps:
(1) providing a Zn-2 ~ 4at% Li-zinc alloy as a suture matrix;
(2) providing an alkaline alcohol thermal reaction solution containing ammonia water, alcohol and deionized water;
(3) pretreating the suture line substrate;
(4) placing the pretreated suture matrix in a high-pressure reaction kettle added with alkaline alcohol heat reaction liquid for coating growth, performing alkaline alcohol heat treatment on the surface of the matrix, and constructing a micro-nano zinc oxide array with controllable degradation rate and a light-operated antibacterial function on the surface of the matrix;
(5) and (4) taking out the suture obtained in the step (4), leaching and drying the suture by using alcohol, acetone and deionized water, and then sterilizing to obtain the light-operated antibacterial degradable zinc alloy suture material.
Further, the alkaline alcohol-thermal reaction solution of step (2) contains 10 ~ 50 vol.% of ammonia water, 50 ~ 90 vol.% of absolute ethanol, and the balance of deionized water.
Further, the reaction parameters of the alkali liquor alcohol heat treatment in the step (4) are that the reaction temperature is 60 ~ 120 ℃, and the reaction time is 2 ~ 24 h.
Advantageous effects
(1) The light-operated antibacterial degradable zinc alloy suture material disclosed by the invention is composed of a zinc alloy matrix and a uniform and compact zinc oxide nanorod coating, meets the mechanical property requirement required by epidermal tissues, and can be matched with the epidermal tissue recovery reconstruction rates of wound suture positions of different degrees by adjusting the heat preservation time and the heat preservation temperature to control the thickness, the density and the micro-morphology of the surface coating; the zinc oxide coating on the surface of the composite material can control degradation and gradually degrade along with the restoration and reconstruction of epidermal tissues.
(2) The nano zinc oxide array structure on the surface of the material has unique optical, semiconductor and piezoelectric properties, can easily absorb ultraviolet light, has potential photosensitivity and can be used as a photosensitizer. Under the unique photocatalysis effect of light irradiation, Reactive Oxygen Species (ROS) which can generate hydroxyl and hydrogen can effectively decompose organic compounds to destroy the structure of a bacterial cell membrane and inhibit the activity of certain membrane enzymes through the generation of reactive oxygen.
(3) The zinc alloy matrix of the material has the advantages of degradation rate matched with human tissue cell recovery and reconstruction rate, excellent mechanical property, capability of biological absorption and degradation and the like, and can participate in energy metabolism of organisms and control emotion;
regulating cellular metabolism and homeostasis.
Drawings
FIG. 1 is a field emission electron micrograph of a uniform dense coating of a zinc oxide nanorod array on the surface of a suture in example 1.
Figure 2 is an energy spectrum of a uniform dense coating of zinc oxide nanorod arrays on the surface of a suture in example 1.
FIGS. 3(a) and (b) are the electron micrographs of the antibacterial effect of the suture in example 1 without treatment and the suture after the treatment of the alkaline alcoholic thermal reaction under the light condition, respectively.
FIGS. 4(a) and (b) are the electron micrographs of the antibacterial effect of the untreated suture and the suture subjected to the alkaline alcoholic thermal reaction treatment in example 1 under the condition of being protected from light, respectively.
Detailed description of the preferred embodiment
Example 1
(1) The surface of the suture material is pretreated, the 600#, 800#, 1000# metallographic abrasive paper is used for grinding from coarse sand to fine sand step by step, after polishing, absolute ethyl alcohol and deionized water are used for ultrasonic cleaning, and drying is carried out for standby.
(2) Preparing alkali liquor alcohol heat: preparing 40ml of solution containing 2ml of ammonia water with the concentration of 30% and 18ml of absolute ethyl alcohol by adopting an ammonia water and absolute ethyl alcohol solution system, adding deionized water to dilute to 40ml, and stirring and mixing uniformly at normal temperature for later use.
(3) Alkali liquor alcohol heat treatment: putting the pretreated zinc alloy wire into reaction kettle equipment, and adding prepared alkali liquor for alcohol heating; and opening the vacuum drying oven, setting the reaction temperature to 95 ℃, setting the reaction time to 120min, and after the temperature of the reaction kettle rises to the set temperature, putting the prepared reaction kettle into a hearth to perform alcohol thermal oxidation on the reaction kettle.
(4) And after the heat preservation is finished, taking out the material after the material is cooled to room temperature along with the furnace. And (3) leaching with deionized water, ultrasonically cleaning, drying in vacuum, sterilizing, and aseptically storing for later use to obtain the light-operated antibacterial zinc alloy suture material with the surface provided with the micro-nano zinc oxide array and controllable degradation rate.
FIG. 1 is a field emission electron micrograph of a uniform dense coating of a zinc oxide nanorod array on the surface of a suture in example 1.
Figure 2 is an energy spectrum of a uniform dense coating of zinc oxide nanorod arrays on the surface of a suture in example 1.
FIGS. 3(a) and (b) are electron micrographs of the antibacterial effect of the suture of example 1 without treatment and the suture after the treatment of the alkaline alcoholic thermal reaction, respectively. The coating of the zinc oxide nanorod array has a strong antibacterial effect under visible light.
FIGS. 4(a) and (b) are electron micrographs of the antibacterial effect of the suture of example 1 without treatment and the suture after the alkaline alcoholic thermal reaction treatment, respectively. It can be seen that the coating of the zinc oxide nanorod array has a weak antibacterial effect in the absence of light.
Example 2
(1) The surface of the suture material is pretreated, the 600#, 800#, 1000# metallographic abrasive paper is used for grinding from coarse sand to fine sand step by step, after polishing, absolute ethyl alcohol and deionized water are used for ultrasonic cleaning, and drying is carried out for standby.
(2) Preparing alkali liquor alcohol heat: preparing 40ml of solution containing 2ml of ammonia water with the concentration of 30% and 18ml of absolute ethyl alcohol by adopting an ammonia water and absolute ethyl alcohol solution system, adding deionized water to dilute to 40ml, and stirring and mixing uniformly at normal temperature for later use.
(3) Alkali liquor alcohol heat treatment: putting the zinc alloy wire into reaction kettle equipment, and adding prepared alkali liquor for alcohol heating; and opening the vacuum drying oven, setting the reaction temperature to 80 ℃, setting the reaction time to 360min, and after the temperature of the reaction kettle rises to the set temperature, putting the prepared reaction kettle into a hearth to perform alcohol thermal oxidation on the reaction kettle.
(4) And after the heat preservation is finished, taking out the material after the material is cooled to room temperature along with the furnace. And (3) leaching with deionized water, ultrasonically cleaning, drying in vacuum, sterilizing, and aseptically storing for later use to obtain the light-operated antibacterial zinc alloy suture material with the surface provided with the micro-nano zinc oxide array and controllable degradation rate.
Example 3
(1) The surface of the suture material is pretreated, the 600#, 800#, 1000# metallographic abrasive paper is used for grinding from coarse sand to fine sand step by step, after polishing, absolute ethyl alcohol and deionized water are used for ultrasonic cleaning, and drying is carried out for standby.
(2) Preparing alkali liquor alcohol heat: preparing 40ml of solution containing 2ml of ammonia water with the concentration of 30% and 18ml of absolute ethyl alcohol by adopting an ammonia water and absolute ethyl alcohol solution system, adding deionized water to dilute to 40ml, and stirring and mixing uniformly at normal temperature for later use.
(3) Alkali liquor alcohol heat treatment: putting the zinc alloy wire into reaction kettle equipment, and adding prepared alkali liquor for alcohol heating; and opening the vacuum drying oven, setting the reaction temperature to 95 ℃, setting the reaction time to 1440min, and after the temperature rises to the set temperature, putting the prepared reaction kettle into a hearth to perform alcohol thermal oxidation on the reaction kettle.
(4) And after the heat preservation is finished, taking out the material after the material is cooled to room temperature along with the furnace. And (3) leaching with deionized water, ultrasonically cleaning, drying in vacuum, sterilizing, and aseptically storing for later use to obtain the light-operated antibacterial zinc alloy suture material with the surface provided with the micro-nano zinc oxide array and controllable degradation rate.

Claims (3)

1. A light-operated antibacterial degradable zinc alloy suture material is characterized in that a matrix of the suture material is Zn-2 ~ 4at% Li-zinc alloy, a zinc oxide micro-nano rod array coating is arranged on the surface of the suture material, the coating is obtained by in-situ growth on the surface of the zinc alloy matrix by adopting an alkali liquor alcohol thermal synthesis method, and has the characteristics of uniformity, compactness, antibacterial and anti-inflammatory effects and controllable degradation rate, and the preparation method of the light-operated antibacterial degradable zinc alloy suture material comprises the following steps:
(1) providing a Zn-2 ~ 4at% Li-zinc alloy as a suture matrix;
(2) providing an alkaline alcohol thermal reaction solution containing ammonia water, alcohol and deionized water;
(3) pretreating the suture line substrate;
(4) placing the pretreated suture matrix in a high-pressure reaction kettle added with alkaline alcohol heat reaction liquid for coating growth, performing alkaline alcohol heat treatment on the surface of the matrix, and constructing a micro-nano zinc oxide array with controllable degradation rate and a light-operated antibacterial function on the surface of the matrix;
(5) and (4) taking out the suture obtained in the step (4), leaching and drying the suture by using alcohol, acetone and deionized water, and then sterilizing to obtain the light-operated antibacterial degradable zinc alloy suture material.
2. The method for preparing a light-operated antibacterial degradable zinc alloy suture material according to claim 1, wherein the alkaline alcohol-thermal reaction solution of step (2) comprises 10 ~ 50 vol.% ammonia water, 50 ~ 90 vol.% absolute ethyl alcohol, and the balance deionized water.
3. The method for preparing the light-operated antibacterial degradable zinc alloy suture material according to claim 1, wherein the reaction parameters of the alkali liquor alcohol heat treatment in the step (4) are that the reaction temperature is 60 ~ 120 ℃ and the reaction time is 2 ~ 24 h.
CN201910880513.9A 2019-09-18 2019-09-18 Light-operated antibacterial degradable zinc alloy suture material and preparation method thereof Withdrawn CN110585475A (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN111558080A (en) * 2020-06-15 2020-08-21 南昌大学 Antibacterial silk suture line with double-light response function and preparation method thereof
CN112226767A (en) * 2020-09-29 2021-01-15 西安交通大学 Hydroxyapatite nanorod biological coating and preparation method thereof
CN114569801A (en) * 2022-02-16 2022-06-03 苏州奥芮济医疗科技有限公司 Controlled-degradation zinc-based beauty treatment line and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111558080A (en) * 2020-06-15 2020-08-21 南昌大学 Antibacterial silk suture line with double-light response function and preparation method thereof
CN112226767A (en) * 2020-09-29 2021-01-15 西安交通大学 Hydroxyapatite nanorod biological coating and preparation method thereof
CN112226767B (en) * 2020-09-29 2021-12-28 西安交通大学 Hydroxyapatite nanorod biological coating and preparation method thereof
CN114569801A (en) * 2022-02-16 2022-06-03 苏州奥芮济医疗科技有限公司 Controlled-degradation zinc-based beauty treatment line and preparation method thereof
CN114569801B (en) * 2022-02-16 2022-11-18 苏州奥芮济医疗科技有限公司 Controlled-degradation zinc-based beauty treatment line and preparation method thereof

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Application publication date: 20191220