CN113750295A - Nano-antibacterial coating material based on nanogold cluster, preparation method and implant - Google Patents

Nano-antibacterial coating material based on nanogold cluster, preparation method and implant Download PDF

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CN113750295A
CN113750295A CN202111044606.1A CN202111044606A CN113750295A CN 113750295 A CN113750295 A CN 113750295A CN 202111044606 A CN202111044606 A CN 202111044606A CN 113750295 A CN113750295 A CN 113750295A
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nano
coating material
nanogold
antibacterial coating
preparation
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CN113750295B (en
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刘艳
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Shenzhen Yige Lubrication Technology Co ltd
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Shenzhen Yige Lubrication Technology Co ltd
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    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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Abstract

The invention discloses a nano-antibacterial coating material based on a nano-gold cluster, a preparation method and an endophyte. The method comprises the following steps: s01, preparing nanogold base solution; and S02, mixing with vitamin C or the derivative thereof, and mixing with titanium ions and zinc ions to obtain the nano-gold cluster-based nano-antibacterial coating material. The nano-gold cluster-based nano-antibacterial coating material obtained by the method has good antibacterial performance on MRSA.

Description

Nano-antibacterial coating material based on nanogold cluster, preparation method and implant
Technical Field
The invention belongs to the technical field of medical materials, and particularly relates to a nano-antibacterial coating material based on a nano-gold cluster, a preparation method and an endophyte.
Background
Medical metal materials are the first materials used in orthopedics. In order to meet the continuously developing requirements of medical science, the surface modification of the medical metal material is a research hotspot on the premise of not changing the performance of the bulk material. The antibacterial performance of the orthopedic medical metal material is one of the important performances of the medical metal material.
CN112190767A discloses a nano antibacterial coating material. The material can be attached to the surface of the metal titanium to form an antibacterial layer. The material takes a pMBA-AuNCs cluster as a basic constitutional unit, and forms a nano metal oxide material with a three-dimensional network structure through IVB group quadrivalent ions and copper ions. Clinically, some patients are allergic to copper ions contained in internal plants, and adverse reactions are easily caused.
Disclosure of Invention
The researchers of the invention investigate the influence of different anions in the nano-gold antibacterial material, and try to replace copper ions with zinc ions, and the invention is based on the discovery of the research.
The first aspect of the invention discloses a preparation method of a nano antibacterial coating material based on nano gold clusters, which comprises the following steps:
s01, preparing nanogold base solution;
and S02, mixing with vitamin C or the derivative thereof, and mixing with titanium ions and zinc ions to obtain the nano-gold cluster-based nano-antibacterial coating material.
In some preferred embodiments of the present invention, S02 further comprises the step of adding a quaternary ammonium salt;
preferably, the quaternary ammonium salt is selected from one or more of benzalkonium chloride, benzalkonium bromide and dodecyl dimethyl phenoxy ethyl ammonium bromide;
preferably, the concentration of the quaternary ammonium salt in the prepared nano-gold cluster-based nano-antibacterial coating material is 100-1000 mg/L.
The nano-antibacterial coating material containing the quaternary ammonium salt and based on the nano-gold clusters is antibacterial and antiviral.
In some preferred embodiments of the present invention, in S01, the raw materials for preparing the nanogold liquid include tetrachloroauric acid, p-mercaptobenzoic acid, and sodium tetrahydroborate.
In some preferred embodiments of the present invention, in S01, the nanogold liquid is prepared with a molar ratio of tetrachloroauric acid, p-mercaptobenzoic acid, and sodium tetrahydroborate of 1: (1.5-2.5): (1.5-2.5), preferably 1:2: 2.
In some preferred embodiments of the present invention, in S01, the step of preparing the nanogold base solution includes:
s11, mixing tetrachloroauric acid and p-mercaptobenzoic acid in ultrapure water, stirring, adding a sodium hydroxide aqueous solution until precipitates are dissolved, adding sodium tetrahydroborate, and stirring;
and S12, adding hydrochloric acid to precipitate all nanogold clusters, centrifuging, washing with ultrapure water, drying, and dissolving with methanol.
In some preferred embodiments of the present invention, in S02, the vitamin C derivative is vitamin C phosphate.
In some preferred embodiments of the present invention, in S02, the ascorbyl phosphate is selected from at least one of sodium ascorbyl phosphate or magnesium ascorbyl phosphate.
In some preferred embodiments of the present invention, the molar ratio of the nanogold clusters to the vitamin C or phosphate in S02 is (0.8-1.2): (0.001-0.1), preferably 1: (0.01-0.05), and more preferably 1: 0.03.
In some preferred embodiments of the present invention, in S02, the nanogold clusters and vitamin C or phosphate, TiCl4、ZnCl2The molar ratio of (0.8-1.2): (0.001-0.1): (8-12): 1.5-2.5), preferably 1 (0.01-0.05):10:2, more preferably 1:0.03:10: 2.
In some preferred embodiments of the present invention, the preparing of the nanogold base solution is performed under heating, and the PID parameter control of the heating rod is performed by the attenuation curve method of the following formula:
Δ(K)＝30[101e(k)-201e(k-1)+100e(k-2)]；
wherein a, b, c and d are constants and take values of 25-30, 90-100, 180-200 and 90-110 respectively.
The second aspect of the invention is to disclose the nano-gold cluster-based nano-antibacterial coating material obtained by the preparation method of the first aspect.
The third aspect of the invention is to disclose the implant comprising the nano-gold cluster-based nano-antibacterial coating material obtained by the preparation method of the first aspect, and further comprising a metal substrate, an alloy substrate or a glass substrate.
In some preferred embodiments of the invention, the titanium alloy substrate inner plant is treated by mixing with concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 1:1 for 10min, washed with water, dried, added with the nano-gold cluster-based nano-antibacterial coating material obtained by the preparation method of the first aspect, and dried to obtain the antibacterial inner plant.
The invention has the beneficial effects that:
(1) the nano-gold cluster-based nano-antibacterial coating material obtained by the method has good antibacterial performance for MRSA.
(2) The process of the invention, with Zn2+Substitute for Cu2+The problem of copper ion allergy to the internal plants of the patient is avoided, and meanwhile, the antibacterial performance is not influenced.
(3) The method of the invention discovers that Zn exists in a system of the nano-gold clusters2+The antibacterial effect of the copper-based antibacterial material is obviously superior to that of Cu2 +. It has also been unexpectedly discovered that the addition of vitamin C and its analogs can significantly increase Zn2+The antibacterial property of (1).
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless otherwise specified, the examples and comparative examples are parallel tests with the same components, component contents, preparation steps, preparation parameters.
Example 1
The preparation method of the nano antibacterial coating material based on the nano gold clusters comprises the following steps:
(1) preparing the nano gold cluster liquid:
mixing tetrachloroauric acid and p-mercaptobenzoic acid in the molar ratio of 1:2 in ultrapure water, stirring, adding sodium hydroxide aqueous solution until precipitate is dissolved, adding sodium tetrahydroborate in an amount which is 2 times that of tetrachloroauric acid, and stirring;
adding hydrochloric acid to precipitate all nanogold clusters, centrifuging, washing with ultrapure water, drying, and dissolving with methanol for later use.
(2) Preparation of nano antibacterial coating
Adding magnesium phosphate vitamin C into the nanogold cluster methanol solution, carrying out ultrasonic treatment, and adding TiCl4And ZnCl2And carrying out ultrasonic treatment to obtain the nano antibacterial coating material based on the nano gold clusters.
Nano gold cluster and vitamin C magnesium phosphate, TiCl4、ZnCl2The molar ratio in the solution is: 1:0.01: 10: 2.
example 2
The preparation method of the nano antibacterial coating material based on the nano gold clusters comprises the following steps:
(1) preparing the nano gold cluster liquid:
mixing tetrachloroauric acid and p-mercaptobenzoic acid in the molar ratio of 1:2 in ultrapure water, stirring, adding sodium hydroxide aqueous solution until precipitate is dissolved, adding sodium tetrahydroborate in an amount which is 2 times that of tetrachloroauric acid, and stirring;
adding hydrochloric acid to precipitate all nanogold clusters, centrifuging, washing with ultrapure water, drying, and dissolving with methanol for later use.
(2) Preparation of nano antibacterial coating
Adding vitamin C sodium phosphate into the nanogold cluster methanol solution, performing ultrasonic treatment, and adding TiCl4And ZnCl2And carrying out ultrasonic treatment to obtain the nano antibacterial coating material based on the nano gold clusters.
Gold nanocluster and vitamin C sodium phosphate, TiCl4、ZnCl2The molar ratio in the solution is: 1:0.01: 10: 2.
example 3
The preparation method of the nano antibacterial coating material based on the nano gold clusters comprises the following steps:
(1) preparing the nano gold cluster liquid:
mixing tetrachloroauric acid and p-mercaptobenzoic acid in the molar ratio of 1:2 in ultrapure water, stirring, adding sodium hydroxide aqueous solution until precipitate is dissolved, adding sodium tetrahydroborate in an amount which is 2 times that of tetrachloroauric acid, and stirring;
adding hydrochloric acid to precipitate all nanogold clusters, centrifuging, washing with ultrapure water, drying, and dissolving with methanol for later use.
(2) Preparation of nano antibacterial coating
Adding magnesium phosphate vitamin C into the nanogold cluster methanol solution, carrying out ultrasonic treatment, and adding TiCl4And ZnCl2And carrying out ultrasonic treatment to obtain the nano antibacterial coating material based on the nano gold clusters.
Nano gold cluster and vitamin C magnesium phosphate, TiCl4、ZnCl2The molar ratio in the solution is: 1:0.02: 10: 2.
example 4
The preparation method of the nano antibacterial coating material based on the nano gold clusters comprises the following steps:
(1) preparing the nano gold cluster liquid:
mixing tetrachloroauric acid and p-mercaptobenzoic acid in the molar ratio of 1:2 in ultrapure water, stirring, adding sodium hydroxide aqueous solution until precipitate is dissolved, adding sodium tetrahydroborate in an amount which is 2 times that of tetrachloroauric acid, and stirring;
adding hydrochloric acid to precipitate all nanogold clusters, centrifuging, washing with ultrapure water, drying, and dissolving with methanol for later use.
(2) Preparation of nano antibacterial coating
Adding magnesium phosphate vitamin C into the nanogold cluster methanol solution, carrying out ultrasonic treatment, and adding TiCl4And ZnCl2And carrying out ultrasonic treatment to obtain the nano antibacterial coating material based on the nano gold clusters.
Nano gold cluster and vitamin C magnesium phosphate, TiCl4、ZnCl2Mols in solutionThe ratio is as follows: 1:0.03:10: 2.
example 5
The preparation method of the nano antibacterial coating material based on the nano gold clusters comprises the following steps:
(1) preparing the nano gold cluster liquid:
mixing tetrachloroauric acid and p-mercaptobenzoic acid in the molar ratio of 1:2 in ultrapure water, stirring, adding sodium hydroxide aqueous solution until precipitate is dissolved, adding sodium tetrahydroborate in an amount which is 2 times that of tetrachloroauric acid, and stirring;
adding hydrochloric acid to precipitate all nanogold clusters, centrifuging, washing with ultrapure water, drying, and dissolving with methanol for later use.
(2) Preparation of nano antibacterial coating
Adding magnesium phosphate vitamin C into the nanogold cluster methanol solution, carrying out ultrasonic treatment, and adding TiCl4And ZnCl2And carrying out ultrasonic treatment to obtain the nano antibacterial coating material based on the nano gold clusters.
Nano gold cluster and vitamin C magnesium phosphate, TiCl4、ZnCl2The molar ratio in the solution is: 1:0.05: 10: 2.
example 6
The preparation method of the nano antibacterial coating material based on the nano gold clusters comprises the following steps:
(1) preparing the nano gold cluster liquid:
mixing tetrachloroauric acid and p-mercaptobenzoic acid in the molar ratio of 1:2 in ultrapure water, stirring, adding sodium hydroxide aqueous solution until precipitate is dissolved, adding sodium tetrahydroborate in an amount which is 2 times that of tetrachloroauric acid, and stirring;
adding hydrochloric acid to precipitate all nanogold clusters, centrifuging, washing with ultrapure water, drying, and dissolving with methanol for later use.
(2) Preparation of nano antibacterial coating
Adding magnesium phosphate vitamin C into the nanogold cluster methanol solution, carrying out ultrasonic treatment, and adding TiCl4And ZnCl2Performing ultrasonic treatment to obtain the nano-gold cluster-based nano-scale resistBacteria coating material.
Nano gold cluster and vitamin C magnesium phosphate, TiCl4、ZnCl2The molar ratio in the solution is: 1:0.002: 10: 2.
example 7
The preparation method of the nano antibacterial coating material based on the nano gold clusters comprises the following steps:
(1) preparing the nano gold cluster liquid:
mixing tetrachloroauric acid and p-mercaptobenzoic acid in the molar ratio of 1:2 in ultrapure water, stirring, adding sodium hydroxide aqueous solution until precipitate is dissolved, adding sodium tetrahydroborate in an amount which is 2 times that of tetrachloroauric acid, and stirring;
adding hydrochloric acid to precipitate all nanogold clusters, centrifuging, washing with ultrapure water, drying, and dissolving with methanol for later use.
(2) Preparation of nano antibacterial coating
Adding vitamin C into the methanol solution of the nanogold cluster, carrying out ultrasonic treatment, and adding TiCl4And ZnCl2And carrying out ultrasonic treatment to obtain the nano antibacterial coating material based on the nano gold clusters.
Nanogold clusters and vitamin C, TiCl4、ZnCl2The molar ratio in the solution is: 1:0.01: 10: 2.
example 8
The preparation method of the nano antibacterial coating material based on the nano gold cluster is different from the embodiment 1 in that the preparation of the nano gold base solution is carried out under the heating condition, and the PID parameter control of the heating rod is carried out by an attenuation curve method of the following formula:
Δ(K)＝30[101e(k)-201e(k-1)+100e(k-2)]；
wherein a, b, c and d are constants and take values of 25-30, 90-100, 180-200 and 90-110 respectively.
The temperature control method of the embodiment has the advantages of high temperature rise speed and accurate temperature control.
Comparative example 1
The preparation method of the nano antibacterial coating material based on the nano gold clusters is different from the preparation method of the nano antibacterial coating material in example 1 in that no vitamin C magnesium phosphate is added.
Comparative example 2
The preparation method of the nano antibacterial coating material based on the nano gold cluster is different from the embodiment 1 in that the magnesium phosphate without vitamin C is added and the CuCl is used simultaneously2Replacing ZnCl2。
Examples of the experiments
And (3) mixing the titanium alloy sheet with hydrogen peroxide and concentrated sulfuric acid in a volume ratio of 1:1 for 10min, washing, drying, dropwise adding the coating materials of the examples and the comparative examples, and drying to obtain an experimental sample. The antibacterial properties were examined according to the method of CN112190767A, verification example 2, and the results are shown in Table 1.
TABLE 1 antibacterial Properties of NanoAu cluster-based Nanoantibacterial coating Material
Figure BDA0003250761730000111
Figure BDA0003250761730000121
In the same column of data, marked with different lower case letters to represent significant difference, P is less than 0.05
The results show that comparative example 1Zn in a system of nanogold clusters2+The antibacterial effect is obviously better than that of comparative example 2Cu2+. The Zn can be obviously improved by adding vitamin C and the like into a system of the nano gold cluster2+Wherein the effect of the vitamin C phosphate of examples 1-6 is significantly better than that of the vitamin C of example 7. Examples 1-6 vitamin C phosphate is also best exemplified by example 4.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims (10)

1. The preparation method of the nano antibacterial coating material based on the nano gold clusters is characterized by comprising the following steps:
s01, preparing nanogold base solution;
and S02, mixing with vitamin C or the derivative thereof, and mixing with titanium ions and zinc ions to obtain the nano-gold cluster-based nano-antibacterial coating material.
2. The method according to claim 1, wherein in S02, a step of adding a quaternary ammonium salt;
preferably, the quaternary ammonium salt is selected from one or more of benzalkonium chloride, benzalkonium bromide and dodecyl dimethyl phenoxy ethyl ammonium bromide;
preferably, the concentration of the quaternary ammonium salt in the prepared nano-gold cluster-based nano-antibacterial coating material is 100-1000 mg/L.
3. The preparation method according to claim 1 or 2, wherein in S01, raw materials for preparing the nanogold liquid include tetrachloroauric acid, p-mercaptobenzoic acid, and sodium tetrahydroborate;
preferably, in S01, the molar ratio of tetrachloroauric acid, p-mercaptobenzoic acid and sodium tetrahydroborate for preparing the nano-gold base solution is 1: (1.5-2.5): (1.5-2.5), preferably 1:2: 2.
4. The method according to any one of claims 1 to 3, wherein the step of preparing the nanogold base solution in S01 comprises:
s11, mixing tetrachloroauric acid and p-mercaptobenzoic acid in ultrapure water, stirring, adding a sodium hydroxide aqueous solution until precipitates are dissolved, adding sodium tetrahydroborate, and stirring;
and S12, adding hydrochloric acid to precipitate all nanogold clusters, centrifuging, washing with ultrapure water, drying, and dissolving with methanol.
5. The method according to any one of claims 1 to 4, wherein the vitamin C derivative is vitamin C phosphate in S02.
6. The method according to any one of claims 1 to 5, wherein in S02, the ascorbyl phosphate is at least one selected from sodium ascorbyl phosphate and magnesium ascorbyl phosphate.
7. The method according to any one of claims 1 to 6, wherein the molar ratio of the nanogold clusters to the vitamin C or phosphate in S02 is (0.8-1.2): (0.001-0.1), preferably 1 (0.01-0.05), more preferably 1: 0.03.
8. The method according to any one of claims 1 to 7, wherein, in S02, the nanoclusters are formed of gold nanoparticles and ascorbic acid or a phosphate salt, TiCl4、ZnCl2The molar ratio of (0.8-1.2): (0.001-0.1): (8-12): 1.5-2.5), preferably 1 (0.01-0.05):10:2, more preferably 1:0.03:10: 2.
9. The nano-gold cluster-based nano-antibacterial coating material obtained by the preparation method according to any one of claims 1 to 8.
10. An endophyte comprising a nano antimicrobial coating material according to claim 9, further comprising a metal substrate, an alloy substrate or a glass substrate.
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