A polyphenol coating, its preparation method and application

Abstract

The present application relates to coating, in order to be able to more efficient and mild preparation polyphenol coating on the surface of material, provide a kind of preparation method of polyphenol coating, comprising the following preparation steps: (1) configuration Tanfloc aqueous solution;(2) adjust the Tanfloc aqueous solution obtained in step (1), so that it enters colloidal suspension state, obtain modified solution;(3) the carrier material is placed in the modified solution prepared in step (2), i.e. the modified coating can be prepared on the surface of carrier material.The polyphenol coating and its preparation method of the present application can efficiently prepare polyphenol coating on the surface of material under mild conditions.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coating, in particular to a polyphenol coating, a preparation method and application thereof. BACKGROUND

[0002] In the field of medical technology, coatings have been widely used for the surface modification of medical implants, such as catheter coatings in the cardiovascular field and deposited coatings on the surface of implants. By modifying the surface of medical implants with coatings, the biocompatibility of the implant surface can be increased, and the implant surface can also be given certain functions, such as anticoagulation, antibiosis, and cell adhesion promotion.

[0003] However, for existing coatings, most of them have the problems of long preparation time and harsh preparation conditions. A small part of coatings that can be prepared quickly under mild conditions either have the problem of insufficient thickness of single-layer deposition or the problem of unstable coatings, or the problem of complicated process due to the need to introduce other molecules or ions for co-deposition to increase the thickness. There are also many fast coatings that have too high requirements for the preparation interface, and once the interface is contaminated, it is difficult to deposit. Moreover, existing coatings are limited to modification before implantation, and it is difficult to modify the surface of medical implants that have been implanted in the body.

[0004] Tanfloc is a polymeric polyphenol substance that is widely used in wastewater treatment and has good biocompatibility and antioxidant properties. Some scholars have used it to co-deposit with various functional molecules (such as heparin and hyaluronic acid) on the surface of implants or glass to prepare coatings, which have achieved the effects of anticoagulation and promotion of osteoblast growth. However, the preparation of the coatings reported so far requires the use of layer-by-layer self-assembly with other molecules (which have potential toxicity), and the process is complicated, with a total preparation time often exceeding 40 minutes of clinical operation time, limiting its application scenarios to before implantation in the body. For some medical implants that have been implanted in the body (such as oral implants and bone screws), it is difficult to prepare them in the body. In addition, the acidic environment with pH = 5-5.5 and the low-osmotic environment required for the preparation of the coating are not tolerable in the body, and a mild condition is needed for the preparation of the coating. The existing technology cannot achieve the simple and rapid preparation of the coating under mild conditions. SUMMARY

[0005] The purpose of the present application is to provide a polyphenol coating and a preparation method thereof, which can efficiently prepare a polyphenol coating on the surface of a material under mild conditions.

[0006] The embodiments of the present application are implemented by the following technical solutions: the preparation method of the polyphenol coating of the present application comprises the following preparation steps:

[0007] (1) configuring Tanfloc aqueous solution, wherein the concentration of Tanfloc is 0.05-20 mg / ml;

[0008] (2) adjusting Tanfloc aqueous solution obtained in step (1) to enter colloidal suspension state, to obtain modified solution;

[0009] (3) placing carrier material in modified solution prepared in step (2), and incubating for 1 min or more under the condition of ultrasonic or oscillation, to prepare modified coating on the surface of carrier material. The carrier material includes but is not limited to metal, polymer and other common medical materials.

[0010] Further, in step (2), the pH of the modified solution is adjusted to 5.5-8.5 by using alkaline solution. The alkaline solution includes but is not limited to sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like.

[0011] Further, in step (2), the Tanfloc aqueous solution can also be treated by using salt solution to form colloidal Tanfloc solution. The salt solution includes but is not limited to sodium chloride, potassium chloride and the like. The addition of salt solution can make Tanfloc solution form colloidal solution, so the concentration of salt solution and the amount of addition are not specifically limited, as long as the salt solution is added to Tanfloc aqueous solution to form colloidal solution.

[0012] The technical scheme of the embodiment of the present application has at least the following advantages and beneficial effects:

[0013] (1) In the preparation condition, the present preparation method adjusts the preparation environment from acidic to neutral environment, without introducing other molecules, which is more conducive to in vivo preparation. Moreover, the coating is prepared by using colloidal suspension method, which avoids the complicated defect of the reported LbL coating process, and does not need to introduce other molecules, so that the coating is quickly prepared under mild conditions.

[0014] (2) In the technical sensitivity of preparation, the present preparation method uses the method of adjusting pH to change Tanfloc from solution state to colloidal small particles in suspension state, so that better adsorption effect is obtained, and the technical sensitivity is reduced, so that the coating can be formed on the surface even if the implant is contaminated.

[0015] (3) In the thickness and loading of the prepared coating, compared with the traditional polyphenol coating (1-2 nm of single molecule coating), the present preparation method uses colloidal suspension polyphenol to prepare thicker macromolecular polyphenol coating (close to 10 nm per layer), and the loading is larger. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1is the structural formula of Tanfloc used in Examples 1-6 of the present invention;

[0017] Figure 2 The XPS results provided in Example 1 of the present invention;

[0018] Figure 3 The contact angle results provided by Example 1 of the present invention;

[0019] Figure 4 The zeta potential results provided in Example 1 of the present invention;

[0020] Figure 5 This is the XPS result provided by Example 4 of the present invention. DETAILED DESCRIPTION

[0021] The structural formula of Tanfloc used in Examples 1-6 is shown in the attached Figure 1 shown.

[0022] Example 1

[0023] This embodiment provides a method for preparing a polyphenol coating, comprising the following steps:

[0024] (1) Cleaning the carrier material: First, send the polished carrier material into an ultrasonic cleaning machine, and clean it in acetone and anhydrous alcohol using 15-30kHz ultrasonic waves for 5-10 minutes respectively, and then dry it.

[0025] (2) Prepare a 1 mg / ml Tanfloc solution, adjust the pH to 7.0 using 1 M sodium hydroxide, and immerse the solution in a colloidal suspension to form a modified solution; immerse the washed support material in the modified solution and soak it under ultrasound for 10 minutes.

[0026] (3) The modified coating can be obtained by washing away the unadsorbed Tanfloc with R0 water.

[0027] XPS was used to detect the coating state on the surface of the carrier material. The results are shown in the attached figure. Figure 2 As shown in the attached Figure 2 It can be seen that Figure 2 The XPS results on the left show an inversion of the Ti / C peaks and the emergence of a new N peak, demonstrating that Tanfloc in a colloidal suspension can form a coating on the surface of medical implants. The SEM results on the right show that the coating is nearly 10 nm thick, demonstrating that this technology can quickly form coatings on medical implant surfaces under mild conditions.

[0028] Attachment Figure 3 The contact angle changes before and after the polyphenol coating is deposited on the carrier material. From the results, it can be seen that the contact angle of the carrier material surface with polyphenol coating is significantly reduced.Figure 4 The surface zeta potential of the carrier material before and after the polyphenol coating is deposited, and the results show that the zeta potential of the polyphenol coating surface is significantly smaller. The above results show that the polyphenol coating not only forms a coating on the surface of the carrier material, and the appearance of the coating significantly changes the physicochemical properties of the material surface.

[0029] Example 2

[0030] The present embodiment provides a preparation method of a polyphenol-copper ion coating, comprising the following steps:

[0031] (1) The carrier material is cleaned. The polished carrier is first sent into an ultrasonic cleaner, and then cleaned in acetone and anhydrous alcohol using ultrasonic waves of 15-30 kHz for 5-10 minutes, respectively, and then dried.

[0032] (2) A Tanfloc solution of 1 mg / ml is prepared, and 6M sodium hydroxide is used to adjust the pH to 7.0. The solution is immersed in a colloidal suspension state to form a modified solution. The cleaned carrier material is immersed in the modified solution and soaked for 10 minutes under ultrasonic conditions.

[0033] (3) The unabsorbed Tanfloc is cleaned using RO water to obtain a modified coating.

[0034] (4) The carrier material with the modified coating is immersed in a copper chloride solution of 1 mg / ml for 3 minutes.

[0035] (5) The unabsorbed ions are cleaned using RO water to obtain a Tanfloc-copper ion composite coating.

[0036] Example 3

[0037] The present embodiment provides a preparation method of a polyphenol coating, comprising the following steps:

[0038] (1) The carrier material is cleaned. The polished carrier is first sent into an ultrasonic cleaner, and then cleaned in acetone and anhydrous alcohol using ultrasonic waves of 15-30 kHz for 5-10 minutes, respectively, and then dried.

[0039] (2) A Tanfloc solution of 1 mg / ml is prepared, and an equal amount of normal saline is added. The solution is immersed in a colloidal suspension state to form a modified solution. The cleaned carrier material is immersed in the colloidal suspension solution and soaked for 10 minutes under ultrasonic conditions.

[0040] (3) The unabsorbed Tanfloc is cleaned using RO water to obtain a coating.

[0041] Example 4

[0042] The present embodiment provides a method for preparing a polyphenol coating on a contaminated implant surface, comprising the following steps:

[0043] (1) cleaning the carrier material, first, the polished carrier is sent into an ultrasonic cleaner, and then cleaned in acetone and anhydrous alcohol respectively by using ultrasonic waves of 15-30 kHz for 5-10 min, and then dried.

[0044] (2) preparing the surface of the contaminated carrier material, the carrier material is soaked in a 5 ug / ml LPS aqueous solution for 1 hour, and then the unabsorbed LPS is washed away using RO water, and dried to obtain the LPS-contaminated carrier material;

[0045] (3) preparing a 1 mg / ml Tanfloc solution, adjusting the pH to 7.0 using 1M sodium hydroxide, and immersing the solution in a colloidal suspension state to form a modified solution; the contaminated carrier material obtained in step (2) is immersed in the modified solution and soaked for 10 minutes under a shaking bed.

[0046] (3) using RO water to wash away the unabsorbed Tanfloc to obtain the polyphenol coating.

[0047] Meanwhile, XPS is used to detect the polyphenol coating obtained in this embodiment and the polyphenol coating of the control group (the control group is to directly soak the carrier material in the tanfloc solution (non-modified solution)), and the results are as follows Figure 5 Figure 5 It can be seen that the deposition amount of unmodified Tanfloc on the surface of the LPS-contaminated medical implant is less Figure 5 A, Ti / C peak failed to reverse), and the Tanfloc in the modified solution can be deposited on the surface of the LPS-contaminated medical implant in large amounts Figure 5 B, Ti / C peak reversal). It is proved that even after being contaminated by LPS (a common bacterial contaminant), the method can form a polyphenol coating on the surface of the medical implant.

[0048] Example 5

[0049] The present embodiment provides a method for preparing a polyphenol coating on an in vivo implant, comprising the following steps:

[0050] (1) preparing a 1 mg / ml Tanfloc solution, adjusting the pH to 7.0 using 1M sodium hydroxide, and immersing the solution in a colloidal suspension state to form a modified solution;

[0051] (2) after the in vivo implant is exposed during the operation, the modified solution of step (1) is used to flush the surface of the implant for 3-5 minutes, and the excess liquid is sucked by a suction device;

[0052] ​(3) using physiological saline to rinse off the excess liquid.

[0053] Example 6

[0054] The present embodiment provides a preparation method for preparing a polyphenol coating on a contaminated implant surface, comprising the following steps:

[0055] (1) preparing a Tanfloc solution of 1 mg / ml, using 1M sodium hydroxide to adjust the pH to 7.0, the solution is immersed in colloidal suspension state to form a modified solution;

[0056] (2) after exposing the implant screw thread in the mouth in the operation, using an ultrasonic cleaner to rinse the modified solution on the implant surface for 3-5 minutes, and using a suction device to suck the excess liquid;

[0057] (3) using physiological saline to rinse off the excess liquid.

[0058] The above is only the preferred embodiment of the present application, and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a polyphenol coating, characterized in that: The method comprises the following preparation steps: (1) Prepare a Tanfloc aqueous solution; the structural formula of the Tanfloc is shown below; (2) adjusting the Tanfloc aqueous solution obtained in step (1) to enter a colloidal suspension state to obtain a modified solution; (3) placing the carrier material in the modified solution prepared in step (2) to prepare a modified coating on the surface of the carrier material; In step (2), the Tanfloc aqueous solution is adjusted with an alkaline solution so that the pH of the modified solution is between 5.5 and 8.5, or the Tanfloc aqueous solution is treated with physiological saline so that the Tanfloc aqueous solution forms a colloid.

2. The method for preparing a polyphenol coating according to claim 1, wherein: In step (3), the carrier material is immersed in the modified solution for a time greater than or equal to 1 min.

3. The method for preparing a polyphenol coating according to claim 1, wherein: In step (3), when the carrier material is placed in the modified solution, the modified solution is placed in an ultrasonic or oscillating environment.

4. The method for preparing a polyphenol coating according to claim 1, wherein: In step (1), the concentration of Tanfloc in the Tanfloc aqueous solution is 0.05-20 mg / ml.

5. A polyphenol coating, characterized in that The polyphenol coating is prepared by the preparation method of any one of claims 1 to 4.

6. The method for preparing the polyphenol coating according to any one of claims 1 to 4 is applied to surface modification of medical materials.

7. The polyphenol coating according to claim 5 is used for surface modification of medical materials.

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