EP4271429A1 - Implants intracorporels revêtus de polydopamine par un procédé d'électropolymérisation - Google Patents

Implants intracorporels revêtus de polydopamine par un procédé d'électropolymérisation

Info

Publication number
EP4271429A1
EP4271429A1 EP21769827.3A EP21769827A EP4271429A1 EP 4271429 A1 EP4271429 A1 EP 4271429A1 EP 21769827 A EP21769827 A EP 21769827A EP 4271429 A1 EP4271429 A1 EP 4271429A1
Authority
EP
European Patent Office
Prior art keywords
implant
electropolymerization
electrolyte
coating
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21769827.3A
Other languages
German (de)
English (en)
Inventor
Afife Binnaz HAZAR
Oguler SAZCI
Gulcin GENC
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yildiz Teknik Universitesi
Original Assignee
Yildiz Teknik Universitesi
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yildiz Teknik Universitesi filed Critical Yildiz Teknik Universitesi
Publication of EP4271429A1 publication Critical patent/EP4271429A1/fr
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/204—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses

Definitions

  • the present invention relates to medical implant technologies.
  • the present invention relates to a method and product for dental implants.
  • a dental implant is an artificial tooth root placed in the jawbone in order to restore the function and impaired aesthetics of the missing tooth.
  • the dental implant treatment is highly successful today, there are still serious losses due to some complications such as peri-mucositis and peri-implantitis.
  • Osseointegration is defined as the microscopic structural and functional connection between the intraosseous load-bearing implant and living bone tissue.
  • An inadequate osseointegration of the implant with the bone, deterioration of the bacterial balance after unsuccessful osseointegration, infection of the soft tissues around the implant caused by the bone loss are the most important causes for dental implants loss. The occurrence of these complications are highly dependent on the patient's awareness of oral hygiene and the experience of the physician, as well as the material type and surface properties of the implant.
  • Microstructural changes on the dental implant surface are effective in the response of the tissues and cells to the implant.
  • physical, chemical, physicochemical processes and/or combinations thereof are applied to the surface.
  • the possibility of inflammation in the tissues around the implant is reduced.
  • existing surface treatments are not sufficient to prevent the occurrence of diseases such as peri-mucositis and peri-implantitis.
  • all of said methods may cause problems in implant-tissue compatibility.
  • non-surgical periodontal treatments such as curette and mechanical treatment with ultrasonic devices, laser surface cleaning, and antimicrobial treatments as well as chemical decontamination and regenerative and resective surgical treatments can be used.
  • the implant On the surfaces of the dental implants, in order to ensure the primary stability, increase the biological response and improve the osseointegration process in a positive way, a number of modifications are made on dental implant surfaces so as to improve tissue response, with the development of the technology and the increase in the number of researches.
  • the implant is conical or cylindrical, differences in length and diameter, number of threads, depth or shape, surface roughness value, morphology of the oxide layer on the surface, different surface topographies, and increasing the energy of the implant by binding different active groups or ions (Ca +2 , PO 4 3 ' etc.) on the surface, etc. configure the behavior of the implant in the tissue. In some of these methods, there are situations that weaken the biocompatibility, while in some of them, biocompatibility may increase.
  • the principal object of the present invention is to eliminate the prior art deficiencies.
  • Another object of the present invention is to increase the hydrophilicity of the surfaces of the medical and dental implants by means of a method that is fast and low-cost, and easy to monitor and control.
  • a polydopamine (PDA) biopolymer is deposited on the surface by electropolymerization method in order to increase the surface energy and improve the bone-implant compatibility due to the increase in surface wettability.
  • PDA polydopamine
  • the main purpose of its use is to ensure that different groups are simultaneously attached to the surface, given that it has the ability to adhere to almost any substance by virtue of its active ends. With the adhesive property of PDA and the superior properties of other groups, it is possible to increase the hydrophilicity and bioactivity of the implant surfaces. The coating times of less than 24 hours yield hydrophilicity below 50°.
  • the present invention provides a method for increasing the hydrophilicity of a surface of an intracorporeal implant of conductive material.
  • the method comprises the step of coating said implant with a polymer layer by electropolymerization.
  • the step of coating the implant with the polymer layer comprises the following: i. immersing the implant as a working electrode in an electrolyte designed to provide a source of monomer; ii. electropolymerization coating of the implant by applying a voltage to said working electrode in the presence of a reference electrode and a counter electrode immersed in the electrolyte.
  • a preferred embodiment of the method comprises applying cyclic voltammetry in electropolymerization according to the following parameters: • a voltage ranging from -2 V to +2 V;
  • the method preferably comprises applying a voltage in the range of -1 V to +1 V and selecting an electropolymerization time in the range of 30 min to 24 hours.
  • the scanning rate can be 0.1 V/s.
  • the method preferably comprises using a dopamine-containing monomer as a monomer for coating with said polymer layer.
  • a PDA layer is obtained on the implant surface.
  • the dopamine-containing monomer may be dopamine HCI.
  • a preferred embodiment of the method may include adjusting the concentration of the monomer in the electrolyte at the start of electropolymerization to be in the range of 1 mg/mL to 4 mg/mL, and preparing the electrolyte to be a buffered conductive solution.
  • the electrolyte may be buffered to a pH of 7.4.
  • the electrolyte may be a tris buffered saline.
  • the tris buffer may be present in the electrolyte at a concentration of 20 mM.
  • Ag-AgCI can be used as the material of the electrode and Pt can be used as the material of the counter electrode.
  • An exemplary embodiment of the method may include subjecting the implant surface to a pre-treatment prior to electropolymerization.
  • Said pre-treatment may be selected from washing, oxide layer removal, or sandblasting.
  • Said conductive material may contain Co-Cr, Co-Ni-Cr, Co-Cr-Mo, Fe-Cr-Ni-Mo, a titanium alloy, a shape memory alloy, stainless steel, or a conductive polymer.
  • the conductive material may contain a titanium alloy selected from Ti-6AI-4V, Ti-6AI-4V-ELI, Ti-6AI-7Nb, Ti-5AI-2.5Fe.
  • the conductive material may contain a shape memory alloy selected from Ni-Ti, Cu-Zn-AI, Cu-AI-Ni.
  • the conductive material may contain a conductive polymer selected from PA, PPy, PT, PEDOT, PANI.
  • Figure 1 is an image for the contact angle interpreted in Example 4, for a sample of a substrate (a disc sample of Ti-6AI-4V-ELI) without electropolymerization coating.
  • Figure 2 is an image for the contact angle interpreted in Example 4, for the PDA-coated surface (surface of the PDA-coated Ti-6AI-4V-ELI disc sample) by applying electropolymerization in the context of example 2, in order to observe the effect of the inventive improvement.
  • Figure 3 is the side-by-side and simultaneous photographic images of the (a) PDA- uncoated reference dental implant and (b) the PDA-coated implant, after water was dropped thereon in example 5.
  • the electropolymerization method may be applied to any conductive surface.
  • materials with conductive surfaces suitable for PDA coating by electropolymerization may include titanium alloys (e.g., Ti-6AI-4V, Ti-6AI-4V-ELI, Ti-6AI-7Nb, Ti-5AI-2.5Fe), Co- Cr, Co-Ni-Cr, Co-Cr-Mo, Fe-Cr-Ni-Mo, shape memory alloys (e.g., Ni-Ti, Cu-Zn-AI, Cu-AI- Ni), stainless steel and conductive polymers (e.g., PA, PPy, PT, PEDOT, PANI).
  • the surface of the substrate may be subjected to one or more of the pre-treatments known in the art, as needed.
  • the electropolymerization method generates a coating layer (PDA coating layer) on the surface of a substrate placed in the environment (sample, in the case of the present invention: medical implant, especially dental implant) by causing oxidation and reduction reactions in the solution by means of a potential applied between a working electrode and a counter electrode in an electrolytic cell.
  • the electrolytic cell is preferably connected to a potentiostat device.
  • the potentiostat device is used to keep the potential between the working electrode and the reference electrode, i.e., the voltage value, constant.
  • the substrate (sample) to be coated is coupled to the electrolytic cell as a "working electrode".
  • Ag/AgCI can be used as the reference electrode and platinum as the counter electrode. Changing the reference electrode causes a change in the numerical values of the results, but does not cause a change in their interpretation. Therefore, different materials can be selected as the reference electrode and the counter electrode.
  • cyclic voltammetry In the present invention, it is possible and preferred to apply cyclic voltammetry (CV) in carrying out the electropolymerization.
  • CV cyclic voltammetry
  • a negative or positive potential is applied to the working electrode over a predetermined range of values.
  • current values are obtained depending on the changing potential value.
  • Monitoring the current values throughout the coating process allows commenting on the progress of the coating process. A decrease observed in the current value indicates that the conductivity of the surface has decreased and the non-conductive polydopamine has been successfully coated on the surface. Therefore, it is possible to precisely monitor the performance of the inventive method.
  • the controllability of the parameters in the electropolymerization method is higher than that of the traditional method of immersion coating.
  • the time required for the electropolymerization coating to take place is shorter than that in the prior art methods. Therefore, the method of the invention is attractive both in terms of accuracy and precision, and in terms of speed-based economic advantage, and it has high industrial applicability.
  • the commercial end products expected to be obtained once the invention is used in the industry may include the following:
  • An exemplary substrate with a conductive surface is selected in preparation for a proper coating process.
  • the surface of the substrate may be subjected a pre-treatment, for example pre-cleaning by washing.
  • the substrate used in this exemplary experiment is a sample made of Ti-6AI-4V-ELI, which is suitable for use in medical and especially dental implants as a sample of conductive surface material.
  • the sample was chosen to be in the form of a disk, due to its flat surface, in order to facilitate the measurement of the contact angle after the coating process.
  • the cleaned substrate in Example 1 was coated by electropolymerization method.
  • the coating process comprises the following: i. immersing the substrate as a working electrode in an electrolyte (coating solution) designed to provide a source of dopamine (monomer); ii. electropolymerization coating of the substrate by applying a voltage to said working electrode in the presence of a reference electrode and a counter electrode immersed in the electrolyte.
  • the source of dopamine (here, dopamine HCI) was chosen as a monomer, thereby obtaining a PDA layer as the polymer layer covering the surface of the substrate.
  • Dopamine HCI is selected as the dopamine source. Accordingly, the electrolyte is designed to:
  • dopamine HCI dopamine HCI
  • TBS tris buffered saline
  • - applied voltage (potential value) ranging from: preferably -2 V to +2 V, more preferably -1 V to +1 V; in this example, a range of -1 V to +1 V is applied;
  • - voltage change rate preferably in the range of 0.02 V/s to 0.5 V/s, for example/preferably 0.1 V/s; in this example, 0.1 V/s was applied;
  • - number of cycles for example, 5 to 100 cycles, for example/preferably 100 cycles; in this example, 100 cycles are applied;
  • - electropolymerization time preferably in the range of 30 minutes to 24 hours.
  • Ag-AgCI was used as the material of the reference electrode and Pt was used as the material of the counter electrode.
  • the electropolymerization coating process was carried out in a triple-mouthed container (balloon) as an electrolytic cell (in terms of having suitable inlets for the reference electrode, counter electrode and anode).
  • the electropolymerization was optionally carried out in/under nitrogen or oxygen (or in/under air being a mixture thereof).
  • the substrate (sample) was removed from the electrolyte (coating solution), rinsed and then dried.
  • the rinsing was optionally carried out in an ultrasonic bath using ultra-pure water for 15 minutes.
  • the drying was optionally carried out in nitrogen environment.
  • Example 2 An image of the contact angle was captured for a substrate surface (a PDA-uncoated Ti- 6AI-4V-ELI disc sample) on which the electropolymerization coating was not applied in Example 2, which is presented in Fig. 1.
  • the contact angle on the uncoated surface was measured as 68.26° (an average of 68.24° and 68.27°), and the hydrophilicity level of said surface was taken as a reference.
  • the contact angle is reduced from 68.26° to 15.81°, and hydrophilicity is increased with the PDA coating.
  • an oxide layer on the surface of the sample that is intended to be coated can be removed.
  • a constant potential was applied for 30 seconds at a voltage of -3V as a pretreatment for the removal of the oxide layer on the surface of the sample (titanium- based disc).
  • a substrate with a high conductive surface was obtained which is suitable for a highly efficient electropolymerization.
  • Example 4 a coating having a similar performance to the results in Example 4 and Example 5 was successfully obtained.
  • the surface of the sample (titanium-based disc) was roughened with a sandblasting material (CaP sand).
  • the titanium disc sample was roughened with the sandblasting material (CaP sand).
  • a substrate is obtained having a high surface area (or surface energy) per unit projected area, suitable for a highly efficient el ectropolymerization .
  • electropolymerization was performed using CV in the context of Example 3. The parameters used are given below:
  • Example 4 a coating having a similar performance to the results in Example 4 and Example 5 was successfully obtained.

Landscapes

  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dermatology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)

Abstract

La présente invention concerne un procédé pour augmenter l'hydrophilicité d'une surface d'un implant intracorporel de matériau conducteur. Le procédé comprend l'étape consistant à revêtir ledit implant d'une couche polymère par électropolymérisation.
EP21769827.3A 2020-12-29 2021-06-14 Implants intracorporels revêtus de polydopamine par un procédé d'électropolymérisation Pending EP4271429A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2020/22312A TR202022312A2 (tr) 2020-12-29 2020-12-29 Elektropolimerizasyon yöntemi ile yüzeyi polidopamin kaplanmış vücut içi implantlar.
PCT/TR2021/050598 WO2022146301A1 (fr) 2020-12-29 2021-06-14 Implants intracorporels revêtus de polydopamine par un procédé d'électropolymérisation

Publications (1)

Publication Number Publication Date
EP4271429A1 true EP4271429A1 (fr) 2023-11-08

Family

ID=77739119

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21769827.3A Pending EP4271429A1 (fr) 2020-12-29 2021-06-14 Implants intracorporels revêtus de polydopamine par un procédé d'électropolymérisation

Country Status (3)

Country Link
EP (1) EP4271429A1 (fr)
TR (1) TR202022312A2 (fr)
WO (1) WO2022146301A1 (fr)

Also Published As

Publication number Publication date
WO2022146301A1 (fr) 2022-07-07
TR202022312A2 (tr) 2022-07-21

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