Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

• the present disclosure is related to medical device and biomaterial coatings.
• the present disclosure is particularly related to a coating which has a superamphiphobic character providing both superoleophobicity and superhydrophobicity for coating medical device and biomaterial surfaces, is biocompatible as determined in vitro and in vivo, is curable with UV rays and has a unique chemical composition.
• the invention is related to superhydrophobic coatings and particularly to superhydrophobic coatings containing particles which can attach covalently to various surfaces.
• the said invention is a superhydrophobic coating which contains a plurality of particles and a resin. Particles attach to the resin covalently and the resin does not fill up the pores of superhydrophobic particles, thus the three dimensional surface topology of superhydrophobic particles is maintained.
• the invention is related to a method for producing superhydrophobic film and coating from polypropylene plastic, and to a film and coating produced by using this method.
• the method applied to achieve the objectives of this invention essentially consists of the stages of dissolving isotactic polypropylene in a solvent at a certain temperature; pouring this solution onto the material to be coated in a certain temperature range and vaporizing the solution, and drying the coating completely.
• proposed coatings only provides the superhydrophobic character.
• no coating type could be found which provides both superhydrophobic and superoleophobic character at the same time, has a superamphiphobic character and is biocompatible as determined both in vitro and in vivo.
• the present disclosure is related to UV-curable, biocompatible, superamphiphobic coating which meet the aforementioned requirements, eliminate all disadvantages and bring some additional advantages, and synthesis method for such compounds.
• the primary aim of the invention is to provide a coating which has a superamphiphobic character providing both superoleophobicity and superhydrophobicity for coating medical device and biomaterial surfaces, is biocompatible as determined in vitro and in vivo, is curable with UV rays and has a unique chemical composition.
• An aim of the invention is to provide superhydrophobic and superoleophobic character to medical devices and biomaterials through its superamphiphobic character.
• Another aim of the invention is to provide a coating which is curable with UV rays in a very short time for coating medical devices and biomaterials.
• Another aim of the invention is to provide medical devices and biomaterials with biocompatible character thanks to its biocompatible character.
• Another aim of the invention is to prevent adhesion of such biomaterials to be used inside the body as implants to the live tissue, therefore allow them to be placed and removed without causing any damage on the tissue, thus shorten the treatment and recovery period by means of its superamphiphobic character.
• the invention is a UV-curable coating composition providing medical device or biomaterial surfaces with superamphiphobic and biocompatible character, wherein it contains,
• the invention is a method of coating with the mentioned coating composition wherein it consists of the following process steps:
• the invention also includes medical devices or biomaterials coated with the mentioned method.
• Figure 1 shows the angles of contact of unprocessed glass samples (a, b, c); coated glass samples (d, e, f); unprocessed CP-Ti samples (g, h, i); coated CP-Ti samples with water, ethylene glycol and hexadecane, respectively.
• Figure 2 shows FTIR spectrums of the coating prepared for the method of curing with UV.
• Figure 3 shows NMR result of the coating prepared for the method of curing with UV.
• Figure 4 shows XPS spectrums of the coating prepared for the method of curing with UV.
• Figure 5 shows 3D surface profiles of (a) unprocessed titanium, (b) superamphiphobic polymeric film.
• Figure 6 shows (a) 2000X surface morphology of unprocessed CP-Ti, superamphiphobic polymeric structure; (b) 5000X surface morphology of unprocessed CP-Ti, superamphiphobic polymeric structure; (c) sectional SEM views of superamphiphobic polymeric film after UV coating.
• Figure 7 is a graphic showing EDS analysis results of polymeric coated CP-Ti film.
• Figure 8 shows optical light conductivity UV-vis spectrums of unprocessed and superhydrophobic polymeric coated glass material.
• Figure 9 is a graphic showing OCP curve of unprocessed and polymeric coated CP-Ti material.
• Figure 10 is a graphic showing potentiodynamic polarization curve of unprocessed and superamphiphobic polymeric coated CP-Ti material.
• Figure 1 1 shows SEM views of (a) unprocessed CP-Ti, (b) superamphiphobic polymeric coated CP- Ti material after corrosion.
• Figure 12 shows graphics of (a) Nyquist curves (unprocessed and polymeric coating); (b) Bode curves (unprocessed and polymeric coating).
• Figure 13 shows graphics of (a) viability levels observed in 3T3 fibroblast cells at the end of 24 hours of incubation; (b) viability levels observed in 3T3 fibroblast cells at the end of 48 hours of incubation.
• Figure 14 shows A- Unprocessed Glass group - Severe neutrophil leukocyte infiltration ( * ); B- Unprocessed Ti group - Severe fibroblast presence (arrow head); C- Polymeric coated Ti group - Medium level fibroblast presence (arrow head); D- Polymeric coated glass group - Medium level fibroblast presence (arrow head).
• Figure 15 shows A- Unprocessed Glass group; B- Unprocessed Ti group - Low level; C- Polymeric coated Ti group - Low level; D- UV glass group - Low level, Collagen type I presence ( * ).
• Figure 16 shows A- Unprocessed Glass group - Low level; B- Unprocessed Ti group - Medium level; C- Polymeric coated Ti group - Medium level; D-UV glass group - Medium level Collagen type III presence ( * ).
• UV-curable, biocompatible, superamphiphobic coating and its preferred embodiments are described just for a better understanding of the subject matter and in a way not to lead to a limiting effect.
• the invention is related to a coating which has a superamphiphobic character providing both superoleophobicity and superhydrophobicity for coating medical device and biomaterial surfaces, is biocompatible as determined in vitro and in vivo, is curable with UV rays and has a unique chemical composition.
• the term“superhydrophobic” is used herein for being water and dirt proof, removing water and dirt. It is characterized with the angle of contact of the water drop left on the surface with the surface. If the angle of contact measured with water is close to or more than 150 degrees, the surface shows a superhydrophobic character.
• the term“superoleophobic” is used for removing the oil on the surface, being oil proof. If the angle of contact is close to or more than 150 degrees as measured with ethylene glycol on the surfaces, it shows a superoleophobic character as defined in the literature.
• the term “superamphiphobic” means that the surface shows both superhydrophobic and superoleophobic character.
• the coating of the invention shows superamphiphobic character. Thanks to this character of the coating, non-polar body fluids and protein-containing substances do not hold on the biomaterial or medical device coated with the coating of the invention. This situation prevents adhesion to instruments on which the coating of the invention is used. Therefore, if biomaterials and surgical procedures compatible with the coating are chosen, the treatment performance is increased positively and the treatment duration is shortened.
• the coating of the invention and the chemical content produced newly and used in the coating have a completely unique value. Therefore, the coating of the invention shows biocompatibility thanks to its different chemical content. The presence of this character has been proven in vivo and in vitro. It outperforms current polymeric coatings with this aspect.
• Table 1 shows chemical composition of the coating of the invention and their component ratios by weight.
• the coating of the invention contains 25-80 % (w/w) of reactive resin, 8-25 % (w/w) of rigidity agent, I Q- 60 % (w/w) of reactive solvent (cross-linker), and 1 -8 % (w/w) of photo-initiator.
• reactive resin herein is fluorous epoxy acrylate; mentioned rigidity agent is tetraethoxysilane hydrolyzed triethoxy isobutylsilane; mentioned reactive solvent (cross-linker agent) is 1 ,6-hexanediol diacrylate; mentioned photo-initiator is 1 -hydroxycyclohexyl phenyl ketone or trimethylsulfonium hydroxide.
• a preferred embodiment of the invention prepared in the studies made within the scope of the invention contains 54.7 % (w/w) of fluorous epoxy acrylate, 19.5 % (w/w) of hydrolyzed TEOS (tetraethoxysilane), 23.4 % (w/w) of 1 ,6-hexanediol diacrylate, 2.4 % (w/w) of Irgacure184 ® (1 -hydroxycyclohexyl phenyl ketone).
• Fluorous epoxy acrylate is the reactive resin component providing basic characteristics of the coating that is subject of the invention.
• the fluorine component which is included by the fluorous epoxy acrylate enhances amphiphobic character of the film.
• To prepare the fluorous epoxy acrylate 27-30 % (v/v) of 1 H,1 H,2H,2H-perfluorohexane-1 -ol or 1 H,1 H-perfluoroheptane-1 -ol) and 53-55 % (v/v) of hexamethylene diisocyanate or 1 ,4-diisoscyanatebutane are mixed in a magnetic stirrer for about 3-4 hours under nitrogen gas at a temperature of 60-70 O.
• the resu lting mixture is added 15-1 7 % (v/v) of N-N dimethylformamide and stirring is continued until the mixture gets clear.
• the clarified mixture is added epoxy acrylate in a way to obtain a total solid content of 85 % (w/v), and stirred in magnetic stirrer for I Q- 12 hours without heating. At the end of this duration, fluorination is completed and fluorous epoxy acrylate is obtained.
• Hydrolyzed tetraethoxysilane or hydrolyzed triethoxy isobutylsilane form the Silicon component in the coating film of the invention, and increase the rigidity of the coating film.
• TEOS tetraethoxysilane
• Triethoxy isobutylsilane 12-14 % (v/v) of water
• 1 -3 % (w/v) of P-toluenesulfonic acid catalyst
• this mixture is stirred in a magnetic stirrer for 10-12 hours at a temperature of 20-25‘C.
• hydrolysis is completed and hydrolyzed rigidity agent is obtained.
• 1-6 hexanediol diacrylate is the reactive solvent component which increases the cross linking rate of the coating film of the invention, and adjusts such physical characteristics of the film as rigidity, durability and resistance to chemical substances.
• 1-hydroxycyclohexyl phenyl ketone or trimethylsulfonium hydroxide is a photo-initiator which initiates polymerization process of the coating of the invention under UV light at a suitable wavelength and energy.
• the coating solution 25-80 % (w/w) of fluorous epoxy acrylate, 8-25 % (w/w) of hydrolyzed tetraethoxysilane or hydrolyzed triethoxy isobutylsilane, 10-60 % (w/w) of 1 ,6-hexanediol diacrylate, and 1 -8 % (w/w) of 1 -hydroxycyclohexyl phenyl ketone or trimethylsulfonium hydroxide are mixed until a homogeneous mixture is obtained.
• the coating solution prepared was applied on CP-Ti (commercially pure titanium) and glass (borosilicate) samples.
• the coating solution prepared was applied on surfaces to be coated homogeneously by using immersion or spin coating methods. Surfaces coated with the composition were exposed to UV light for 150-3600 seconds, preferably for 180 seconds, in a system equipped with a 350 W mercury lamp with a wavelength of 365 nm, in order to cure the coating. During the curing with UV light source, the samples dipped up in the coating solution were placed about 20 cm away from the light source. Surfaces coated and cured with UV were subjected to heat treatment for post-curing for 1 hour in an oven at 90-100 TT After the post-curing process, coated surfaces were put to rest in a fume hood at room temperature for 10-12 hours.
• Superamphiphobic character of the polymeric film formed on the surface was identified with the angle of contact of fluids formed on the surface.
• Superhydrophobicity of the surface was identified with water, superoleophobicity was identified with ethylene glycol; and the surface energy was measured with OWRK/Fowkes method by identifying the angle of contact of three fluids (water, hexane and ethylene glycol). Results of angles of contact on the obtained surface are shown in the Chart 1 , and their views are shown in Figure 1 .
• Figure 1 shows the angles of contact of unprocessed glass samples (a, b, c); coated glass samples (d, e, f); unprocessed CP-Ti samples (g, h, i); coated CP-Ti samples with water, ethylene glycol and hexadecane, respectively. Static angle of contact measurements were taken from“Attension Theta Lite tensiometer” device.
• Figure 2 shows FTIR spectrums of the coating composition prepared for the method of curing with UV. FTIR analysis was made with Thermo Scientific (Nicolet 6700) FT-IR spectrometer. Figure 2 shows FTIR spectrums of the coating solution prepared for the method of curing with UV. The lack of spectrum peak at 1730-2800 crrr 1 shows that the first stage of the solution has been synthesized with the loss of the peak of isocyanate groups(-NCO).
• Figure 3 shows NMR result of the coating composition prepared for the method of curing with UV. It was measured by using Nuclear Magnetic Resonance (NMR) Spectroscopy.
• NMR Nuclear Magnetic Resonance
• H-NMR Spectrum was performed particularly to observe the addition of flour and silicon to the structure.
• Figure 4 shows XPS spectrums of the coating composition prepared for the method of curing with UV.
• Specs-Flex was taken from X-Ray Photoelectron Spectroscopy (XPS) device.
• Percentage ratios of elements contained in the structure were revealed when the results of X-Ray Photoelectron Spectroscopy (XPS) analysis were evaluated. As a result of the XPS analysis made, peak values of carbon, oxygen, fluorine and silicon elements were identified. Accordingly, percentage amounts of silicon which increases the rigidity of the coating material obtained and fluorine which gives superhydrophobicity in the composition were revealed. Accordingly, it was determined that the structure comprises approximately 69% of carbon, 16% of oxygen, 1 1 % fluorine and 5% silicon. Thus, the presence of silicon and fluorine in the structure has been confirmed.
• XPS X-Ray Photoelectron Spectroscopy
• Roughness of unprocessed CP-Ti and superamphiphobic coated surface was measured with a 3D profilometer.
• Figure 5 shows 3D surface profiles of unprocessed titanium and (b) superamphiphobic polymeric film-coated titanium surface. Roughness of surface was measured by using a Bruker Contour GT-K profilometer device. When the said surface profiles are examined, it is observed that the roughness of surface increased after the coating.
• Figure 6 shows (a) 2000X surface morphology of unprocessed CP-Ti, superamphiphobic polymeric structure; (b) 5000X surface morphology of unprocessed CP-Ti, superamphiphobic polymeric structure; (c) sectional SEM views of superamphiphobic polymeric film after UV coating. SEM images was obtained from SEM FEI Quanta 250 device.
• the roughness of surface was increased in order to enhance superhydrophobic and superoleophobic character of surfaces.
• There are micro grooves inside the surface whose surface roughness is increased, and entrained air in mentioned grooves.
• the fluid cannot enter in due to surface tension. Since the surface area contacting with the fluid is small, the affinity between the fluid and the solid surface decreases. Therefore, micro grooves on the surface also shows the superhydrophobicity on the surface. From the image obtained, it is observed that the gaps between particles are quite intense compared with the unprocessed sample.
• the cross-section images are examined, it is seen that a continuous and significant layer is formed on the surface.
• the diffusion layer is seen under the compound layer. It was observed that the thickness of the layer formed on the surface after the coating is between 3- 4 pm.
• FIG. 7 shows EDS analysis results of the film obtained after the coating. Elemental composition of the film was made in EDS, FEI Quanta 250 device. EDS results shows that C, O, F, Si and N, which were expected to form on the film, formed on the coating layer. According to the results shown in Chart 2, polymeric coating components were determined as titanium (56.27%), oxygen (23.31 %), carbon (1 1 .16%), fluorine (3.7%) and silicon (3.29%), nitrogen (2.28%).
• Figure 8 shows UV-vis spectrums of thin film formed on glass plates with the method technique of curing with UV rays. They were taken with a Shimadzu brand UV-3600 model UV-VIS-NIR Spectrometer. The mean permeability of superhydrophobic glass material is about 95% in the rage of 562-940 nm. UV-VIS-
• Electrochemical development was analyzed under conditions simulating biological interaction of samples with human body. For this purpose, measurements were made on unprocessed CP-Ti and coated CP-Ti0 samples with SBF (simulated body fluid) at 37 ⁇ .
• SBF simulated body fluid
• Figure 9 shows the OCP curve of unprocessed and polymeric CP-Ti material. OCP measurements were made on Series G750TM Potentiostat/Galvanostat/ZRA device from GAMRY firm. OCP analysis is important to determine when the system has become stabilized, and when the shifts between different situations such as passive and active behavior will occur.
• Figure 9 shows OCP curves of unprocessed5 and UV-coated CP-Ti samples by keeping them under open grid conditions for 7200 seconds in SBF (simulated body fluid) in order to identify balance potentials of samples. Open circuit potential (OCP) values are more positive means the material is more resistant to corrosion. It is observed from the graphic that the OCP curve obtained from polymeric coated sample with superhydrophobic and superoleophobic character has a superior character compared to unprocessed sample.
• SBF simulated body fluid
• FIG. 10 shows potentiodynamic polarization curves of (a) unprocessed and (b) superamphiphobic polymeric coated CP-Ti samples, and Chart 4 shows the results. Potentiodynamic polarization measurements were made on Series G750TM Potentiostat/Galvanostat/ZRA device from GAMRY firm. After the polymeric coating, the corrosion potential of polymeric coated sample changed positively compared to the unprocessed sample, and the anodic part of the curve reached a lower current density.5 Examining the results obtained, after the corrosion applied in SBF electrolyte, corrosion current density of polymeric coated sample decreased to unprocessed sample.
• the corrosion potential (Ecorr) value of unprocessed CP-Ti is -335 mV/Ag/AgCI, and its corrosion current density (lcorr) value is 1 .43e-4 mA/cm 2 .
• the corrosion current value of polymeric coated CP-Ti is 1 .05e-5 mA/cm 2 .
• Polymeric coating on metal surfaces acts as a barrier, and thus, provides an anodic protection for the metal.
• FIG. 1 shows SEM views of (a) unprocessed CP-Ti, (b) superamphiphobic polymeric coated CP-Ti material after corrosion. SEM images was obtained from SEM, FEI Quanta 250 device. Examining SEM images after corrosion, it is seen that the corrosion damage forming on the surface of unprocessed CP-Ti sample is a damage of well-type. It is observed from these images that, on UV-cured polymeric film, the wells disappear compared to the unprocessed sample, and that corrosion occurs only locally.
• Figure 12 shows Nyquist and Bode Curves of the coating film (taken from Series G750TM Potentiostat/Galvanostat/ZRA device from GAMRY), and Chart 5 shows EIS results.
• the phase angle of unprocessed sample is unstable.
• the polymeric coated sample these values are quite stable.
• the highest phase angle for polymeric coated sample in this region is -44°.
• T his shows that a protective and preventive passive film layer forms on the coated sample.
• impedance values of the coated sample are higher than the values of unprocessed sample. The passive film on the coated sample causes to obtain higher impedance data.
• viability values in control-, control+, polymeric coated metal, polymeric coated glass, unprocessed glass, unprocessed metal and mouse fibroblast cells treated for 24 hours were identified as 100, 18.3, 97.2, 79.2, 96.1 , 93.7, and 88.2%, respectively, in MTT test, and 100, 28.4, 98.7, 98.9, 99.6, 97.5, and 96.5% in LDH test.
• Figure 13 shows cytotoxicity test results with graphics of (a) viability levels observed in 3T3 fibroblast cells at the end of 24 hours of incubation; (b) viability levels observed in 3T3 fibroblast cells at the end of 48 hours of incubation. Viability levels in mouse fibroblast cells treated for 24 hours were read at 450 nm wavelengths in plate spectrometer according to MTT and LDFI tests and absorbance values were obtained, and % viability and cytotoxicity values were calculated with formulas and finally, graphics were created in Excel format.
• In vivo material and method At first, the hair was removed on the area from under the knee up to the thigh of each anesthetized animal, and the application area was sterilized by dying the extremities with liquid povidone iodine (Poviodeks, Kim-Pa, Istanbul, Turkey). After the completion of anesthesia protocol, an incision of about 2 cm width was made on the anterior face of the femur on the rear left legs of each subject. After subcutaneous fascia is retracted, musculus biceps femoris muscle (thigh rear site muscle) was revealed. After a pocket was created with a width in which the implant can fit in the muscle fascia, the implants were placed.
• Necropsy examination was made on the rats after the euthanasia, and implants were removed. Surrounding tissues contacting the implant were taken into a 10% buffered formalin solution. Collected samples were then in embed paraffin blocks after immersed routine alcohol- xylol series. 5 pm sections taken from the blocks were examined with hematoxylene-eosine. The evaluation was made according to the modification of the method used by Lehle et al. (2004). For this purpose, activities such as the neutrophil leukocyte, fibroblast presence, and fibrous capsule formation were evaluated as none (0), low (1 ), medium (2) and severe (3).
• Immunohistochemical examinations After the paraffin on 5 pm sections taken to polylysine slides was removed letting them in the oven for 1 hour, the preparations were passed through xylol and alcohol series. After keeping them in distilled water for 5 minutes, the sections were kept in 3% FI2O2 for 10 min. to ensure endogenous peroxidase inactivation, and then washed with PBS 2 times. They were treated with antigen retrieval solution for 2 x 5 min. at 500 Watt and washed with PBS 3 times in order to reveal the antigen in tissues. In order to prevent non-specific bonding, tissues were contoured with a PAP pen and protein block was dropped on them, and after a waiting duration of 10 min., they were washed with PBS 1 time.
• biotinylated secondary and HRP conjugate were dropped on tissues washed 3 times with PBS respectively, and tissues were left to rest for 15 min.
• DAB 3,3 diaminobenzidine
• SPSS program ver. 16.0 was used in the statistical evaluation.
• the difference between groups was identified with Kruskal Wallis test, and the groups creating the difference were identified with Mann Whitney U test. p ⁇ 0.05 value was considered statistically significant.
• Chart 6 shows neutrophil leukocyte, fibroblast activity and fibrous capsule formation of unprocessed glass, Polymeric coated Ti and Polymeric coated glass samples. Statistical difference was identified between groups (p ⁇ 0.05). It was determined that the neutrophil leukocyte presence was strongest in the unprocessed glass group, and the weakest in polymeric coated Ti group.
• Figure 14 shows A- unprocessed glass group - severe neutrophil leukocyte infiltration ( * ); B- unprocessed Ti group - severe fibroblast presence (arrow head); C- polymeric coated Ti group - medium level fibroblast presence (arrow head); D- polymeric coated glass group - medium level fibroblast presence (arrow head). images were taken from DP72 model Olympus BX52 model light microscope with camera.
• fibroblast activity was strongest in the unprocessed Ti group, and the weakest in polymeric coated Ti group. Whereas 4 of the samples in the unprocessed glass group showed fibroblast activity, 2 of them did not show any fibroblast activity. In the unprocessed Ti group, 4 samples showed severe level, and 1 sample showed medium level fibroblast activity. Fibroblast activity was determined at medium level in all the samples in the polymeric coated Ti group, at medium level in 4 samples in the polymeric coated glass group, and at severe level in 1 sample. It was determined that the unprocessed glass group and polymeric coated Ti group were different than other groups, and the Unprocessed Ti group was different than all the other groups. No statistically significant difference was identified between polymeric coated Ti and polymeric coated glass groups (p ⁇ 0.05).
• Chart 7 shows collagen type I and collagen type III density of Unprocessed glass, Polymeric coated Ti and Polymeric coated glass samples. Collagen type I in fibrous tissue was the highest in polymeric coated Ti.
• Collagen type III in fibrous tissue was the highest in polymeric coated Ti. It was determined that 3 of 4 samples in this group had a severe level of collagen type III. A medium level of collagen type III was observed in unprocessed Ti, polymeric coated Ti, polymeric coated glass groups (p > 0.05).
• collagen type I presence is obtained low in A- Unprocessed Glass group and B- Unprocessed Ti group; low in C- Polymeric coated Ti group and low in D- UV glass group ( * ).
• images were taken from DP72 model Olympus BX52 model light microscope with camera.
• Figure 16 shows that the level of Collagen type III presence is low in in A- Unprocessed Glass group, medium in B- Unprocessed Ti group; medium in C- Polymeric coated Ti group and medium in D- UV glass group ( * ). images were taken from DP72 model Olympus BX52 model light microscope with camera.
• Collagen type I in fibrous tissue was the highest in polymeric coated Ti. It was determined that 5 of 6 samples in this group had a medium level of collagen type I. A low level of collagen type I was observed in unprocessed Ti, polymeric coated Ti, polymeric coated glass groups. It was determined that 3 of 6 samples in unprocessed glass group had a low level of collagen type I, whereas no collagen saving was determined in the other 3 samples ( Figure 15).
• Collagen type III in fibrous tissue was the highest in polymeric coated Ti. It was determined that 5 of 6 samples in this group had a severe level of collagen type III. A medium level of collagen type III was observed in unprocessed Ti, polymeric coated Ti, polymeric coated glass groups. It was determined that 3 of 6 samples in unprocessed glass group had a low level of collagen type III, whereas no collagen savingwas determined in the remaining samples (p ⁇ 0.05) ( Figure 16).
• the coating of the invention shows superhydrophobicity and superoleophobicity at the same time, in other words it is superamphiphobic.
• the coating is obtained in a very short time with UV rays. Biocompatibility properties of the coating film obtained were determined both in vitro and in vitro envoriment. In applications in which a short-term implant treatment is required and the implant is not permanent, an instrument having such a surface characteristic (superamphiphobic) will be separated from the tissue easily. Adhesion during the removal of the implant is at a minimum level compared to uncoated implants.

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