WO1993021969A1 - Novel bioactive coatings and their preparation and use - Google Patents

Novel bioactive coatings and their preparation and use Download PDF

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Publication number
WO1993021969A1
WO1993021969A1 PCT/FI1993/000163 FI9300163W WO9321969A1 WO 1993021969 A1 WO1993021969 A1 WO 1993021969A1 FI 9300163 W FI9300163 W FI 9300163W WO 9321969 A1 WO9321969 A1 WO 9321969A1
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WO
WIPO (PCT)
Prior art keywords
gel
coating material
substrate
titania
implant
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.)
Ceased
Application number
PCT/FI1993/000163
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English (en)
French (fr)
Inventor
Panjian Li
Ilkka Kangasniemi
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.)
Axidental Oy
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Axidental Oy
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
Priority to US08/302,884 priority Critical patent/US5612049A/en
Priority to EP93908970A priority patent/EP0642362B1/en
Priority to DK93908970T priority patent/DK0642362T3/da
Priority to DE69322779T priority patent/DE69322779T2/de
Priority to CA002118036A priority patent/CA2118036C/en
Priority to AU39547/93A priority patent/AU672198B2/en
Application filed by Axidental Oy filed Critical Axidental Oy
Priority to JP51895693A priority patent/JP3220150B2/ja
Priority to RU94045951/14A priority patent/RU2124329C1/ru
Publication of WO1993021969A1 publication Critical patent/WO1993021969A1/en
Priority to KR1019940703393A priority patent/KR950700764A/ko
Anticipated expiration legal-status Critical
Priority to GR990400489T priority patent/GR3029407T3/el
Ceased legal-status Critical Current

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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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/28—Bones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • 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
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • 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
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389—The prosthesis being coated or covered with a particular material
    • A61F2310/00592—Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
    • A61F2310/00796—Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite
    • 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
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • 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
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606—Coatings
    • 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
    • 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
    • A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction

Definitions

  • This invention relates to novel bone-bonding gel-derived titania-based coatings.
  • the invention also includes processes for the preparation of such coatings and their uses as surgical implants.
  • Titanium and its alloys are extensively used in reconstruction surgery as dental and orthopaedic implants because of their excellent biocompatibility with bone tissue (P.I. Branemark, J. Prosthetic Dent. 50:399-410, 1983; D.I. Bardos, D. Williams (ed). Concise Encyclopedia of Medical & Dental Materials, Pergamon Press, Oxford 1990, pp 360-365; R. van Noort, J. Mater. Sci. 22:3801-3811, 1987). This can be explained by the unique characteristics of titanium-bone interface. The extremely slow growth of titanium oxide was observed during the implantation. The TiOH groups within the hydrated oxide layer were considered to be involved in the events leading to osseointegration of the titanium implants (P. Tengwall & I Lundstr ⁇ m, Clinical Materials 9:115-134, 1992). The calcium and phosphorous groups were identified in the few nanometer thick oxide layer (D. Mcqueen et al. Clinical application of
  • Implants can chemically bond to bone through apatite because bone mineral is hydroxyapatite. These bone-bonding implants could be wholly apatite ceramic or coated with apatite using specific techniques such as plasma spray coating process. Furthermore, apatite can also be used as a bioactive phase in some composites to make them bond to bone (K. Verheyen, Resorbable materials with bone bonding ability, PhD thesis, Leiden University, Holland, 1993). In contrast to those apatite-based materials, bioactive glasses and glass-ceramics develop apatite layer onto their surfaces after implantation within bone tissue (L. L. Hench, Bioceramics: from concept to clinics, J. Am. Ceram. Soc.
  • apatite formation can be evaluated for materials by using a metastable calcium phosphate solution, called a simulated body fluid (SBF, Na ⁇ 142, K + 5.0, Mg 2+ 1.5, Ca 2 2.5, Cl- 148, HC0 3 " 4.2, HP0 4 z_ 1.0 and S0 4 2 " 0.5 in mM) .
  • SBF metastable calcium phosphate solution
  • Theizid has been used in in vitro studies to provide information about the process of bone-like apatite formation on these bioactive glasses and glass ceramics because of its ion concentrations nearly equal to those of human ' blood plasma (T Kokubo et al, J Biomed Mater Res 24, 721-734, 1990).
  • silanol groups SiOH
  • the gel-derived silica has abundant SiOH groups whereas both silica glass and quartz do not have.
  • bioactive glasses prepared by sol-gel process were reported to form apatite faster than the same glasses but prepared through conventional melting methods (R. Li et al, J App Biomater 2:231-239, 1991).
  • FIG. 1 represents scanning electron microscopic (SEM) micrographs showing a) hydroxyapatite formation on the bulk (above) and b) coating (below) of gel-derived titania after they are soaked in SBF.
  • SEM scanning electron microscopic
  • Swedish Patent No. 464911 describes a Ti-gel film produced by treating the titanium surface with hydrogen peroxide under certain conditions. The reaction was considered to alter Ti0 2 into Ti0 4 _ x (OH) ⁇ .
  • the patent claimed such a surface to possess anti-inflammatory properties. The inventors suggested that "such a gel-surface resulting from the reactions in vivo might have something to do with a formation of chemical bonding of the bone to the titanium implants". However, the document did not show any evidence or indication that the treated titanium surface might be bioactive. There is no mention of a Ca,P-layer, which is generally accepted as a prerequisite for the bone bonding to occur. Our experiments clearly demonstrated that a Ca,P- layer forms onto the titania-gel derived coating both in vitro and in vivo, which is a basic difference from the Ti- gel surface described in the Swedish patent.
  • the apatite induction capacity of gel-derived titania could be enhanced by the corporation of, for instance, CaO, P 2 0 5 , Na 2 0 or Si0 2 into the titania. They can be introduced during the process to make titania-based materials. As a matter of fact, the effect of these additive compounds on bone- bonding has been determined for bioactive glasses and glass-ceramics (L.L. Hench: "The compositional dependence of bioactive glasses and glass ceramics", P Vincenzine (ed), Ceramics in substitutive and reconstructive surgery, Amsterdam, Elsevier, 1991, pp. 259-274). Al 2 0 3 , B 2 0 3 M0 and K 2 0 may be added as well. They can remain in the oxide form within the coating or, at least to some extent, release the corresponding ions.
  • a galvanic process can also be considered.
  • Our studies have shown that the gel-like surface formed on a negative titanium pole when two pieces of titanium plates were placed at a distance in a hydroxide solution (Ca(0H) 2 in this case) with a proper Ph value under certain voltage.
  • Figure 3 shows SEM photograph of Ti-gel formed on the negative Ti-pole where SEM-EDX showed the accumulation of Ca and P when soaked in SBF (original magnification: 680x, bar (white) 100 ⁇ m) .
  • This gel was thus capable of attracting Ca and P ions from surrounding calcium phosphate solution.
  • Oxides of Ca, P, Na, Si, Al, B, Mg and K may also be added during the galvanic process to improve the coatings.
  • one object of the invention is a novel gel-derived titania-based coating material having abundant TiOH groups for biomedical application, said coating material being capable of inducing apatite formation onto its surface under in vitro conditions, e.g. in a simulated body fluid, and/or calcium phosphate deposition under in vivo conditions.
  • the coating material can further comprise one or more of the following elements either as ions or as oxides: Ca, P, Si, Na, K, B, Mg and Al. These additives are introduced to enhance calcium phosphate formation and improve the stability of the coating.
  • Another object of the invention is a method for the preparation of a gel-derived titania-based coating material according to a sol-gel method.
  • Another object of the invention is a method for the preparation of a gel-derived titania-based coating material by a galvanic process.
  • the process is carried out in a hydroxide solution where titanium is used as the positive as well as the negative pole.
  • a titania gel surface is formed on the negative pole.
  • Another object of the invention is a method for the preparation of a gel-derived titania-based coating material according to a sol-gel method or the galvanic method wherein one or more of the following oxides are added to the process: CaO, P 2 0 5 , Na 2 0, Si0 2 , K 2 0, Al 2 0 3 B 20 3 and MgO.
  • a further object of the invention is an implant for biomedical application comprising of a substrate and a gel derived titania-based coating material thereon, said coating material being capable of inducing apatite formation onto its surface under in vitro conditions, e.g. in a simulated body fluid, and/or calcium phosphate deposition under in vivo conditions.
  • the substrates are tooth, hip or other joint implant substrates, or other biomedical implant substrates.
  • the substrate is a polymeric, metallic, ceramic, carbon substrate or a composite substrate comprising one or more of said components.
  • the substrate is titanium or a titanium alloy.
  • a further object of the invention is an implant for biomedical application comprising of a substrate and a gel- derived titania-based coating material thereon, said coating material being capable of inducing calcium phosphate formation onto its surface in vitro e.g. in a simulated body fluid and/or in vivo, wherein the coating material further comprises one or more of the following elements either as ions or as oxides: Ca, P, Si, Na, K, B, Mg or Al.
  • the implant comprises a substrate and an apatite layer, said layer having been grown on a gel-derived titania coating in a synthetic solution, preferably a SBF solution.
  • the implant comprises a substrate and a layer being essentially a mixture of gel-derived titania and apatite, said apatite component having been grown on a gel-derived titania coating in a synthetic solution, preferably a SBF solution.
  • a titania gel coating was prepared by a dipping process.
  • a substrate is dipped in a ready-to-use titania sol solution and withdrew at the speed of about 5-50 cm/min.
  • the gel film on the substrate was treated at 350-750°C for 3-30 minutes and then allowed out the oven to cool in air.
  • the coating was given a ultrasonic cleaning in: (a) acetone for 3-10 minutes; (b) ethanol for 3-10 minutes. After that, the coating was rinsed with deionized water and dried.
  • the devices can be repeatedly coated for several time to obtain thicker titania gel coatings.
  • the titania sol solution was prepared by hydrolyzation of tetraisopropyl orthotitanate (Ti(C 3 H 7 0) 4 ) . 5-20 grams of this titanium alkoxide was dissolved into 10-30 grams of absolute ethanol. The hydrolyzation of titanium alkoxide takes place when the above solution is mixed at 0°C with another ready-to-use solution with the composition: absolute ethanol 5-15, ethylenglycolmonoethylether (C 4 H 10 O 2 ) 2-5, H 2 0 0.5-1.5 and condensed HC1 0.5-1.5 in gram. The titania sol solution is then used for coating after its aging for 0.5-30 hours.
  • a bulk titania gel was prepared by evaporating HCl-peptized amorphous titania sol 50 nm in size in an oven at 80°C. The gel was heated at 400-700°C for 2 hours.
  • a silica gel was prepared by hydrolysis of tetrahydroxysilane in an aqueous solution containing polyethylene glycol with average molecular weight of 10,000 and small amount of nitric acid. The organic phase was leached out in ethanol-water solution. The gel was heated at 400°C for 2 hours.
  • An alumina gel was prepared by evaporating HCl-peptized amorphous alumina sol 100 x 10 nm in size in an oven at 80°C. The gel was heated at 450°C for 2 hours.
  • a rectangular piece 6 x 6 x 1.5 mm 3 of the gels was soaked in 12 ml of SBF.
  • the concentrations of Ca and P in the fluid were monitored with inductively coupled plasma (ICP) emission spectroscopy during the soaking.
  • ICP inductively coupled plasma
  • the gel pieces were removed from the fluid and their surfaces were-analyzed with a thin-film X-ray diffraction (TF-XRD), Fourier transform infra-red reflection spectroscopy (IRRS) and scanning electron microscopy (SEM) .
  • TF-XRD thin-film X-ray diffraction
  • IRRS Fourier transform infra-red reflection spectroscopy
  • SEM scanning electron microscopy
  • FIG. 4 shows SEM photographs of the surfaces of the silica gel (top) and titania gel (bottom) soaked in SBF for 2 weeks. It can be seen from Figure 4 that a certain kind of deposition is formed on the surfaces of both silica and titania gel. No deposition was observed on an alumina gel. The deposit on the silica and titania gels was identified as a carbonate-containing hydroxy- apatite of small crystallites and/or defective structure, similar to the apatite in the natural bone, by the TF-XRD and IRRS. It is apparent from the results that both gel- derived silica and gel-derived titania induces apatite formation.
  • a model is produced to explain the apatite induction from physiological-related fluids. It is considered that both silica gel and titania gel are capable of inducing apatite formation due to their abundant OH groups and negatively charged surfaces at physiological pH 7.4. The surfaces with negative charge has high affinity for Ca ions which can be accumulated around the surfaces because of Coulomb's force. Meanwhile, phosphate groups are attracted by abundant OH groups as a result of hydrogen bond. Therefore, both calcium ions and phosphate ionic groups rally around the surfaces and accumulate to such extent that heterogeneous nucleation of apatite occurs.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Cardiology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Molecular Biology (AREA)
  • Materials For Medical Uses (AREA)
  • Medicinal Preparation (AREA)
  • Saccharide Compounds (AREA)
  • Prostheses (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
PCT/FI1993/000163 1992-04-23 1993-04-21 Novel bioactive coatings and their preparation and use Ceased WO1993021969A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
JP51895693A JP3220150B2 (ja) 1992-04-23 1993-04-21 新規の生物活性コーティング並びにそれらの製造及び使用
EP93908970A EP0642362B1 (en) 1992-04-23 1993-04-21 Novel bioactive coatings and their preparation and use
DK93908970T DK0642362T3 (da) 1992-04-23 1993-04-21 Nye bioaktive overtræk og deres fremstilling og anvendelse
DE69322779T DE69322779T2 (de) 1992-04-23 1993-04-21 Neue bioaktive beschichtungen und ihre herstellung und verwendung
CA002118036A CA2118036C (en) 1992-04-23 1993-04-21 Novel bioactive coatings and their preparation and use
US08/302,884 US5612049A (en) 1992-04-23 1993-04-21 Bioactive coatings and their preparation and use
RU94045951/14A RU2124329C1 (ru) 1992-04-23 1993-04-21 Покровный материал и способ его получения (варианты), и имплантат для биомедицинского использования (варианты)
AU39547/93A AU672198B2 (en) 1992-04-23 1993-04-21 Novel bioactive coatings and their preparation and use
KR1019940703393A KR950700764A (ko) 1992-04-23 1994-09-29 신규 생활성 코팅재, 그 제조방법 및 용도
GR990400489T GR3029407T3 (en) 1992-04-23 1999-02-16 Novel bioactive coatings and their preparation and use.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI921802A FI91713C (fi) 1992-04-23 1992-04-23 Uusia bioaktiivisia pinnotteita ja niiden valmistus ja käyttö
FI921802 1992-04-23

Publications (1)

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WO1993021969A1 true WO1993021969A1 (en) 1993-11-11

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PCT/FI1993/000163 Ceased WO1993021969A1 (en) 1992-04-23 1993-04-21 Novel bioactive coatings and their preparation and use

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US (1) US5612049A (enExample)
EP (1) EP0642362B1 (enExample)
JP (1) JP3220150B2 (enExample)
KR (1) KR950700764A (enExample)
AT (1) ATE174803T1 (enExample)
AU (1) AU672198B2 (enExample)
CA (1) CA2118036C (enExample)
DE (1) DE69322779T2 (enExample)
DK (1) DK0642362T3 (enExample)
ES (1) ES2125979T3 (enExample)
FI (1) FI91713C (enExample)
GR (1) GR3029407T3 (enExample)
RU (1) RU2124329C1 (enExample)
WO (1) WO1993021969A1 (enExample)

Cited By (13)

* Cited by examiner, † Cited by third party
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WO1996007438A1 (de) * 1994-09-07 1996-03-14 Dot Dünnschicht- Und Oberflächentechnologie Gmbh Verfahren zur elektroabscheidung von hydroxyapatitschichten
WO1997038729A1 (en) * 1996-04-12 1997-10-23 The Regents Of The University Of Michigan In vivo gene transfer methods for wound healing
AU688101B2 (en) * 1994-08-24 1998-03-05 Max-Delbruck-Centrum Fur Molekulare Medizin Live vaccine for the treatment of tumour diseases
US6143037A (en) * 1996-06-12 2000-11-07 The Regents Of The University Of Michigan Compositions and methods for coating medical devices
US6395253B2 (en) 1998-04-23 2002-05-28 The Regents Of The University Of Michigan Microspheres containing condensed polyanionic bioactive agents and methods for their production
DE10243132A1 (de) * 2002-09-17 2004-04-01 Friedrich-Baur-Beteiligungs-Gmbh Antiinfektiöse, biokompatible Titanoxid-Beschichtungen für Implantate sowie Verfahren zu deren Herstellung
US6770740B1 (en) 1999-07-13 2004-08-03 The Regents Of The University Of Michigan Crosslinked DNA condensate compositions and gene delivery methods
US7112442B2 (en) 1996-11-04 2006-09-26 The Regents Of The University Of Michigan Peptides for gene delivery
WO2007088199A3 (en) * 2006-02-03 2007-09-13 Colorobbia Italiana Spa A process for functionalizing titanium metal surfaces with nanometric particles of titanium and products thus functionalized
WO2008056323A1 (en) * 2006-11-10 2008-05-15 Sandvik Intellectual Property Ab Surgical implant composite materials and kits and methods of manufacture
WO2014204290A1 (es) 2013-06-20 2014-12-24 León Gutiérrez Gabriela Nanomaterial de dióxido de titanio nanoparticulado modificado con grupos funcionales y con extractos cítricos adsorbidos en la superficie para la eliminación de amplio espectro de microorganismos
RU2630578C1 (ru) * 2016-10-31 2017-09-11 федеральное государственное бюджетное образовательное учреждение высшего образования "Пермский национальный исследовательский политехнический университет" Способ модифицирования поверхности титановых имплантатов
RU2687792C1 (ru) * 2018-05-07 2019-05-16 Сергей Вячеславович Купряхин Способ изготовления внутрикостного имплантата

Families Citing this family (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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RU2124329C1 (ru) 1999-01-10
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CA2118036C (en) 2005-02-15
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US5612049A (en) 1997-03-18
DE69322779D1 (de) 1999-02-04
FI921802A0 (fi) 1992-04-23
FI91713B (fi) 1994-04-29

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