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WO2010052190A2 - Pansements pour plaie - Google Patents

Pansements pour plaie Download PDF

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Publication number
WO2010052190A2
WO2010052190A2 PCT/EP2009/064465 EP2009064465W WO2010052190A2 WO 2010052190 A2 WO2010052190 A2 WO 2010052190A2 EP 2009064465 W EP2009064465 W EP 2009064465W WO 2010052190 A2 WO2010052190 A2 WO 2010052190A2
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WO
WIPO (PCT)
Prior art keywords
wound dressing
metal oxide
oxide layer
titanium oxide
wound
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/EP2009/064465
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English (en)
Other versions
WO2010052190A3 (fr
Inventor
Staale Petter Lyngstadaas
Håvard Jostein HAUGEN
Sébastien Francis Michel TAXT-LAMOLLE
Ola Nilsen
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Universitetet i Oslo
Original Assignee
Universitetet i Oslo
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Publication date
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Publication of WO2010052190A2 publication Critical patent/WO2010052190A2/fr
Publication of WO2010052190A3 publication Critical patent/WO2010052190A3/fr
Anticipated expiration legal-status Critical
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
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic 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
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing 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
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • 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
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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

Definitions

  • the present invention relates to the field of wound dressings, such as textiles and fabrics More particularly, the present invention relates to photocatalytic wound dressings having anti-microbial, anti-viral, anti-fouling, and/or immunomodulatory effects
  • Modern wound dressings include gauzes (which may be impregnated with an agent designed to help sterility or to speed healing), films, gels, foams, hydrocolloids, alginates, hydrogels and polysaccharide pastes, granules and beads
  • Materials typically used are polymer-based, such as polyamides, silicones, high density polyethylene, polyester, polypropylene, polyurethane, polysulphone
  • a dressing can have a number of purposes, depending on the type, severity and position of the wound, although all purposes are focused towards promoting recovery and preventing further harm from the wound Key purposes of wound dressings are
  • Part 5 is the current problem in wound healing today
  • the microbiology of most wound types is complex, involving both aerobic and anaerobic bacteria (Gilchristet al, The British journal of dermatology, 121 , (1989) 337-44, Mousa, The Journal of hospital infection, 37, (1997) 317-23, Bowler et al, The Journal of burn care & rehabilitation, 25, (2004) 192-6) and these organisms can create a potential problem to both the wound in which they reside ( ⁇ e autoinfection) and the surrounding environment (cross-contamination)
  • This is in particularly relevant to patients with wounds that has (1) increasing signs of bacterial influence, (2) increasing odour, pain or exudates, (3) redness, (4) signs of pseudomonas, (5) oedema, (6) the healing which does not progress normally and/or (7) increased skin temperature.
  • topical antimicrobial agents One of the key approaches for minimising the likelihood of serious wound infections is the use of topical antimicrobial agents.
  • the purpose of these antimicrobial agents is to reduce the microbial load (bioburden) in wounds, and hence the opportunity for infection.
  • these have involved (Bowler, Jones, The Journal of burn care & rehabilitation, 25, (2004) 192-6) the use of broad spectrum antiseptic agents (e.g. iodine and silver) and antibiotics (e.g. neomycin, bacitracin and polymyxin combinations).
  • broad spectrum antiseptic agents e.g. iodine and silver
  • antibiotics e.g. neomycin, bacitracin and polymyxin combinations.
  • the silver ion is the most commonly used topical antimicrobial agents used in Burn Wound Care in the Western World.
  • TiO 2 , titanium (IV) oxide or titania is the naturally formed oxide of titanium and a very well- known and well-researched material due to the stability of its chemical structure, its biocompatibility, and physical, optical and electrical properties.
  • Titanium dioxide occurs in nature as the well-known naturally occurring minerals rutile, anatase and brookite.
  • Zinc oxide and titanium dioxide, particularly in the anatase form, are photocatalysts under ultraviolet light (UV). This has been discussed for example in Maness et al., 1999 (Applied and Environmental Microbiology, Sep 1999, p.4094-4098).
  • titanium dioxide when doped with nitrogen ions or with metal oxide like wolfram trioxide, is also a photocatalyst under visible light.
  • the strong oxidative potential of the positive holes oxidizes water to create hydroxyl radicals. It can also oxidize oxygen or organic materials directly.
  • free radicals actively modulate immune responses, activate macrophages and stimulate the healing process.
  • Atomic Layer Deposition is a technique that deposits films by one atomic layer at a time, allowing process control to achieve ultra thin films.
  • ALD Atomic Layer Deposition
  • reactants are introduced one at a time, with pump/purge cycles in between.
  • ALD reactions are self-saturating surface reactions, limited only to a single layer on the exposed surface to result in a 100% conformal film. Sequential cycles of these reactions enable thickness to be controlled very precisely even at the sub-nanometer level.
  • Aarik et al. discloses the deposition of films Of TiO 2 by the use of ALD technology, wherein the layers produced are between 2 to 560 nm. The films are however deposited on solid surfaces.
  • a layer of titanium oxide onto pliant material such as in US 5,545,886 wherein it is described antimicrobial coatings and powders and a method of forming the same on medical devices
  • the coatings are formed by depositing an antimicrobial biocompatible metal by vapour deposition techniques to produce atomic disorder in the coating so that a sustained release of metal ions sufficient to produce an antimicrobial effect is achieved
  • the coating is formed as a thin film on at least a part of the surface of the medical device, having a thickness which is no greater than needed to provide release of the metal ions Typically a thickness of less than 1 micron has been found to provide sufficient sustained anti-microbial activity
  • Yuranova et al Journal of Molecular Analysis A Chemical 244 (2006) 160- 167) who disclose T ⁇ O 2 -SiO 2 -coated cotton textiles, wherein the thickness of the layers was detected to 20-30 nm
  • WO01 /80920 discloses bioabsorbable materials with antimicrobial coatings or powders which provide an effective and sustainable antimicrobial effect
  • the antimicrobial coating is preferably less than 900 nm or more preferably less than 500 nm
  • the coating or powder of the one or more antimicrobial metals is formed by either physical vapour deposition under specified conditions and/or by forming of the antimicrobial material as a composite material, or by cold working the antimicrobial material containing the antimicrobial metal at conditions which retain the atomic disorder
  • US2008/01 19098 it is disclosed a method for depositing an encapsulation layer onto a surface of polymeric fibers and ballistic resistant fabrics, by using ALD technology These materials are particularly useful for the formation of flexible, soft armour articles, including garments such as vests, pants, hats or other articles of clothings
  • the encapsulation layers are described as a composition of one or more monolayers of the deposited material onto the surface on the fabric which includes various metals and metal oxides as well as other materials
  • the materials described in US2008/011098 are not suitable for medical use
  • said proposed invention solves the problems stated in the above, by providing a wound dressing consisting of one or several coated sol ⁇ d(s), pliant mate ⁇ al(s), said coat ⁇ ng(s) comprising a homogenous and substantially amorphous metal oxide layer comprising predominantly titanium oxide and having a thickness of 200 nm or less
  • said metal oxide layer additionally comprises one or more compounds selected from the group consisting of N, C, S, Cl, and/or one or more compounds selected from the group consisting of Cl and N, and/or one or more compounds selected from the group consisting of Ag, Au, Pd, Pt, Fe, Cl, F, Pb, Zn, Zr, B, Br, Si, Cr, Hg, Sr, Cu, I, Sn, Ta, V, W, Co, Mg, Mn and Cd and/or one or more compounds selected from the group consisting of SnO 2 , CaSnO 3 , FeGaO 3 , BaZrO 3 , ZnO, Nb 2 O 5
  • Some of the above mentioned compounds improve the photocatalytic properties of said metal oxide layer, thereby enhancing the anti-microbiological properties thereof Furthermore, the addition of one or more of the compounds C, S, N and/or Cl to said metal oxide layer makes it possible to change the wavelength at which the metal oxide layer absorbs light, increasing the amount of sources of light which can be used for activating the photocatalytic properties of this layer Other of the above mentioned compounds in themselves provide an antimicrobial effect
  • the invention relates to a wound dressing, wherein said metal oxide layer by being photocatalytic provides anti-microbiological and/or immunomodulatory properties to said wound dressing
  • the present invention relates to a method for reactivating and/or boosting the photocatalytic properties of the wound dressing as disclosed herein, by applying photoactivation with sufficient energy light to said metal oxide layer of said solid, pliant material
  • the present invention relates to a method for producing a wound dressing as disclosed herein comprising improved photocatalytic and anti-microbiological properties, said method comprising the steps of selecting a solid, pliant material, adding said metal oxide layer onto said solid, pliant material, and optionally simultaneously adding one or more compound(s) as defined herein to said metal oxide layer, said one or more compound(s) being dispersed substantially homogenous within said metal oxide layer
  • the method for producing the wound dressing comprises using ALD technology
  • ALD technology The fact that this metal oxide covered solid pliant material is produced by using ALD technology, renders it possible to produce wound dressings comprising thin layers of titanium oxide on their overall surface Wound dressings comprising such homogenous and substantially amorphous layers of titanium oxide generated by using ALD technology has not previously been possible to produce with the techniques available in the art today Furthermore, these layers have been shown to be durable and not to break and flake off during a state-of-the-art use
  • the present invention relates to a method of treating a patient suffering from a wound injury comprising providing said patient with a wound dressing as disclosed herein BRIEF DESCRIPTION OF THE DRAWINGS
  • solid, pliant material refers to a flexible and bendable material In some aspects it may also be considered a soft material, even though it in most instances may be slightly rigid in its texture Hence, the solid, “pliant” material covers all materials from a "soft" material, such as cotton, up to a more robust material, such as a textile
  • the material may hence be a textile or a fabric, and of varying thickness depending on the intended use Examples of solid pliant materials which may be used in the context of the present invention are provided herein, but the invention is not limited thereto
  • wound dressing in the present context is meant a coated solid, pliant material as disclosed herein that is to be placed on a wound or an injured surface on an exterior part of a body in order to protect the wound or the injured surface during healing as well as improve wound healing.
  • coated or “coating” is meant that a homogenous and substantially amorphous layer of metal oxide comprising predominantly titanium oxide is placed, added or attached to, e.g. by using ALD technology as described herein, on a solid pliant material.
  • ALD technology is a self-limiting, sequential surface chemistry method that deposits conformal thin-films of materials onto substrates of varying compositions.
  • ALD film growth is self-limited and based on surface reactions, which makes achieving atomic scale deposition control possible.
  • atomic layer control of film grown can be obtained as fine as ⁇ 0.1 angstroms per monolayer.
  • ALD grown films are conformal, pinhole free, and chemically bonded to the substrate. With ALD it is possible to deposit coatings perfectly uniform in thickness inside deep trenches, porous media and around particles.
  • the film thickness range provided by the ALD technology is usually 1-500 nm.
  • a substantially lower temperature than usual is used, typically in the range of lower than 300 0 C, such as lower than 275, 250, 220, 200, 175, 150, 125, 100, 90, 80, 70, 60, 50, 40, 30 or 2O 0 C.
  • homogenous which in the present context is used to describe the characteristics of the metal oxide layer on the solid pliant material comprising the titanium oxide, refers to a layer which is substantially uniform and even in its structure meaning that it has a thickness which is nearly constant over the whole layer which covers the solid pliant material. Of course there is always some variation in the structure of the layer, even though it may be described as homogenous.
  • amorphous when discussed in the context of the metal oxide layer comprising titanium oxide, optionally in combination with one or more compounds, is meant to indicate that the relation of the atoms to each other is random, and stands interchangeably with non-crystalline atom structure.
  • a substantially amorphous metal oxide layer means that at least 50% of the atoms are present in a non-crystalline form, such as at least 51 , 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, 99 or 100% of the atoms.
  • metal oxide layer comprising predominantly titanium oxide and the like used herein, "predominantly” refers to that the metal oxide layer comprises 50% or more of titanium oxide
  • immunomodulatory refers to the ability to suppress and/or stimulate an immune response in a subject, such as a human being
  • antimicrobial refers to the ability to repress and/or prevent the growth of a microorganism in or on a subject
  • present term may also refer to the killing of the microorganism
  • titanium oxide provides antimicrobial effects by the production of free radicals, which are released after photoactivation, helping in fending off microbes and relieve inflammation This is particularly useful when the titanium oxide is present on a wound dressing
  • microorganisms are bacteria, viruses and fungi
  • photocatalytic refers to the ability to absorb light energy and generate reactive oxygen species that can act as oxidants
  • a photocatalytic layer comprises material which possesses these abilities
  • An example of a photocatalytic material is titanium oxide
  • the photocatalytic function of a material may aid in preventing that microbial material attach to said material due to the activity of the reactive oxygen species
  • Biological "fouling” is the undesirable accumulation of microorganisms, plants, algae, and animals on structures Hence, “anti-fouling” is the process of removing the accumulation, or preventing its accumulation, which in the present context is prevented or inhibited on the wound dressing by the presence of a titanium oxide layer thereon
  • a wound is a type of injury in which skin e g is torn, cut or punctured (an open wound), or where blunt force trauma causes a contusion (a closed wound)
  • skin e g is torn, cut or punctured (an open wound), or where blunt force trauma causes a contusion (a closed wound)
  • blunt force trauma causes a contusion (a closed wound)
  • pathology it specifically refers to a sharp injury which damages the dermis of the skin A wound is subject to infection and therefore must be protected
  • TiO oxide in the present context covers e g TiO, Ti 2 O 3 , Ti 3 O 5 , and TiO 2 DETAILED DESCRIPTION OF THE INVENTION
  • the present invention relates to a wound dressing with improved photocatalytic properties, which is produced by depositing a coating comprising a homogenous and substantially amorphous metal oxide layer comprising predominantly titanium oxide on a solid pliant material, preferably with the aid of an Atomic Layer Deposition (ALD) technique
  • ALD Atomic Layer Deposition
  • the metal oxide layer provided on the solid pliant material has a thickness which is about 200 nm or less, preferably about 100 nm, and even more preferably about 50 nm or less, and which is homogenous and substantially amorphous This has the advantage that break and/or flake off of the metal oxide layer from the solid pliant material is avoided
  • the coating of metal oxide layer comprising predominantly titanium oxide forming a part of said wound dressing provides anti-microbial, anti-viral, anti-fouling and/or immunomodulatory effects thereto, due to the photocatalytic effects provided by the metal oxide layer These properties may be enhanced even more by the addition of further compounds having such effects as described in more detail later
  • the present invention relates to a wound dressing consisting of a coated solid, pliant material, said coating comprising a homogenous and substantially amorphous metal oxide layer comprising predominantly titanium oxide and having a thickness of about 200 nm or less
  • the thickness of said metal oxide layer is about 100 nm or less, such as about 100, 90, 80, 70, 60, 50, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 5 or 2 nm or less
  • the metal oxide layer has a thickness of between 0 04-200, 0 04-100, 0 04-50, 0 04-40, 0 04-25, 0 04-20, 0 04-15, 0 04-10, 0 04-5, 0 5-50, 0 5-25, 0 5-20, 0 5-15, 0 5-10, 0 5-5, 1 -5, 1-10, 1-15, 1-20, or 1- 25 nm, such as 0 5, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11
  • the solid, pliant material forming part of the wound dressing is selected from the group consisting of polyurethane (PUR, TPU, PCU), polyamid, (PA), polyether, polyethylene, (PE), polyester, polypropylene, (PP), poly(tetrafluoroethylene) (PTFE), silicones, cellulose, silk and cotton
  • PUR polyurethane
  • PCU polyamid,
  • PA polyether
  • PE polyethylene
  • PP polypropylene
  • PTFE poly(tetrafluoroethylene)
  • silicones cellulose, silk and cotton
  • the thickness of said metal oxide layer of said wound dressing is less than about 20 nm
  • the thickness of said metal oxide layer is less than about 10 nm
  • the thickness of said metal layer is less than about 5 nm
  • the metal oxide layer has a thickness which is less than about 2 nm
  • said titanium oxide may be selected from the group consisting of TiO, Ti 2 O 3 , Ti 3 O 5 , and TiO 2
  • the thickness of a metal oxide layer comprising predominantly titanium oxide, optionally in combination with one or more compounds as defined herein, on a solid, pliant material according to the present invention is defined by a thickness which is such that it prevents that the metal oxide layer breaks and/or flakes off from the solid, pliant material during slight bending and/or normal use thereof This means for example that the wound dressing should be possible to wear while at the same time also allowing for slight bending of the material without risking that the metal oxide layer is shed off which could cause severe discomfort and that the wound will not heal properly
  • the coated layer of the wound dressing comprises at least 60% titanium oxide, such as at least 65, 70, 75, 80, 85, 90, 95 or 99% titanium oxide
  • the metal oxide layer comprising titanium oxide is amorphous, but occasionally, a minor percentage of the titanium oxides can be present in an anatase form, such as 49, 46, 40, 35, 30, 25, 20, 15, 10, 7, 5, 3, 1 or 0%
  • a metal oxide layer comprising predominantly titanium oxide on the wound dressing generates the possibility to reactivate the anti-microbial, anti-fouling, anti- viral and/or immunomodulatory activities of the wound dressing by simple photoactivation
  • This has the advantage of making it possible to do prolonged local wound care without replacing the dressing every second day as is the general rule today Thereby the wound is left undisturbed for healing for much longer times than has previously been possible
  • the here disclosed technology makes use of free radicals, released from the metal oxides after photoactivation, to fend off microbes and relieve inflammation This reduces the need for antibiotic treatment and thus reduces the risk for development of antibiotic resistant infections.
  • these oxides are promising materials for developing the next generation, bioactive wound dressings.
  • the present invention relates to a wound dressing, wherein said metal oxide layer of said coating additionally comprises one or more compound(s) selected from the group consisting of N, C, S, Cl, and/or one or more compounds selected from the group consisting of Cl and N, and/or one or more compounds selected from the group consisting of Ag, Au, Pd, Pt, Fe, Cl, F, Pb, Zn, Zr, B, Si, Br, Cr, Hg, Sr, Cu, I, Sn, Ta, W, V, Co, Mg, Mn and Cd and/or one or more compounds selected from the group consisting of SnO 2 , CaSnO 3 , FeGaO 3 , BaZrO 3 , ZnO, Nb 2 O 5 , CdS, ZnO 2 , SrBi 2 O 5 , BiAIVO 7 , ZnInS 4 , K6Nb 1O 8O3 o, and/or a combination of compounds selected from said groups of compounds, wherein
  • the addition to the metal oxide layer of one or more of the compounds selected from the group consisting of C, S, N and Cl has the effect that the photocatalytic properties of the metal oxide layer comprising predominantly titanium oxide may be varied.
  • these compounds have the ability of changing the wavelength at which the light is absorbed by the metal oxide layer, allowing for different light sources to be used in the activation and/or boosting of the photocatalytic properties of the metal oxide layer of the wound dressing.
  • not only UV light, but also visible light can be used for this purpose.
  • a subject having the wound dressing does not necessarily have to be exposed to light of high energy, such as UV-light, which may be harmful to the subject.
  • the group consisting of Cl and N as well as the group of inorganic compounds consisting Of SnO 2 , CaSnO 3 , FeGaO 3 , BaZrO 3 , ZnO, Nb 2 O 5 , CdS, ZnO 2 , SrBi 2 O 5 , BiAIVO 7 , ZnInS 4 , K6Nb 1O so3o, provides enhanced photocatalytic properties to the wound dressing material.
  • the metal oxide layer comprising predominantly titanium oxide of the wound dressing according to the present invention comprises about 100% titanium oxide
  • the proportion of titanium oxide present in said metal oxide layer when combined with one or more compounds selected from the group consisting of N, C, S, Cl, and/or one or more compounds selected from the group consisting of Cl and N, and/or one or more compounds selected from the group consisting of Ag, Au, Pd, Pt, Fe, Cl 1 F, Pb, Zn, Zr, B, Br, Cr, Si, Hg, Sr, Cu, I 1 Sn, Ta, W, V, Co, Mg, Mn and Cd, or an oxide thereof and/or one or more compounds selected from the group consisting of SnO 2 , CaSnO 3 , FeGaO 3 , BaZrO 3 , ZnO, Nb 2 O 5 , CdS, ZnO 2 , SrBi 2 O 5 , BiAIVO 7 , ZnInS 4 ,
  • K6Nb 1O 8O3 o, and/or a combination of compounds selected from said groups of compounds is between about 1-99% of said metal oxide layer, such as about 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, 80, 90, 95, 97, 98 or 99% of said metal oxide layer
  • titanium oxide is combined with Zn and/or Ag, wherein equally preferred embodiments is titanium oxide combined with e g C, N, S, Au, Pd, Pt, Fe, Cl, F, Pb, Zr, B, Br, Si, Cr, Hg, Sr, Cu, I, Sn, Ta, W, V, Co, Mg, Mn and/or Cd
  • an oxide of any of the metals disclosed above is added to the metal oxide layer according to the present invention
  • added to the metal oxide layer on the wound dressing according to the present invention may be Ag or an oxide thereof, Zn or an oxide thereof, Zr or an oxide thereof, Co or an oxide thereof, Pt or an oxide thereof, Si or an oxide thereof, Mg or an oxide thereof, Mn or an oxide thereof, Sr or an oxide thereof, W or an oxide thereof, Ta or an oxide thereof, Cu or an oxide thereof, Au or an oxide thereof, Fe or an oxide thereof, Pd or an oxide thereof, Hg or an oxide thereof, Sn or an oxide thereof, B or an oxide thereof, Br or an oxide thereof, Cd or an oxide thereof, Cr or an oxide thereof, Cl or a chloride containing compound, Sr or an oxide thereof, V or an oxide thereof, F or a fluoride/fluorine containing compound, I or a iodide containing compound, N or an oxide thereof, S or an oxide thereof, C or a carbide
  • the present invention relates to method for producing a wound dressing according to the present invention, which wound dressing has improved photocatalytic and anti-microbiological properties, in which method a metal oxide layer as defined herein is added to a solid, pliant material to form said metal oxide layer on said solid pliant material
  • Said method comprises the steps of selecting a solid, pliant material, adding said metal oxide layer onto said solid pliant material and optionally, simultaneously, adding one or more compounds selected from the group consisting of N, C, S, Cl, and/or one or more compounds selected from the group consisting of Cl and N, and/or one or more compounds selected from the group consisting of Ag, Au, Pd, Pt, Fe, Cl, F, Pb, Zn, Zr, B, Br, Cr, Hg, Si, Sr, Cu, I, Sn, Ta, W, V, Co, Mg, Mn and Cd and/or one or more compounds selected from the group consisting of SnO 2 , CaSnO 3 , FeGa
  • said wound dressing is produced using ALD (Atomic Layer Deposition) Technology for attaching said metal oxide layer onto said solid non-pliant material
  • said ALD reaction is performed at a reaction temperature of about 20-500 0 C, such as between 20-400 0 C, 20-300 0 C, 20- 200 0 C, 20-100 0 C, 50-300°C, 50-200°C or 50-150 0 C or 100-200°C
  • said temperature is about 100-200 0 C
  • approximately 12O 0 C is used for the reaction conditions
  • the selection of temperature will affect the structure of the metal oxide layer comprising the titanium oxide which is formed, i e the higher temperature employed, the higher percentage of crystalline structures will be obtained For example for TiO 2 , temperatures above about 160 0 C will increase the crystalline part of the material By adding Cl to the metal oxide layer, this transition temperature will be lowered
  • ALD technology has previously mainly been used to deposit metal oxide layers onto solid materials such as silica, MgO and soda lime glass
  • solid materials such as silica, MgO and soda lime glass
  • the present inventors have now for the first time by using ALD technology been able to produce a wound dressing consisting of a coated solid, pliant material, said coating comprising a homogenous and substantially amorphous metal oxide layer comprising predominantly titanium oxide
  • the new technique using ALD provides a wound dressing with a nano-coating of a metal oxide as disclosed herein which wound dressing allows for manipulation and use of said wound dressing without damaging the metal oxide layer thereon which would allow the metal ox ⁇ de(s) to break and/or flake off there from
  • the latter has been a recognized problem in the art, as the layers of metal oxide which have been deposited onto the material have been too thick, causing the metal oxide layer to break and also accidentally leave metal flakes behind in the wound This is due to the fact that the techniques used so far have not been sensitive enough to be able
  • the present invention relates to a method for treating a subject, such as a human patient or an animal, such as a vertebrate animal, such as a cat, dog, cattle, sheep, pig, rabbit, bird or horse, suffering from a wound, such as a wound injury, comprising providing a wound dressing as defined herein to a subject in need thereof
  • a wound dressing as defined herein to a subject in need thereof
  • the wound dressing does not have to be changed as often as with presently available wound dressings as it is possible to reactivate the anti-microbial, anti-fouling, anti-viral and/or immunomodulatory activities of the wound dressing by simple photoactivation, as described above
  • the present invention relates to a wound dressing as defined herein for use in the preparation of a medical product
  • a solid, pliant material as defined herein for use as a wound dressing
  • the present invention may also be defined in the terms of a solid pliant material comprising a coating of a metal oxide comprising predominantly titanium oxide, optionally comprising one or more compound(s) as disclosed herein, dispersed substantially homogenous within said metal oxide coating, for use as a wound dressing
  • Said solid pliant material comprising a coating of a metal oxide comprising predominantly titanium oxide may also be used in the manufacture of a wound dressing
  • said wound dressing consisting of a coated solid, pliant material, said coating comprising a homogenous and substantially amorphous metal oxide layer comprising predominantly titanium oxide, provides immunomodulatory and/or anti-microbiological properties due to the photocatalytic properties of said metal oxide layer and optionally also via the additional compounds added to the metal oxide layer, which has further been explained herein
  • the immunomodulatory, and/or anti-bacterial properties of said nano-thin layer present on said solid, pliant material is reactivated and/or boosted by applying photoactivation with high energy light or visible light to said metal oxide layer
  • Said high energy light may be selected from, but is not limited to, UV light, blue light or laser light
  • High energy light is defined as light with wavelength lower than 385 nm
  • the present invention is related to a wound dressing, wherein the metal oxide layer present thereon provides anti-fouling properties to said wound dressing thereby avoiding and prohibiting the accumulation and deposition of unwanted organic material thereon It is also encompassed by the present invention, that the anti-fouling properties of said metal oxide layer present on said wound dressing are reactivated and/or boosted by applying photoactivation with high energy light or visible light to said solid, pliant material Said high energy light may be selected from, but it not limited to UV light, blue light or laser light
  • the present invention relates to the use of a wound dressing with a metal oxide layer comprising predominantly titanium dioxide, optionally in combination with one or more metal(s) and/or metal ox ⁇ de(s), as defined herein as a diaper or a fine garment
  • the wound dressing may be used in the manufacture of surgical sutures and surgical membranes and mesh (PTFE) as well as in the manufacture of catheters
  • a wound dressing according to the present invention may also be treated on both sides of the solid, pliant material ( ⁇ e the wound dressing will be coated on the side facing the wound as well as on the side opposite of the wound facing side) Coating on the side of the wound dressing and/or bandage that is not in direct contact with the wound will prevent contamination of the wound dressing or the wound itself by e.g. bacteria, microbes and other harmful agents.
  • TiCI 4 and H 2 O were used to coat the polyamid, a non-solid, pliant material, with TiO 2 Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition
  • the reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications
  • the films were grown using a pulsing scheme of 2 s pulse of TiCI 4 followed by a purge of 1 s Water was then admitted using a pulse of 2 s followed by a purge of 1 s This complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles) Films was formed in a relatively
  • the deposition may be expressed accordingly
  • the resulting layer may be practically amorphous
  • the amorphous film may optionally be converted into the TiO 2 forms rutile or anatase by post annealing
  • the structure may be controlled in situ as described in J Aarik et al , J Cryst Growth 148 268 (1995) where anatase is deposited in the range 165 - 350 0 C and rutile is obtained at temperatures above 350 0 C
  • the surface is smooth since the Sa is 243 nm and Sq (root mean square) 226 nm
  • TiCI 4 and H 2 O was used to coat poly(tetrafluoroethylene) (PTFE) with TiO 2 Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition
  • the reactor pressure is maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications
  • the films was grown using a pulsing scheme of 2 s pulse of TiCI 4 followed by a purge of 1 s Water is then admitted using a pulse of 2 s followed by a purge of 1 s
  • This complete pulsing scheme makes up one pulsing cycle and the films are made using different numbers of such cycles (typically from 20-2000 cycles)
  • Films was formed in a relatively large temperature interval as shown in Figure 1 Using a deposition temperature of 160
  • the deposition may be expressed accordingly
  • the resulting layer may be practically amorphous
  • the amorphous film may optionally be converted into the TiO 2 forms rutile or anatase by post annealing
  • the structure may be controlled in situ as described in J Aarik et al , J Cryst Growth 148 268 (1995) where anatase is deposited in the range 165 - 350 0 C and rutile is obtained at temperatures above 350 0 C
  • the resulting layer of titanium oxide layer did not affect the pliability or appearance of the material
  • Experiments on the mechanical properties to be performed are stretching and bending of the material 1) Bending 45 degrees, 2) Bending 60 degrees, 3) Bending 90 degrees 4) Bending 180 degrees, 5) Consecutive bending at 180 degrees fifty times
  • the mechanical experiment no sign of flakes or detachment of in the coating layer was observed even when examined at high magnification in a scanning electron microscope Moreover, the deposition of TiO 2 as illustrated by the smooth appearance mechanical stability of the photocatalyst layer visualized in the SEM after mechanical stress testing
  • the films were grown using a pulsing scheme of 2 s pulse of TiCI 4 followed by a purge of 1 s Water is then admitted using a pulse of 2 s followed by a purge of 1 s
  • This complete pulsing scheme makes up one pulsing cycle and the films are made using different numbers of such cycles (typically from 20-2000 cycles)
  • Films were formed in a relatively large temperature interval as shown in Figure 1 Using a deposition temperature of 120 0 C a growth rate of 0 046 nm/cycle is obtained Thus the coating procedure used 200 cycles, and gave a titanium oxide thickness of ⁇ 10 nm
  • the deposition may be expressed accordingly Step 1 T ⁇ CI 4 (g) + I-OH ⁇ 1-0-TiCI 3 + HCI(g)
  • the surface is smooth since the Sa is 283 nm and Sq (root mean square) 298 nm
  • the resulting layer of titanium oxide layer did not affect the pliability or appearance of the material
  • Experiments on the mechanical properties to be performed are stretching and bending of the material 1 ) Bending 45 degrees, 2) Bending 60 degrees, 3) Bending 90 degrees 4) Bending 180 degrees, 5) Consecutive bending at 180 degrees fifty times
  • the mechanical experiment no sign of flakes or detachment of in the coating layer was observed even when examined at high magnification in a scanning electron microscope Moreover, the deposition of TiO 2 as illustrated by the smooth appearance mechanical stability of the photocatalyst layer visualized in the SEM after mechanical stress testing
  • TITANIUM OXIDE DOPED WITH NITROGEN ON POLYURETHANE FIBER TiO x Ny surfaces may be produced by varying the usage of H 2 O and NH 3 as precursor in the reaction scheme described for growth of TiO 2 by the means of co-pulsing The doping took place on a polyurethane fiber
  • the reaction scheme may be as follows
  • Photocatalytic degradation measurements was performed on a solid layer of stearic acid (CH 3 (CH 2 ) 16 CO 2 H, Aldrich, 95%) UV illumination is done with a dental UV lamp that emits at wavelengths 340-410 nm with a peak maximum at 365 nm
  • the change in steric acid layer thickness is monitored by measuring infrared absorption spectrum in a transmission mode by Perkin-Elmer Spectrum FTIRI instrument (Spotlight 400, Perkin Elmer, Norway) Films 1 and 2 absorbed significantly more visible light With samples 1-5 the photocatalytic activity decreases with increasing nitrogen concentration Nitrogen doping by the present method can thus be regarded as detrimental to photocatalytic activity
  • ALD was used in the preparation of nitrogen-doped TiO 2 films which are excited by visible light (A > 380 nm)
  • Cotton fibers were coated with a doped titanium oxide surface This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), NH 3 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition
  • the reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications
  • the doping of the titanium oxide layer was performed by alternating the pulsing of T ⁇ CI 4 (g) and H 2 O(g) separated by pulses of an ammonia gas as mentioned above
  • This complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • Polyamid fibers were coated with titanium oxide doped sulphide surface This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), S (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition
  • the reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 500 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications
  • the doping of the titanium oxide layer was performed by alternating the pulsing of TI(OI- Pr) 4 (g) and H 2 O(g) separated by pulses of hydrogen sulphide gas The alternative process which occurs is
  • This complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • PTFE Poly(tetrafluoroethylene) fibers were coated with titanium oxide doped with fluorine surface This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), Cl 2 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing of T ⁇ CI4(g) and H2O(g) separated by pulses of an chloridric gas The alternative process which occur is
  • Cotton fibers were coated with titanium oxide doped with fluorine and nitrogen surface This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), F 2(g) (Fluka, 99%), NH 3 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing of T ⁇ CI 4 (g) and H 2 O(g)separated by pulses of an fluorine and ammonia gas, creating a fluoride and nitrogen doped titanium oxide The alternative process which occur is
  • This complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • Silk fibers were coated with titanium oxide doped with magnesium oxide surface This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), MgCp 2 (g) (Fluka, 99%), H 2 O (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 500 cm 3 m ⁇ n ⁇ 1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by adding some alternating the pulsing of MgCp 2 (g) and H 2 O (g) into the procedure for depositing TiO 2 The complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • EXAMPLE 12 TITANIUM OXIDE DOPED WITH SILICON Polyurethane fibers were coated with titanium oxide doped with silicon This was performed by ALD (Atomic Layer Deposition) Films are grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), SiCI 2 H 2 (g) (Fluka, 99%), H2 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 500 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by addition of alternating pulsing of SiCI 2 H 2 (g) and H 2 O (g) In order to catalyze the growth of SiO 2 from SiCI 2 H 2
  • Polyester fibers were coated with titanium oxide doped with chromium oxide This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • Polyether fibers were coated with titanium oxide doped with cobalt This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), Co(thd) 2 (g) (Fluka, 99%), O 3 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing of Co(thd) 2 (g) and O 3 (g)
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • EXAMPLE 15 TITANIUM OXIDE DOPED WITH ZINC AND FLUOR Polyethylene fibers were coated with titanium oxide doped with zinc and fluorine This was performed by ALD (Atomic Layer Deposition) Films are grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), Zn(OAc) 2 (g) (Fluka, 99%), NH 4 F (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications. The doping of the titanium oxide layer was performed by alternating the pulsing of Zn(OAc)2 (g) and NH 4 F (g).
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles).
  • Silicones fibers were coated with titanium oxide doped with copper oxide. This was performed by ALD (Atomic Layer Deposition). Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka; 98%), Cu(thd) 2 (g) (Fluka, 99%), and O 3 (distilled) as precursors. Both precursors were kept at room temperature in vessels outside the reactor during the deposition. The reactor pressure was maintained at ca. 1.8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 min "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99.9995% inert gas (N 2 + Ar) according to specifications. The doping of the titanium oxide layer was performed by alternating the pulsing of Cu(thd) 2 (g) and O 3 (g).
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles).
  • Silicones fibers were coated with titanium oxide doped with zinc oxide. This was performed by ALD (Atomic Layer Deposition). Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka; 98%), ZnCI 2 (g) (Fluka, 99%), and H 2 O (distilled) as precursors. Both precursors were kept at room temperature in vessels outside the reactor during the deposition. The reactor pressure was maintained at ca. 1.8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 min "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99.9995% inert gas (N 2 + Ar) according to specifications. The doping of the titanium oxide layer was performed by alternating the pulsing of ZnCI 2 (g) and H 2 O (g).
  • Polypropylene (PP) fibers were coated with titanium oxide doped with zirconium oxide
  • ALD Atomic Layer Deposition
  • TiCI 4 Feuka, 98%), ZrCI 4 (g) (Fluka, 99%), and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition
  • the reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications
  • the doping of the titanium oxide layer was performed by alternating the pulsing of ZrCI 4 (g) and H 2 O (g)
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • Cotton fibers were coated with titanium oxide doped with zirconium titanium oxide This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F- 120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), ZrCI4 (g) (Fluka, 99%), T ⁇ (OPr)4 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing of ZrCI4 (g) , H 2 O (g) and T ⁇ (OPr)4 (g)
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • TITANIUM OXIDE DOPED WITH PALLADIUM Silk fibers were coated with titanium oxide doped with palladium This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), Pd(thd) 2 (g) (Fluka, 99%), H 2 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing of Pd(thd) 2 (g) and H 2 (g)
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • Cotton fibers were coated with titanium oxide doped with iron This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), Fe(thd) 3 (g) (Fluka, 99%), H2 (Fluka, 99%) and O 3 (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 m ⁇ n ⁇ 1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing of Fe(thd) 3 (g) and O 3 (g)
  • the complete pulsing scheme makes up one pulsing cycle and the films was made using different numbers of such cycles (typically from 20-2000 cycles)
  • PTFE fibers were coated with titanium oxide doped with platinium This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), Pt(CpMe)Me3 (g) (Fluka, 99%), O 2 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition
  • the reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 m ⁇ n ⁇ 1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications
  • the doping of the titanium oxide layer was performed by alternating the pulsing of Pt(CpMe)Me3 (g) and O 2 (g)
  • Polyurethane fibers were coated with titanium oxide doped with vanadium oxide This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • Silicones fibers were coated with titanium oxide doped with boron and nitrogen This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using T ⁇ CI4 (Fluka, 98%), BCI3 (g) (Fluka, 99%), NH3 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure is maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm3 m ⁇ n-1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing of BCI3 (g) and NH3 (g)
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • TITANIUM OXIDE DOPED WITH TANTALUM Silk fibers were coated with titanium oxide doped with tantalum This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), TaCI5 (g) (Fluka, 99%), and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm3 m ⁇ n-1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing of TaCI5 (g) and H2O (g)
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • Polyamid (PA) fibers were coated with titanium oxide doped with tantalum and nitride This was performed by ALD (Atomic Layer Deposition) Films was grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), TaCI 5 (g) (Fluka, 99%), NH 3 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing Of TaCI 5 (g) and NH 3 (g)
  • the complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles)
  • Polyurethane fibers were coated with titanium oxide doped with silver This was performed by ALD (Atomic Layer Deposition) Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka, 98%), Ag(O2CtBu)(Pet3) (g) (Fluka, 99%), H 2 (Fluka, 99%) and H 2 O (distilled) as precursors Both precursors were kept at room temperature in vessels outside the reactor during the deposition The reactor pressure was maintained at ca 1 8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 mm "1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99 9995% inert gas (N 2 + Ar) according to specifications The doping of the titanium oxide layer was performed by alternating the pulsing of Ag(O 2 CtBu)(Pet3) (g) and H 2 (g)
  • Polypropylene fibers were coated with titanium oxide doped with bromine. This was performed by ALD (Atomic Layer Deposition). Films were grown in a commercial F-120
  • Sat reactor ASM Microchemistry
  • TiCI 4 Fluka; 98%), Br 2 (Fluka; 99%) and H 2 O (distilled) as precursors. Both precursors were kept at room temperature in vessels outside the reactor during the deposition.
  • the reactor pressure was maintained at ca. 1.8 mbar by employing an N 2 carrier-gas flow of 300 cm 3 min ⁇ 1 supplied from a Nitrox 3001 nitrogen purifier with a purity of 99.9995% inert gas (N 2 + Ar) according to specifications.
  • the doping of the titanium oxide layer is performed by alternating the pulsing of TiCI 4 (g) and H 2 O(g) separated by pulses of an Br 2 (g).
  • the alternative process which occurs is:
  • This complete pulsing scheme makes up one pulsing cycle and the films were made using different numbers of such cycles (typically from 20-2000 cycles).
  • EXAMPLE 29 TITANIUM OXIDE DOPED WITH WOLFRAM Polyethylene fibers were coated with titanium oxide doped with wolfram. This was performed by ALD (Atomic Layer Deposition). Films were grown in a commercial F-120 Sat reactor (ASM Microchemistry) by using TiCI 4 (Fluka; 98%), WF 6 (g) (Fluka, 99%), and H 2 O (distilled) as precursors. Both precursors were kept at room temperature in vessels outside the reactor during the deposition. The reactor pressure was maintained at ca.
  • the wound dressings were viewed in a tabletop scanning electron microscope (TM1000, Hitachi, Toyko, Japan) The thickness if the layer was found through XRD measurement to be 9 5 nm)
  • Uncoated wound dressing were used as control ( Figure 3) The coating is uniform and not dependent on the 3D structure
  • the wound dressing were seeded with anti-fouling endotoxin components such as LPS ( composed of lipid A (), core oligosaccharide and O-antigen) (Figure 7), and PepG (Staphylococcus aureus peptidoglycan) Images were taken by FTIR microscope (SPOTLIGHT 400, PerkinElmer, Norway) before and after a light source was used FTIR results showed that the phosphoric -oxygen and carbon-oxygen doubling bonding for the LPS and also the carbon-oxygen doubling bonding for the PepG was broken, thus destroying the endotoxin
  • LPS composed of lipid A (), core oligosaccharide and O-antigen
  • PepG Staphylococcus aureus peptidoglycan
  • the wound dressings were viewed in a tabletop scanning electron microscope (TM1000, Hitachi, Toyko, Japan) The thickness if the layer was found through XRD measurement to be 9 5 nm) Uncoated wound dressing were used as control ( Figure 4)
  • the coating is uniform and not dependent on the 3D structure
  • the coated layer was tested mechanically, and no sign of cracks nor flakes was observed after applied mechanical stretching and bending of the material (Figure 6)
  • a wound dressing was coated as described in example 1. Furthermore, this polymer was investigated in TEM analysis (A Philips BioTwinCM120 TEM). The results are presented in Figure 8, where one polymer fibres was imaged by TEM from the control (uncoated) and from the tested wound dressing (coated). A dark nano thin layer was observed around the polymer fibres from the coated wound dressing, while nothing was visible from the control fibres.
  • the atomic layer deposition (ALD) technique was able to coat all the fibres from the entire wound dressing, and not only the outer part of the thick polymer dressing. The layer coating the fibres was of a constant thickness and pin-hole free.
  • the cytotoxicity of wound dressings with different TiO 2 surface coating thickness was tested in vitro according to ISO 10993-5: 1999(E).
  • the method used was measurement of LDH activity of NHDF cells after 24 h of cultivation in extracts of wound dressings.
  • the toxicity was evaluated qualitatively by light microscopy.
  • the toxicity tests were carried out on the extracts of 1 cm 2 of the different wound dressings. 5 samples were prepared per group and sterilised in by washing with ethanol for 15 min at room temperature. They were subsequently dried on a sterile bench over night. The samples were transferred into the wells of sterile 24-well plates (Nunclon Surface, Thermo Fisher Scientific) and 1 ml of cell growth medium was added to each well. The extraction took place for 24 h at 37°C. The resulting extract was subsequently transferred to sterile microcentrifuge tubes and used immediately Cell cultivation
  • FGM*2 contains.
  • hFGF human recombinant fibroblast growth factor
  • Insulin 50 mg/ml
  • Amphotericin-B 10 ml FBS Fetal bovine serum
  • the cells underwent 1 subculture before seeding them for toxicity testing (the passage used for the cultivation was thus P13)
  • a mixture of 100 ⁇ l cell suspension made with fresh media and 100 ⁇ l of cell medium from the extract was given to each well of a 96-well plate (TPP, Switzerland), resulting in a total of 200 ⁇ l media containing 10000 cells per well
  • Each extract was tested in triplicates After incubation for 24 h at 37°C, the medium was carefully removed from the wells and stored in microcentrifuge tubes at 4 0 C until analysis
  • the Cytotoxicity Detection kit from Roche Diagnostics (Roche Diagnostics Norge AS) was used for measurement of the LDH activity 50 ⁇ l of medium was mixed with equal amounts of the dye solution The results were read with the Elisa Reader at a wavelength of 492 nm LDH analysis was done in duplicates The results were calculated in % relative to positive and negative control The averages were compared by Student's t-test P values ⁇ 0 05 were considered significant (noted *), and highly significant when p-values ⁇ 0 01 (noted ** )
  • the wound dressing (MePore, Monlycke, Sweden) was coated as described in example 1 with a layer of 5 nm and 10 nm of TiO 2 The results (figure 9), showed that the coated wound dressings had no more toxic effect on the cell culture than the commercially available uncoated one Moreover, no difference in biocompatibility was observed for the 5nm and the 10 nm coated wound dressing
  • This example describes the anti-bacterial potential that the TiO 2 coated wound dressing have when UV-light activated, compared to the non-coated one
  • the first output was to test if the coated wound dressing could be UV-light activated and work as anti-bacterial protection
  • the wound dressing coated with 5nm Of TiO 2 and an uncoated wound dressing were chosen, and Staphylococcus aureus were selected as the bacteria to be tested in this experiment
  • test groups 500 ⁇ l from a broth of Staph Aureus was diluted in 4ml of PBS (Dulbecco's PBS, Sigma- Ald ⁇ ch, St Louis, MO, USA) (stock solution) A drop of 10 ⁇ l of this stock solution was place on the top of the wound dressing.

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Abstract

La présente invention porte sur le domaine des pansements pour plaie, tels que des textiles et des tissus, qui ont été dotés d'une couche homogène et sensiblement amorphe d'un oxyde métallique comprenant de façon prédominante de l'oxyde de titane. Les pansements pour plaie ont des propriétés photocatalytiques qui induisent des effets anti-encrassement et antimicrobiens. De plus, en raison du fait que la couche d'oxyde de métal est très mince, on peut éviter la rupture et l'écaillage de morceaux de métal du pansement de plaie.
PCT/EP2009/064465 2008-11-04 2009-11-02 Pansements pour plaie Ceased WO2010052190A2 (fr)

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GB2514539A (en) * 2013-04-09 2014-12-03 Innovia Films Ltd UV protected films
EP2854878A4 (fr) * 2012-06-04 2016-01-13 Migrata U K Ltd Dispositif médical pour le traitement de plaies
WO2017004231A1 (fr) * 2015-06-29 2017-01-05 3M Innovative Properties Company Articles antimicrobiens et leurs procédés d'utilisation
CN106494049A (zh) * 2016-12-29 2017-03-15 上海护理佳实业有限公司 一种复合弹性材料与卫生制品
CN107866234A (zh) * 2016-09-27 2018-04-03 中国地质大学（北京） 一种高活性ZnIn2S4/TiO2 Z体系催化剂材料及其制备方法
US20180193514A1 (en) * 2017-01-10 2018-07-12 Sambo Co., Ltd. Bacterial adsorption dressing with nonphotocatalyst and method of manufacturing the same
CN109621979A (zh) * 2018-12-13 2019-04-16 上海纳米技术及应用国家工程研究中心有限公司 一种ZnO/锌铟硫纳米异质结的制备方法
EP3714908A1 (fr) 2019-03-29 2020-09-30 Picosun Oy Dispositif pour le traitement des plaies, son procédé de fabrication et ses utilisations
CN112121234A (zh) * 2020-08-21 2020-12-25 中国科学院金属研究所 一种具有可控、持久抗感染骨科内植入物及其制备方法
CN116531404A (zh) * 2023-06-15 2023-08-04 中南大学湘雅医院 Cu-N-TiO2光催化剂在治疗皮肤创面愈合药物中的应用
RU2834694C1 (ru) * 2024-02-14 2025-02-12 Федеральное государственное автономное образовательное учреждение высшего образования "Балтийский федеральный университет имени Иммануила Канта" (БФУ им. И. Канта) Способ создания перевязочного материала на основе хитозана, оксида цинка и серебра
CN119548324A (zh) * 2025-01-14 2025-03-04 中国人民解放军总医院第一医学中心 一种伤口敷料固定设备
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US20080119098A1 (en) * 2006-11-21 2008-05-22 Igor Palley Atomic layer deposition on fibrous materials
WO2010052191A2 (fr) * 2008-11-04 2010-05-14 Universitetet I Oslo Matières solides flexibles revêtues

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EP2854878A4 (fr) * 2012-06-04 2016-01-13 Migrata U K Ltd Dispositif médical pour le traitement de plaies
GB2514539A (en) * 2013-04-09 2014-12-03 Innovia Films Ltd UV protected films
US11571490B2 (en) 2015-06-29 2023-02-07 3M Innovative Properties Company Anti-microbial articles and methods of using same
WO2017004231A1 (fr) * 2015-06-29 2017-01-05 3M Innovative Properties Company Articles antimicrobiens et leurs procédés d'utilisation
JP2018522763A (ja) * 2015-06-29 2018-08-16 スリーエム イノベイティブ プロパティズ カンパニー 抗菌性物品及びその使用方法
CN108136065A (zh) * 2015-06-29 2018-06-08 3M创新有限公司 抗微生物制品及其使用方法
CN107866234B (zh) * 2016-09-27 2020-06-23 中国地质大学（北京） 一种高活性ZnIn2S4/TiO2 Z体系催化剂材料制备方法
CN107866234A (zh) * 2016-09-27 2018-04-03 中国地质大学（北京） 一种高活性ZnIn2S4/TiO2 Z体系催化剂材料及其制备方法
CN106494049A (zh) * 2016-12-29 2017-03-15 上海护理佳实业有限公司 一种复合弹性材料与卫生制品
US10912856B2 (en) * 2017-01-10 2021-02-09 Sambo Advanced Materials Inc. Bacterial adsorption dressing with nonphotocatalyst and method of manufacturing the same
US20180193514A1 (en) * 2017-01-10 2018-07-12 Sambo Co., Ltd. Bacterial adsorption dressing with nonphotocatalyst and method of manufacturing the same
CN109621979A (zh) * 2018-12-13 2019-04-16 上海纳米技术及应用国家工程研究中心有限公司 一种ZnO/锌铟硫纳米异质结的制备方法
CN109621979B (zh) * 2018-12-13 2021-09-21 上海纳米技术及应用国家工程研究中心有限公司 一种ZnO/锌铟硫纳米异质结的制备方法
EP3714908A1 (fr) 2019-03-29 2020-09-30 Picosun Oy Dispositif pour le traitement des plaies, son procédé de fabrication et ses utilisations
US20200306090A1 (en) * 2019-03-29 2020-10-01 Picosun Oy Device for wound care, method to manufacture and uses thereof
CN112121234A (zh) * 2020-08-21 2020-12-25 中国科学院金属研究所 一种具有可控、持久抗感染骨科内植入物及其制备方法
CN116531404A (zh) * 2023-06-15 2023-08-04 中南大学湘雅医院 Cu-N-TiO2光催化剂在治疗皮肤创面愈合药物中的应用
WO2025131960A1 (fr) 2023-12-18 2025-06-26 Paul Hartmann Ag Dispositif médical antimicrobien
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RU2834694C1 (ru) * 2024-02-14 2025-02-12 Федеральное государственное автономное образовательное учреждение высшего образования "Балтийский федеральный университет имени Иммануила Канта" (БФУ им. И. Канта) Способ создания перевязочного материала на основе хитозана, оксида цинка и серебра
CN119548324A (zh) * 2025-01-14 2025-03-04 中国人民解放军总医院第一医学中心 一种伤口敷料固定设备

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