FIELD OF THE INVENTION

The present invention relates to the field of solid pliant materials, such as textiles and fabrics, which have been provided with a coating of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly a metal oxide, such as titanium oxide The production of these materials involves the use of ALD (Atomic Layer Deposition) technology When prepared, these materials may be used within the field of medicine as wound dressings, as well as for everyday use in sporting clothes and general outdoor usage, such as in tents, sails and in sun blinds The present invention also describes methods for producing such solid pliant materials

BACKGROUND TO THE INVENTION

TiO ₂ , titanium (IV) oxide, or titania is the naturally occurring 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 Zink oxide and Titanium dioxide, particularly in the anatase form, are photocatalysts under ultraviolet light This has been discussed for example in the report from Maness et al (Maness et al, Applied and Environmental Microbiology, 65, (1999) 4094-8) Recently, it has been found that titanium dioxide, when spiked with nitrogen ions, is also a photocatalyst under visible light Titanium dioxide is a photocatalyst when irradiated with light The light is absorbed by the oxide material triggering a chemical reaction that, in the presence of water, ends with the oxidation of water to create hydroxyl radicals The reaction can also produce oxygen radicals or even oxidize organic materials directly Moreover, free radicals actively modulate immune responses, activate macrophages and stimulate the healing process

In order to deposit titania onto a suitable catalyst support, researchers have investigated and developed various techniques and methods such as anodization, electrodeposition, sol-gel, reactive dc magnetronic sputtering, chemical vapour deposition, electrostatic sol- spray deposition and aerosol pyrolysis The process of selecting a suitable deposition method depends on the type of catalyst support (Li Puma et al, Journal of Hazardous Materials, 157, (2008) 209-19) For example Hemissi et al (Hemissi et al, Digest Journal of Nanomateπals and Biostructures, 2, (2007) 299-305) discloses a method for deposing thin layers of titanium dioxide by a dip-coating method (sol-gel method)

Atomic Layer Deposition (ALD) is a technique that deposits films by one atomic layer at a time, allowing process control to achieve ultra thin films In ALD, 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

Several groups have previously described the deposition of titanium oxide onto solid surfaces by the usage of ALD technology, such as Aaπk et al (Aarik et al, Journal of Crystal Growth, 148, (1995) 268-75) who discloses the deposition of films of TiO ₂ on solid surfaces by the use of ALD technology, wherein the layers produced are between 2 to 560 nm

Available in the art are also alternative methods for applying a layer of titanium oxide onto pliant material, such as in US 5,545,886 wherein it is described how to produce 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 anti-microbial 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 Another example is Yuranova et al (Yuranova et al, Journal of Molecular Catalysis A Chemical, 244, (2006) 160-7) who disclose Tι0 ₂ -Sι0 ₂ -coated cotton textiles, wherein the thickness of the layers was detected to 20-30 nm These layers produced are however not homogenous but instead irregular in thickness and shape, introducing shear forces and brittlement if the material is mechanically manipulated Yet another example is found in WO01/80920 (Burrell et al, (2001) US Patent 6719987, PCT CA01/00498), which 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

In US2008/0119098 (Palley et al, (2008) US 2008/0119098 A1 ) a method is disclosed 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 garnments 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 use of pliant materials also extends to the field of medicine, such as for wound dressing applications Modern wound dressings (Lait et al, Journal of clinical nursing, 7, (1998) 11-7, Bishop, Critical care nursing clinics of North America, 16, (2004) 145-77, Jones, International wound journal, 3, (2006) 79-86) 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 a wound dressings are

1 ) Stem bleeding - Helps to seal the wound to expedite the clotting process

2) Absorb exudates - Soak up blood, plasma and other fluids exuded from the wound, containing it in one place

3) Ease pain - Some dressings may have a pain relieving effect, and others may have a placebo effect

4) Debridement of the wound - The removal of slough and foreign objects

5) Protection from infection, inflammation and mechanical damage, and 6) Promote healing - through granulation and epithelialisation

Protection from infection, inflammation and mechanical damage is the current problem in wound healing to day The microbiology of most wound types is complex, involving both aerobic and anaerobic bacteria (Gilchrist et 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 (ι e autoinfection) and the surrounding environment (cross-contamination) This is in particular relevant to patients with wounds that have (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 Patients with low to moderately exuding wounds, such as leg and foot ulcers, pressure ulcers and partial thickness burns, are also particularly susceptible to these indications If one can modulate local inflammatory responses and hinder bacterial (re)colonιzatιon in the wound without disturbing the healing process, a significant step forward would be achieved in modern wound care

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 Typically 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) The silver ion is the most commonly used topical antimicrobial agents used in bum wound care in the western world The historical use of silver extending back several hundred years has been extensively reviewed by Klasen (Klasen, Burns, 26, (2000) 131-8, Klasen, Burns, 26, (2000) 117-30)The US patent for Acticoat was filed by Burrell who raised the issue of the role of topical silver treatment for wound care in an era of increasing bacterial antibiotic resistance (Burrell, Ym, (2001 ) US Patent 6719987, PCT CA01/00498). In 1999, he reported on the comparative evaluation of the antimicrobial activity of Acticoat demonstrating a lower minimum inhibitory concentration, a lower bactericidal concentration, and faster bacterial killing (Ym et al, The Journal of burn care & rehabilitation, 20, (1999) 195-200). However, the use of silver ions in wound dressings has not had the clinical success as was anticipated It is costly to manufacture and has not provided predictable results so far Additional drawbacks are that it cannot be used on patients with a known sensitivity to silver, during radiation treatment or X-ray examinations, ultrasound, diathermy or Magnetic Resonance imaging or together with oxidising agents, such as hypochlorite solutions or hydrogen peroxide

Hence, in view of the above, there is a need in the art for pliant materials with thin coatings of a metal oxide, such as titanium oxide, which are workable, wear resistant materials which can be used in a wide variety of contexts There is also the need to provide such wear-resistant materials while at the same time maintaining and/or improving the photocatalytic properties of these materials, which photocatalytic properties can aid in e.g. avoiding the growth of microorganisms on such materials.

For providing improved medical applications of such pliant materials, different techniques such as Sol-Gel casting have been tried, but the resulting coatings have all been to thick and brittle, causing the coating to flake off when the dressing is manipulated.

Microparticles ("flakes") from such dressings released into the wound are also known to produce foreign body reactions that hamper a proper healing process. Hence, there also exists an additional need within this field to provide an improved wound dressing which solves the problems associated with the wound dressings available today.

There also exists a need in the art to provide improved materials for outdoor use which are wear resistant and which can withstand hard weather, attacks of microorganisms as well as the strain of UV exposure, while at the same time maintaining its properties.

SUMMARY OF THE INVENTION

The proposed invention solves the problems stated in the above, by providing a solid, pliant material comprising a coating having a thickness of 200 nm or less consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly of a metal oxide, such as titanium oxide. The addition of a linkage layer to this solid, pliant material provides the advantage that the metal oxide is more firmly attached to said pliant material, and that it provides protection against damaging UV light exposure and against potentially harmful reactive oxygen species produced during photoactivation of the layer. Taken together, these features provide an improved material suitable for use within several areas, such as outdoor use or medicine. The use of a linker to achieve these effects is not previously known in the art and hence constitutes an improvement to similar materials. Furthermore, this metal oxide covered solid pliant material is produced by ALD technology, which renders it possible to produce nano-thin layers onto these types of solid pliant materials. Additionally, these metal oxide containing layers have been shown to be durable and not to break and flake off during use. This is especially important when these materials are used in medicine as wound dressings, as flakes from the metal oxide layer are very damaging to the patient.

In particular, the present invention relates to a solid pliant material wherein said linkage layer comprises AI ₂ O ₃ , N or an oxide thereof, or S or an oxide thereof, or a combination thereof. The photocatalytic layer of the coating may additionally comprise one or more compound(s) selected from the group consisting of N, C, S, Cl, and/or one or more compound(s) selected from the group consisting of Cl and N, and/or one or more compound(s) selected from the group consisting of Au, Pd, Pt, Fe, Cl, F, Pb, Zr, B, Br, Si, Cr, Hg, Sr, Cu, I, Sn, Ta, V, W, Co, Mg, Mn and Cd and/or one or more compound(s) 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 8O ₃ o, and/or a combination of compounds selected from said groups of compounds, wherein said one or more compound(s) selected from one or more group(s) of compounds are dispersed substantially homogenous within said photocatalytic layer These compounds provide improved properties to the coating of the solid pliant material, which properties are further discussed herein

The present invention also relates to a method for producing a solid, pliant material with a coating as defined herein, wherein said method preferably utilizes ALD technology

Furthermore, the present invention relates to a method for reactivating and/or boosting the photocatalytic properties of the photocatalytic layer of the coating of said solid pliant material

In a further aspect, the present invention relates to a solid, pliant material with a coating, for use a wound dressing

In yet another aspect, the invention relates to a solid, pliant material with a coating for use in the manufacture of clothing A clothing may in the context of the present invention be an outdoor textile, an UV protective clothing, an UV protective coating for sails and tents, a sun blind, a shoe sole, a sport clothing, a cloth, a textile for furniture, a textile of domestic use such as washing cloths, curtains, fine garments to be used for woman dresses, scarves or men suits, necktie, bandannas, but is not limited thereto

The present invention also relates to a method for changing the light properties of a solid, pliant material with a coating as defined herein comprising adding one or more of the compound(s) selected from the group consisting of C, S, N, and Cl, to said photocatalytic layer

The present invention also relates to a method for improving the anti-microbiological and/or the anti-fouling properties of a solid pliant material comprising adding one or more compound(s) selected from the group consisting of of Ag, Au, Pd, Pt, Fe, Cl, F, Pb, Zn, Zr, B, Br, Cr, Si, Hg, Sr, Cu, I, Sn, Ta, V, W, Co, Mg, Mn and Cd to said photocatalytic layer Said layer may in the present context provide immunomodulatory properties to said solid, pliant material

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 ALCVD of AI ₂ O ₃

Figure 2 Growth rate of TiO ₂ from TiCI ₄ and H ₂ O and AI ₂ O ₃ from TMA and H ₂ O as a function of temperature using a pulsing sequence of 2 s of 2 s metal precursor, 1 s purge, 2 s H ₂ O, and 1 s purge

Figure 3 High resolution SEM image of AI ₂ O ₃ linker layer No visible cracks or flakes are seen after mechanical loading (50 bending of 180% and 15% elongation) Figure 4 High resolution SEM image of titanium oxide layer on top of linker layer No visible cracks or flakes are seen after mechanical loading (50 bending of 180% and 15% elongation) The surface is smooth

Figure 5 Bending test showing no visible cracks or flake of after 0°, 45°, 90°, 180° and extreme motions Figure 6 Uncoated and coated polyacrylate (PA) fibres imaged by TEM at three different magnifications The presence of the metal oxides covering the fibres was visible due to high contrast in electron absorbance between the polymer and the oxides (pictures B, D and F) However, no layer was observed for the non coated fibres (A, C and E) Figure 7 Biocompatible test for different layers coated on a wound dressing with TiO ₂ , AI ₂ O ₃ and AI ₂ O ₃ +TιO ₂ , showing that the latter category performed better A linker layer of 5 nm AI ₂ O ₃ and 10 nm TiO ₂ had lowest toxic effect No difference was found from ALD depostion from 120 ⁰ C and 8O ⁰ C deposition temperature ( ^* p<0 05, ^** p<0 01) UV irradation was as well done prior to cell deposition Irradiating both the polymeric fibers with TiO ₂ and AI ₂ O ₃ coatings worsen the toxic effect, meaning that the polymer was degraded due to the UV light The samples with a linker layer (AI ₂ O ₃ ) and TiO ₂ on top did not show this behaviour and had instead a reduced toxicity This was due to the linker layer presence that enhanced the TiO ₂ biocompatibility

Figure 8 Population of staphilococcus aureus bacteria on wound dressing with no coating, coating with only 10 nm of TiO ₂ and coating with linker layer of AI ₂ O ₃ and TiO ₂ on top (5 nm + 5 nm) The latter group performed significantly better and reduced the initial bacteria population by log scale values DEFINITIONS

In the present context, the terms titanium dioxide, titanium oxide and titania may be used interchangeably herein, all referring to TiO ₂

In the expression "photocatalytic layer comprising predominantly a metal oxide", and the like used herein, "predominantly" refers to that the photocatalytic layer comprises 50% or more of a metal oxide

In the present context, the term "solid, pliant material" refers to a flexible and bendabie 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, for e g a sail This 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

ALD technology (Atomic Layer Deposition) 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 By keeping the precursors separate throughout the coating process, atomic layer control of film grown can be obtained as fine as ~ 0 1 angstroms per monolayer ALD grown films are conformal, pin- hole 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

When applying ALD technology on a solid pliant material, a substantially lower temperature 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, 75, 60 or 5O ⁰ C

The term "homogenous" which in the present context is used to describe the characteristics of the photocatalyst layer on the solid pliant material 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 By a "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

By "coated" or "coating" is meant that a homogenous and substantially amorphous layer of metal oxide comprising predominantly titanium oxide is placed, e g by using ALD technology as described herein, on a solid pliant material

In the present context, the term "amorphous" when discussed in the context of the photocatalytic layer comprising a metal oxide, optionally in combination with one or more compound(s) as defined herein, is meant to indicate that the relation of the atoms to each other is random, and stands interchangeably with non-crystalline atom structure In the present context, a "substantially amorphous photocatalytic 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%

The term "immunomodulatory" as used herein refers to the ability to suppress and/or stimulate an immune response in a subject, such as a human being

The term "anti-microbial" as used herein, refers to the ability to repress and/or prevent the growth of a microorganism in or on a subject The present term may also refer to the killing of the microorganism In the present context, the metal oxide, such as the titanium oxide provides anti-microbial effects by the production of free radicals, which are released after photo activation, helping in fending off microbes and relieve inflammation This is particularly useful when the titanium oxide is present on a wound dressing Examples of microorganisms are bacteria, fungi and viruses

A "linker", as disclosed herein, refers to a composition comprising one or more ingredients which will aid in the attachment of the photocatalytic layer of the coating according to the present invention, which photocatalytic layer comprises a metal oxide, onto the surface of the solid pliant material via said linker Hence, a "linkage layer" as referred to herein, refers to a layer which comprises one or more linkers, as defined herein This linker when present on the solid pliant material will provide an environment which is favourable for the metal oxide to adhere to, and which will improve the strength of attachment of the photocatalytic layer to the solid pliant material via the linkage layer In addition, the presence of the linker on the surface of said solid pliant material will protect the material from products of the photocatalytic activity, such as reactive oxygen species, as well as reducing the amount of UV radiation that is let through the pliant material, thereby reducing UV light induced damages. Examples of linkers are provided herein, but the invention is not limited thereto.

The term "photocatalytic" as used herein, refers to the ability to absorb light energy and generate reactive oxygen species that can act as oxidants. In the present context, a photocatalytic layer comprises materials which possess these abilities. An example of a photocatalytic material is titanium oxide. The photocatalytic function of a material may aid in preventing that microbial materials 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.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a solid pliant material comprising a coating having a thickness of about 200 nm or less consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly a metal oxide.

This solid pliant material has improved photocatalytic properties, due to the presence of a metal oxide, such as titanium oxide, in said photocatalytic layer, as well as improved anti- microbiological properties due to the presence of additional compounds therein. The solid pliant material preferably is produced by an Atomic Layer Deposition (ALD) technique.

Accordingly, in a first aspect, the present invention relates to a solid, pliant material comprising a coating having a thickness of about 200 nm or less consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly a metal oxide.

In one embodiment, said solid, pliant material comprises a photocatalytic layer wherein said metal oxide is selected from the group consisting of TiO, Ti ₂ O ₃ , Ti ₃ O ₅ and TiO ₂ . In one embodiment, the thickness of said coating is 100 nm or less, such as 50, 10, 5 nm or less In other embodiments, the thickness of said coating 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 In other embodiments, the coating 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 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 22 or 25 nm

Preferably, the thickness of said coating is defined by a thickness which is such that it prevents that the coating layer breaks and/or flakes off from the solid, pliant material during slight bending and/or normal use thereof This means for example that when the material is used as a wound dressing, this 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

Preferably, said linkage layer comprises one or more of the compound(s) AI ₂ O ₃ , N or an oxide thereof, S or an oxide thereof, AI ₂ O ₃ , SiO ₂ , Ta ₂ O ₅ , ZrO ₂ , HfO ₂ , ZnO, MgO, Cr ₂ O ₃ , Co ₂ O ₃ , NiO, FeO, Ga ₂ O ₃ , GeO ₂ , V ₂ O ₅ , Y ₂ O ₃ , rare earth oxides, CaO, In ₂ O ₃ , SnO ₂ , PbO, MoO ₃ and WO ₃ TiN, TaN, SiN ₄ , AIN, Hf ₃ N ₄ and Zr ₃ N ₄ or any combination thereof

The presence of the linkage layer provides improved properties to the solid pliant material as it makes the photocatalytic layer adhere even stronger to the material It also aids in minimizing the potential harmful effects of prolonged exposure to UV light This is especially important for the materials that are to be used outdoors

In one preferred aspect, the present invention relates to a solid pliant material comprising a coating, wherein the photocatalytic 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 Au, Pd, Pt, Fe, Cl, F, Pb, Zr, B, Br ₁ Si, 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 8O ₃ o, and/or a combination of compounds selected from said groups of compounds, wherein said one or more compound(s) selected from one or more group(s) of compounds are dispersed substantially homogenous within said photocatalytic layer The addition of these further compounds to the photocatalytic layer of said coating has several beneficial effects Firstly, the group consisting of C, S, N and Cl provides the possibility of altering the wavelength at which the photocatalytic layer absorbs light This makes is possible to vary the light source that is used for boosting the photocatalytic properties of the photocatalytic layer When a solid pliant material according to the present invention is used as a wound dressing, the material can hence be re-activated by photo activation several times without being removed from the wound, thus relieving the patient from discomfort and pain due to frequent dressing changes, and at the same time leaving the wound to heal up undisturbed In the present context, the photocatalytic properties of the solid pliant material may be altered by the addition to say metal oxide layer of one or more of the compounds selected from the group consisting of C, S, N and Cl 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 Hence, in view thereof, not only UV light, but also visible light can be used for this purpose, which is a more convenient and safe source of energy, and which will not be damaging to the patient

Secondly, 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 , and K6Nb ₁₀₈₀₃₀ , provides enhanced photocatalytic properties to the photocatalytic layer of the coating of the solid pliant material

Thirdly, the addition of one or more of the compounds selected from Au, Pd, Pt, Fe, Cl, F, Pb, Zr, B, Br, Si, Cr, Hg, Sr, Cu, I, Sn, Ta, W, V, Co, Mg, Mn and Cd, or any oxide thereof, has the effect of additionally strengthening the anti-microbial properties of the solid pliant material, which will avoid that microorganisms, such as bacteria, adhere and stay in the material

In one embodiment, the photocatalytic layer of a coating according to the present invention comprises about 100% titanium oxide

In another embodiment, the proportion of titanium oxide present in said photocatalytic layer of said coating, when combined with one or more compounds selected from the group consisting of N, C, S, Cl ₁ 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 Au, Pd, Pt, Fe, Cl, F, Pb, Zr, B, Br, Si, Cr, Hg, Sr, Cu, I, 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 8O} 3o, and/or a combination of compounds selected from said groups of compounds, is between about 1-99% of said photocatalytic layer, such as about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, 97, 98 or 99% of said photocatalytic layer.

In a presently preferred embodiment, 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 Cd or combinations thereof.

In other aspects of the present invention, an oxide of any of the compounds provided herein is added to the photocatalytic layer of a coating according to the present invention. Hence, 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, V or an oxide thereof, Cl or a chloride containing compound (not oxide, see below also), Sr 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 containing compound, but is not limited thereto.

In such combination, it is presently preferred that the proportions of the other compounds mentioned herein and titanium oxide are respectively and approximately 1/99, 2/98, 3/97, 4/96, 5/95, 6/94, 7/93, 8/92, 9/91 , 10/90, 20/80, 30/70, 40/60 or 50/50.

Preferably, a photocatalytic layer comprising titanium oxide is amorphous, but occasionally, a minor percentage of the titanium oxides can be present in an anatase form.

The solid pliant material referred to herein may be selected from a variety of sources, and will depend on the intended use thereof. Herein, the solid pliant material may be selected from any of the materials polyacrylonitrile(PAN), cis 1 ,4-poly butadiene (PBD), trans 1 ,4- poly butadiene (PBD), poly 1-butene (PB), polybutylene terephthalate (PBT), poly caprolactam (Nylon 6), polycarbonate(PC), polyamid (PA), poly 2,6-dιmethyl-1 ,4- phenylene ether (PPE), poly ether ether ketone(PEEK), polyetheπmide (PEI), polyethylene (PE)(LDPE)(MDPE)(HDPE)(UHMW), polyester, polyether, poly ethylene hexamethylene dicarbamate (PEHD), polyethylene oxide (PEO), polyethylene sulphide (PES), polyethylene terephthalate (PET), polyhexamethylene adipamide (Nylon 6,6) (PHMA), polyhexamethylene sebacamide (Nylon 6,10) (PHMS), polyimide (Pl), poly isobutylene (PIB), poly methyl methacrylate (PMMA), poly methyl pentene (PMP), poly m- methyl styrene (PMMS), poly p-methyl styrene (PPMS), poly oxymethylene (POM), poly pentamethylene hexamethylene dicarbamate (PPHD), poly m-phenylene isophthalamide (PMIA), poly phenylene oxide (PPO), poly p-phenylene sulphide (PPS), poly p-phenylene terephthalamide (PPTA), poly propylene (PP), poly propylene oxide (PPOX), polystyrene (PS), poly tetrafluoro ethylene (PTFE), poly urethane (PU), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), polyvinyledene fluoride (PVDF), polyvinyl methyl ether (PVME), latex, actetate, carbon, polyaniline, polythiophene, polypyrrole, or a synthetic copolymer such as ABS plastic, SBR, Nitrile rubber, styrene-acrylonitrile, styrene-isoprene-styrene (SIS) and ethylene-vinyl acetate, polyurethane and polyethylene glycol (aka elastane, spandex, lycra, Elaspan, or a natural polymer such as collagen, hydrocolloids, satin, Angora, alpaca wool, vicuna wool, llama wool, and camel hair, linen, rubber, silk, cotton, wool, rayon, cellulosic fiber, natural fiber, velvet, or the plant textiles/biopolymers, Polyglonic acid, Polylactic acid, polyglycolic acid, alginate, chitosan, grass, rush, hemp, and sisal, fibres from pulpwood trees, cotton, rice, hemp, and nettle, viscose or a mineral textile, such as glass wool, or any combination thereof

The photocatalytic layer of the coating present on the solid pliant material provides antimicrobial, anti-fouling, anti-viral and/or immunomodulatory activities to said material by simple photoactivation making it possible to obtain materials which may be used both for outdoor use, the photocatalytic properties preventing microbial growth on the material, as well as in materials suitable for use in the field of medicine, such as wound dressings, due to the same properties Also, the possibility of boosting these photocatalytic effects with light makes it possible to do e g prolonged local wound care without replacing the dressing every second day as is the general rule today Hence, the herein disclosed technology and materials makes use of free radicals, released from the metal oxides after photo activation, 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 In addition thereto, other compounds as defined herein may be added to the photocatalytic layer of the coating according to the present invention to further improve the anti-microbial properties Thus, these solid pliant materials as disclosed herein are promising materials for developing the next generation, bioactive wound dressings

In yet another aspect, the present invention relates to a method for producing a solid, pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly a metal oxide as defined herein, comprising the steps of selecting a solid, pliant material, adding said linkage layer to said solid, pliant material as defined herein, adding said photocatalytic layer onto said linkage layer as defined herein, and optionally adding one or more compound(s) as defined herein, to said photocatalytic layer simultaneously as said photocatalytic layer is added to attach to said linkage layer In one preferred embodiment of the present method, said one or more compound(s) as defined herein are added to said photocatalytic layer by co-pulsing and/or mixing said compounds into said photocatalytic layer Co-pulsing in the present context, is a process wherein the reactants are injected into the reaction chamber either together in pulses, or individually in sequences of pulses

In the context of the present invention said method is preferably performed by using ALD (Atomic Liquid Deposition) Technology, said ALD reaction being performed at a reaction temperature of about 20-500 ⁰ C In a preferred embodiment, said ALD reaction is performed at a reaction temperature of about 20-500 ⁰ C, such as between about 20- 400 ⁰ C, 20-300°C, 20-200 ⁰ C, 20-100 ⁰ C, 50-300°C, 50-200 ⁰ C or 50-150°C or 100-200 ⁰ C In a more preferred embodiment, said temperature is between about 100-200 ⁰ C In a yet more preferred embodiment, approximately 120 ⁰ C is used for the reaction conditions

The selection of temperature will affect the structure of the photocatalytic layer comprising the metal oxide being formed, i e the higher temperature employed, the higher percentage of crystalline structures will be obtained For example for TiO ₂ , temperatures above about 16O ⁰ C will increase the crystalline part of the material By adding Cl to the metal oxide layer, this transition temperature will be lowered

Furthermore, the use of ALD to provide a nanoscale coating makes it possible to produce durable coatings on solid pliant materials, such as wound dressings, that maintain their flexibility and soft characteristics throughout the use

ALD technology has previously only been used to deposit metal oxide layers onto solid materials such as silica, MgO and soda lime glass Surprisingly, the present inventors have now for the first time by using ALD technology been able to produce a solid pliant material comprising a coating having a thickness of 200 nm or less consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly of a metal oxide Hence, using ALD techniques, as well as the presence of the linkage layer more firmly adhering the photocatalytic layer onto the material, provides a solid pliant material that allows for manipulation and use minimizing the risk of damaging the coating thereon which would allow the coating to break and/or flake off from the material The latter has been a recognized problem in the art, as the layers of e g a metal oxide which have been deposited onto such a material have been too thick and has also not been firmly attached, causing the coating to break and also accidentally leave metal flakes behind, which is a severe problems when these materials are used as wound dressings This is due to the fact that the techniques used so far have not been sensitive enough to be able to provide such thin layers thereby avoiding these events, in combination with the fact that the coatings present on the materials have not been firmly attached

In another aspect, the present invention relates to a method for reactivating and/or boosting the photocatalytic properties of the photocatalytic layer of a coating on a solid pliant material as defined herein, comprising applying photoactivation with high energy light or visible light to said photocatalytic layer of said solid, pliant material Said high energy light may be UV light, blue light or laser light High energy light is defined as light with wavelength lower than approximately 385 nm

In yet another aspect, the present invention relates to a solid, pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly a metal oxide, as defined herein, for use as a wound dressing

The invention also relates to a solid, pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly of a metal oxide, as defined herein, in the manufacture of a wound dressing

In the context of the present invention, when said solid, pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly of a metal oxide, as defined herein, is used as a wound dressing, this material is preferably selected from the group consisting of Polyurethane (PUR, TPU PCU), Polyamid (PA), Polyether, Polyethylene, (PE), Polyester, Polypropylene, (PP), poly(tetrafluoroethylene) (PTFE), silicones, silk and cotton

In another aspect, the present invention relates to a method for treating a patient suffering from a wound injury, wherein a solid, pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly of a metal oxide, as defined herein, in a form suitable for a wound dressing as defined herein is provided to a patient in need thereof

In a preferred aspect, the present invention relates to such a material in the preparation of a medical product

In the context of the present invention, said solid pliant material comprising a coating consisting of a photocatalytic layer consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly of a metal oxide, for use as a wound dressing provides immunomodulatory and/or anti- microbiological properties due to the photocatalytic properties of said coating, which has further been explained herein

In yet another embodiment, the invention relates to a method for reactivating and/or boosting the solid pliant material according to the present invention, thereby providing anti-microbial, immunomodulatory and/or anti-fouling properties to said photocatalytic layer of said coating by applying photo activation with high energy light or visible light to said wound dressing In one embodiment, said high energy light is UV light, blue light or laser light The photocatalytic layer also provides anti-fouling properties to said material thereby avoiding and prohibiting the accumulation and deposition of unwanted organic material thereon Also the anti-fouling properties may be boosted and/or reactivated by applying photo activation thereto

In yet another aspect of the present invention, a solid pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer as defined herein may also be used in the manufacture of surgical sutures and surgical membranes and mesh (PTFE) as well as in the manufacture of catheters

In yet another aspect, the invention relates to the use of a solid pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer as defined herein in the manufacture of clothing In preferred aspects thereof, said clothing is an outdoor textile, an UV protective clothing, an UV protective coating for sails and tents, a sun blind, a shoe sole, a sport clothing, a cloth, a textile for furniture, a textile of domestic use such as washing cloths, curtains, fine garments to be used for woman dresses, scarves, men suits, necktie, or a bandannas In yet another aspect, the present invention is related to the use of a solid pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer as defined herein as a material for clothing, outdoor textile, UV protective clothing, UV protective coating for sails and tents, sun blinds, shoe soles, sport clothing, a textile of domestic use such as washing cloths, curtains, fine garments to be used for woman dresses, scarves, men suits, necktie, a bandannas, and/or a cloth, such as a cloth for kitchen use, and to the manufacture thereof The photocatalytic properties of the photocatalytic layer present on said solid, pliant material provides anti-fouling and anti-microbial properties thereto and thereby prohibits the accumulation and deposition of unwanted organic material thereon It is also encompassed by the present invention, that the anti-fouling properties of said photocatalytic layer present on said solid, pliant material are reactivated and/or boosted by applying photo activation with high energy light or visible light to said solid, pliant material Furthermore, due to the presence of the linkage layer in said coating, the damaging effects of UV light are decreased, as previously explained herein

Hence, the materials of the present invention also finds use in materials for e g sails, tents, outdoor sportswear, and shoe soles, and/or to the manufacture thereof, wherein the metal oxide layer in the material provides anti-fouling properties to these products preventing accumulation and deposition of unwanted material on surfaces, which most often occur in an aquatic environment As previously mentioned, the presence of a linkage layer also prevents the material, when in the form of polymers, from being degraded by UV light

In yet another aspect, the invention relates to a method for changing the light absorbing properties of a solid pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer as defined herein, comprising adding one or more of the compound(s) selected from the group consisting of C, S, N, and Cl ₁ to the photocatalytic layer of said coating present on said solid pliant material In yet another aspect, the invention relates to a method for improving the anti- microbiological and/or the anti-fouling properties of a solid pliant material comprising a coating consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer as defined herein comprising adding one or more compound(s) selected from the group consisting of Au, Pd, Pt, Fe, Cl, F, Pb, Zr, B, Br, Si, Cr, Hg, Sr, Cu, I, Sn, Ta, W, V, Co, Mg, Mn and Cd to said photocatalytic layer.

In yet another aspect, the present invention relates to the use of a solid, pliant material comprising a coating having a thickness of 200 nm or less consisting of an inner linkage layer and an outer homogenous and substantially amorphous photocatalytic layer comprising predominantly of a metal oxide, optionally in combination with one or more compounds as defined herein, as a diaper or a fine garment.

EXPERIMENTAL SECTION

Surprisingly it was found that a atomic layer deposition of complex nano-meter thick coatings onto a substrate of pliable material/textile, consisting of an inner linkage layer and an outer photocatalyst layer provided protection for the substrate from both irradiation (UV-light) and free radicals, and at the same time improved the self-cleaning, anti-fouling and anti-microbial properties of the coating Moreover, by doping the layers with specific atoms, the photocatalytic effect could be improved at specific wavelengths providing a method for further increasing the efficacy and effectiveness of the photocatalytic coating Finally, the applications of said nano-layer coatings surprisingly will not affect the mechanical properties of the substrate (pliability, flexibility, elasticity etc ), but rather enhance the strength and stability of said materials

EXAMPLE 1 A LINKAGE LAYER CONSISTING OF AI ₂ O ₃ To facilitate attachment of the photocatalytic layer onto the surface of pliable materials, and to protect and stabilize said material from harmful irradiation and effects from the photocatalyst, a linkage was deposited directly onto the material before the photocatalyst was deposited The linker should ideally provide a chemical anchor for the active photocatalyst and provide a barrier against free radicals released from the photocatalyst while not affecting the efficacy of the photocatalyst itself One such candidate linker tested was aluminium (III) oxide (AI ₂ O ₃ )

A layer Of AI ₂ O ₃ was deposited on elastomeric polyurethane (Pellethane™) using the ALD (atomic layer deposition) technique in a F-120 Sat reactor (ASM Microchemistry) (Figure 1 ) The deposition was performed using AI(CH ₃ ) ₃ (trimethylaluminium, TMA) (Witco) and O ₃ as precursors at a deposition temperature of 100 ⁰ C The TMA precursor was used at room temperature while the O ₃ precursor was delivered from an OT-020 ozone generator provided with 99 999% O ₂ (AGA) at a rate of 500 seem A thickness of 5 nm was reached after 51 deposition cycles

Deposition of a photocatalyst layer consisting of titanium dioxide onto the AI ₂ O ₃ layer was performed by atomic layer deposition

The resulting layer of AI ₂ O ₃ did not affect the pliability or appearance of the material Experiments on the mechanical properties of the following sequencing 1) Bending 45 degrees, 2) Bending 60 degrees, 3) Bending 90 degrees 4) Bending 180 degrees, 5) Consecutive bending at 180 degrees fifty times, 6) Elongation (stretching) of material up to 15% (Figure 3) showed that the layer was firmly attached to the substrate and that it did not flaked off after the six different testing modes, even when examined at high magnification in a scanning electron microscope Moreover, the AI ₂ O ₃ layer provided an excellent anchorage for the deposition Of TiO ₂

The surface was examined in a blue light profilometer (PLU 2300, Sensofar, Spain) and a set of roughness parameters were quantified (n=5) The result was displayed in Table 1 The surface was smooth since the Sa was 213 nm and Sq (root mean square) 286 nm

Table 1 Roughness parameters from blue light Profilometer of a titanium oxide layer on top of a AI ₂ O ₃ linker (Sa = roughness average, Sq = Root-Mean-Square (RMS) deviation of the surface, Computes the efficient value for the amplitudes of the surface (RMS), Sp, Maximum height of summits, Height between the highest peak and the mean plane, Sv Maximum depth of valleys, Depth between the mean plane and the deepest valley, St =Total height of the surface, Height between the highest peak and the deepest hole, Ssk, Skewness of the height distribution, A negative Ssk indicates that the surface was composed with principally one plateau and deep and fine valleys In this case, the distribution was sloping to the top A positive Ssk indicates a surface with lots of peaks on a plane The distribution was sloping to the bottom Due to the big exponent used, this was very sensitive to the sampling and to the noise of the measurement Sku = Kurtosis of the height distribution, Sku>3 = summits very steep Positive, sharp peaks, negative, flat peaks Due to the big exponent used, this was very sensitive to the sampling and to the noise of the measurement Sz = Ten Point Height of the surface, calculated by the mean Szi on zones with a width equal to the auto-correlation length of the surface, Smmr= Mean material volume ratio )

Parameter Sa Sci SQ Sp Sv Sskw Ssk Sku Sz Smmr Unit μm μm μm μm μm μm3/μm2

Mean 0 213 1 572 0 286 1 135 0 825 0 643 0 670 6 805 1 100 0 890

EXAMPLE 2 A LINKAGE LAYER CONSISTING OF SULPHIDE

To facilitate attachment of the photocatalytic layer onto the surface of pliable materials, and to protect and stabilize said material from harmful irradiation and effects from the photocatalyst, a linkage layer was deposited directly onto the material before the photocatalyst was deposited The linker should ideally provide a chemical anchor for the active photocatalyst and provide a barrier against free radicals released from the photocatalyst while not affecting the efficacy of the photocatalyst itself One such candidate linker was a layer of sulphide

The linker (a layer of sulphide) was to be deposited on silk fibres using the ALD (atomic layer deposition) technique in a F-120 Sat reactor (ASM Microchemistry) Nitrogen (Messer, 99 999%) was used both as a carrier and purging gas With N ₂ flows of typically 500 seem, the operating pressure was around 2-5 mbar while the base pressure was below 5x10 ^~3 mbar ZnS was deposited using DEZn (Morton, electronic grade) and H ₂ S (Messer, 99 8%) as precursors DEZn and H ₂ S precursor vapours were led into the reactor from external containers held at a fixed temperature of 2O ⁰ C, the flows were controlled with needle valves The H ₂ S flow was set to 5-5 5 seem (continuous flow) The thickness of the linage layer was about 10 nm Depending on the cycle in the ALD reactor (typically 20- 20 000), the layer thickness was varied from 0 5 to 500 nm

Deposition of a photocatalyst layer consisting of titanium dioxide onto the sulphide layer was to be performed by ALD

The resulting layer of sulphide will not affect the pliability or appearance of the material Experiments on the mechanical properties were performed where stretching and bending was performed on 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

EXAMPLE 3 A LINKAGE LAYER CONSISTING OF NITRIDE To facilitate attachment of the photocatalytic layer onto the surface of pliable materials, and to protect and stabilize said material from harmful irradiation and effects from the photocatalyst, a linkage was deposited directly onto the material before the photocatalyst was deposited The linker should ideally provide a chemical anchor for the active photocatalyst and provide a barrier against free radicals released from the photocatalyst while not affecting the efficacy of the photocatalyst itself One such candidate linker tested here was a layer of nitride

The linker (a layer of nitride) was to be deposited onto cotton fibres using the ALD (atomic layer deposition) technique in a F-120 Sat reactor (ASM Microchemistry) with continuous nitrogen carrier gas flow through the reactor The pressure of the reactor during the growth was about 3 2 mbar Titanium tetrachloride (TiCI ₄ ) and ammonia (NH ₃ ) were used as precursors TMA improves the film quality and makes it possible to use lower growth temperature. TiCI ₄ pulse length was 400 ms, and purge time 7 s. TMA pulse length was 200 ms and purge time 2 s. NH ₃ pulse time was 300 ms and purge time 7 s. The growth temperature was 165 ⁰ C and the liquid precursors (TiCI ₄ and TMA) was kept at 20° C. The vapour pressures for the TiCI ₄ and TMA at 20 ° C were 11.4 and 9.8 mbar, respectively. Ammonia tank was at room temperature. The thickness of the lineage layer was about 10 nm. Depending on the cycle in the ALD reactor (typically 20- 20 000), the layer thickness was varied from 0.5 to 500 nm. Deposition of a photocatalyst layer consisting of titanium dioxide doped with (Nitrogen, Sulphide, Fluorine, Chlor, Boron, Aluminium, Silicon, Phosphorus, Vanadium, Chromium, Iron, Zinc, Germanium, Cadmium, Scandium, Tin Tantalum, Manganese, Cobalt, Nickel, Copper, Gallium, Strontium, Yttrium, Zirconium, Niobium, Molybdenum, Ruthenium, Palladium, Indium, Antimony, Barium, Cerium, Praseodymium, Neodymium, Samarium, Europium, Gadolinium, Dysprosium, Holmium, Erbium, Thulium, Lutetium, Hafnium, Tungsten, Iridium, Platinum, Bismuth, and/or hybrid layer combination thereof) onto the nitride layer was performed by atomic layer deposition either by co-pulsing or applying several precursors and reactant at the same time.

The resulting layer of nitride did not affect the pliability or appearance of the material. Experiments on the mechanical properties was performed where stretching and bending was performed on 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.

EXAMPLE 4 COATING OF PHOTOCATALYTIC LAYER

TiCI ₄ and H ₂ O were used to coat the non-solid, pliant material with TiO ₂ on top of a linker AI ₂ O ₃ as described in example 1. 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 min ^~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 were formed in a relatively large temperature interval as shown in Figure 2. Using a deposition temperature of 120 ⁰ C we obtained a growth rate of 0 046 nm/cycle Thus the coating procedure used 200 cycles, which gave a titanium oxide thickness of < 10 nm

The deposition may be expressed accordingly Step 1

TιCU(g) + I-OH → 1-0-TiCI ₃ + HCI(g)

Step 2

1-0-TiCI ₃ + H ₂ O(g) -> 1-0-Ti-(OH) ₃ + 3HCI(g)

The reactions may be shifted so that the liberation of HCI(g) was more in step 1 and less in step 2 depending on the reaction conditions See R L Puurunen, J Appl Phys 97 (2005) 121301

By performing the deposition at a reactor temperature at or below 165 ⁰ C, 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 Alternatively, the structure may be controlled in situ as described in J Aarik et al , J Cryst Growth 148 268 (1995) where anatase was deposited in the range 165 - 350 ⁰ C and rutile was 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 performed were 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 After the mechanical experiment no sign of flakes or detachment of in the coating layer was observed (Figure 4) 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 (Figure 4 and Figure 5)

EXAMPLE 5 TITANIUM OXIDE DOPED WITH NITROGEN

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 reaction scheme may be as follows Step 1 :

TiCI ₄ (g) + I-OH → 1-0-TiCI ₃ + HCI(g)

Step 2a: 1-0-TiCI ₃ + 3H ₂ O(g) → |-O-Ti-(OH) ₃ + 3HCI(g)

Step 2b:

1-0-TiCI ₃ + 3NH ₃ (g) → |-O-Ti-(NH ₂ ) ₃ + 3HCI(g)

The nitrogen concentrations of samples made from reaction above were determined by XPS and were listed in Table 1. The binding energy of nitrogen in all the samples were significantly lower (peak at 395 eV) indicating the presence of Ti-N bonding. In these films nitrogen was thus located at substitutional sites which resulted from incomplete oxidation of TiN during growth. Sample A3 had approximately an equal amount of both of these types of nitrogen present. The atomic formula of sample 1 would thus be TiO _{1 98} SN ₀ 0 ₁₂ , if only the N 1s peak at 395 eV was used. This was quite close to other reported visible light active TiO ₂ - _x N _x photocatalysts.

Table 2. Nitrogen concentrations measured by XPS and estimated band gap energies of the nitrogen-doped TiO ₂ films

Sample Nitrogen concentration (at.%) Band gap energy (eV)

1 0.8 3Λ

2 3.8 3.1

3 8.1 2.9

4 19.2 1.3

5 13.4 2.1

Photocatalytic degradation measurements were performed on a solid layer of stearic acid (CH ₃ (CH ₂ ) _I6 CO ₂ H, Aldrich, 95%). UV illumination was 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 was 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 were excited by visible light (λ > 380 nm)

Photo-induced super-hydrophilicity was an important property of TiO ₂ and good results have been reported for TιO ₂ _ _x N _x (R Asahi, T Monkawa, T Ohwaki, K Aoki and Y Taga, Science 293 (2001 ), p 269 ) The wetting properties of the films were studied by measuring their contact angles with water as a function of UV or visible light irradiation None of the samples became super-hydrophihc (contact angle below 10°) when visible light was used for irradiation However, when UV light was used some samples did show super-hydrophihc behaviour

EXAMPLE 6 TITANIUM OXIDE DOPED WITH NITROGEN

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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 TιCI ₄ (g) and H ₂ O(g) separated by pulses of an ammonia gas as mentioned above One alternative process was

Ti(Oi-Pr) _{4 (} g) + NH _{3 (g)} = TιO _x N _y(s) + H-ι-Pr _(g) (1) where ι-Pr was isopropyl, and x and y were arbitrary numbers

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 7 TITANIUM OXIDE DOPED WITH SULPHIDE

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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 Tι(Oι-Pr) ₄ (g) and H ₂ O(g) separated by pulses of hydrogen sulphide gas The alternative process which occurs was

Ti(Oi-Pr) _{4 (} g) + H ₂ S _(g) = TιO _x S _y(s) + H-ι-Pr _(g) (1 ) where ι-Pr was isopropyl, and x and y were arbitrary numbers

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 8 TITANIUM OXIDE DOPED WITH FLUORINE

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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 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 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 Tι(Oι-Pr) ₄ (g) and H ₂ O(g) separated by pulses of an fluorine gas The alternative process which occurs was

Ti(Oi-Pr) _{4 (g)} + NH ₄ F _(g) = TιO _x F _y(s) + H-ι-Pr _(g) + NH ₃ (g) (1 ) where ι-Pr was isopropyl, and x and y were arbitrary numbers

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 9 TITANIUM OXIDE DOPED WITH CHLOR Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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 Ti(Oi-Pr) ₄ (g) and H ₂ O(g) separated by pulses of an chloridric gas. The alternative process which occurs was:

Ti(Oi-Pr) _{4 (g)} + Cl _{2 (g)} = TiO _x Cl _y(s) + H-i-Pr _(g) (1 ) where i-Pr was isopropyl, and x and y were arbitrary numbers.

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 10 TITANIUM OXIDE DQPED WITH FLUORINE AND NITROGEN

Linker was produced as described in example 1. On top of the linker layer, a doped titanium oxide surface was created. 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 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 Ti(Oi-Pr) 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 occurs was:

Ti(Oi-Pr) _{4 (g)} + NH ₄ F _(g) = TiO _x F _y(s) + H-i-Pr _(g) + NH ₃ ( _g) (1 )

Ti(Oi-Pr) _{4 (g)} + NH _{3 (g)} = TiO _x N _y(s) + H-i-Pr _(g) (2) where i-Pr was isopropyl, and x and y were arbitrary numbers.

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 11 TITANIUM OXIDE DOPED WITH MAGNESIUM OXIDE

Linker was produced as described in example 1. On top of the linker layer, a doped titanium oxide surface was created. 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 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 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 cycles (typically from 20-2000 cycles)

EXAMPLE 12 TITANIUM OXIDE DOPED WITH MANGANESE OXIDE

Linker was produced as described in example 3 On top of the linker layer, a doped titanium oxide surface was created 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%), Mn(thd) ₃ (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 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 adding alternating pulsing of Mn(thd) ₃ (g) and O ₃ (g) to the process of deposition of TiO ₂

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 13 TITANIUM OXIDE DOPED WITH SILICON

Linker was produced as described in example 2 On top of the linker layer, a doped titanium oxide surface was created 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%), 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 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 and H ₂ O, some pyridine was added to the SiCI ₂ H ₂ pulses

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) EXAMPLE 14 TITANIUM OXIDE DOPED WITH CHROMIUM OXIDE

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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%), Cr(thd) ₃ (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 mιn ^~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 Cr(thd) ₃ (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 COBALT

Linker was produced as described in example 2 On top of the linker layer, a doped titanium oxide surface was created 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 16 TITANIUM OXIDE DOPED WITH ZINC AND FLUOR

Linker was produced as described in example 3 On top of the linker layer, a doped titanium oxide surface was created 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%), 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)

EXAMPLE 17 TITANIUM OXIDE DOPED WITH COPPER OXIDE

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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 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 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)

EXAMPLE 18 TITANIUM OXIDE DOPED WITH ZINC OXIDE Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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 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 ZnCI ₂ (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) EXAMPLE 19 TITANIUM OXIDE DOPED WITH ZIRCONIUM OXIDE

Linker was produced as described in example 3 On top of the linker layer, a doped titanium oxide surface was created 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%), 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)

EXAMPLE 20 TITANIUM OXIDE DOPED WITH ZIRCONIUM TITANIUM OXIDE

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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%), ZrCI ₄ (g) (Fluka, 99%), Ti(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 Ti(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)

EXAMPLE 21 TITANIUM OXIDE DOPED WITH PALLADIUM

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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)

EXAMPLE 22 TITANIUM OXIDE DOPED WITH IRON

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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 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 Fe(thd) ₃ (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 23 TITANIUM OXIDE DOPED WITH PLATINIUM

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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)Me ₃ (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 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 Pt(CpMe)Me ₃ (g) and O 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) EXAMPLE 24 TITANIUM OXIDE DOPED WITH VANADIUM OXIDE

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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%), VOCI ₃ (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 VOCI ₃ (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)

EXAMPLE 25 TITANIUM OXIDE DOPED WITH BORON AND NITROGEN

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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%), BCI ₃ (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 BCI ₃ (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)

EXAMPLE 26 TITANIUM OXIDE DOPED WITH TANTALUM

Linker was produced as described in example 2 On top of the linker layer, a doped titanium oxide surface was created 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%), TaCI ₅ (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 TaCI ₅ (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)

EXAMPLE 27 TITANIUM OXIDE DOPED WITH TANTALUM AND NITRIDE

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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%), 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)

EXAMPLE 28 TITANIUM OXIDE DOPED WITH SILVER

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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)

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 29 TITANIUM OXIDE DOPED WITH BROMINE

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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%), 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 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 Tι(Oι-Pr) ₄ (g) and H ₂ O(g) separated by pulses of an Br ₂ (g) The alternative process which occurs was

Ti(Oi-Pr) _{4 (g)} + Br _{2 (g)} = TιO _x Br _y(s) + H-ι-Pr _(g) (1 ) where ι-Pr was isopropyl, and x and y were arbitrary numbers

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 30 TITANIUM OXIDE DOPED WITH ALUMINUM OXIDE Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface was created 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%), AI(CH ₃ ) ₃ (trimethylaluminium, TMA) (Witco) (g) (Fluka, 99%), and H ₂ O (distilled) and O ₃ 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 mιn ^~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 AI(CH ₃ ) ₃ (g) and H ₂ O (g) by means of co-pulsing

AI(CH ₃ ) ₃ (trimethylaluminium, TMA) (Witco) and O ₃ as precursors at a deposition temperature

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 31 TITANIUM OXIDE DOPED WITH WOLFRAM

Linker was produced as described in example 1 On top of the linker layer, a doped titanium oxide surface doped with aluminium oxide was created 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 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 WF ₆ (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)

EXAMPLE 32 ANTI-FOULING COATING OF WOUND DRESSINGS BASED ON ALGINATE

Wound dressing (Melgisorb®, Molnlycke Health Care, Sweden) (n=2) was coated in a commercial F-120 Sat reactor (ASM Microchemistry) as described in example 4 and 5 The linker as described in examples 1 protected the alginate from degradation from the photocatalytic effect of the doped titanium oxide layer

TiO ₂ coated on the wound dressing material needs be flexible enough to withstand mechanical loading/bending such that the anti-fouling layer do not flake of the non-pliant material Therefore mechanical tests with stretching and bending were performed Bending of 90 degrees, then stretching of 15% showed no instability of the coating or flakes, as 50 bending of 180 degrees and a stretching of 15%

The wound dressing was seeded with anti-fouling endotoxin components such as LPS (composed of lipid A ore oligosaccharide and 0-antιgen) 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 EXAMPLE 33 ANTI-FOULING COATING OF WOUND DRESSINGS BASED ON POLYAMID ENCAPSULATED IN SILICONE

A non-pliant material made of polyamide fibres encapsulated in silicone, wound dressing (Mepitel®, Mόlnlycke Health Care, Sweden) and (A=Melgisorb® , Mόlnlycke Health Care, Sweden) (n=2) was coated in a commercial F-120 Sat reactor (ASM Microchemistry) as described in example 4 and 5. The wound dressings was viewed in a tabletop scanning electron microscope (TM1000, Hitachi, Toyko, Japan).

Uncoated wound dressing was used as control. The coating was 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.

The wound dressing was seeded with anti-fouling components such as LPS, PepG Images was taken by FTIR microscope (SPOTLIGHT 400, PerkinElmer, Norway) before and after a light source was used.

EXAMPLE 34 ANTI-FOULING COATING OF COTTONS

In order to protect cotton from staining, an anti-fouling layer was deposited as described in example 4 and 5. The linker as described in example 1 did protect the silk and rayon from degradation from the photocatalytic effect of the doped titanium oxide layer. The cotton was stained with household butter After exposure to strong sunlight, the stain started to fade.

EXAMPLE 35 ANTI-FOULING COATING OF FINE GARMENTS (WOOL, SILK and RAYON) In order to protect fine garment such as wool, from staining, an anti-fouling layer was deposited as described in example 4 and 5 The linker as described in examples 1 did protect the silk and rayon from degradation from the photocatalytic effect of the doped titanium oxide layer The silk and rayon fibres from a woman dress were stained with red wine After exposure to strong sunlight, the stain started to fade

EXAMPLE 36 ANTI-FOULING COATING OF KITCHEN CLOTHS (70% polyester and 30% polyamid)

Kitchen cloths (typically composition 70%polyester and 30%polyamιde) were prone to be infected with bio-fouling materials An ordinary kitchen cloth was coated with anti-fouling coating as described in example 4 and used regularly in a household for three days without washing The colour turned from yellow to greyish After applying direct sun light, the colour returned to yellow after some hours. When applying UV light, the colour returned after somewhat faster.

EXAMPLE 37 ANTI-FOULING COATING OF TABLE CLOTH Table cloths (typically composition PVC and polyester) were prone to be stained with wine, food etc. An ordinary table cloth was coated with anti-fouling coating as described in example 5 and used regularly in a household for three days without washing. Three stains was made, red wine, white wine and tomato sauce. The white colour of the table cloth returned after applying bright sun light.

EXAMPLE 38 ANTi-FOULING COATING OF SUN SHADE PROTECTION Sun protections which are outdoors all year around were stained due to weather condition. A sun protection made of cotton, or polyester, or polypropylene, acrylic was coated with anti-fouling coating as described in example 5 and used one season without washing. The sun protection textile remained white throughout the whole seasons whereas the uncoated sun protection (placed next to the coated one) received a 5-10 stains.

EXAMPLE 39 ANTI-FOULING COATING OF DUVET AND CUSHIONS Duvets and cushions are difficult items to clean. The protective layer around a duvet and cushion was coated with anti-fouling coating as described in example 5 and used one season without washing. Stains were visible (light yellow). After hanging the textile outside for one afternoon, the textile regained its colour.

EXAMPLE 40 ANTI-FOULING COATING OF SPORTSWEAR

Sportswears are often susceptible to bio-fouling. Two set of Lycra® sport t-shirt (made of block co-polymer of polyurethane and polyethylene glycol) were purchased. One was coated as described in example 5 and one was uncoated. One volunteer went for one hour run in daylight with first the uncoated and then the coated t-shirt: they were soaking wet under the armpits. After hanging the textile outside for one afternoon, the odour difference under the armpits between the two t-shirts was remarkable, where the coated t- shirt had almost no odour. The uncoated Lycra® t-shirt was also be slightly stained under the armpits. EXAMPLE 41 ANTI-FOULING COATING OF SPORT WEAR, NEOPRENE

Sportswears are often being susceptible for bio-fouling, particular wetsuits that are difficult to clean which were made of neoprene (Polychloroprene), as well as a premature degradation due to sunlight exposure when drying in the sun outside Neoprene wetsuit was coated as described in example 5 One volunteer used the wetsuits for one summer, and compared it with his partner's wetsuit The coated wetsuits did hang outside in daylight every time after use The odour difference between the two wetsuits was remarkable where the coated one had almost no odour and no stains A difference was visible between the colour of the coated neoprene and the uncoated one the coated wetsuit kept its original colour while the uncoated one changed to a lighter stain

EXAMPLE 42 ANTI-FOULING COATING OF SAILS (POLYAMID, POLYESTER, PET, PEN)

Sails are degenerated due to the UV light A coating as described in example 4 was performed on a sail consisting of polyamide, aramide, polyester, polyethylene naphthalate and PET Similar sail was uncoated and the two samples were placed outside for 4 months After this period the fibres was examined in FTIRI (Spotlight 400, Perkin Elmer,

Norway) Degradation of the uncoated fibre was visible in the 5 micrometer levels whereas the coated sail showed no sign of degeneration A tensile test was also performed (Zwick, ZwickRoell, UIm, Germany) and significant changes in the tensile properties was found suggesting a chemically deterioration of the uncoated sail

EXAMPLE 43 ANTI-FOULING COATING OF SHOE SOLE

Shoe soles are often being susceptible for bio-fouling and strong odour To set of shoe soles of mix fibers of cotton and wool was purchased One coated as described in example 5 and one uncoated One volunteer did wear the shoes for 48 hours without removing the sole, the coated sole in left shoe and uncoated in right After 48 hours, a distinct odour was detected The shoes were placed outside in strong sun light After the some exposure time, the coated shoe sole had significantly less odour

EXAMPLE 44 ANTI-FOULING COATING OF PROTECTIVE TEXTILE

Protective textile such as car seats, seat cushions, sofa, chair are often made of syntethic fibers and natural fibers A set of such material were coated with titanium oxide doped with AI ₂ O ₂ with AI ₂ O ₃ as a linker (as described in example 1 and example 31) The doped layer was shown to be hydrophobic (water contact angle >90) Staining such as wine and chocholate was less susceptible for the fabric with this coating In addition colour stains were removed after applying UV lamp EXAMPLE 45 UNIFORM COATING OF THE LINKER AND PHOTOCATALYTIC LAYER

A wound dressing was coated as described in example 1 Furthermore, this polymeer was investigated in TEM analysis (A Philips BιoTwιnCM120 TEM) The results are presented in Figure 6, where the polymer fibres 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 The layer coating the fibres was of a constant thickness and pin-hole free

EXAMPLE 46 CHEMICAL DEGRADATION OF POLYMER DUE TO REACTOR TEMPERATURE

Uncoated Mepore (Molnlycke Health Care AB ₁ Goteborg, Sweden) wound dressings were used in this experiment These wound dressings are made with non-woven polyester fabric coated with a layer of an acrylic adhesive and a polyurethane cover Their tolerance to the warm temperatures was performed on rectangular (1x2 cm ² ) samples The chemical tests were done at different temperatures room temperature (control at 23 ⁰ C), 120°C for 3 hours, 15O ⁰ C for 3 hours The infrared (IR) spectrum of each sample was measured 10 times by Fourier Transform Infrared spectrometry (Spectrum 400 FTIR/FT- NIR Spectrometer, Perkin Elmer, Waltham MA, USA) The peaks from 1770 to 1630 nm and from 1572 to 1492 nm were chosen since they belong to C=O and C-O-C chemical bonds, respectively The average of the various ratios was extracted from the 3 groups of samples (control at 23°C, 12O ⁰ C and 150°C) The results obtained for 120 and 150 ⁰ C were compared with the control group All data were tested for normality distribution prior to comparison The significant level was tested with a RANK ON ANOVA with Tukey test (SigmaStat 3 5, Symantec Inc, St Louis, USA) with a significant level of P < 0 05 No statistical difference between control sample and the test samples no polymer degradation when exposed to a temperature of 15O ⁰ C for 3 hours

EXAMPLE 47 CHEMICAL DEGRADATION OF POLYMER DUE TO REACTOR REAGENTS

Mepore (Molnlycke Health Care AB, Goteborg, Sweden) wound dressings uncoated, coated with TiO ₂ (5 nm) and coated with AI ₂ O ₃ (5 nm) + TiO ₂ (5 nm) were used in this experiment The eventual degradation of the polymer composing the wound dressing due to reactor reagents during the ALD process (described in examples 1 and 4) was tested The surface chemical composition of these 3 groups was analysed by Fourier Transform Infrared spectrometry (Spectrum 400 FTIR/FT-NIR Spectrometer, Perkin Elmer, Waltham MA, USA) The peaks from 1770 to 1630 nm and from 1572 to 1492 nm were chosen since they belong to C=O and C-O-C chemical bonds, respectively The average of the various ratios were extracted from the 3 groups of samples (uncoated, coated with TiO ₂ (5 nm) and coated with AI ₂ O ₃ (5 nm) + TiO ₂ (5 nm)) The results obtained were compared with the control group (uncoated wound dressing) Data were tested for normality distribution prior to comparison The significant level was tested with a RANK ON ANOVA with Tukey test (SigmaStat 3 5, Symantec Inc, St Louis, USA) with a significant level of P < 0 05 A statistical difference was found between control and wound dressing coated with TiO ₂ indicating a degradation due to one reagent during the ALD process (believed to be chlore gas) No statistical difference between control and wound dressing coated with AI ₂ O ₃ + TiO ₂ the linker layer of AI2O3 is believed to protect the polymer fibres from chlore gas during the ALD process

EXAMPLE 48 BIOCOMPATIBILITY OF TiO ₂ LAYER

The cytotoxicity of wound dressings with different surface coatings 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 In addition, 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 (Table 1) 5 samples were prepared per group and sterilised in by washing with ethanol for 15 mm at room tempertaure 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 ⁰ C The resulting extract was subsequently transferred to sterile microcentrifuge tubes and used immediately

Table 1 Groups of samples tested for cytotoxicity

Test group n

Positive control 100% toxicity 1% Triton X-IOO in the cell suspension 3

. 0% toxicity Cell growth medium without any extract 3 Negative control , , Control plastic Extract from well in 24-well plate 5x3

Non irradiated 5x3

Uncoated dressing 15 mm UV 5x3

Non irradiated 5x3

5 nm AI ₂ O ₃ 15 mm UV 5x3

Non irradiated

10 nm AI ₂ O ₃ 15 mm UV

Non irradiated

5 nm AI ₂ O ₃ + 5 nm TiO ₂ 15 mm UV

5 nm Al ₂ O ₃ + 10 nm TiO ₂ 120 ⁰ C Non irradiated deposition temperature 15 mm UV

5 nm AI ₂ O ₃ + 10 nm TiO ₂ 80 ⁰ C Non irradiated 5x3 deposition temperature 15 mm UV 5x3

Non irradiated

5 nm AI ₂ O ₃ + 15 nm TiO ₂ 15 mm UV

Cell cultivation

Cell line NHDF AD

Cell type Normal human dermal fibroblasts - adult, passage 11

Medium FBM + FGM*2 (Clonetics)

+ 5 ml PEST (100 U/ml Penicilin, 100 μg/ml Streptomycin) ^{CC CC} ccnnππnn

XXXX XX

^O O ^OJ O ^OJ O ^JJJJ

FGM*2 contains

1 μg/ml hFGF (human recombinant fibroblast growth factor)

5 mg/ml Insulin

50 mg/ml Gentamicin

50 μg/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 μl cell suspension made with fresh media and 100 μl of cell medium from the extract was given to each well of a 96-well plate (TPP, Switzerland), resulting in a total of 200 μl media containing 10000 cells per well Each extract was tested in triplicates After incubation for 24 h at 37 ⁰ C, the medium was carefullt removed from the wells and stored in microcentrifuge tubes at 4°C until analysis

The Cytotoxicity Detection kit from Roche Diagnostics (Roche Diagnostics Norge AS) was used for measurement of the LDH activity 50 μl of medium was mixed with equal amounts of the dye solution The results were read with the Ehsa 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 p-values < 0.01 highly significant (noted **). The wound dressing which had a linker layer of 5 nm AI ₂ O ₃ and 10 nm TiO ₂ on top at both deposition temperature of 8O ⁰ C and 120 ⁰ C performed significantly better than only layer of TiO ₂ or AI ₂ O ₃ . When UV light irradation was applied prior to testing, the biocompatibility decreased for the group with the linker layer, whereas the wound dressing with the TiO ₂ layer had a significant increased toxicity (decrease biocompatibility). This showed that the linker layer was protecting the polymeric fiber from the free radical being release from the TiO ₂ layer when activated by UV light. Also the samples with the AI ₂ O ₃ coating alone had an increased in toxicity after UV exposure when AI ₂ O ₃ was too thin (5 nm). This was due to the fact that AI ₂ O ₃ allowed the UV light to enter the polymer fibres and being degradation of the polymer (figure 7).

EXAMPLE 49 ANTI-BACTERIAL EFFECT OF TiO2 LAYER

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 works as protection anti- bacterial. The second output was to determine if a linker layer of AI ₂ O ₃ between the wound dressing and the TiO ₂ coating would have an effect on the anti-bacterial potential of the overall coating.

Wound dressing treatment: The wound dressing composed of polyacrylate (PA) fibres were coated with TiO ₂ (10nm), and with AI ₂ O ₃ (5nm) + TiO ₂ (5nm) by ALD (atomic layer deposition technique in gas phase) as described in example 1 and 4

Bacteria: Staphylococcus aureus (S. aureus) are important human commensal and opportunistic pathogens responsible for a wide range of infections. They are one of the most known bacteria responsible for post-surgery infection. Therefore, S. aureus were chosen for this experiment.

Procedure:

Small squares (5x5mm ² ) of wound dressing were cut. The anti-bacterial effect of the three wound dressings were tested with increasing UV light exposures: O minutes (control), 5 min, 15 min and 30 min (test groups). 500μl from a broth of S. aureus was diluted in 4ml of PBS (Dulbecco's PBS, Sigma- Aldrich, St Louis, MO, USA) (stock solution). A drop of 10μl of this stock solution was placed on the top of the wound dressing. Once the UV light exposure of the test groups reached, the small squares of wound dressing were individually placed in 1.5 ml Eppendorf tubes containing 500μl of cell culture medium (without antibiotics) of from Invitrogen (GIBSCO MEM, Invitrogen, Carlsbad, CA, USA). All the Eppendorf tubes containing the wound dressing and the bacteria were placed in an incubator, in the dark, at 37 ⁰ C for 20 hours. After 20 hours, all the samples were taken out of the incubator. A Spectrometer (Perkin Elmer UV-Vis 200) was calibrated with only 700μl of cell media for the base line. Then, the three Eppendorf tubes containing only 500μl of cell media + 10μl of the stock solution was analysed. Then, one by one the test tubes were shaked and a volume of 400μl from each tube was mixed with 300μl of cell media. The 1.5ml cuvettes contained 700μl of liquid to be analysed. The samples were analysed only at 325nm and 425nm. The results are presented in Figure 8 and showed that the wound dressing with the linker layer of 5 nm AI ₂ O ₃ covered by 5 nm TiO ₂ reduced the initial bacteria population by several log scale value when exposed to 15 min UV irradation. The experiment also showed also that the wound dressing coated with the linker layer of 5 nm AI ₂ O ₃ and 5 nm TiO ₂ was significant more effective than the wound dressing with only 10 nm TiO ₂ coating layer.

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