WO2008063134A1 - Procédé de production d'un motif à mouillabilité discriminative - Google Patents

Procédé de production d'un motif à mouillabilité discriminative Download PDF

Info

Publication number
WO2008063134A1
WO2008063134A1 PCT/SG2006/000362 SG2006000362W WO2008063134A1 WO 2008063134 A1 WO2008063134 A1 WO 2008063134A1 SG 2006000362 W SG2006000362 W SG 2006000362W WO 2008063134 A1 WO2008063134 A1 WO 2008063134A1
Authority
WO
WIPO (PCT)
Prior art keywords
matter
silane
photocatalytic
oxidisable
substrate
Prior art date
Application number
PCT/SG2006/000362
Other languages
English (en)
Inventor
Nam Yong Kim
Y. Jackie Ying
Hua Zhang
Yong Yeow Lee
Kwong Joo Leck
Original Assignee
Agency For Science, Technology And Research
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agency For Science, Technology And Research filed Critical Agency For Science, Technology And Research
Priority to PCT/SG2006/000362 priority Critical patent/WO2008063134A1/fr
Publication of WO2008063134A1 publication Critical patent/WO2008063134A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B01J2219/00527—Sheets
    • B01J2219/00533—Sheets essentially rectangular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00596—Solid-phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B01J2219/00612—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports the surface being inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
    • B01J2219/00614—Delimitation of the attachment areas
    • B01J2219/00617—Delimitation of the attachment areas by chemical means
    • B01J2219/00619—Delimitation of the attachment areas by chemical means using hydrophilic or hydrophobic regions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00659—Two-dimensional arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B01J2219/00722—Nucleotides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B01J2219/00725—Peptides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B01J2219/0074—Biological products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation

Definitions

  • the present invention relates to a method of producing a pattern of discriminative wettability on the surface of a substrate.
  • Microarrays of biomaterials consisting of either DNA, proteins or cells, have found widespread applications in disease diagnosis, pathogen detection, biomarker discovery and analysis of biomarker interaction. Often the scope and performance of bio-microarrays are determined by the quality of coatings employed for surface patterning. Patterned surfaces have been fabricated by many methods including micro-contact printing micro-fluidic lithography and conventional photolithography. [003] Using such methods, hydrophilic-hydrophobic micropatterns have also been obtained. Kanta et al.
  • Japanese patent application 2005-003803 discloses a method of manufacturing hydrophobicity difference patterns by irradiating fluoroalkylsilane coated glass in the presence of an additional titanium oxide coated glass plate. In the method of this publication, the two surfaces are separated by a distance of less than 200 ⁇ m.
  • a different approach of obtaining a micropattern generates a surface with silicon-hydrogen bonds (English abstract of international patent application WO 2006/046699). In some areas the silicon-hydrogen surface is then reacted with a water- repellent compound in a hydrosilylation reaction, while in other areas it is reacted to a hydrophilic area.
  • micro-contact printing and micro-fluidic lithography have limited practical applications due to several disadvantages. They lack for example reliability and consistency, particularly in industrial scale-up. Furthermore, the methods of micro- contact printing and micro-fluidic lithography are often incompatible with popular coating conditions, such as long exposure to organic solvents or high-temperature vapour-phase deposition. Similarly, conventional photolithographic methods for surface patterning limit the range of coating reagents and methods available due to the presence of photoresist films. In addition, the photoresist films could leave residual materials on the surface, which could interfere with subsequent surface coating. Most important of all, these patterned surfaces can be used only once in spite of the significant fabrication cost and time involved. [005] These methods are generally also cost intensive, so that it would be desirable to provide a micropattern, at least parts of which can be reused without the requirement to produce a new substrate with an entire new pattern.
  • the present invention provides a method of producing a pattern of discriminative wettability on the surface of a substrate.
  • the method includes providing a substrate.
  • the method further includes patterning the surface of the substrate. By a respective patterning a plurality of accessible surface areas is defined.
  • the method also includes depositing only on said plurality of accessible surface areas photocatalytic matter.
  • the method further includes depositing on the entire surface, including the plurality of accessible surface areas, oxidisable matter.
  • the oxidisable matter is of a wettability that differs from the wettability of the photocatalytic matter.
  • the oxidisable matter is furthermore at least essentially inert to an exposure of electromagnetic radiation that is sufficient to cause the photocatalytic matter to catalyse the oxidation of the oxidisable matter.
  • the method also includes exposing the entire surface to electromagnetic radiation. As a result the photocatalytic matter catalyses the oxididation of such oxidisable matter that is in contact therewith. Thereby the oxidisable matter is removed from the plurality of surface areas. The photocatalytic matter on these surface areas is thereby exposed. Furthermore the oxidisable matter on the remaining surface of the substrate is at least essentially preserved. As a result a pattern of discriminative wettability is formed.
  • the remaining area of the surface is thus covered with oxidisable matter.
  • the plurality of surface areas is covered with photocatalytic matter.
  • the photocatalytic matter is removed by etching, thereby uncovering the plurality of surface areas and exposing the substrate surface in the respective surface areas. The surface can then be reused for e.g. depositing photocatalytic matter thereon.
  • the method includes depositing on the entire surface, including the plurality of accessible surface areas, oxidisable matter that is hydrophobic.
  • the hydrophobic oxidisable matter is of a lower wettability for water when compared to the photocatalytic matter.
  • the hydrophobic oxidisable matter is at least essentially inert to an exposure of electromagnetic radiation that is sufficient to cause the photocatalytic matter to catalyse the oxidation of the hydrophobic oxidisable matter.
  • the photocatalytic matter catalyses the oxididation of such hydrophobic oxidisable matter that is in contact therewith.
  • hydrophobic oxidisable matter is removed from the plurality of surface areas.
  • the photocatalytic matter on these surface areas is thereby exposed.
  • hydrophobic oxidisable matter on the remaining surface of the substrate is at least essentially preserved. As a result a pattern of discriminative hydrophobicity, and thereby of discriminative wettability, is formed.
  • this method of the invention further includes depositing a substance, which may include a molecule with a linking moiety, on the photocatalytic matter that covers the plurality of surface areas. Depositing such matter may be used for immobilising a molecule on the plurality of surface areas, for example via a respective linking moiety.
  • the present invention provides a further method of producing a pattern of discriminative wettability on the surface of a substrate.
  • This method also includes providing a substrate.
  • the method further includes depositing on the entire surface of the substrate photocatalytic matter.
  • the method includes vapour coating the entire surface with oxidisable matter.
  • the oxidisable matter is of a wettability that differs from the wettability of the photocatalytic matter.
  • the oxidisable matter is furthermore at least essentially inert to an exposure of electromagnetic radiation that is sufficient to cause the photocatalytic matter to catalyse the oxidation of the oxidisable matter.
  • the method further includes patterning the surface of the substrate. By a respective patterning a plurality of accessible surface areas is defined.
  • the method also includes exposing only said plurality of accessible surface areas to electromagnetic radiation.
  • the photocatalytic matter catalyses the oxidation of such oxidisable matter that is in contact therewith.
  • the oxidisable matter is removed from the plurality of surface areas.
  • the photocatalytic matter on these surface areas is thereby exposed.
  • the oxidisable matter on the remaining surface of the substrate is at least essentially preserved. As a result a pattern of discriminative wettability is formed.
  • the present invention provides a further method of producing a pattern of discriminative wettability on the surface of a substrate.
  • the method includes providing a substrate.
  • the method further includes depositing on the entire surface of the substrate photocatalytic matter. Further, the method includes depositing on the entire surface oxidisable matter.
  • the oxidisable matter is of a wettability that differs from the wettability of the photocatalytic matter.
  • the oxidisable matter is furthermore at least essentially inert to an exposure of electromagnetic radiation that is sufficient to cause the photocatalytic matter to catalyse the oxidation of the oxidisable matter.
  • the method further includes patterning the surface of the substrate. By a respective patterning a plurality of accessible surface areas is defined.
  • the method also includes exposing only said plurality of accessible surface areas to electromagnetic radiation.
  • the photocatalytic matter catalyses the oxididation of such oxidisable matter that is in contact therewith.
  • the oxidisable matter is removed from the plurality of surface areas.
  • the photocatalytic matter on these surface areas is thereby exposed.
  • the oxidisable matter on the remaining surface of the substrate is at least essentially preserved.
  • the method further includes at least essentially removing the photocatalytic matter by means of etching.
  • the method includes at least essentially uncovering the plurality of surface areas of the substrate.
  • the method also includes at least essentially preserving the oxidisable matter on the remaining surface of the substrate.
  • a pattern of discriminative wettability is formed.
  • the invention relates to a pattern of discriminative wettability on the surface of a substrate, obtained by a method of the present invention.
  • Figure 1 depicts a surface of a substrate (2) with a pattern of discriminative wettability, as well as schematic indications referring to methods of producing a respective pattern according to the present invention.
  • the pattern includes surface areas of photocatalytic matter (4) and oxidisable matter (5).
  • FIG. 2A depicts a schematic representation of a method according to the present invention.
  • the box depicts the basic steps of the method.
  • I On a surface (1) of a substrate (2) a plurality of accessible surface areas (3) is patterned, on which photocatalytic matter is to be deposited.
  • II Photocatalytic matter (4) is deposited on the respective surface areas.
  • Ill Since the photocatalytic matter (4) only covers the plurality of accessible surface areas, the remaining surface area of the substrate remains unaltered.
  • IV Hydrophobic oxidisable matter (5) is deposited on the surface (1).
  • V Both the previously unaltered surface of the substrate (2) and the photocatalytic matter (4) are covered with the hydrophobic oxidisable matter (5), which therefore covers the entire surface (1).
  • VI The entire surface covered with the hydrophobic oxidisable matter (5) is exposed to electromagnetic radiation.
  • VII As a result the photocatalytic matter (4) oxidises the hydrophobic oxidisable matter (5) that is in contact therewith, causing the removal of such hydrophobic oxidisable matter that covers the photocatalytic matter (4).
  • VIII Optionally the uncovered titanium oxide may be removed by etching.
  • IX Thereby the substrate surface (1) is uncovered in the plurality of surface areas and only the remaining surface area of the substrate remains covered by the hydrophobic oxidisable matter (5).
  • X As a further option, a substance that includes a molecule with a linking moiety (6) can be deposited on the plurality of surface areas.
  • XI Thereby the photocatalytic matter (4) is covered with such substance (6).
  • XII A target molecule (7) with an affinity for the linking moiety (6) can be deposited on the plurality of surface areas.
  • XIII As a result, the target molecule (7) is immobilised via the molecule with a linking moiety (6).
  • the substance including a molecule with a linking moiety (6), as well as any target molecule (7) immobilised thereon, may be removed together with the titanium oxide by etching (VIII).
  • the substance including a molecule with a linking moiety (6), including any target molecule (7) immobilised thereon may be removed by exposing the entire surfaced to electromagnetic radiation (XIV).
  • Fig. 2B depicts a schematic representation of exemplary methods of depositing photocatalytic matter (4) on the plurality of surface areas (cf. Fig. 2A).
  • a photomask (4) above the surface (1) of a substrate (2), to cover the remaining surface (I) of the substrate.
  • II Using a sputter photocatalytic matter (4) is deposited on the surface.
  • Ill Due to the use of the photomask the photocatalytic matter (4) only covers the plurality of surface areas (cf. Fig. 2A).
  • FIG. 2C depicts a schematic representation of a further method according to the present invention.
  • photocatalytic matter (2) using a sputter (I).
  • Hydrophobic oxidisable matter (5) is deposited on the substrate (1) (II).
  • a photomask (7) is placed above the hydrophobic surface (III), which is exposed to electromagnetic radiation (IV) via the photomask, causing the photocatalytic matter to catalyse the removal of hydrophobic oxidisable matter that covers the photocatalytic matter.
  • the uncovered photocatalytic matter may be removed by etching (V), thereby exposing the substrate surface.
  • Figure 3 depicts examples of haloalkylsilanes that may be used as hydrophobic oxidisable matter in a method according to the invention.
  • Figure 4 depicts advancing or receding contact angles of water on mixed anatase- amorphous titanium oxide surfaces subjected to different periods of UV irradiation. The uncertainty in contact angle measurement was ⁇ 2°.
  • Figure 5A depicts a photograph of a glass chip with a surface that comprises a pattern of discriminative hydrophobicity. Stained aqueous solution (dark) is adsorbed only on the hydrophilic areas of the surface.
  • Figure 5B shows a typical fluorescence image of a respectively patterned glass chip, where the wash solution (0.05 % Tween 20 in 50 mM Tris buffer containing 10 ⁇ M Fluorescein) is adsorbed only onto the hydrophilic glass areas.
  • Figure 6 depicts the adsorption and growth of HepG2 cells on hydrophilic areas of a surface produced according to a method of the invention, comprising pattern of discriminative hydrophobicity. Photos were taken on (A, D) day 1, (B, E) day 6, and (C, F) day 8, after the chip was seeded with 0.8 ⁇ l of HepG2 cells (20 cells/ ⁇ l).
  • the present invention provides a method of producing a pattern of discriminative wettability on the surface of a substrate.
  • Any surface may be used for the method of the invention, on which a selected photocatalytic matter and selected oxidisable matter can be deposited (see below).
  • the surface may for instance be of any shape and material, as long as it is capable of accommodating a photocatalytic matter and oxidisable matter, and as long as it is compatible with the selected conditions for depositing and irradiating.
  • Any desired substrate may be used.
  • the substrate may for example be made of or comprise any material, as long as its surface is suitable for the method of the invention (see above).
  • the substrate is of a solid material.
  • a suitable surface including a surface of such a substrate, may comprise a metal, a metalloid, ceramics, a metal oxide, a metalloid oxide or oxide ceramics.
  • suitable metalloids include, but are not limited to silicon, boron, germanium, antimony and composites thereof.
  • suitable metals include, but are not limited to iron (e.g. steel), aluminium, gold, silver, chromium, tin, copper, titanium, zinc, aluminium, lead and composites thereof.
  • a respective oxide of any of these metalloids and metals may be used as a metalloid oxide or metal oxide respectively.
  • the surface may be of quartz or glass.
  • a silicon oxide or germanium oxide surface may be obtained by etching a silicon substrate or germanium substrate, respectively, with piranha solution, i.e. a mixture of sulphuric acid and hydrogen peroxide solution at a molar ratio of 7:3.
  • piranha solution i.e. a mixture of sulphuric acid and hydrogen peroxide solution at a molar ratio of 7:3.
  • ceramics include, but are not limited to, silicate ceramics, oxide ceramics, carbide ceramics or nitride ceramics.
  • the surface of the substrate may be of any geometric properties.
  • the surface may for example be at least essentially smooth.
  • the surface may also be rough to any degree as long as it allows for the deposition of a selected photocatalytic matter and selected oxidisable matter. Where desired, the roughness of the surface may be altered.
  • a metal oxide or metalloid oxide surface e.g. a silicon oxide surface
  • the surface may be ground by means of sand paper (Ferrari, M., et al. Applied Physics Letters (2006) 88, 203125-1 -203125-3).
  • the surface may be etched (cf. e.g. Cao, M. et al., J.
  • the surface is at least essentially homogenous. In some embodiments the surface is furthermore at least essentially flat.
  • the surface may be polar or apolar, e.g. hydrophilic or hydrophobic. It may for instance be of different, similar or of the same hydrophobic properties when compared to the properties of the hydrophobic oxidisable matter used in the method of the present invention.
  • the method of the invention includes providing a substrate with a surface as described above and patterning the surface of the substrate such that a plurality of accessible surface areas is defined. Patterning the surface of the substrate usually includes selecting thereon a plurality of areas. On the plurality of surface areas photocatalytic matter is to be deposited as described below. The selected plurality of areas may include areas of any dimension and size. Some or all of the respective areas may be identical, similar or different in size and shape. In some embodiments all areas of the plurality of surface areas are identical. In some embodiments each area of the plurality of surface areas is of a maximal width in the plane of the surface that is that is below about 2 cm.
  • the maximal width in the plane of the surface may be selected in the range of about 0.1 ⁇ m to about 5 cm, such as the range of about 1 ⁇ m to about 1 cm or the range of 10 ⁇ m to about to about 10 mm, for instance the range of about 100 ⁇ m to about 2000 ⁇ m.
  • the maximal width in the plane of the surface may be about 10 ⁇ m to about 500 ⁇ m.
  • some or all areas of the plurality of surface areas may be of a uniform width in the plane of the surface.
  • An area of the plurality of surface areas may for instance be of the shape of a circle when viewed from above the respective surface. In other embodiments a respective area may include any number of widths in the plane of the surface.
  • An area of the plurality of surface areas may for instance be of the shape of an egg, letters V, U, X or H, a triangle, a rectangle, a square, or any oligoedron.
  • the areas of the plurality of surface areas define a micro pattern.
  • any number of these areas, including all areas of the plurality of surface areas, is connected to form a continuous pattern, hi other embodiments any number of separate areas is arranged in such a way that as a whole they appear as a pattern.
  • Patterning the surface of the substrate may furthermore include the use of additional matter in order to distinguish the selected plurality of areas from the remaining area of the surface.
  • the remaining surface of the substrate may be covered with a mask, such as a photomask. It may in some embodiments be desired to select a photomask with an elastomeric film/coating of a selected thickness. Such a selection may for example be desired in order to improve the resolution of depositing photocatalytic matter on the surface of the substrate. An elastomeric film is likely to improve the contact between the mask and substrate and to minimize the diffusion of photocatalytic material between mask and substrate. It may furthermore be desired to apply additional pressure to further improve the contact.
  • a photoresist may be deposited on the remaining surface of the substrate (cf. Fig. 2B for a graphic illustration).
  • a plurality of stamps may be positioned above the plurality of accessible surface areas.
  • the method of the invention further includes depositing only on the plurality of accessible surface areas photocatalytic matter.
  • photocatalytic matter refers to any matter that fulfils the following two conditions. Firstly, photocatalytic matter is capable of catalysing a chemical reaction, such as an oxidation. Secondly, this capability is altered when exposed to electromagnetic radiation such as light. Photocatalytic matter may for instance be inactive when not exposed to electromagnetic radiation, but its capability of catalysing a chemical reaction is accelerated or induced upon being exposed to electromagnetic radiation. Photocatalytic matter may also be capable of catalysing a chemical reaction when not exposed to electromagnetic radiation, but the respective capability is partially or completely lost upon exposure to electromagnetic radiation. In typical embodiments, the photocatalytic matter becomes capable of catalysing a chemical reaction once exposed to electromagnetic radiation.
  • a respective chemical reaction typically results in degrading chemical compounds and/or biological material.
  • the photocatalytic matter should at least be capable of assisting or starting a chemical reaction that can be exploited to degrade a desired hydrophilic compound (see below).
  • an exposure to light, in particular UV light causes the generation of active oxygen as a result of a photo redox reaction.
  • the active oxygen is capable of oxidising matter in contact with or vicinity to the titanium dioxide.
  • a standard method used in the art to assess the photocatalytic activity of matter of interest includes bringing 4-nitrophenol or rhodamine in vicinity or contact to the matter of interest, irradiating with e.g. UV light, and monitoring or determining the degradation of 4- nitrophenol or respectively rhodamine.
  • Another standard method includes contacting water with the photocatalytic matter
  • Any photocatalytic matter may be used in the method of the present invention that is capable of causing selected oxidisable matter to be at least essentially degraded (see below).
  • the photocatalytic matter may for instance comprise a single photocatalytic compound, a mixture of photocatalytic compounds or a composite material of compounds that possesses photocatalytic activity.
  • Two illustrative examples of a photocatalytic compound are a metal oxide and a metal sulphide.
  • a metal oxide examples include, but are not limited to, a titanium oxide, a tin oxide, a lanthanum oxide, a tantalum oxide, a gadolinium oxide, a tungsten oxide, a nickel oxide, a copper oxide, a niobium oxide, a ruthenium oxide, a cerium oxide and any combination thereof.
  • a titanium oxide in the following also abbreviated as TiO x (in which x is typically 1 or 2), may be titanium dioxide, TiO 2 (in e.g. anatase or rutile forms), a niobium oxide may be Nb 2 O 5 , and a tantalum oxide may be Ta 2 O 5 .
  • a metal sulphide zinc sulphide, ZnS, molybdenum sulphide, MoS 2 , and cadmium sulphide, CdS.
  • An illustrative example of a composite material of compounds that possesses photocatalytic activity is a mixed oxide of at least two metals.
  • Examples of a mixed oxide of at least two metals include, but are not limited to, a zirconium/titanium oxide, a tantalum/titanium oxide, a silver/chromium oxide, a silver/molybdenum oxide, a silver/manganese oxide, a silver/tungsten oxide, a potassium/ cerium/tantalum oxide, a potassium/cerium/niobium oxide.
  • the photocatalytic matter may be of any wettability. It may for example be of the same or a different wettability when compared to the surface of the substrate as provided in the method of the invention. In some embodiments the photocatalytic matter is hydrophilic.
  • the photocatalytic matter may also include a cocatalyst molecule such as platinum, palladium, ruthenium a ruthenium oxide, an iridium oxide or a nickel oxide.
  • a dopant such as iron, palladium or a platinum complex may be used where desired.
  • ⁇ Nature Materials (2006) 5, 665-670 have for instance characterised the atomic steps on the surface of anatase TiO 2 , which may be used as the photocatalytic matter in a method of the present invention, and determined the stabilities of the respective oxide steps.
  • the photocatalytic matter may be deposited by any means.
  • the photocatalytic matter is a metal oxide or a mixture of metal oxides, it may for example be deposited by flame hydrolysis deposition (FHD), plasma enhanced chemical vapour deposition (PECVD), inductive coupled plasma enhanced chemical vapour deposition (ICP- CVD) or the sol-gel method.
  • FHD flame hydrolysis deposition
  • PECVD plasma enhanced chemical vapour deposition
  • ICP- CVD inductive coupled plasma enhanced chemical vapour deposition
  • the photocatalytic matter is for example deposited by means of sputtering.
  • the photocatalytic matter is deposited by means of the sol-gel process.
  • a titanate sol may be generated by hydrolysis of tetrabutyl-titanate or tetrapropyl-titanate.
  • any suitable protocol such as sol-gel protocols using acid-catalysed, base-catalysed and two-step acid-base catalysed procedures may be followed.
  • the photocatalytic matter is deposited by means of chemical vapour decomposition.
  • the respective deposition process such as sputtering, a sol-gel process or a chemical vapour decomposition coating process used in the present invention can be performed according to any protocol.
  • the photocatalytic matter deposited according to the method of the present invention may form any topography. It may for instance be deposited in form of a layer.
  • a respective layer may be of any desired thickness. In typical embodiments, a respective thickness is selected in the range between about 1 and about 1000 nm, such as for example, 1.5 nm.
  • the oxidisable matter forms a film on the surface. In one embodiment a respective film is a monolayer.
  • Depositing the photocatalytic matter only on the plurality of accessible surface areas may be achieved by any means. Numerous methods of selectively depositing matter on a surface are established in the art. As an example, microcontact printing, microfluidic patterning, microfluidic lithography, cleaved edge overgrowth, or shadowed evaporation may be used. As a further example, a photoresist may be used in combination with e.g. lithography (involving irradiation with visible light, UV light or X-ray, including the use of a laser, with an ion beam, with an electron beam, or a scanning probe). In this way the remaining surface may be covered with a photoresist (see Fig.
  • an exposure to an elevated temperature may cause the decomposition of the photoresist (see Fig. 2B, steps IIA and IIB), thus removing the photocatalytic matter in contact therewith ("lift-off).
  • photocatalytic matter is removed from the remaining surface area(s).
  • an electron beam, fast iron bombardment, or laser microstructuring may be used to selectively remove photocatalytic matter from any area of the surface that is not selected or where it is not desired.
  • a mask such as a photomask
  • a respective mask may cover the remaining surface of the substrate, thus preventing the deposition of photocatalytic matter thereon.
  • a method of such an embodiment may include first covering the remaining surface of the substrate with a mask and subsequently depositing the photocatalytic matter on the surface. Thereby photocatalytic matter is deposited only on the plurality of accessible surface areas.
  • the present method of the invention further includes depositing oxidisable matter on the entire surface.
  • Any oxidisable matter may be used that can be deposited on the selected plurality of surface areas and that is capable of at least essentially withstanding a selected exposure to electromagnetic radiation that is sufficient to cause the photocatalytic matter to catalyse the oxidation of the oxidisable matter (see below).
  • the oxidisable matter may for example be at least essentially inert to such an exposure of electromagnetic radiation.
  • the oxidisable matter is of wettability that differs from the wettability of the photocatalytic matter. It may for instance be of a lower wettability for water when compared to the photocatalytic matter.
  • the oxidisable matter may be characterised by an advancing contact angle (see below) for water that is at least 5° higher or 5° lower than the advancing contact angle for water of the photocatalytic matter.
  • the oxidisable matter may have an advancing contact angle for water that is 10° higher than the advancing contact angle for water of the photocatalytic matter.
  • the oxidisable matter may have an advancing contact angle for water that is 10° lower than the advancing contact angle for water of the photocatalytic matter.
  • the oxidisable matter is hydrophobic.
  • Hydrophobic (“water-fearing”) matter has a tendency to separate from water.
  • hydrophilic (“water-loving”) matter generally contains molecules which can form dipole-dipole interactions with water molecules and thus have a high wettability for water (see also below).
  • hydrophobic matter is apolar and possesses an even distribution of electron density.
  • lipophilic lipophilic
  • Lipophilic matter attracts non-polar organic compounds, such as oils, fats, or greases. It is understood that the terms "hydrophobic” and “lipophilic” are not synonymous.
  • perfluorocarbon compounds are both hydrophobic and oleophobic, i.e. lack an affinity for oils. Such compounds accordingly have a tendency to separate from both water and hydrocarbons (though the latter to a lesser extent than from water).
  • hydrophobic matter refers to the state of respective matter after it has been deposited onto the surface. Before or during the process of depositing, the respective matter may in some embodiments be at least partially polar or include polar moieties. As an example, a molecule with a functional group containing a polar bond may provide apolar matter by a chemical reaction of the functional group with the surface. It is furthermore a known fact that the wettability of matter may change upon depositing and that from hydrophobic or hydrophilic characteristics of matter not necessarily a conclusion with respect to the hydrophobicity of a coating of such matter can be drawn. Accordingly, hydrophobic surfaces can be obtained by depositing onto the surface a material that is intrinsically hydrophilic.
  • a hydrophobic surface can be formed by electrospinning (see e.g. Zhu, M., et al., J. Mater. Sd. (2006) 41, 12, 3793-3797).
  • Suitable oxidisable matter may for example include a wax such as paraffin wax, a fat (e.g. grease), an oil, a fatty acid, a silane, including an organofunctional silane such as a haloalkylsilane (see Fig. 3 for examples), a siloxane, a perfluoroalkane, a silazane, a stannane (in particular a tin-organic compound), a polymer such as a polysiloxane (silicone) and a composite of a polymer and inorganic particles.
  • a wax such as paraffin wax
  • a fat e.g. grease
  • an oil e.g. oil
  • a fatty acid e.g. 3
  • silane including an organofunctional silane such as a haloalkylsilane (see Fig. 3 for examples), a siloxane, a perfluoroalkane, a silazane, a
  • a silane used in a method according to the present invention includes at least one Si-Cl or Si-OR' bond, wherein R' may be any aliphatic, cycloaliphatic, aromatic, arylaliphatic, or arylcycloaliphatic moiety.
  • a suitable silane may be a compound of the general formula (I): R ⁇ SiX-i- m .
  • m is an integer between 1 and 3.
  • R 1 is an aliphatic, cycloaliphatic, aromatic, arylaliphatic, or arylcycloaliphatic hydrocarbyl group.
  • X is an alkoxy group or Cl.
  • R 1 is an aliphatic, cycloaliphatic, aromatic, arylaliphatic, or arylcycloaliphatic hydrocarbyl group.
  • a respective silane include, but are not limited to, trichloroethylsilane (Chemical Abstracts No. 115-21-9), trichlorooctylsilane (Chemical Abstracts No. 5283-66-9), trichlorocyclohexylsilane (CAS No. 98-12-4), (3,4,5,6- tetrafluoro-o-phenylene)bis[trichlorosilane] (CAS No.
  • R 1 and R 1 are independently selected aliphatic, cycloaliphatic, aromatic, arylaliphatic, or arylcycloaliphatic hydrocarbyl groups.
  • Examples of a respective silane include, but are not limited to, dichlorodimethylsilane (CAS No. 75- 78-5), dichloromethylphenylsilane (CAS No. 149-74-6), dichloro(4-fluorophenyl)methyl- silane (CAS No. 1422-90-8), dichloroethenyl(phenylethynyl)-silane (CAS No. 95598-23-5), dichloromethyl[4-(phenylmethoxy)phenyl]silane (CAS No.
  • R 1 , R 1 and R 1 are independently selected aliphatic, cycloaliphatic, aromatic, arylaliphatic, or arylcycloaliphatic hydrocarbyl groups.
  • Examples of a respective silane include, but are not limited to, chlorotrimethylsilane (CAS No. 75-77- 4), chlorodecyldimethylsilane (CAS No. 38051-57-9), chlorotriphenylsilane (CAS No. 76- 86-8), trans- l-chloro-4-(l,l-dimethylethyl)-l-methyl-silacyclohexane (CAS No.
  • a respective silane is a haloalkylsilane.
  • a haloalkylsilane may for instance be a fluoroalkylsilane.
  • a respective fluoroalkylsilane is of general formula (II)
  • R 7 to R 9 are independently selected aliphatic, cycloaliphatic, aromatic, arylaliphatic, or arylcycloaliphatic hydrocarbyl groups.
  • Examples of a respective haloalkylsilane include, but are not limited to, triethoxy(heptafluoro- propyl)silane (Chemical Abstracts No. 874906-86-2), tributoxy(2,2-difluoroethyl)silane (Chemical Abstracts No. 4168-06-3), (2,2-difluoroethyl)trimethoxysilane (CAS No. 994-46- T), trimethoxy(l,l,2,2-tetrafluoroethyl)silane (CAS No. 356-49-0), trimethoxy(nonafluoro- butyl)-silane (CAS No.
  • trimethoxy(undecafluoropentyl)silane (CAS No. 84464- 04-0), trimethoxy(pentadecafluoroheptyl)silane (CAS No. 84464-06-2), trimethoxy(trideca- fluorohexyl) silane (CAS No. 84464-05-1), (heptadecafluorooctyl)trimethoxysilane (CAS No. 88101-77-3), (heptafluoropropyl)trimethoxysilane (CAS No.
  • a respective fluoroalkylalkylsilane is of general formula (IH) wherein n is an integer between 0 and 10.
  • R 7 to R 9 are independently selected aliphatic, cycloaliphatic, aromatic, arylaliphatic, or arylcycloaliphatic hydrocarbyl groups.
  • Examples of a respective haloalkylsilane include, but are not limited to, diethoxy(trifmoro- methyl)methylsilane (CAS No. 167408-24-4), dimethoxybis(trifluoromethyl)silane (CAS No. 173162-24-8), diethoxy[2,2,2-trifluoro-l,l-bis(trifluoromethyl)ethyl](trifiuoroethenyl)- silane (CAS No. 841313-62-0), dimethoxymethyl(2,2,2-trifluoro-l-methylethyl)silane (CAS No.
  • a respective fluoroalkylsilane is of general formula (FV)
  • R 7 to R 9 are independently selected aliphatic, cycloaliphatic, aromatic, arylaliphatic, or arylcycloaliphatic hydrocarbyl groups.
  • Examples of a respective haloalkylsilane include, but are not limited to, methoxydimethyl(pentadeca- fluoroheptyl)silane (CAS No. 855774-07-1), ethoxydimethyl(trifluorovinyl)silane (CAS No. 5674-84-0), ethoxytris(trifluoromethyl)silane (CAS No. 156514-86-2), ethoxydimethyl- (tridecafluorohexyl)silane (CAS No. 178317-29-8), dodecyloxy)methyl(l-methylethyl)- (pentafluorophenyl)silane (CAS No.
  • Any aliphatic, cycloaliphatic, aromatic, arylaliphatic or arylcycloaliphatic hydrocarbyl group included in the moieties R 2 to R 9 in formulas (II) to (V) may include 1-3 heteroatoms, i.e. atoms that differ from carbon, selected from the group consisting of N, O,
  • (V) may furthermore be connected so as to define an aliphatic or aromatic ring structure.
  • haloalkylsilane examples include, but are not limited to, chloropropylmethyldimethoxysilane, triethoxychlorobutylsilane, trichlorochloropropylsilane, dimethylchlorochloropropylsilane, (dichloromethyl)trimethylsilane, trimethyl(trichloro- methyl)silane, fluorooctylmethyldimethoxysilane, triethoxy(heptafluoropropyl)silane, dime- thylbis( 1 , 1 ,2,2-tetrafluoroethyl)-silane, (2-chloro- 1 , 1 ,2-trifluoro ethyl)trimethylsilane, dimethyl ⁇ , 1 ,2,2,3 ,3 ,4,4-octafluorobutyl)(l , 1 ,2,2-tetrafluoroe
  • a tin-organic compound is an alkyl stannane, such as tetrapropyl-stannane, bis[4-(l , 1 -dimethylethyl)phenyl]dimethyl-stannane, chloro(4-hexyl- phenyl)dimethyl-stannane, 6-(tributylstannyl)-3-pyridinamine or 3-methyl-6-(4-pyridinyl- methyl)-8-(tributylstannyl)-quinoline.
  • alkyl stannane such as tetrapropyl-stannane, bis[4-(l , 1 -dimethylethyl)phenyl]dimethyl-stannane, chloro(4-hexyl- phenyl)dimethyl-stannane, 6-(tributylstannyl)-3-pyridinamine or 3-methyl-6-(4-pyridinyl-
  • a further illustrative example of a tin-organic compound is a haloalkylstannane, such as dimethylbis(pentafluoroethyl)-stannane, triethyl- (trifluoroethenyl)-stannane, triphenyl(trifluoroethenyl)-stannane, tributyl(pentafluoroethyl)- tin, tributyl(trichloromethyl)-stannane or tributyl(l,2-difluoro-2-iodoethenyl)-stannane.
  • haloalkylstannane such as dimethylbis(pentafluoroethyl)-stannane, triethyl- (trifluoroethenyl)-stannane, triphenyl(trifluoroethenyl)-stannane, tributy
  • tetrafluoromethane gas may be deposited on the surface by means of atmospheric radio frequency glow-discharge plasma deposition.
  • a mixture of tetrafluoromethane and hydrogen can be used in a carrier gas such as helium (Kim, S.H., et al., Langmuir (2005) 21, 26, 12213-12217).
  • plasma deposition by electrical discharge of tetrafluoromethane gas may be used (e.g. Woodward, I.S., et al. Plasma Chem. Plasma Process (2006) 26, 507-516).
  • a plasma of a perfluoroalkane such as octafluorocyclobutan (C 4 F 8 ), hexafluoroethane (C 2 F 6 ) or tetrafluormethane (CF 4 ), may be used to form a perfluoroalkane-poryrner and to deposit it onto the surface.
  • a respective polymer of controllable thickness may for instance be deposited on a surface using an inductively coupled plasma reactive ion etcher equipment as described by Kolari &
  • haloalkylsilane for instance of general formula (V) may be deposited onto the surface:
  • R 7 to R 9 are independently selected aliphatic, cycloaliphatic, aromatic, arylaliphatic, or arylcycloaliphatic hydrocarbyl groups.
  • Examples of a respective haloalkylsilane include, but are not limited to, [1,1,2,3,4,4- heptafluoro-3-(trifiuoromethyl)butyl]trimethylsilane (CAS No. 71126-99-3), trimethyl- (l,l,3,3,3-pentafluoro ⁇ ropyl)silane (CAS No. 62281-41-8), (2,3,3,4,4,4-hexafluorobutyl)- trimethylsilane (CAS No. 309-20-6), ethyl(heptafluoropropyl)methylvinylsilane (CAS No.
  • a siloxane may be deposited onto the surface. This may for instance be achieved by spin-coating a long-chain alkyl- or alkenyltrichlorosilane, such as octadecyltrichlorosilane, dodecyltrichlorosilane or ⁇ -undecenyltrichlorosilane, onto the surface as described by e.g. Franzka et al. (Thin Solid Films (2005) 488, 124-131).
  • a long-chain alkyl- or alkenyltrichlorosilane such as octadecyltrichlorosilane, dodecyltrichlorosilane or ⁇ -undecenyltrichlorosilane
  • a polymer such as a poly(alkyl)pyrrole, poly(hydroxy- butyrate-co-valerate), phenyltris(trifluoromethyl)silane homopolymer (CAS No. 205814-01- 3) or polytetrafluoroethylene may be used as respective oxidisable matter.
  • an electrochemical polymerisation of an alkylpyrrole such as 1-n- octadecylpyrrole
  • an electrochemical polymerisation of an alkylpyrrole such as 1-n- octadecylpyrrole
  • a polymerisation of a perfluorocarbon compound such as tetrafluoro ethylene may be carried out.
  • a perfluorocarbon compound such as tetrafluoro ethylene
  • an obtained polymer such as polytetrafluoroethylene is deposited on a provided surface (see Favia, P., et al. Surface and Coatings Technology (2003), 169 ill '0, 609-612).
  • a solution of poly(hydroxybutyrate-co-valerate) may be deposited onto a surface by means of electro spinning (Zhu, M., et al., 2006, supra).
  • the deposition of other polymers on a surface is a standard technique well known in the art.
  • polystyrene spheres may be deposited (Gu et al., 2002, supra).
  • An example of a composite of a polymer and inorganic particles that may be used as oxidisable matter is a microsphere of calcium carbonate and polyvinylidenedifluoride
  • PVDF polyvinyl-triethoxysilane
  • a coating solution of polymer microspheres is obtained (Yan, L., et al., Journal of Materials Science Letters (2003) 22, 1713-1717).
  • a further example of a composite of apolymer and inorganic particles are silica nanoparticles coated with a fiuorocarbon polymer.
  • Such nanoparticles can be deposited on a surface by first dip coating the surface with silica nanoparticles and subsequently coating the surface with a respective polymer, such as FC735 (Ferrari, M., et al., 2006, supra).
  • the oxidisable matter may be deposited by any means. Illustrative examples have already been given above. Furthermore, depending on the nature of the oxidisable matter used, other means of depositing the same may be applied, such as for example spin-coating, dip-coating, flame hydrolysis deposition, chemical vapour deposition (including plasma enhanced chemical vapour deposition, inductive coupled plasma enhanced chemical vapour deposition or hot filament chemical vapour deposition), physical vapour deposition (including plasma-assisted physical vapour deposition and electron beam physical vapour deposition), atomic layer deposition (including plasma-assisted atomic layer deposition), dense plasma focus deposition, pulsed laser deposition, the sol-gel process, thermoreactive diffusion deposition, or thermal diffusion deposition, where applicable.
  • chemical vapour deposition including plasma enhanced chemical vapour deposition, inductive coupled plasma enhanced chemical vapour deposition or hot filament chemical vapour deposition
  • physical vapour deposition including plasma-assisted physical vapour deposition and electron beam physical vapour deposition
  • atomic layer deposition including plasma-a
  • a thin layer of oxidisable matter on the substrate surface for example a film. It can generally be expected that thin layer of oxidisable matter will produce a better quality/accuracy in patterning because the radicals generated from photocatalytic matter can only reach a limited distance.
  • the oxidisable matter provides the entire surface, including the plurality of accessible surface areas, with a wettability that differs from the wettability of the photocatalytic matter. In some embodiments it also provides the entire surface with a wettability that differs from the wettability of the surface of the substrate, i.e. as provided before depositing any matter thereon. Thereby a surface with an at least essentially uniform wettability for water is produced.
  • the wettability of the surface differs from the wettability of the photo catalytic matter, and in some embodiments also from the wettability of the surface of the substrate as such.
  • the oxidisable matter may be hydrophobic, including for example superhydrophobic, for instance with a contact angle for water of more than 150°.
  • Such hydrophobic oxidisable matter renders the entire surface, including the plurality of accessible surface areas, hydrophobic, in particular more hydrophobic than the photocatalytic matter.
  • a surface with a low wettability for water is thereby produced.
  • a surface pattern may nevertheless in some embodiments be detectable, for example in terms of the topography of the surface.
  • a common way of defining the wettability of a surface is the contact angle (also termed wetting angle) between a water droplet in thermal equilibrium on a horizontal surface, which is generally smooth and homogeneous, typically surrounded by a gas such as air.
  • a contact angle ⁇ is given by the angle between the interface of water droplet and the horizontal surface.
  • Such a contact angle ⁇ is a thermodynamic variable that depends on the interfacial tensions of the surfaces involved. It reflects the balance of forces exerted by an attraction of molecules within the water phase to each other versus the attraction or repulsion those droplet molecules experience towards the surface molecules.
  • the most commonly used technique of determining the contact angle is the so called static or sessile drop method.
  • the measurement usually involves a successive addition of water droplets until a plateau in the contact angle is reached. The value at a respective plateau is called the advancing contact angle.
  • a further value that may be used to characterise a surface is the so called receding contact angle. It is measured when the contact point of a liquid droplet on a surface begins to change upon retracting the liquid of the droplet. The difference between advancing and receding contact angles can be taken as an indication as to the non-uniformity of the chemical and/or physical nature of a surface.
  • Further means of determining the contact angle include the Wilhemly Plate method, the Captive Air Bubble method, the Capillary Rise method, and the Tilted-drop measurement.
  • a contact angle ⁇ of zero degrees results in wetting, while a contact angle ⁇ between about 0 and about 90 degrees results typically in spreading of a water droplet, in particular at values in the range below about 45 degrees.
  • Contact angles ⁇ greater than about 90 degrees indicate the fluid tends to bead or shrink away from the solid surface.
  • the hydrophobic oxidisable matter provides the surface, including the selected area thereof, with a wettability for water that can be characterised by an advancing contact angle ⁇ of about 50 degrees or higher, such as about 90 degrees or higher or at least about 100 degrees or higher. It is furthermore understood that the contact angle is an indication of the hydrophobicity of a surface as compared to other surfaces. A surface with a higher contact angle (with respect to water) can therefore generally be taken to be of higher hydrophobicity than a surface with a lower contact angle.
  • the present method of the invention further includes exposing the entire surface to electromagnetic radiation.
  • the respective radiation may be selected within any range of wavelengths of the electromagnetic spectrum. If desired, one distinct wavelength or a set of distinct wavelengths may be selected, or one or more defined regions of the electromagnetic spectrum. Examples of regions of the electromagnetic spectrum that may be chosen include, but are not limited to, visible light, ultraviolet light or infrared light.
  • Visible light corresponds to a wavelength range of about 400 to about 700 nanometers
  • ultraviolet light corresponds to a wavelength range of about 30 to about 400 nanometers
  • infrared light corresponds to a wavelength range of about 700 nanometers to about 1 millimeter
  • a wavelength is for instance selected within the near UV (380 to 200 nm), while in other embodiments it is for instance selected within the far UV (200 to 10 nM).
  • the wavelength may be selected to be 300 nm or shorter, for instance 254 nm or
  • UV light may also be pulsed.
  • An illustrative example of a means of providing UV light of a respective wavelength of 248 nm is a KrF laser.
  • the electromagnetic radiation may be of any intensity and the exposure of any length as long as it is sufficient to render the photocatalytic matter capable of catalysing the oxididation of the selected oxidisable matter (see above).
  • the required exposure time will depend on the power of the electromagnetic radiation used, hi typical embodiments where UV light is used as electromagnetic radiation, the energy density is of at least 50 mJ/cm 2 , such as for example of at least 100 mJ/cm 2 . Accordingly, the photocatalytic matter catalyses the oxidation of such oxidisable matter that is in contact therewith (see above).
  • oxidisable matter that is in contact with photocatalytic matter is removed from the plurality of surface areas. Accordingly, only the remaining area of the surface retains, at least essentially, the wettability provided by the oxidisable matter.
  • the remaining area of the surface remains hydrophobic in embodiments where hydrophobic oxidisable matter is used.
  • the photocatalytic matter in the plurality of surface areas is being exposed. This is due to the fact that exposing the surface to electromagnetic radiation shows little or no impact on the oxidisable matter that is not in contact with the photocatalytic matter.
  • exposing the entire surface to electromagnetic radiation renders the photocatalytic matter hydrophilic.
  • a respective hydrophobic property of the photocatalytic matter may for example be a wettability that can be characterised by an advancing contact angle ⁇ of about 90 degrees or lower, such as about 50 degrees or lower or about 25 degrees or lower.
  • the advancing contact angle may for example be selected in the range of about 0 degrees to about 25 degrees.
  • titanium dioxide becomes superhydrophilic upon irradiation. This effect is thought to be the result of surface oxygen vacancies, generated by irradiation. These oxygen vacancies are thought to lead to the adsorption of water molecules.
  • the hydrophilicity of the surface generated by irradiation may however not last for extended periods of time. Titanium dioxide that has been irradiated is for example known to become less hydrophilic upon storage in the absence of an inert gas atmosphere. Freshly generated mesoporous titanium dioxide films have for example been found to show contact angles of 10-15 ° (Yu, J., et al., New J. Chem. (2002) 26, 607-613). However, after storage in the dark for 3 months, contact angels of about 60 ° were determined. Upon irradiation with a 15 W 365 nm UV lamp contact angels dropped to below 5 ° (ibid.).
  • photocatalytic matter is deposited on the entire surface of the substrate.
  • oxidisable matter as described above, is vapour coated on the entire surface.
  • the surface of the substrate is also patterned as explained above.
  • only the plurality of accessible surface areas is exposed to electromagnetic radiation.
  • the photocatalytic matter catalyses the oxidation of oxidisable matter that is in contact therewith.
  • the oxidisable matter is thereby removed from the plurality of surface areas.
  • the photocatalytic matter on these surface areas is exposed and the oxidisable matter on the remaining surface of the substrate is at least essentially preserved. Accordingly, in this method there is also a pattern of discriminative wettability formed.
  • a method according to the invention further includes depositing a substance only on the plurality of surface areas, where photocatalytic matter is deposited.
  • Any desired substance may be deposited.
  • the substance may for instance be hydrophilic or hydrophobic.
  • the substance may be deposited by any means, for example using a plasma process or a sol gel process (see above for further examples).
  • the respective substance is deposited after the entire surface has been exposed to electromagnetic radiation (see above).
  • hydrophobic matter may for example be deposited as described above.
  • a hydrophilic substance may for example be deposited on the surface.
  • suitable hydrophilic substance include, but are not limited to, a polymer, e.g. a polymer obtained from ethylene oxide or from an acrylate, a polycarbonate, a polyimide, silica, a polysaccharide (including hyaluronan, dextran and cellulose) or a glycosaminoglycan.
  • silica may be desposited by means of the sol-gel method, e.g.
  • a hydrogel may be formed on the plurality of accessible surface areas by disposing a pregel-solution and subsequent spin-coating as described by Jakobs and Hanein ⁇ Colloids & Surfaces A: Physiochem. Eng. Aspects (2006) 290, 33-40).
  • a thin liquid film that can undergo dewetting in water may be deposited, which may for example include octyl p-methoxycinnamate and octylsilyl titanium dioxide particles (see abstract of Ruroda, A. et al., Journal of Oleo Science (2006) 55, 6, 277). Thereby a further dewetting pattern can be formed within the existing wettability pattern of the surface.
  • the substance may include a molecule with a linking moiety.
  • a respective substance may for example include functional groups that allow for the covalent attachment of a target molecule such as a protein or a nucleic acid molecule.
  • a linking molecule may be an aliphatic compound with a backbone of 4 - 50 carbon atoms, of which some may be exchanged by N, O, Si or S atoms, and a reactive functional group.
  • reactive functional groups include, but are not limited to, aldehydes, carboxylic acids, esters, imido esters, anhydrides, acyl nitriles, acyl halides, semicarbazides, acyl azides, isocyanates, sulphonate esters, sulfonyl halides, or aryl halides, which may for example react with an amino group of a capture molecule, or alkyl sulphonates, aryl halides, acrylamides, maleimides, haloacetamides or aziridines, which may for example react with a thio group of a capture molecule or a carboxylic acid, an anhydride, an isocyanate, a phosphoramidite, a halotriazine, an acyl halide, an acyl nitrile, an alkyl halide, an alkyl sulphonate or a maleimide, which may for example react with a
  • a silane or stannane may be used as the respective substance, which includes a respective functional group, such as an aldehyde moiety, an amino moiety or a thiol moiety.
  • a respective functional group such as an aldehyde moiety, an amino moiety or a thiol moiety.
  • the molecule with a linking moiety is a silane, it may for example be a monomethoxysilane, a dimethoxysilane, a trimethoxysilane, a monochlorosilane, a dichlorosilane or a trichloroysilane.
  • the respective silane may for instance include, such as be terminated with, an aldehyde, an amine, an epoxy or an anhydride moiety.
  • silane with an aldehyde moiety examples include trimethoxysilylbutyraldehyde (Chemical Abstracts No. 501004-24-6), triethoxy- silylbutyraldehyde (Chemical Abstracts No. 88276-92-0), 4-(triethoxysilyl)-l,3- cyclopentanedicarboxaldehyde (Chemical Abstracts No.
  • silane with an amine moiety examples include 1- (trimethoxysilyl)-methanamine (CAS-No 71408-48-5), (aminopropyl)methyldiethoxysilane (CAS-No 3179-76-8), [(diethoxymethylsilyl)methyl]amine (CAS-No 18186-77-1), amino- methyltriethoxysilane (CAS-No 18306-83-7), ⁇ -aminobutyltrimethoxysilane (CAS-No 36394-66-8) and l-l-(trimethoxysilyl)-propanamine (CAS-No 112309-66-7).
  • silane with a thiol moiety examples include 2-(trimethoxysilyl)-ethanethiol (CAS-No 7538-45-6), 2-(dimethoxymethylsilyl)-ethanethiol (CAS-No 14857-98-8), l-(triethoxysilyl)- 1,2-ethanedithiol (CAS-No 32318-39-1), l,l-dimethoxy-silacyclopentane-3 -thiol (CAS-No 35932-31-1), and 5-mercaptopentyltriethoxysilane (CAS-No 63392-36-9).
  • a respective silane or stannane may be deposited by any means (see also above).
  • the surface may for instance be exposed to a silane or stannane solution or a silane or stannane vapour.
  • a solution of (3-aminopropyl)dimethoxysilane in ethanol can provide amino groups for the coupling to molecules such as proteins (Klose, T, et al., Colloids and Surfaces B: Biointerfaces (2006) 51, 1-9).
  • a solution of triethoxysilylbutyraldehyde in toluene/0.1% acetic acid can provide aldehyde groups that can likewise be used for subsequent coupling (see the Examples below).
  • chlorine-doped polypyrrole may be electrochemically deposited onto the surface (Sanghvi, A. et al., Nature Materials (2005) 4, 496-502). Peptides, oligonucleotides or oligosaccharides etc. can then react with the chlorine-groups on the surface to provide a moiety that can specifically bind to target matter, e.g. analytes such as peptides, proteins, oligonucleotides, nucleic acids or polysaccharides. Respective peptides may be selected by means of phage display (ibid.).
  • a polymer with reactive amino groups may be deposited on the surface such as N-(2-hydroxypropyl)methacrylamide copolymers containing 4- nitrophenyl ester (using the monomer N-meth-acryloylglycylglycine) or thiazolidine-2- thione groups (using 3-(6-methacrylamidohexanoyl)thiazolidine-2-thione or 3-(N- methacryloylglycylglycyl)thiazolidine-2-thione monomers).
  • the obtained polymers are capable of reacting with amino groups of lysine residues of proteins (see Subr, V et al., Biomacromolecules (2006) 7, 122-130).
  • the present inventors have found that generally little or no deposition of the respective substance occurs on the hydrophobic matter.
  • a silane is used as oxidisable matter and a dense film thereof is formed on the surface of the substrate, no surface hydroxyl group is available for depositing e.g. a further silane on the respective dense film. Accordingly, depositing the substance only on the plurality of surface areas, i.e. where photocatalytic matter is deposited, does usually not require any means that prevents the deposition of the substance on the remaining surface.
  • the linking moiety is a receptor molecule for a target molecule such as a protein, a nucleic acid, a polysaccharide or any combination thereof.
  • the linking moiety and the target molecule may define a specific binding pair.
  • Examples of a respective receptor molecule include, but are not limited to immunoglobulin, a mutein based on a polypeptide of the lipocalin family, a glubody, a protein based on the ankyrin or crystalline scaffold, an avimer, the T7 epitope, maltose binding protein, the HSV epitope of herpes simplex virus glycoprotein D, the hemagglutinin epitope, and the myc epitope of the transcription factor c-myc, an oligonucleotide, an oligosaccharide, an oligopeptide, biotin, dinitrophenol, digoxigenin and a metal chelator (cf. also below).
  • a respective metal chelator such as ethylenediamine, ethylenediaminetetraacetic acid (EDTA), ethylene glycol tetraacetic acid (EGTA), diethylenetriaminepentaacetic acid (DTPA), N,N-bis(carboxymethyl)grycine (also called nitrilotriacetic acid, NTA), l,2-bis(o-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid (BAPTA), 2,3-dimercapto-l-propanol (dimercaprol), porphine or heme may be used in cases where the target molecule is a metal ion.
  • EDTA ethylenediaminetetraacetic acid
  • EGTA ethylene glycol tetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • NTA N,N-bis(carboxymethyl)grycine
  • BAPTA 2,3-dimercapto
  • EDTA forms a complex with most monovalent, divalent, trivalent and tetravalent metal ions, such as e.g. silver (Ag ), calcium (Ca 2+ ), manganese (Mn 2+ ), copper (Cu 2+ ), iron (Fe 3+ ), cobalt (Co 3+ ) and zirconium (Zr 4+ ), while BAPTA is specific for Ca 2+ .
  • a respective metal chelator in a complex with a respective metal ion or metal ions defines the linking moiety.
  • Such a complex is for example a receptor molecule for a peptide of a defined sequence, which may also be included in a protein.
  • a standard method used in the art is the formation of a complex between an oligohistidine tag and copper (Cu 2+ ), nickel (Ni 2+ ), cobalt (Co 2+ ), or zink (Zn 2+ ) ions, which are presented by means of the chelator nitrilotriacetic acid (NTA).
  • NTA chelator nitrilotriacetic acid
  • the linking moiety which may be included into a respective molecule (including a macromolecule) of the substance before, during or after the substance has been deposited on the surface, may be converted into another linking moiety. This may for example be desired to obtain a linking moiety that has a chosen degree of specifity for selected target matter.
  • the linking moiety may for instance be reacted with a receptor molecule for a target molecule.
  • the receptor molecule and the target molecule define a specific binding pair (see above and below).
  • a complex such as a coordinative complex, or a covalent bond may be formed.
  • the previous linking moiety is being converted into another linking moiety.
  • a respective method of the present invention may include contacting the surface of the substrate with a receptor molecule for a target molecule (see also above).
  • the receptor molecule is capable of interacting with the linking moiety, such that a complex between the receptor molecule and the linking moiety is formed.
  • the formation of this complex may, in some embodiments, result in, or be part of, the formation of a covalent bond.
  • the receptor molecule is immobilised on the plurality of surface areas via the linking moiety.
  • the linking moiety has in turn been converted into another linking moiety.
  • Aldehyde, amino or thiol groups may for example be reacted with a peptide, protein, oligosaccharide, an oligonucleotide or any other molecule that has a desired specifity for a selected target molecule (see e.g. Sanghvi et al., 2005, supra, for a specific example).
  • the resulting moiety may for instance be a moiety that is known in the art as an "affinity tag".
  • moieties include, but are not limited to biotin, dinitrophenol, digoxigenin, oligohistidine, polyhistidine, an immunoglobulin domain, maltose-binding protein, glutathione-S-transferase (GST), calmodulin binding peptide (CBP), FLAG'- peptide, the T7 epitope (Ala-Ser-Met-Thr-Gly-Gly-Gln-Gln-Met-Gly), maltose binding protein (MBP), the HSV epitope of the sequence Gln-Pro-Glu-Leu-Ala-Pro-Glu-Asp-Pro- Glu-Asp of herpes simplex virus glycoprotein D, the hemagglutinin (HA) epitope of the sequence Tyr-Pro-Tyr-Asp-Val-Pro-Asp-Tyr-Ala and the "myc" epitope of the transcription factor c-myc of the sequence Glu-Gl
  • a respective moiety may also be an antibody, a fragment thereof or a proteinaceous binding molecule with antibody-like functions.
  • (recombinant) antibody fragments are Fab fragments, Fv fragments, single- chain Fv fragments (scFv), diabodies or domain antibodies (Holt, LJ., et al., Trends Biotechnol. (2003), 21, 11, 484-490).
  • An example of a proteinaceous binding molecule with antibody-like functions is a mutein based on a polypeptide of the lipocalin family (WO 03/029462, Beste et al., Proc. Natl. Acad.
  • Lipocalins such as the bilin binding protein, the human neutrophil gelatinase-associated lipocalin, human Apolipoprotein D or glycodelin, posses natural ligand-binding sites that can be modified so that they bind to selected small protein regions known as haptens.
  • glubodies see WO 96/23879
  • proteins based on the ankyrin scaffold proteins based on the ankyrin scaffold (Mosavi, L.K., et al., Protein Science (2004) 13, 6, 1435-1448) or crystalline scaffold (WO 01/04144) the proteins described in Skerra, J MoI. Recognit. (2000) 13, 167-187, and avimers.
  • Avimers contain so called A-domains that occur as strings of multiple domains in several cell surface receptors (Silverman, J, et al., Nature Biotechnology (2005) 23, 1556-1561).
  • a modifying agent may be used that further increases the affinity of the respective moiety for any or a certain form, class etc. of target matter.
  • the method further includes immobilising target matter, such as a target molecule, on the plurality of surface areas. This may for example be achieved via the linking moiety, whether by way of formation of a complex or by means of a covalent bond. Any matter may be the target matter and any molecule may likewise be selected as a target molecule.
  • target matter may be an analyte that is included in a sample, for example a sample derived from human or non-human animals, plants, bacteria, viruses, spores, fungi, or protozoa, or from organic or inorganic material of synthetic or biological origin.
  • a respective analyte may for instance be a protein, a nucleic acid molecule, a solvent molecule, a pesticide molecule, a saccharide molecule, an allergen, a hormone, a virus or a cell.
  • a detectable marker may be coupled to a molecule with a linking moiety. This may for instance be carried out to monitor the deposition of the respective molecule with a linking moiety.
  • the available linking moieties may be reacted to any degree. Using a low concentration or amount of a respective marker, a selected percentage of linking moieties may for example remain available for a reaction with a target molecule or for a conversion to another linking moiety (see above).
  • a respective marker compound may also be included in a reagent used for the conversion of a linking moiety to another linking moiety.
  • Such a marker may be an optically detectable label, a fluorophore, or a chromophore.
  • suitable labels include, but are not limited to, an organic molecule, an enzyme, a radioactive, fluorescent, and/or chromogenic moiety, a luminescent moiety, a hapten, digoxigenin, biotin, a metal complex, a metal and colloidal gold.
  • radioactive amino acid fluorescein isothiocyanate, 5,6-carboxymethyl fluorescein, Texas red, nitrobenz-2-oxa-l,3-diazol-4-yl, coumarin, dansyl chloride, rhodamine, amino-methyl coumarin, Eosin, Erythrosin, BODIPY®, Cascade Blue®, Oregon Green®, pyrene, lissamine, xanthene, acridine, oxazines, phycoerythrin, Cy3, Cy3.5, Cy5, Cy5.5, and Cy7enzymes, alkaline phosphatase, soybean peroxidase, or horseradish peroxidase may serve as a few illustrative examples.
  • the photocatalytic matter is in many embodiments capable of catalysing a reaction that results in the removal of the respective substance (cf. above).
  • the present method of the invention may include a recycling step, during which the respective substance, including any potential target matter that may be bound thereto, is removed from the surface.
  • the method may include exposing the entire surface to electromagnetic radiation as explained above. As a result the photocatalytic matter catalyses the oxidation of the respective substance that is in contact therewith. Thereby the substance is being removed from the plurality of surface areas. The hydrophobic matter on the remaining surface of the substrate is again at least essentially preserved.
  • the photocatalytic matter may be removed. This may for instance be achieved by means of etching. Etching may for example be performed using a Br ⁇ nstedt base, such as metal hydroxide, or a Br ⁇ nsted acid.
  • a Br ⁇ nstedt base such as metal hydroxide
  • a Br ⁇ nsted acid such as sodium hydroxide
  • hydrochloric acid or concentrated sulfuric acid may be used to remove the same.
  • suitable metal hydroxides include, but are not limited to sodium hydroxide, NaOH, potassium hydroxide, KOH, lithium hydroxide, LiOH, and calcium hydroxide, CaOH.
  • etching By removing the photocatalytic matter, e.g. by etching, the surface of the substrate in the plurality of surface areas is uncovered and hydrophobic matter on the remaining surface is at least essentially preserved.
  • the photocatalytic matter may be more hydrophilic than the oxidisable matter, which may for instance be hydrophobic.
  • an accurate removable of the photocatalytic matter by means of etching can for instance be achieved by dipping the surface of the substrate in an etching solution and removing it within in a couple of seconds.
  • the substrate may be left in air or in immiscible and inert liquid.
  • An illustrative example of a respective immiscible and inert liquid is a perfluorocarbon liquid, e.g. if the solution if highly volatile.
  • a respective procedure may be desired in order to minimize the degradation of the oxidisable matter due to extended exposure to an etching solution.
  • Exposing the surface of the substrate by means of etching may for instance be desired where the substrate is intended to be used for electrical applications.
  • the substrate may for instance be or comprise indium-tin oxide glass.
  • a layer of indium-tin oxide can be fabricated to serve as photocatalytic matter while being conductive, for example by way of an electron shower bombarding the respective surface as for instance described by Yumoto et al. ⁇ Thin Solid Films (1999) 345, 38-41).
  • a layer of for example TiO x may be deposited on top of indium-tin oxide.
  • Patterning the surface of a respective substrate with areas of hydrophobic matter may be performed as described above, including subsequent etching of photocatalytic matter used. Thereby a pattern with a wettability contrast between the indium-tin oxide glass and the hydrophobic matter is obtained.
  • Such a wettability contrast of a respective substrate surface can be switchable by means of electrowerting (see abstract of Chen, P., 232nd ACS National Meeting, San Francisco, Sept 10-14 2006, COLL- 556).
  • photocatalytic matter is deposited on the entire surface of the substrate (cf. also above).
  • oxidisable matter as described above, is deposited on the entire surface.
  • the oxidisable matter may be deposited by any means, as explained above, hi this method of the invention the surface of the substrate is also patterned as explained above. In this method of the invention only the plurality of accessible surface areas is exposed to electromagnetic radiation.
  • the photocatalytic matter catalyses the oxidation of oxidisable matter that is in contact therewith. The oxidisable matter is thereby removed from the plurality of surface areas.
  • the photocatalytic matter on these surface areas is exposed and the oxidisable matter on the remaining surface of the substrate is at least essentially preserved.
  • This method further includes at least essentially removing the photocatalytic matter by means of etching (see above). Thereby the plurality of surface areas of the substrate is at least essentially uncovered. The oxidisable matter on the remaining surface of the substrate is at least essentially preserved. Accordingly, in this method there is also a pattern of discriminative wettability formed.
  • Example 1 Generation of a pattern of TiO Y and Heptadecafluoro-1,1.,2.,2- tetrahydrodecvDtriethoxysilane (FTES) on a glass surface
  • the box in Fig. 2A illustrates the method used in the present example.
  • hydrophilic-hydrophobic micropatterns were generated on glass chips.
  • a 4-inch glass wafer was diced to rectangular chips with dimensions of 38 mm x 18 mm.
  • V(H 2 SO 4 )A ⁇ (H 2 O 2 ) 7/3, at 110 0 C for 0.5 h, the chip was rinsed with Milli-Q H 2 O and dried with N 2 .
  • the glass chips were coated with TiO x at room temperature or at 500 0 C using a home-made sputter via a mask with 100-2000 ⁇ m diameter through-holes (step II in Fig. 2A).
  • This step produced patterned coatings of amorphous TiO x or a mixture of anatase-amorphous TiO x on the glass surface (Luca, D. J., Optoelectron. Adv. Mater. (2005) 7, 625).
  • the power of Ti source was 200 W.
  • the Ar and O 2 gas flows rates were 25.2 and 10.8 seem, respectively.
  • the chamber pressure for sputtering was 2 mTorr.
  • TiO x -coated glass chips were vapour-coated with FTES (Heptadecafluoro-l,l,2,2-tetrahydrodecyl)triethoxysilane (Gelest, Inc., Morrisville, PA) at 115 0 C for 2 h under 1 mTorr pressure to form a hydrophobic coating (step IV in Fig. 2A; Beck, M., et al., Microelectron. Eng. (2002) 61-62, 441).
  • FTES Hydrochloro-l,l,2,2-tetrahydrodecyl
  • step IV step IV in Fig. 2A; Beck, M., et al., Microelectron. Eng. (2002) 61-62, 441).
  • TiO x can oxidise organic adsorbates under UV irradiation.
  • Example 2 Secondary coating using a silane
  • the present example illustrates a further coating of a patterned surface generated as described in Example 1, as well as its recycling.
  • This secondary coating corresponds to step X depicted in Fig. 2A.
  • the additional coating of the hydrophilic surface was obtained by exposing the chip to a silane solution. The chip was exposed to 0.5 % triethoxysilylbutyraldehyde and 0.1 % acetic acid in toluene for 20 min. As a result, the bare TiO x surface became modified with an aldehyde-terminated silane coating. The absence of contact angle changes on the hydrophobic surface suggests negligible effect of the secondary coating step on the hydrophobic surface.
  • the secondary coating on the hydrophilic TiO x patterns was conveniently recycled by exposing the entire chip to UV irradiation again as described above. Upon undergoing solution-phase silylation the secondary coating was generated again.
  • Example 3 Generation of a pattern of FTES on a glass surface
  • the present example illustrates the removal and recycling of TiOy from a patterned surface generated as described in Example 1. This removal/recycling corresponds to step VIII depicted in Fig. 2A.
  • a glass chip patterned with hydrophilic TiO x was further processed to expose a bare glass surface.
  • the TiO x film on the chip was etched by dipping the chip in 45 % KOH. This was followed by 15 sec of incubation in air, and rinsing with H 2 O.
  • the resulting chip consisted of bare glass in the hydrophilic areas.
  • Figure 4 A shows dark aqueous ink drops selectively adsorbed onto the hydrophilic areas (1.2 mm diameter) of the chip.
  • Hydrophilic-hydrophobic patterned glass chips are currently being examined for bio-microarray applications such as enzyme-linked immunosorbent assay (ELISA) and cell- based microarray.
  • ELISA enzyme-linked immunosorbent assay
  • each hydrophilic spot functions as a well, where the immobilization of antibodies occurs.
  • a wash solution such as in the present example 50 mM of Tris buffer with 0.05 % Tween 20.
  • a wash solution such as in the present example 50 mM of Tris buffer with 0.05 % Tween 20.
  • a patterned chip was dipped into a typical ELISA wash buffer (50 mM of Tris buffer with 0.05 % Tween 20) containing 10 ⁇ M Fluorescein, and removed immediately thereafter. As shown in the fluorescence microscopy image ( Figure 4B), the fluorescent buffer was only noted on the hydrophilic spots with no visible wetting of the hydrophobic perfluorocarbon surface.
  • Example 5 Cell adsorption and growth
  • the present example demonstrates that a chip with a patterned surface, obtained as described above, may be used to cultivate cells as well as to perform cell-based assays.
  • the patterned surface exposing TiO x or bare glass in the hydrophilic areas was examined for cell adsorption and growth.
  • a chip patterned with 1.2 mm-diameter hydrophilic areas was prepared and sterilized by 25 kGy dose of ⁇ irradiation or by autoclaving at 121 0 C for 20 min.
  • the chip placed within a sterile Petri dish, was seeded with 0.8 ⁇ l of HepG2 cells at a concentration of 2xl0 4 cells/mL) in cell culture medium (DMEM containing 1000 mg/L glucose, 10 % fetal bovine serum (FBS), 1 % penicillin/streptomycin) on the hydrophilic areas.
  • DMEM cell culture medium
  • FBS fetal bovine serum
  • penicillin/streptomycin penicillin/streptomycin
  • Example 6 Formation of a wettability pattern using a continuous TiO Y layer
  • FIG. 2C This example illustrates a method depicted in Fig. 2C. Following this method, micropatterns are directly generated on the glass surface using a machined mask placed in between the sputter and the glass, to selectively deposit or block the formation of TiO x layer on glass.
  • a TiO x layer was sputtered onto a glass chip (see above) using the customized Filtered Cathodic Vacuum Arc (FCVA) sputtering machine, manufactured by NanoFilm Technologies International Pte Ltd, under these conditions: DC Power 200W; Argon (25.2sccm); Oxygen (10.8sccm); room temperature or 500 0 C; Chamber pressure 2mTorr.
  • FCVA Filtered Cathodic Vacuum Arc
  • the resulting patterned coatings are either of amorphous TiO x or mixture of anatase/amorphous TiO x , followed by vapour-coating of fluoroalkylsilane in a custom- designed vacuum oven manufactured by Diversified Vacuum Inc. (Suffolk, VA, USA).
  • FTES was vapor-coated at 115 0 C under vacuum to form a hydrophobic surface (step II in Fig. 2C).
  • the FTES-coated TiO x chips covered with a photomask (with patterns of 100- 2000 ⁇ m, step III in Fig. 2C), were irradiated with UV for 2 h (step IV in Fig. 2C). Thereafter the chips were instantly dipped in 45 % KOH, followed by 15 sec of incubation in air (step V in Fig. 2C) to remove the exposed TiO x patterns, resulting in patterned chips.

Landscapes

  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production d'un motif à mouillabilité discriminative sur la surface d'un substrat (2). Le procédé consiste à tracer un motif sur la surface du substrat de façon à définir une pluralité de zones de surface accessibles. Le procédé consiste aussi à déposer uniquement sur la pluralité de zones de surface accessibles une matière photocatalytique (4), et à déposer sur la totalité de la surface une matière oxydable (5). La matière oxydable (5) présente une mouillabilité différente de celle de la matière photocatalytique (4), et est au moins sensiblement inerte à une exposition à un rayonnement électromagnétique qui suffit à entraîner la catalyse de l'oxydation de la matière oxydable (5) par la matière photocatalytique (4). Le procédé consiste en outre à exposer la totalité de la surface à un rayonnement électromagnétique de sorte que la matière photocatalytique (4) catalyse l'oxydation de la matière oxydable (5) avec laquelle elle est en contact. La matière oxydable (5) est ainsi retirée de la pluralité de zones de surface et la matière photocatalytique (4) sur ces zones de surface est exposée, tandis que la matière oxydable (5) est au moins sensiblement préservée sur la surface restante du substrat.
PCT/SG2006/000362 2006-11-24 2006-11-24 Procédé de production d'un motif à mouillabilité discriminative WO2008063134A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/SG2006/000362 WO2008063134A1 (fr) 2006-11-24 2006-11-24 Procédé de production d'un motif à mouillabilité discriminative

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/SG2006/000362 WO2008063134A1 (fr) 2006-11-24 2006-11-24 Procédé de production d'un motif à mouillabilité discriminative

Publications (1)

Publication Number Publication Date
WO2008063134A1 true WO2008063134A1 (fr) 2008-05-29

Family

ID=39429975

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SG2006/000362 WO2008063134A1 (fr) 2006-11-24 2006-11-24 Procédé de production d'un motif à mouillabilité discriminative

Country Status (1)

Country Link
WO (1) WO2008063134A1 (fr)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7928038B2 (en) 2006-11-21 2011-04-19 Applied Biosystems, Llc Intermediates and methods for forming passivated surfaces on oxide layers and articles produced thereby
US8173198B2 (en) 2008-07-23 2012-05-08 Life Technologies Corporation Deposition of metal oxides onto surfaces as an immobilization vehicle for carboxylated or phophated particles or polymers
US8741158B2 (en) 2010-10-08 2014-06-03 Ut-Battelle, Llc Superhydrophobic transparent glass (STG) thin film articles
US9771656B2 (en) 2012-08-28 2017-09-26 Ut-Battelle, Llc Superhydrophobic films and methods for making superhydrophobic films
CN108603307A (zh) * 2015-12-01 2018-09-28 特韦斯特生物科学公司 功能化表面及其制备
US10583415B2 (en) 2013-08-05 2020-03-10 Twist Bioscience Corporation De novo synthesized gene libraries
US10669304B2 (en) 2015-02-04 2020-06-02 Twist Bioscience Corporation Methods and devices for de novo oligonucleic acid assembly
US10696965B2 (en) 2017-06-12 2020-06-30 Twist Bioscience Corporation Methods for seamless nucleic acid assembly
US10744477B2 (en) 2015-04-21 2020-08-18 Twist Bioscience Corporation Devices and methods for oligonucleic acid library synthesis
US10754994B2 (en) 2016-09-21 2020-08-25 Twist Bioscience Corporation Nucleic acid based data storage
US10844373B2 (en) 2015-09-18 2020-11-24 Twist Bioscience Corporation Oligonucleic acid variant libraries and synthesis thereof
US10844479B2 (en) 2014-02-21 2020-11-24 Ut-Battelle, Llc Transparent omniphobic thin film articles
US10894959B2 (en) 2017-03-15 2021-01-19 Twist Bioscience Corporation Variant libraries of the immunological synapse and synthesis thereof
US10894242B2 (en) 2017-10-20 2021-01-19 Twist Bioscience Corporation Heated nanowells for polynucleotide synthesis
US10907274B2 (en) 2016-12-16 2021-02-02 Twist Bioscience Corporation Variant libraries of the immunological synapse and synthesis thereof
US10936953B2 (en) 2018-01-04 2021-03-02 Twist Bioscience Corporation DNA-based digital information storage with sidewall electrodes
US10975372B2 (en) 2016-08-22 2021-04-13 Twist Bioscience Corporation De novo synthesized nucleic acid libraries
US11292919B2 (en) 2010-10-08 2022-04-05 Ut-Battelle, Llc Anti-fingerprint coatings
US11332738B2 (en) 2019-06-21 2022-05-17 Twist Bioscience Corporation Barcode-based nucleic acid sequence assembly
US11377676B2 (en) 2017-06-12 2022-07-05 Twist Bioscience Corporation Methods for seamless nucleic acid assembly
US11407837B2 (en) 2017-09-11 2022-08-09 Twist Bioscience Corporation GPCR binding proteins and synthesis thereof
US11492665B2 (en) 2018-05-18 2022-11-08 Twist Bioscience Corporation Polynucleotides, reagents, and methods for nucleic acid hybridization
US11492728B2 (en) 2019-02-26 2022-11-08 Twist Bioscience Corporation Variant nucleic acid libraries for antibody optimization
US11492727B2 (en) 2019-02-26 2022-11-08 Twist Bioscience Corporation Variant nucleic acid libraries for GLP1 receptor
US11512347B2 (en) 2015-09-22 2022-11-29 Twist Bioscience Corporation Flexible substrates for nucleic acid synthesis
US11550939B2 (en) 2017-02-22 2023-01-10 Twist Bioscience Corporation Nucleic acid based data storage using enzymatic bioencryption

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030087073A1 (en) * 2001-10-16 2003-05-08 Hironori Kobayashi Methods for producing pattern-forming body
US20060121745A1 (en) * 2004-10-08 2006-06-08 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing display device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030087073A1 (en) * 2001-10-16 2003-05-08 Hironori Kobayashi Methods for producing pattern-forming body
US20060121745A1 (en) * 2004-10-08 2006-06-08 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing display device

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7928038B2 (en) 2006-11-21 2011-04-19 Applied Biosystems, Llc Intermediates and methods for forming passivated surfaces on oxide layers and articles produced thereby
US8173198B2 (en) 2008-07-23 2012-05-08 Life Technologies Corporation Deposition of metal oxides onto surfaces as an immobilization vehicle for carboxylated or phophated particles or polymers
US11292288B2 (en) 2010-10-08 2022-04-05 Ut-Battelle, Llc Superhydrophobic transparent glass (STG) thin film articles
US8741158B2 (en) 2010-10-08 2014-06-03 Ut-Battelle, Llc Superhydrophobic transparent glass (STG) thin film articles
US11292919B2 (en) 2010-10-08 2022-04-05 Ut-Battelle, Llc Anti-fingerprint coatings
US9771656B2 (en) 2012-08-28 2017-09-26 Ut-Battelle, Llc Superhydrophobic films and methods for making superhydrophobic films
US10773232B2 (en) 2013-08-05 2020-09-15 Twist Bioscience Corporation De novo synthesized gene libraries
US10583415B2 (en) 2013-08-05 2020-03-10 Twist Bioscience Corporation De novo synthesized gene libraries
US10618024B2 (en) 2013-08-05 2020-04-14 Twist Bioscience Corporation De novo synthesized gene libraries
US10632445B2 (en) 2013-08-05 2020-04-28 Twist Bioscience Corporation De novo synthesized gene libraries
US10639609B2 (en) 2013-08-05 2020-05-05 Twist Bioscience Corporation De novo synthesized gene libraries
US11559778B2 (en) 2013-08-05 2023-01-24 Twist Bioscience Corporation De novo synthesized gene libraries
US11185837B2 (en) 2013-08-05 2021-11-30 Twist Bioscience Corporation De novo synthesized gene libraries
US11452980B2 (en) 2013-08-05 2022-09-27 Twist Bioscience Corporation De novo synthesized gene libraries
US10844479B2 (en) 2014-02-21 2020-11-24 Ut-Battelle, Llc Transparent omniphobic thin film articles
US10669304B2 (en) 2015-02-04 2020-06-02 Twist Bioscience Corporation Methods and devices for de novo oligonucleic acid assembly
US11697668B2 (en) 2015-02-04 2023-07-11 Twist Bioscience Corporation Methods and devices for de novo oligonucleic acid assembly
US10744477B2 (en) 2015-04-21 2020-08-18 Twist Bioscience Corporation Devices and methods for oligonucleic acid library synthesis
US11691118B2 (en) 2015-04-21 2023-07-04 Twist Bioscience Corporation Devices and methods for oligonucleic acid library synthesis
US11807956B2 (en) 2015-09-18 2023-11-07 Twist Bioscience Corporation Oligonucleic acid variant libraries and synthesis thereof
US10844373B2 (en) 2015-09-18 2020-11-24 Twist Bioscience Corporation Oligonucleic acid variant libraries and synthesis thereof
US11512347B2 (en) 2015-09-22 2022-11-29 Twist Bioscience Corporation Flexible substrates for nucleic acid synthesis
US10384189B2 (en) 2015-12-01 2019-08-20 Twist Bioscience Corporation Functionalized surfaces and preparation thereof
US10987648B2 (en) 2015-12-01 2021-04-27 Twist Bioscience Corporation Functionalized surfaces and preparation thereof
EP3384077A4 (fr) * 2015-12-01 2019-05-08 Twist Bioscience Corporation Surfaces fonctionnalisées et leur préparation
CN108603307A (zh) * 2015-12-01 2018-09-28 特韦斯特生物科学公司 功能化表面及其制备
US10975372B2 (en) 2016-08-22 2021-04-13 Twist Bioscience Corporation De novo synthesized nucleic acid libraries
US10754994B2 (en) 2016-09-21 2020-08-25 Twist Bioscience Corporation Nucleic acid based data storage
US11263354B2 (en) 2016-09-21 2022-03-01 Twist Bioscience Corporation Nucleic acid based data storage
US11562103B2 (en) 2016-09-21 2023-01-24 Twist Bioscience Corporation Nucleic acid based data storage
US10907274B2 (en) 2016-12-16 2021-02-02 Twist Bioscience Corporation Variant libraries of the immunological synapse and synthesis thereof
US11550939B2 (en) 2017-02-22 2023-01-10 Twist Bioscience Corporation Nucleic acid based data storage using enzymatic bioencryption
US10894959B2 (en) 2017-03-15 2021-01-19 Twist Bioscience Corporation Variant libraries of the immunological synapse and synthesis thereof
US11332740B2 (en) 2017-06-12 2022-05-17 Twist Bioscience Corporation Methods for seamless nucleic acid assembly
US10696965B2 (en) 2017-06-12 2020-06-30 Twist Bioscience Corporation Methods for seamless nucleic acid assembly
US11377676B2 (en) 2017-06-12 2022-07-05 Twist Bioscience Corporation Methods for seamless nucleic acid assembly
US11407837B2 (en) 2017-09-11 2022-08-09 Twist Bioscience Corporation GPCR binding proteins and synthesis thereof
US10894242B2 (en) 2017-10-20 2021-01-19 Twist Bioscience Corporation Heated nanowells for polynucleotide synthesis
US11745159B2 (en) 2017-10-20 2023-09-05 Twist Bioscience Corporation Heated nanowells for polynucleotide synthesis
US10936953B2 (en) 2018-01-04 2021-03-02 Twist Bioscience Corporation DNA-based digital information storage with sidewall electrodes
US11492665B2 (en) 2018-05-18 2022-11-08 Twist Bioscience Corporation Polynucleotides, reagents, and methods for nucleic acid hybridization
US11732294B2 (en) 2018-05-18 2023-08-22 Twist Bioscience Corporation Polynucleotides, reagents, and methods for nucleic acid hybridization
US11492727B2 (en) 2019-02-26 2022-11-08 Twist Bioscience Corporation Variant nucleic acid libraries for GLP1 receptor
US11492728B2 (en) 2019-02-26 2022-11-08 Twist Bioscience Corporation Variant nucleic acid libraries for antibody optimization
US11332738B2 (en) 2019-06-21 2022-05-17 Twist Bioscience Corporation Barcode-based nucleic acid sequence assembly

Similar Documents

Publication Publication Date Title
WO2008063134A1 (fr) Procédé de production d'un motif à mouillabilité discriminative
US20060263516A1 (en) Hydrophobic coating
Metwalli et al. Surface characterizations of mono-, di-, and tri-aminosilane treated glass substrates
JP4849799B2 (ja) 平面光学導波管組み立て品、およびこれの製造方法
WO2004090065A1 (fr) Revetement superhydrophobe durable
US20050121782A1 (en) Selectively adherent substrate and method for producing the same
JP2005531029A5 (fr)
EP1291655A2 (fr) Substrat pour l'immobilization de la matière physiologique et méthode pour sa fabrication
JP4505287B2 (ja) マイクロチップ並びにその製造方法及びそれを用いた検査方法
WO1998040323A1 (fr) Substrat dote d'une surface de traitement
US20050272268A1 (en) Method of producing substrate having patterned organosilane layer and method of using the substrate having the patterned organosilane layer
JP3923856B2 (ja) マイクロアレイチップの製造方法
JP2000144056A (ja) 水滴滑落性に優れた表面処理基材及びその製造方法
US6503567B2 (en) Transparent substrate and method of manufacturing the same
Honda et al. Polymer coating glass to improve the protein antifouling effect
US6521334B1 (en) Transparent substrate and method of manufacturing the same
US20030129740A1 (en) Method of preparing substrate having functional group pattern for immobilizing physiological material
Jung et al. Characterization of octadecyltrichlorosilane self-assembled monolayers on silicon (100) surface
WO2005113129A1 (fr) Procede sol-gel de fonctionnalisation d'une surface d'un substrat solide
US20050214841A1 (en) Substrate for biochip
JP2004045421A (ja) 生物学的結合の光学的検出に使用する試験表面の製造方法
JP4011159B2 (ja) 光学的分析装置測定チップ用積層体
US8470247B2 (en) Surfaces resistant to non-specific protein adsorption and methods of producing the same
KR100634505B1 (ko) 패턴화된 박막층을 갖는 마이크로어레이 기판 및마이크로어레이, 상기 마이크로어레이 기판 및마이크로어레이를 제조하는 방법
Coombs et al. Spatial characteristics of contact pin-printed silanes and bioconjugates on oxidized porous silicon

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 06813142

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06813142

Country of ref document: EP

Kind code of ref document: A1