Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/001—General methods for coating; Devices therefor
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
  • C23C4/123—Spraying molten metal
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/40—Coatings comprising at least one inhomogeneous layer
  • C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/11—Deposition methods from solutions or suspensions
  • C03C2218/119—Deposition methods from solutions or suspensions by printing
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/34—Masking

Definitions

• the present invention relates generally to inorganic porous substrates and more particularly to a method of making inorganic porous substrates utilizing nanoparticles deposited onto a substrate.
• the generation of particles having certain predetermined properties is advantageous in order to optimize, for example, in vivo delivery, bioavailability, stability of the pharmaceutical and physiological compatibility.
• the optical, mechanical, biochemical and catalytic properties of particles are closely related to the size of the particles and the size of the compounds comprising the particles .
• Porous microstructures are of great interest to many research and commercial areas. Three-dimensional structures made from nanoparticles provide optimum surface area. Enhanced surface area is an enabling physical property for many applications, such as custom spotted microarrays, high display of surface area for catalysis, high display of luminescent elements and the like. Conventional methods of producing enhanced surface area, such as the method described in PCT Publication No.
• the conventional ball milling processes for manufacturing slides for use in the manufacture of microarrays have the following disadvantages: lot to lot variability between ball milled preparations of 1737TM microparticles, broad heterogeneous particle size distributions, requirement for post processing deposition of the ball milled microparticles by either tape casting or screen printing, particle sizes are especially large and do not yield ultimate nanoparticle surface areas, screen printing has been shown to yield missing spot effects on microarrays due to irregular surface patterns and limitation of the process to 1737TM glasses. [0008] It would be advantageous to have methods for producing particles in the nanometer size range (average particle sizes 500nm or less) thus minimizing the size variation and composition variation evident in conventional ball milling processes for making inorganic porous substrates .
• the average particle sizes are, for example, 400nm or less, 300nm or less, 200nm or less, lOOnm or less or 80nm or less.
• a method of depositing nanoparticles onto a base substrate to produce an inorganic porous substrate using flame spray pyrolysis comprises providing a solution comprising glass precursors and a solvent, atomizing the solution to form aerosol droplets, synthesizing nanoparticles from the aerosol particles using a flame and either subsequently or simultaneously sintering the nanoparticles onto the base substrate .
• a method of making a coated inorganic porous substrate comprises providing a solution comprising glass precursors and a solvent, atomizing the solution to form aerosol droplets, passing the aerosol droplets through a flame under conditions sufficient to generate nanoparticles, depositing the nanoparticles onto a base substrate to form the inorganic porous substrate, and coating the inorganic porous substrate with a material selected from a silane, a polymer and combinations thereof.
• Another embodiment is a method comprising providing a solution comprising glass precursors and a solvent, atomizing the solution to form aerosol droplets, passing the aerosol droplets through a flame under conditions sufficient to generate nanoparticles, depositing the nanoparticles onto a base substrate to form an inorganic porous substrate, coating the inorganic porous substrate with a material selected from a silane, a polymer and combinations thereof, and depositing a biomolecule onto the coated inorganic porous substrate.
• Figure 1 is a scanning electron microscope (SEM) photomicrograph of nanoparticles deposited onto a substrate comprising surface area of 176 m2/g.
• Figure 2 is an X-ray diffraction plot of the nanoparticles of Figure 1.
• Figure 3 is a photograph of nanoparticles deposited onto a base substrate that is a glass microscope slide.
• Figure 4 is a photograph of nanoparticles deposited onto a base substrate that is a microwell format.
• Figure 5 is an SEM photomicrograph of the morphology of an inorganic porous substrate on a 1737TM slide in cross- section after being sintered at 800°C for 2 hours in air atmosphere .
• Figure 6 is an SEM photomicrograph of the morphology of an inorganic porous substrate on a 1737TM slide after being sintered at 800°C for 2 hours in air atmosphere.
• Figure 7 is an SEM photomicrograph of the morphology of an inorganic porous substrate on a 1737TM slide after being sintered at 800 0 C for 2 hours in air atmosphere.
• Figure 8 shows Cy3/Cy5 signal-to-noise bioassay data for two porous substrates made according to the present invention on slides.
• Figure 9 shows an image of hybridized microarrays printed on two porous substrates made according to the present invention on slides as compared to a control porous substrate (left) made according to a conventional attrition ball milled and screen printing process on a slide.
• a solution is provided, for example, at room temperature, comprising glass precursors such as components of a multicomponent glass, for example, Si, Al, B, Ca, Mg, Sr, K, Ba, Ni and Co.
• the glass precursors are organic derivatives that will pyrolyze to their corresponding oxides.
• the glass precursors are dissolved in a flammable solvent, such as an alcohol.
• Organic solvents that could be used include methanol, ethanol, propanol, higher alcohols (including all possible isomers of carbon chains) , methoxy-alcohols, alkoxy- alcohols, hydrocarbon solvents (e.g. mineral spirits), ketones (e.g. acetone), ethers (e.g. dimethyl ether, methyl-ethyl ether) or mixtures thereof.
• the solution is converted by atomizing into a spray of aerosol droplets.
• Atomizing can be achieved by a variety of methods, for example, through an external mixing air-assisted nozzle.
• the spray of aerosol droplets is converted into oxide nanoparticles using flame spray pyrolysis, wherein the composition of each particle is determined by the composition of the liquid which is atomized.
• a source of flammable gas can also be used in conjunction with the heat in some applications.
• Sources of heat comprise combustion by ignition of the flammable spray with a flame or a spark.
• the oxide nanoparticles are then deposited onto a substrate to form an inorganic porous substrate.
• Table 1 shows examples of liquid compositions of the solution used to generate nanoparticles according to one embodiment.
• the solutions were prepared in a nitrogen filled drybox to minimize particulate formation during mixing due to hydrolysis of the glass nanoparticle precursors upon exposure to moist air.
• the order of mixing of the composition glass nanoparticle precursors can affect the properties of the resulting solution and thus the glass nanoparticle precursors were mixed as presented in Table 1 (top to bottom) .
• Glass precursors for Si ⁇ 2 , Al 2 Os, B 2 Os, CaO, MgO, SrO, K 2 O and BaO can include tetraethylorthosilicate, aluminum tri-sec-butoxide, boron-tri-ethoxide, calcium 2- methoxyethoxide in 2-methoxyethanol, magnesium 2- methoxyethoxide in 2-methoxyethanol, strontium iso- propoxide, potassium tert-butoxide and barium methoxypropoxlde in methoxypropanol respectively.
• the solution according to the embodiment illustrated in Table 1 also comprises anhydrous ethanol, 18 M ⁇ /cm water (as an alternative, other purity of water can be used either more pure or less pure) and 2 M HCl.
• glass precursors for NiO, C0 3 O4 were added to the solution. These precursors were Nickel (II) acetylacetonate and Cobalt (III) acetylacetonate respectively.
• the solution comprising the glass nanoparticle precursors and the solvent was stirred until the solid glass nanoparticle precursors were dissolved, in order to minimize plugging of the atomizer.
• a commercial external air-assisted atomizer (Schlick Atomizing Technologies model 970 S4) was used in conjunction with a flame spray burner and incorporated into a nanoparticulate generating apparatus.
• the flame spray burner was used to generate a pilot flame that ignites the flammable spray comprising the solution and combustible gases.
• the burner conditions used were as follows: a flow of methane at a rate of 3.6 L/min, a flow of oxygen at a rate of 3.4 L/min, a flow of nitrogen shield gas at a rate of 10 L/min.
• the conditions at the nozzle of the atomizer were as follows: a flow of atomizing oxygen at a rate of 25 L/min, a differential pressure across the nozzle of 1 Bar and a liquid flow rate of solution at a rate of 7.5 mL/min.
• Oxide nanoparticles were deposited directly onto 1737TM substrates in either 96-well format or I"x3" slide format.
• the 1737TM substrates were placed in a chamber and exposed to the air-borne soot (oxide nanoparticles) generated by the burner before venting to a wet scrubber particle pollution abatement system. After deposition, the slides were heated in an air atmosphere furnace for 2 hours at 75O 0 C to fix the oxide nanoparticles to the substrate by partial sintering.
• the deposited oxide nanoparticles can be sintered onto the substrates at temperatures of 700°C or more, or at temperatures of 750 0 C or more, or at temperatures of 800 0 C or more, or at temperatures of 850°C or more or at temperatures of 900°C or more depending on the composition of the oxide nanoparticles and the intended application.
• Table 1 shows normalized oxide nanoparticle compositions (analysis was done on bulk powders comprising the nanoparticles which are commensurate with the compositions deposited on the porous substrate by ICP Mass Spectroscopy) resulting from the flame spray pyrolysis method of the solutions described in Table 1 according to one embodiment .
• Table 3 shows the experimentally determined wt% of compositions 3, 4, 5 and 6 of oxide nanoparticles produced by the combustion of the solution and flammable spray utilizing flame spray pyrolysis according to another embodiment.
• the oxide nanoparticle compositions include adsorbed combustion products, which comprise approximately 7 to 9 weight percentages (wt%) .
• wt% weight percentages
• Nanoparticles were generated and deposited onto a substrate using the methods described above.
• Figures 1 and 2 illustrate that the exemplified porous substrate comprising nanoparticles (analysis was done on bulk powders comprising the nanoparticles which are commensurate with the compositions deposited on the porous substrate) is amorphous and glassy, as shown by the first peak 2 of the X-ray diffraction plot.
• the second peak 3 shows a minor component B(OH) 3 which is a crystalline phase of boric acid. This minor component is removed upon sintering of the inorganic porous substrate.
• the deposited nanoparticles 1 are approximately 80nm in mean diameter and have a surface area of approximately 170 m 2 /g.
• increased control over particle collection efficiency and particle packing density can be achieved by heating the substrates during deposition and/or can be facilitated through electrostatic deposition methods.
• a charge can be provided on the base substrate by placement of the base substrate between two oppositely charged electrodes and/or a charge can be induced on the nanoparticles by charging the particles using a corona charger or other charging techniques known in the art.
• Exemplary electrostatic methods and apparatuses are described in commonly owned US Patent Application No. 11/712149, the disclosure of which is incorporated herein by reference in its entirety.
• the base substrate can be heated during the deposition process at temperatures of 400°C to 800 0 C during deposition in order to increase the deposition of the nanoparticles or to increase the particle packing or densification of the porous substrate.
• the deposited oxide nanoparticles can be thermally adhered (sintered) onto the base substrate either by heating during the deposition process or as a subsequent and separate step. Further densification of the surface can be subsequently done for certain applications through additional heat treatments of the inorganic porous substrate.
• the sintering process is achieved by heating the inorganic porous substrates under appropriate conditions such as temperature, duration of heating and rate of cooling. These conditions are selected for the appropriate oxide being sintered. Local heat generation for sintering can be achieved by oven bake, CO 2 LASER sinter and microwave sinter. Other methods for forming interparticle connections may include wet methods as are known in the art, such sol-gel methods.
• the base substrate can comprise a slide 4 or a microplate 6 format as shown in Figure 3 and Figure 4 respectively.
• Slides are typically 1 inch by 3 inches.
• Nanoparticles can be deposited onto substrates which comprise a microplate insert format.
• Typical microplate insert formats are 3 inches by 4.5 inches.
• a portion of the base substrate can be masked such that a pattern of inorganic porous substrate is formed on the base substrate.
• a mask for example, a stainless steel plate can have holes drilled in a microplate format, for example, 96 or 384 well formats. The mask with holes can be positioned between the base substrate and the airborne nanoparticles such that the nanoparticles are deposited only on the unmasked areas. After deposition, the mask can be removed and the porous substrate comprising areas of deposited nanoparticles 5 can be sintered and/or coated. A holey plate can then be adhered to the base substrate forming a microwell plate such that the deposited nanoparticles are located at the bottom of some or all of the wells of the microwell plate.
• Figure 5 illustrate the morphology of the porous substrate 7 comprising oxide nanoparticles deposited onto a microscope slide substrate 8 and sintered at 800 0 C for 2 hours in an air atmosphere furnace.
• the structure of the sintered nanoparticles is web-like, resulting from the viscous flow and/or surface diffusion of the nanoparticles during heat treatment (e.g. sintering) .
• the sintering process causes the nanoparticles to form a series of interconnected webs 11 defining interconnected pores 10 located between the webs.
• the interconnected pores defined by the interconnected webs transverse the width of the porous substrate from a first surface 23 of the porous substrate to a first surface 22 of the substrate.
• the interconnected webs range in size from 0.1 to 1 microns.
• the interconnected pores defined by the webs are 25 microns or less and the thickness of the porous substrate is from 8 to 10 microns.
• Figure 5 shows the porous substrate in cross-section comprising interconnected pores.
• Figure 6 shows the porous substrate (topical view) comprising interconnected pores 9 which are 20 microns or less in size. In some embodiments, the interconnected pores are 5 microns or less in size.
• Figure 7 shows the porous substrate comprising interconnected webs 11 and interconnected pores 10 which are 1 micron or less in size.
• This interconnected web and interconnected pore microstructure is advantageous in that it provides a more uniform distribution of material, for example, biological material, silane, cells and the like when the material is coated onto the porous substrate.
• Nanoparticles which are deposited onto the surface of a base substrate by the above-mentioned methods can undergo subsequent processing steps depending on the intended application.
• the inorganic porous substrates can be subsequently coated with a number of materials, for example, polymers and silanes to form a coated porous substrate.
• the coated porous substrates are useful for covalent or non-covalent attachment of biomolecules .
• Silanes have been shown to modify the surface characteristics of glass and to subsequently affect the interaction of the surface with biological molecules (e.g. DNA, proteins, and even cells) .
• Silanes can be used to provide either covalent attachment chemistry for the retention of DNA or a non-covalent retention of DNA by charge attraction.
• multiple characteristics of the silane molecules can be used to provide a hydrophobic, as well as charged surface, which can also be used to attach DNA either covalently or non-covalently .
• Examples of silane molecules which can provide the hydrophobic charged surface are (but not limited to) amine functionalized silanes (e.g.
• Silane coating can be performed either by solution phase coating or CVD coating.
• the solution coating process involves either dip coating or immersing the inorganic porous substrate into an organic carrier solvent such as isopropyl alcohol (IPA) and a percentage by volume of silane.
• IPA isopropyl alcohol
• the silane is allowed time to coat and then the process is stopped by removal of the inorganic porous substrate from the coating bath and is followed by subsequent wash steps.
• the CVD process involves placing the dry nanoparticle surface into a sealed coating chamber and then allowing exposure of a silane vapor that is generated by either heat or vacuum.
• Figure 8 shows Cy3/Cy5, A/B respectively, signal-to-noise bioassay data for two inorganic porous substrate microarrays 12 and 13 made according another embodiment of the present invention as compared to a control porous substrate microarrays 14 made according to a conventional attrition ball milled and screen printing process.
• Figure 9 shows the image of the hybridized microarrays printed on two inorganic porous substrates 16 and 17 made according to the present invention as compared to a control porous substrate 15 made according to a conventional attrition ball milled and screen printing process.
• Biomolecules can be deposited onto the inorganic porous substrates according to the present invention by a number of deposition techniques as are known to one skilled in the art of microarray manufacturing, for example, printing with pins, quills or printing from a reservior comprising biomolecules.
• biomolecules can be suspended in a bioassay solution.
• the pins are introduced into the bioassay solution.
• some of the biomolecules are adhered to the pins.
• the pins then contact the coated inorganic porous substrate and the biomolecules are transferred to the coated inorganic porous substrate. This process is repeated multiple times and a microarray format of printed spots of biomolecules is produced.
• the defect "missing spots” can occur on a microarray for a number of reasons such as the inability to distinguish the printed spot for the background noise of the coated inorganic porous substrate (referred to as signal-to-noise) , the lack of biomolecules transferring to the coated inorganic porous substrate during printing due to the surface roughness of the coated inorganic porous substrate or due to a lack of uniformity in the coating of the coated inorganic porous substrate or a combination thereof.
• Preliminary data as evident in Figure 8 and Figure 9 indicates that the inorganic porous substrates made according to the present invention result in minimizing the "missing spots" problem inherent in the conventionally manufactured inorganic porous substrates.
• the signal-to- noise is also higher (lower background) in Cy3/Cy5, A/B respectively in Figure 8, tests compared to conventional screen-printed attrition ball milled porous substrates.
• Porous substrates according to the present invention can be used for binding and functional assays, for example, of G- protein coupled receptors (GPCR) .
• GPCR G- protein coupled receptors

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Nanotechnology (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Crystallography & Structural Chemistry (AREA)
• Composite Materials (AREA)
• Physics & Mathematics (AREA)
• Dispersion Chemistry (AREA)
• Pharmacology & Pharmacy (AREA)
• Health & Medical Sciences (AREA)
• Bioinformatics & Cheminformatics (AREA)
• Biophysics (AREA)
• Biotechnology (AREA)
• General Engineering & Computer Science (AREA)
• General Health & Medical Sciences (AREA)
• Medical Informatics (AREA)
• Medicinal Chemistry (AREA)
• Molecular Biology (AREA)
• Metallurgy (AREA)
• Mechanical Engineering (AREA)
• Plasma & Fusion (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Surface Treatment Of Glass (AREA)
• Glass Compositions (AREA)
• Apparatus Associated With Microorganisms And Enzymes (AREA)
• Porous Artificial Stone Or Porous Ceramic Products (AREA)
• Chemical Vapour Deposition (AREA)
• Coating By Spraying Or Casting (AREA)
• Silicon Compounds (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=39887317

Family Applications (1)

Country Status (4)

Families Citing this family (18)

Family Cites Families (20)

• 2007
  • 2007-08-10 US US11/891,519 patent/US20080268165A1/en not_active Abandoned
• 2008
  • 2008-04-10 EP EP08826246A patent/EP2061728A2/de not_active Withdrawn
  • 2008-04-10 JP JP2010506201A patent/JP2010526208A/ja not_active Withdrawn
  • 2008-04-10 WO PCT/US2008/004628 patent/WO2009008930A2/en not_active Ceased

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events