Synthesis and screening combinatorial arrays of zeolites

• US 6,649,413 B1
• Filed: 11/28/2000
• Issued: 11/18/2003
• Est. Priority Date: 10/18/1994
• Status: Expired due to Fees

• Current Assignee: Symyx Solutions, Inc.
• Original Assignee: Symyx Technologies Incorporated (Dassault Systemes SA), Lawrence Berkeley National Laboratory (University of California)
• Inventors: Schultz, Peter G., Xiang, Xiaodong, Goldwasser, Isy
• Primary Examiner(s): Soderquist, Arlen
• Application Number:
  US09/728,201
• Time in Patent Office: 1,085 Days
• Field of Search: 436/4-5, 436/37, 436/155, 436/159, 436/164, 436/171, 436/174, 436/176, 436/181, 436/183
• US Class Current: 506/11
• CPC Class Codes: B01J 19/0046 Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays synthesis methods per se C40B50/00
• CPC Class Codes: B01J 2219/00313 the reactor vessels being formed by arrays of wells in blocks
• CPC Class Codes: B01J 2219/00317 Microwell devices, i.e. having large numbers of wells
• CPC Class Codes: B01J 2219/00378 Piezoelectric or ink jet dispensers
• CPC Class Codes: B01J 2219/0043 for direct application of reagents, e.g. through openings in a shutter
• CPC Class Codes: B01J 2219/00432 Photolithographic masks
• CPC Class Codes: B01J 2219/00436 Maskless processes
• CPC Class Codes: B01J 2219/00441 using lasers
• CPC Class Codes: B01J 2219/00443 Thin film deposition
• CPC Class Codes: B01J 2219/00475 Sheets
• CPC Class Codes: B01J 2219/005 Beads
• CPC Class Codes: B01J 2219/00511 Walls of reactor vessels
• CPC Class Codes: B01J 2219/00515 in the shape of strings
• CPC Class Codes: B01J 2219/0052 in the shape of elongated tubes
• CPC Class Codes: B01J 2219/00527 Sheets
• CPC Class Codes: B01J 2219/00531 essentially square
• CPC Class Codes: B01J 2219/00533 essentially rectangular
• CPC Class Codes: B01J 2219/00536 in the shape of disks
• CPC Class Codes: B01J 2219/0054 Means for coding or tagging the apparatus or the reagents
• CPC Class Codes: B01J 2219/00585 Parallel processes
• CPC Class Codes: B01J 2219/0059 : Sequential processes
• CPC Class Codes: B01J 2219/00592 : Split-and-pool, mix-and-divide processes
• CPC Class Codes: B01J 2219/00596 : Solid-phase processes
• CPC Class Codes: B01J 2219/00605 : the compounds being directly bound or immobilised to solid supports
• CPC Class Codes: B01J 2219/0061 : The surface being organic
• CPC Class Codes: B01J 2219/00612 : the surface being inorganic
• CPC Class Codes: B01J 2219/00619 : using hydrophilic or hydrophobic regions
• CPC Class Codes: B01J 2219/00621 : by physical means, e.g. trenches, raised areas
• CPC Class Codes: B01J 2219/00626 : Covalent
• CPC Class Codes: B01J 2219/00628 : Ionic
• CPC Class Codes: B01J 2219/0063 : Other, e.g. van der Waals forces, hydrogen bonding
• CPC Class Codes: B01J 2219/00635 : by reactive plasma treatment
• CPC Class Codes: B01J 2219/00637 : by coating it with another layer
• CPC Class Codes: B01J 2219/00644 : the porous medium being present in discrete locations, e.g. gel pads
• CPC Class Codes: B01J 2219/00646 : the compounds being bound to beads immobilised on the solid supports
• CPC Class Codes: B01J 2219/00648 : by the use of solid beads
• CPC Class Codes: B01J 2219/00659 : Two-dimensional arrays
• CPC Class Codes: B01J 2219/00689 : using computers
• CPC Class Codes: B01J 2219/00691 : using robots
• CPC Class Codes: B01J 2219/00711 : Light-directed synthesis
• CPC Class Codes: B01J 2219/0072 : Organic compounds
• CPC Class Codes: B01J 2219/00722 : Nucleotides
• CPC Class Codes: B01J 2219/00736 : Non-biologic macromolecules, e.g. polymeric compounds
• CPC Class Codes: B01J 2219/00745 : Inorganic compounds
• CPC Class Codes: B01J 2219/00747 : Catalysts
• CPC Class Codes: B01J 2219/00752 : Alloys
• CPC Class Codes: B01J 2219/00754 : Metal oxides
• CPC Class Codes: B82Y 25/00 : Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
• CPC Class Codes: B82Y 30/00 : Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 51/006 : Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen cobaltates C01G51/40
• CPC Class Codes: C01G 51/68 : containing rare earth, e.g. La0.3Sr0.7CoO3
• CPC Class Codes: C01P 2002/34 : perovskite-type (ABO3)
• CPC Class Codes: C01P 2002/52 : containing elements as dopants
• CPC Class Codes: C01P 2002/72 : by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/84 : one phase coated with the other
• CPC Class Codes: C01P 2006/40 : Electric properties
• CPC Class Codes: C01P 2006/42 : Magnetic properties
• CPC Class Codes: C04B 2235/3206 : Magnesium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3208 : Calcium oxide or oxide-forming salts thereof, e.g. lime
• CPC Class Codes: C04B 2235/3213 : Strontium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3215 : Barium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3224 : Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
• CPC Class Codes: C04B 2235/3225 : Yttrium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3227 : Lanthanum oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3262 : Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
• CPC Class Codes: C04B 2235/327 : Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3275 : Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
• CPC Class Codes: C04B 2235/3284 : Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
• CPC Class Codes: C04B 2235/3286 : Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
• CPC Class Codes: C04B 2235/3296 : Lead oxides, plumbates or oxide forming salts thereof, e.g. silver plumbate
• CPC Class Codes: C04B 2235/3298 : Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
• CPC Class Codes: C04B 2235/3418 : Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
• CPC Class Codes: C04B 2235/3463 : Alumino-silicates other than clay, e.g. mullite
• CPC Class Codes: C04B 2235/656 : characterised by specific heating conditions during heat treatment
• CPC Class Codes: C04B 2235/761 : Unit-cell parameters, e.g. lattice constants
• CPC Class Codes: C04B 2235/762 : Cubic symmetry, e.g. beta-SiC
• CPC Class Codes: C04B 2235/768 : Perovskite structure ABO3
• CPC Class Codes: C04B 2235/96 : Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
• CPC Class Codes: C04B 35/01 : based on oxide ceramics
• CPC Class Codes: C04B 35/16 : based on silicates other than clay zircon C04B35/48
• CPC Class Codes: C04B 35/4508 : Type 1-2-3
• CPC Class Codes: C04B 35/4521 : containing bismuth oxide
• CPC Class Codes: C04B 35/4525 : also containing lead oxide
• CPC Class Codes: C04B 35/62218 : obtaining ceramic films, e.g. by using temporary supports
• CPC Class Codes: C23C 14/042 : using masks
• CPC Class Codes: C23C 14/087 : of copper or solid solutions thereof
• CPC Class Codes: C23C 16/042 : using masks
• CPC Class Codes: C40B 30/08 : by measuring catalytic activity
• CPC Class Codes: C40B 40/14 : Libraries containing macromolecular compounds and not covered by groups C40B40/06 - C40B40/12
• CPC Class Codes: C40B 40/18 : Libraries containing only inorganic compounds or inorganic materials
• CPC Class Codes: C40B 60/08 : Integrated apparatus specially adapted for both creating and screening libraries
• CPC Class Codes: C40B 60/14 : for creating libraries
• CPC Class Codes: C40B 70/00 : Tags or labels specially adapted for combinatorial chemistry or libraries, e.g. fluorescent tags or bar codes
• CPC Class Codes: C40B 80/00 : Linkers or spacers specially adapted for combinatorial chemistry or libraries, e.g. traceless linkers or safety-catch linkers
• CPC Class Codes: G01R 33/16 : Measuring susceptibility G01R33/1238 takes precedence
• CPC Class Codes: H01F 1/401 : diluted
• CPC Class Codes: H01F 1/407 : Diluted non-magnetic ions in a magnetic cation-sublattice, e.g. perovskites, La1-x(Ba,Sr)xMnO3
• CPC Class Codes: H01F 10/007 : ultrathin or granular films H01F10/005 and H01F10/3227 take precedence; applying ultrathin or granular layers to substrates H01F41/301
• CPC Class Codes: H01F 10/193 : Magnetic semiconductor compounds in general H01F1/40; multilayers, e.g. superlattices H01F10/3213
• CPC Class Codes: H01F 10/1933 : Perovskites
• CPC Class Codes: H01F 41/18 : by cathode sputtering
• CPC Class Codes: H01F 41/34 : in patterns, e.g. by lithography
• CPC Class Codes: H10N 50/85 : Magnetic active materials
• CPC Class Codes: Y10T 428/24479 : including variation in thickness
• CPC Class Codes: Y10T 428/24612 : Composite web or sheet
• CPC Class Codes: Y10T 428/2462 : with partial filling of valleys on outer surface
• CPC Class Codes: Y10T 428/31 : Surface property or characteristic of web, sheet or block
• CPC Class Codes: Y10T 428/31645 : Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31855 : Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31931 : Polyene monomer-containing
• CPC Class Codes: Y10T 436/25 : including sample preparation
• CPC Class Codes: Y10T 436/2525 : Stabilizing or preserving
• CPC Class Codes: Y10T 436/255 : including use of a solid sorbent, semipermeable membrane, or liquid extraction
• CPC Class Codes: Y10T 436/25875 : Gaseous sample or with change of physical state

Abstract

Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

Claims

1. A method for preparing an ray of materials, the method comprising

delivering components of a first zeolite material to a first predefined region of a substrate using an automated dispenser,

delivering components of a second zeolite material to a second predefined region of a substrate using an automated dispenser,

simultaneously mixing the components of each of the first and second zeolite materials, and

simultaneously reacting the delivered components to form first and second zeolite materials at the first and second regions of the substrate, respectively.

2. A method for evaluating new zeolite catalysts, the method comprising

preparing an array of zeolite materials according to the method of claim 1, and screening the zeolite materials for microstructure.

3. A method for evaluating new zeolite catalysts, the method comprising

preparing an array of zeolite materials according to the method of claim 1, and

screening the zeolite materials for catalysis.

4. The method of claim 1 wherein the components of the zeolite materials are hydrothermally reacted to form the zeolite materials.

5. The method of claim 1 wherein the components of the zeolite materials are reacted in a sealed container at a temperature of about 100°

C. to form the zeolite materials.

6. The method of any one of claim 1 wherein the zeolites comprise hydrated silicates.

7. The method of any one of claim 1 wherein the zeolites comprise hydrated silicates of aluminum and sodium.

8. The method of any one of claim 1 wherein the zeolites comprise hydrated silicates of aluminum and calcium.

9. The method of claim 1 wherein the concentration or stoichiometry of the zeolite components are varied in a gradient as compared between regions, and the components of the zeolite materials are hydrothermally reacted to form the zeolite materials, the method further comprising

independently controlling the reaction conditions at the first region and the second region of the substrate.

13. A method for identifying materials having catalytic properties, the method comprising preparing an array of materials by the method according to claim 1 or 10, and screening the array of materials in parallel for catalysis.

15. The method of claim 1 or 10 wherein the components of the materials are delivered in the form of a solution or a slurry.

16. The method of claim 1 or 10 wherein a components of the first material and a components of the second material are simultaneously delivered to the substrate using an automated dispenser adapted to deliver components to multiple redefined regions of the substrate.

17. The method of claim 1 or 10 wherein at least some components of the first material and at least some components of the second material are sequentially delivered to the substrate.

18. The method of claim 1 or 10 wherein the order of delivery of the components is varied as compared between regions.

19. The method of claim 1 or 10 wherein the concentration or stoichiometry of the components are varied in a gradient as compared between regions.

20. The method of claim 1 or 10 wherein the components of the materials are reacted under a set of reaction conditions.

21. The method of claim 1 or 10 further comprising independently controlling the reaction conditions at the first region and the second region of the substrate.

22. The method of claim 21 wherein the temperatures at the first region and the second region of the substrate are independently controlled.

23. The method of claim 21 wherein the reaction times at the first region and the second region of the substrate are independently controlled.

24. The method of claim 21 wherein the reaction solvents at the first region and the second region of the substrate are independently controlled.

25. The method of claim 21 wherein the reaction conditions are controllably varied between the first region and the second region of the substrate.

26. The method of claim 1 or 10 wherein the components of each of the first and second materials are mixed using mechanical techniques.

27. The method of claim 1 or 10, wherein components of materials are delivered to each of an array of at least 100 discrete regions of the substrate;

and wherein materials are formed in at least said 100 discrete regions of the substrate.

28. The method of claim 27, wherein each material formed in a said discrete region is within an area of about 1 mm² or less.

29. The method of claims 1 or 10 wherein a component of the first material or a component of the second material are delivered to the substrate in a solution comprising a polar solvent.

30. The method of claims 1 or 10, wherein the regions of the substrate are defined by wells.

31. The method of claims 1 or 10 wherein the substrate is placed in a sealed container for reaction of the delivered components.

46. The method of claim 1, 10 or 32 wherein the reactant components are pressurized under an inert atmosphere, oxygen or other gas.

10. A method for preparing an array of materials, the method comprising:

delivering components of at least a first material to at least a first predefined region of a substrate using an automated dispenser;

delivering components of at least a second material to at least a second predefined region of a substrate using an automated dispenser;

simultaneously mixing the components of each of the first and second materials, and

simultaneously hydrothermally reacting the delivered components under pressure to form at least the first and second materials at the first and second regions of the substrate, respectively.

11. A method for identifying materials, the method comprising preparing an array of materials according to the method of claim 10, and screening the materials for microstructure.

12. A method for identifying materials, the method comprising preparing an array of materials according to the method of claim 10, and screening the materials for catalysis.

14. The method of claim 10 wherein the first material and the second material are inorganic materials.

32. A method for generating data useful for identifying materials having a property of interest, the method comprising

preparing an array of materials by a method that includes delivering components of at least a first material in the form of a solution or slurry to at least a first predefined region of a substrate, and delivering components of at least a second material in the form of a solution or slurry to at least a second predefined region of a substrate,

simultaneously hydrothermally reacting the delivered components to form at least the first and second materials at the first and second regions of the substrate, respectively,

allowing the first and second materials to crystallize at the first and second regions of the substrate, respectively, and

screening the crystallized first and second materials for a morphological or chemical property of interest.

33. The method of claim 32 further comprising varying the hydrothermal reaction conditions between the first region and the second region of the substrate.

34. The method of claim 32 further comprising varying the stoichiometry of the components of the first and second materials as compared between regions.

35. The method of claim 32 further comprising simultaneously mixing the components of each of the first and second materials during the hydrothermal synthesis reaction.

36. The method of claim 32 wherein the first and second materials are inorganic materials.

37. The method of claim 32 wherein the first and second materials are zeolites.

38. The method of claim 32 wherein the crystallized first and second materials are screened for a morphological property.

39. The method of claim 32 wherein the crystallized first and second materials are screened for microstructure.

40. The method of claim 32 wherein the crystallized first and second materials are screened for crystallinity.

41. The method of claim 32 wherein the crystallized first and second materials are screened for a chemical property.

42. The method of claim 32 wherein the crystallized first and second materials are screened for catalysis.

43. The method of claim 32 wherein the crystallized first and second materials are screened in parallel for catalysis.

44. The method of claim 32, wherein the regions of the substrate are defined by wells.

45. The method of claim 32 wherein the substrate is placed in a sealed container for hydrothermal reaction of the delivered components.