Chemical processing microsystems comprising parallel flow microreactors and methods for using same

• US 6,749,814 B1
• Filed: 03/03/2000
• Issued: 06/15/2004
• Est. Priority Date: 03/03/1999
• Status: Expired due to Fees

• Current Assignee: Freeslate Inc. (Unchained Labs Inc.)
• Original Assignee: Symyx Technologies Incorporated (Dassault Systemes SA)
• Inventors: Bergh, H. Sam, Guan, Shenheng
• Primary Examiner(s): Warden, Jill
• Assistant Examiner(s): QUAN, ELIZABETH S
• Application Number:
  US09/518,794
• Time in Patent Office: 1,565 Days
• Field of Search: 422/99-104, 422/129-131
• US Class Current: 422/130
• CPC Class Codes: B01F 25/41 Mixers of the fractal type
• CPC Class Codes: B01F 35/7182 with means for feeding the material with a fractal or tree-type distribution in a surface
• 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 19/0093 Microreactors, e.g. miniaturised or microfabricated reactors laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027
• CPC Class Codes: B01J 2219/00286 Reactor vessels with top and bottom openings
• CPC Class Codes: B01J 2219/00306 Reactor vessels in a multiple arrangement
• CPC Class Codes: B01J 2219/00308 interchangeably mounted in racks or blocks
• 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 2219/00337 Valves
• CPC Class Codes: B01J 2219/00351 Means for dispensing and evacuation of reagents
• CPC Class Codes: B01J 2219/00353 Pumps
• CPC Class Codes: B01J 2219/00389 Feeding through valves
• CPC Class Codes: B01J 2219/00418 using pressure
• CPC Class Codes: B01J 2219/00452 Means for the recovery of reactants or products
• CPC Class Codes: B01J 2219/00479 Means for mixing reactants or products in the reaction vessels
• CPC Class Codes: B01J 2219/00495 Means for heating or cooling the reaction vessels
• CPC Class Codes: B01J 2219/00585 Parallel 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 2219/00621 : by physical means, e.g. trenches, raised areas
• CPC Class Codes: B01J 2219/00626 : Covalent
• 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 2219/00641 : the porous medium being continuous, e.g. porous oxide substrates
• CPC Class Codes: B01J 2219/00657 : One-dimensional arrays
• CPC Class Codes: B01J 2219/00659 : Two-dimensional arrays
• CPC Class Codes: B01J 2219/00704 : integrated with the reactor apparatus
• CPC Class Codes: B01J 2219/00707 : separated from the reactor apparatus
• CPC Class Codes: B01J 2219/0072 : Organic compounds
• CPC Class Codes: B01J 2219/00745 : Inorganic compounds
• CPC Class Codes: B01J 2219/00747 : Catalysts
• CPC Class Codes: B01J 2219/00759 : Purification of compounds synthesised
• CPC Class Codes: B01L 2200/0689 : Sealing
• CPC Class Codes: B01L 2200/146 : Employing pressure sensors
• CPC Class Codes: B01L 2300/0864 : comprising only one inlet and multiple receiving wells, e.g. for separation, splitting
• CPC Class Codes: B01L 2300/0874 : Three dimensional network
• CPC Class Codes: B01L 2300/0887 : Laminated structure
• CPC Class Codes: B01L 2300/14 : Means for pressure control
• CPC Class Codes: B01L 2300/18 : Means for temperature control
• CPC Class Codes: B01L 2400/0487 : fluid pressure, pneumatics
• CPC Class Codes: B01L 3/5025 : for parallel transport of multiple samples
• CPC Class Codes: B01L 3/5027 : by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip B01L3/5023 takes precedence; micromixers B01F33/30; microreactors for synthesis B01J19/0093; microcapillary devices in general B81B1/00
• CPC Class Codes: B01L 3/502707 : characterised by the manufacture of the container or its components by shaping or joining plastic parts B29C59/00, B29C65/00; by laminating B32B37/00; manufacture of microstructural devices in general B81C
• CPC Class Codes: B01L 3/502715 : characterised by interfacing components, e.g. fluidic, electrical, optical or mechanical interfaces
• CPC Class Codes: B01L 7/54 : using spatial temperature gradients
• CPC Class Codes: C01B 3/40 : characterised by the catalyst
• CPC Class Codes: C07C 17/23 : by dehalogenation
• CPC Class Codes: C07C 45/34 : in unsaturated compounds
• CPC Class Codes: C07C 45/35 : in propene or isobutene
• CPC Class Codes: C07C 45/38 : being a primary hydroxyl group
• CPC Class Codes: C07C 45/46 : Friedel-Crafts reactions
• CPC Class Codes: C07C 45/54 : of compounds containing doubly bound oxygen atoms, e.g. esters
• CPC Class Codes: C07C 45/72 : by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
• CPC Class Codes: C07C 47/04 : Formaldehyde
• CPC Class Codes: C07C 47/06 : Acetaldehyde
• CPC Class Codes: C07C 47/127 : Glyoxal
• CPC Class Codes: C07C 47/22 : Acryaldehyde; Methacryaldehyde
• CPC Class Codes: C07C 49/403 : of a six-membered ring
• CPC Class Codes: C40B 30/08 : by measuring catalytic activity
• CPC Class Codes: C40B 40/18 : Libraries containing only inorganic compounds or inorganic materials
• CPC Class Codes: G01N 2035/00158 : Elements containing microarrays, i.e. "biochip"
• CPC Class Codes: G01N 30/466 : with separation columns in parallel
• CPC Class Codes: G01N 30/90 : Plate chromatography, e.g. thin layer or paper chromatography
• CPC Class Codes: G01N 31/10 : using catalysis
• CPC Class Codes: G01N 35/028 : having reaction cells in the form of microtitration plates
• CPC Class Codes: Y10T 137/87885 : Sectional block structure
• CPC Class Codes: Y10T 436/117497 : with a continuously flowing sample or carrier stream
• CPC Class Codes: Y10T 436/118339 : with formation of a segmented stream
• CPC Class Codes: Y10T 436/2575 : Volumetric liquid transfer

Abstract

A chemical processing microsystem useful for identifying and optimizing materials (e.g., catalysts) that enhance chemical processes or for characterizing and/or optimizing chemical processes is disclosed. The chemical processing microsystem comprises a plurality of microreactors 600 and, in a preferred embodiment, a plurality of microseparators 900 integral with the chemical processing microsystem 10. The microreactors 600 are preferably diffusion-mixed microreactors formed in a plurality of laminae that include a modular, interchangeable candidate-material array 100. The material array 100 comprises a plurality of different candidate materials (e.g., catalysts), preferably arranged at separate, individually addressable portions of a substrate (e.g., wafer). The microseparators 900 are similarly formed in a plurality of laminae that include a modular, interchangeable adsorbent array 700. The adsorbent array 700 comprises one or more adsorbents, preferably arranged at separate, individually, addressable portions of a substrate to spatially correspond to the plurality of different candidate materials. Modular microfluidic distribution systems are also disclosed. The chemical processing microsystem can be integrated into a material evaluation system that enables a comprehensive combinatorial material science research program.

Claims

1. A chemical processing microsystem comprising a parallel flow microreactor for evaluating catalyzed reactions, the parallel microreactor comprising

a microreactor structure comprising four or more microreactors formed in a plurality of adjacent laminae, each of the four or more microreactors comprising a surface defining a reaction cavity having a volume of not more than about 3 ml for carrying out a chemical reaction of interest, an inlet port in fluid communication with the reaction cavity, and an outlet port in fluid communication with the reaction cavity,

a fluid distribution system for simultaneously supplying one or more reactants from one or more reactant sources to the inlet port of each of the four or more microreactors through a passive microfluidic fluid-supply manifold and for simultaneously discharging a reactor effluent from the outlet port of each of the four or more microreactors to one or more effluent sinks, and

a temperature control device effective for controlling the temperature of the reaction cavity to be above 100°

C. during the chemical reaction of interest,

at least one of the plurality of laminae being adaptable for use as a material-containing laminate that forms a portion of the cavity-defining surface of the four or more microreactors, the material-containing laminate comprising a substrate for containing at least four catalyst materials arranged on the substrate such that they are individually resident in the reaction cavities of the four or more microreactors, the four or more microreactors being accessible for loading the material-containing laminate prior to carrying out the chemical reaction of interest, and for unloading the material-containing laminate after the chemical reaction of interest.

2. The microsystem of claim 1 further comprising a releasable seal between the material-containing laminate and one or more adjacent laminae in which the microreactors are formed.

3. The microsystem of claim 2 wherein the releasable seal is a gasket.

4. The microsystem of claim 2 wherein the releasable seal is a graphite gasket.

5. The microsystem of claim 1 wherein the microsystem comprises

a first laminate having first and second surfaces in spaced, substantially parallel relationship to each other, and an array of the at least four materials,

a second laminate having a first surface in releasable contact with the second surface of the first laminate, a second surface in spaced, substantially parallel relationship to the first surface, and an array of four or more wells defined by interior edges of the first surface of the second laminate and by interior surfaces of the second laminate, the array of wells having an arrangement that corresponds to the array of at least four materials formed in the first laminate, such that taken together, the first and second laminates form an array of four or more material-containing microreactors.

6. The chemical processing microsystem of claim 1 wherein the microsystem comprises

a first laminate having first and second surfaces in spaced, substantially parallel relationship to each other, and an array of the at least four materials,

a releasable seal adjacent the second surface of the first laminate,

a second laminate having a first surface adjacent the releasable seal, a second surface in spaced, substantially parallel relationship to the first surface, and an array of four or more apertures defined by interior edges and interior surfaces of the second laminate, and

a third laminate having a first surface bonded to the second surface of the second laminate such that, taken together, the second and third laminates form a composite substructure comprising an array of four or more wells defined by the interior edges and interior surfaces of the second laminate and those portions of the first surface of the third laminate circumscribed by such interior edges,

the array of wells formed in the composite substructure having an arrangement that corresponds to the array of the at least four materials of the first laminate, such that taken together, the first, second and third laminates form an array of four or more material-containing microreactors.

7. The chemical processing microsystem of claim 1 wherein

the microreactor structure comprises ten or more microreactors, and the microfluidic fluid-supply manifold is formed in a plurality of adjacent laminae, the manifold being in sealed contact with a component of the microreactor structure, the manifold comprising one or more common ports adaptable for fluid communication with one or more reactant sources, ten or more terminal ports adaptable for fluid delivery to the ten or more microreactors, and a distribution channel providing fluid communication between the one or more common ports and each of the ten or more terminal ports, the ratio of the number of terminal ports to the number of common ports being not less than about 10:

1.

8. The microsystem of claim 7 comprising twenty or more microreactors wherein the ratio of the number of terminal ports to the number of common ports is not less than about 20:

1.

9. The microsystem of claim 7 comprising thirty or more microreactors wherein the ratio of the number of terminal ports to the number of common ports is not less than about 30:

1.

10. The microsystem of claim 7 comprising fifty or more microreactors wherein the ratio of the number of terminal ports to the number of common ports is not less than about 50:

1.

11. The microsystem of claim 7 comprising one-hundred or more microreactors wherein the ratio of the number of terminal ports to the number of common ports is not less than about 100:

1.

12. The microsystem of claim 7 wherein the fluid distribution system comprises a manifold having substantially the same resistance to flow between the one or more common ports and each of the ten or more terminal ports, such that the fluid distribution system provides substantially the same flow through each of the ten or more microreactors.

13. The microsystem of claim 7 comprising sixteen or more microreactors, wherein the fluid distribution manifold comprises

a common port adaptable for fluid communication with one or more fluid sources or sinks,

2ⁿ terminal ports adaptable for fluid delivery to or fluid recovery from 2ⁿ microreactors, n being an integer not less than 4, and

a distribution channel providing fluid communication between the common port and each of the 2ⁿ terminal ports, the distribution channel having a hydraulic radius of not more than about 2.5 mm and comprising 2ⁿ−

1 channel sections connected with each other through 2ⁿ−

1 binary junctions, each of the 2ⁿ−

1 channel sections having at least three access ports serving as the common port, as a connection port for a binary junction, or as a terminal port.

14. The microsystem of claim 13 wherein the 2ⁿ−

1 channel sections are linear channel sections.

15. The microsystem of claim 13 wherein the ten or more microreactors are arranged in a substantially planar array with planar density of not less than about 1 microreactor/cm².

16. The microsystem of claim 7 wherein the ten or more microreactors are formed in a plurality of laminae.

17. The microsystem of claim 7 wherein the ten or more microreactors are formed in a plurality of laminae, and the fluid distribution manifold is formed in at least one laminate other than the laminae in which the ten or more microreactors are formed.

18. The microsystem of claim 7 wherein the chemical processing microsystem further comprises at least ten different candidate materials individually resident in the ten or more microreactors.

19. The microsystem of claim 7 wherein the distribution channels are adapted such that the pressure drop in each of the fluid distribution channels is larger than the pressure drop in its associated microreactor.

20. The microsystem of claim 7 wherein the microfluidic fluid distribution manifold is releasably sealed with a component of the microreactor structure, such that the manifold can be modularly interchanged with another microfluidic fluid distribution manifold.

21. The chemical processing microsystem of claim 1 wherein the reaction cavity of the microreactors has a volume of not more than about 100 μ

l and a geometry defined by ratios of distances X, Y, and Z measured within the reaction cavity along three mutually orthogonal lines having a common point of intersection at a midpoint of the longest line, Z, the X;

Z and Y;

Z ratios each ranging from about 1;

2 to about 1;

1.

22. The microsystem of claim 21 wherein the volume of the reaction cavity is not more than about 1 μ

l.

23. The microsystem of claim 21 wherein the X:

Z and Y;

Z ratios each range from about 2;

3 to about 1;

1.

24. The microsystem of claim 21 wherein the X:

Z and Y;

Z ratios each range from about 3;

4 to about 1;

1.

25. The microsystem of claim 21 wherein the X:

Z and Y;

Z ratios are each about 1;

1.

26. The microsystem of claim 21 wherein the chemical processing microsystem further comprises at least four different candidate materials individually resident in the four or more microreactors.

27. The microsystem of claim 21 wherein the microsystem has an essential absence of active mixing elements.

28. The microsystem of claim 21 wherein the microsystem has an essential absence of active mixing elements and static mixing elements.

29. The microsystem of claim 21 wherein the reactor geometry is adapted so that the microreactors are diffusion-mixed microreactors.

30. The microsystem of claim 21 wherein the reactor geometry and the inlet port geometry is adapted so that the microreactors are diffusion-mixed without substantial back-diffusion of reactants into a reactant supply manifold of the fluid distribution system.

31. The chemical processing microsystem of claim 1 wherein the volume of at least two of the four or more microreactors is different.

32. The chemical processing microsystem of claim 1 wherein the volume of at least four of the four or more microreactors is different.

33. The chemical processing microsystem of claim 1 wherein the four or more microreactors are arranged in a substantially planar array and having a planar density of not less than about 5 microreactors/cm².

34. The microsystem of claim 33 wherein the microreactors are arranged in a substantially planar array with a planar density of at least 10 microreactors/cm².

35. The microsystem of claim 33 wherein the microreactors are arranged in a substantially planar array with a planar density of at least 25 microreactors/cm².

36. The microsystem of claim 33 wherein the microreactors are arranged in a substantially planar array with a planar density of at least 50 microreactors/cm².

37. The microsystem of claim 33 wherein the chemical processing microsystem further comprises at least four different candidate materials individually resident in the four or more microreactors.

38. The chemical processing microsystem of claim 1 further comprising

a parallel microseparator comprising four or more microseparators, each of the four or more microseparators comprising a surface defining a separation cavity for separating at least one component of a reactor effluent, an inlet port in fluid communication with the outlet port of one of the microreactors for receiving the reactor effluent therefrom, and an outlet port in fluid communication with the separation cavity for discharging the separated effluent therefrom, the microseparators being formed in a plurality of adjacent laminae, at least one of the laminae being adaptable for use as an adsorbent-containing laminate comprising a substrate and one or more adsorbent materials for adsorbing at least one component of the reactor effluent, the four or more microseparators being accessible for loading the adsorbent-containing laminate prior to carrying out the chemical reaction of interest, and for unloading the adsorbent-containing laminate after the chemical reaction of interest, and

a fluid discharge system for discharging the separated effluent from the outlet port of each separation cavity to one or more effluent sinks.

39. The microsystem of claim 38 wherein the chemical processing microsystem further comprises at least four different candidate materials individually resident in the four or more microreactors.

40. The microsystem of claim 38 wherein the microseparators further comprise an adsorbent material that is substantially selective to a reaction product of interest.

41. The microsystem of claim 38 further comprising a releasable seal between the adsorbent-containing laminate and one or more adjacent laminae in which the microseparators are formed.

42. The microsystem of claim 38 wherein the four or more microreactors are formed in a plurality of laminae.

43. The microsystem of claim 38 wherein the four or more microreactors are formed in a plurality of adjacent laminae, at least one of the laminae being a candidate material-containing laminate comprising a substrate and the at least four candidate materials at separate portions of the substrate.

44. The microsystem of claim 38 wherein the four or more microreactors are formed in a first plurality of laminae and the four or more microseparators are formed in a second plurality of laminae, the microsystem further comprising a temperature control block between the first plurality of laminae and the second plurality of laminae.

45. The microsystem of claim 38 wherein the four or more microreactors and the four or more microseparators are formed in a common plurality of laminae.

46. The microsystem of claim 38 wherein each of the four or more microreactors are substantially coplanar with each other and each of the four or more microseparators are substantially coplanar with each other.

47. The chemical processing microsystem of claim 1 wherein

the microreactor structure comprises two-hundred-fifty or more microreactors, the material-containing laminate further comprises at least four candidate materials so that the candidate materials are individually resident in the reaction cavity of separate microreactors, each of the candidate materials comprising an inorganic material, a metal-ligand or a non-biological organic material, and

the microfluidic fluid-supply manifold is formed in a plurality of laminae.

48. The microsystem of claim 47 wherein the reaction cavity of each of the two-hundred-fifty or more microreactors has a volume of less than about 10 μ

l.

49. The microsystem of claim 47 wherein the reaction cavity of each of the two-hundred-fifty or more microreactors has a volume of not more than about 5 μ

l.

50. The microsystem of claim 47 wherein the reaction cavity of each of the two-hundred-fifty or more microreactors has a volume of not more than about 1 μ

l.

51. The microsystem of claim 47 wherein the amount of the candidate material in each of the candidate-material containing microreactors is not more than about 5 mg.

52. The microsystem of claim 47 wherein the amount of the candidate material in each of the candidate-material containing microreactors is not more than about 1 mg.

53. The microsystem of claim 47 wherein the candidate material comprises an inorganic material.

54. The microsystem of claim 47 wherein the candidate material comprises a metal-ligand.

55. The microsystem of claim 47 wherein the candidate material comprises a non-biological organic material.

56. The microsystem of claim 47 wherein the candidate material consists essentially of elements or compounds selected from the group consisting of an inorganic material, a metal-ligand and a non-biological organic material.

57. The microsystem of claim 47 wherein the candidate material is a film of material formed on a surface of the reaction cavity.

58. The microsystem of claim 47 comprising four-hundred or more microreactors.

59. The microsystem of claim 47 comprising one-thousand or more microreactors.

60. The microsystem of claim 47 wherein the at least four materials are at least four different materials.

61. The microsystem of claim 47 wherein at least eight different candidate materials are individually resident in the reaction cavities of separate microreactors.

62. The microsystem of claim 47 wherein at least fifty different candidate materials are individually resident in the reaction cavities of separate microreactors.

63. The microsystem of claim 47 wherein at least two-hundred-fifty different candidate materials are individually resident in the reaction cavities of separate microreactors.

64. The microsystem of claim 47 wherein different candidate materials are individually resident in the reaction cavities of at least 90% of the microreactors.

65. The microsystem of claim 47 wherein the reaction cavities have a volume that is substantially the same for each of the microreactors.

66. The microsystem of claim 47 wherein the reaction cavities have a volume that is different for at least two of the microreactors.

67. The microsystem of claim 47 further comprising an analytical detection system in fluid communication with the outlet port of one or more of the microreactors.

68. The microsystem of claim 47 wherein each of the two-hundred-fifty or more microreactors is accessible for loading candidate catalyst materials prior to carrying out the chemical reaction of interest and for unloading materials after the chemical reaction of interest.

69. The microsystem of claim 47 wherein a portion of the reaction cavity-defining surface of each of the two-hundred-fifty or more microreactors is formed by a material-containing laminate comprising, a substrate and the at least four materials at separate portions of the substrate.

70. The microsystem of claim 47 wherein the microreactors are formed in a plurality of adjacent laminae.

71. The microsystem of claim 47 wherein the microreactors are formed in a plurality of adjacent laminae, at least one of the laminae being a material-containing laminate comprising a substrate and the at least four materials at separate portions of the substrate, the microsystem further comprising a releasable seal between the material-containing laminate and one or more adjacent laminae in which the microreactors are formed.

72. The microsystem of claim 47 wherein the microreactors are formed in a plurality of adjacent laminae, at least one of the laminae being a material-containing laminate comprising a substrate and the at least four materials at separate portions of the substrate, the material-containing laminate having an essential absence of fluid distribution components.

73. The microsystem of claim 47 wherein the microreactors are formed in a plurality of adjacent laminae, at least one of the laminae being a material-containing laminate comprising a substrate and the at least four materials at separate portions of the substrate, the material-containing laminate having an essential absence of temperature control components.

74. The microsystem of claim 47 wherein the fluid distribution system comprises a manifold comprising at least one common port adaptable for fluid communication with one or more external reactant sources or one or more external reactor effluent sinks, two-hundred-fifty or more terminal ports adaptable for fluid delivery to or fluid recovery from the two-hundred-fifty or more microreactors, and a distribution channel providing fluid communication between the at least one common port and each of the two-hundred-fifty or more terminal ports, the ratio of the number of terminal ports to the number of common ports being not less than about 10:

1.

75. The microsystem of claim 74 wherein the ratio of the number of terminal ports to the number of common ports is not less than 100:

1.

76. The microsystem of claim 74 wherein the ratio of the number of terminal ports t he number of common ports is not less than 200:

1.

77. The microsystem of claim 47 wherein the fluid-distribution system comprises

a fluid distribution manifold comprising a common port adaptable for fluid communication with one or more external reactant sources or one or more external effluent sinks,

2ⁿ terminal ports adaptable for fluid delivery to or fluid recovery from 2ⁿ microreactors, n being an integer not less than 4, and

a distribution channel providing fluid communication between the common port and each of the 2ⁿ terminal ports, the distribution channel comprising 2ⁿ−

1 channel sections connected with each other through 2ⁿ−

1 binary junctions, each of the 2ⁿ−

1 channel sections having at least three access ports serving as the common port, as a connection port for a binary junction, or as a terminal port.

78. The microsystem of claim 77 wherein each of the channel sections are linear.

79. The microsystem of claim 77 wherein n is an integer of not less than 6.

80. The microsystem of claim 77 wherein n is an integer of not less than 8.

81. The microsystem of claim 77 wherein the microreactors are arranged in a substantially planar array with a planar density of at least 1 microreactor/cm².

82. The microsystem of claim 47 wherein the reaction cavity of each of the two-hundred-fifty or more microreactors has a geometry defined by ratios of distances X, Y, and Z measured within the reaction cavity along three mutually orthogonal lines having a common point of intersection at a midpoint of the longest line, Z, the X:

Z and Y;

Z ratios each ranging from about 1;

2 to about 1;

1.

83. The microsystem of claim 82 wherein the X:

Z and Y;

Z ratios each range from about 2;

3 to about 1;

1.

84. The microsystem of claim 82 wherein the X:

Z and Y;

Z ratios each range from about 3;

4 to about 1;

1.

85. The microsystem of claim 47 wherein the microreactors are arranged in a substantially planar array with a planar density of at least 1 microreactor/cm².

86. The microsystem of claim 47 wherein the microreactors are arranged in a substantially planar array with a planar density of at least 5 microreactors/cm².

87. The microsystem of claim 47 wherein the microreactors are arranged in a substantially planar array with a planar density of at least 10 microreactors/cm².

88. The microsystem of claim 47 wherein the microreactors are arranged in a substantially planar array with a planar density of at least 5 microreactors/cm² and the reaction cavity of each of the two-hundred-fifty or more microreactors has a volume of not more than about 1 μ

l.

89. The microsystem of claim 47 further comprising two-hundred-fifty or more microseparators, each of the two-hundred-fifty or more microseparators comprising a surface defining a separation cavity for separating at least one component of the reactor effluent, an inlet port in fluid communication with the outlet port of one of the microreactors for receiving the reactor effluent therefrom, and an outlet port in fluid communication with the separation cavity for discharging the separated effluent therefrom.

90. The microsystem of claim 89 wherein the microseparators further comprise an adsorbent material.

91. The microsystem of claim 89 wherein the microseparators are formed in a plurally of adjacent laminae, at least one of the laminae being an adsorbent-containing laminate comprising a substrate and one or more adsorbent materials for adsorbing at least one component of the reactor effluent, the microsystem further comprising a releasable seal between the adsorbent-containing laminate and one or more adjacent laminae in which the microseparators are formed.

92. The microsystem of claim 47 wherein

the two-hundred-fifty or more microreactors are formed in a plurality of adjacent laminae and are arranged in a substantially planar array with a planar density of at least about 1 microreactor/cm², at least one of the laminae being a material-containing laminate comprising a substrate and at least eight different candidate-materials at separate portions of the substrate, the material-containing laminate having an essential absence of fluid distribution components,

the fluid distribution system comprises a manifold comprising at least one common port adaptable for fluid communication with one or more external reactant sources or one or more external reactor effluent sinks, two-hundred-fifty or more terminal ports adaptable for fluid delivery to or fluid recovery from the two-hundred-fifty or more microreactors, and a distribution channel providing fluid communication between the at least one common port and each of the two-hundred-fifty or more terminal ports, the ratio of the number of terminal ports to the number of common ports being not less than about 10:

1.

93. The microsystem of claim 92 further comprising a releasable seal between the material-containing laminate and one or more adjacent laminae in which the microreactors are formed.

94. The microsystem of claim 92 wherein the reaction cavity of each of the two-hundred-fifty or more microreactors has a geometry defined by ratios of distances X, Y, and Z measured within the reaction cavity along three mutually orthogonal lines having a common point of intersection at a midpoint of the longest line, Z, the X:

Z and Y;

Z ratios each ranging from about 1;

2 to about 1;

1.

95. The microsystem of claim 92 further comprising two-hundred-fifty or more microseparators formed in a plurality of adjacent laminae, at least one of the laminae being an adsorbent-containing laminate comprising a substrate and one or more adsorbent materials for adsorbing at least one component of the reactor effluent, each of the two-hundred-fifty or more microseparators comprising a surface defining a separation cavity for separating at least one component of the reactor effluent, an inlet port in fluid communication with the outlet port of one of the microreactors for receiving the reactor effluent therefrom, and an outlet port in fluid communication with the separation cavity for discharging the separated effluent therefrom.

96. The chemical processing microsystem of claim 1 in a system for identifying and characterizing materials that enhance a chemical reaction, the system further comprising

a plurality of parallel microseparators, each of the plurality of microseparators comprising an adsorbent material that is selective for one or more reaction products of interest, and

a fluid distribution system for simultaneously supplying one or more reactants from one or more reactant sources to the plurality of microreactors, for simultaneously transferring reactor effluent from the plurality of microreactors to the plurality of microseparators, and for simultaneously discharging the separated effluent from the microseparators,

a station for applying a detection agent to the adsorbent material such that the detection agent can react with the one or more adsorbed reaction products to form a detectable species, and

a detector for detecting the detectable species.

97. The system of claim 96 wherein the detection agent is a dye or colorant.

98. The system of claim 96 wherein the station is a spray station.

99. The system of claim 96 wherein the detector is a parallel detector.

100. The system of claim 96 wherein the detector is a CCD camera.

101. The system of claim 96 wherein the microseparators are formed in a plurality of adjacent laminae, at least one of the laminae being adaptable for use as an adsorbent-containing laminate comprising a substrate and one or more adsorbent materials for adsorbing at least one component of the reactor effluent, the four or more microseparators being accessible for loading the adsorbent-containing laminate prior to carrying out the chemical reaction of interest, and for unloading the adsorbent-containing laminate after the chemical reaction of interest, so that the adsorbent-containing laminate can be transferred to the detection-agent application station.

102. The microsystem of claim 1 wherein the microfluidic fluid-supply manifold is formed in a plurality of adjacent laminae comprising at least one laminate separate from the plurality of adjacent laminae in which the microreactors are formed.

103. The microsystem of claim 1 wherein the temperature control device is effective for controlling the temperature of the reaction cavity to be above about 200°

C. during the chemical reaction of interest.

104. The microsystem of claim 1 wherein the temperature control device is effective for controlling the temperature of the reaction cavity during the chemical reaction of interest to range from about 100°

C. to about 500°

C.

105. The microsystem of claim 1 wherein the temperature control device is effective for controlling the temperature of the reaction cavity during the chemical reaction of interest to range from about 100°

C. to about 800°

C.

106. The microsystem of claim 1 wherein the fluid distribution system effective for supplying one or more gaseous reactants through the microfluidic fluid-supply manifold.

107. The microsystem of claim 1 wherein the fluid distribution system is effective for supplying one or more gaseous reactants through the microfluidic fluid-supply manifold, and the temperature control device is effective for controlling the temperature of the reaction cavity to be above about 200°

C. during the chemical reaction of interest.

108. The microsystem of claim 107 wherein the chemical processing microsystem further comprises four or more inorganic candidate catalyst materials individually resident in each of the four or more microreactors.

125. The microsystem of claims 1 or 109 wherein the at least four materials are selected from the group consisting of inorganic materials, metal-ligand materials and non-biological organic materials.

126. The microsystem of claims 1 or 109 wherein the microfluidic fluid-supply manifold is formed in a plurality of adjacent laminae.

127. The microsystem of claims 1 or 109 wherein the microfluidic fluid-supply manifold comprises a common port adaptable for fluid communication with one or more reactant sources, four or more terminal ports adapted for fluid delivery to the four or more microreactors, and a distribution channel providing fluid communication between the common port and each of the four or more terminal ports, the flow paths defined between the common port and each microreactors having equal conductance.

128. The microsystem of claims 1 or 109 wherein the microfluidic fluid-supply manifold comprises a common port adaptable for fluid communication with one or more reactant sources, four or more terminal ports adapted for fluid delivery to the four or more microreactors, and a distribution channel providing fluid communication between the common port and each of the four or more terminal ports, the distribution channels being adapted such that the pressure drop in each of the fluid distribution channels is larger than the pressure drop in its associated microreactor.

129. The microsystem of claims 1, 109 or 117 wherein the at least four materials are at least four different materials.

130. The microsystem of claims 1, 109, 116, 7, 21, 33 or 38 wherein the reaction cavity has a volume of not more than about 100 μ

l.

131. The microsystem of claims 1, 109, 116, 7, 21, 33 or 38 wherein the reaction cavity has a volume of not more than about 10 μ

l.

132. The microsystem of claims 1, 109, 116, 7, 21, 33 or 38 comprising one-hundred or more microreactors and at least one-hundred different candidate materials individually resident in the reaction cavities of the one-hundred or more microreactors, the at least one-hundred candidate materials being selected from the group consisting of inorganic materials, metal-ligand materials and non-biological organic materials.

133. The microsystem of claims 1, 109, 116, 7, 21, 33 or 38 wherein the microreactors are arranged in a substantially planar array with planar density of not less than about 1 microreactor/cm².

134. The microsystem of claims 7, 21, 33 or 38 further comprising at least four different candidate materials individually resident in the reaction cavities of the four or more microreactors, the at least four candidate materials being selected from the group consisting of inorganic materials, metal-ligand materials and non-biological organic materials.

135. A method for using the chemical processing microsystem of any one of claims 1, 109, 116, 7, 21, 31, 33, 38 or 47 for identifying or optimizing catalysts for a chemical reaction of interest, the method comprising

loading at least four materials into the microreactors of the chemical processing microsystem,

simultaneously contacting each of the at least four materials with the one or more reactants in the microreactors under reaction conditions for the reaction of interest,

simultaneously discharging a reactor effluent from the material-containing microreactors, and

evaluating the at least four materials for catalytic activity for the chemical reaction of interest.

136. A method for using the chemical processing microsystem of any one of claims 1, 109, 116, 7, 21, 31, 33, 38 or 47 for evaluating or optimizing process conditions for a chemical reaction of interest, the method comprising

simultaneously supplying one or more reactants to each of four or more microreactors of the chemical processing microsystem,

controlling a first set of reaction conditions to be substantially identical in each of the microreactors,

controlling a second set of reaction conditions to be varied between two or more of the microreactors,

simultaneously discharging a reactor effluent from each of the four or more microreactors, and

evaluating the effect of varying the second set of reaction conditions.

137. The microsystem of claims 1, 109, 7, 21, 31, 33 or 47 wherein the fluid distribution system discharges the reactor effluent from the outlet port of each of the four or more microreactors to one or more effluent sinks through a microfluidic effluent-distribution manifold.

138. The microsystem of claims 1, 109, 7, 21, 31, 33 or 47 wherein the fluid distribution system discharges the reactor effluent from the outlet port of each of the four or more microreactors to one or more effluent sinks through a microfluidic effluent-distribution manifold formed in a plurality of adjacent laminae.

139. The microsystem of claims 1, 109, 7, 21, 31, 33 or 47 wherein the fluid distribution system discharges the reactor effluent from the outlet port of each separation cavity to one or more effluent sinks through a microfluidic effluent-distribution manifold formed in a plurality of adjacent laminae.

140. The microsystem of claims 7, 21, 31, 33, 47 or 96 wherein the microfluidic fluid distribution manifold is a microfluidic fluid-supply manifold for simultaneously supplying one or more reactants from one or more reactant sources to the inlet port of each of the microreactors.

141. The microsystem of claims 38 or 96 wherein the fluid distribution system discharges the separated effluent from the outlet port of each separation cavity to one or more effluent sinks through a microfluidic effluent-distribution manifold.

142. The system of claims 38 or 101 wherein the adsorbent-containing laminate further comprises thin-layer chromatography channels associated in corresponding arrangement with each of the separation cavities, each of the thin-layer chromatography channels comprising one or more mobile phase inlet ports, one or more mobile-phase outlet ports, and an adsorbent material that is substantially selective for one or more analytes of interest.

109. A chemical processing microsystem comprising a parallel flow microreactor for evaluating catalyzed reactions, the parallel microreactor comprising

a microreactor structure comprising four or more microreactors formed in a plurality of adjacent laminae, each of the four or more microreactors comprising a surface defining a reaction cavity having a volume of not more than about 3 ml for carrying out a chemical reaction of interest, an inlet port in fluid communication with the reaction cavity, and an outlet port in fluid communication with the reaction cavity,

a fluid distribution system for simultaneously supplying one or more reactants from one or more reactant sources to the inlet port of each of the four or more microreactors through a microfluidic fluid-supply manifold and for simultaneously discharging a reactor effluent from the outlet port of each of the four or more microreactors to one or more effluent sinks, and

a temperature control device effective for controlling the temperature of the reaction cavity to be above 100°

C. during the chemical reaction of interest,

at least one of the plurality of laminae being adaptable for use as a material-containing laminate that forms a portion of the cavity-defining surface of the four or more microreactors, the material-containing laminate comprising a substrate for containing at least four catalyst materials arranged on the substrate such that they are individually resident in the reaction cavities of the four or more microreactors, the material-containing laminate having an essential absence of fluid distribution components, the four or more microreactors being accessible for loading the material-containing laminate prior to carrying out the chemical reaction of interest, and for unloading the material-containing laminate after the chemical reaction of interest.

110. The microsystem of claim 109 wherein the material-containing laminate further has an essential absence of temperature control components.

111. The microsystem of claim 109 wherein the material-containing laminate consists essentially of the substrate and the at least four materials.

112. The microsystem of claim 109 wherein the material-containing laminate consists of the substrate and the at least four materials.

113. The microsystem of claim 109 wherein the microreactors are substantially coplanar with each other.

114. The microsystem of claim 109 wherein the at least one surface of the material-containing laminate is in releasable contact with a surface of adjacent laminae in which the microreactors are formed.

115. The microsystem of claim 109 further comprising a releasable seal between the material-containing laminate and one or more adjacent laminae in which the microreactors are formed.

116. The chemical processing microsystem of claim 109 wherein the material-containing laminate comprises a film of material on at least a portion of the surface defining the reaction cavity of each of the four or more microreactors, the material being selected from the group consisting of inorganic materials, metal-ligand materials and non-biological organic materials.

117. The chemical processing microsystem of claim 116 wherein at least four materials are individually resident as surface films in the four or more microreactors.

118. The chemical processing microsystem of claim 116 wherein the material film is formed by a method selected from physical vapor deposition, chemical vapor deposition, plasma-assisted chemical vapor deposition, electrodeposition, electrochemical deposition, coating techniques, or solution-based techniques.

119. The chemical processing microsystem of claim 116 wherein the material film is formed by solution-based techniques.

120. The chemical processing microsystem of claim 116 wherein the material film is formed by sol-gel techniques.

121. The chemical processing microsystem of claim 116 wherein the material film is prepared by a method that includes forming a film of a catalyst support material on at least a portion of the surface that can define the reaction cavity, and impregnating the catalyst support material with a catalyst or a catalyst precursor.

122. The chemical processing microsystem of claim 109 wherein

the microreactor structure comprises ten or more microreactors, and

the microfluidic fluid-supply manifold is formed in a plurality of adjacent laminae, the manifold being in sealed contact with a component of the microreactor structure, the manifold comprising one or more common ports adaptable for fluid communication with one or more reactant sources, ten or more terminal ports adaptable for fluid delivery to the ten or more microreactors, and a distribution channel providing fluid communication between the one or more common ports and each of the ten or more terminal ports, the ratio of the number of terminal ports to the number of common ports being not less than about 10: 1.

123. The chemical processing microsystem of claim 109 wherein the reaction cavity of the microreactors has a volume of not more than about 100 μ

l and a geometry defined by ratios of distances X, Y, and Z measured within the reaction cavity along three mutually orthogonal lines having a common point of intersection at a midpoint of the longest line, Z, the X;

Z and Y;

Z ratios each ranging from about 1;

2 to about 1;

1.

124. The chemical processing microsystem of claim 109 further comprising

a parallel microseparator comprising four or more microseparators, each of the four or more microseparators comprising a surface defining a separation cavity for separating at least one component of a reactor effluent, an inlet port in fluid communication with the outlet port of one of the microreactors for receiving the reactor effluent therefrom, and an outlet port in fluid communication with the separation cavity for discharging the separated effluent therefrom, the microseparators being formed in a plurality of adjacent laminae, at least one of the laminae being adaptable for use as an adsorbent-containing laminate comprising a substrate and one or more adsorbent materials for adsorbing at least one component of the reactor effluent, the four or more microseparators being accessible for loading the adsorbent-containing laminate prior to carrying out the chemical reaction of interest, and for unloading the adsorbent-containing laminate after the chemical reaction of interest, and

a fluid discharge system for discharging the separated effluent from the outlet port of each separation cavity to one or more effluent sinks.