Methods for optically encoding an object with upconverting materials and compositions used therein

• US 20050136486A1
• Filed: 07/12/2004
• Published: 06/23/2005
• Est. Priority Date: 07/12/2003
• Status: Active Grant

• Current Assignee: Parallel Synthesis Technologies, Inc.
• Original Assignee: Parallel Synthesis Technologies, Inc.
• Inventors: Haushalter, Robert C.
• Granted Patent: US 8,796,030 B2
• Time in Patent Office: Days
• US Class Current: 435/7.200
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 5/00 Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• CPC Class Codes: C12Q 1/6825 Nucleic acid detection involving sensors
• CPC Class Codes: G01N 2458/40 Rare earth chelates
• CPC Class Codes: G01N 33/588 with semiconductor nanocrystal label, e.g. quantum dots
• CPC Class Codes: G06K 19/022 Processes or apparatus therefor
• CPC Class Codes: G06K 19/06028 using bar codes
• CPC Class Codes: G06K 19/0614 the marking being selective to wavelength, e.g. color barcode or barcodes only visible under UV or IR methods or arrangements for sensing record carriers using a selected wavelength, see G06K7/12
• CPC Class Codes: G06K 7/12 using a selected wavelength, e.g. to sense red marks and ignore blue marks
• CPC Class Codes: G06K 7/1408 the method being specifically adapted for the type of code
• CPC Class Codes: Y10T 436/13 Tracers or tags

Abstract

The present invention relates generally to encoding samples. More specifically, it relates to barcodes and compositions involving upconverters and methods including them. In a composition aspect of the invention, a composition comprising two or more lanthanide materials is provided. Each lanthanide material comprises a host, an absorber, and an emitter, and the materials emit detectable electromagnetic radiation upon excitation with absorbable electromagnetic energy. One or more relative ratios of emission intensities uniquely identify the composition.

Claims

1. An upconverting composition comprising two or more lanthanide materials, wherein each lanthanide material comprises a host, an absorber, and one or more emitters, and wherein the materials emit detectable electromagnetic radiation upon excitation with absorbable electromagnetic energy, and wherein the emitted radiation is less than 800 nanometers and the absorbed radiation is greater than 800 nanometers, and wherein one or more relative ratios of emission intensities uniquely identify the composition.

3. The composition according to claim 1, wherein the host is an oxide, oxysulfide, aluminate, gallate or halide.

5. The composition according to claim 3, wherein one or more hosts are selected from a group consisting of two or more of the following compounds:

sodium yttrium fluoride, lanthanum fluoride, lanthanum oxysulfide, yttrium oxysulfide, yttrium fluoride, yttrium gallate, yttrium aluminum garnet, gadolinium fluoride, barium yttrium fluoride, and gadolinium oxysulfide.

7. The composition according to claim 1, wherein the materials comprise one or more absorber and one or more emitting centers, and wherein the absorbers are selected from the group consisting of ytterbium, erbium and samarium, and wherein the emitting centers are selected from a group consisting of erbium, holmium, terbium, thulium, praseodymium, neodymium and dysprosium.

9. The composition according to claim 5, wherein the molar ratio of absorber to emitting center is between 1:

1 and 2000;

1.

11. The composition according to claim 9, wherein the emitting center is erbium, and wherein the molar ratio of absorber to emitting center is between 20:

1 and 100;

1.

13. The composition according to claim 9, wherein the two or more emitting centers are selected from a group consisting of thulium, praseodymium, neodymium, dysprosium and holmium, and wherein the molar ratio of absorber to emitting center is between 500:

1 and 2000;

1.

15. The composition according to claim 1, wherein the two or more lanthanide materials are selected from a group consisting of the following:

Na(Y_xYb_yEr_z)F₄, wherein x is 0.7 to 0.9, y is 0.09 to 0.29, and z is 0.05 to 0.01;

Na(Y_xYb_yHo₂)F₄, wherein x is 0.7 to 0.9, y is 0.0995 to 0.2995, and z is 0.0005 to 0.001;

Na(Y_xYb_yTm₂)F₄, wherein x is 0.7 to 0.9, y is 0.0995 to 0.2995, and z is 0.0005 to 0.0001;

(Y_xYb_yEr_z)O₃, wherein x is 0.7 to 0.9, y is 0.05 to 0.12, and z is 0.05 to 0.12; and

, (Y_xYb_yEr_z)O₂, wherein X is O or S and x is 0.7 to 0.9, y is 0.05 to 0.12, and z is 0.05 to 0.12.

17. The composition according to claim 15, wherein the composition further comprises a dye.

19. The composition according to claim 15, wherein the composition further comprises a quantum dot.

21. The composition according to claim 15, wherein the dye is selected from a group consisting of rhodamines, cyanines, xanthenes, acridines, oxazines, porphyrins, and phthalocyanines.

23. The composition according to claim 19, wherein the quantum dot comprises cadmium sulfide, cadmium sulfide, zinc selenide or cadmium telluride.

25. The composition according to claim 1, wherein the composition is combined with a probe.

27. The composition according to claim 1, wherein the composition is combined with a paper document or an optical medium.

29. The composition according to claim 1, wherein the composition is combined with an organic molecule.

57. An apparatus for identifying an object, wherein the object is combined with a composition of claim 1 or 2, wherein the apparatus comprises:

a) an infrared laser diode for exciting the lanthanide materials;

b) a detector, wherein the detector comprises one or more photomultiplier tubes or one or more charge-coupled devices, for measuring the detectable electromagnetic radiation emitted from the lanthanide materials; and

,

c) a processing unit for quantifying the emitted, detectable electromagnetic radiation, calculating the one or more relative ratios of emission intensities, assigning a unique code to all calculated relative ratios, and reading the unique codes to identify the object wherein the apparatus is capable of temporally resolving the emission from the composition of claim 1 or 2 from emissions from organic dye and quantum dot reporters.

58. The apparatus according to claim 57, wherein the object is combined with a composition of claim 3 or 4.

59. The apparatus according to claim 57, wherein the object is combined with a composition of claim 5 or 6.

60. The composition according to claim 1, wherein the lanthanide material is prepared by the thermolysis of a solution of a soluble lanthanide compound.

62. The composition according to claim 60, wherein the soluble lanthanide compound is selected from a group of lanthanide nitrates, acetates, halides, perchlorates, sulfates and citrates.

64. The composition according to claim 60, wherein the soluble lanthanide compound is dissolved in water or aqueous solutions.

66. The composition according to claim 60, wherein the soluble lanthanide compound is a lanthanide nitrate, sulfate or acetate dissolved in water.

68. The composition according to claim 60, wherein the solution is imbibed into the pores of a porous glass, ceramic or organic polymer particle and subsequently subjected to thermolysis.

70. The composition according to claim 1, wherein the composition is in the form of a colloidal suspension.

74. The composition according to claim 60, wherein the soluble lanthanide compound is nebulized from an ultrasonic nebulization source and carried into a high temperature zone whereupon thermolysis occurs.

76. The composition according to claim 60, wherein the soluble lanthanide compound is dissolved in a combustible solvent or gas, or solvent and gas mixture, and subjected to flame spray pyrolysis.

78. The composition according to claim 60, wherein the soluble lanthanide compound is dissolved in water and co-mixed with a combustible solvent or gas, or solvent or gas mixture and subjected to flame spray pyrolysis.

80. The composition according to claim 60, wherein the solution is subjected to freeze drying or frozen solvent sublimation before thermolysis.

82. A process to prepare the compositions of claim 1 or 2 comprising:

a) dissolving a soluble lanthanide material in a solvent; and

,

b) subjecting the solution to a suitably high thermal treatment to decompose the precursor into a solid state material, thereby forming the composition.

83. The process according to claim 80, wherein the composition is of claim 3 or 4.

84. The process according to claim 80, wherein the composition is of claim 5 or 6.

85. A method for identifying and sorting objects encoded with compositions as in claim 1 or claim 2 in a Flow Cytometer, wherein identifying and sorting comprises the steps of:

a) contacting organic cy3/cy5 emitters and RUP compositions as in claim 1 and/or claim 2 to objects.

b) moving the objects at a speed of 0.02 m/s to 30 m/s past one or more photomultipliers and one or more CCD detectors.

c) irradiating the objects with radiations having wavelengths of 532 nm and 633 nm, thereby inducing emission from the cy3/cy5 emitters

d) analyze the signal from the PMT induced by emission from the cy3/cy5 emitters.

e) irradiating the objects with radiation having a wavelength greater than 800 nm, thereby inducing emission from the RUP at a radiation wavelength less than 800 nm, wherein each emitter emits at a different wavelength;

f) measuring relative integrated emission intensities from the emitters within a different wavelength range for each RUP emitter;

g) calculating relative ratios of the integrated emission intensities from the emitters; and

,

h) assigning a unique code to each calculated relative ratio; and

,

i) processing the unique code to identify and sort the objects.

j) associating the unique code with the correct cy3/cy5 emission profile.

86. An apparatus for identifying and sorting objects in a Flow Cytometer, wherein the objects are combined with a composition of claim 1 or 2, and organic cy3/cy5 emitters, and wherein the apparatus comprises:

a) an infrared laser diode for exciting the materials and two visible lasers with wavelength of 532 nm and 633 mm for exciting cy3/cy5 emitters;

b) a detector, wherein the detector comprises one or more photomultiplier tubes or one or more charge-coupled devices, for measuring the detectable electromagnetic radiation emitted from the materials; and

,

d) a filter which is placed in front of CCD.

c) a processing unit for quantifying the emitted, detectable electromagnetic radiation, calculating the one or more relative ratios of emission intensities, assigning a unique code to all calculated relative ratios, and reading the unique codes to identify the object, and

wherein the apparatus is capable of temporally resolving the emission from the composition of claim 1 or 2 from emissions from organic dye and quantum dot reporters.

87. The composition according to claim 29 wherein the organic molecule is a polynucleotide, DNA or RNA.

89. The composition according to claim 29 wherein the organic molecule is a protein, polypeptide or antibody.

93. The composition according to claim 29 where the object is a glass or polymer bead or microsphere.

97. The composition according to claim 29 where the object is a glass or polymer bead or microsphere coated with DNA, RNA or a polynucleotide.

101. The composition according to claim 29 where the object is a glass or polymer bead or microsphere coated with a protein, polypeptide or antibody.

2. An upconverting composition comprising a lanthanide material, wherein the lanthanide material comprises a host, an absorber and two or more emitters, and wherein the material emits detectable electromagnetic radiation upon excitation with absorbable electromagnetic energy, and wherein the emitted radiation is less than 800 nanometers and the absorbed radiation is greater than 800 nanometers, and wherein one or more relative ratios of emission intensities uniquely identify the composition.

4. The composition according to claim 2, wherein the host is an oxide, oxysulfide, aluminate, gallate or halide.

6. The composition according to claim 4, wherein the host is selected from a group consisting of sodium yttrium fluoride, lanthanum fluoride, lanthanum oxysulfide, yttrium oxysulfide, yttrium fluoride, yttrium gallate, yttrium aluminum garnet, gadolinium fluoride, barium yttrium fluoride, and gadolinium oxysulfide.

8. The composition according to claim 2, wherein the material comprises an absorber and two or more emitting centers, and wherein the absorber selected from a group consisting of ytterbium, erbium and samarium, and wherein the emitting center is selected from a group consisting of erbium, holmium, erbium, thulium, praseodymium, neodymium and dysprosium.

10. The composition according to claim 6, wherein the molar ratio of absorber to emitting center is between 1:

1 and 2000;

1.

12. The composition according to claim 10, wherein the emitting center is erbium, and wherein the molar ratio of absorber to emitting center is between 20:

1 and 100;

1.

14. The composition according to claim 10, wherein the two or more emitting centers are selected from a group consisting of thulium, praseodymium, neodymium, dysprosium and holmium, and wherein the molar ratio of absorber to emitting center is between 500:

1 and 2000;

1.

16. The composition according to claim 2, wherein the lanthanide material is selected from a group consisting of the following:

Na(Y_xYb_y(RE)_z)F₄, wherein x is 0.7 to 0.9, y is 0.09 to 0.29, and z is 0.0005 to 0.08;

(Y_xYb_y(RE)_z)O₂X, wherein X is O or S and x is 0.7 to 0.9, y is 0.05 to 0.12, and z is 0.05 to 0.12;

wherein RE is a group of two or more lanthanide elements.

18. The composition according to claim 16, wherein the composition further comprises a dye.

20. The composition according to claim 16, wherein the composition further comprises a quantum dot.

22. The composition according to claim 16, wherein the dye is selected from a group consisting of rhodamines, cyanines, xanthenes, acridines, oxazines, porphyrins, and phthalocyanines.

24. The composition according to claim 20, wherein the quantum dot comprises cadmium sulfide, zinc sulfide, zinc selenide, cadmium selenide or cadmium telluride.

26. The composition according to claim 2, wherein the composition is combined with a probe.

28. The composition according to claim 2, wherein the composition is combined with a paper document or an optical medium.

30. The composition according to claim 2, wherein the composition is combined with an organic molecule.

61. The composition according to claim 2, wherein the lanthanide material is prepared by the thermolysis of a solution of a soluble lanthanide compound.

63. The composition according to claim 61, wherein the soluble lanthanide compound is selected from a group of lanthanide nitrates, acetates, halides, perchlorates, sulfates and citrates.

65. The composition according to claim 61, wherein the soluble lanthanide compound is dissolved in water or aqueous solutions.

67. The composition according to claim 61, wherein the soluble lanthanide compound is a lanthanide nitrate, sulfate or acetate dissolved in water.

69. The composition according to claim 61, wherein the solution is imbibed into the pores of a porous glass, ceramic or organic polymer particle and subsequently subjected to thermolysis.

71. The composition according to claim 2, wherein the composition is in the form of a colloidal suspension.

75. The composition according to claim 61, wherein the soluble lanthanide compound is nebulized from an ultrasonic nebulization source and carried to into a high temperature zone whereupon thermolysis occurs.

77. The composition according to claim 61, wherein the soluble lanthanide compound is dissolved in a combustible solvent or gas, or solvent and gas mixture, and subjected to flame spray pyrolysis.

79. The composition according to claim 61, wherein the soluble lanthanide compound is dissolved in water and co-mixed with a combustible solvent or gas, or solvent or gas mixture and subjected to flame spray pyrolysis.

81. The composition according to claim 61, wherein the solution is subjected to freeze drying or frozen solvent sublimation before thermolysis.

88. The composition according to claim 30 wherein the organic molecule is a polynucleotide, DNA or RNA.

90. The composition according to claim 30 wherein the organic molecule is a protein, polypeptide or antibody.

94. The composition according to claim 30 where the object is a glass or polymer bead or microsphere.

98. The composition according to claim 30 where the object is a glass or polymer bead or microsphere coated with DNA, RNA or a polynucleotide.

102. The composition according to claim 30 where the object is a glass or polymer bead or microsphere coated with a protein, polypeptide or antibody.

31. A method of optically encoding an object, wherein the method comprises combining the object with a composition comprising two or more lanthanide materials, wherein each lanthanide material comprises a host, an absorber and one and more emitters, and wherein the materials emit detectable electromagnetic radiation upon excitation with absorbable electromagnetic energy.

32. A method of identifying an object according to claim 31, wherein identifying comprises the steps of:

a) irradiating the lanthanide materials with radiation having a wavelength greater than 800 nm, thereby inducing emission from the emitters at a radiation wavelength less than 800 nm, wherein each emitter emits at a different wavelength;

b) measuring relative integrated emission intensities from the emitters within a different wavelength range for each emitter;

c) calculating relative ratios of the integrated emission intensities from the emitters; and

,

d) assigning a unique code to each calculated relative ratio; and

,

e) processing the unique code to identify the object.

35. The method according to claim 31, wherein the host is an oxide, oxysulfide, aluminate, gallate or halide.

37. The method according to claim 35, wherein one or more hosts are selected from a group consisting of two or more of the following compounds:

sodium yttrium fluoride, lanthanum fluoride, lanthanum oxysulfide, yttrium oxysulfide, yttrium fluoride, yttrium gallate, yttrium aluminum garnet, gadolinium fluoride, barium yttrium fluoride, and gadolinium oxysulfide.

39. The method according to claim 31, wherein the materials comprise one or more absorber and one or more emitting centers, and wherein the absorbers are selected from the group consisting of ytterbium, erbium and samarium, and wherein the emitting centers are selected from a group consisting of erbium, holmium, terbium, thulium, praseodymium, neodymium and dysprosium.

41. The method according to claim 39, wherein the molar ratio of absorber to emitting center is between 1:

1 and 2000;

1.

43. The method according to claim 41, wherein the emitting center is erbium, and wherein the molar ratio of absorber to emitting center is between 20:

1 and 100;

1.

45. The method according to claim 41, wherein the two or more emitting centers are selected from a group consisting of thulium, praseodymium, neodymium, dysprosium and holmium, and wherein the molar ratio of absorber to emitting center is between 500:

1 and 2000;

1.

47. The method according to claim 31, wherein the materials are irradiated using an infrared laser diode or an incandescent filament.

49. The method according to claim 31, wherein the emission intensities are measured using a photomultiplier device, and avalanche photodiode, a charge-coupled device, a CID device, a photographic film emulsion, a photochemical reaction yielding detectable products, or through visual observation.

51. The method according to claim 31, wherein the object is a probe.

53. The method according to claim 31, wherein the object is a paper document or optical medium.

55. The method according to claim 31, wherein the object is an organic molecule.

72. The method according to claim 31, wherein the lanthanide is in the form of a colloidal suspension.

91. A method according to claim 31 where the object is a DNA, RNA or polynucleotide molecule.

95. A method according to claim 31 where the object is a glass or polymer bead or microsphere.

99. The method according to claim 31 where the object is a glass or polymer bead or microsphere coated with DNA, RNA or a polynucleotide.

103. The method according to claim 31 where the object is a glass or polymer bead or microsphere coated with a protein, polypeptide or antibody.

33. A method of optically encoding an object, wherein the method comprises combining the object with a composition comprising a lanthanide material, wherein the lanthanide material comprises a host, an absorber and two or more emitters, and wherein the material emits detectable electromagnetic radiation upon excitation with absorbable electromagnetic energy.

34. A method of identifying an object according to claim 33, wherein identifying comprises the steps of:

a) irradiating the lanthanide material with radiation having a wavelength greater than 800 nm, thereby inducing emission from the emitters at a radiation wavelength less than 800 nm, wherein each emitter emits at a different wavelength;

b) measuring a relative integrated emission intensity from the emitters within a different wavelength range for each emitter;

c) calculating relative ratios of the integrated emission intensities from the emitters; and

,

d) assigning a unique code to each calculated relative ratio; and

,

e) processing the unique code to identify the object.

36. The method according to claim 33, wherein the host is an oxide, oxysulfide, aluminte, gallate or halide.

38. The method according to claim 36, wherein one or more hosts are selected from a group consisting of two or more of the following compounds:

sodium yttrium fluoride, lanthanum fluoride, lanthanum oxysulfide, yttrium oxysulfide, yttrium fluoride, yttrium gallate, yttrium aluminum garnet, gadolinium fluoride, barium yttrium fluoride, and gadolinium oxysulfide.

40. The method according to claim 33, wherein the material comprises an absorber and two or more emitting centers, and wherein the absorber selected from a group consisting of ytterbium, erbium and samarium, and wherein the emitting center is selected from a group consisting of erbium, holmium, erbium, thulium, praseodymium, neodymium and dysprosium.

42. The method according to claim 40, wherein the molar ratio of absorber to emitting center is between 1:

1 and 2000;

1.

44. The method according to claim 42, wherein the emitting center is erbium, and wherein the molar ratio of absorber to emitting center is between 20:

1 and 100;

1.

46. The method according to claim 42, wherein the two or more emitting centers are selected from a group consisting of thulium, praseodymium, neodymium, dysprosium and holmium, and wherein the molar ratio of absorber to emitting center is between 500:

1 and 2000;

1.

48. The method according to claim 33, wherein the material is irradiated using an infrared laser diode or an incandescent filament.

50. The method according to claim 33, wherein the emission intensities are measured using a photomultiplier device, and avalanche photodiode, a charge-coupled device, a CID device, a photographic film emulsion, a photochemical reaction yielding detectable products, or through visual observation.

52. The method according to claim 33, wherein the object is a probe.

54. The method according to claim 33, wherein the object is a paper document or optical medium.

56. The method according to claim 33, wherein the object is an organic molecule.

73. The method according to claim 33, wherein the lanthanide is in the form of a colloidal suspension.

92. A method according to claim 33 where the object is a DNA, RNA or polynucleotide molecule.

96. A method according to claim 33 where the object is a glass or polymer bead or microsphere.

100. The method according to claim 33 where the object is a glass or polymer bead or microsphere coated with DNA, RNA or a polynucleotide.

104. he method according to claim 33 where the object is a glass or polymer bead or microsphere coated with a protein, polypeptide or antibody.