Emissive compositions with internal standard and related techniques

• US 20080085566A1
• Filed: 11/10/2006
• Published: 04/10/2008
• Est. Priority Date: 10/05/2006
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Liao, Jessica H., Swager, Timothy M.
• Granted Patent: US 8,802,447 B2
• Time in Patent Office: Days
• US Class Current: 436/172
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 11/574 with zinc or cadmium
• CPC Class Codes: C09K 2211/1416 Condensed systems
• CPC Class Codes: C09K 2211/1425 Non-condensed systems
• CPC Class Codes: C09K 2211/182 of the rare earth metals, i.e. Sc, Y or lanthanide
• CPC Class Codes: G01N 2021/6432 Quenching
• CPC Class Codes: G01N 33/442 Resins; Plastics
• CPC Class Codes: G01N 33/5432 Liposomes or microcapsules
• CPC Class Codes: G01N 33/544 the carrier being organic
• CPC Class Codes: G01N 33/545 Synthetic resin
• CPC Class Codes: G01N 33/553 Metal or metal coated
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer

Abstract

The present invention provides materials, devices, and methods related to determination of an analyte. In some embodiments, an analyte may be determined by monitoring, for example, a change in an optical signal of a luminescent material (e.g., particle) upon exposure to an analyte. The present invention may be particularly advantageous in that some embodiments may comprise an emissive species useful as an internal reference standard. Methods of the invention may also be useful in the quantitative determination of an analyte. In some cases, the present invention may allow for selective determination of an analyte.

Claims

1. A particle, comprising:

a core,

an outer layer at least partially encapsulating the core, wherein the outer layer comprises a polymer material having a first emission upon exposure to a set of conditions, and

a species having a second emission upon exposure to said set of conditions, wherein the species is integrally connected to at least a portion of the particle.

2. A particle as in claim 1, wherein a characteristic of the first emission is affected by an analyte for determination by the particle, and the second emission is essentially unaffected by the analyte.

3. A particle as in claim 2, wherein the characteristic is luminescence intensity.

4. A particle as in claim 1, wherein the core comprises a polymeric material.

5. A particle as in claim 1, wherein the core comprises polystyrene, polyacrylate, poly(methyl methacrylate), polyethylene, polypropylene, poly(vinyl chloride), poly(vinyl benzoate), poly(vinyl acetate), polyacrylamide, poly(vinyl butyral), polyurethane, polacetal, polycarbonate, polyester, polyether, polybutadiene, substituted derivatives thereof, or combinations thereof.

6. A particle as in claim 1, wherein the core comprises polystyrene.

7. A particle as in claim 1, wherein the species is dispersed throughout the core.

8. A particle as in claim 1, wherein the species is dispersed throughout the outer layer.

9. A particle as in claim 1, wherein the species is a metal compound or a dye molecule.

10. A particle as in claim 1, wherein the species is europium.

11. A particle as in claim 1, wherein the core comprises polystyrene and a plurality of europium atoms dispersed throughout the core.

12. A particle as in claim 1, wherein the outer layer comprises a polyarylene, polyarylene vinylene, polyarylene ethynylene, or ladder polymer.

13. A particle as in claim 1, wherein the outer layer comprises a polymer having the structure,

14. A particle as in claim 13, wherein B and D are each alkyne.

15. A particle as in claim 1, wherein the luminescent polymer comprises the structure,

16. A particle as in claim 15, wherein Y² and Z² are each ethylene glycol chains.

17. A particle as in claim 15, wherein Y² and Z² are each ethylene glycol chains substituted with a carboxylic acid group.

18. A particle as in claim 1, wherein the particle has a particle size between 0.001 and 10 microns.

19. A particle as in claim 1, wherein the particle has a particle size between 0.01 and 5.0 microns.

20. A particle as in claim 1, wherein the particle has a particle size between 0.01 and 3.0 microns.

21. A particle as in claim 1, wherein the particles has a particle size between 0.1 and 1.0 micron.

22. A particle as in claim 1, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 100 nm.

23. A particle as in claim 1, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 125 nm.

24. A particle as in claim 1, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 150 nm.

25. A particle as in claim 1, further comprising a support material integrally connected to at least a portion of the particle such that the particle is substantially contained within the support material.

26. A particle as in claim 25, further comprising a quencher molecule attached to at least a portion of the support material via a linker such that the quencher molecule is not capable of interacting with the particle.

27. A particle, comprising:

a core,

an outer layer at least partially encapsulating the core, wherein the outer layer comprises a polymer material having an emission, and

a support material integrally connected to at least a portion of the particle such that the particle is substantially contained within the support material.

28. A particle as in claim 27, wherein the core comprises a polymeric material.

29. A particle as in claim 27, wherein the core comprises polystyrene, polyacrylate, poly(methyl methacrylate), polyethylene, polypropylene, poly(vinyl chloride), poly(vinyl benzoate), poly(vinyl acetate), polyacrylamide, poly(vinyl butyral), polyurethane, polacetal, polycarbonate, polyester, polyether, polybutadiene, substituted derivatives thereof, or combinations thereof.

30. A particle as in claim 27, wherein the core comprises polystyrene.

31. A particle as in claim 27, wherein the species is dispersed throughout the core.

32. A particle as in claim 27, wherein the species is dispersed throughout the outer layer.

33. A particle as in claim 27, wherein the species is a metal compound or a dye molecule.

34. A particle as in claim 27, wherein the species is europium.

35. A particle as in claim 27, wherein the core comprises polystyrene and a plurality of europium atoms dispersed throughout the core.

36. A particle as in claim 27, wherein the outer layer comprises a polyarylene, polyarylene vinylene, polyarylene ethynylene, or ladder polymer.

37. A particle as in claim 27, wherein the outer layer comprises a polymer having the structure,

38. A particle as in claim 37, wherein B and D are each alkyne.

39. A particle as in claim 27, wherein the luminescent polymer comprises the structure,

40. A particle as in claim 39, wherein Y² and Z² are each ethylene glycol chains.

41. A particle as in claim 39, wherein Y² and Z² are each ethylene glycol chains substituted with a carboxylic acid group.

42. A particle as in claim 27, wherein the support material comprises a polymer.

43. A particle as in claim 27, wherein the support material comprises a hydrogel.

44. A particle as in claim 27, wherein the support material comprises a polyacrylamide, silicon hydrogel, polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylate, or combinations thereof, and the like.

45. A particle as in claim 27, wherein the support material comprises polyacryamide and poly(N,N′

-dimethylenebisacrylamide).

46. A particle as in claim 27, wherein the support material is a semi-permeable material.

47. A particle as in claim 27, wherein the particle has a particle size between 0.001 and 10 microns.

48. A particle as in claim 27, wherein the particle has a particle size between 0.01 and 5.0 microns.

49. A particle as in claim 27, wherein the particle has a particle size between 0.01 and 3.0 microns.

50. A particle as in claim 27, wherein the particles has a particle size between 0.1 and 1.0 micron.

51. A particle as in claim 27, further comprising a species having an emission, wherein the polymer material has a first emission and the species has a second emission upon exposure to a set of conditions, and wherein a characteristic of the first emission is affected by an analyte for determination by the particle, and the second emission is essentially unaffected by the analyte.

52. A particle as in claim 51, wherein the characteristic is luminescence intensity.

53. A particle as in claim 51, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 100 nm.

54. A particle as in claim 51, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 125 nm.

55. A particle as in claim 51, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 150 nm.

56. A particle as in claim 27, further comprising a quencher molecule attached to at least a portion of the support material via a linker such that the quencher molecule is not capable of interacting with the particle.

57. A particle, comprising:

a polymer material having a first emission upon exposure to a set of conditions, and

a species having a second emission upon exposure to said set of conditions,

wherein a characteristic of the first emission is affected by an analyte for determination by the particle, and the second emission is essentially unaffected by the analyte.

58. A sensor, comprising:

a particle comprising a core comprising a polymeric material and an outer layer at least partially encapsulating the core, wherein the outer layer comprises an emissive polymer material;

a source of energy applicable to the particle to cause an emission of radiation; and

an emission detector positioned to detect the emission.

59. A sensor as in claim 58, wherein the core comprises a polymeric material.

60. A sensor as in claim 58, wherein the core comprises polystyrene, polyacrylate, poly(methyl methacrylate), polyethylene, polypropylene, poly(vinyl chloride), poly(vinyl benzoate), poly(vinyl acetate), polyacrylamide, poly(vinyl butyral), polyurethane, polacetal, polycarbonate, polyester, polyether, polybutadiene, substituted derivatives thereof, or combinations thereof.

61. A sensor as in claim 58, wherein the core comprises polystyrene.

62. A sensor as in claim 58, wherein the species is dispersed throughout the core.

63. A sensor as in claim 58, wherein the species is dispersed throughout the outer layer.

64. A sensor as in claim 58, wherein the species is a metal compound or a dye molecule.

65. A sensor as in claim 58, wherein the species is europium.

66. A sensor as in claim 58, wherein the core comprises polystyrene and a plurality of europium atoms dispersed throughout the core.

67. A sensor as in claim 58, wherein the outer layer comprises a polyarylene, polyarylene vinylene, polyarylene ethynylene, or ladder polymer.

68. A sensor as in claim 58, wherein the outer layer comprises a polymer having the structure,

69. A sensor as in claim 68, wherein B and D are each alkyne.

70. A sensor as in claim 58, wherein the luminescent polymer comprises the structure,

71. A sensor as in claim 70, wherein Y² and Z² are each ethylene glycol chains.

72. A sensor as in claim 70, wherein Y² and Z² are each ethylene glycol chains substituted with a carboxylic acid group.

73. A sensor as in claim 58, wherein the particle has a particle size between 0.001 and 10 microns.

74. A sensor as in claim 58, wherein the particle has a particle size between 0.01 and 5.0 microns.

75. A sensor as in claim 58, wherein the particle has a particle size between 0.01 and 3.0 microns.

76. A sensor as in claim 58, wherein the particle has a particle size between 0.1 and 1.0 micron.

77. A sensor as in claim 58, further comprising a plurality of particles.

78. A sensor as in claim 77, wherein the plurality of particles is dispersed within a support material.

79. A sensor as in claim 78, wherein the support material comprises a polymer.

80. A particle as in claim 78, wherein the support material comprises a hydrogel.

81. A particle as in claim 78, wherein the support material comprises a polyacrylamide, silicon hydrogel, polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylate, or combinations thereof, and the like.

82. A particle as in claim 78, wherein the support material comprises polyacryamide and poly(N,N′

-dimethylenebisacrylamide).

83. A particle as in claim 78, wherein the support material is a semi-permeable material.

84. A particle as in claim 78, further comprising a quencher molecule attached to at least a portion of the support material via a linker such that the quencher molecule is not capable of interacting with the particle.

85. A sensor as in claim 58, the particle further comprising a species having an emission, wherein the polymer material has a first emission and the species has a second emission upon exposure to a set of conditions, and wherein a characteristic of the first emission is affected by an analyte for determination by the particle, and the second emission is essentially unaffected by the analyte.

86. A sensor as in claim 85, wherein the characteristic is luminescence intensity.

87. A sensor as in claim 85, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 100 nm.

88. A sensor as in claim 85, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 125 nm.

89. A sensor as in claim 85, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 150 nm.

90. A method for determination of an analyte, comprising:

providing a particle having an emission, wherein the particle comprises a core and an outer layer at least partially encapsulating the core, wherein the outer layer comprises an emissive polymer material;

exposing the particle to a sample suspected of containing an analyte wherein the analyte, if present, interacts with the particle to produce a change in the emission of the particle; and

determining the change in the emission of the particle, thereby determining the analyte.

91. A method as in claim 90, wherein the change comprises a decrease in luminescence intensity.

92. A method as in claim 90, wherein the change comprises an increase in luminescence intensity.

93. A method as in claim 90, wherein the change comprises a change in the wavelength of the luminescence.

94. A method as in claim 90, wherein the change is caused by a photoinduced charge transfer reaction between the emissive polymer material and the analyte.

95. A method as in claim 90, wherein the core comprises a polymeric material.

96. A method as in claim 90, wherein the core comprises polystyrene, polyacrylate, poly(methyl methacrylate), polyethylene, polypropylene, poly(vinyl chloride), poly(vinyl benzoate), poly(vinyl acetate), polyacrylamide, poly(vinyl butyral), polyurethane, polacetal, polycarbonate, polyester, polyether, polybutadiene, substituted derivatives thereof, or combinations thereof.

97. A method as in claim 90, wherein the core comprises polystyrene.

98. A method as in claim 90, wherein the outer layer comprises a polyarylene, polyarylene vinylene, polyarylene ethynylene, or ladder polymer.

99. A method as in claim 90, wherein the outer layer comprises a polymer having the structure,

100. A method as in claim 99, wherein B and D are each alkyne.

101. A method as in claim 90, wherein the luminescent polymer comprises the structure,

102. A method as in claim 90, wherein Y² and Z² are each ethylene glycol chains.

103. A method as in claim 90, wherein Y² and Z² are each ethylene glycol chains substituted with a carboxylic acid group.

104. A method as in claim 90, the particle further comprising a species having an emission, wherein the polymer material has a first emission and the species has a second emission upon exposure to a set of conditions, and wherein a characteristic of the first emission is affected by the analyte, if present, and the second emission is essentially unaffected by the analyte, if present.

105. A method as in claim 104, wherein the characteristic is luminescence intensity.

106. A method as in claim 104, wherein the species is a metal compound or a dye molecule.

107. A method as in claim 104, wherein the species is europium.

108. A method as in claim 104, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 100 nm.

109. A method as in claim 104, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 125 nm.

110. A method as in claim 104, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 150 nm.

111. A method as in claim 90, wherein the core comprises polystyrene and a plurality of europium atoms dispersed throughout the core.

112. A method as in claim 90, further comprising a plurality of particles.

113. A method as in claim 112, wherein the plurality of particles is dispersed within a support material.

114. A method as in claim 113, wherein the support material comprises a polymer.

115. A method as in claim 113, wherein the support material comprises a hydrogel.

116. A method as in claim 113, wherein the support material comprises a polyacrylamide, silicon hydrogel, polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylate, or combinations thereof, and the like.

117. A method as in claim 113, wherein the support material comprises polyacryamide and poly(N,N′

-dimethylenebisacrylamide).

118. A method as in claim 113, wherein the support material is a semi-permeable material.

119. A method as in claim 113, wherein the support material further comprises a quencher molecule attached to at least a portion of the support material via a linker such that the quencher molecule is not capable of interacting with the particle.

120. A method as in claim 119, wherein the interaction between the analyte and the particle comprises cleavage of the linker such that the quencher molecule interacts with the particle to produce a change in the emission of the particle

121. A method as in claim 90, wherein the particle has a particle size between 0.001 and 10 microns.

122. A method as in claim 90, wherein the particle has a particle size between 0.01 and 5.0 microns.

123. A method as in claim 90, wherein the particle has a particle size between 0.01 and 3.0 microns.

124. A method as in claim 90, wherein the particle has a particle size between 0.1 and 1.0 micron.

125. A method for quantitative determination of the concentration of an analyte, comprising:

providing a particle comprising a polymer material and a species, wherein, upon exposure to a set of conditions, the polymer material has a first emission and the species has a second emission, wherein the maximum of the first emission and the maximum of the second emission are separated by at least 50 nm;

determining a first ratio between a characteristic of the first emission and a characteristic of the second emission;

exposing the particle to an analyte, wherein the analyte interacts with the polymer material to produce a third emission;

determining, upon exposure to said set of conditions, a second ratio between a characteristic of the second emission and a characteristic of the third emission, wherein the second ratio is different than the first ratio; and

determining the difference between the first ratio and the second ratio, thereby quantitatively determining the concentration of the analyte.

126. A method as in claim 125, wherein the first ratio is a ratio between the luminescence intensity of the first emission and the luminescence intensity of the second emission, and the second ratio is a ratio between the luminescence intensity of the second emission and the luminescence intensity of the third emission.

127. A method as in claim 125, wherein the luminescence intensity of the third emission is decreased relative to the luminescence intensity of the first emission.

128. A method as in claim 125, wherein the luminescence intensity of the third emission is increased relative to the luminescence intensity of the first emission.

129. A method as in claim 125, wherein the wavelength of the third emission is shifted relative to the wavelength of the first emission.

130. A method as in claim 125, wherein the change is caused by a photoinduced charge transfer reaction between the particle and the analyte.

131. A method as in claim 125, wherein the core comprises a polymeric material.

132. A method as in claim 125, wherein the core comprises polystyrene, polyacrylate, poly(methyl methacrylate), polyethylene, polypropylene, poly(vinyl chloride), poly(vinyl benzoate), poly(vinyl acetate), polyacrylamide, poly(vinyl butyral), polyurethane, polacetal, polycarbonate, polyester, polyether, polybutadiene, substituted derivatives thereof, or combinations thereof.

133. A method as in claim 125, wherein the core comprises polystyrene.

134. A method as in claim 125, wherein the outer layer comprises a polymer having the structure,

135. A method as in claim 134, wherein B and E are each alkyne.

136. A method as in claim 125, wherein the luminescent polymer comprises the structure,

137. A method as in claim 136, wherein Y² and Z² are each ethylene glycol chains.

138. A method as in claim 136, wherein Y² and Z² are each ethylene glycol chains substituted with a carboxylic acid group.

139. A method as in claim 125, the particle further comprising a species having an emission, wherein the polymer material has a first emission and the species has a second emission upon exposure to a set of conditions, and wherein a characteristic of the first emission is affected by the analyte, if present, and the second emission is essentially unaffected by the analyte, if present.

140. A method as in claim 139, wherein the characteristic is luminescence intensity.

141. A method as in claim 139, wherein the species is a metal compound or a dye molecule.

142. A method as in claim 139, wherein the species is europium.

143. A method as in claim 139, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 100 nm.

144. A method as in claim 139, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 125 nm.

145. A method as in claim 139, wherein the maximum of the first emission is separated from the maximum of the second emission by at least 150 nm.

146. A method as in claim 125, wherein the core comprises polystyrene and a plurality of europium atoms dispersed throughout the core.

147. A method as in claim 125, further comprising a plurality of particles.

148. A method as in claim 147, wherein the plurality of particles is dispersed within a support material.

149. A method as in claim 148, wherein the support material comprises a polymer.

150. A method as in claim 148, wherein the support material comprises a hydrogel.

151. A method as in claim 148, wherein the support material comprises a polyacrylamide, silicon hydrogel, polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylate, or combinations thereof, and the like.

152. A method as in claim 148, wherein the support material comprises polyacryamide and poly(N,N′

-dimethylenebisacrylamide).

153. A method as in claim 148, wherein the support material is a semi-permeable material.

154. A method as in claim 148, wherein the support material further comprises a quencher molecule attached to at least a portion of the support material via a linker such that the quencher molecule is not capable of interacting with the particle.

155. A method as in claim 154, wherein the interaction between the analyte and the particle comprises cleavage of the linker such that the quencher molecule interacts with the particle to produce a change in the emission of the particle.

156. A method as in claim 125, wherein the particle has a particle size between 0.001 and 10 microns.

157. A method as in claim 125, wherein the particle has a particle size between 0.01 and 5.0 microns.

158. A method as in claim 125, wherein the particle has a particle size between 0.01 and 3.0 microns.

159. A method as in claim 125, wherein the particle has a particle size between 0.1 and 1.0 micron.