Two-photon upconverting dyes and applications

• US 5,912,257 A
• Filed: 09/05/1996
• Issued: 06/15/1999
• Est. Priority Date: 09/06/1995
• Status: Expired due to Fees

• Current Assignee: The Research Foundation for The State University of New York (State University of New York)
• Original Assignee: The Research Foundation for The State University of New York (State University of New York)
• Inventors: He, Guang S., Gvishi, Raz, Bhawalkar, Jayant D., Zhao, Chan F., Ruland, Gary E., Prasad, Paras N., Zieba, Jaroslaw, Cheng, Ping Chin, Pan, Shan Jen
• Primary Examiner(s): NORTHINGTON DAVIS, ZINNA
• Application Number:
  US08/712,143
• Time in Patent Office: 1,013 Days
• Field of Search: 8/636, 8/680, 250/338.1, 252/542, 264/1.33, 430/338, 430/343, 514/356, 514/709, 522/6, 546/329, 568/34
• US Class Current: 514/356
• CPC Class Codes: A61K 41/008 Two-Photon or Multi-Photon PDT, e.g. with upconverting dyes or photosensitisers
• CPC Class Codes: A61K 49/0021 the fluorescent group being a small organic molecule
• CPC Class Codes: A61K 49/0084 liposome, i.e. bilayered vesicular structure
• CPC Class Codes: A61P 31/12 Antivirals
• CPC Class Codes: A61P 35/00 Antineoplastic agents
• CPC Class Codes: A61P 43/00 Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
• CPC Class Codes: G11C 13/04 using optical elements ; using other beam accessed elements, e.g. electron or ion beam

Abstract

Styryl dyes and compositions which exhibit superior two-photon absorption cross-sections and are useful in two-photon pumped cavity lasing, two-photon pumped upconversion lasing, optical power limiting, optical power stabilization, optical signal reshaping, and infrared beam detection and indication are disclosed. Also disclosed are multiphasic nanostructured composites which include a glass having pores, an optically active coating material on the pore surface, and a polymeric material in the pores. These composites are useful in producing multifunctional optical materials, such as broadly tunable lasers. Methods for killing cells and viruses using a photosensitizer and a two-photon upconverting dye are also described. These methods are especially useful to kill cells and viruses in biological materials, such as in photodynamic therapy of tumors and cancers or blood purification protocols. Media and methods for recording data in a three-dimensional matrix which includes a plurality of dye molecules is also described. The data storage methods and media have approximately 10¹² volume elements per square centimeter, and each of the volume elements can store a single bit, digital information, or analog information. The data storage methods and media of the present invention are particularly useful for storing or archiving a series of two-dimensional black and white or color images, such as frames of a movie.

Claims

1. A compound having the formula:

##STR29## wherein R² is unsubstituted alkyl,

R¹ and R³ are selected from the group consisting of hydroxyalkyl, sulfoalkyl, and carboxyalkyl,

A and B are hydrogen, and

Y is a counterion.

4. A compound according to claim 1, having the formula:

5. A compound according to claim 1, having the formula:

2. A compound having the formula:

##STR30##

3. A compound having the formula:

6. A composition comprising:

a matrix material and

a compound having the formula;

##STR31## wherein n is 0;

A is hydrogen;

D is an amine having the formula NR¹ R² ;

R¹ and R² are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties;

Y is a counterion;

Q had the formula;

##STR32## R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties;

dispersed in said matrix.

7. A composition according to claim 6, wherein R¹ is 2-hydroxyethyl, R² is methyl, and R³ is 6-hydroxyhexyl.

8. A composition comprising:

a matrix and

a compound having the formula;

##STR33## wherein R² is unsubstituted alkyl,

R¹ and R³ are selected from the group consisting of hydroxyalkyl, sulfoalkyl, and carboxyalkyl,

A and B are hydrogen, and

Y is a counterion dispersed in said matrix.

9. A composition comprising:

a matrix material and

a compound having the formula;

##STR34## wherein D is an electron donating group;

Q is an electron acceptor selected from the group consisting of electron acceptors having the formulae;

##STR35## W is an electron accepting group, R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

n is an integer from 0 to 4,

A, B, and C are substitutents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion dispersed in said matrix, wherein said matrix material is selected from the group consisting of a polymer, a glass, and a liquid.

11. A composition according to claim 9, wherein said matrix material is a polymer.

12. A composition according to claim 11, wherein the polymer is selected from the group consisting of a polyurethane, a polyester, a polyalkyacrylic acid or ester, an epoxy, a polyimide, a polyamide, a phenal-formaldehyde polymer, a urea-formaldehyde polymer, a melamine-formaldehyde polymer, and mixtures thereof.

13. A composition according to claim 9, wherein said matrix material is a glass.

14. A composition according to claim 9, wherein said matrix material is a liquid.

10. A composition comprising:

a matrix material and

a compound having the formula;

##STR36## wherein D is an electron donating group;

Q is an electron acceptor selected from the group consisting of electron acceptors having the formulae;

##STR37## W is an electron accepting group, R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

n is an integer from 0 to 4,

A, B, and C are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion dispersed in said matrix, wherein the composition is a free standing film, forms a coating on a substrate, forms a fiber or forms a three dimensional solid having at least two parallel sides separated by a distance from about 2 to about 20 mm.

17. A composition according to claim 10, wherein said composition is a free standing film.

18. A composition according to claim 17, wherein the film is from about 0.001 to about 1 mm thick.

19. A composition according to claim 10, wherein said composition forms a coating on a substrate.

20. A composition according to claim 19, wherein the coating is from about 0.01 to about 0.05 mm thick.

21. A composition according to claim 10, wherein said composition forms a fiber.

22. A composition according to claim 10, wherein said composition forms a three dimensional solid having at least two parallel sides separated by a distance from about 2 to about 20 mm.

15. A composition comprising:

a matrix material and

a compound having the formula;

##STR38## wherein D is an electron donating group;

Q is an electron acceptor selected from the group consisting of electron acceptors having the formulae;

##STR39## W is an electron accepting group, R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

n is an integer from 0 to 4,

A, B, and C are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion dispersed in said matrix, wherein said compound is present in said matrix material in a concentration from about 0.001M to about 0.1M.

16. A composition according to claim 15, wherein said compound is present in said matrix material in a concentration from about 0.0015M to about 0.01M.

23. A method of detecting infrared radiation comprising:

placing a compound having the formula;

##STR40## wherein n is 0;

A is hydrogen;

D is an amine having the formula NR¹ R² ;

R¹ and R² are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties;

Y is a counterion;

Q has the formula;

##STR41## R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties;

at a location potentially exposed to the infrared radiation and

evaluating whether the compound has been exposed to the infrared radiation at the location.

24. A method according to claim 23, wherein R¹ is 2-hydroxyethyl, R² is methyl, and R³ is 6-hydroxyhexyl.

25. A method of detecting infrared radiation comprising:

placing a compound having the formula;

##STR42## wherein R¹ and R² are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

A and B are substitutents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is tetraphenylborate

at a location potentially exposed to the infrared radiation and

evaluating whether the compound has been exposed to the infrared radiation at the location.

26. A method of detecting infrared radiation comprising:

placing a compound having the formula;

##STR43## wherein A and B are hydrogen,

R¹, R², and R³ are the same or different and are selected from the group consisting of unsubstituted alkyl, hydroxyalkyl, sulfoalkyl, and carboxyalkyl, and

Y is a counterion at a location potentially exposed to the infrared radiation and

evaluating whether the compound has been exposed to the infrared radiation at the location.

27. A method according to claim 26, wherein R² is unsubstituted alkyl and R¹ and R³ are selected from the group consisting of hydroxyalkyl, sulfoalkyl, and carboxyalkyl.

28. A method of detecting infrared radiation comprising:

placing a compound having the formula;

##STR44## wherein D is an electron donating group;

Q is an electron acceptor selected from the group consisting of electron acceptors having the formulae;

##STR45## W is an electron accepting group, R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

n is an integer from 0 to 4,

A, B, and C are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion at a location potentially exposed to the infrared radiation and

evaluating whether the compound has been exposed to the infrared radiation at the location, wherein the compound is dispersed in a matrix material.

29. A method according to claim 28, wherein the matrix material is a polymer.

30. A method according to claim 29, wherein the polymer is selected from the group consisting of a polyurethane, a polyester, a polyalkyacrylic acid or ester, an epoxy, a polyimide, a polyamide, a phenal-formaldehyde polymer, a urea-formaldehyde polymer, a melamine-formaldehyde polymer, and mixtures thereof.

31. A method according to claim 28, wherein the matrix material is a glass.

32. A method according to claim 28, wherein the matrix material is a liquid.

33. A method according to claim 28, wherein the compound is present in the matrix material in a concentration from about 0.001M to about 0.01M.

34. A method according to claim 33, wherein the compound is present in the matrix material in a concentration from about 0.001M to about 0.1M.

37. A method of detecting cross-sectional shape of an infrared laser beam comprising:

detecting infrared radiation in accordance with the method of claim 28 at various locations potentially exposed to an infrared laser beam and

correlating the infrared radiation detected at the various locations to the cross-sectional shape of the infrared laser beam.

38. A method of detecting cross-sectional intensity profile of an infrared laser beam comprising:

detecting infrared radiation intensity in accordance with the method of claim 28 at various locations potentially exposed to an infrared laser beam and

correlating the infrared radiation intensity detected at the various locations to the cross-sectional intensity profile of the infrared laser beam.

39. A method of detecting a temporal intensity profile of an infrared laser beam comprising:

detecting infrared radiation intensity at a location potentially exposed to an infrared laser beam in accordance with the method of claim 28 at various times and

correlating the infrared radiation intensity detected at the various times with the temporal intensity profile of the infrared laser beam.

35. A method of detecting infrared radiation comprising:

placing a compound having the formula;

##STR46## wherein D is an electron donating group;

Q is an electron acceptor selected from the group consisting of electron acceptors having the formulae;

##STR47## W is an electron accepting group, R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

n is an integer from 0 to 4,

A, B, and C are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion at a location potentially exposed to the infrared radiation and

evaluating whether the compound has been exposed to the infrared radiation at the location, wherein the infrared radiation has a wavelength fromabout 700 to about 1300 nm.

36. A method of detecting infrared radiation comprising:

placing a compound having the formula;

##STR48## wherein D is an electron donating group;

Q is an electron acceptor selected from the group consisting of electron acceptors having the formuale;

##STR49## W is an electron accepting group, R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

n is an integer from 0 to 4,

A, B, and C are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion at a location potentially exposed to the infrared radiation and

evaluating whether the compound has been exposed to the infrared radiation at the location, wherein the infrared radiation is laser radiation produced by a Nd-YAG laser.

40. A method for reducing intensity of infrared radiation comprising:

providing a compound having the formula;

##STR50## wherein D is an electron donating group;

Q is an electron acceptor selected from the group consisting of electron acceptors having the formulae;

##STR51## W is an electron accepting group, R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

n is an integer from 0 to 4,

A, B, and C are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion and

passing infrared radiation through the compound, whereby the compound reduces intensity of the infrared radiation.

41. A method according to claim 40, wherein n is 0;

A is hydrogen;

D is an amine having the formula NR¹ R² ;

R¹ and R² are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties; and

Q has the formula;

##STR52##

42. A method according to claim 41, wherein R¹ is 2-hydroxyethyl, R² is methyl, and R³ is 6-hydroxyhexyl.

43. A method according to claim 40, wherein the compound has the formula:

wherein

R¹ and R² are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties.

44. A method according to claim 43, wherein Y is tetraphenylborate.

45. A method according to claim 43, wherein A and B are hydrogen and R¹, R², and R³ are the same or different and are selected from the group consisting of unsubstituted alkyl, hydroxyalkyl, sulfoalkyl, and carboxyalkyl.

46. A method according to claim 45, wherein R² is unsubstituted alkyl and R¹ and R³ are selected from the group consisting of hydroxyalkyl, sulfoalkyl, and carboxyalkyl.

47. A method according to claim 40, wherein the compound is dispersed in a matrix material.

48. A method according to claim 47, wherein the matrix material is a polymer.

49. A method according to claim 48, wherein the polymer is selected from the group consisting of a polyurethane, a polyester, a polyalkyacrylic acid or ester, an epoxy, a polyimide, a polyamide, a phenal-formaldehyde polymer, a urea-formaldehyde polymer, a melamine-formaldehyde polymer, and mixtures thereof.

50. A method according to claim 47, wherein the matrix material is a glass.

51. A method according to claim 47, wherein the matrix material is a liquid.

52. A method according to claim 47, wherein the compound is present in the matrix material in a concentration from about 0.001M to about 0.1M.

53. A method according to claim 52, wherein the compound is present in the matrix material in a concentration from about 0.0015M to about 0.01M.

54. A method according to claim 40, wherein the infrared radiation has a wavelength from about 700 to about 1300 nm.

55. A method according to claim 40, wherein the infrared radiation is laser radiation produced by a Nd-YAG laser.

56. A method for protecting a sensitive infrared detector from damage caused by intense radiation comprising:

reducing intensity of infrared radiation according to the method of claim 40 by placing the compound between the sensitive infrared detector and a source of infrared radiation.

57. An device for detecting infrared radiation comprising:

an infrared detector and

a window comprising a compound having the formula;

##STR53## wherein R¹, R², and R³ are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

A and B are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion positioned at a location where incident infrared radiation passes through the window prior to entering said detector.

58. Eye wear having transparent surfaces containing a compound having the formula:

##STR54## wherein R¹, R², and R³ are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

A and B are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is counterion.

59. A method for converting infrared radiation to visible radiation comprising:

providing a compound having the formula;

##STR55## wherein D is an electron donating group;

Q is an electron acceptor selected from the group consisting of electron acceptors having the formulae;

##STR56## W is an electron accepting group, R³ is selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

n is an integer from 0 to 4,

A, B, and C are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion

and

exposing the compound to infrared radiation, whereby the compound converts the infrared radiation to visible radiation.

60. A method according to claim 59, wherein n is 0;

A is hydrogen;

D is an amine having the formula NR¹ R² ;

R¹ and R² are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties; and

Q has the formula;

##STR57##

61. A method according to claim 60, wherein R¹ is 2-hydroxyethyl, R² is methyl, and R³ is 6-hydroxyhexyl.

62. A method according to claim 59, wherein the compound has the formula:

wherein

R¹ and R² are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties.

63. A method according to claim 62, wherein Y is tetrapehnylborate.

64. A method according to claim 62, wherein A and B are hydrogen and R¹, R², and R³ are the same or different and are selected from the group consisting of unsubstituted alkyl, hydroxyalkyl, sulfoalkyl, and carboxyalkyl.

65. A method according to claim 59, wherein R² is unsubstituted alkyl and R¹ and R³ are selected from the group consisting of hydroxyalkyl, sulfoalkyl, and carboxyalkyl.

66. A method according to claim 59, wherein the compound is dispersed in a matrix material.

67. A method according to claim 66, wherein the matrix material is a polymer.

68. A method according to claim 67, wherein the polymer is selected from the group consisting of a polyurethane, a polyester, a polyalkyacrylic acid or ester, an epoxy, a polyimide, a polyamide, a phenal-formaldehyde polymer, a urea-formaldehyde polymer, a melamine-formaldehyde polymer, and mixtures thereof.

69. A method according to claim 66, wherein the matrix material is a glass.

70. A method according to claim 66, wherein the matrix material is a liquid.

71. A method according to claim 66, wherein the matrix material is a glass or a polymer in the form of an optical fiber.

72. A method according to claim 66, wherein the matrix material is a glass or a polymer in the form of a three dimensional solid having at least two parallel sides separated by a distance from 2 to 20 mm.

73. A method according to claim 66, wherein the compound is present in the matrix material in a concentration from about 0.001M to about 0.1M.

74. A method according to claim 73, wherein the compound is present in the matrix material in a concentration from about 0.0015M to about 0.01M.

75. A method according to claim 59, wherein the infrared radiation has a wavelength from about 700 to about 1300 nm.

76. A method according to claim 59, wherein the infrared radiation is laser radiation produced by a Nd-YAG laser.

77. A method according to claim 59, wherein the visible radiation is coherent.

78. A method according to claim 59, wherein the visible radiation is incoherent.

79. A method according to claim 59, wherein the visible radiation has a wavelength from about 350 to about 680 nm.

80. A laser comprising:

a source capable of producing infrared radiation and

a compound having the formula;

##STR58## wherein R¹, R², and R³ are the same or different and are selected from the group consisting of substituted or unsubstituted alkyl or substituted or unsubstituted aryl moieties,

A and B are substituents of their rings and are each independently selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, sulfoalkyl, carboxyalkyl, and hydrogen, and

Y is a counterion positioned at a location where infrared radiation from said source exposes said compound, whereby said compound converts the infrared radiation to visible radiation.