Photopolymerizable Compositions

• US 20110117477A1
• Filed: 04/15/2009
• Published: 05/19/2011
• Est. Priority Date: 04/16/2008
• Status: Abandoned Application

• Current Assignee: Smart Holograms Ltd.
• Original Assignee: Smart Holograms Ltd.
• Inventors: Horgan, Adrian M.D., Pareek, Pradeep
• Application Number:
  US12/988,140
• Publication Number:
  US 20110117477A1
• Time in Patent Office: Days
• US Class Current: 430/2
• CPC Class Codes: G01N 21/4788 Diffraction for sizing particles G01N15/0205
• CPC Class Codes: G03F 7/001 Phase modulating patterns, e.g. refractive index patterns
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/0388 with ethylenic or acetylenic bands in the side chains of the photopolymer
• CPC Class Codes: G03H 1/02 Details of features involved during the holographic process; Replication of holograms without interference recording
• CPC Class Codes: G03H 2001/0044 holographic fringes deformations; holographic sensors holographic rain sensor in vehicles B60S1/084
• CPC Class Codes: G03H 2001/0264 Organic recording material
• CPC Class Codes: G03H 2001/186 Swelling or shrinking the holographic record or compensation thereof, e.g. for controlling the reconstructed wavelength G03H2001/0033, G03H2250/44 take precedence
• CPC Class Codes: G11B 7/24044 for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage G11B7/24038 takes precedence
• CPC Class Codes: G11B 7/245 containing a polymeric component
• CPC Class Codes: G11B 7/2532 comprising metals

Abstract

Currently known holographic recording media and sensors have a number of disadvantages, for example, silver halide-based recording media is expensive to produce and unsuitable for use in certain sensor applications, and photopolymer-based recording media make it difficult to record multiple holographic images, thus, generally, rendering them unsuitable for use in sensors. Holographic recording media according to an embodiment of the present invention may comprise a polymer matrix and a chemical group that dimerizes by forming a cyclic bridge through photocycloaddition. These holographic recording media are cost-effective, allow recording of multiple holographic images, and enable production of sensors with controlled observable response to an external stimulus.

Claims

1. A holographic sensor, comprising:

(a) a holographic recording media comprising a polymer matrix; and

(b) at least one holographic image recorded in said holographic recording media as diffraction fringes, wherein the diffraction fringes comprise a dimeric structure that includes a cyclic bridge; and

wherein said holographic recording media responds to an external stimulus by providing at least one output signal.

4. The holographic sensor of claim 1, wherein the dimeric structure crosslinks the polymer matrix.

5. The holographic sensor of claim 1, wherein the polymer matrix is in addition to crosslinking through dimeric structures that are part of the diffraction fringes further randomly crosslinked through crosslinking groups different from the dimeric structure.

15. The holographic sensor of claim 1, wherein the diffraction fringes comprise (i) dark fringes with relatively low density of dimeric structures, and (ii) bright fringes associated with relatively high density of dimeric structures, and the polymer matrix responds to an external stimulus with a higher degree of swelling in the dark fringes than in the bright fringes, leading to a variation in reproduction wavelength of the holographic image recorded in the holographic recording media.

19. The holographic sensor of claim 1, wherein the polymer matrix comprises gelatin, or a polymer of one or more of 2-hydroxyethylmethacrylate (HEMA), 2-hydroxypropylmethacrylate (HPMA), N,N-dimethylacrylamide (DMAA), poly(ethylene glycol) mono-methacrylate (PEGMA), vinyl acetate, acrylamide, N-isopropylacrylamide, acrylic acid (AA), methacrylic acid (MAA), N,N-methylenebisacrylamide (BIS), ethyleneglycol dimethacrylate (EDMA), 2-acrylamido-2-methylpropane sulfonic acid (AMPS), sodium salt of methacrylic acid, 2-(dimethylaminoethyl)methacrylate (DMAEMA), Styrene 4-sulfonic acid, and 2-(N,N Dimethyl-N-(2-methacryloxyethyl)ammonium)ethanoic acid.

20. The holographic sensor of claim 19, wherein the cyclic bridge is a cyclobutyl.

21. The holographic sensor of claim 20, wherein the diffraction fringes comprise a dimer of one or more of cinnamoyl, chalcone, anthracene, coumarin, stilbazolium, maleimide, or a derivatives thereof.

22. The holographic sensor of claim 21, wherein the interference fringes comprise a dimer represented by the formula:

23. The holographic sensor of claim 1, wherein the dimerisable chemical groups are covalently bonded to the polymer matrix and the polymer matrix comprises a polymer of first compounds comprising the dimerisable chemical groups, and second compounds selected from the group consisting of 2-hydroxyethylmethacrylate (HEMA), 2-hydroxypropylmethacrylate (HPMA), N,N-dimethylacrylamide (DMAA), poly(ethylene glycol) mono-methacrylate (PEGMA), vinyl acetate, acrylamide, N-isopropylacrylamide, acrylic acid (AA), methacrylic acid (MAA), N,N-methylenebisacrylamide (BIS), ethyleneglycol dimethacrylate (EDMA), 2-acrylamido-2-methylpropane sulfonic acid (AMPS), sodium salt of methacrylic acid, 2-(dimethylaminoethyl)methacrylate (DMAEMA), Styrene 4-sulfonic acid, and 2-(N,N Dimethyl-N-(2-methacryloxyethyl)ammonium)ethanoic acid.

26. The holographic sensor of claim 23, wherein the diffraction fringes comprise a dimeric structure represented by the formula:

29. The holographic sensor of claim 26, wherein the diffraction fringes comprise a dimer represented by the formula:

35. The holographic sensor of claim 1, further comprising a plurality of functional dimeric structures that include a cyclic bridge formed by dimerization via photocycloaddition of a first dimerisable chemical group covalently attached to the polymer matrix and an adduct of formula D-FG, wherein D is a second dimerisable chemical group and FG is a functionality conferring group.

42. The holographic sensor of claim 35, wherein the functional dimeric structures are represented by structural formula (VIII):

43. The holographic sensor of claim 42, wherein the functional dimeric structures are represented by structural formula (VIIb):

44. The holographic sensor of claim 43, wherein:

R₁ and R₂ are each independently a hydrogen, a halogen, a C1-C6 alkyl, or a C3-C6 cycloalkyl, each optionally substituted with —

OH, —

NR^bR^c, or a halogen;

R′

₃ is a linear or branched C1-C6 dialkyl or C3-C6 cyclic dialkyl or poly(ethylene glycol) with average molecular weight of ≦

12000; and

R₄, R₅ and R₆ are each independently a hydrogen or a C1-C6 alkyl.

45. The holographic sensor of claim 43, wherein:

R₁ and R₂ are each independently a C1-C6 alkyl, optionally substituted with —

OH, —

NR^bR^c, or a halogen; and

R′

₃ is a linear or branched C1-C10 dialkyl or —

(PEG)<sub>mol wt≦

12000</sub>-.

46. The holographic sensor of claim 45, wherein the functional dimeric structures are represented by structural formula (VIIc):

47. The holographic sensor of claim 46, wherein FG is a ligand, antibody, enzyme, protein, chelator, receptor, stimulus responsive oligomer or stimulus responsive polymer.

48. The holographic sensor of claim 46, wherein FG is a phenyl boronic acid or bis boronic acid.

49. The holographic sensor of claim 43, wherein FG is represented by structural formula (IXa) or (IXb):

50. The holographic sensor of claim 49, wherein FG is represented by structural formula:

51. The holographic sensor of claim 1, further comprising a plurality of functional dimeric structures that include a cyclic bridge formed by dimerization via photocycloaddition of a first dimerisable chemical group covalently attached to the polymer matrix and an adduct of formula D-FG, wherein D is a second dimerisable chemical group and FG is a functionality conferring group, wherein the functional dimeric structure comprises a substructure represented by structural formula (X):

52. The holographic sensor of claim 1, wherein the holographic recording media further comprises a plurality of receptor groups covalently bonded to the polymer matrix.

53. The holographic sensor of claim 52, wherein the polymer matrix comprises a polymer prepared by copolymerization of monomers comprising the receptor groups, monomers comprising dimerisable chemical groups and one or more compounds selected from the group consisting of 2-hydroxyethylmethacrylate (HEMA), 2-hydroxypropylmethacrylate (HPMA), N,N-dimethylacrylamide (DMAA), poly(ethylene glycol) mono-methacrylate (PEGMA), vinyl acetate, acrylamide, N-isopropylacrylamide, acrylic acid (AA), methacrylic acid (MAA), N,N-methylenebisacrylamide (BIS), ethyleneglycol dimethacrylate (EDMA), 2-acrylamido-2-methylpropane sulfonic acid (AMPS), sodium salt of methacrylic acid, 2-(dimethylaminoethyl)methacrylate (DMAEMA), Styrene 4-sulfonic acid, and 2-(N,N Dimethyl-N-(2-methacryloxyethyl)ammonium)ethanoic acid.

160. The holographic sensor of claim 1, wherein the cyclic bridge is a cyclobutyl.

161. The holographic sensor of claim 1, wherein the diffraction fringes comprise a dimer of one or more of cinnamoyl, chalcone, anthracene, coumarin, stilbazolium, maleimide, or a derivatives thereof.

2-3. -3. (canceled)

6-14. -14. (canceled)

16-18. -18. (canceled)

24-25. -25. (canceled)

27-28. -28. (canceled)

30-34. -34. (canceled)

36-41. -41. (canceled)

54. The holographic sensor of 53, wherein the receptor groups are 3-acrylamidophenylboronic acid.

55. A holographic recording media, comprising:

(a) a polymer matrix; and

(b) a plurality of dimerisable chemical groups;

wherein

(i) the dimerisable chemical groups dimerize by forming a cyclic bridge through photocycloaddition; and

(ii) the dimerisable chemical groups are distributed throughout the polymer matrix in a density sufficient to allow (1) recording of a hologram by dimerization of part of the dimerisable chemical groups and (2) detection of a change of the optical properties of the hologram upon response of the polymer matrix to the presence of an external stimulus.

56-91. -91. (canceled)

92. A method for recording a holographic image, the method comprising:

controlling (i) the fraction of dimerization of dimerisable chemical groups that form dimeric structures by photocycloaddition and (ii) retention of spatial positions of the dimeric structures, relative to each other and to dimerisable chemical groups that did not dimerize, to record the holographic image and enable a controlled observable response of the recorded holographic image, in a later presence of an external stimulus.

93-94. -94. (canceled)

95. A method of detecting the presence of an external stimulus, comprising:

(1) providing a holographic sensor including;

(a) a holographic recording media comprising a polymer matrix; and

(b) at least one holographic image recorded in said holographic recording media as diffraction fringes, wherein the diffraction fringes comprise a dimeric structure that includes a cyclic bridge; and

wherein said holographic recording media responds to an external stimulus by providing at least one output signal; and

(2) detecting the presence of the at least one output signal to detect the presence of the external stimulus.

96. The method of claim 95, wherein the external stimulus is a fluid comprising an analyte and wherein providing the holographic sensor comprises swelling the holographic recording media.

97. The method of claim 96, wherein the swelling of the holographic recording media depends on the concentration of the analyte in the fluid.

98-159. -159. (canceled)