On-demand photoinitiated polymerization
Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.
1. A composition comprising:
(a) a masking compound capable of photoisomerization between a first isomer and a second isomer upon absorption of electromagnetic energy at a first wavelength and intensity; and
(b) a prepolymer capable of polymerization or crosslinking upon photoinitiation with electromagnetic energy at a second wavelength and intensity;
wherein the masking compound is present in an amount sufficient to block polymerization or crosslinking of the prepolymer at the second wavelength unless or until the masking compound is photoisomerized from the first isomer to the second isomer; and
wherein the composition is an intraocular implant further comprising a matrix material.
2. The composition of claim 1 , wherein the first isomer of the masking compound absorbs more light at the second wavelength than does the second isomer of the masking compound.
3. The composition of claim 1 , wherein the prepolymer comprises a photocrosslinker or a photoinitiator.
4. The composition of claim 3 , wherein the photocrosslinker or photoinitiator has an absorption maximum that is about 50 nm or less from the absorption maximum of the first isomer of the masking compound.
5. The composition of claim 1 , wherein the masking compound is described by the structure of formula (I):
(Z 1 ) n1 —Y—(Z 2 ) n2 (I)
wherein Y is a photoisomerizable moiety;
n 1 and n 2 are each independently 0, 1, 2 or 3; and
each Z 1 and Z 2 is independently a polymerizable moiety or a crosslinking moiety that is connected to Y via an optional linker.
6. The composition of claim 5 , wherein Y is a photoisomerizable azoarylene, fulgide, spiropyran, naphthopyran, quinone, spirooxazine, nitrone, thioindigo, diarylethene, or dithienylethylene moiety.
7. The composition of claim 5 , wherein each Z 1 and Z 2 is independently a polymerizable or a crosslinking vinyl, vinylidene, diene, olefin, allyl, acrylate, acrylamide, or acrylic acid moiety.
8. The composition of claim 5 , wherein the optional linker is of 1 to 20 atoms in length.
9. The composition of claim 5 , wherein Y is a stilbene or azobenzene.
10. The composition of claim 5 , wherein the masking compound is described by the structure of formula (II):
where
n 3 and n 4 are each independently 0, 1, 2, or 3;
each Z 3 and Z 4 is independently a polymerizable or crosslinking vinyl, vinylidene, diene, olefin, allyl, acrylate, acrylamide, or acrylic acid moiety;
L 3 and L 4 are independently linkers of 1 to 6 atoms in length;
n 5 and n 6 are each independently 0, 1, 2, 3, 4, or 5, provided that when (Z 3 ) n3 -L 3 - is present, n 5 is not 5, and when -L 4 -(Z 4 ) n4 is present, n 6 is not 5; and
each R is independently a hydrogen, alkyl, alkenyl, aryl, heterocycle, halogen, haloalkyl, perhaloalkyl, amino, hydroxyl, ether, nitro, cyano, carboxy, acyl, amido, ester, thio, thioether, sulfonyl, or sulfonamide.
11. The composition of claim 5 , wherein the masking compound is described by the structure of formula (III):
where
L 3 and L 4 are independently —(CH 2 ) m1 —Z 4 —(CH 2 ) m2 —;
m 1 and m 2 are each independently 0, 1, 2, 3, 4, 5, or 6;
n 5 and n 6 are each independently 0, 1, 2, 3, or 4;
Z 4 is a carbonyl, ester, amido, carbamate, sulfonyl, sulfonamide, ether, thioether, or urea moiety; and
each R is independently a hydrogen, alkyl, alkenyl, aryl, heterocycle, halogen, haloalkyl, perhaloalkyl, amino, hydroxyl, ether, nitro, cyano, carboxy, acyl, amido, ester, thio, thioether, sulfonyl, or sulfonamide.
12. The composition of claim 11 , wherein the masking compound is described by the structure:
13. The composition of claim 5 , wherein the masking compound is described by the structure of formula (IV) or (V):
where R 1 -R 8 are each independently hydrogen, hydrocarbyl, heterocycle, halogen, haloalkyl, perhaloalkyl, amino, hydroxyl, ether, nitro, cyano, carboxy, acyl, amido, ester, thiol, thioether, sulfonyl, or sulfonamide.
14. The composition of claim 13 , wherein at least one R 1 -R 8 is -L 5 -O—CH 2 CH═CH 2 , where L 5 is an optional linker group.
15. The composition of claim 14 , wherein each L 5 is a C 1 -C 6 alkyl chain.
16. The composition of claim 14 , wherein each L 5 is absent.
17. The composition of claim 13 , wherein, each of R 1 -R 8 is hydrogen.
18. The composition of claim 5 , wherein the masking compound is described by the structure of formula (VI):
where,
A is a heterocycle ring;
N 7 is 0 or an integer from 1 to 5;
each R is independently hydrogen, -L 5 -(Z 5 ) m where m is 1, 2 or 3, a hydrocarbyl, heterocycle, halogen, haloalkyl, perhaloalkyl, amino, hydroxyl, ether, nitro, cyano, carboxy, acyl, amido, ester, thiol, thioether, sulfonyl, or sulfonamide; and
R 11 -R 15 are each independently hydrogen, a hydrocarbyl, heterocycle, halogen, haloalkyl, perhaloalkyl, amino, hydroxyl, ether, nitro, cyano, carboxy, acyl, amido, ester, thiol, thioether, sulfonyl, sulfonamide, or -L 5 -Z 5 ;
where L 5 is a linker and each Z 5 is independently a polymerizable group or a crosslinking group.
19. The composition of claim 18 , wherein A is a N-linked heterocycle of formula
where Q is O or N—R 21 , where R 21 is hydrogen, alkyl, aryl, acyl, heterocycle, or -L 5 -Z 5 .
20. The composition of claim 19 , wherein each L 5 is independently a C 1 -C 6 alkyl chain.
21. The composition of claim 19 , wherein at least one of R 11 -R 15 and R 21 comprises an allyl or a vinyl group.
22. The composition of claim 19 , wherein R 13 is —(CH 2 ) m1 -L 6 -(CH 2 ) m2 —Z 5 where m1 and m2 are each independently 0 or an integer from 1 to 6, and L 6 is a carbonyl, ester, amido, carbamate, sulfonyl, sulfonamide, ether, a thioether, or urea group.
23. The composition of claim 22 , wherein m1 is 2 and m2 is 0.
24. The method of claim 23 , wherein L 3 and L 4 are —O— or —O—(CH 2 ) m , where m is 1, 2, 3, 4, 5, or 6.
25. The composition of claim 24 , wherein n 5 and n 6 are both 0.
26. The composition of claim 22 , wherein L 6 is —O—.
27. The composition of claim 19 , wherein at least one of R 11 -R 15 and R 21 comprises -L 7 -O—CH 2 CH═CH 2 , wherein L 7 is independently a C 1 -C 6 alkyl chain.
28. The composition of claim 19 , wherein Q is O.
29. The composition of claim 28 , wherein at least one of R 11 -R 15 is nitro.
30. The composition of claim 29 , wherein R 13 is nitro, and R 11 , R 12 , R 14 and R 15 are hydrogen.
31. The composition of claim 5 , wherein the masking compound is one of the following structures:
32. The composition of claim 1 , wherein the prepolymer comprises an acrylamide, acrylate, acrylonitrile, epoxy, methaacrylamide, methacrylate, unsaturated polyester, urethane, vinyl ester, or a combination thereof.
33. The composition of claim 1 further comprising a photoinitiator.
34. The composition of claim 1 , wherein the first photoisomer of the masking compound is present in a quantity sufficient to prevent polymerization or crosslinking of the prepolymer upon exposure of the composition to ambient sunlight.
35. The composition of claim 1 , wherein the intraocular implant is inserted into an eye.