Light sensitive initiator integrated polydimethylsiloxane
Disclosed herein is a surface functionalized poly(dimethylsiloxane) (PDMS) and methods for making the same. The surface functionalized poly(dimethylsiloxane) (PDMS) disclosed herein is applicable in the general field of microfluidics, bioMEMS (bio-microelectromechanical systems), soft lithography and other related biotechnology fields.
1. A compound of Formula I:
wherein:
R 1 is hydrogen or methyl;
R 2 is alkyl substituted with an oxo and halo group;
X is selected from the group consisting of nitro, —N(R 3 ) 3 + , trifluoromethyl, cyano, —C(O)OR 3 , —C(O)R 3 , where R 3 is hydrogen or alkyl; and
L 1 and L 2 are independently selected from the group consisting of a direct bond, methylene optionally substituted with 1-2 R 4 groups, (C 2 -C 12 )alkylene optionally substituted with 1-4 R 4 groups, (C 6 -C 12 )arylene optionally substituted with 1-4 R 4 groups, (C 3 -C 12 )cycloalkylene optionally substituted with 1-4 R 4 groups, (C 3 -C 12 )heterocycloalkylene optionally substituted with 1-4 R 4 groups, and (C 6 -C 12 )heteroarylene optionally substituted with 1-4 R 4 groups; and
R 4 is selected from the group consisting of halo, nitro, cyano, oxo, aminoacyl, aminoacyloxy, carboxyl, carboxyl ester, carbonate ester, aminosulfonyl, (C 1 -C 10 )alkyl, (C 1 -C 10 )haloalkyl, (C 1 -C 10 )alkoxy, (C 6 -C 12 )aryl, (C 5 -C 12 )heteroaryl, (C 6 -C 12 )aryloxy, (C 3 -C 12 )cycloalkyl and (C 3 -C 12 )heterocycloalkyl.
2. The compound of claim 1 , wherein R 1 is hydrogen.
3. The compound of claim 1 , wherein X is nitro.
4. The compound of claim 1 , wherein L 1 and L 2 are (C 1 -C 12 )alkylene.
5. The compound of claim 1 , wherein R 1 is hydrogen; X is nitro; and L 1 and L 2 are (C 1 -C 12 )alkylene.
6. A surface functionalized poly(dimethylsiloxane) (PDMS), comprising a polydimethyl siloxane (PDMS) substrate having a compound of Formula III incorporated therein:
wherein:
R 1 is hydrogen or methyl;
R 2 is selected from the group consisting of alkyl optionally substituted with 1-3 R 4 groups, haloalkyl optionally substituted with 1-3 R 4 groups, aryl optionally substituted with 1-4 R 4 groups, cycloalkyl optionally substituted with 1-4 R 4 groups, heterocycloalkyl optionally substituted with 1-4 R 4 groups, and heteroaryl optionally substituted with 1-4 R 4 groups;
X is selected from the group consisting of nitro, —N(R 3 ) 3 + , trifluoromethyl, cyano, —C(O)OR 3 , —C(O)R 3 , where R 3 is hydrogen or alkyl; and
L 1 and L 2 are independently selected from the group consisting of a direct bond, methylene optionally substituted with 1-2 R 4 groups, (C 2 -C 12 )alkylene optionally substituted with 1-4 R 4 groups, (C 6 -C 12 )arylene optionally substituted with 1-4 R 4 groups, (C 3 -C 12 )cycloalkylene optionally substituted with 1-4 R 4 groups, (C 3 -C 12 )heterocycloalkylene optionally substituted with 1-4 R 4 groups, and (C 6 -C 12 )heteroarylene optionally substituted with 1-4 R 4 groups; and
R 4 is selected from the group consisting of halo, nitro, cyano, oxo, aminoacyl, aminoacyloxy, carboxyl, carboxyl ester, carbonate ester, aminosulfonyl, (C 1 -C 10 )alkyl, (C 1 -C 10 )haloalkyl, (C 1 -C 10 )alkoxy, (C 6 -C 12 )aryl, (C 5 -C 12 )heteroaryl, (C 6 -C 12 )aryloxy, (C 3 -C 12 )cycloalkyl and (C 3 -C 12 )heterocycloalkyl.
7. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 6 , wherein R 1 is hydrogen.
8. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 6 , wherein R 2 is alkyl substituted with an oxo and halo group.
9. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 6 , wherein X is nitro.
10. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 6 , wherein L 1 and L 2 are (C 1 -C 12 )alkylene.
11. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 6 , wherein R 1 is hydrogen; R 2 is alkyl substituted with an oxo and halo group; X is nitro; and L 1 and L 2 are (C 1 -C 12 )alkylene.
12. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 6 , wherein the compound is incorporated therein at a ratio of from about 11:0.5 to about 11:10 −3 .
13. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 6 , further comprising a functionalized polymer layer bonded to the compound of Formula III.
14. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 13 , wherein the functionalized polymer layer comprises oligo(ethylene glycol).
15. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 6 , having a contact angle of from about 90 to about 120 degrees.
16. The surface functionalized poly(dimethylsiloxane) (PDMS) of claim 6 , having a contact angle of about 114 degrees.
17. A method of preparing a surface functionalized poly(dimethylsiloxane) (PDMS) substrate, comprising contacting a monomer mixture with a compound of Formula I under polymerization conditions:
wherein:
R 1 is hydrogen or methyl;
R 2 is selected from the group consisting of alkyl optionally substituted with 1-3 R 4 groups, haloalkyl optionally substituted with 1-3 R 4 groups, aryl optionally substituted with 1-4 R 4 groups, cycloalkyl optionally substituted with 1-4 R 4 groups, heterocycloalkyl optionally substituted with 1-4 R 4 groups, and heteroaryl optionally substituted with 1-4 R 4 groups;
X is selected from the group consisting of nitro, —N(R 3 ) 3 + , trifluoromethyl, cyano, —C(O)OR 3 , —C(O)R 3 , where R 3 is hydrogen or alkyl; and
L 1 and L 2 are independently selected from the group consisting of a direct bond, methylene optionally substituted with 1-2 R 4 groups, (C 2 -C 12 )alkylene optionally substituted with 1-4 R 4 groups, (C 6 -C 12 )arylene optionally substituted with 1-4 R 4 groups, (C 3 -C 12 )cycloalkylene optionally substituted with 1-4 R 4 groups, (C 3 -C 12 )heterocycloalkylene optionally substituted with 1-4 R 4 groups, and (C 6 -C 12 )heteroarylene optionally substituted with 1-4 R 4 groups; and
R 4 is selected from the group consisting of halo, nitro, cyano, oxo, aminoacyl, aminoacyloxy, carboxyl, carboxyl ester, carbonate ester, aminosulfonyl, (C 1 -C 10 )alkyl, (C 1 -C 10 )haloalkyl, (C 1 -C 10 )alkoxy, (C 6 -C 12 )aryl, (C 5 -C 12 )heteroaryl, (C 6 -C 12 )aryloxy, (C 3 -C 12 )cycloalkyl and (C 3 -C 12 )heterocycloalkyl;
to provide a functionalized poly(dimethylsiloxane) (PDMS) substrate.
18. The method of claim 17 , wherein the compound is of Formula II:
19. The method of claim 18 , wherein the monomer mixture comprises a poly(dimethylmethylvinylsiloxane) prepolymer.