Photo-cleavable primer compositions and methods of use
In one embodiment, the present application discloses a photo-cleavable surface binding compound of the Formula I and Formula II: wherein the variables EG, EG1, SP1, SP2, SP3, Ar and BG are as defined herein. In another embodiment, the application discloses a method for forming a coating on a surface of a substrate using the surface binding compound.
1. A surface binding compound of the Formula I:
wherein:
each a is independently 1, 2, 3, 4 or 5;
m is 1, 2 or 3; n is 1, 2 or 3; i is 1, 2 or 3;
each EG is an end group independently selected from the group consisting of CH 2 ═CH—, CH 2 ═C(C 1-3 alkyl)-, CH 2 ═CHC(O)—, CH 2 ═C(C 1-3 alkyl)C(O)—, CH 2 ═CHC(O)O—, CH 2 ═C(C 1-3 alkyl)C(O)O—, CH 2 ═C(phenyl)C(O)O—, and CH 2 ═C(C 1-3 alkyl)S(O) n O—, wherein each R, R 1 , R 2 and R 3 is independently H and C 1-3 alkyl, X − is Cl − , Br − and I − and Y + is H + or N + R 1 R 2 R 3 ;
each of SP1, SP2 and SP3 is a spacer independently selected from the group consisting of —O—, —C(O)—, —S—, —S(O)—, —S(O) 2 —, —N—, —NH—, —NCH 3 —, —C—, —CH—, —(CH 2 ) q —, —(CH(OH)) q —, —(CH 2 CH(OH)CH 2 ) q —, —(C(CH 3 ) 2 ) q —, —(CH(CH 3 )) q —, —NH(CH 2 ) 2 NH—, —OC(O)—, —CO 2 —, —NHCH 2 CH 2 C(O)—, —OCH 2 CH 2 C(O)—, —C(O)CH 2 CH 2 C(O)—, —C(O)NHCH 2 CH 2 NH—, —NHCH 2 C(O)—, —NHC(O)—, —C(O)N—, —NC(O)—, —C(O)NH—, —NCH 3 C(O)—, —C(O)NCH 3 —, —(CH 2 CH 2 O) p CH 2 CH 2 —, —CH 2 CH 2 —(CH 2 CH 2 O) p —, —OCH(CH 2 O—) 2 —, —(CH 2 ) q —N + R 1 R 2 —, —(CH 2 ) q —PO 4 − —, —N + R 1 R 2 —, —PO 4 − —, —(CH 2 ) q —N + R 1 R 2 —X − —, —(CH 2 ) q —PO 4 − Y + —, —N + R 1 R 2 —X − —, —PO 4 − Y + —, —SO 4 − Y + —, —O—PO − (O)O—(CH 2 ) 2-4 —N + (R 1 R 2 )—, -(AA) r -, aryl, cyclopentanyl, cyclohexanyl, unsubstituted phenylenyl and phenylenyl substituted by 1 or 2 substituents selected from the group consisting of halo, CF 3 —, CF 3 O—, CH 3 O—, —C(O)OH, —C(O)OC 1-3 alkyl, —C(O)CH 3 , —CN, —NH 2 , —OH, —NHCH 3 , —N(CH 3 ) 2 and C 1-3 alkyl, wherein each AA is independently an amino acid, p is 1-6, q is 1-6 and r is 1-6;
provided that:
a) at least one of SP1, SP2 and SP3 is a spacer selected from the group consisting of A, A1, A2, B, C, D, E, F, and G:
wherein:
Z is selected from the group consisting of C, S, S(O), P(OH) and P(OR);
each E is independently selected from the group consisting of halo, CF 3 —, CF 3 O—, and HO— and e is 0, 1, 2 or 3; and
provided that
b) when one of SP1, SP2 and SP3 is not a spacer selected from the group consisting of A, B, C, D, E, F, and G, then each of the group
is independently selected from the group consisting of:
wherein:
each Z is independently selected from the group consisting of C, S, S(O), P(OH) and P(OR)
Ar is an aryl or heteroaryl group;
each BG is a bonding group independently selected from the group consisting of —OH, —SiR 2 OH, —COOH, —SO 3 H, and —P(O) 3 OH.
2. A surface binding compound of the Formula II:
wherein:
m is 1, 2 or 3; n is 1, 2 or 3; i is 1, 2 or 3;
each EG and EG1 is an end group independently selected from the group consisting of a C 1-12 alkyl, CH 2 ═CH—, CH 2 ═C(C 1-3 alkyl)-, CH 2 ═CHC(O)—, CH 2 ═C(C 1-3 alkyl)C(O)—, CH 2 ═CHC(O)O—, CH 2 ═C(C 1-3 alkyl)C(O)O—, CH 2 ═C(phenyl)C(O)O—, and CH 2 ═C(C 1-3 alkyl)S(O) n O—;
each of SP1, SP2 and SP3 is a spacer independently selected from the group consisting of —O—, —C(O)—, —S—, —S(O)—, —S(O) 2 —, —N—, —NH—, —NCH 3 —, —C—, —CH—, —(CH 2 ) q —, —(CH(OH)) q —, —(CH 2 CH(OH)CH 2 ) q —, —(C(CH 3 ) 2 ) q —, —(CH(CH 3 )) q —, —NH(CH 2 ) 2 NH—, —OC(O)—, —CO 2 —, —NHCH 2 CH 2 C(O)—, —OCH 2 CH 2 C(O)—, —C(O)CH 2 CH 2 C(O)—, —C(O)NHCH 2 CH 2 NH—, —NHCH 2 C(O)—, —NHC(O)—, —C(O)N—, —NC(O)—, —C(O)NH—, —NCH 3 C(O)—, —C(O)NCH 3 —, —(CH 2 CH 2 O) p CH 2 CH 2 —, —CH 2 CH 2 —(CH 2 CH 2 O) p —, —OCH(CH 2 O—) 2 —, —(CH 2 ) q —N + R 1 R 2 —, —(CH 2 ) q —PO 4 − —, —N + R 1 R 2 —, —PO 4 − —, —(CH 2 ) q —N + R 1 R 2 —X − —, —(CH 2 ) q —PO 4 − Y + —, —N + R 1 R 2 —X − —, —PO 4 − Y + —, —SO 4 − Y + —, —O—PO − (O)O—(CH 2 ) 2-4 —N + (R 1 R 2 )—, -(AA) r -, aryl, cyclopentanyl, cyclohexanyl, unsubstituted phenylenyl and phenylenyl substituted by 1 or 2 substituents selected from the group consisting of halo, CF 3 —, CF 3 O—, CH 3 O—, —C(O)OH, —C(O)OC 1-3 alkyl, —C(O)CH 3 , —CN, —NH 2 , —OH, —NHCH 3 , —N(CH 3 ) 2 and C 1-3 alkyl, wherein each AA is independently an amino acid, p is 1-6, q is 1-6 and r is 1-6;
provided that at least one of SP1, SP2 and SP3 is a spacer selected from the group consisting of A, A1, A2, B, C, D, E, F, and G:
wherein:
Z is selected from the group consisting of C, S, S(O), P(OH) and P(OR);
each E is independently selected from the group consisting of halo, CF 3 —, CF 3 O—, and HO— and e is 0, 1, 2 or 3; and
provided that when EG and EG1 are both CH 2 ═C(CH 3 )C(O)O—(CH 2 CH 2 )OC(O)— or CH 2 ═C(CH 3 )C(O)NH—(CH 2 CH 2 )OC(O)—, then the spacer is not
3. The surface binding compound of claim 1 , wherein each EG and EG1 is independently selected from the group consisting of a C 1-12 alkyl, CH 2 ═CHC(O)O—, CH 2 ═C(C 1-3 alkyl)C(O)O—, CH 2 ═C(phenyl)C(O)O—, CH 2 ═C(C 1-3 alkyl)S(O) n O—.
4. The surface binding compound of claim 1 , wherein each of SP1, SP2 and SP3 is a spacer independently selected from the group consisting of —(CH 2 ) q —, —NH(CH 2 ) 2 NH—, —NHCH 2 CH 2 C(O)—, —C(O)NHCH 2 CH 2 NH—, —NHCH 2 C(O)—, —NHC(O)—, —C(O)N—, —NC(O)—, —C(O)NH—, —NCH 3 C(O)—, —C(O)NCH 3 —, —(CH 2 CH 2 O) p CH 2 CH 2 —, —CH 2 CH 2 —(CH 2 CH 2 O) p — and —OCH(CH 2 O—) 2 —.
5. The surface binding compound of claim 1 , wherein each of SP1, SP2 and SP3 is a spacer independently selected from the group consisting of —N + R 1 R 2 —, —PO 4 − —, —N + R 1 R 2 X − —, —PO 4 − Y + —, —SO 4 − Y + —, —(CH 2 ) q —N + R 1 R 2 —, —(CH 2 ) q —PO 4 − —, —(CH 2 ) q —N + R 1 R 2 —X − —, —(CH 2 ) q —PO 4 − Y + — and —O—PO − (O)O—(CH 2 ) 2-4 —N + (R 1 R 2 )—.
6. The surface binding compound of claim 1 , wherein each SP1, SP2 and SP3 is a spacer independently selected from the group consisting of —CH 2 CH 2 —C(O)NHCH 2 CH 2 NH—C(O)NCH 3 —, —NHC(O)—(CH 2 CH 2 O) p —(CH 2 ) q —, —(CH 2 CH 2 O) p CH 2 CH 2 —C(O)NCH 3 —(CH 2 CH 2 O) p CH 2 CH 2 —, —NHCH 2 CH 2 C(O)—(CH 2 ) q —PO 4 − —, —PO 4 − —(CH 2 ) q —N + R 1 R 2 X − —, —(CH 2 CH 2 O) p —(CH 2 ) q —PO 4 − , —N + R 1 R 2 X − —(CH 2 ) q —PO 4 − and —PO 4 − —(CH 2 CH 2 O) p —N + R 1 R 2 X − —.
7. The surface binding compound of claim 1 , wherein each BG is a bonding group independently selected from the group consisting of —OH, —SiR 2 OH, —COOH, —SO 3 H, —P(O) 3 OH, —CONH 2 and —CSNH 2 .
8. The surface binding compound of claim 1 , wherein —SP3- is —CH 2 — and Ar—(BG) a is selected from the group consisting of 2,3-dihydroxyphenyl, 3,4-dihydroxyphenyl, 2,3,4-trihydroxyphenyl, 3,4,5-trihydroxyphenyl, 2,3,4,5-tetrahydroxyphenyl, 2,3,4,5,6-pentahydroxyphenyl, 2,3-dicarboxyphenyl, 2,3,4-tricarboxyphenyl, 3,4,5-tricarboxylphenyl, 2,3,4,5-tetracarboxyphenyl, 2,3,4,5,6-pentacarboxyphenyl, 2,3-disiloxyphenyl, 2,3,4-trisiloxyphenyl, 3,4,5-trisiloxyphenyl, 2,3,4,5-tetrasiloxyphenyl and 2,3,4,5,6-pentasiloxyphenyl.