Thiol-Modified Surface Immobilization Article And Method

A label-free bio sensor article comprising:

• a substrate having a tie-layer attached to the substrate surface, and a polymer attached to the tie-layer, the attached polymer being a thiol-modified surface comprised of mers of the formula (I):
• where
• A is a tie-layer attachment group;
• a comprises a thiol containing mer, the thiol being suitable to immobilize a maleimide-modified bioentity;
• b comprises an amide or a carboxylic acid containing mer;
• c comprises at least one mer having the tie-layer attachment group A;
• a, b, and c are each independently an integer from 1 to about 100,000;
• in, a, p, q, r, and s, are each independently 0 or 1;
• X is —N(R3)(R4), or —OR3;
• each R1 is independently a divalent (C1-4hydrocarbyl;
• each R2 is independently —H or monovalent (C1-4hydrocarbyl;
• R3 and R4 are each independently —H, or a monovalent substituted or unsubstituted (C1-10)hydrocarbyl;
• R5 is a divalent alkyl amide or alkoxylate amide spacer of the formulas —(CH2)u—C(O)N(R3)— or —(CH2CH2O)u—C(O)N(R3)—, where u is an integer from 1 to 10;
• R6 is independently —H or —COOH;
• and
• each R7 is independently a carbon-carbon bond or a divalent substituted or unsubstituted (C1-4) hydrocarbyl,
• and a salt thereof, or a combination of a non-salt and a salt,
• or mers of the formula (II):
• where
• a comprises a half-thiol half-acid containing mer, the thiol being suitable to immobilize a maleimide-modified bioentity;
• b comprises at least one mer having a tie-layer attachment group A;
• a and b are each independently integers from 1 to about 100,000;
• n and m are each independently either 0 or 1;
• R1 is a divalent substituted or unsubstituted (C1-10)hydrocarbyl;
• R2 is a H or (C1-4)hydrocarbyl;
• R3 is —H or a monovalent substituted or unsubstituted (C1-10)hydrocarbyl;
• and
• R7 is a carbon-carbon bond or a divalent substituted or unsubstituted (C1-4) hydrocarbyl,
• and a salt thereof, or a combination of a non-salt and a salt,
• or mers of the formula (III):
• where
• a comprises a half-thiol half-acid containing mer, the thiol being suitable to immobilize a maleimide-modified bioentity;
• b comprises at least one mer having a tie-layer attachment group A;
• c comprises a half-amide half-acid containing mer;
• a, b, and c are each independently an integer from 1 to about 100,000;
• n and m are each independently 0 or 1;
• R1 is a divalent substituted or unsubstituted (C1-10)hydrocarbyl;
• R2 is a H or (C1-4)hydrocarbyl;
• R3 and R4 are each independently —H or a monovalent substituted or unsubstituted (C1-10)hydrocarbyl;
• and
• R7 is a carbon-carbon bond or substituted or unsubstituted (C1-4) hydrocarbyl, and a salt thereof, or a combination of a non-salt and a salt.