Biomimetic peptoid polymers
The present invention provides for novel peptoid oligomers that are capable of self-assembling into two-dimensional sheet structures. The peptoid oligomers can have alternately hydrophilic or polar side-chains and hydrophobic or apolar side-chains. The peptoid oligomers, and the two-dimensional sheet structures, can be applied to biological applications where the peptoid plays a role as a biological scaffold or building block. Also, the two-dimensional sheet structures of the present invention can be used as two-dimensional nanostructures in device applications.
1. A peptoid based two-dimensional sheet comprising a plurality of peptoid oligomers having the structure:
wherein R 1 is a hydrophilic or polar side-chain and R 2 is a hydrophobic or apolar side-chain, or R 2 is a hydrophilic or polar side-chain and R 1 is a hydrophobic or apolar side-chain, R 3 is H or a capping group, and n is an integer equal to or greater than 4; wherein the structure within the brackets is a monomer subunit and each monomer subunits can be identical or distinct from each other; or
wherein (a) R 4 is a hydrophilic or polar side-chain and R 5 is a hydrophobic or apolar side-chain, and R 6 is a negative-charged hydrophilic or polar hydrophilic side-chain and R 7 is a hydrophobic or apolar side-chain, wherein R 4 and R 6 are positive-charged or basic and negative-charged or acidic side-chains, respectively, or vice versa, or (b) R 5 is a hydrophilic or polar side-chain and R 4 is a hydrophobic or apolar side-chain, and R 7 is a negative-charged hydrophilic or polar hydrophilic side-chain and R 6 is a hydrophobic or apolar side-chain, wherein R 5 and R 7 are positive-charged or basic and negative-charged or acidic side-chains, respectively, or vice versa; R 8 is H or a capping group; n 1 and n 2 are an integer equal to or greater than 2; and, n 1 and n 2 are equal to each other;
wherein the plurality of peptoid oligomers are self-assembled with each other into the two-dimensional sheet.
2. The peptoid based two-dimensional sheet of claim 1 , wherein each side-chain is independently R a , —OR a , —NR a R b , —SO 1, 2, 3, 4 R a , —C(O)R a , —C(O)OR a , —OC(O)R a , —OC(O)OR a , —NR b C(O)R a , —C(O)NR a R b , —OC(O)NR a R b , NR c C(O)NR a R b , —NR b C(O)OR a , —R a O—R b , —R a —NR b R c , —SO 3 , —SO 4 , —SO 2 NH—R a , —R a —S—R b , —R a —S(O)—R b , —R a —S(O) 2 —R b , —OR a —O—R b , —NR a R b —O—R c , —SO 1, 2, 3, 4 R a —O—R b , —C(O)R a —O—R b , —C(O)OR a —O—R b , —OC(O)R a —O—R b , —OC(O)OR a —O—R b , —NR b C(O)R a —O—R c , —C(O)NR a R b —O—R c , —OC(O)NR a R b —O—R c , —NR c C(O)NR a R b —O—R d , —NR b C(O)OR a —O—R c , —OR a —S—R b , —NR a R b —S—R c , —SO 1, 2, 3, 4 R a—S—R b , —C(O)R a —S—R b , —C(O)OR a —S—R b , —OC(O)R a —S—R b , —OC(O)OR a —S—R b , —NR b C(O)R a —S—R c , —C(O)NR a R b —S—R c , —OC(O)NR a R b —S—R c , —NR c C(O)NR a R b —S—R d , —NR b C(O)OR a —S—R c , —OR a —NR b R d , —NR a R b —NR c R d , —SO 1, 2, 3, 4 R a —NR b R d , —C(O)R a —NR b R d , —C(O)OR a —NR b R d , —OC(O)R a —N—R b R d , —OC(O)OR a —NR b R d , —NR b C(O)R a —NR c R d , —C(O)NR a R b —NR c R d , —OC(O)NR a R b —NR c R d , —NR c C(O)NR a R b —NHR d , —NR b C(O)OR a —NR c R d , —PO 3 , —PO 4 , —PO 2 —R a , —R a —PO 3 , —R a —PO 4 , —R a —PO 2 —R b ; wherein R a , R b , R c , and R d are each independently H, alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl;
wherein R a , R b , R c and R d is each independently substituted with 0-6 halo, NO 2 , —OH, lower alkyl, —SH, —SO 3 , —NH 2 , —C(O)OH, lower acyl, lower acyloxy, lower alkylamino, lower dialkylamino, trihalomethyl, —CN, lower alkylthio, lower alkylsufinyl, or lower alkylsulfonyl; wherein the number of carbon atoms in the longest carbon chain of R a , R b , R c , and R d is equal to or less than eighteen; and the proviso than when the side-chain is R a , R a comprises at least two carbon atoms.
3. The peptoid based two-dimensional sheet of claim 1 , wherein one hydrophilic or polar side-chain out of a plurality of hydrophilic or polar side-chains within each oligomer comprises a functional group.
4. The peptoid based two-dimensional sheet of claim 3 , wherein the functional group is a dye or a point of attachment to link to another molecule of interest.
5. The peptoid based two-dimensional sheet of claim 1 , wherein the apolar side-chain is an aralkyl.
6. The peptoid based two-dimensional sheet of claim 5 , wherein the aralkyl is —CH 2 —CH 2 —C 6 H 5 .
7. The peptoid based two-dimensional sheet of claim 1 , wherein the polar side-chain is a carboxylated alkyl or an aminated alkyl.
8. The peptoid based two-dimensional sheet of claim 7 , wherein the carboxylated alkyl is —CH 2 —CH 2 —COOH.
9. The peptoid based two-dimensional sheet of claim 7 , wherein the aminated alkyl is —CH 2 —CH 2 —NH 2 .
10. The peptoid based two-dimensional sheet of claim 4 , wherein the dye is a fluorescent dye.
11. The peptoid based two-dimensional sheet of claim 2 , wherein the capping group is R a and the capping group does not prevent the peptoid oligomer from self-assembling into a two-dimensional sheet with other peptoid oligomers.
12. The peptoid based two-dimensional sheet of claim 2 , wherein each hydrophilic or polar side-chain is a side-chain that comprises one or more —OCH 3 , diol, triol, sugar, —PO 3 , —PO 4 , —PO 2 —R b , —SO 3 , —SO 4 , or —SO 2 NH—R b , one or more ionic charge, is capable of hydrogen-bonding, and/or has a net log P value that is less than 0.
13. The peptoid based two-dimensional sheet of claim 1 , wherein each hydrophilic side-chain is —R,—X, wherein X is —OH, —C(O)H, —C(O)OH, —SH, —NH 2 , or —C(O)—NH 2 , wherein R a is an alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl, wherein the number of carbon atoms in the longest carbon chain of R a is equal to or less than eighteen; and R a comprises at least two carbon atoms.
14. The peptoid based two-dimensional sheet of claim 1 , wherein each hydrophobic or apolar side-chain is a side-chain that does not comprises an ionic charge, is not capable of hydrogen-bonding, or has a net log P value that is equal to or more than 0.5.
15. The peptoid based two-dimensional sheet of claim 14 , wherein each hydrophobic side-chain has a net log P value that is equal to or more than 1 or 2.
16. The peptoid based two-dimensional sheet of claim 1 , wherein each hydrophobic side-chain is —R a —Y, wherein Y is a lower alkyl, a benzene, or a benzene substituted with any lower alkyl, wherein R a is an alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, or aralkynyl, wherein the number of carbon atoms in the longest carbon chain of R a is equal to or less than eighteen; and R a comprises at least two carbon atoms.
17. The peptoid based two-dimensional sheet of claim 1 , wherein the peptoid oligomer comprises 10 or more monomer subunits.