Synthetic polymers and methods of making and using the same

1. A polymer having a formula:

wherein

each of T and T e is a terminal group selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;

R 1 and each R n independently is selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;

Y 1 and each Y p independently is selected from a bond, —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

W 1 and each W a independently is selected from —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

Z 1 and each Z b independently is selected from heteroaryl, oxygen, sulfur, or NR 4 , wherein R 4 is selected from hydrogen, aliphatic, cyclic heteroaliphatic comprising one or more heteroatoms selected from oxygen, sulfur, selenium, phosphorous, or oxidized forms thereof, acyclic heteroaliphatic, heteroaryl, or aryl;

L 1 and each L q independently is selected from aliphatic, heteroaliphatic, aryl, or heteroaryl;

m ranges from 2 to 1000; and

wherein at least one of R 1 , Y 1 , W 1 , Z 1 , or L 1 is different from at least one R n , Y p , W a , Z b , or L q , respectively.

2. The polymer of claim 1 , wherein two or more R n groups are different.

3. The polymer of claim 1 , wherein two or more W a groups, L q groups, or Z b groups are different.

4. The polymer of claim 1 , wherein T and T e independently are selected from an amine, an alkylene oxide, an alkylene amino, or an alkylene thio.

5. The polymer of claim 1 , wherein T and T e independently are or comprise a solid support.

6. The polymer of claim 1 , wherein R 1 and each of R n independently is selected from C 1-25 alkyl, C 1-25 heteroalkyl, or C 6-15 aryl.

7. The polymer of claim 1 , wherein R 1 and each of R n independently is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, septyl, octyl, nonyl, decyl, phenyl, propyne, —(CH 2 )—C 6 H 4 —Cl, —(CH 2 ) 2 NH 2 , —(CH 2 ) 2 NHBOC, —(CH 2 ) 2 COOH, or —(CH 2 ) 2 COO t Bu.

8. The polymer of claim 1 , wherein each of W 1 , W a , Z 1 , and Z b independently are selected from NH, S, or O.

9. The polymer of claim 1 , wherein each of L 1 and L q independently are selected from —(CH 2 ) 2 —, —(CH 2 ) 3 —, —C(Me)H—CH 2 —, —CH 2 —C(Me)H—, —C(Me)H—C(Me)H—, —C(Naphthyl)H—C(Naphthyl)H—, and —(CH 2 ) 2 —O—(CH 2 ) 2 —.

10. The polymer of claim 1 , wherein the polymer has a formula

wherein each R 5 independently is selected from aliphatic, heteroaliphatic, heteroaryl, or aryl.

11. The polymer of claim 10 , wherein the polymer comprises at least one R 5 group and R 5 is ethyl or naphthyl.

12. The polymer of claim 1 , wherein the polymer is a heteropolymer having a formula selected from

wherein

each R 2 and R 3 independently is selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;

each Y 2 and Y 3 independently is selected from —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

each W 2 and W 3 independently is selected from —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

each Z 2 and Z 3 independently is selected from heteroaryl, oxygen, sulfur, or NR 4 , wherein R 4 is selected from hydrogen, aliphatic, cyclic heteroaliphatic comprising one or more heteroatoms selected from oxygen, sulfur, selenium, phosphorous, or oxidized forms thereof, acyclic heteroaliphatic, heteroaryl, or aryl;

each L 2 and L 3 independently is selected from aliphatic, heteroaliphatic, aryl, or heteroaryl;

at least one of R 1 , Y 1 , W 1 , Z 1 , or L 1 is different from at least one of R 2 or R 3 , at least one of Y 2 or Y 3 , at least one of W 2 or W 3 , at least one of Z 2 or Z 3 , or at least one of L 2 or L 3 , respectively; and

n′ and p′ independently are 1 to 1000.

13. A homopolymer having a formula

wherein each of T and T e is a terminal group selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;

each R 1 is the same and is selected from cyclic heteroaliphatic; acyclic heteroaliphatic selected from C 5-25 alkoxy, C 4-25 hydroxyl, C 2-25 thioether, C 1-25 thiol, C 1-25 amine, or C 1-25 haloalkyl; aryl; heteroaryl; aliphatic-aryl; aliphatic-heteroaryl; heteroaliphatic-aryl; or heteroaliphatic-heteroaryl;

each Y 1 is the same and is selected from —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

each W 1 is the same and is selected from —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

each Z 1 is the same and is selected from heteroaryl, oxygen, sulfur, or NR 4 , wherein R 4 is selected from hydrogen, aliphatic, cyclic heteroaliphatic comprising one or more heteroatoms selected from oxygen, sulfur, selenium, phosphorous, or oxidized forms thereof, acyclic heteroaliphatic, heteroaryl, or aryl;

each L 1 is the same and is selected from aliphatic, heteroaliphatic, aryl, or heteroaryl; and

m ranges from 2 to 1000.

14. The polymer of claim 1 , wherein:

any one or more of R 1 or R n is not butyl if any one or more of Y 1 or Y p is NR 4 where R 4 is butyl and any one or more of L 1 or L q is phenyl or -Ph-O-Ph-;

any one or more of L 1 or L q does not form a piperazine ring with W 1 , W a , Z 1 or Z b ;

any one or more of R 1 or R n is not —(CH 2 ) 2 [O(CH 2 )] 3 NH 2 if Y 1 or Y p is NR 4 where R 4 is hydrogen;

any one or more of L 1 or L q is not —C(O)— if Y 1 or Y p is a bond and R 1 or R n is phenyl; or

the polymer is not a dendrimer.

15. The polymer of claim 1 , having a structure selected from

16. The polymer of claim 1 , wherein the polymer forms a membrane, amorphous particles, or crystals.

17. A method of making a linear heteropolymer, comprising:

coupling, at a first temperature, a first position of a first starting material with a terminal group;

coupling, at a second temperature, a second position of the first starting material with a linker group or a side chain group;

coupling, at a third temperature, a third position of the first starting material with a linker group or a side chain group to form a first monomer unit of the polymer;

coupling, at the first temperature, the first monomer unit of the polymer with a first position of a second starting material;

coupling, at the second temperature, a second position of the second starting material with a linker group or a side chain group;

coupling, at the third temperature, a third position of the second starting material with a linker group or a side chain group to form a second monomer unit of the polymer;

coupling, at the first temperature, the second monomer unit of the polymer with a first position of a third starting material;

coupling, at the second temperature, a second position of the third starting material with a linker group or a side chain group; and

coupling, at the third temperature, a third position of the third starting material with a linker group or a side chain group to form a third monomer unit of the polymer; wherein the polymer has a formula

wherein

each of T and T e is a terminal group selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;

R 1 and each R n independently is selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;

Y 1 and each Y p independently is selected from a bond, —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

W 1 and each W a independently is selected from —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

Z 1 and each Z b independently is selected from heteroaryl, oxygen, sulfur, or NR 4 , wherein R 4 is selected from hydrogen, aliphatic, cyclic heteroaliphatic comprising one or more heteroatoms selected from oxygen, sulfur, selenium, phosphorous, or oxidized forms thereof, acyclic heteroaliphatic, heteroaryl, or aryl;

L 1 and each L q independently is selected from aliphatic, heteroaliphatic, aryl, or heteroaryl;

m ranges from 2 to 1000; and

wherein at least one of R 1 , Y 1 , W 1 , Z 1 , or L 1 is different from at least one R n , Y p , W a , Z b , or L q , respectively.

18. The method of claim 17 , wherein the first temperature ranges from −25° C. to 5° C., the second temperature ranges from 18° C. to 40° C., and the third temperature ranges from 70° C. to 140° C.

19. The method of claim 17 , wherein the linker group comprises a protecting group and the method further comprises exposing the linker group to an acid or a base to remove the protecting group.

20. The method of claim 17 , wherein the terminal group comprises a solid support and the method further comprises exposing the polymer to an acid to remove the solid support.

21. A method of making a linear heteropolymer, comprising:

coupling a first position of a first molecular precursor comprising a first side chain, a first linker group, or both with a terminal group;

coupling a second position of the first molecular precursor with a second molecular precursor comprising a second side chain, a second linker group, or both thereby forming a covalent bond between the first molecular precursor and the second molecular precursor; and

coupling the second molecular precursor with a third molecular precursor comprising a third side chain, a third linker group, or both thereby forming a covalent bond between the second molecular precursor and the third molecular precursor;

wherein the first side chain is different from one or both of the second side chain or the third side chain, and wherein the heteropolymer has a formula

wherein

each of T and T e is a terminal group selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;

R 1 and each R n independently is selected from heteroaliphatic, aliphatic, aryl, heteroaryl, aliphatic-aryl, aliphatic-heteroaryl, heteroaliphatic-aryl, or heteroaliphatic-heteroaryl;

Y 1 and each Y p independently is selected from a bond, —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

W 1 and each W a independently is selected from —C(R 4 ) 2 , oxygen, sulfur, or NR 4 , wherein each R 4 independently is selected from hydrogen, aliphatic, heteroaliphatic, aryl, or heteroaryl;

Z 1 and each Z b independently is selected from heteroaryl, oxygen, sulfur, or NR 4 , wherein R 4 is selected from hydrogen, aliphatic, cyclic heteroaliphatic comprising one or more heteroatoms selected from oxygen, sulfur, selenium, phosphorous, or oxidized forms thereof, acyclic heteroaliphatic, heteroaryl, or aryl;

L 1 and each L q independently is selected from aliphatic, heteroaliphatic, aryl, or heteroaryl;

wherein at least one of R 1 , Y 1 , W 1 , Z 1 , or L 1 is different from at least one R n , Y p , W a , Z b , or L q , respectively; and

m ranges from 2 to 1000.

22. The method of claim 21 , wherein each of the first linker group, the second linker group, and the third linker group comprises a protecting group and the method further comprises exposing the protecting group to an acid or a base to facilitate coupling the first molecular precursor, the second molecular precursor, and the third molecular precursor.

23. The method of claim 21 , wherein the terminal group comprises a solid support, and the method further comprises exposing the solid support to an acid to cleave the solid support from the terminal group.

24. The polymer of claim 13 , wherein the polymer is selected from