Functional oligomers and functional polymers including hydroxylated polymers and conjugates thereof and uses thereof

1. A functional oligomer or functional polymer comprising:

i) one or more instances of linear units, wherein each instance of the linear units is of the formula:

ii) one or more instances of functional units, wherein each instance of the functional units is independently of the formula:

C(═O)—O—, —C(═O)—O—C(═O)—, —S(═O)—OH, —S(═O)-(a leaving group), —S(═O) 2 —OH, —S(═O) 2 -(a leaving group), —OH, or —O-(a leaving group).

iii) optionally one or more instances of crosslinking units, wherein each instance of the crosslinking units is of the formula:

and

iv) optionally one or more additional linear units, one or more additional terminal units, and/or one or more additional crosslinking units;

wherein:

each instance of Z is independently a single bond, C(R P ) 2 , or O;

each instance of R P is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;

each instance of is independently a single or double bond;

each instance of R H is independently hydrogen, halogen, unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, —OR a , —OCN, —OC(═O)R a , —OC(═S)R a , —OC(═O)OR a , —OC(═O)N(R a ) 2 ,—OS(═O)R a , —OS(═O)OR a , —OS(═O)N(R a ) 2 , —OS(═O) 2 R a , —OS(═O) 2 OR a , —OS(═O) 2 N(R a ) 2 , —OSi(R a ) 3 , —OSi(R a ) 2 (OR a ), —OSi(R a )(OR a ) 2 , —OSi(OR a ) 3 , oxo, —N(R a ) 2 , —N═C(R a ) 2 , ═NR a , —NC, —NCO, —N 3 , —NO 2 , —NR a C(═O)R a , —NR a C(═O)OR a ,—NR a C(═O)N(R a ) 2 ,—NR a S(═O)R a , —NR a S(═O)OR a , —NR a S(═O)N(R a ) 2 , —NR a S(═O) 2 R a , —NR a S(═O) 2 OR a , —NR a S(═O) 2 N(R a ) 2 , —SR a ,—SCN, —S(═O)R a , —S(═O)OR a , —S(═O)N(R a ) 2 , —S(═O) 2 R a , —S(═O) 2 OR a , —S(═O) 2 N(R a ) 2 , —SeR a , halogen, —CN, —C(═NR a )R a , —C(═NR a )OR a , —C(═NR a )N(R a ) 2 , —C(═O)R a , —C(═O)OR a , —C(═O)SR a , —C(═S)OR a , or —C(═O)N(R a ) 2 ;

or the two instances of R H of one or more instances of

are joined with the intervening carbon atoms to independently form a substituted or unsubstituted, monocyclic carbocyclic ring, unsubstituted, monocyclic heterocyclic ring, unsubstituted, monocyclic aryl ring, or substituted or unsubstituted, monocyclic heteroaryl ring;

each instance of R a is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted, monocyclic carbocyclyl, substituted or unsubstituted, monocyclic heterocyclyl, substituted or unsubstituted, monocyclic aryl, substituted or unsubstituted, monocyclic heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom, or two instances of R a are joined to form substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl;

each instance of R J is independently —OR a , —OCN, —OC(═O)R a , —OC(═S)R a , —OC(═O)OR a , —OC(═O)N(R a ) 2 ,—OS(═O)R a , —OS(═O)OR a , —OS(═O)N(R a ) 2 , —OS(═O) 2 R a , —OS(═O) 2 OR a , —OS(═O) 2 N(R a ) 2 , —OSi(R a ) 3 , —OSi(R a ) 2 (OR a ), —OSi(R a )(OR a ) 2 , —OSi(OR a ) 3 , oxo, —N(R a ) 2 , —N═C(R a ) 2 , ═NR a , —NC, —NCO, —N 3 , —NO 2 , —NR a C(═O)R a , —NR a C(═O)OR a , —NRC(═O)N(R a ) 2 ,—NR a S(═O)R a , —NR a S(═O)OR a , —NR a S(═O)N(R a ) 2 , —NR a S(═O) 2 R a , —NR a S(═O) 2 OR a , —NR a S(═O) 2 N(R a ) 2 , —SR a , —SCN, —S(═O)R a , —S(═O)OR a , —S(═O)N(R a ) 2 , —S(═O) 2 R a , —S(═O) 2 OR a , —S(═O) 2 N(R a ) 2 , —SeR a , halogen, —CN, C(═NR a )R a , —C(═NR a )OR a , —C(═NR a )N(R a ) 2 , —C(═O)R a , —C(═O)OR a , —C(═O)SR a , —C(═S)OR a , or —C(═O)N(R a ) 2 ;

each instance of R S is independently hydrogen or —OR a ;

each instance of w is independently 0, 1, 2, 3, or 4;

each instance of h is independently 0, 1, 2, or 3;

each instance of i is independently 0, 1, 2, or 3;

each instance of R U is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstitutedcarbocyclyl, substituted or unsubstitutedheterocyclyl, substituted or unsubstituted aryl, substituted or unsubstitutedheteroaryl, —OR a , —OCN, —OC(═O)R a , —OC(═S)R a , —OC(═O)OR a , —OC(═O)N(R a ) 2 ,—OS(═O)R a , —OS(═O)OR a , —OS(═O)N(R a ) 2 , —OS(═O) 2 R a , —OS(═O) 2 OR a , —OS(═O) 2 N(R a ) 2 , —OSi(R a ) 3 , —OSi(R a ) 2 (OR a ), —OSi(R a )(OR a ) 2 , —OSi(OR a ) 3 , oxo, —N(R a ) 2 , —N═C(R a ) 2 , ═NR a , —NC, —NCO, —N 3 , —NO 2 , —NRC(═O)R a , —NR a C(═O)OR a , —NR a C(═O)N(R a ) 2 ,—NR a S(═O)R a , —NR a S(═O)OR a , —NR a S(═O)N(R a ) 2 , —NR a S(═O) 2 R a , —NR a S(═O) 2 OR a , —NR a S(═O) 2 N(R a ) 2 , —SR a , —SCN, —S(═O)R a , —S(═O)OR a , —S(═O)N(R a ) 2 , —S(═O) 2 R a , —S(═O) 2 OR a , —S(═O) 2 N(R a ) 2 , —SeR a , halogen, —CN, —C(═NR a )R a , —C(═NR a )OR a , —C(═NR a )N(R a ) 2 , —C(═O)R a , —C(═O)OR a , —C(═O)SR a , —C(═S)OR a , or —C(═O)N(R a ) 2 ; and

each instance of RT is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

2. A hydroxylated polymer prepared by hydrolyzing a copolymer prepared by a method comprising polymerizing in the presence of a metathesis catalyst:

i) one or more instances of a first monomer, wherein each instance of the first monomer is independently of the formula:

or salt thereof, wherein:

each instance of

is Ring B, wherein each instance of Ring B is independently a substituted or unsubstituted, monocyclic carbocyclic ring, unsubstituted, monocyclic heterocyclic ring, unsubstituted, monocyclic aryl ring, or substituted or unsubstituted, monocyclic heteroaryl ring;

each instance of Z is independently C(R P ) 2 or O;

each instance of R P is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl; and

each instance of is independently a single bond or double bond; and

ii) one or more instances of a second monomer, wherein each instance of the second monomer is of Formula (B):

or a salt thereof; wherein:

each instance of Y is independently O or C(R Q ) 2 ;

each instance of R Q is independently hydrogen, halogen, or substituted or unsubstituted, C1-6 alkyl;

each instance of R k is independently hydrogen, halogen, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —OR N ;

each instance of R N is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or an oxygen protecting group;

each instance of j is independently 1, 2, or 3; and

each instance of k is independently 0, 1, 2, or 3;

wherein any two instances of the first monomer are the same as or different from each other, and any two instances of the second monomer are the same as or different from each other; and

wherein the step of hydrolyzing the copolymer comprises hydrolyzing one or more instances of the —O—Si bonds of the copolymer to form —OH.

3. The functional oligomer or functional polymer of claim 1 , wherein the functional oligomer or functional is prepared by a method comprising hydrolyzing a copolymer prepared by a method comprising polymerizing in the presence of a metathesis catalyst:

i) one or more instances of a first monomer, wherein each instance of the first monomer is of the formula:

or salt thereof;

ii) one or more instances of a second monomer, wherein each instance of the second monomer is of the formula:

or a salt thereof; wherein:

Y is O or C(R Q ) 2 ;

each instance of R Q is independently hydrogen, halogen, or substituted or unsubstituted, C 1-6 alkyl;

each instance of R k is independently hydrogen, halogen, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or —OR N ;

each instance of R N is independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, C 1-10 alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or an oxygen protecting group;

j is 1, 2, or 3; and

k is 0, 1, 2, or 3; and

iii) optionally one or more instances of a third monomer;

wherein any two instances of the first monomer are the same as or different from each other, any two instances of the second monomer are the same as or different from each other, any two instances of the third monomer are the same as or different from each other, and each instance of the first monomer, the second monomer, and the third monomer if present, is different from each other; and

wherein the step of hydrolyzing the copolymer comprises hydrolyzing one or more instances of the —O—Si bonds of the copolymer to form —OH.

4. The functional oligomer or functional polymer of claim 1 , wherein the functional oligomer or functional polymer is prepared by a method comprising hydrolyzing a copolymer prepared by a method comprising polymerizing in the presence of a metathesis catalyst:

i) one or more instances of a first monomer, wherein each instance of the first monomer is of the formula:

or salt thereof;

ii) one or more instances of a second monomer, wherein each instance of the second monomer is of the formula:

or a salt thereof; and

iii) optionally one or more instances of a third monomer;

wherein any two instances of the first monomer are the same as or different from each other, any two instances of the second monomer are the same as or different from each other, any two instances of the third monomer are the same as or different from each other, and each instance of the first monomer, the second monomer, and the third monomer if present, is different from each other; and

wherein the step of hydrolyzing the copolymer comprises hydrolyzing one or more instances of

the copolymer to form

5. The functional oligomer or functional polymer of claim 1 , wherein each instance of the linear units is of the formula:

6. The functional oligomer or functional polymer of claim 1 , wherein each instance of the linear units is independently of the formula:

7. The functional oligomer or functional polymer of claim 1 , wherein at least one instance of the functional units is independently of the formula:

8. The functional oligomer or functional polymer of claim 1 , wherein at least one instance of the functional units is independently of the formula:

9. A composition comprising:

a hydroxylated polymer of claim 2 ; and

optionally an excipient.

10. A kit comprising:

a hydroxylated polymer of claim 2 ; and

instructions for using the hydroxylated polymer.

11. A conjugate prepared by reacting a hydroxy-reacting substance with a hydroxylated polymer of claim 2 , wherein hydroxy-reacting substance comprises at least one instance of a hydroxy-reacting moiety.

12. A composition comprising:

a conjugate of claim 11 ; and

optionally an excipient.

13. A kit comprising:

a conjugate of claim 11 ; and

instructions for using the conjugate.

14. The functional oligomer or functional polymer of claim 1 , wherein at least one instance of Z is CH 2 .

15. The functional oligomer or functional polymer of claim 1 , wherein the two instances of R H of one or more instances of

are joined with the intervening carbon atoms to independently form a substituted or unsubstituted, monocyclic carbocyclic ring.

16. The functional oligomer or functional polymer of claim 1 , wherein:

at least one instance of the functional units is independently of the formula:

and

at least one instance of R J is —OH.

17. The functional oligomer or functional polymer of claim 16 , wherein at least one instance of R 5 is hydrogen.

18. The functional oligomer or functional polymer of claim 1 , wherein at least one instance of the functional units is independently of the formula:

19. The functional oligomer or functional polymer of claim 1 , wherein at least one instance of the functional units is independently of the formula:

20. The functional oligomer or functional polymer of claim 1 , wherein at least one instance of the functional units is independently of the formula:

21. The functional oligomer or functional polymer of claim 1 , wherein at least one instance of the crosslinking units is independently of the formula:

22. The functional oligomer or functional polymer of claim 1 , wherein at least one instance of R is substituted or unsubstituted alkenyl, wherein the attachment point is a double bond.

23. The functional oligomer or functional polymer of claim 1 , wherein the functional oligomer or functional polymer is crosslinked.

24. The functional oligomer or functional polymer of claim 1 , wherein the average molecular weight of the functional oligomer or functional polymer as determined by gel permeation chromatography is between 1 kDa and 8 kDa, inclusive.

25. The functional oligomer or functional polymer of claim 4 , wherein at least one instance of Z is CH 2 .

26. The functional oligomer or functional polymer of claim 4 , wherein two instances of R H of one or more instances of

are joined with the intervening carbon atoms to independently form a substituted or unsubstituted, monocyclic carbocyclic ring.

27. The functional oligomer or functional polymer of claim 4 , wherein at least one instance of the first monomer is of the formula:

28. The functional oligomer or functional polymer of claim 4 , wherein at least one instance of the second monomer is of the formula:

29. The hydroxylated polymer of claim 2 , wherein each instance of the first monomer is independently of Formula (D1) or (D2):

or a salt thereof, wherein:

each instance of x is independently 0, 1, or 2; and

each instance of y is independently 0, 1, or 2.

30. The hydroxylated polymer of claim 2 , wherein at least one instance of Z is CH 2 .

31. The hydroxylated polymer of claim 2 , wherein at least one instance of Ring B is independently a substituted or unsubstituted, monocyclic carbocyclic ring.

32. The hydroxylated polymer of claim 2 , wherein at least one instance of the first monomer is of the formula:

33. The hydroxylated polymer of claim 2 , wherein each instance of Y is O.

34. The hydroxylated polymer of claim 2 , wherein each instance of the second monomer is of the formula:

or a salt thereof.

35. The hydroxylated polymer of claim 2 , wherein each instance of the second monomer is of the formula:

or a salt thereof.

36. The hydroxylated polymer of claim 2 , wherein the molar ratio of the one or more instances of the first monomer to the second monomer is between 6:1 and 19:1, inclusive.

37. The hydroxylated polymer of claim 2 , wherein the hydroxylated polymer is crosslinked.

38. The hydroxylated polymer of claim 2 , wherein the average molecular weight of the hydroxylated polymer as determined by gel permeation chromatography is between 1 kDa and 8 kDa, inclusive.

39. The conjugate of claim 11 , wherein the hydroxy-reacting substance is lactide, polyethylene glycol, or polysiloxane, wherein the polysiloxane comprises at least one instance of a hydroxy-reacting moiety, wherein at least one instance of the hydroxy-reacting moiety is Si(IV)—H, Si(IV)-(a leaving group), C(IV)-(a leaving group), —C(═O)—OH, —C(═O)-(a leaving group), —C(=O)-O-, -C(= 0 )-O-C(=O)-, -S(=O)-OH, -S(=O)-(a leaving group), -S(=O) 2 -OH, -S(= 0 ) 2 -(a leaving group), -OH, or -O-(a leaving group).