Functionalized coating polymers and uses thereof

1. A method comprising:

(i) introducing a coating solution to an internal bore of a column, the coating solution comprising a polymer, a thermally activated initiator, and a solvent, wherein the polymer comprises a structure having formula (I) or (VI) or (VII):

 or

 or

 or a salt thereof, wherein:

each of R 1 and R 12 is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkoxyalkyl, optionally substituted aryl, optionally substituted alkaryl, optionally substituted alkenyl, halo, or optionally substituted haloalkyl;

each Ak 1 , Ak 2 , and Ak 3 is, independently, a bond, optionally substituted alkylene, optionally substituted arylene, oxy, or optionally substituted heteroalkylene; and

each of R 2 , R 3 , R 4 , R 9 , R 10 , and R 11 is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkoxyalkyl, optionally substituted aryl, hydroxyl, optionally substituted hydroxyalkyl, optionally substituted hydroxyaryl, halo, or optionally substituted haloalkyl, wherein at least one of R 2 , R 3 , R 4 , R 9 , R 10 , and R 11 comprises a hydroxyl; and

(ii) heating the column to a first temperature above a thermal initiation temperature characteristic of the thermally activated initiator, thereby crosslinking the polymer in the presence of the thermally activated initiator to provide a film.

2. The method of claim 1 , wherein the thermal initiation temperature is of from about 30° C. to about 120° C.

3. The method of claim 2 , wherein the first temperature is of from about 40° C. to 130° C.

4. The method of claim 1 , further comprising, after step (i):

removing the solvent from the internal bore of the column, thereby providing a layer comprising the polymer and the thermally activated initiator disposed on a surface of the internal bore.

5. The method of claim 1 , wherein the thermally activated initiator is an azo-based initiator.

6. The method of claim 5 , wherein the azo-based initiator is 2,2′-azobisisobutyronitrile, 2,2′-azobis(N-butyl-2-methylpropionamide), 1,1′-azobis(cyanocyclohexane), 1,1′-azobis(cyclohexane-1-carbonitrile), 2,2′-azobis(2-methylbutyronitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2,4-dimethylvaleronitrile), and/or 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile.

7. The method of claim 1 , wherein the solvent is a polar, aprotic solvent.

8. The method of claim 1 , wherein the solvent has a boiling point that is less than the thermal initiation temperature.

9. The method of claim 1 , wherein the film has a thickness of from about 50 nm to about 1 μm.

10. The method of claim 1 , further comprising, before step (i):

exposing the internal bore of the column to a silanization agent; and

removing the silanization agent, thereby providing a silanized surface to be introduced to the coating solution.

11. The method of claim 1 , wherein the coating solution comprises about 0.01% (w/v) to about 5% (w/v) of the polymer and about 0.00001% (w/v) to about 0.2% (w/v) of the thermally activated initiator.

12. The method of claim 1 , wherein R 2 , R 4 , R 9 , and/or R 11 is hydroxyl or optionally substituted hydroxyalkyl; and/or wherein R 2 , R 3 , R 9 , and/or R 10 is halo or optionally substituted haloalkyl.

13. The method of claim 1 , wherein the polymer comprises a structure having formula (IIIa) or (IIIb):

or

or a salt thereof, wherein:

each of R 1 , R 5 , R 6 , R 7 , and R 8 is, independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkoxyalkyl, optionally substituted aryl, optionally substituted alkaryl, optionally substituted alkenyl, halo, or optionally substituted haloalkyl;

Ak 1 is a bond, optionally substituted alkylene, optionally substituted arylene, oxy, or optionally substituted heteroalkylene;

Ar 1 is optionally substituted alkylene, optionally substituted arylene, oxy, or optionally substituted heteroalkylene;

each of R 2 , R 3 , and R 4 is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkoxyalkyl, optionally substituted aryl, hydroxyl, optionally substituted hydroxyalkyl, optionally substituted hydroxyaryl, halo, or optionally substituted haloalkyl, wherein at least one of R 2 , R 3 , and R 4 comprises a hydroxyl; and

each of n1 and n2 is, independently, a number of from about 0.5 to 50.

14. The method of claim 13 , wherein the ratio of n1 to n2 is of from about 1:5 to 5:1.

15. The method of claim 1 , wherein the polymer comprises a structure having formula (VIIIa) or (VIIIb) or (IXa) or (IXb):

or

or

or

or a salt thereof, wherein:

each of R 1 , R 5 , R 6 , R 7 , R 8 , and R 12 is, independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkoxyalkyl, optionally substituted aryl, optionally substituted alkaryl, optionally substituted alkenyl, halo, or optionally substituted haloalkyl;

each of Ak 1 , Ak 2 , and Ak 3 is, independently, a bond, optionally substituted alkylene, optionally substituted arylene, oxy, or optionally substituted heteroalkylene;

Ar 1 is optionally substituted alkylene, optionally substituted arylene, oxy, or optionally substituted heteroalkylene;

each of R 2 , R 3 , R 4 , R 9 , R 10 , and R 11 is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkoxyalkyl, optionally substituted aryl, hydroxyl, optionally substituted hydroxyalkyl, optionally substituted hydroxyaryl, halo, or optionally substituted haloalkyl, wherein at least one of R 2 , R 3 , R 4 , R 9 , R 10 , and R 11 comprises a hydroxyl; and

each of n1 and n2 is, independently, a number of from about 0.5 to 50.

16. A method of detecting an organophosphorous agent, the method comprising:

(i) providing a column having a film disposed within an internal bore of the column, the film comprising a polymer that comprises a structure having formula (I) or (II):

 or

 or a salt thereof, wherein:

R 1 is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkoxyalkyl, optionally substituted aryl, optionally substituted alkaryl, optionally substituted alkenyl, halo, or optionally substituted haloalkyl;

each of Ak 1 and X is, independently, a bond, optionally substituted alkylene, oxy, or optionally substituted heteroalkylene; and

each of R 2 , R 3 , and R 4 is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkoxyalkyl, optionally substituted aryl, hydroxyl, optionally substituted hydroxyalkyl, optionally substituted hydroxyaryl, halo, or optionally substituted haloalkyl, wherein at least one of R 2 , R 3 , and R 4 comprises a hydroxyl; and

(ii) injecting a test sample into the internal bore of the column, wherein the organophosphorous agent, if present, binds to the film.