Charge-bearing cyclodextrin polymeric materials and methods of making and using same

1. A porous polymeric material comprising a plurality of cyclodextrins crosslinked with a plurality of polyisocyanate crosslinkers, wherein one or more of the plurality of cyclodextrins are bound to a linker of formula (I):

wherein

A is an aryl or heteroaryl moiety;

each R 1 is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 3 haloalkyl, aryl, heteroaryl, —CF 3 , —SO 3 H, —CN, —NO 2 , —NH 2 , —NCO, —C(O) 2 R 3 , —C(O)N(R 3 ) 2 , and -halogen;

each R 2 is independently H, —OH, —O-metal cation, alkyl, aryl, heteroaryl, —SH, —S-metal cation, —S-alkyl, —C(O) 2 H, or —C(O)NH 2 ;

each R 3 is independently —H, —C 1 -C 6 alkyl, —C 1 -C 3 haloalkyl, -aryl, —C(O)N(R a )(R b ), —C(O)R c , —CO 2 R c , —SO 2 N(R a )(R b ), or —SOR c , wherein each R a , R b , and R c is independently H, or C 1 -C 6 alkyl;

each W is independently a bond, an alkylene group, an arylene group, a heteroarylene group, —O-arylene-, —(CH 2 ) a -arylene-, —SO 2 -arylene-, —NH-arylene-, —S-arylene-, —O— heteroarylene-, —(CH 2 ) a -heteroarylene-, —SO 2 -heteraoarylene-, —NH-heteroarylene-, —S— heteroarylene-, —(—O—(CH 2 ) a —) x —, —(—NH—(CH 2 ) a —) x —, —(—S—(CH 2 ) a —) x —,

wherein a is 0-100 and x is 1-100, and each arylene or heteroarylene moiety can be substituted or unsubstituted;

each Z is an anionic moiety;

each L is

A′ is a covalent bond to A;

Z′ is a covalent bond to Z;

* is a covalent bond to ;

is a point of attachment to the plurality of cyclodextrin carbon atoms;

x is 0-8;

y 1 is 1-4;

y 2 is 1-4; and

y 3 is 0-4.

2. The porous polymeric material of claim 1 , wherein each Z is

3. The porous polymeric material of claim 1 , wherein each cyclodextrin is selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and combinations thereof.

4. The porous polymeric material of claim 1 , wherein x and y 3 are each 0.

5. The porous polymeric material of claim 1 , wherein the aryl moiety is

wherein represents any of the substituents attached to A in formula (I).

6. The porous polymeric material of claim 5 , wherein the aryl diisocyanate crosslinker is 4,4′-methylene diphenyl diisocyanate, the aryl moiety is

and x and y 3 are each 0.

7. The porous polymeric material of claim 6 , wherein each cyclodextrin is a β-cyclodextrin.

8. The porous polymeric material of claim 5 , wherein the aryl diisocyanate crosslinker is toluene 2,4-diisocyanate, the aryl moiety is

and x and y 3 are each 0.

9. The porous polymeric material of claim 8 , wherein each cyclodextrin is a β-cyclodextrin.

10. The porous polymeric material of claim 1 , wherein the porous polymeric material has a surface area from about 10 m 2 /g to about 2,000 m 2 /g.

11. A method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 1 , whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material.

12. A method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 7 , whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material.

13. A porous polymeric material comprising a plurality of cyclodextrins crosslinked with a plurality of acid chloride-containing crosslinkers or ester-containing crosslinkers, wherein one or more of the plurality of cyclodextrins are bound to a linker of formula (I):

wherein

A is an aryl or heteroaryl moiety;

each R 1 is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 3 haloalkyl, aryl, heteroaryl, —CF 3 , —SO 3 H, —CN, —NO 2 , —NH 2 , —NCO, —C(O) 2 R 3 , —C(O)N(R 3 ) 2 , and -halogen;

each R 2 is independently H, —OH, —O-metal cation, alkyl, aryl, heteroaryl, —SH, —S-metal cation, —S-alkyl, —C(O) 2 H, or —C(O)NH 2 ;

each R 3 is independently —H, —C 1 -C 6 alkyl, —C 1 -C 3 haloalkyl, -aryl, —C(O)N(R a )(R b ), —C(O)R c , —CO 2 R c , —SO 2 N(R a )(R b ), or —SOR c , wherein each R a , R b , and R c is independently H, or C 1 -C 6 alkyl;

each W is independently a bond, an alkylene group, an arylene group, a heteroarylene group, —O-arylene-, —(CH 2 ) a -arylene-, —SO 2 -arylene-, —NH-arylene-, —S-arylene-, —O— heteroarylene-, —(CH 2 ) a -heteroarylene-, —SO 2 -heteraoarylene-, —NH-heteroarylene-, —S— heteroarylene-, —(—O—(CH 2 ) a —) x —, —(—NH—(CH 2 ) a —) x —, —(—S—(CH 2 ) a —) x —,

wherein a is 0-100 and x is 1-100, and each arylene or heteroarylene moiety can be substituted or unsubstituted;

each Z is a cationic or anionic moiety;

each L is

A′ is a covalent bond to A;

Z′ is a covalent bond to Z;

* is a covalent bond to ;

is a point of attachment to the plurality of cyclodextrin carbon atoms;

x is 0-8;

y 1 is 1-4;

y 2 is 1-4; and

y 3 is 0-4.

14. The porous polymeric material of claim 13 , wherein each Z is an anionic moiety and the anionic moiety is

15. The porous polymeric material of claim 13 , wherein each Z is a cationic moiety and the cationic moiety is —N(R 3 ) 3 + , —P(R 3 ) 3 + , —S(R 3 ) 2 + , or -Heteroaryl + .

16. The porous polymeric material of claim 15 , wherein each cationic moiety is —N(R 3 ) 3 + .

17. The porous polymeric material of claim 15 , wherein each cationic moiety is —N(Me) 3 + .

18. The porous polymeric material of claim 13 , wherein each cyclodextrin is selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and combinations thereof.

19. The porous polymeric material of claim 13 , wherein x and y 3 are each 0.

20. The porous polymeric material of claim 13 , wherein the aryl moiety is

wherein represents any of the substituents attached to A in formula (I).

21. The porous polymeric material of claim 20 , wherein the aryl moiety is

and x and y 3 are each 0.

22. The porous polymeric material of claim 21 , wherein each cyclodextrin is a β-cyclodextrin.

23. The porous polymeric material of claim 20 , wherein the aryl moiety is

and x and y 3 are each 0.

24. The porous polymeric material of claim 23 , wherein each cyclodextrin is a β-cyclodextrin.

25. The porous polymeric material of claim 20 , wherein the aryl moiety is

and x and y 3 are each 0.

26. The porous polymeric material of claim 25 , wherein each cyclodextrin is a β-cyclodextrin.

27. The porous polymeric material of claim 13 , wherein the porous polymeric material has a surface area from about 10 m 2 /g to about 2,000 m 2 /g.

28. A method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 13 , whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material.

29. A method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 24 , whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material.

30. A method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 26 , whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material.