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 aryl diisocyanate crosslinkers, wherein one or more of the plurality of cyclodextrins are bound to a linker of formula (I):

wherein

A is an aryl 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 , and each R a and R b 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 —N(Me) 3 ;

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 instance of —W—Z is taken together to form

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

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 instance of —W—Z is taken together to form

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

9. The porous polymeric material of claim 8 , wherein the linker comprising formula (I) has the following structure

wherein the oxygen atom denoted with the * is a glycosidic oxygen from one of the plurality of cyclodextrins.

10. 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 9 , 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.

11. 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.

12. The porous polymeric material of claim 11 , wherein each instance of —W—Z is taken together to form

13. The porous polymeric material of claim 12 , wherein each cyclodextrin is a β-cyclodextrin.

14. The porous polymeric material of claim 13 , wherein the linker comprising formula (I) has the following structure

wherein the oxygen atom denoted with the * is a glycosidic oxygen from one of the plurality of cyclodextrins.

15. 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 14 , 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.

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

17. 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.