Functionalized cyclodextrin polymer for adsorption of perfluoroalkyl and polyfluoroalkyl substances in water

Abstract

Disclosed herein are mesoporous polymeric materials and methods for preparing and using the same. The mesoporous polymeric material comprises a network of cyclodextrin moieties crosslinked by a plurality of crosslinks.

Description

[0001] FUNCTIONALIZED CYCLODEXTRIN POLYMER FOR ADSORPTION OF

[0002] PERFLUOROALKYL AND POLYFLUOROALKYL SUBSTANCES IN WATER

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application claims priority to U.S. Provisional Patent Application No. 63 / 648,636, filed May 16, 2024. The contents of which is incorporated by reference in its entirety.

[0005] STATEMENT REGARDING FEDERALLY FUNDED RESEARCH

[0006] This invention was made with government support under grant number ER18-1026 awarded by the Department of Defense. The government has certain rights in the invention.

[0007] BACKGROUND

[0008] Per- and polyfluoroalkyl substances (PFASs) are fluorinated surfactants1'4applied in industrial processes5-7(e.g., pesticide formulations, waterproofing textiles, and oil production) and consumer products8'9(e.g., cosmetics, firefighting foams and food packaging). Their manufacture and use have contaminated water resources around the world, and their bioaccumulative nature, toxicity at low levels of chronic exposure, and environmental persistence motivate efforts to prevent and remediate PFAS contamination.4, 10-12Anionic perfluorocarboxylic acids (PFCAs) and perfluorosulfonic acids (PFSAs) are the most widely detected classes of anionic PFASs, whose structures include long-chain derivatives, such as the eight carbon perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), and short-chain derivatives, such as the four-carbon- containing perfluorobutanoic acid (PFBA) and perfluorobutanesulfonic acid (PFBS). The shortchain PFASs are now also widespread and are more mobile in the environment, and more resistant to degradation or removal efforts than long-chain PFASs.3Conventional adsorbents, such as activated carbons (ACs),13-15ion exchange resins,15-16and inorganic minerals17-19have been widely studied and applied for PFAS removal. However, these adsorbents generally suffer from shortcomings, such as moderate or low affinity for long- and short-chain PFASs, and fouling by dissolved natural organic matters and inorganic constituents found in natural and engineered water systems.20-23As a result, there exists a need for new polymeric material as efficient adsorbents for per- and polyfluoroalkyl substances (PFASs). SUMMARY OF THE INVENTION

[0009] Disclosed herein are mesoporous polymeric materials and methods for preparing and using the same. One aspect of the invention provides for a mesoporous polymeric material comprising a network of cyclodextrin moieties crosslinked by a plurality of crosslinks. The network comprises

[0010] or any combination thereof. A is an unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl. R1and

[0011] R2are independently alkylammonium-substituted aryl, alkylphosphonium-substituted aryl, alkylphosphonium-substituted biaryl, or hydrogen. The alkylammonium-substituted aryl is

[0012] R3is independently selected from hydrogen, alkyl, hydroxyalkyl, alkanoyl, or carboxy alkyl. Another aspect of the invention provides for purifying a fluid sample comprising one or more pollutants. The method comprises contacting the fluid sample with the mesoporous polymeric material as described herein. The methods disclosed herein may be used to adsorb at least 50 wt % of the total amount of the one or more pollutants in the fluid sample. Another aspect of the invention provides for a method of preparing a mesoporous polymeric material comprising a network of cyclodextrin moieties crosslinked by a plurality of crosslinks. The method comprises contacting a functionalized cyclodextrin monomer with a comonomer in the presence of a free radical initiator under conditions sufficient to prepare the network of cyclodextrin moieties crosslinked by a plurality of crosslinks. The functionalized cyclodextrin monomer comprises or any combination thereof. The comonomer comprises a formula of

[0013] A is an unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl. R1and R2are independently alkylammonium-substituted aryl, alkylphosphonium-substituted aryl, alkylphosphonium-substituted biaryl, or hydrogen. The alkylammonium-substituted aryl is

[0014] R3is independently selected from hydrogen, alkyl, hydroxyalkyl, alkanoyl, or carboxy alkyl.

[0015] These and other aspects and embodiments of the invention will be further described herein.

[0016] BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Non-limiting embodiments of the present invention will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the invention shown where illustration is not necessary to allow those of ordinary skill in the art to understand the invention.

[0018] FIG. 1 illustrates (A) a general scheme showing the adsorption of PFAS by styrene- functionalized / fcyclodextrin (StyDex) polymers, and (B) structural features of exemplary StyDex polymers according to an aspect as disclosed herein.

[0019] FIG. 2 shows graphs of the removal of 1 ug L-1PFAAs by 10 mg L-1of StyDex 1-5 in

[0020] Mih-Q water with a contact time of 0.5 h (A), 9 h (B), or 48 h (C). The comonomer structure is depicted for each StyDex below. The error bars represent the standard deviation of triplicate samples. Experiments were conducted at particle sizes >425 μm.

[0021] FIG. 3 shows graphs of the removal of 1 μg L-1PFAAs by StyDex 4 and 5 in Mili-Q water with a contact time of 0.5, 9 or 48 h. Adsorbent dose is either 5 mg L-1(A) or 1 mg L-1(B). Experiments were conducted at particle sizes 125-212 μm. The comonomer structures are depicted for each StyDex. Each point represents the percent removal of a PFAA by the polymer at the specified contact time. A total of thirty-nine points correspond to triplicate measurements of thirteen PFAA removal samples. The median is depicted as a bolded horizontal line in a box, which represents the removal by the polymer for all selected PFAAs regardless the chain-length or anionic head group. Outliers are depicted as open circles and are defined as 1.5 times outside of the interquartile range below the lower quartiles. Outliers indicate that the ineffective removal of a particular PFAA is not representative of the overall efficiency of the polymer for the selected PFAAs. ***, **, *, and ns represent p < 0.001, p < 0.01, p < 0.05 and p >0.05, respectively.

[0022] FIG. 4 shows graphs of the removal of 1 μg L-1PFAAs by 10 mg L-1of StyDex 5, 7, 8, and 9 in Mili-Q water with a contact time of 0.5 h (A) 9 h (B), or 48 h (C). The comonomer structure is depicted for each StyDex polymer below. The error bars represent the standard deviation of triplicate samples. Experiments with StyDex 5, 7, and 8 were conducted at particle sizes >425 μm; experiments with StyDex 9 were conducted at particle sizes of 125-212 μm.

[0023] FIG. 5 shows graphs of the removal of 1 μg L-1PFAAs and neutral contaminants by 1 mg L-1StyDex (PFAAs) or 10 mg L-1StyDex (neutral contaminants) 10, 4 and 11 in Mili-Q water (A) or a 2 mM NaCl matrix (B) with a contact time of 48 h. Experiments were conducted at particle sizes of 125-212 μm. The relative size of cyclodextrin cavity is depicted for each StyDex below. The error bars represent the standard deviation of triplicate samples.

[0024] FIG. 6 shows graphs of the removal of 1 μg L-1PFCAs and GenX by 0.1 mg L-1of StyDex polymers containing 1-16 equiv of comonomer d or comonomer e (as indicated) with a contact time of 0.5 h (A and B), 9 h (C and D), or 48 h (E and F). Experiments were conducted at particle sizes of 125-212 μm. Perfluoroalkyl sulfonic acid (PFSA) removal results are plotted separately (Figure 30). The error bars represent standard deviation of triplicate samples.

[0025] FIG. 7 illustrates a scheme for the synthesis of StyDex monomers a and y, according to an aspect of the disclosure herein. FIG. 8 illustrates the CPMAS13C ssNMR spectrum of StyDex 1. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 1 (bottom) stacked against solution13C NMR spectra of StyDex monomer β (top) and comonomer a (middle).

[0026] FIG. 9 illustrates the CPMAS13C ssNMR spectrum of StyDex 2. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 2 (bottom) stacked against solution13C NMR spectra of StyDex monomer β (top) and comonomer b (middle).

[0027] FIG. 10 illustrates the CPMAS13C ssNMR spectrum of StyDex 3. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 3 (bottom) stacked against solution13C NMR spectra of StyDex monomer β (top) and comonomer c (middle).

[0028] FIG. 11 illustrates the CPMAS13C ssNMR spectrum of StyDex 4. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 4 (bottom) stacked against solution13C NMR spectra of StyDex monomer β (top) and comonomer d (middle).

[0029] FIG. 12 illustrates the CPMAS13C ssNMR spectrum of StyDex 5. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 5 (bottom) stacked against solution13C NMR spectra of StyDex monomer β (top) and comonomer e (middle).

[0030] FIG. 13 illustrates the CPMAS13C ssNMR spectrum of StyDex 6. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 6 (bottom) stacked against solution13C NMR spectra of StyDex monomer β (top) and comonomer f (middle).

[0031] FIG. 14 illustrates the CPMAS13C ssNMR spectrum of StyDex 7. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 7 (bottom) stacked against solution13C NMR spectra of StyDex monomer β (top) and comonomer g (middle).

[0032] FIG. 15 illustrates the CPMAS13C ssNMR spectrum of StyDex 8. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 8 (bottom) stacked against solution13C NMR spectra of StyDex monomer β (top) and comonomer h (middle).

[0033] FIG. 16 illustrates the CPMAS13C ssNMR spectrum of StyDex 9. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 9 (bottom) stacked against solution13C NMR spectra of StyDex monomer β (top) and comonomer i (middle).

[0034] FIG. 17 illustrates the CPMAS13C ssNMR spectrum of StyDex 10. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 10 (bottom) stacked against solution13C NMR spectra of StyDex monomer α (top) and comonomer d (middle). FIG. 18 illustrates the CPMAS13C ssNMR spectrum of StyDex 11. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 11 (bottom) stacked against solution13C NMR spectra of StyDex monomer γ (top) and comonomer d (middle).

[0035] FIG. 19 illustrates the CPMAS13C ssNMR spectrum of StyDex 12. CPMAS13C ssNMR spectrum (400 MHz, 298 K, Adamantane / KBr) of StyDex 12 (bottom) stacked against solution13C NMR spectra of StyDex monomer β’ (top) and comonomer d (middle).

[0036] FIG. 20 illustrates the31P ssNMR spectra (162 MHz, 298 K, NH4H2PO4) of StyDex 5-8 containing phosphorous-based comonomers e-h. The comonomer structures are depicted for each StyDex. The relative shift of the phosphorous resonance in each spectrum is consistent with those observed in solution31P NMR spectrum of the corresponding comonomers.

[0037] FIG. 21 illustrates the31P ssNMR spectra (162 MHz, 298 K, NH4H2PO4) of StyDex 5 and 17-20, which were prepared with different feed ratio of comonomer e. StyDex 17 was prepared with 1 equiv of comonomer d with respect to β. StyDex 5, 2 equiv; StyDex 18, 4 equiv; StyDex 19, 8 equiv; StyDex 20, 16 equiv. No internal standard was used when taking these spectra, therefore, the data are not quantitative to determine the comonomer incorporation ratio.

[0038] FIG. 22 illustrates a graph of the swelling ratio of StyDex polymers containing either comonomer d (StyDex 4 and 13-16) or comonomer e (StyDex 5 and 17-20) in Milli-Q water over 24 h. StyDex 13, 4 and 14-16 were synthesized with 1, 2, 4, 8, and 16 equiv of comonomer d, respectively. Similarly, StyDex 17, 5 and 18-20 were synthesized with 1-16 equiv. of comonomer e. Error bars represent standard deviation of triplicate samples.

[0039] FIG. 23 shows graphs of the removal of 1 μg L-1PFAAs by 10 mg L-1StyDex 5 (teal bar) and StyDex 6 (dark gold bar) in Milli-Q water with 0.5 h (A), 9 h (B), or 48 h (C) contact time. The comonomer structure is depicted for each StyDex. Error bars represent standard deviation of triplicate samples. Experiments with StyDex 5 were conducted at particle sizes >425 μm; experiments with StyDex 6 were conducted at particle sizes of 125-212 μm.

[0040] FIG. 24 shows graphs of the removal of 1 μg L-1PFAAs by 1 mg L-1StyDex 5 (teal bar) and StyDex 6 (dark gold bar) in Milli-Q water with 0.5 h (A), 9 h (B), or 48 h (C) contact time. The comonomer structure is depicted for each StyDex. Error bars represent standard deviation of triplicate samples. Experiments were conducted at particle sizes of 125-212 μm.

[0041] FIG. 25 shows a graph of the removal of 1 μg L-1PFAAs by 10 mg L-1StyDex 4 and StyDex 5 in Milli-Q water (solid bar) and 2 mM NaCl matrix (striped bar) with a contact time of 9 h. The comonomer structure is depicted for each StyDex. Error bars represent standard deviation of triplicate samples. Experiments were conducted at particle sizes >425 μm.

[0042] FIG. 26 shows a graph of the removal of 1 μg L-1PFAAs by 10 mg L-1StyDex 10, 4, and StyDex 11 in Milli-Q water with a contact time of 0.5 h (A), 9 h (B), or 48 h (C). The cyclodextrin derivative (a. β or y) in each polymer is depicted. All three polymers contain the same feed ratio of comonomer d. Error bars represent standard deviation of triplicate samples. Experiments with StyDex 4 were conducted at particle sizes >425 μm; experiments with StyDex 10 and 11 were conducted at particle sizes of 125-212 μm.

[0043] FIG. 27 shows a graph of the removal of 1 μg L-1PFAAs by 10 mg L-1StyDex 4 and StyDex 12 in Milli-Q water with a contact time of 0.5 h (A), 9 h (B), or 48 h (C). The regiochemistry of β (StyDex 4) and β’ (StyDex 12) is depicted. The pendants represent styrene groups. Experiments with StyDex 4 were conducted at particle sizes >425 μm; experiments with StyDex 12 were conducted at particle sizes of 125-212 μm.

[0044] FIG. 28 shows graphs of the removal of 1 μg L-1PFAAs by 10 mg L-1StyDex 13, 4, 14, 15, and 16, which were prepared with 1, 2, 4, 8, or 16 equiv of comonomer d, respectively, with respect to 1 equiv of β. The contact times were 0.5 h (A), 9 h (B) and 48 h (C). The comonomer structure is depicted on the right. Error bars represent standard deviation of triplicate samples. Experiments with StyDex 4, 13, and 14 were conducted at particle sizes >425 μm; experiments with StyDex 15 and 16 were conducted at particle sizes of 125-212 μm.

[0045] FIG. 29 shows graphs of the removal of 1 μg L-1PFAAs by 10 mg L-1StyDex 17, 4, 18, 19 and 20, which were prepared with 1, 2, 4, 8, or 16 equiv of comonomer e, respectively, with respect to 1 equiv of β. The contact times were 0.5 h (A), 9 h (B) and 48 h (C). The comonomer structure is depicted on the right. Error bars represent standard deviation of triplicate samples. Experiments with StyDex 5, 17, and 18 were conducted at particle sizes >425 μm; experiments with StyDex 19 and 20 were conducted at particle sizes of 125-212 μm.

[0046] FIG. 30 shows graphs of the removal of 1 μg L-1PF SA by 0.1 mg L-1of StyDex polymers containing 1-16 equiv of comonomer d or comonomer e with a contact time of 0.5 h (A and B), 9 h (C and D), or 48 h (E and F). The error bars represent standard deviation of triplicate samples. Experiments were conducted at particle sizes of 125-212 μm.

[0047] FIG. 31 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 1 at 77K. FIG. 32 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 2 at 77K.

[0048] FIG. 33 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 3 at 77K.

[0049] FIG. 34 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 4 at 77K.

[0050] FIG. 35 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 5 at 77K.

[0051] FIG. 36 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 6 at 77K.

[0052] FIG. 37 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 7 at 77K.

[0053] FIG. 38 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 8 at 77K.

[0054] FIG. 39 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 9 at 77K.

[0055] FIG. 40 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 10 at 77K.

[0056] FIG. 41 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 11 at 77K.

[0057] FIG. 42 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 12 at 77K.

[0058] FIG. 43 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 13 at 77K.

[0059] FIG. 44 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 14 at 77K.

[0060] FIG. 45 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 15 at 77K.

[0061] FIG. 46 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 16 at 77K. FIG. 47 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 17 at 77K.

[0062] FIG. 48 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 18 at 77K.

[0063] FIG. 49 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 19 at 77K.

[0064] FIG. 50 shows (A) N2 adsorption-desorption isotherms and (B) pore width distribution for StyDex 20 at 77K.

[0065] DETAILED DESCRIPTION OF THE INVENTION

[0066] Disclosed herein are functionalized cyclodextrin monomers and polymers prepared from the same for water remediation. The present technology provides for a modular, permanently porous, and crosslinked functionalized CD polymers with a controllable binding environment and tunable compositions of comonomers to remove PFASs of different chain lengths and other micropollutants from water. The modularity of this platform and reliability of radical polymerization enabled abroad range of comonomers to be incorporated. This structural versatility in turn enables performance trends to be studied as a function of the adsorbent structure and water matrix.

[0067] As demonstrated in the Examples, the styrene-functionalized cyclodextrinβ (-StyDex) polymers achieve exceptional removal efficiencies of PFCAs and PFSAs at an adsorbent loading as low as 1 mg L-1. The Examples also demonstrate that removal of shorter chain PFASs that are conventionally difficult to remove. These results demonstrate that functionalized CD polymers are useful adsorbents for the remediation of anionic PFAS. Furthermore, the unprecedented control afforded by the platform allows the polymers to be tailored to target other organic micropollutants, including cationic and neutral PFAS by varying the comonomer structures.

[0068] One aspect of the technology is a mesoporous polymeric material. The term “mesoporous polymeric material” refers to porous cyclodextrin polymeric materials (P-CDPs). The P-CDPs are comprised of insoluble polymers of cyclodextrin. Cyclodextrins are macrocycles that may be inexpensively and sustainably produced from glucose. The polymers of cyclodextrin are comprised of cyclodextrin moieties that are derived from cyclodextrins. The cyclodextrin moiety(s) can be derived from naturally occurring cyclodextrins (e.g., alpha-, beta-, and gamma-, comprising 6, 7, and 8 glucose units, respectively) or synthetic cyclodextrins. The cyclodextrin moiety has at least one — 0 — bond derived from an — OH group on the cyclodextrin from which it is derived. The cyclodextrin moieties can comprise 3-20 glucose units, including 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 glucose units, inclusive of all ranges therebetween. In many embodiments, the cyclodextrin moieties are derived from starch, and comprise 6-9 glucose units. The polymeric materials may comprise two or more different cyclodextrin moieties. In particular embodiments, the P-CDP is comprised of insoluble polymers of beta-cyclodextrin (beta-CD).

[0069] The P-CDP can also comprise cyclodextrin derivatives or modified cyclodextrins. The derivatives of cyclodextrin consist mainly of molecules wherein some of the OH groups are converted to OR groups. The cyclodextrin derivatives can, for example, have one or more additional moieties that provide additional functionality, such as desirable solubility behavior and affinity characteristics. Examples of suitable cyclodextrin derivative materials include methylated cyclodextrins (e.g., RAMEB, randomly methylated beta-cyclodextrins), hydroxyalkylated cyclodextrins (e.g., hydroxypropyl-cyclodextrin and hydroxypropyl-gamma-cyclodextrin), acetylated cyclodextrins (e.g., acetyl-gamma-cyclodextrin), reactive cyclodextrins (e.g., chlorotriazinyl-CD), branched cyclodextrins (e.g., glucosyl-beta-cyclodextrin and maltosyl- cyclodextrin), sulfobutyl-cyclodextrin, and sulfated cyclodextrins. For example, the cyclodextrin moiety further comprises a moiety that binds (e.g., with specificity) a metal such as arsenic, cadmium, copper, or lead.

[0070] The P-CDP can also comprise cyclodextrin derivatives as disclosed in U.S. Pat. No. 6,881,712 including, e.g., cyclodextrin derivatives with short chain alkyl groups such as methylated cyclodextrins, and ethylated cyclodextrins, wherein R is a methyl or an ethyl group; those with hydroxyalkyl substituted groups, such as hydroxypropyl cyclodextrins and / or hydroxyethyl cyclodextrins, wherein R is a — CH2 — CH(OH) — CH3 or a XH2CH2 — OH group; branched cyclodextrins such as maltose-bonded cyclodextrins; cationic cyclodextrins such as those containing 2-hydroxy-3-(dimethylamino)propyl ether, wherein R is CH2 — CH(OH) — CH2 — N(CHS)2 which is cationic at low pH; quaternary ammonium, e.g., 2-hydroxy-3- (trimethylammonio)propyl ether chloride groups, wherein R is CH2 — CH(OH) — CH2N+(CH3)3d"; anionic cyclodextrins such as carboxymethyl cyclodextrins, cyclodextrin sulfates, and cyclodextrin succinylates; amphoteric cyclodextrins such as carboxymethyl / quaternary ammonium cyclodextrins; cyclodextrins wherein at least one glucopyranose unit has a 3-6-anhydro-cyclomaltostructure, e.g., the mono-3-6- anhydrocyclodextrins, as disclosed in “Optimal Performances with Minimal Chemical Modification of Cyclodextrins”, F.Diedaini-Pilard and B.Perly, The 7th International Cyclodextrin Symposium Abstracts, April 1994, p . 49 said references being incorporated herein by reference; and mixtures thereof. Other cyclodextrin derivatives are disclosed in U.S. Pat. No. 3,426,011, Parmerter et al., issued Feb. 4, 1969; U.S. Pat. Nos. 3,453,257; 3,453,258; 3,453,259; and 3,453,260, all in the names of Parmerter et al., and all issued Jul. 1, 1969; U.S. Pat. No. 3,459,731, Gramera et al., issued Aug. 5, 1969; U.S. Pat. No. 3,553,191, Parmerter et al., issued Jan. 5, 1971; U.S. Pat. No. 3,565,887, Parmerter et al., issued Feb. 23, 1971; U.S. Pat. No. 4,535,152, Szejtli et al., issued Aug. 13, 1985; U.S. Pat. No. 4,616,008, Hirai et al., issued Oct. 7, 1986; U.S. Pat. No. 4,678,598, Ogino et al., issued Jul. 7, 1987; U.S. Pat. No. 4,638,058, Brandt et al., issued Jan. 20, 1987; and U.S. Pat. No. 4,746,734, Tsuchiyama et al., issued May 24, 1988; all of said patents being incorporated herein by reference.

[0071] The term cyclodextrin may refer to any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha cyclodextrin, betacyclodextrin, gamma-cyclodextrin and / or their derivatives and / or mixtures thereof. The alphacyclodextrin consists of six glucose units, the beta-cyclodextrin consists of seven glucose units, and the gamma-cyclodextrin consists of eight glucose units arranged in donut-shaped rings. The specific coupling and conformation of the glucose units give the cyclodextrins rigid, conical molecular structures with hollow interiors of specific volumes. The "lining" of each internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms; therefore, this surface is fairly hydrophobic. The unique shape and physical chemical properties of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity.

[0072] As used herein, the term “beta-cyclodextrin” refers to a cyclic oligosaccharide consisting of seven glucose subunits joined by α- ( 1 ,4) glycosidic bonds forming a truncated conical structure. Beta-cyclodextrin has a molecular structure of

[0073]

[0074] Each R may be independently selected from hydrogen, alkyl, hydroxyalkyl, alkanoyl, carboxyalkyl, or moiety capable of reacting to prepare the mesoporous polymeric material. In some embodiments, the moiety capable of reacting to prepare the mesoporous polymeric material is a stryenic double bond.

[0075] As used herein, the term “crosslink” refers to a monomer capable of forming a covalent linkage between one or more cyclodextrins or polymers. For example, if the crosslinker reacts at the end of the polymer it may covalently react with one cyclodextrin moiety of the polymer (e.g., via the styrenic double bond of the functionalized cyclodextrin described herein). The crosslink may or may not further react with other monomers or cyclodextrin units or polymers. For example, the crosslink may be bound to 1, 2, 3, or 4+ monomers or functionalized cyclodextrin units or polymers.

[0076] The mesoporous polymeric material comprises a network of cyclodextrin moieties crosslinked by a plurality of crosslinks. The network comprises

[0077]

[0078] or any combination thereof. The wavy lines on the bonds extending from the glucose subunit of the cyclodextrin moiety indicate the points where the cyclodextrin moiety is repeated to form the CD moiety. Each of the glucose subunits may be independently functionalized. Suitably some or all of the glucose subunits may be functionalized with one or more reactive moieties for forming the network. The wavy lines indicate the points where a polymeric unit may be repeated.

[0079] In some embodiments, A is an unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl. In some embodiments, A is phenyl. A can be covalently bound to the cyclodextrin moiety through an ether bond or a thioether bond.

[0080] In some embodiments, R1and R2are independently alkylammonium-substituted aryl, alkylphosphonium-substituted aryl, alkylphosphonium-substituted biaryl, or hydrogen. In some embodiments, the alkylammonium-substituted aryl is . In some embodiments, the alkylphosphonium-substituted aryl is In some embodiments, the alkylphosphonium-substituted biaryl is

[0081] R5, R6, and R7are independently Ci-6 alkyl or aryl. In some embodiments, R5R6, and R7are independently Ci-6 alkyl, suitably methyl, ethyl, propyl, butyl, pentyl, or hexyl, or aryl, suitably phenyl. In some embodiments, one of R5, R6, and R7is methyl and the other of R5, R6, and R7are a C4-6 alkyl or aryl. In some embodiments, two of R5, R6, and R7are methyl and the other of R5, R6, and R7is a C4-6 alkyl or aryl. In some embodiments, one of R5, R6, and R7is ethyl and the other two of R5, R6, and R7are a C4-6 alkyl or aryl. In some embodiments, two of R5, R6, and R7are ethyl and the other of R5, R6, and R7is a C4-6 alkyl or aryl. In some embodiments, one of R5, R6, and R7is methyl, one of the other of R5, R6, and R7is a Ci-6 alkyl, and the other of R5, R6, and R7is aryl. In some embodiments, R5is methyl, and R6and R7are Ci-6 alkyl or aryl.

[0082] In some embodiments, A1is an aryl. For example, A1is -C6H4-.

[0083] In some embodiments, B is a biaryl.

[0084] In some embodiments, one of R1and R2is alkylammonium-substituted aryl. In some embodiments, one of R1and R2is -C6H4-CH2N+(CH3)(CH3)(C4H9).

[0085] In some embodiments, R3is independently selected from hydrogen, alkyl, hydroxyalkyl, or alkanoyl. In some embodiments, R3is hydrogen.

[0086] The term “aryl” refers to cyclic, aromatic hydrocarbon groups that have 1 to 3 aromatic rings, including monocyclic or bicyclic groups such as phenyl, biphenyl or naphthyl. Where containing two aromatic rings (bicyclic, etc.), the aromatic rings of the aryl group may be joined at a single point (e.g., biphenyl), or fused (e.g., naphthyl). The aryl group may be optionally substituted by one or more substituents, e.g., 1 to 5 substituents, at any point of attachment. The substituents can themselves be optionally substituted. Furthermore, when containing two fused rings the aryl groups herein defined may have an unsaturated or partially saturated ring fused with a fully saturated ring. Exemplary ring systems of these aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, anthracenyl, phenalenyl, phenanthrenyl, indanyl, indenyl, tetrahydronaphthalenyl, tetrahydrobenzoannulenyl, and the like.

[0087] The term “heteroaryl” refers to a monovalent monocyclic or polycyclic aromatic radical of 5 to 18 ring atoms or a polycyclic aromatic radical, containing one or more ring heteroatoms selected from N, 0, or S, the remaining ring atoms being C. Heteroaryl as herein defined also means a polycyclic (e.g., bicyclic) heteroaromatic group wherein the heteroatom is selected from N, 0, or S. The aromatic radical is optionally substituted independently with one or more substituents described herein. The substituents can themselves be optionally substituted. Examples include, but are not limited to, benzothiophene, furyl, thienyl, pyrrolyl, pyridyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrimidinyl, imidazolyl, isoxazolyl, oxazolyl, oxadiazolyl, pyrazinyl, indolyl, thiophen-2-yl, quinolyl, benzopyranyl, isothiazolyl, thiazolyl, thiadiazolyl, thieno[3,2- b]thiophene, triazolyl, triazinyl, imidazo[l,2-b]pyrazolyl, furo[2,3-c]pyridinyl, imidazo[l,2- a]pyridinyl, indazolyl, pyrrolo[2,3-c]pyridinyl, pyrrolo[3,2-c]pyridinyl, pyrazolo[3,4-c]pyridinyl, benzoimidazolyl, thieno[3,2-c]pyridinyl, thieno[2,3-c]pyridinyl, thieno[2,3-b]pyridinyl, benzothiazolyl, indolyl, indolinyl, indolinonyl, dihydrobenzothiophenyl, dihydrobenzofuranyl, benzofuran, chromanyl, thiochromanyl, tetrahydroquinolinyl, dihydrobenzothiazine, dihydrobenzoxanyl, quinolinyl, isoquinolinyl, 1,6-naphthyridinyl, benzo[de]isoquinolinyl, pyrido[4,3-b][l,6]naphthyridinyl, thieno[2,3-b]pyrazinyl, quinazolinyl, tetrazolo[l,5-a]pyridinyl,

[0088] [1.2.4]triazolo[4,3-a]pyridinyl, isoindolyl, pyrrolo[2,3-b]pyridinyl, pyrrolo[3,4-b]pyridinyl, pyrrolo[3,2-b]pyridinyl, imidazo[5,4-b]pyridinyl, pyrrolo[l,2-a]pyrimidinyl, tetrahydropyrrolo[l,2-a]pyrimidinyl, 3,4-dihydro-2H- l / v-pyrrolo[2, 1-bj pyrimidine, dibenzo[b,d]thiophene, pyridin-2-one, furo[3,2-c]pyridinyl, furo[2,3-c]pyridinyl, lH-pyrido[3,4- b][l,4]thiazinyl, benzooxazolyl, benzoisoxazolyl, furo[2,3-b]pyridinyl, benzothiophenyl, 1,5- naphthyridinyl, furo[3,2-b]pyridine, [l,2,4]triazolo[l,5-a]pyridinyl, benzo [1,2,3 ]triazolyl, imidazo[l,2-a]pyrimidinyl, [l,2,4]triazolo[4,3-b]pyridazinyl, benzo[c][l,2,5]thiadiazolyl, benzo [c]

[0089] [1.2.5]oxadiazole, l,3-dihydro-2H-benzo[d]imidazol-2-one, 3,4-dihydro-2H-pyrazolo[l,5- b][l,2]oxazinyl, 4,5,6,7-tetrahydropyrazolo[l,5-ajpyridinyl, thiazolo[5,4-d]thiazolyl, imidazo[2,l- b][l,3,4]thiadiazolyl, thieno[2,3-b]pyrrolyl, 3H-indolyl, and derivatives thereof. Furthermore, when containing two fused rings the heteroaryl groups herein defined may have an unsaturated or partially saturated ring fused with a fully saturated ring.

[0090] The term “alkyl” refers to a straight chain or branched saturated chain having from 1 to 10 carbon atoms. Representative saturated alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-m ethyl- 1 -propyl, 2-methyl-2 -propyl, 2-methyl- 1 -butyl, 3 -methyl- 1 -butyl, 2-methyl-3 -butyl, 2,2-dimethyl- 1-propyl, 2-methyl- 1 -pentyl, 3-methyl- 1-pentyl, 4-methyl- 1- pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl- 1 -butyl, 3,3- dimethyl- 1 -butyl, 2-ethyl- 1 -butyl, butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and the like, and longer alkyl groups, such as heptyl, and octyl and the like. An alkyl group can be unsubstituted or substituted. Alkyl groups containing three or more carbon atoms may be straight or branched. As used herein, “lower alkyl” means an alkyl having from 1 to 6 carbon atoms.

[0091] As used herein, the term “hydroxyalkyl” refers to a hydroxy derivative of an alkylene group (-alkylene-OH).

[0092] The term “alkylene” or “alkylenyl” refers to a divalent radical derived from a straight or branched, saturated alkyl chain, for example, of 1 to 10 carbon atoms or of 1 to 6 carbon atoms (C1-C6alkylenyl) or of 1 to 4 carbon atoms or of 1 to 3 carbon atoms (C1-C3 alkylenyl) or of 2 to 6 carbon atoms (C2-C6 alkylenyl). Examples of C1-C6alkylenyl include, but are not limited to, - CH2-, -CH2CH2-, -C(CH3)2CH2CH2CH2-, -C(CH3)2CH2CH2-, -CH2CH2CH2CH2-, and- CH2CH(CH3)CH2-.

[0093] As used herein, the term “alkanoyl” refers to a moiety having a structure of -C(=O)-R, wherein R group is an alkyl.

[0094] As used herein, the term “carboxyalkyl” refers to a carboxyl derivative of an alkylene group (-alkylene-C(=O)OH).

[0095] In some embodiments, the mesoporous polymeric material has a BET surface area greater than 200 m2g-1. In some embodiments, the mesoporous polymeric material has a BET surface area greater than 210 m2g-1, greater than 220 m2g-1, greater than 230 m2g-1, greater than 240 m2g-1, greater than 250 m2g-1, greater than 260 m2g-1, greater than 270 m2g-1, greater than 280 m2g-1, greater than 290 m2g-1, or greater than 3000 m2g'1.

[0096] As used herein, the terms “aryl,” “heteroaryl,” “biaryl,” or “phenyl” can refer to a group linking two different parts of a molecule, e.g., , which are understood to be a divalent group. The attachment points on these divalent groups can be at any suitable position, for example, a divalent phenyl (-C6H4-) can be , or

[0097] As used herein, the term “BET surface area” refers to the specific surface area of a material evaluated by the BET (Brunauer, Emmett and Teller) theory. The specific surface area is expressed in units of area per mass of sample (m2 / g). The specific surface area of a material is determined by the physical adsorption of a gas (typically nitrogen, krypton, or argon) onto the surface of the sample at cryogenic temperatures (typically liquid nitrogen or liquid argon temperatures). The choice of gas to be used is dependent on the expected surface area and the properties of the sample. Once the amount of adsorbate gas has been measured (either by a volumetric or continuous flow technique), calculations which assume a monomolecular layer of the known gas are applied. BET surface area analysis must be done in the linear region of the BET plot, which could be systematically evaluated using the Rouquerol transform. In some embodiments, the mesoporous polymeric material is prepared from a functionalized cyclodextrin monomer comprising or any combination thereof and comonomer comprising

[0098] The definitions of R1, R2, R3, and for the above functionalized cyclodextrin monomer and comonomer used in the preparation are the same as those described herein for a network of crosslinked cyclodextrin moieties. In some embodiments, the comonomer and functionalized cyclodextrin monomer are incorporated into the mesoporous polymeric material in a ratio of 1 : 1 to 16: 1. In some embodiments, the comonomer and functionalized cyclodextrin monomer are incorporated in a ratio of 16:1 to 1 :1, 14: 1 to 1 : 1, 12: 1 to 1 : 1, 10: 1 to 1 :1, 8: 1 to 1 : 1, 6: 1 to 1 : 1, 4: 1 to 1 :1, or 2:l to 1 :1.

[0099] Another aspect of the technology is to provide a method of purifying a fluid sample comprising one or more pollutants. The method comprises contacting the fluid sample with the mesoporous polymeric material described herein. The methods allow for at least 50 wt % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the mesoporous polymeric material. In some embodiments, at least 55 wt %, at least 60 wt %, at least 65 wt %, at least 70 wt %, at least 75 wt %, at least 80 wt %, at least 85 wt %, at least 90 wt %, or at least 95 wt % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the mesoporous polymeric material.

[0100] As used herein, the term “adsorbent” refers to solid polymeric materials as described herein which remove contaminants or pollutants, typically but not exclusively organic molecules, from a fluid medium such as a liquid (e.g., water) or a gas (e.g., air or other commercially useful gases such as nitrogen, argon, helium, carbon dioxide, anesthesia gases, etc.). Such terms do not imply any specific physical mechanism (e.g., adsorption vs. absorption).

[0101] As used herein, the term “fluid sample” refers to liquid sample such as drinking water, wastewater, ground water, aqueous extract from contaminated soil, or landfill leachate.

[0102] In some embodiments, the pollutant is an anionic micropollutant. In some embodiments, the anionic micropollutant is a perfluorinated alkyl compound. In some embodiments, the perfluorinated alkyl compound is selected from PFCA, PFSA, or combinations thereof.

[0103] As used herein, the term “micropollutanf ’ refers to chemicals present in water resources at ng L"1to μg L-1concentrations as a consequence of human activities. Concerns about their negative effects on human health and the environment motivate the development of technologies that remove MPs more effectively. Micropollutants encompass a range of organic and inorganic pollutants of anthropogenic origin. Micropollutants occur above natural background levels due to human activity and may persist in the environment for decades or centuries due to slow degradation. Micropollutants may be characterized by their use or chemical characteristics. Micropollutants may include industrial chemicals (such as flame retardants or surfactants, per- and polyfluoroalkyl substances (PFAS)), pharmaceuticals, food and beverage additives, or agricultural chemicals. Micropollutant (MP) span a wide variety of physiochemical properties including surface charge, size, and chemical functionality. Charged MPs can be cationic, anionic, or zwitterionic and are typically difficult to remove in the presence of complex matrix constituents like natural organic matter (NOM) using conventional adsorption materials like activated carbon.

[0104] As used herein, the term “PFAS” refers to per- and polyfluoroalkyl substances. PFAS are a group of chemicals used to make fluoropolymer coatings and products that resist heat, oil, stains, grease, and water. Fluoropolymer coatings can be in a variety of products. These include clothing, furniture, adhesives, food packaging, heat-resistant non-stick cooking surfaces, and the insulation of electrical wire. PFAS are also used in many other consumer, commercial, and industrial products, including aqueous film forming foam (AFFF), which is used to extinguish fires. Many PFAS are a concern because they do not break down in the environment, can move through soils and contaminate drinking water sources, build up (bioaccumulate) in fish and wildlife. PFAS have been found in rivers and lakes and in many types of animals on land and in the water.

[0105] Anionic PFASs present a particular environmental problem because of their resistance to biodegradation or chemical transformation and correlation to negative health effects. PFASs have been used in the formulations of thousands of consumer goods and are present in aqueous filmforming foam (AFFF) formulations used to suppress aviation fires in training scenarios. As a result, they have contaminated surface and ground waters near thousands of airports and military installations. In 2018, the Environmental Working Group reported that over 110 million people in the United States were exposed to drinking water with PFAS concentrations above 2.5 ng L-1. PFASs have been linked to cancers, liver damage, thyroid disease and other health problems.

[0106] As used herein, the term “PFCA” refers to perfluorinated carboxylic acids (PFCAs), or perfluoroalkylcarboxylic acids. PFCAs are compounds of the formula CnF(2n+1)CO2H. The simplest example is trifluoroacetic acid. These compounds are organofluorine analogues of ordinary carboxylic acids, but they are stronger by several pKa units and they exhibit great hydrophobic character.

[0107] As used herein, the term “PF SA” refers to perfluorosulfonic acids and are chemical compounds of the formula CnF(2n+1)SO3H. The simplest example of a perfluorosulfonic acid is the trifluoromethanesulfonic acid. Another aspect of the technology is to provide a method of preparing a mesoporous polymeric material comprising a network of cyclodextrin moieties crosslinked by a plurality of cyclodextrin branch units. The method comprises contacting a functionalized cyclodextrin monomer with a comonomer in the presence of a free radical initiator under conditions sufficient to prepare the network of cyclodextrin moieties crosslinked by a plurality of crosslinks (e.g., cyclodextrin branch units).

[0108] In some embodiments, the functionalized cyclodextrin monomer comprises or any combination thereof,

[0109] In some embodiments, the comonomer comprises formula

[0110] In some embodiments, for the above formula:

[0111] A is an unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl;

[0112] R1and R2are independently alkylammonium-substituted aryl, alkylphosphoniun- substituted aryl, alkylphosphonium-substituted biaryl, or hydrogen;

[0113] R3is independently selected from hydrogen, alkyl, hydroxyalkyl, alkanoyl, or carboxy alkyl; the alkylammonium-substituted aryl is the alkylphosphonium-substituted aryl is the alkylphosphonium-substituted biaryl is

[0114] R5, R6, and R7are independently Ci-6 alkyl or aryl;

[0115] A1is an aryl; and

[0116] B is a biaryl.

[0117] In some embodiments, the free radical initiator is AIBN. AIBN is the chemical azobisisobutyronitrile (CAS No. 78-67-1). Other examples of suitable free radical initiators for the methods of preparing the mesoporous polymeric material described herein include, but are not limited to, AMBN, ADVN, ACVA, dimethyl 2,2'-azobis(2-methylpropionate), AAPH, 2,2'- azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, TBHP, a,α- Dimethylbenzyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, BPO, dicyandiamide, cyclohexyl tosylate, diphenyl(methyl)sulfonium tetrafluoroborate, benzyl(4-hydroxyphenyl)- methylsulfonium hexafluoroantimonate, (4-hydroxyphenyl)methyl-(2-methylbenzyl)sulfonium hexafluoroantimonate, the atom transfer radical polymerization catalysts and initiators described in Chem. Rev. 2001, 101, 9, 2921-2990, the xanthate chain transfer agent / initiator described in Macromolecules 2017, 50, 19, 7433-7447, and nitroxi de-based initiators described in pChem

[0118] Record, 2005, 5, 27-35 and p Polymer Reviews, 2011, 51, 2, 104-137. In some embodiments, the molar ratio of the functionalized cyclodextrin monomer to the comonomer is from 1 :16 to 2: 1. In some embodiments, the molar ratio of the functionalized cyclodextrin monomer to the comonomer is from 1 :16 to 1 : 1, from 1 : 15 to 1 :1, from 1: 14 to 1 : 1, from 1: 13 to 1: 1, from 1 :12 to 1 :1, from 1 :11 to 1 :1, from 1 : 10 to 1: 1, from 1 :9 to 1: 1, from 1 :8 to 1: 1, from 1 :7 to 1: 1, from 1 :6 to 1 : 1, from 1 :5 to 1 : 1, from 1 :4 to 1 : 1, from 1 :3 to 1 : 1, or from 1 :2 to 1 : 1.

[0119] In some embodiments, the conditions comprise a reaction temperature from 40 °C to 100 °C. In some embodiments, the conditions comprise a reaction temperature from 60 °C to 100 °C, 70 °C to 90 °C, or from 75 °C to 85 °C.

[0120] In some embodiments, the conditions comprise a reaction time of less than 1.5 hours, or less than 1.3 hours, or less than 1.1 hours.

[0121] In some embodiments, the conditions comprise a reaction solvent selected from dimethylformamide. Other examples of suitable solvents for the methods of preparing the mesoporous polymeric material described herein include, but are not limited to, water, toluene, benzene, acetonitrile, acetone, ethyl acetate, methanol, A-methyl-2-pyrrolidinone, and tetrahydrofuran.

[0122] In some embodiments, the network of cyclodextrin moieties crosslinked by a plurality of crosslinks is produced in a yield of greater than 85% or greater than 90%. In some embodiments, the network of cyclodextrin moieties crosslinked by a plurality of crosslinks is produced in a yield of greater than 92%, greater than 94%, greater than 96%, greater than 98%, or greater than 99%.

[0123] In some embodiments, the method further comprises extraction of the network of cyclodextrin moieties crosslinked by a plurality of crosslinks in methanol. In some embodiments, the method further comprises activation of the network of cyclodextrin moieties crosslinked by a plurality of crosslinks by supercritical carbon dioxide. In some embodiments, activation happens after extraction. As used herein, the term “supercritical carbon dioxide” refers to the fluid state of carbon dioxide where it is held at or above its critical temperature and critical pressure.

[0124] Unless otherwise specified or indicated by context, the terms “a”, “an”, and “the” mean “one or more.” For example, “a molecule” should be interpreted to mean “one or more molecules.”

[0125] As used herein, “about”, “approximately,” “substantially,” and “significantly” will be understood by persons of ordinary skill in the art and will vary to some extent on the context in which they are used. If there are uses of the term which are not clear to persons of ordinary skill in the art given the context in which it is used, “about” and “approximately” will mean plus or minus <10% of the particular term and “substantially” and “significantly” will mean plus or minus >10% of the particular term.

[0126] As used herein, the terms “include” and “including” have the same meaning as the terms “comprise” and “comprising.” The terms “comprise” and “comprising” should be interpreted as being “open” transitional terms that permit the inclusion of additional components further to those components recited in the claims. The terms “consist” and “consisting of’ should be interpreted as being “closed” transitional terms that do not permit the inclusion additional components other than the components recited in the claims. The term “consisting essentially of’ should be interpreted to be partially closed and allowing the inclusion only of additional components that do not fundamentally alter the nature of the claimed subject matter.

[0127] All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0128] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0129] Preferred aspects of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred aspects may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect a person having ordinary skill in the art to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

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[0152] EXAMPLES

[0153] The Examples include systematic evaluation of some of the variables that influence material properties and PFAA adsorption by StyDex derivatives and polymers, such as the comonomer structure and loading, the regiochemistry of the CD monomer, and the CD size (Figure 1). The following Examples include the synthesis, characterization, and material and adsorption properties of 20 StyDex derivatives and polymers.

[0154] Example 1

[0155] Per- and polyfluoroalkyl substances (PFASs) are a class of fluorinated surfactants used in many industrial and consumer products including firefighting foams, food packaging, cookware, waterproof textiles, and personal care products.1'4PFASs are bioaccumulative and environmentally persistent due to their innate thermal and chemical stability.5'7Chronic exposure to even trace amounts of some PFASs has been associated with adverse health impacts, such as high cholesterol, thyroid disease, low birth weight, liver damage and kidney cancer.8'10Our understanding of the negative effects associated with many individual PFASs and PF AS mixtures continues to develop.11, 12Because of their widespread use and environmental persistence, PFAS contamination is now a major health and environmental crisis, affecting water resources around the world.13'17In March 2023, the U.S. EPA proposed enforceable limits for six PFASs in drinking water.18For example, the proposed maximum contaminant levels (MCLs) for two legacy perfluoroalkyl acids (PFAAs), perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are 4 ng L-1, along with combined limits at similar concentrations for four others.19, 20As PFAS regulations are established around the world, it is clear that PFASs should be phased out for all but the most critical and environmentally containable use cases, while legacy contamination is addressed through environmental remediation and degradation into benign byproducts.21'26

[0156] Crosslinked β-cyclodextrin (β-CD) polymers have emerged as promising adsorbents to remove PFASs and other classes of organic contaminants (e.g., pharmaceuticals and organic dyes) from water.27'33Compared to conventional adsorbents, such as granular activated carbon (GAC) or ion-exchange (IX) resins, β-CD polymers generally exhibit faster adsorption kinetics, higher affinity and capacity, and limited interference from natural organic matter or inorganic constituents that reduce the removal efficiencies of GACs and IX resins.34'36The inventors recently reported a general approach to prepare porous styrene-functionalized β-cyclodextrin (StyDex) polymers that were more modular and amenable for fundamental PFAS adsorption studies than the previous generation of CD polymers.32The first example of this next-generation approach used a radical copolymerization between a modified β-CD monomer with seven polymerizable styrene groups covalently linked at the 6’ positions of β-CD and vinyl comonomers, such as methacrylate derivatives bearing quaternary ammonium groups. The resulting cationic polymer exhibited excellent removal of many PFASs in batch experiments at the low adsorbent dose of 1 mg L-1. Based on studies in nanopure water and aqueous electrolyte solutions, PFAS adsorption mechanisms of the StyDex polymer are hypothesized to include hydrophobic interactions with the polymer surface, host-guest interactions with the β-CD cavities, and electrostatic attraction with the cationic comonomers. In a separate study, the cationic StyDex polymer outperformed GAC and IX resins in removing selected PFAAs and pharmaceuticals from full-scale municipal wastewater effluent samples, based on batch adsorption experiments and breakthrough times in rapid small-scale column tests.37EXPERIMENTAL SECTION

[0157] Materials. All chemicals and reagents used in synthesis were either purchased from commercial sources and used as received, or prepared following literature procedures, a- Cyclodextrin (>98%), β-cyclodextrin (>97%), y-cyclodextrin (>98%), 4-vinylbenzyl chloride (90%), 2,2’-azobis(2-methylpropionitrile) (AIBN, 98%), 2-aminoethyl methacrylate hydrochloride (90%), [2-(methacryloyloxy)ethyl]trimethylammonium chloride solution (75% in H2O), 2-(dimethylamino)ethyl methacrylate (98%), l-bromo-4-(cholormethyl)benzene (>97%), 4- vinylphenylboronic acid (>95%), palladium(II) acetate (99%), cesium carbonate (99%), tri cyclohexylphosphine tetrafluoroborate (PCy3 HBF4, 97%), trimethylphosphine solution (1.0 M in toluene), tri-n-butylphosphine (97%), triphenylphosphine (99%), LC-MS grade methanol, LC- MS grade water, HPLC grade acetone, and ammonium acetate (>98%) were purchased from Sigma- Aldrich and used as received. N, N'-Dimethylbutylamine (>97%) and (vinylbenzyl)trimethyl ammonium chloride (97%) were purchased from Santa Cruz Biotechnology and used as received. Azoxystrobin (99.4%), diazinon (98.5%), and linuron (99.7%) were purchased from Fluka and used as received.

[0158] Eight perfluoroalkylcarboxylic acids (PFCAs), ranging from 4-11 carbon atoms, were purchased as a mixture dissolved in methanol at a concentration of 2 mg L-1each (PFC-MXA, Wellington Laboratories). Four perfluoroalkylsulfonic acids (PFSAs), consisting of 4, 6-8 carbon atoms, were purchased as a mixture dissolved in methanol at a concentration of 2 mg L-1each (PFS-MXA, Wellington Laboratories). Perfluoro-2-methyl-3-oxahexanoic acid (GenX) was purchased as a solid (SynQuest Laboratories) and dissolved in MeOH at a concentration of 1 g L- k The thirteen PFAAs were combined into a single spike mixture to yield a concentration of 0.5 mg L-1each by diluting the stock solutions (PFC-MXA, PFS-MXA, and GenX) using 98:2 of Milli-Q water:MeOH. This spike mixture was added to experimental samples to generate an initial concentration of 1 μg L-1for each PFAA in rotator batch experiments. Nine isotope-labeled internal standards (ILISs) were purchased as a mixture dissolved in methanol at a concentration of 2 mg L-1each (MPFAC-MXA, Wellington Laboratories). The nine ILISs were combined into a single spike mixture to yield a concentration of 250 μg L-1each by diluting stock MPFAC-MXA using Milli-Q water. Three non-PFAA analytes: azoxystrobin, linuron, and diazinon were purchased as solids (Fluka) and dissolved in MeOH at a concentration of 1 g L-1. The three neutral contaminants were combined into a single spike mixture to yield a concentration of 1 mg L-1each by diluting the stock solutions using 98:2 of Milli-Q water eOH. The stock solutions were stored at -20 °C and the spike mixtures were stored at 4 °C until usage. A summary of all PFAA and non- PFAA standards and their respective ILISs used for quantification is provided in the Examples.

[0159] Safety Statement: Trimethyl phosphine solution (1.0 M in toluene) is a pyrophoric compound and should be handled carefully by appropriately trained individuals using inert atmosphere techniques. Refer to the compound’s Safety Data Sheet (SDS). Synthesis of StyDex Monomers a and y. The inventors previously reported the synthesis and characterization of StyDex monomer β32This synthetic approach was adapted to prepare StyDex monomers a and y (Figure 7). The synthesis of intermediates, per-6-iodo-α- cyclodextrin, per-6-iodo-y-cyclodextrin, per-6-thiol-α- cyclodextrin (thiol-α- CD), and per-6-thiol-y-cyclodextrin (thiol-y-CD) is detailed in the Examples. A general synthesis of a and y was performed as follows: thiol-α- CD or thiol-y-CD (5 mmol, 1 equiv) was dissolved in DMSO (60 mL) and degassed with N2 sparging for 30 min. Potassium carbonate (15 mmol, 3 equiv for thiol-α- CD or 20 mmol, 4.5 equiv for thiol-y-CD) was added. The reaction mixture was stirred at room temperature for an additional 30 min. 4-Vinylbenzyl chloride (30.5 mmol, 6.1 equiv for thiol-α- CD or 40.5 mmol, 8.1 equiv for thiol-y-CD) was then added dropwise to the mixture under N2 atmosphere. The mixture was stirred at room temperature for 24 h, precipitated into brine (500 mL), and stirred for an additional 10 min before filtering. The filtrate was washed with copious amounts of methanol, superficially dried, and then resuspended in methanol (200 mL). This process was repeated three times. The resulting filtrate was dried on a high vacuum line at room temperature for 24 h, yielding StyDex monomers a and y as off-white powders with isolated yields of 86 and 82%, respectively. The solid monomers were stored at -8 °C to minimize autopolymerization. A summary of and13C nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HMRS) spectra assignments for a and y is listed in the Examples.

[0160] Synthesis of Comonomers e-i. Comonomers e-i were synthesized via a nucleophilic substitution reaction between a nucleophile (trimethyl phosphine, triphenylphosphine, tri- / z- butylphosphine, or N, N'-dimethylbutylamine) and 4-vinylbenzyl chloride (Scheme 1). A general nucleophilic substitution was performed as follows: 4-Vinylbenzyl chloride (10.00 mmol, 1.5 equiv) and nucleophile (6.67 mmol, 1 equiv) were dissolved in anhydrous toluene (40 mL) in a dry Schlenk flask. The solution was heated at 50 °C for 14 h under N2 atmosphere, with gradual precipitation of the comonomer product observed. The precipitate was filtered, washed with toluene (3 x 20 mL), and dried on a high vacuum line for 24 h at room temperature, yielding comonomers e, g, h, and i as white solids with isolated yields between 53-92% and no chromatography required to purify any of the final products. Note: trimethylphosphine is a pyrophoric compound and should be handled carefully by appropriately trained individuals using inert atmosphere techniques. To prepare comonomer f, 4-chl oromethyl-4’ -vinyl- 1, 1’ -biphenyl (f) was first synthesized based on a Suzuki-Miyaura coupling procedure reported by Pei and coworkers.38The Suzuki-Miyaura product f underwent a nucleophilic substitution reaction with trimethylphosphine in anhydrous toluene as described above, yielding comonomer f. Detailed synthetic procedures and spectroscopic characterization of f and f are provided in the Examples.

[0161] Synthesis of StyDex polymers. StyDex 1-20 were prepared via radical polymerization between a StyDex monomer (a, β, β ’, or y) and a vinyl comonomer (a-i) using azobi s(isobutyronitrile) (AIBN) as a free radical initiator (Figure I).32A general polymerization was performed as follows: StyDex monomer (0.50 mmol, 1 equiv), comonomer (1.00 mmol, 2 equiv), and AIBN (0.20 mmol, 0.4 equiv) were dissolved in DMF (4 mL) in a dry Schlenk flask. Note: 1, 4, 8, or 16 equiv of either comonomer d or e is also compatible using this procedure. The monomer solution was subjected to three freeze-pump-thaw cycles and heated to 80 °C for 1 h, with polymer gelling observed within 30 min. The crosslinked solid gel was broken apart with a metal spatula, transferred to a teabag, and sealed with staples. This teabag was subjected to an overnight continuous liquid / solid extraction in methanol, followed by supercritical CO2 washing in which the residual solvents were replaced by CO2, resulting in StyDex 1-20 with high isolated yields at multi gram scales (Table 1). StyDex 1-12 were prepared with a feed ratio of 2 equiv of comonomer a-i, as described in the general polymerization. StyDex 13-20, which contains 1, 4, 8, or 16 equiv of either comonomer d or e, were also synthesized following this procedure.

[0162] Characterization. The monomers were characterized by1H,13C, and31P NMR spectroscopy, high resolution mass spectrometry (HRMS), and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS). The StyDex polymers were characterized by cross polarization magic angle spinning (CPMAS)13C solid-state (ss) NMR spectroscopy, N2 porosimetry, Fourier transform infrared (FTIR) spectroscopy, zeta potential, and C, H, N, P and S combustion analysis.

[0163] Instrumentation. Activation of polymers by supercritical CO2 washing was performed on a Leica EM CPD 300. Prior to supercritical CO2 washing, all polymer samples were placed in tea bags and Soxhlet extracted in methanol for 14 hours. Wet polymer samples were placed into the drying chamber of the instrument. The drying chamber was cooled to 15°C and filled with CO2 at the “slow” setting with 120 s delay. After the delay, CO2 exchange occurred at the speed setting of “5” for 80 cycles. The samples were then cooled to 40°C on the “slow” setting. The pressure in the chamber was also released on the “Slow 50%” setting. The polymer porosity and Brunauer- Emmett-Teller surface areas (SBET) were collected on a Micromeritics ASAP 2420 Accelerated Surface Area and Porosity Analyzer. Approximately 30-40 mg of polymer was used for each analysis. The polymers were degassed on the instrument at 100 °C for 24 h until the off-gas rate was constantly reading less than 1.0 μmHg / min. N2 isotherms were generated by incremental exposure to ultrahigh purity nitrogen up to 1 atm in a liquid nitrogen bath at 77K. The SBETwere calculated using the linear region (P / Po of 0.05-0.15) of the isotherm using adsorption models included in the instrument software (Micromeritics ASAP-2420 V4.00). Pore size distributions were analyzed using non-local density functional theory (NLDFT) analysis on the MicroActive software using a model of N2 being adsorbed and desorbed into cylindrical pores of a porous oxide surface. Solution1H,13C, and31P NMR spectra were acquired on a Bruker AvanceIII-500 MHz spectrometer with a TXO 5mm Prodigy probe w / Z-Gradient, or a Bruker AdvanceIII-500 MHz spectrometer with a CryoProbe 5mm DCH w / Z-Gradient. All solution spectra were recorded at 25 °C with 32 scans and calibrated using DMSO-d6as an internal reference, 2.50 ppm for 'H NMR and 39.52 ppm for13C NMR. All spectra are phase and baseline corrected. CPMAS13C and31P ssNMR spectra were acquired on a Bruker Avancelll HD 400 MHz spectrometer with a 4mm HX probe w / Z-Gradient. All ssNMR spectra were recorded at 25 °C and calibrated using adamantane as an external reference at 38.3 ppm for13C NMR. The reference was converted to tetramethylsilane at 0.00 ppm. The sample spinning rate was controlled by a Bruker pneumatic MAS unit at 10 kHz. For13C spectra, 8192 scans were collected for each sample. For31P spectra, 64 scans were collected for each sample. FTIR data were collected at 25 °C on a ThermoFisher Nicol et iS20 FTIR Spectrometer equipped with a ZnSe ATR attachment. The spectrum was collected in attenuated total reflectance mode in the range of 4000 to 600 cm'1. The data were averaged over 32 scans. The OMNIC software was used for the data acquisition. HRMS spectra of monomers were acquired on an Agilent 6545 Q-TOF Mass Spectrometer, with Electrospray Ionization (ESI) as an ion source. The instrument is equipped with an Agilent 1200 Series HPLC binary pump and autosampler. Analysis was performed with direct injection with methanol as solvent unless specified otherwise. Data acquisition and analysis were done using Agilent MassHunter Data Workstation and Qualitative Analysis software. See Examples for PFAA quantification and instrumentation. MALDI-TOF mass spectra were collected Bruker Rapiflex MALDI-TOF, using FlexControl data acquisition software. Samples were prepared using a 2,5- dihydroxybenzoic acid (DHB) matrix. A saturated solution of sample in 2,5-DHB matrix was first prepared and followed by subsequent dilutions at 1:20 (samplematrix) prior to analysis. All measurements were taken in reflectron positive (RP) mode. All data was processed using FlexAnalysis software. Elemental Analysis of C, H, N, P and S was performed by Robertson Microlit Laboratories. Combustion analysis was used for carbon, hydrogen, and nitrogen on a Perkin-Elmer Model 2400 CHN Analyzer, and titration was used for sulfur and phosphorus. Zeta (ζ )potential of each StyDex polymer suspension was collected at 25 °C on a Malvern Instruments Zetasizer Nano ZSP. A 1 mg / mL StyDex polymer suspension was created and stirred overnight. A 2 mL aliquot of the stock suspension was added to 18 mL of 10 mM NaCl solution (pH adjusted to 7) and stirred for 4 h at 25 °C prior to measurement. For each measurement, 1 mL aliquot was added to a disposable capillary cuvette DTS1070 sample cell (Malvern Panalytical). Triplicate measurements per polymer sample was taken.

[0164] Rotator Batch Experiments. Batch adsorption experiments were designed and performed as previously described.32, 34'36, 39-42Briefly, experiments were conducted in 15 mL polypropylene (PP) centrifuge tubes (Corning) with either a 10 mL Mili-Q water matrix with a pH range from 5.6 to 6.6 or a 10 mL NaCl matrix (2 mM). The PFAA spike mixture (thirteen PFAAs, 0.5 mg L-1each) was added into the PP tube to generate an initial concentration of 1 μg L-1for each PFAA. The spiked centrifuge tubes were loaded onto a tube revolver (ThermoFisher) and rotated overnight at 40 rpm to provide a homogeneous solution. To prepare the adsorbent dose of 0.1, 1, or 10 mg L-1, stock adsorbent suspensions were first created. For example, 10 mg of a StyDex polymer was added to a 20 mL amber vial containing 10 mL Mili-Q water, sonicated for 1 min to break up small aggregates, and stirred for 60 min to yield a homogenous suspension at 1 g L-1. The stock adsorbent suspension was subsequently spiked into the PP tube to yield the desired adsorbent dose. Sample tubes containing target PFAA concentration and adsorbent dose were placed onto the tube revolver and rotated for 0.5, 9 or 48 h at 40 rpm and 23 °C. At the predetermined time, 8 mL of experimental sample was filtered with a 0.45 μm cellulose acetate syringe filter (Restek) into a 10 mL glass LC-MS vial (ThermoFisher), spiked with 12 μL of the isotope-labeled internal standard (ILIS) mixture (250 μg L-1) to yield a target concentration of 375 ng L-1, and stored at 4 °C until analysis. The neutral contaminant sample tubes were prepared following the same procedure but without the addition of ILIS mixture. Control samples were prepared following the same procedure and conditions without the addition of StyDex polymer. For analytical methods, ILIS mixture preparation, PFAA and neutral contaminant analyte quantification and data analysis, see Examples. Experiments were conducted with StyDex polymers at particle sizes of 125-212 μm or >425 μm as described in each section.

[0165] Example 2

[0166] RESULTS AND DISCUSSION

[0167] Characterization of StyDex monomers and comonomers. The inventors previously reported the synthesis and characterization of StyDex monomer β, in which styrene groups were selectively installed at each of the seven 6’ positions (C-6) of β-CD.32To evaluate the effect of the CD size on PFAA adsorption, this synthetic approach was adapted to prepare StyDex monomers a and y (Figure 7). The primary hydroxyl groups (C-6) of α-CD and y-CD were converted first to iodines and then to thiols. The enhanced nucleophilicity and acidity of thiols relative to the remaining hydroxyl groups (C-2 and C-3) of α- CD and y-CD allowed selective benzylation in the presence of K2CO3 and 4-vinylbenzyl chloride, yielding the monomers a and 7. The 'H NMR spectra of a and y confirmed successful installation of six and eight styrene groups per CD molecule, respectively, based on the appearance of aromatic and vinylic resonances in the 5.0-7.5 ppm region and the disappearance of thiol resonances at 2.16 ppm. The integration of the aromatic resonances (7.0-7.5 ppm) relative to the resonance of α- CD at 4.81 ppm or y-CD at 4.89 ppm was consistent with either six or eight styrene groups per CD, respectively. Data from HRMS acquisitions and the13C NMR spectra of a and y were also consistent with their expected structures. The inventors separately evaluated whether the regiochemistry of the CD functionalization affected PFAA adsorption. Instead of limiting the functionalization to the 6’ positions, styrene groups were non-selectively installed at the 2’, 3’, and 6’ positions of / TCD, based on a previously reported procedure.37This direct etherification between β-CD and 4-vinylbenzyl chloride in the presence of NaOH yielded monomer β ’ with a distribution of styrene groups at the 2’, 3’, and 6’ positions of the glucose subunits of β-CD, in contrast to the three-step synthesis of β in which styrene groups are exclusively located at the 6’ positions. An average of 7.4 styrene groups per CD were incorporated for β ’, as estimated based on the integration of aromatic proton resonances relative to β-CD resonances in 3.5-5.0 ppm region. The distribution of [M+Na]+adducts in the MALDI-TOF MS chromatogram was also consistent with this degree of functionalization The MALDI-TOF MS spectrum of StyDex monomer β’ shows the monomer was observed with a distribution of [M+Na]+ adducts. The most abundant adduct (m / z=l 969.351) correspond to seven styrene groups per β-CD molecule. On average, 7.4 styrenes per β-CD molecule was estimated for StyDex monomer p’, based on a previously reported method.37To evaluate the effect of comonomer structure on PFAA adsorption, the inventors selected nine methacrylic or styrenic vinyl comonomers containing primary and tertiary amines, quaternary ammonium ions, and quaternary phosphonium ions (Figure 1). Comonomers a-d were commercially available.

[0168] Comonomers e-i were synthesized via nucleophilic substitution reactions (Schemes 1 and 2). The1H,13C and31P NMR spectra and HRMS of comonomers e-i were consistent with their expected structures.

[0169] Characterization of StyDex 1-20. Radical polymerization provides a tunable and versatile method to adjust StyDex compositions to establish structure-adsorption relationships (Table 1). For example, the inventors synthesized StyDex 1-4 to evaluate the PFAA adsorption of various ammonium cations, which are found in both commercial and novel adsorbents, compared to StyDex 5, which instead contains phosphorus-based cationic groups. To probe the effect of comonomer hydrophobicity, the performance of StyDex 6 was compared to that of StyDex 3-5. StyDex 7-9 were studied to understand the effect of steric shielding around the cation by alkyl or aryl substituents. StyDex 4, 10, and 11 probe the effect of the CD size on the selectivity of PFAA adsorption. The performances of StyDex 12 and StyDex 4 were compared to illustrate how the regiochemistry of styrene substitution on the CD monomer impacts PFAA adsorption, whereas StyDex 13-20 were synthesized to explore the effect of comonomer loading.

[0170] Table 1. Characterization of StyDex Polymers.

[0171] aMeasured incorporation ratio was derived based on C, H, N, P, and S combustion analysis. bzeta potentials were measured in 10 mM NaCl (pH=7) at room temperature.

[0172] The CPMAS13C ssNMR spectra of StyDex 1-20 confirmed the incorporation of StyDex monomers and comonomers in all cases. In the ssNMR spectra, the resonance corresponding to the vinyl carbon atoms (113 ppm) of StyDex monomers was either not detected or very small, suggesting a high degree of polymerization (Figures 8-19). Broadened resonances between 20 and 55 ppm indicate the formation of the polymer backbone from vinyl carbons of both monomers. In the spectra of StyDex 1-3, carbonyl carbon atoms of the methacrylate comonomers were observed at 176 ppm, a shift from 166 ppm in solution NMR of comonomers a-c (Figures 8-10). The characteristic N-m ethyl or N-m ethylene carbon atoms were observed for StyDex 1-4 and 9-12 (Figures 8-11, 16-19). The spectra of StyDex 4 and 10-12, which contain different StyDex monomers but the same feed ratio of comonomer d, are nearly indistinguishable (Figures 11, 17- 19). However, in the spectrum of StyDex 4, a double peak was observed between the 50-55 ppm region, as opposed to the single peak corresponding to N-m ethyl carbon atoms for StyDex 10-12. The characteristic P -methyl or P-methylene carbon atoms were observed at 7.91 ppm for StyDex 5 and 6 (Figures 12 and 13) and at 13.22 ppm and 23.55 ppm for StyDex 8 (Figure 15). However, they were not observed for StyDex 7, because they are obscured by other resonances between 20- 55 ppm (Figure 14). The31P ssNMR of StyDex 5-8 and 17-20 further confirmed the incorporation of phosphonium ion-containing comonomers, based on the observed resonances between 20 and 30 ppm (Figures 20 and 21). IR spectroscopy of StyDex 1-20 was also consistent with their expected structures.

[0173] StyDex derivatives 1-20 were formed as porous crosslinked networks with compositions similar to the comonomer feed ratios. To verify the expected comonomer composition of each StyDex polymer, particularly for StyDex 13-20 that were prepared with 1-16 mol equiv of comonomers d or e with respect to one mol of StyDex monomer, the inventors calculated the comonomer incorporation ratio, following a previously reported method based on combustion analysis of C, H, N, P and S.32In general, the measured incorporation ratio is consistent with the feed ratio for most StyDex polymers, except for StyDex 15, 16, 19, and 20. In these polymers with higher comonomer loading, the measured incorporation ratio is lower than the monomer feed ratios, such as 12.6: 1 (d :) and 11.3: 1 (e / / ) instead of 16: 1 (Table 1). These lower incorporation ratios are also consistent with the lower isolated yields at 16 equiv of comonomer d (88%) and e (86%) compared to other StyDex polymers (Table 1). The porosity, Brunauer-Emmett-Teller ( SBET) surface area, and pore width distribution of StyDex 1-20 were characterized by N2 porosimetry (Figures 31-50). Most StyDex polymers exhibited permanent porosity and SBETbetween 10 and 270 m2g'1, which is similar to many CD- containing polymers (Table I).31, 32The pore width distributions of StyDex 1-20 ranged from 18 to 60 A, with exception of StyDex 1 which exhibited up to 80 A pore width (Figures 31-50). The most common pore width is between 18 and 30 A. The inventors note that SBETis generally lower for polymers containing styrenic comonomers (80-200 m2g'1) compared to ones containing methacrylic comonomers (240-270 m2g'1). Furthermore, polymers with higher comonomer loadings resulted in reduced SBET, as evident by StyDex 13-20 (Table 1), which the inventors attribute to a lower degree of crosslinking due to decreasing weight content of StyDex monomers, which function as crosslinkers. This trend between the degree of crosslinking and SBETis consistent with other porous materials.27, 43, 44StyDex 16 and 20 exhibited the highest swelling ratios despite having a lower SBETthan polymers in their respective loading series (Figure 22). For example, the swelling ratio of StyDex 15 (SBET: 20 m2g'1) is 1030% compared to 290% for StyDex 4 (SBET: 150 m2g'1), following a 24 h soaking of the polymer in Milli-Q water. Lastly, all StyDex polymers, except StyDex 2, were found to exhibit positively charged surfaces, based on the measured zeta potentials of these polymer suspensions in a 10 mM NaCl solution at neutral pH (Table 1). This observation is consistent with polymers containing cationic functional groups as well as past materials.32The zeta potential of StyDex 2 was found to be weakly negative (-7.7 ± 2.6 mV ), indicating that the experimental pH (7) is greater than the point of zero charge of the polymer.45,46Overall, the physical and spectroscopic characterization performed on this large series of StyDex polymers formed crosslinked networks, most of which were microporous and mesoporous, with the expected structures and cationic permanent surface charges. These polymers were next evaluated in batch adsorption experiments to elucidate the effect of their structural variations on PFAA adsorption.

[0174] Effect of Comonomer Structure on Adsorption Kinetics. Batch adsorption experiments revealed how the comonomer structure affects PFAA adsorption. StyDex polymers containing quaternary ammonium and phosphonium ions exhibited faster adsorption kinetics than the polymers containing primary or tertiary amines. The inventors evaluated removal efficiencies of 10 mg L-1of StyDex 1-5 for thirteen PFAAs (initial concentrations of 1 μg L-1each) in Milli-Q water with a contact time of 0.5 h, 0.9 h, or 48 h, providing insight into adsorption kinetics and the extent of equilibrium removal. StyDex polymers were prepared with various comonomers at the same feed ratio, including primary amines (StyDex 1), tertiary amines (StyDex 2), quaternary ammonium ions (StyDex 3 and 4), and quaternary phosphonium ions (StyDex 5). StyDex 1 and 2 exhibited relatively slow adsorption kinetics, based on 28-56% and 17-30% removal of the PFAAs, respectively, after 0.5 h contact time (Figure 2A). StyDex 2 exhibited slower kinetics than StyDex 1 for all PFAAs, which is consistent with its negatively charged surface, as determined by its zeta potential of -7.7 ± 2.6 mV (Table 1). In contrast, 55-99% removal was observed by StyDex 3-5, suggesting that amine-functionalized StyDex 1 and 2 are relatively ineffective at adsorption. This observation corroborates pH-dependent adsorption of amine-functionalized adsorbents as the extent of amine protonation, which is favored under acidic conditions, affects the number of electrostatic interactions.46'48Quaternary ammonium and phosphonium ions do not have available Bronsted acid-base processes over typical pH ranges encountered in water, such that PFAA removal is likely to be largely pH-independent. This behavior is demonstrated through the effective PFAA removal performance of StyDex 3-5 after 0.5 h contact time (Figure 2A).47The fast adsorption kinetics of these polymers is also consistent with past systems.32, 33Generally, adsorbents with high BET and mesoporosity exhibit fast adsorption kinetics due to more readily available pore-facilitated diffusion of adsorbates.49, 50Nevertheless, for StyDex 1 and 2, which had the highest SBET (270 and 240 m2g'1, respectively, Table 1), their adsorption kinetics were significantly slower, further demonstrating the influence of the comonomer structure on PFAA adsorption kinetics.

[0175] Effect of Relative Comonomer Hydrophobicity on Adsorption Kinetics. The relative hydrophobicity of the comonomer structure also affects adsorption kinetics. StyDex 4, which contains styrenic quaternary ammonium comonomers, exhibited higher removal for each of the selected PFAAs after 0.5 and 9 h contact times than StyDex 3, which has less hydrophobic methacrylic comonomers (Figure 2A). The inventors attribute the enhanced adsorption kinetics to the hydrophobic local environments generated by the styrenic comonomers, which have more capacity for hydrophobic interactions with the fluoroalkyl tails of PFAAs. To further evaluate this effect, StyDex 6, which contains biphenyl phosphonium ions (comonomer f), was compared to StyDex 5, which is based on the corresponding sytrenic comonomer d. The inventors found that StyDex 5 and 6 exhibited similar PFAA removal efficiencies at adsorbent doses of 1 mg L-1and 10 mg L-1and after 0.5, 9 and 48 h contact times, suggesting that the additional aromatic ring does not further enhance adsorption kinetics (Figures 23 and 24). This observation potentially suggests a nuanced range of relative hydrophobicities of the local environment that are favorable for PFAA adsorption kinetics.

[0176] Effect of Comonomer Structure on Equilibrium Adsorption. Equilibrium adsorption experiments performed after 48 h contact time provided further insights into favorable comonomer structures for PFAA adsorption. In general, PFAA removal increased for StyDex 1-6 with longer contact times, except for some short-chain PFAAs in which desorption was observed between 9 h and 48 h (Figures 2, 23 and 24). For example, the average removal of the short-chain PFBA by StyDex 1 and 2 decreased from 32% and 29%, respectively, after 9 h contact time and to 14% and 10%, respectively, after 48 h contact time (Figures 2B and 2C). The inventors attribute the decreased equilibrium removal to competitive adsorption among PFAAs, in which the adsorption of long-chain PFAAs is more favorable than short-chain PFAAs.51This conclusion is further supported by the increase of long-chain PFAA removal after 48 h, such as a 5% increase in PFUnA removal by StyDex 2 (Figure 2C). StyDex 3-5 outperformed StyDex 1 and 2, based on higher removal efficiency (generally >90%) for each of the selected PFAAs, suggesting that quaternary ammonium and phosphonium ions result in both fast adsorption kinetics and high equilibrium removal (Figure 2C). Despite the kinetic advantage of StyDex 4 over StyDex 3, the two polymers exhibited similar extents of equilibrium removal across the selected PFAAs, except for PFBA, PFPeA, and PFHxS (Figure 2C). This finding suggests that the relative hydrophobicity of the comonomer structure does not influence the extent of equilibrium removal, which is further supported by the similar PFAA adsorption observed at 10 mg L-1and 1 mg L-1of StyDex 5 and 6 after 48 h contact time (Figures 23 and 24).

[0177] Effect of Cation Identity on PFAA Adsorption. The structure of the cationic comonomer influences PFAA adsorption. Quaternary ammonium and phosphonium ions differ both in size and charge distribution. For example, the positive charge of the phosphonium ion is localized on phosphorus, whereas the positive charge of the ammonium ion is more distributed among the carbon atoms bonded to nitrogen.52'54Because of these differences, phosphonium-containing materials (e.g., ionic liquids and polyelectrolytes) have shown superior material properties compared to their ammonium ion counterparts.52, 55, 56However, the inventors found that StyDex 4 and 5 exhibited similar SBET(ca. 150 m2g-1), as well as similar swelling ratios (ca. 280%) and positive zeta potentials of 9.2 ± 3.9 and 6.5 ± 3.6, respectively (Table 1 and Figure 22). To investigate the effect of cation identity on PFAA adsorption, the inventors further evaluated StyDex 4 and 5 at adsorbent doses of 5 mg L-1and 1 mg L-1(Figure 3). The removal results are graphed as box and whisker plots, in which the median of each box represents the removal efficiency of the polymer for all selected PFAAs, regardless of alkyl chain-length or anionic head group. For example, 5 mg L-1of StyDex 4 exhibited a median removal of 78% for the selected PFAAs after 0.5 h, compared to the median removal of 87% by StyDex 5 (Figure 3 A). Based on unpaired two-samples Wilcoxon test, StyDex 5 exhibited statistically significant, faster kinetics after 0.5 h than StyDex 4 at an adsorbent dose of 5 mg L-1(p<0.001) and 1 mg L-1(p<0.05). Moreover, 5 mg L-1of StyDex 5 also exhibited near complete removal of the selected PFAAs, which is statistically significant (p<0.001) relative to the median removal of 93% by StyDex 4, suggesting that polymers containing phosphonium ions resulted in faster adsorption kinetics than ammonium ions (Figure 3). In contrast, 10 mg L-1of StyDex 4 and 5 exhibited similar extents of PFAA adsorption (Figure 2).

[0178] In contrast to their differences in adsorption rate, the cation identity did not result in different resistance to adsorption inhibition. The inventors evaluated 10 mg L-1of StyDex 4 and 5 in a 2 mM NaCl matrix after 9 h contact time to probe how these ions inhibit PFAA removal for polymers containing ammonium and phosphonium ions (Figure 25). The inventors previously attributed adsorption inhibition to either direct-site competition in which inorganic anions compete with the selected PFAAs for adsorption sites, or an increased screening effect that attenuates electrostatic interactions at higher electrolyte concentrations.32Similar levels of adsorption inhibition were observed for StyDex 4 and 5 across the selected PFAAs in a 2 mM NaCl matrix, indicating that the cation identity did not result in differences in adsorption inhibition (Figure 25). Nonetheless, these results demonstrated that quaternary phosphonium ions can enhance bulk PFAA adsorption kinetics and represent alternatives to quaternary ammonium ions.

[0179] Effect of Steric Shielding of the Cation on PFAA Adsorption. Steric shielding of the cation by either alkyl or aryl substituents resulted in slower adsorption kinetics and variable equilibrium removal. To probe the effect of steric shielding of the cation on PFAA adsorption, the inventors evaluated quaternary phosphonium comonomers with trimethyl (StyDex 5), triphenyl (StyDex 7), and tri-«-butyl (Stydex 8) substituents at an adsorbent dose of 10 mg L-1. StyDex 5 clearly outperformed StyDex 7 and 8 after 0.5 h contact time (Figure 4), based on 76-98% removal across the selected PFAAs by StyDex 5 compared to 0-10% by StyDex 7 and 0-30% by StyDex 8 (Figure 4). This finding was in spite of StyDex 7 and 8 exhibiting more positive zeta potentials of 16.3 ± 3.8 and 18.7 ± 1.9 mV, respectively, compared to 6.5 ± 3.6 mV for StyDex 5. The inventors attribute this difference to steric interactions between triphenyl and tri-n-butyl substituents and the PFAAs (Table 1). These results did not discriminate between alkyl and aryl substituents, based on overlapping error bars for each PFAA (Figure 4). Following longer contact time, PFAA adsorption significantly improved for StyDex 7 and 8, based on 52-91% and 69-88% removal after 48 h contact time, respectively. Consequently, steric shielding of the cation influences adsorption kinetics more strongly than adsorption affinity. StyDex 7 and 8 also exhibited variable equilibrium removal after 48 h, based on large error bars for each of the selected PFAA (Figure 4B and C), which the inventors attribute to steric shielding of the cation reducing the probability of favorable adsorption interactions.

[0180] Effect of a Hydrophobic Group on an Accessible Cation. The combination of having a hydrophobic group adj acent to an accessible cation center was found to exhibit superior adsorption kinetics and equilibrium removal. StyDex 9, which contains benzylic N, N'-dimethybutyl ammonium ions, exhibited effective and comparable removal across the selected PFAAs as StyDex 4 and 5 at 10 mg L-1dose and 0.5 h (Figures 2 and 4). Furthermore, StyDex 9 achieved near complete removal (>95%) of the selected PFAAs after 9 h and did not exhibit desorption of short-chain PFAAs, as shown by similar levels of removal between 9 h and 48 h contact times (Figure 4). Notably, StyDex 9 was the most effective polymer composition in this study. This finding further supports the importance of both an accessible cation center and a hydrophobic comonomer structure. Together, these results demonstrated the nuanced effects of steric shielding of the cation on PFAA adsorption kinetics and equilibrium removal.

[0181] Effect of the CD Size on PFAA Adsorption. StyDex polymers containing β-CD exhibited superior PFAA and neutral contaminant adsorption in an aqueous electrolyte when compared to their α-CD and y-CD analogs, demonstrating the importance of size-selective host-guest interactions. Weiss-Errico and O’Shea quantified the strength of host-guest complexes between PFOA and CDs of various sizes, based on NMR titration experiments. They found that PFOA binds strongly to β-CD (K1:1 = 5x105M-1), weakly to y-CD (K1:1 = 800 M-1), and had no measurable binding to α- CD.57The inventors hypothesized that crosslinked β-CD-based polymers are selective adsorbents for PFAA, because they combine the key physisorption mechanisms of GACs and IX resins while also providing size-selective host-guest binding sites. CD rings are also important for targeting a broader scope of contaminants. To evaluate these interactions within a polymer network and in the presence of electrostatic and hydrophobic forces, the inventors evaluated 1 mg L-1of f>- CD-based StyDex 4, α- CD-based StyDex 10, and y-CD-based StyDex 11, given similar removal efficiencies observed at 10 mg L-1dose (Figure 26). The individual CD cavity volumes of StyDex 4, 10, and 11 are 262 A3, 174 A3, and 427 A3, respectively. Each polymer contains two molar equiv. of comonomer d per mol of the StyDex monomer to directly compare the effect of the CD size.

[0182] Following 48 h contact time, 1 mg L-1of StyDex 4 exhibited the most effective short-chain PFAA adsorption, based on 62% PFBA and 84% PFPeA removal by StyDex 4, compared to 44% and 59%, respectively, by StyDex 10 or 50% and 78%, respectively, by StyDex 11 (Figure 5A). The inventors attribute the effective short-chain PFAA adsorption by StyDex 4 to the presence of selective host-guest binding sites provided by β-CD As PFAA chain length increases, StyDex 4, 10, and 11 generally exhibited similar removal efficiencies, with the exception of StyDex 10 for PFHxA, PFHpA, and GenX in which StyDex 10 exhibited reduced removal despite having the most positive zeta potential (26.1 ± 0.5 mV, Figure 5A and Table 1). The similar removal efficiencies may indicate that β-CD cavities exhibit lower affinities than other binding sites at dilute contaminant concentrations, and thus are mainly advantageous in increasing adsorbent capacity.

[0183] To better probe the extent of host-guest interactions among StyDex 4, 10, and 11, electrostatic attractions by quaternary ammonium ions were attenuated in a 2 mM NaCl matrix. For example, PFBA adsorption was completely inhibited in the salt matrix for all three polymers, which is consistent with the fact that short-chain PFAA adsorption primarily relies on electrostatic attraction (Figure 5B).32StyDex 4 exhibited significantly superior adsorption across the selected PFAAs than StyDex 10 and 11, such as 20% PFHpA removal by StyDex 4 compared to less than 2% removal by both StyDex 10 and 11 (Figure 5B). Assuming the selected PFAAs experience similar extent of hydrophobic interactions with the surface of each polymer based on similar material properties, the inventors attribute the superior removal efficiency by StyDex 4 to its selective host-guest sites.

[0184] Effect of the CD Size on Neutral Contaminant Adsorption StyDex 4 continued to exhibit superior removal of neutral contaminants when compared to StyDex 10 and StyDex 11, highlighting the advantage of host-guest sites in targeting a broader scope of contaminants. The inventors selected three neutral contaminants: the herbicide linuron, the insecticide diazinon, and the fungicide azoxystrobin, which exhibited high affinity for a nonionic β-CD polymer based on a previous generation of crosslinking chemistry.58In both Mili-Q water and 2 mM NaCl matrices, StyDex 4 clearly outperformed StyDex 10 and StyDex 11, which the inventors attribute to the ability of β-CD to form host-guest complexes with linuron, diazinon and azoxystrobin (Figure 5A). Ineffective removal of linuron by StyDex 10 suggests that the contaminant exceeds the size of a- CD cavities, and that host-guest interactions are the primary adsorption mechanism for this contaminant. These results collectively demonstrated the importance of host-guest binding sites to target PFAAs and neutral contaminants that form selective host-guest complexes with β-CD. Furthermore, StyDex polymers can be tailored with a- and y-CDs, in combination with charged comonomers, for adsorption of a broad scope of contaminants.

[0185] Effect of the CD Functionalization Regiochemistry on PFAA Adsorption. The regiochemistry of non-selective CD monomer functionalization exhibited more effective PFAA adsorption. StyDex 4 was prepared with β, which was functionalized with styrene groups exclusively on the 6’ positions of β-CD. In contrast, StyDex 12 was prepared with β ’, which contains a distribution of styrene groups on the 2’, 3’, and 6’ positions of β-CD. Based on the removal results after 0.5, 9 and 48 h contact times at an adsorbent dose of 10 mg L-1, StyDex 12 exhibited overall more effective PFAA adsorption than StyDex 4, particularly for short-chain PFAAs (Figure 27). This finding suggests that some degree of functionalization of secondary hydroxyl groups of / FCD does not affect PFAA adsorption as the remaining hydroxyl groups can participate in hydrogen bonding with PFAAs. Furthermore, the styrene groups in β ’ were not observed to block PFAA from entering β-CD cavity. The results demonstrates that polymers prepared from the one-step synthesis of StyDex monomer p as opposed to the three-step syntheses for p, resulted in effective PFAA adsorption, which is advantageous for material scalability considerations.

[0186] Effect of the Comonomer Loading on PFAA Adsorption. StyDex polymers prepared with different loadings of quaternary ammonium ions (StyDex 4, 13-16) and quaternary phosphonium ions (StyDex 5, 17-20) exhibited different material properties and PFAA adsorption. The inventors evaluated 0.1 mg L-1of StyDex polymers in each series with a contact time of 0.5, 9, and 48 h. Notably, this is the lowest adsorbent dose the inventors have ever studied for β-CD-based polymers. As expected, the overall removal efficiencies of both polymer series significantly decreased due to the low adsorbent dose. For short-chain perfluoroalkyl carboxylic acids (PFCAs), both polymer series generally experienced minimal removal after 0.5 h contact time regardless of the comonomer loading or the cation identity (Figure 6A and B). This finding suggests that 0.1 mg L-1of both polymer series lack the sufficient amount of active adsorption sites for fast PFCA adsorption kinetics. At 10 mg L-1dose, both polymer series, except for StyDex 17, exhibited over 78% removal of the selected PFAAs after 0.5 h contact time, which the inventors attribute to the presence of sufficient active adsorption sites due to the higher adsorbent dose (Figures 28 and 29). After 9 h contact time, short-chain PFCA removal by both polymer series improved as expected (Figure 6 A and B). The inventors found that StyDex 4 (2 equiv) and StyDex 16 (16 equiv) exhibited significantly better removal of long-chain PFCAs with 8-11 carbon atoms after all three contact times (Figure 6A, C, and E). For the phosphonium polymer series, StyDex 18 (4 equiv) and StyDex 20 (16 equiv) had more effective removal of PFCAs with 8-11 carbon atoms after 9 and 48 h contact times (Figure 6D and E). Both trends were also observed for long- chain PFSAs with 6-8 carbon atoms (Figure 30). This finding potentially indicates the presence of multiple adsorption mechanisms that are independently optimized at different comonomer loadings. For example, lower comonomer loading (2 or 4 equiv) optimizes the transport of PFAA to the CD cavity, while higher comonomer loading (16 equiv) may result in more favorable electrostatic interaction. However, this is purely speculation and the measured removal differences may be attributed to a difference in copolymer morphology at the respective optimal loadings. Furthermore, removal results from comonomer loading series at either 10 or 0.1 mg L-1demonstrated a threshold for sufficient removal. At 10 mg L-1adsorbent dose, adsorption kinetics and the extent of equilibrium removal by quaternary ammonium series was generally not affected in contrast to their phosphonium analogs (Figures 28 and 29). At 0.1 mg L-1, removal performance by both polymer series was influenced depending on the PFAA chain-length, the comonomer loading, and the cation identity.

[0187] Example 3

[0188] Monomer Synthesis and Characterization (Figure 7)

[0189] Prior to the synthesis of StyDex monomers a and y, α- cyclodextrin (<z-CD) and y- cyclodextrin (y-CD) were dried on a high vacuum line at 80 °C for 24 h. Triphenylphosphine (92.52 mmol, 18 equiv to 1 equiv α- CD or 24 equiv to 1 equiv y-CD) and iodine (92.52 mmol, 18 equiv to 1 equiv α- CD or 24 equiv to 1 equiv y-CD) were dissolved in anhydrous DMF (100 mL) in a dry round bottom flask and stirred at room temp for 30 min under a N2 atmosphere. To this stirred solution, a-CD (5.14 mmol, 1 equiv) or y-CD (3.86 mmol, 1 equiv) was added and heated at 80 °C for 15 h under a N2 atmosphere. The solution was then concentrated under vacuum to half the volume. Sodium methoxide in methanol (4.4 M, 24 mL) was added to adjust the pH of the solution to 9-10. The solution was kept at room temperature for 30 min to destroy the formate esters formed in the reaction and then precipitated into cold methanol (1 L). The filtrate was washed with copious amounts of methanol, superficially dried, and then resuspended in methanol (1 L) for several days. Methanol was replaced every two days until the final product filtrate ran clean. The final product was dried on a high vacuum line at room temperature for 24 h, yielding per-6-iodo-rz-cyclodextrin (iodo-rz-CD) and per-6-iodo-y-cyclodextrin (iodo-y-CD) with isolated yields of 82 and 80%, respectively.

[0190] To a dry round bottom flask, iodo-rz-CD or iodo-y-CD (5 mmol, 1 equiv) was dissolved in anhydrous DMF (100 mL). Thiourea (32.5 mmol, 6.5 equiv to 1 equiv iodo- α- CD or 8.5 equiv to 1 equiv iodo-y-CD) was then added and the reaction mixture was heated to 70 °C under a N2 atmosphere. After 19 h, the mixture was concentrated under vacuum to give a yellow oil, which was dissolved in deionized water (50 mL). Sodium hydroxide (13 mmol) was added, and the reaction mixture heated to a gentle reflux for 1 h under a N2 atmosphere. The resulting suspension was acidified with aqueous NaHSO4to precipitate the product. The product was filtered, washed thoroughly with deionized water (50 mL), and superficially dried. The product was then resuspended in deionized water (50 mL) and the minimum amount of sodium hydroxide was added to give a clear solution. The product was then reprecipitated with the addition of NaHSO4The resulting fine precipitate was filtered off and dried on a high vacuum line for 48 h at room temperature, yielding per-6-thiol-rz-cyclodextrin and per-6-thiol-y-cyclodextrin as off-white powders with isolated yields of 84 and 78%, respectively. For the synthesis of StyDex monomers a and y, refer to the Experimental Section of the main article.

[0191] Heptakis-(6-deoxy-6-vinylbenzyl)-rz-Cyclodextrin, StyDex monomer a. 1H NMR (500 MHz, DMSO-d6): 6 7.23 (d, 12H), 7.15 (d, 12H), 6.61 (dd, 6H), 5.71 (d, 6H), 5.66 (d, 6H), 5.54 (d, 6H), 5.19 (d, 6H), 4.87 (d, 6H), 3.99-3.87 (m, 6H), 3.87-3.73 (m, 12 H), 3.73-3.60 (q, 12H), 3.55 (t, 6H), 3.04-2.71 (m, 12H) ppm.13C NMR (126 MHz, DMSO-d6): 5 138.33, 136.32, 135.49, 129.14, 125.99, 113.71, 101.96, 84.81, 72.77, 71.92, 71.76, 36.49, 32.55 ppm. ESI-HRMS (m / z): calculated for C90H108O24S6, 1765.56; found, 1788.5486 as [M+Na]+.

[0192] Heptakis-(6-deoxy-6-vinylbenzyl)-y-Cyclodextrin, StyDex monomer y.1H NMR (500 MHz, DMSO-d6): 5 7.20 (d, 16H), 7.10 (d, 16H), 6.60 (dd, 8H), 6.06-5.85 (m, 16H), 5.74-5.65 (m, 8H), 5.18 (d, 8H), 4.96 (d, 8H), 3.90-3.48 (m, 40H), 3.05 (d, 8H), 2.81 (dd, 8H) ppm.13C NMR (126 MHz, DMSO-d6): 6 138.26, 137.37, 135.50, 129.01, 125.91, 113,73, 102.04, 84.47, 72.51, 72.39, 72.17, 36.57, 32.95 ppm. ESI-HRMS (m / z): calculated for C120H144O32S8, 2353.74; found, 2376.7309 as [M+Na]+.

[0193] Note: The synthesis and characterization of β and have been previously reported.32, 37

[0194] See Reference 32 below for and Reference 2 below for β ’.

[0195] Scheme 1. Synthesis of Comonomers e, g, h, and i.

[0196] 4-Vinylbenzyl(trimethyl) phosphonium chloride, comonomer e. 'H NMR (500 MHz, DMSO-d6): δ 7.52 (d, 2H), 7.30 (dd, 2H), 6.74 (dd, 1H), 5.86 (d, 1H), 5.30 (d, 1H), 3.82 (d, 2H),

[0197] 1.81 (d, 9H) ppm.13C NMR (126 MHz, DMSO-d6): δ 136.67, 136.03, 130.15, 129.04, 126.82, 114.91, 21.91, 6.98 ppm. ESI-HRMS (m / z): calculated for C12H1P+, 193.11; found, 193.1167.

[0198] 4-Vinylbenzyl(triphenyl) phosphonium chloride, comonomer g. 'H NMR (500 MHz, DMSO-d6): δ 7.93-7.88 (m, 3H), 7.78-7.67 (m, 12H), 7.33 (d, 2H), 6.96 (dd, 2H), 6.65 (dd, 1H),

[0199] 5.82 (d, 1H), 5.26 (d, 1H), 5.22 (d, 2H) ppm.13C NMR (126 MHz, DMSO-d6): 5 137.02, 135.77, 135.10, 134.05, 131.11, 130.11, 127.43, 126.45, 117.94, 115.33, 28.01 ppm. ESI-HRMS (m / z): calculated for C27H24P+, 379.16; found, 379.1641.

[0200] 4-Vinylbenzyl(tri-zz-buty;) phosphonium chloride, comonomer h. 'H NMR (500 MHz, DMSO-d6): δ 7.52 (d, 2 H), 7.36 (dd, 2H), 6.74 (dd, 1H), 5.87 (d, 1H), 5.29 (d, 1H), 3.92 (d, 2H), 2.26-2.13 (m, 6 H), 1.48-1.32 (m, 12 H), 0.88 (t, 9H) ppm.13C NMR (126 MHz, DMSO-d6): 8 136.73, 135.94, 130.27, 128.95, 126.78, 114.92, 25.16, 23.37, 22.54, 17.37, 13.22 ppm. ESI- HRMS (m / z): calculated for C21H35P+ 318.25; found, 319.2560 as [M+H]+ 4-Vinylbenzyl(;V,A’-dimethylbutyl) ammonium chloride, comonomer i.!H NMR (500 MHz, DMSO-d6): δ 7.60 (d, 2H), 7.55 (d, 2H), 6.79 (dd, 1H), 5.95 (d, 1H), 5.37 (d, 1H), 4.59 (s, 2H), 3.32-3.25 (m, 2H), 2.98 (s, 6H), 1.81-1.72 (m, 2 H), 1.36-1.26 (m, 2 H), 0.94 (t, 3 H) ppm.13C NMR (126 MHz, DMSO-d6): δ 138.79, 135.86, 133.28, 127.66, 126.48, 116.08, 65.71, 63.15, 49.05, 23.81, 19.30, 13.55 ppm. ESI-HRMS (w / z): calculated for Ci5H24N+, 218.19; found, 218.1910.

[0201] Scheme 2. Synthesis of Comonomer f.

[0202] To prepare comonomer f, 4-chloromethyl-4’-vinyl-l,l’-biphenyl (f) was first synthesized based on a Suzuki-Miyaura coupling procedure reported by Pei and coworkers (Scheme 2).381- Bromo-4-(chloromethyl)benzene (1.2 mmol, 1 equiv), 4-vinylphenylboronic acid (1.2 mmol, 1 equiv), palladium(II) acetate (0.024 mmol, 0.02 equiv), and PCy3 HBF4 (0.048 mmol, 0.04 equiv) were dissolved in toluene (4 mL) in a dry Schlenk flask. Insoluble cesium carbonate (2.4 mmol, 2 equiv) was added to the toluene solution. The mixture was then degassed for 10 min and filled with N2. Additional toluene (4 mL) and H2O (400 pL) were added to the mixture under a N2 atmosphere. The mixture was heated at 80 °C for 2h under N2. After the completion of the reaction, the reaction mixture was cooled to room temperature, quenched with H2O (40 mL), and extracted with ethyl acetate (3 x 20 mL). The combined ethyl acetate extracts were dried over anhydrous Na2SO4 and filtered and subjected to a rotary evaporation. The residue was purified by flash column chromatography on silica gel using 60-to-40 hexane-to-ethyl acetate, yielding f as a clear liquid with an isolated yield of 47%. The Suzuki-Miyaura product f (1.00 mmol, 1.0 equiv) and trimethylphosphine (1.50 mmol, 1.5 equiv) were dissolved in anhydrous toluene (6 mL) in a dry Schlenk flask. The solution was heated at 50 °C for 14 h under N2 atmosphere, with gradual precipitation of the comonomer product observed. The precipitate was filtered, washed with toluene (3 x 20 mL), and dried on a high vacuum line for 24 h at room temperature, yielding comonomer f with an overall isolated yields of 42% over two steps.

[0203] 4-Chloromethyl-4’-vinyl-l,r-biphenyl(trimethyl) phosphonium chloride, comonomer f.1H NMR (500 MHz, DMSO-d6): 8 7.76 (d, 2H), 7.69 (d, 2H), 7.58 (d, 2H), 7.41 (dd, 2H), 6.78 (dd, 1H), 5.89 (d, 1H), 5.31 (d, 1H), 3.84 (d, 2H), 1.83 (d, 9H) ppm.13C NMR (126 MHz, DMSO- d6): 6 139.03, 138.64, 136.50, 136.12, 130.53, 128.71, 127.31, 126.79, 114.64, 29.16, 7.04 ppm. ESI-HRMS (w / z): calculated for CISH22P+, 269.15; found, 269.1449.

[0204] The1H NMR spectra of comonomers e-i were consistent with their expected structures, based on the appearance of aromatic resonances in the 6.8-7.8 ppm region as well as the appearance of the three vinylic resonances in the 5.0-7.0 ppm region. The characteristic coupling with methylene and methyl resonances by the phosphorous nucleus was observed as doublets at 3.82 ppm and 1.81 ppm, respectively, for both e and f. Similarly, a doublet corresponding to the methylene resonances was observed at 5.18 ppm for g, in addition to the appearance of triphenyl resonances in the 7.5-8.0 ppm region. Comonomer h contains ten pairs of methylene protons, which appear as a sharp doublet at 3.92 ppm and as multiplets at 2.20 ppm and 1.39 ppm. The characteristic coupling with methylene and methyl resonances by nitrogen nucleus was observed as multiplets at 4.59 ppm, 3.30 ppm, and 2.98 ppm for i. The integration of each proton resonance relative to the vinylic resonance at 6.75 ppm was consistent with the correct number of proton resonances for comonomers e-i. The31P spectra of comonomers e-h revealed that the phenyl substituents of g resulted in the largest shielding of phosphorous nucleus at 32.61 ppm, whereas / / -butyl substituents of h resulted in the least shielding at 22.65 ppm. The13C spectra of comonomers e-i also indicated the correct number of carbon resonances. Furthermore, high resolution mass spectrometry of comonomers e-i confirmed their expected structures (Figures 20 -24).

[0205] Example 4

[0206] Polymer characterization

[0207] C, H, N, P and S combustion analysis was performed by Robertson Microlit Laboratories. Measured incorporation ratio (comonomer / StyDex monomer) for each StyDex polymer was calculated based on a previously reported method.32The results are shown in Table 2. Table 2. C, H, N, P, and S Combustion Analysis Results n / a. = not available Swelling Test

[0208] For the swelling test, 100 mg of StyDex polymer was dried on a high vacuum line at room temperature overnight. The dry mass (Wd) was recorded for each polymer, with a mass difference of 1-4 mg observed for most polymers. The dried polymer was added to a 20 mL polypropylene bottle filled with 15 mL of Milli-Q water. After 24 h, the polymer was carefully filtered using a 0.2 μm cellulose acetate membrane filter (Sterlitech). The wall of the bottle was rinsed several times with Milli-Q water. Excess water on the surface of the polymer was removed using Kim wipes. The wet mass (Ws) of each polymer was recorded. Triplicate samples were setup for each polymer. The swelling ratio (%) was calculated using Equation 1 : Swelling ratio ( 100 (1)

[0209] Example 5

[0210] PFAA and Neutral Pollutant Quantification and Analytical Methods

[0211] Samples from rotator batch experiments were measured by large-volume injection and high-performance liquid chromatography (HPLC) coupled with a quadrupole-orbitrap mass spectrometer (ThermoFischer Scientific) using a parallel reaction monitoring (PRM) method for PFAA quantification and a full-scan MS and data-dependent MS2 acquisition method for neutral contaminant quantification.

[0212] For PFAAs, the HPLC-HRMS was operated with ESI in negative polarity mode. The mobile phase consisted of (A) 20 mM ammonium acetate in LC-MS grade water and (B) LC-MS grade methanol (100 %). Samples were injected at 5 mL volumes onto a Hypersil Gold dC18 12 μm 2.1 x 20 mm trap column (ThermoFisher Scientific) at room temperature (21- 22°C) via a loading pump (LPG) delivering 1 mL min1of a mobile phase gradient at 99% A and eluted onto an Atlantis® dC18 5 μm 2.1 x 150 mm analytical column (Waters) at 25°C via an elution pump (HPG) delivering 0.3 mL min'1of a mobile phase gradient at 60% A. The mobile phase gradient program is described in Table 6. Table 3 and Table 4 provide more details on the PFAA analytes.

[0213] For neutral contaminants (azoxy strobin, diazinon, and linuron), the HPLC-HRMS was operated with ESI in positive polarity mode. The mobile phase consisted of (A) LC-MS grade water and (B) LC-MS grade methanol both amended with 0.1 vol% formic acid. Samples were injected at 5 mL volumes onto an XB ridge C-18 Intelligent Speed (2.1 mm x 20 mm; particle size 5 μm) trap column (Waters) at room temperature (21- 22°C) via a loading pump (LPG) delivering 1 mL min'1of a mobile phase gradient at 99% A and eluted onto an XB ridge C18 (2.1 mm x 50 mm; particle size 3.5 μm) analytical column (Waters) at 25°C via an elution pump (HPG) delivering 0.3 mL min1of a mobile phase gradient at 60% A. The mobile phase gradient program is described in Table 7. Table 5 provides more details on the neutral contaminant analytes.

[0214] For all analytes, a calibration curve (n = 9) was prepared with concentrations ranging from 0 to 1000 ng L-1and spiked with 12 pL of the ILIS mixture (250 μg L-1) for the PFAAs or no ILISs for the neutral contaminant analytes. Quantification was from the calibration curve using product ion-to-ILIS peak area ratio responses by 1 / x weighted linear least-squares regression for PFAAs or parent ion peak area responses by 1 / x weighted linear least-squares regression for neutral contaminant analytes. Calibration curves were run at the beginning of the analytical run. Instrument blanks (with no target analytes) were run before and after the calibration curve and each batch of triplicate samples. One quality control (QC) sample (with target analytes) was placed at the start of every analytical sequence, to ensure minimal contamination and adequate MS performance (QC tolerance set at ± 30%). Analytes were quantified if the recovery in the control experiment was between 50% and 150% of the spiked amount and the calibration curve had an R2value greater than 0.85. The inventors note that four PFAAs that were included in the experiments did not pass the QC procedures and are excluded from Table 3 and from the discussion in the manuscript (the PFCAs with 12-14 carbon atoms and the PFSA with 10 carbon atoms).

[0215] The average and the standard deviation of removal efficiency was calculated based on the measured concentrations of the triplicate experimental samples. The removal efficiency (%) by each StyDex polymer was determined using Equation 2: (2) in which Co (μg L-1) is the average measured concentration of an analyte in the spike controls (no adsorbent); and Ct (μg L-1) is the concentration of an analyte in water at sampling time t. Any incidental analyte losses were assumed to occur to the same extent in control and experimental samples, and were not explicitly considered in Equation 2.

[0216] Table 3. Summary of all PFAAs that passed the QC procedure and were included in the data analysis and ILISs.

[0217]

[0218] aMixtures were supplied by Wellington Laboratories or, in the case of Perfluoro-2-methyl-3 -oxahexanoic acid, by SynQuest Laboratories

[0219] Table 4. Analytical information of PF AA target compounds and their respective ILISs.

[0220] aPFCA is carboxylic acid, PFSA is sulfonic acid, Other is neither carboxylic acid nor sulfonic acid.bNumber of fluorinated carbon.

[0221] Table 5. Analytical information of azoxystrobin, diazinon, and linuron. a. Units in ng L-1; reported LODs are direct inject concentration; b. “Fragment” means most intense fragment used for LOD determination.

[0222] Table 6. The mobile phase gradient program (PFAAs).

[0223] "Mobile Phase A consisted of 20 mM ammonium acetate in LC-MS grade water.bMobile Phase B consisted of LC-MS grade methanol (100 %).

[0224] Table 7. The mobile phase gradient program (neutral contaminants).

[0225] "Mobile Phase A consisted of 0.1 vol% formic acid in LC-MS grade water.bMobile Phase B consisted of 0.1 vol% formic acid in LC-MS grade methanol. Example 6

[0226] CONCLUSIONS

[0227] A StyDex polymer containing A, A ’-dimethylbutyl ammonium ions exhibited the most effective PFAA adsorption out of all the polymers studied, indicating that performance depends strongly on the specific identities of hydrophobic groups attached to the ammonium cations. Furthermore, a StyDex polymer containing β-CD was found to exhibit size-selective host-guest interactions with PFAAs and other organic contaminants in aqueous electrolyte when compared to otherwise similar polymers containing either α- CD or y-CD. The inventors also showed that StyDex polymers containing β-CD monomers with an average of about seven styrene groups and random regiochemistry performed similarly to polymers derived from the previous β-CD monomer prepared with exactly seven styrenes located at each 6’ position. Because the former monomer can be prepared directly from β-CD in a single step, this finding is encouraging for material scalability. Together, these results offered important insights into design criteria and the potential for StyDex polymers to address societal challenges for PFAS removal.

[0228] Among polymers containing common nitrogen-based functional groups featured in commercial and novel adsorbents, StyDex 3 and 4, which contain quaternary ammonium ions, exhibited superior PFAA adsorption kinetics and equilibrium removal compared to StyDex 1 and 2, which contain either primary or tertiary amines, respectively. StyDex 4, which contains a more hydrophobic styrenic comonomer structure compared to methacrylic comonomer structure of StyDex 3, exhibited enhanced PFAA adsorption kinetics. However, an additional aromatic ring, the biphenyl group of StyDex 6, did not result in further enhancement of adsorption kinetics. StyDex 5, which contains quaternary phosphonium ions, exhibited comparable PFAA adsorption compared to their quaternary ammonium analogs at various adsorbent doses, suggesting that quaternary phosphonium groups represent alternatives to ammonium groups for PFAA adsorption. Steric shielding of the cation by either aryl (StyDex 7) or aryl substituents (StyDex 8) resulted in significantly slower adsorption kinetics and variable equilibrium removal, highlighting the importance of accessible cations for rapid PFAA uptake. The inventors found that StyDex 9, which contains a comonomer that combines a hydrophobic group attached to a still-accessible cation, exhibited the most effective PFAA adsorption out of all polymers studied. This finding further demonstrates the importance of steric shielding of the cation and the hydrophobicity of the comonomer structure. Size-selective host-guest interactions preferentially target PFAA and a broader scope of contaminants, based on β- CD-based StyDex 4 outperforming α- CD-based StyDex 10 and y-CD-based StyDex 11 in aqueous electrolyte. StyDex 12, which was prepared with StyDex monomer β ’ that contains non-selective regiochemistry of styrene groups, exhibited more effective PFAA adsorption than StyDex 4 containing regio-selective styrene groups. This finding is advantageous for material scalability given the facile, one-step room temperature synthesis of β as opposed to the three-step synthesis of β Lastly, the inventors found that the comonomer loading affects both material properties and PFAA adsorption. StyDex polymers containing high cation loading exhibited significantly reduced SBET, yet superior PFAA adsorption kinetics and equilibrium removal. The removal results at either 10 or 0.1 mg L-1adsorbent dose demonstrated a threshold for sufficient removal. At 10 mg L-1dose, StyDex polymers containing high cation density exhibited superior PFAA adsorption. At 0.1 mg L-1, the inventors found 2 and 16 equiv of quaternary ammonium ions or 4 and 16 equiv of quaternary phosphonium ions to exhibit superior PFAA adsorption, which suggest multiple adsorption mechanisms are independently effective at different comonomer loading.

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Claims

CLAIMSWe claim:

1. A mesoporous polymeric material comprising a network of cyclodextrin moi eties crosslinked by a plurality of crosslinks, the network comprisingor any combination thereof, wherein— A is an unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl;R1and R2are independently alkylammonium-substituted aryl, alkylphosphoniumsubstituted aryl, alkylphosphonium-substituted biaryl, or hydrogen;R3is independently selected from hydrogen, alkyl, hydroxyalkyl, alkanoyl, or carboxy alkyl; the alkylammonium-substituted aryl isthe alkylphosphonium-substituted aryl is; the alkylphosphonium-substituted biaryl isR5, R6, and R7are independently Ci-6 alkyl or aryl;A1is an aryl; andB is a biaryl.

2. The mesoporous polymeric material of claim 1, wherein A is phenyl.

3. The mesoporous polymeric material of any one of claims 1-2, wherein one of R1and R2is the alkylammonium-substituted aryl.

4. The mesoporous polymeric material of claim 3, wherein A1is phenyl.

5. The mesoporous polymeric material of claim 3, wherein one of R1and R2is -C6H4- CH2N+(CH3)(CH3)(C4H9).

6. The mesoporous polymeric material of any one of claims 1-5, wherein R3is hydrogen.

7. The mesoporous polymeric material of any one of claims 1-6, wherein the cyclodextrin moieties comprise beta-CD.

8. A mesoporous polymeric material of any one of claims 1-7, wherein A is covalently bound to the cyclodextrin through a thioether bond.

9. A mesoporous polymeric material of any one of claims 1-7, wherein A is covalently bound to the cyclodextrin through an ether bond.

10. A mesoporous polymeric material of any one of claims 1-9 prepared from a functionalized cyclodextrin monomer comprising11. The mesoporous polymeric material of claim 10, wherein the comonomer and functionalized cyclodextrin monomer are incorporated into the mesoporous polymeric material in a ratio of 1 : 1 to 16:

112. The mesoporous polymeric material of any one of claims 1-11, wherein R5is methyl and R6and R7are Ci-6 alkyl or aryl.

13. A method of purifying a fluid sample comprising a micropollutant, the method comprising contacting the fluid sample with the mesoporous polymeric material of any one of claims 1-12, thereby concentration of the micropollutant in the fluid sample is reduced.

14. The method of claim 13, wherein the micropollutant is an anionic micropollutant.

15. The method of claim 13, wherein the anionic micropollutant is a perfluorinated alkyl compound.

16. The method of claim 13, wherein the perfluorinated alkyl compound is selected from a perfluorocarboxylic acid, a perfluorosulfonic acid, or combinations thereof.

17. A method of preparing a mesoporous polymeric material comprising a network of cyclodextrin moieties crosslinked by a plurality of crosslinks, the method comprising contacting a functionalized cyclodextrin monomer with a comonomer in the presence of a free radical initiator under conditions sufficient to prepare the network of cyclodextrin moieties crosslinked by a plurality of crosslinks, wherein the functionalized cyclodextrin monomer comprisesor any combination thereof, and the comonomer comprises formulawhereinA is an unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl;R1and R2are independently alkylammonium-substituted aryl, alkylphosphoniun- substituted aryl, alkylphosphonium-substituted biaryl, or hydrogen;R3is independently selected from hydrogen, alkyl, hydroxyalkyl, alkanoyl, or carboxyalkyl; the alkylammonium-substituted aryl isthe alkylphosphonium-substituted aryl isthe alkylphosphonium-substituted biaryl isR5, R6, and R7are independently Ci-6 alkyl or aryl;A1is an aryl; andB is a biaryl.

18. The method of claim 17, wherein R3is hydrogen.

19. The method of any one of claims 17-18, wherein the cyclodextrin moieties comprise beta-CD.

20. The method of any one of claims 17-19, wherein A is covalently bound to the cyclodextrin moiety through a thioether bond.

21. The method of any one of claims 17-19, wherein A is covalently bound to the cyclodextrin moiety through an ether bond.

22. The method of any one of claims 17-21, wherein the comonomer and functionalized cyclodextrin monomer are incorporated in a ratio of 1 : 1 to 16: 1.

23. The method of any one of claims 17-22, wherein the free radical initiator is 2,2'- Azobis(2-methylpropionitrile (AIBN).

24. The method of any one of claims 17-23, wherein the molar ratio of the functionalized cyclodextrin monomer to the comonomer is from 1 : 16 to 1 : 1.

25. The method of any one of claims 17-24, wherein the conditions comprise a reaction temperature from 40 °C to 100 °C.

26. The method of any one of claims 17-25, wherein the conditions comprise a reaction time of less than 1.5 hours.

27. The method of any one of claims 17-26, wherein the conditions comprise a reaction solvent selected from dimethylformamide.

28. The method of any one of claims 17-27, wherein the network of cyclodextrin moieties crosslinked by a plurality of crosslinks is produced in a yield of greater than 90%.

29. The method of any one of 17-28, further comprising extracting the network of cyclodextrin moieties crosslinked by a plurality of crosslinks in methanol.

30. The method of any one of claims 17-29, further comprising activating the network of cyclodextrin moieties crosslinked by a plurality of crosslinks with supercritical carbon dioxide.

31. The method of any one of claims 17-30, wherein R5is methyl and R6and R7are Ci-6 alkyl or aryl.

32. The method of any one of claims 17-31, wherein R5and R6are methyl and R7is Ci-6 alkyl or aryl.

33. The method of any one of claims 17-32, wherein one of R1and R2is -C6H4- CH2N+(CH3)(CH3)(C4H9).

34. The method of any one of claims 17-32, wherein R1and R2are -C6H4-CH2N+(CH3)(CH3)(C4H9).

35. A mesoporous polymeric material produced by the method of any one of claims 17-34.

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