Resins containing soft cations for selective PFAS sorption from water and methods of making the same

Abstract

The present disclosure relates materials and methods related to the removal of per-and polyfluorinated alkyl compounds from water. More specifically, the materials disclosed herein are functionalized resins made from crosslinked polymers containing a cationic headgroup bound to the resin, which can be used to remove the per-and polyfluorinated alkyl compounds from water.

Description

RESINS CONTAINING SOFT CATIONS FOR SELECTIVE PFAS SORPTION FROM WATER AND METHODS OF MAKING THE SAMETECHNICAL FIELD

[0001] The present disclosure relates to materials and methods related to the removal of per- and polyfluorinated alkyl compounds from water. More specifically, the materials disclosed herein are functionalized resins made from crosslinked polymers containing a cationic head group bound to the resin, which can be used to remove the per- and polyfluorinated alkyl compounds from water.GOVERNEMNT SUPPORT

[0002] This invention was made with government support under Grant Number W912HQ20C0034 awarded by the Department of Defense. The government has certain rights in the invention.BACKGROUND

[0003] Per- and polyfluoroalkyl substances (PFAS) are a class of synthetic chemicals which are ubiquitous in consumer products, packaging materials, aqueous fire-fighting foams, and as surfactants used in industrial production of fluoropolymers.5 7In part due to this ubiquity, PFAS contaminate waterways worldwide.8,9Some legacy PFAS, including perfluorooctanoic acid (PFOA) and perfluorosulfonic acid (PFOS), have been linked to numerous adverse health effects.10 15As a result, the US EPA has set a non-enforceable health advisory limit (HAL) of 70 ng / L for combined concentrations of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS).16These PFAS were phased out in the U.S., although they still contaminate ground and surface water worldwide. Their replacements, including perfluoroalkyl ether acids such as hexafluoropropylene-dimer acid (HFPO-DA, GenX), now pose many of the same risks as legacy PFAS including PFOS and PFOA.8 17In 2023, the US EPA released proposed maximum contaminant limits (MCLs) for six PFAS, including levels for PFOA and PFOS at 4 part per trillion (ppt) each.18

[0004] Conventional water remediation strategies, such as flocculation, chlorination, andozonolysis, are ineffective to remove PFAS from water.19One of the most effective methods to remove PFAS from water is to sorb them out of water and onto a resin.20 22The primary challenge for developing resins effective for PFAS remediation is that other organic and inorganic matter is present in water at 3-6 orders of magnitude higher concentration than PFAS.23Commercial water purification resins, such as granular activated carbon (GAC) and ion exchange (IX) resins, demonstrate limited success removing short-chain PFAS from water and exhibit breakthrough at moderate bed volumes.24This is partially due to the fact that these resins were designed as broad spectrum adsorbents; because they adsorb a wide variety of water contaminants, they become saturated by non-PFAS ions and organic matter and lack the selectivity and capacity to remove short-chain PFAS from water. Emerging materials, such as porous polymeric resins,25 33and ion exchange materials that contain a fluorinated co ponent34 38demonstrate promising initial results removing PFAS from pure water. However, while porous polymeric resins17 25demonstrate high capacity in pure water, they adsorb organic contaminants non-specifically and, thus, are prone to saturation by non-fluorinated species.

[0005] Thus, there is a need to remove per- and polyfluorinated alkyl compounds from water to make it safer for the public. These and other challenges are addressed by the subject matter disclosed herein.SUMMARY

[0006] In accordance with the purpose(s) of the currently disclosed subject matter or problems to be solved by the invention, as embodied and broadly described herein, it is an object of the present invention to provide a functionalized resin made from crosslinked polymers a cationic head group bound to the resin. In an embodiment, the functionalized resin is a compound of Formula (I):R-L-CFormula (I) wherein R is a resin scaffold material selected from the group consisting of styrene- based polymers and acrylic-based polymers;L is a substituted or unsubstituted (C1-C5) alkyl linker;C is a cationic head group according to Formula (A) or (B):Formula (A) Formula (B) wherein n is 1 or 2; m is an integer selected from 0, 1, 2, 3 and 4;X is selected from CR2, NR3, S, N and O; andRi, R2 and R3, in each instance, are -H, substituted or unsubstituted (Ci-Ce) alkyl or substituted or unsubstituted benzyl.

[0007] In another aspect, the subject matter described herein is directed to methods of preparing a functionalized resin as disclosed herein, the method comprising: contacting a scaffold resin material with a nitrogen-containing heterocycle in a polar aprotic solvent to afford a reaction mixture; and filtering the reaction mixture to obtain a functionalized resin as disclosed herein.

[0008] In another aspect, the subject matter described herein is directed to methods for removing PFAS from a PFAS contaminated water supply, the method comprising: a) contacting the PFAS contaminated water supply with a functionalized resin as disclosed herein; b) adsorbing of one or more PFAS contaminants onto the functionalized resin; and c) isolating the PFAS bound functionalized resin from the mixture.

[0009] These and other aspects are disclosed in further detail below.BRIEF DESCRIPTION OF THE FIGURES

[0010] FIG. 1 shows the synthesis of functionalized resins (FRs) from halogenated polystyrene beads and heterocycles.

[0011] FIG. 2 shows the batch equilibrium sorption of PFAS by FRs after 21 hours. [NaCl] = 200 mg / L, [PFAS]0 = lug / L each. Average of duplicate experiments shown.

[0012] FIG. 3 shows the Mini-RSSCT leveraging FR-nBu-imid as the granular sorbent using Settled Conventional water, Orange County, North Carolina.

[0013] FIG. 4 shows the removal of PFAS from water. [PFAS]0 = 1 ug / L. [NaCl] = 200 mg / L. Results shown are averages of duplicate experiments, t = 21 hr.

[0014] FIG. 5 shows the removal of PFAS from spiked settled conventional water. [PFAS]0 = lug / L. Results shown are averages of duplicate experiments, t = 21 hr.

[0015] FIG. 6 shows sorbent regenerability as measured by PFAS release in 10% NaCl solution. FRs were first stirred in water containing NOM (50 mg / L) and PFAS ([PFAS]0 = 1000 ng / L each). After 21 hours, sorbents were transferred to 10% NaCl solution and stirred 1 hr. PFAS release was determined using LC-MS.

[0016] FIG. 7 shows Mini-RSSCT Removal of PFMOAA from settled conventional water, Sweeney Water Treatment Plant, Wilmington, North Carolina. Macro-FR-4tBupyr outperforms commercial macroporous ion exchange resin CalRes 2301. Source water concentration: 7 ppt PFMOAA.

[0017] FIG. 8 shows a comparison of the cumulative removal of PFMOAA by CalRes 2301, Macro-FR-2,4-Lut, and Macro-FR-4-tBupyr in a pilot study at a municipal drinking water treatment plant that purifies groundwater.DETAILED DESCRIPTION

[0018] The present invention can be understood more readily by reference to the following detailed description of the invention and the Examples included therein. It should be noted that all references mentioned throughout the disclosure are incorporated by reference herein in their entirety.

[0019] Before the present compounds, compositions, articles, systems, devices, and / or methods are disclosed and described, it is to be understood that they are not limited to specificsynthetic methods unless otherwise specified, or to particular components unless otherwise specified, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, example methods and materials are now described.

[0020] Given the challenges for current PFAS adsorption resins, designing a resin that was more specific for PFAS compared to competing organic matter in water would be of particular interest as such a resin would enhance selectivity for PFAS sorption and lead to higher performing materials for PFAS remediation from a wide variety of waters.

[0021] To design a resin specific for PFAS, it was sought to identify an intermolecular chemical interaction that would target the unique properties of PFAS compared to other common organic matter found in water. Hard-soft acid-base (HSAB) theory is a framework described by Dr. Ralph Pearson in 196339to explain the interactions and reactivity between Lewis acids and bases. Generally, the theory states that hard acids and bases are small, compact, and non- polarizable. In contrast, soft acids and bases are larger, more polarizable, and have their electrons distributed over a larger area or numerous atoms. The cornerstone of this theory for understanding reactivity is that hard acids preferentially react with hard bases and soft acids preferentially react with soft bases.

[0022] Anionic PFAS (carboxylates or sulfonates) are bases that have their charge distributed over multiple atoms due to resonance. Furthermore, the electronegativity of the fluorine atoms polarizes the anions by inductively withdrawing electron density. These combined properties make anionic PFAS soft bases. This contrasts with natural organic matter found in water such as humic acids. The carboxylate functionalities in these substances are typically bound to electron rich aryl groups or aliphatic hydrocarbons,40making them comparatively harder bases than PFAS.

[0023] Current ion exchange resins for water purification are predominately based on crosslinked poly(styrene-co-divinylbenzene).41Ammonium cations are currently used to bind PFAS, however not very efficiently. Thus, the current application is directed to developing an alternative to ammonium cation resins for the PFAS removal.

[0024] One approach for improving PFAS removal of current ammonium cation ions would be to introduce different types of cations. For example, by installing a softer cation in the currently disclosed resins relative to ammonium on a crosslinked poly(styrene-co-divinylbenzene) resin could promote not only better PFAS removal but also could promote selectivity for PFAS removal over organic matter. Further, soft cations bind weaker to humic acids relative to ammonium, which provide for more efficient regeneration of the resin after its saturation with a combination of organic matter and PFAS. Nitrogen-containing aromatic heterocycles were identified as readily accessible derivatives that, upon alkylation, create Lewis acid cations whose charge would be delocalized over multiple atoms. The aromaticity of the heterocycles ensures charge delocalization through resonance, and the variety of substitution enables the tuning of both electronic (i.e. polarizability) and steric parameters. This approach creates a variety of ion exchange resins functionalized with soft cations in order to understand structure-property relationships and identify resins with high performance for PFAS remediation due to selective acid-base interactions.

[0025] As described herein, in embodiments, are functionalized resins made from crosslinked polymers containing a cationic head group bound to the resin, which can be used to remove the per- and polyfluorinated alkyl compounds from water. These resins are intended for removal of PFAS from solutions, where the functionalized resins exhibit at least one benefit such as: 1) reduced life-time cost compared with other novel sorbents used to remove per- and polyfluorinated alkyl compounds; 2) increased ease of synthetic scale-up; 3) increased ease for tuning the chemical and physical characteristics of the functionalized resin; 4) improved removal of PFAS from water, especially when compared to methods such as granular activated carbon or ion exchange resins; 5) improved removal of short-chain PFAS, especially when compared to methods such as granular activated carbon or ion exchange resins; 6) improved removal of PFAS from the functionalized resin for regeneration, especially when compared to methods such as granular activated carbon or ion exchange resins; 7) tunable particle size of the functionalized resins; 8) tunable porosity of the functionalized resin.

[0026] These functionalized resins are described in more detail below.A. DEFINITIONS

[0027] Listed below are definitions of various terms used to describe this invention. Thesedefinitions apply to the terms as they are used throughout this specification, unless otherwise limited in specific instances, either individually or as part of a larger group.

[0028] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a monomer” or “an alkyl group” includes mixtures of two or more such monomers or alkyl groups.

[0029] Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. Thus, the term “about,” when referring to a value is meant to encompass variations of, in some embodiments ± 10%, in some embodiments ± 5%, in some embodiments ± 2%, in some embodiments ± 1%, in some embodiments ± 0.5%, and in some embodiments ± 0.1% from the specified amount, as such variations are appropriate to perform the disclosed methods or employ the disclosed compounds. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit between two particular units is also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0030] References in the specification and concluding claims to parts by weight of a particular element or component in a composition denote the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present at a weight ratio of 2:5 and are present in such ratio regardless of whether additional components are contained in the compositions.

[0031] A weight percent (wt%) of a component, unless specifically stated to the contrary, is based on the total weight of the vehicle or composition in which the component is included.

[0032] As used herein, the terms “optional” and “optionally” mean that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0033] As used herein, the term “soft cation” refers to a cationic Lewis base where the charge is distributed among multiple atoms due to resonance, which makes the cation easily polarizable.

[0034] As used herein, the term “modified clay” refers to a clay material that is a refined version of natural clay and incorporates various additives to improve its physical, chemical, and mechanical properties. Unlike traditional clay, which is limited in its applications due to inherent weaknesses, “modified clay” exhibits enhanced durability, water resistance, thermal stability, and aesthetic appeal.

[0035] As used herein, the term “modified cellulose”, refers to a chemically modified cellulose wherein its hydroxyl groups in the cellulose chains have been derivatized to ethers, esters, acids, etc.

[0036] As used herein, the term “modified silica” refers to silica that has been chemically or physically treated to change its surface composition. Specifically, the surface of the silica has been modified to contain anionic or cationic functional groups.

[0037] As used herein, the term “modified polymers” refers to polymers that have undergone a reaction to modify their chemical structure, typically resulting in the addition of a functional group.

[0038] As used herein, the term “modified carbon” refers to a form of carbon material where its surface properties have been altered through chemical or physical processes, typically by adding functional groups to the carbon structure, to enhance its specific applications.

[0039] As used herein, the term “alkyl” refers to a straight or branched chain hydrocarbon containing from 1 to 20 carbon atoms. Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3 -methylhexyl, 2,2-dimethylpentyl, 2,3 -dimethylpentyl, n-heptyl, n-octyl, n- nonyl, n-decyl, and the like. The alkyl group can also be substituted or unsubstituted. Substitutedalkyl groups may be substituted with groups selected from halo (i.e., fluoro, chloro, bromo, iodo), alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclo, heterocycloalkyl, hydroxyl, alkoxy (thereby creating a polyalkoxy such as polyethylene glycol), alkenyloxy, alkynyloxy, haloalkoxy, cycloalkoxy, cycloalkylalkyloxy, aryloxy, arylalkyloxy, heterocyclooxy, heterocyclolalkyloxy, mercapto, carboxy, alkylamino, alkenylamino, alkynylamino, haloalkylamino, cycloalkylamino, cycloalkylalkylamino, arylamino, arylalkylamino, heterocycloamino, heterocycloalkylamino, disubstituted-amino, ester, amide, nitro, or cyano. A “lower alkyl” group is an alkyl group containing from one to six (e.g., from one to four) carbon atoms. Non-limiting examples of alkyls include C1-C8 alkyl, C1-C6 alkyl, C1-C3 alkyl, and Cl alkyl.

[0040] As used herein, the term “polymer” refers to a relatively high molecular weight organic compound, natural or synthetic, whose structure can be represented by a repeated small unit, the monomer or repeat unit (e.g., polyethylene, rubber, cellulose). Synthetic polymers are typically formed by addition or condensation polymerization of monomers.

[0041] As used herein, the term “copolymer” refers to a polymer formed from two or more different repeating units (monomer residues). Non-limiting examples of copolymers include an alternating copolymer, a random copolymer, a block copolymer, or a graft copolymer. It is also contemplated that, in certain embodiments, various block segments of a block copolymer can themselves comprise copolymers.

[0042] As used herein, the term “oligomer” refers to a relatively low molecular weight polymer in which the number of repeating units is between two and ten, for example from two to eight, from two to six, or from two to four. In one aspect, a collection of oligomers can have an average number of repeating units of from about two to about ten, for example, from about two to about eight, from about two to about six, or form about two to about four.

[0043] As used herein, the term “crosslinked polymer” refers to a polymer having bonds linking one polymer chain to another.

[0044] The term “alkenyl” as used herein is a hydrocarbon group of 2 to 20 carbon atoms with a structural formula containing at least one carbon-carbon double bond. The alkenyl group can beunsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein. Non-limiting examples of alkenyls include C2-18 alkenyl, C2-12 alkenyl, C2- 8 alkenyl, C2-6 alkenyl, and C2-3 alkenyl.

[0045] The term “alkynyl” as used herein is a hydrocarbon group of 2 to 20 carbon atoms with a structural formula containing at least one carbon-carbon triple bond. The alkynyl group can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein. Non-limiting examples of alkynyl include C2-18 alkynyl, C2-12 alkynyl, C2-8 alkynyl, C2-6 alkynyl 1, and C2-3 alkynyl.

[0046] As used herein, the term “alkoxy,” used alone or as part of another group, means an - OR group, where R is an alkyl group as defined herein.

[0047] As used herein, the term “halo” refers to any suitable halogen, including -F, -Cl, -Br, and -I.

[0048] As used herein, the term “thiol” and “mercapto” refers to an -SH group.

[0049] As used herein, the term “cyano” as used herein refers to a -CN group.

[0050] As used herein, the term “carboxylic acid” refers to a -C(O)OH group.

[0051] As used herein, the term “hydroxyl” refers to an -OH group.

[0052] As used herein, the term “nitro” refers to an -NO2 group.

[0053] As used herein, the term “acyl,” used alone or as part of another group, refers to a - C(O)R group, where R is any suitable substituent such as aryl, alkyl, alkenyl, alkynyl, cycloalkyl or other suitable substituent as described herein.

[0054] As used herein, the term “alkylthio,” used alone or as part of another group, refers toan alkyl group, as defined herein, appended to the parent molecular moiety through a thio moiety, as defined herein. Representative examples of alkylthio include, but are not limited to, methylthio, ethylthio, tert-butylthio, hexylthio, and the like.

[0055] As used herein, the term “amino” means an -NH2 group.

[0056] As used herein, the term “alkylamino” or “mono-substituted amino,” used alone or as part of another group, means an -NHR group, where R is an alkyl group.

[0057] As used herein, the term “di substituted amino”, used alone or as part of another group, means an-NRaRb group, where Raand Rb are independently selected from the groups alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclo, and heterocycloalkyl.

[0058] As used herein, the term “leaving group” has the same meaning that is generally known in the art. Accordingly, the term “leaving group” as used herein is defined as a group which is readily broken away from its union with the carbon atoms. It is one which readily joins, for example, with an active hydrogen atom to split out a compound containing the hydrogen atom and the leaving group. Leaving groups are generally electron attracting groups either because of their electronegativity or because they have an inductive effect. Leaving groups are defined throughout the art, such as in U.S. Pat. No. 4,394,519 to Carpino, et al. which is incorporated herein by reference. Non-limiting examples of leaving groups include halo (i.e., Cl, Br, and I), CN, and sulfonates.

[0059] As used herein, the term “substituent” refers to one or more atoms that form a functional group that replace a hydrogen atom. Examples of substituents include, but are not limited to -Cl, Br, I, F, OH, OCH3, COOH, COOCH3, -NH2, CN, NO2, CHO, OCOCH3, etc.

[0060] As used herein, the terms “nucleophilic compound,” “nucleophile,” and the like mean an organic compound that may be acyclic or cyclic and comprises at least one atom carrying a free electron pair, which may or may not carry a charge, preferably a nitrogen, oxygen, sulfur or phosphorus atom, or comprises a carbon atom that may donate its electron pair.

[0061] As used herein, the terms “electrophilic compound,” “electrophile,” and the like referto a neutral or positively charged chemical species which is attracted to negative sources and which tends to accept electron pairs in order to form a chemical bond.

[0062] As used herein, the term “contacting” refers to reagents in close proximity so that a reaction may occur.

[0063] The term “heteroaryl” or “heteroaromatic” refers to a monovalent aromatic moiety made up of 5- or 6-membered rings and includes fused ring systems (at least one of which is aromatic) of 5-20 atoms, containing one or more heteroatoms independently selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl groups are pyridinyl (including, for example, 2-hydroxypyridinyl), imidazolyl, imidazopyridinyl, pyrimidinyl (including, for example, 4- hydroxypyrimidinyl), pyrazolyl, triazolyl (including, for example, 3-amino-l,2-4-triazole or 3- mercapto-l,2,4-triazole), pyrazinyl (including, for example, aminopyrazine), tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxadiazolyl, oxazolyl, isothiazolyl, pyrrolyl, quinolinyl, isoquinolinyl, tetrahydroisoquinolinyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, indolizinyl, phthalazinyl, pyridazinyl, triazinyl, isoindolyl, pteridinyl, purinyl, oxadiazolyl, triazolyl, thiadiazolyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, and furopyridinyl. The heteroaryl groups are thus, in some embodiments, monocyclic or bicyclic. Heteroaryl groups are optionally substituted independently with one or more substituents described herein.

[0064] The term “aryl” refers to a hydrocarbon monocyclic, bicyclic or tricyclic aromatic ring system. Aryl groups may be optionally substituted with one or more substituents. In one embodiment, 0, 1, 2, 3, 4, 5 or 6 atoms of each ring of an aryl group may be substituted by a substituent. Examples of aryl groups include phenyl, naphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, and the like.

[0065] As used herein, the term “substituted” refers to a moiety (such as heteroaryl, aryl, cycloalkyl, alkyl, and / or alkenyl) wherein the moiety is bonded to one or more additional organic or inorganic substituent radicals. In some embodiments, the substituted moiety comprises 1, 2, 3, 4, or 5 additional substituent groups or radicals. Suitable organic and inorganic substituent radicals include, but are not limited to, halogen, hydroxyl, cycloalkyl, aryl, substituted aryl, heteroaryl, heterocyclic ring, substituted heterocyclic ring, amino, mono-substituted amino, di -substitutedamino, acyloxy, nitro, cyano, carboxy, carboalkoxy, alkyl carboxamide, substituted alkyl carboxamide, dialkyl carboxamide, substituted dialkyl carboxamide, alkyl sulfonyl, alkylsulfmyl, thioalkyl, alkoxy, substituted alkoxy or haloalkoxy radicals, wherein the terms are defined herein. Unless otherwise indicated herein, the organic substituents can comprise from 1 to 4 or from 5 to 8 carbon atoms. When a substituted moiety is bonded thereon with more than one substituent radical, then the substituent radicals may be the same or different.

[0066] As used herein, the term “unsubstituted” refers to a moiety (such as heteroaryl, aryl, alkenyl, and / or alkyl) that is not bonded to one or more additional organic or inorganic substituent radical as described above, meaning that such a moiety is only substituted with hydrogens. It will be understood that the structures provided herein and any recitation of "substitution" or "substituted with" includes the implicit proviso that such structures and substitution are in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc.

[0067] It will be understood that the structures provided herein and any recitation of “substitution” or “substituted with” includes the implicit proviso that such structures and substitution are in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc.B. FUNCTIONALIZED RESIN

[0068] Disclosed herein are materials to be used for the removal of per- and polyfluorinated alkyl compounds from water. More specifically, the materials disclosed herein are functionalized resins comprising the following components: a resin scaffold material, a linker, and a cationic head group. Each component is described in more detail below.1. SCAFFOLD MATERIAL

[0069] The resin disclosed herein is in the form of particles composed of a scaffold material such as carbon, clay, cellulose, silica, and polymers. In some embodiments, scaffold materials canbe modified, for example, modified carbon, modified clay, modified cellulose, modified silica, and / or modified polymers. In some embodiments, the scaffold materials are modified on the surface. In some embodiments, the scaffold materials are modified on the surface and throughout the material. In some embodiments, the resin is a gel resin. In some embodiments, the resin is a porous resin (e.g., macro-, meso- and / or microporous). A skilled artisan would generally be familiar with the types of modifications that can be carried out for each of these scaffold materials.

[0070] In some embodiments, the scaffold material is a crosslinked polymer. The crosslinked polymer is selected from a styrene-based polymer and an acrylic-based polymer. In some embodiments, the crosslinked polymer is a homopolymer. In some embodiments, the crosslinked polymer contains at least two or three different repeat units. In some embodiments, the crosslinked polymer is a copolymer (i.e., contains two different repeat units).

[0071] In some embodiments, the scaffold material is a crosslinked styrene-based polymer, wherein the polymer comprises at least one styrene repeat unit. In some embodiments, the crosslinked styrene-based polymer is a homopolymer, e.g., polystyrene. In some embodiments, the crosslinked styrene-based polymer is a copolymer. For example, in some embodiments, the copolymer contains styrene monomer (chloromethyl)styrene and divinylbenzene. In some embodiments, the crosslinked styrene-based polymer contains less than about 50 wt.%, about 45 wt.%, about 40 wt.%, about 35 wt.%, about 30 wt.%, about 25 wt.%, about 20 wt.%, about 15 wt.%, about 10 wt.%, or less than about 5 wt.% styrene repeat units. In some embodiments, the crosslinked styrene-based polymer contains from about 5 wt.% to about 60 wt.%, from about 10 wt.% to about 55 wt.%, from about 15 wt.% to about 55 wt.% from about 20 wt.% to about 50 wt.% from about 25 wt.% to about 50 wt.% from about 30 wt.% to about 50 wt.% from about 35 wt.% to about 50 wt.% from or about 40 wt.% to about 50 wt.% styrene repeat units.

[0072] In some embodiments, the scaffold material is a crosslinked acrylic-based polymer, wherein the polymer comprises at least one acrylic repeat unit (e.g., acrylic acid, methacrylic acid). In some embodiments, the crosslinked acrylic-based polymer is a homopolymer, e.g., acrylic homopolymer. In some embodiments, the crosslinked acrylic-based polymer is a co-polymer, e.g., ethylene- acrylic acid. In some embodiments, the crosslinked acrylic-based polymer contains less than about 50 wt.%, about 45 wt.%, about 40 wt.%, about 35 wt.%, about 30 wt.%, about 25 wt.%,about 20 wt.%, about 15 wt.%, about 10 wt.%, or less than about 5 wt.% acrylic repeat units. In some embodiments, the acrylic-based polymer contains from about 5 wt.% to about 60 wt.%, from about 10 wt.% to about 55 wt.%, from about 15 wt.% to about 55 wt.% from about 20 wt.% to about 50 wt.% from about 25 wt.% to about 50 wt.% from about 30 wt.% to about 50 wt.% from about 35 wt.% to about 50 wt.% from or about 40 wt.% to about 50 wt.% acrylic repeat units.

[0073] In some embodiments, the scaffold material is a crosslinked polymer as disclosed herein. In such polymers, the crosslinking density can vary. For example, in some embodiments, the polymer is crosslinked with a crosslinking density of from about 0.1% to about 30%, from about 0.1% to about 25%, from about 0.1% to about 20%, from about 0.5% to about 15%, from about 1% to about 12%, from about 1.5% to about 10%, from about 2% to about 8%, from about 2.5% to about 5%, or from about 3% to about 5%. In some embodiments, the crosslinking density is less than about 30%, about 25%, about 20%, about 18%, about 16%, about 14%, about 12%, about 10%, about 9%, about 8%, about 7%, about 6%, about 5%, about 4%, about 3%, about 2%, about 1.5%, about 1.2%, or is less than about 1%. In addition, or in the alternative, the crosslinking density is more than about 0.1%, about 0.5%, about 0.75, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, about 4.5%, about 5%, about 5.5%, about 6%, about 6.5%, about 7%, about 7.5% about 8%, about 8.5%, about 9%, about 9.5%, about 10%, about 12%, about 14%, about 16%, about 18%, about 20%, about 24%, or more than about 28%.

[0074] In some embodiments, the scaffold materials can have a pore volume. In such embodiments, the pore volume of the scaffold material can vary. In some embodiments, the pore volume ranges of from about 0.001 cm3 / g to about 0.75 cm3 / g, from about 0.001 cm3 / g to about 0.50 cm3 / g, from about 0.01 cm3 / g to about 0.50 cm3 / g, from about 0.10 cm3 / g to about 0.40 cm3 / g, from about 0.15 cm3 / g to about 0.30 cm3 / g, from about 0.17 cm3 / g to about 0.30 cm3 / g, from about 0.20 cm3 / g to about 0.30 cm3 / g from about 0.22 cm3 / g to about 0.28 cm3 / g, from about 0.22 cm3 / g to about 0.25 cm3 / g, from about 0.25 cm3 / g to about 0.28 cm3 / g, or from about 0.24 cm3 / g to about 0.26 cm3 / g. In some embodiments, the pore volume is less than about 0.40 cm3 / g, less than about 0.35 cm3 / g, less than about 0.30 cm3 / g, less than about 0.28 cm3 / g, less than about 0.27 cm3 / g, less than about 0.26 cm3 / g, less than about 0.25 cm3 / g, less than about 0.20 cm3 / g, less than about 0.18 cm3 / g, less than about 0.16 cm3 / g, less than about 0.14 cm3 / g, less than about 0.12, cm3 / g or less than about 0.10 cm3 / g, wherein the lower limit of such ranges is 0 cm3 / g.

[0075] In some embodiments, the scaffold material is macroporous. Macropoprous resins are generally referred to as polymer resins with a permanent pore structure. In such embodiments, the average pore diameter is greater than 50 nm. However, in some embodiments, the scaffold may also contain mesopores (2-50 nm) and / or micropores (< 2nm). For example, in some embodiments, the scaffold material disclosed herein is macroporous comprising an average pore diameter ranging of from about 50 nm to about 200 nm, from about 50 nm to about 150 nm, from about 50 nm to about 100 nm or from about 50 nm to about 75 nm.

[0076] In some embodiment, the scaffold material is mesoporous. In such embodiments, the average pore diameter is less than about 50 nm but may also contain macropores (>50 nm). For example, in some embodiments, the scaffold material disclosed herein is mesoporous comprising an average pore diameter ranging of from about 2 nm to about 49 nm, from about 5 nm to about 45 nm, from about 10 nm to about 40 nm, from about 15 to about 35 nm, or from about 20 nm to about 30 nm.

[0077] In some embodiments, the scaffold material is microporous. In such embodiments, the average pore diameter is less than 2 nm but may also contain mesopores (2-50 nm) and macropores (>50 nm). For example, in some embodiments, the scaffold material disclosed herein is microporous comprising an average pore diameter ranging of from about 0.1 nm to about 1.99 nm, from about 0.25 nm to about 1.8 nm, from about 0.5 nm to about 1.5 nm, from about 0.75 to about 1 .25 nm, or from about 0.85 nm to about 1 .05 nm.

[0078] In a particular embodiment, the scaffold material has an average poor diameter ranging from about 0.010 microns to about 120 microns, from about 0.010 microns to about 100 microns, from about 0.01 microns to about 100 microns, from about 10 microns to about 100 microns, from about 50 microns to about to about 100 microns, from about 75 microns to about 100 microns, from about 85 microns to about 100 microns, from about 90 microns to about 100 microns, or from about 95 microns to 100 microns. In some embodiments, the scaffold material has an average poor diameter ranging from about 0.0010 microns to about 100 microns, from about 0.005 microns to about 10 microns, from about 0.005 microns to about 1 microns, from about 0.007 microns to about 0.1 microns, from about 0.007 microns to about 0.015 microns, from about 0.008 microns to about 0.012 microns, from about 0.008 microns to about 0.010 microns, or from about 0.010microns to 0.12 microns. In some embodiments, the scaffold material has an average poor diameter ranging from about 0.010 microns to about 97 microns. In some of these embodiments, the scaffold material is microporous.

[0079] In some embodiments, the scaffold material is a gel resin. Gel resins have no permanent porosity and the only surface one measures is the surface area between the outside of the resin bead and the liquid, i.e., water. In water, gel resins swell.

[0080] In some embodiments, the scaffold material has a surface area. The surface area can vary. In some embodiments, the surface area of the scaffold material is at least about 0.0001 m2 / g, at least about 0.001 m2 / g, at least about 0.009 m2 / g, at least about 0.01 m2 / g, at least about 0.1 m2 / g, at least about 1 m2 / g, at least about 10 m2 / g, at least about 25 m2 / g, at least about 40 m2 / g, at least about 50 m2 / g, at least about 75 m2 / g, at least about 100 m2 / g, at least about 125 m2 / g, at least about 150 m2 / g, at least about 175 m2 / g, at least about 200 m2 / g, at least about 250 m2 / g, at least about 300 m2 / g, at least about 350 m2 / g, at least about 400 m2 / g, at least about 500 m2 / g, at least about 600 m2 / g, at least about 700 m2 / g, at least about 800 m2 / g, at least about 900 m2 / g, at least about 1,000 m2 / g, at least about 5,000 m2 / g, or at least about 1,000 m2 / g. In addition, or in the alternative to, the surface area of the scaffold material is less than about 100,000 m2 / g, less than about 50,000 m2 / g, less than about 25,000 m2 / g, less than about 20,000 m2 / g, less than about 15,000 m2 / g, less than about 10,000, less than about 5,000 m2 / g, less than about 1,000 m2 / g, less than about 850 m2 / g, less than about 650 m2 / g, less than about 500 m2 / g, less than about 350 m2 / g, less than about 250 m2 / g, less than about 150 m2 / g, less than about 100 m2 / g, less than about 10 m2 / g, less than about 75 m2 / g, less than about 50 m2 / g. In such embodiments, the scaffold material can be a macroporous resin.

[0081] The scaffold material is formed into particles to produce the resin. Thus, the resin particles can be in the form of any three-dimensional shape. In some embodiments, such three- dimensional shape is well defined and / or characterized. For example, in some embodiments, the resin is shaped into particles comprising shapes such as, but not limited to, spheres, ellipsoids, cylinders, cubes, and / or wedges. In some embodiments, the three-dimensional shape of the resin particles are not well defined and / or characterized (e.g., shapes obtained after grinding). In such embodiments, the resin particles are shaped into random three-dimensional shapes, e.g., sphere-like.

[0082] In a particular embodiment, the resin particles are shaped into spheres and / or ellipsoids, such as beads, granules, platelets and / or prills. In another embodiment, the resin particles are shaped into cylinders such as rods.

[0083] In some embodiments, the particle size of the resin can vary. In some embodiments, the particle can have a mean average diameter of from about 10 pm to about 2,000 pm, from about 3 pm to about 1,750 pm, from about 5 pm to about 1,500 pm, from about 50 pm to about 1,400 pm, from about 100 pm to about 1,300 pm, from about 200 pm to about 1,200 pm, from about 300 pm to about 1,100 pm, from about 400 pm to about 1,000 pm, from about 450 pm to about 900 pm, from about 500 pm to about 800 pm, or from about 600 pm to about 700 pm. In some embodiments, particle can have a mean average diameter of from about 1 pm to about 500 pm, from about 5 pm to about 250 pm, from about 8 pm to about 150 pm, from about 10 pm to 100 pm, or from about 50 pm to 100 pm. In some embodiments, particle can have a mean average diameter of from about 800 pm to about 2,000 pm, from about 900 pm to about 2,000 pm, from about 1,000 pm to about 1,750 pm, from about 1,250 pm to about 1,500 pm. In some embodiments, the particle can have a mean average diameter of from about 100 pm to about 900 pm. In some embodiments, the mean average diameter of the particle ranges from about 200 pm to about 1200 pm.

[0084] The surface area of the particle resin can vary. In some embodiments, the surface area is at least about 0.0001 m2 / g, at least about 0.001 m2 / g, at least about 0.009 m2 / g, at least about 0.01 m2 / g, at least about 0.1 m2 / g, at least about 1 m2 / g, at least about 10 m2 / g, at least about 25 m2 / g, at least about 40 m2 / g, at least about 50 m2 / g, at least about 75 m2 / g, at least about 100 m2 / g, at least about 125 m2 / g, at least about 150 m2 / g, at least about 175 m2 / g, at least about 200 m2 / g, at least about 250 m2 / g, at least about 300 m2 / g, at least about 350 m2 / g, at least about 400 m2 / g, at least about 500 m2 / g, at least about 600 m2 / g, at least about 700 m2 / g, at least about 800 m2 / g, at least about 900 m2 / g, at least about 1,000 m2 / g, at least about 5,000 m2 / g, or at least about 1,000 m2 / g. In addition, or in the alternative to, the surface area of the particle resin is less than about 100,000 m2 / g, less than about 50,000 m2 / g, less than about 25,000 m2 / g, less than about 20,000 m2 / g, less than about 15,000 m2 / g, less than about 10,000, less than about 5,000 m2 / g, less thanabout 1,000 m2 / g, less than about 850 m2 / g, less than about 650 m2 / g, less than about 500 m2 / g, less than about 350 m2 / g, less than about 250 m2 / g, less than about 150 m2 / g, less than about 100 m2 / g, less than about 10 m2 / g, less than about 75 m2 / g, less than about 50 m2 / g.

[0085] In a specific embodiment, the scaffold material is a crosslinked poly(styrene-co- divinylbenzene). In such an embodiment, the crosslinking density of the scaffold material is from about 0.8% to about 1.2%.2. LINKER

[0086] The functionalized resin disclosed herein comprises a linker. In some embodiments, the linker is selected from an aliphatic linker, an aromatic linker, and an oligoether linker, although the linker should not be limited thereto. In some embodiments, the linker is unsubstituted. In some embodiments, the linker is substituted with at least one substituent or more.

[0087] In some embodiments, the linker is an aliphatic linker. In some embodiments, the aliphatic linker is a (C1-C20) alkyl group, a (C1-C15) alkyl group, a (C1-C10) alkyl group, a (Ci-Ce) alkyl group, or a (C1-C3) alkyl group. In some embodiments, the aliphatic linker is a (Ci-Ce) alkyl group. In some embodiments, the aliphatic linker is -CH2-, -CH2CH2-, -CH2CH2CH2-, - CH2CH(CH3)-, -CH2CH2CH2CH2-, -CH2CH2CH(CH3)-, -CH2CH(CH3)CH2-, CH2CH2CH2CH2CH2-, -CH2CH2CH(CH3)CH2-, -CH2CH2CH2CH2CH2CH2-, or CH2CH2CH(CH3)CH2CH2-. In such embodiments, the aliphatic linker can be substituted with one or more substituents as disclosed herein. In some embodiments, the aliphatic linker is substituted with 1, 2, 3, 4, 5 or 6 substituents. In some embodiments, the aliphatic linker is -CH2-.

[0088] In some embodiments, the aliphatic linker is a (C2-C20) alkylene group, a (C2-C14) alkylene group, a (C2-Cs) alkylene group or a (C2-C4) alkylene group, wherein the aliphatic linker contains at least one double bond or more. In some embodiments, the linker contains 1, 2, 3, or 4 double bonds. In some embodiments, the linker is a (C2-C8) alkylene group. Exemplary aliphatic linkers include, but are not limited to, (C=C)-, -(CH=CH-CH=CH-)-, -(CH=CH-CH=CH- CH=CH)-, or -(CH=CH-CH=CH-CH=CH-CH=CH)-. In such embodiments, the aliphatic linker can be substituted with one or more substituents as disclosed herein. In such embodiments, the aliphatic linker is substituted with 1, 2, 3, 4, 5 or 6 substituents.

[0089] In some embodiments, the aliphatic linker is a (C2-C20) alkynyl group, a (C2-C14) alkynyl group, a (C2-C8) alkynyl group, or a (C2-C4) alkynyl group, wherein the aliphatic linker contains at least one triple bond or more. In some embodiments, the linker contains 1, 2, or 3 triple bonds. Exemplary linker include, but are not limited to:

[0090] In such embodiments, the linker can be substituted with one or more substituents as disclosed herein. In such embodiments, the aliphatic linker is substituted with 1, 2, 3, 4, 5 or 6 substituents.

[0091] In some embodiments, the linker is an aromatic linker. An aromatic linker contains at least one aryl or heteroaryl ring. In some embodiments the aromatic linker refers to a linker containing at least one aryl ring, which can be a hydrocarbon monocyclic, bicyclic or tricyclic aromatic ring system. The aryl ring(s) in such linkers may be substituted with one or more substituents as disclosed herein. In one embodiment, 0, 1, 2, 3, 4, 5 or 6 atoms of each ring of an aryl ring may be substituted by a substituent. Examples of aryl rings include phenyl, naphthyl, anthracenyl, fluorenyl, indenyl, azulenyl. In some embodiments, the aromatic linker contains at least one phenyl or benzyl ring. In such embodiments, the phenyl or benzyl ring can be substituted or unsubstituted.

[0092] In some embodiments, the aromatic linker refers to a linker containing 5- or 6- membered heteroaryl ring(s) and includes fused ring systems (at least one of which is aromatic) of 5-20 atoms, containing one or more heteroatoms independently selected from nitrogen, oxygen, and sulfur. Exemplary heteroaryls that are contained in the aromatic linker include, but are not limited to, pyridinyl (including, for example, 2-hydroxypyridinyl), imidazolyl, imidazopyridinyl, pyrimidinyl (including, for example, 4 hydroxypyrimidinyl), pyrazolyl, triazolyl (including, forexample, 3-amino-l,2-4-triazole or 3 mercapto- 1, 2, 4-triazole), pyrazinyl (including, for example, aminopyrazine), tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxadiazolyl, oxazolyl, isothiazolyl, pyrrolyl, quinolinyl, isoquinolinyl, tetrahydroisoquinolinyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, indolizinyl, phthalazinyl, pyridazinyl, triazinyl, isoindolyl, pteridinyl, purinyl, oxadiazolyl, thiadiazolyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, oxazol-2(3H)-onyl, and furopyridinyl. The heteroaryl groups are thus, in some embodiments, monocyclic or bicyclic. Heteroaryl groups can be unsubstituted or can be substituted with one or more substituents as disclosed herein.

[0093] In some embodiments, the linker is an oligoether linker. In some embodiments, the oligoether linker is a linker of Formula (C):-[-O-(Ci-C 12) alkyl-]n-Formula (C) wherein n is an integer from about 1 to about 100.

[0094] In some embodiments, n is an integer from about 1 to about 20, from about 1 to about 10, from about 1 to about 8, from about 1 to about 6, from about 1 to about 4, or from about 1 to about 2. In some embodiments, n is an integer less than about 20, less than about 18, less than about 16, less than about 14, less than about 12, less than about 10, less than about 8, less than about 7, less than about 6, less than about 5, less than about 4, less than about 3, or less than about 2.

[0095] In some embodiments, the (C1-C12) alkyl group in Formula C is selected from a (Ci- C10) alkyl group, from a (Ci-Cs) alkyl group, from a (Ci-Ce) alkyl group, from a (C1-C4) alkyl group, and a (C1-C2) alkyl group.

[0096] In some embodiments, the oligoether linker is unsubstituted. In some embodiments, the oligoether is substituted with one or more substituents as disclosed herein. In some embodiments, the oligoether is substituted with 1, 2, 3, 4, 5, or 6 substituents.3. CATIONIC HEAD GROUP

[0097] The functionalized resin disclosed herein comprises a cationic head group. In some embodiments, the cationic head group is a heterocycle. In some embodiments, the cationic head group contains at least one heteroatom selected from the group consisting of nitrogen (N), oxygen (O), and sulfur (S). In some embodiments, the cationic head group contains a single N atom. In some embodiments, the cationic head group contains N and O. In some embodiments, the cationic head group contains N and S. In some embodiments, the cationic head group contains, two N atoms. In some embodiments the cationic head group contains no more than one or two heteroatoms. In some embodiments, the cationic head group is a heterobiaryl. In some embodiments, the cationic head group contains at least one N atom and is referred to as nitrogencontaining heterocycle. In some embodiments, the heterocycle is aromatic, e.g., a heteroaryl.

[0098] In some embodiments, the cationic head group is a compound of Formula (A) or (B):Formula (A) Formula (B) wherein n is 1 or 2; m is an integer selected from 0, 1, 2, 3 and 4;X is selected from CR2, NR3, S, N and O; andRi, R2 and R3, in each instance, are -H, substituted or unsubstituted (Ci-Ce) alkyl or substituted or unsubstituted benzyl.

[0099] In some embodiments, the cationic head group is aromatic.

[0100] In some embodiments, the cationic head group is a compound of Formula (A). In some embodiments, n is 1. In some embodiments, n is 1 and X is O. In some embodiments, n is 1, m is 0, and X is O. In some embodiments, n is 1 and X is S. In some embodiments, n is 1, m is 0, andX is S. In some embodiments, the cationic head group is

[0101] In some embodiments, n is i and m is 0. In some embodiments, the cationic head group is a compound of Formula (A.l)Formula (A. l)Wherein R3 is substituted or unsubstituted (C1-C5) alkyl or substituted or unsubstituted benzyl.

[0102] In some embodiments, the cationic head group is a compound of Formula (B). In some embodiments, n is 1. In some embodiments, n is 1 and m is 0 In some embodiments, the cationic head group is a compound Formula (B. l)Formula (B.l) wherein X is S, O, or NR3; andR3 is substituted or unsubstituted (C1-C5) alkyl or substituted or unsubstituted benzyl.

[0103] Thus, in some embodiment, the cationic head group is a compound of Formula (A.l) or (B.l):Formula (A.1) Formula (B. l) wherein X is S, O, or NR3; andR3 is substituted or unsubstituted (Ci-Ce) alkyl or substituted or unsubstituted benzyl.

[0104] In some embodiments, the cationic head group is a compound of Formula (A.l), wherein R3 is substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, R3 is -CH3. In some embodiments, the cationic head group is a compound of Formula (A.l), wherein R3 is unsubstituted benzyl. In some embodiments, the cationic head group is

[0105] In some embodiments, the cationic headgroup is a compound of Formula (B.l). In some embodiments, X is O. In some embodiments, X is S. In some embodiments, X is NR3, wherein R3 is substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, R3 is -CH3. In some

[0106] In some embodiments, the cationic head group is selected from

[0107] In some embodiments, n is 2 in Formula (A). In some embodiments, n is 2 and X is CR2 or N. In some embodiments, the cationic head group is a compound of Formula (A.2):Formula (A.2) wherein m is 0, 1, 2, 3 or 4; andRi and R2, in each instance, are -H or substituted or unsubstituted (C1-C5) alkyl.

[0108] In some embodiments, m is 0, 1 or 2. In some embodiments, m is 0 and R2 is -H. In some embodiments, m is 0 or 1. In some embodiments, m is 0 or 1; and R2 is substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, m is 0 or 1; and R2 is substituted or unsubstituted (Ci-Ce) alkyl and Ri is substituted or unsubstituted (C1-C5) alkyl. In some embodiments, m is 0 or 1; Ri is substituted or unsubstituted (C1-C5) alkyl; and R2 is -CH3 or - C(CH3)3. In some embodiments, m is 0, Ri is substituted or unsubstituted (C1-C5) alkyl, and R2 is -C(CH3)3. In some embodiments, m is 1, Ri is substituted or unsubstituted (C1-C5) alkyl, and R2 is -CH3.

[0109] In some embodiments, n is 2 and X is N. In some embodiments, the cationic head group is a compound of Formula (A.3):Formula (A.3) wherein m is 0, 1, 2, 3, or 4; andRi, in each instance, is -H or (Ci-Ce) alkyl.

[0110] In some embodiments, m is 0, 2, or 4. In some embodiments, m is 0. In some embodiments, m is 2 and Ri in each instance is substituted or (Ci-Ce) alkyl. In some embodiments,m is 4 and Ri in each instance is substituted or (Ci-Ce) alkyl. In some embodiments, m is 2 and Ri in each instance is -CH3. In some embodiments, m is 4 and Ri in each instance is -CH3

[0111] In some embodiments, the cationic head group is selected from:

[0112] In one embodiments, cationic head group is selected froman aliphatic linker (i.e., -CH2-). In such embodiments, the functionalized resin is porous (e.g., microporous). In such embodiments, the functionalized resin with such head groups are in the form of a gel. In such embodiments, the scaffold material is a crosslinked styrene-based polymer (e.g., poly(styrene-Co-divinylbenzene).

[0113] In some embodiments, the functionalized resin comprises more than one cationic headgroup. In some embodiments, the functionalized cationic head group comprises a first cationic head group and a second cationic head group. In some embodiments, the first and the second cationic head group is selected from compounds of Formula (A) and / or Formula (B). In some embodiments, only the first cationic head group is a compound selected from Formula (A) and (B), whereas the second cationic head group can be a compound not disclosed herein.

[0114] The concentration of each cationic head group present in the functionalized resin canvary. For example, in some embodiments, the first cationic head group will be present in the functionalized resin at a higher concentration than the second cationic head group. In some embodiments, the first cationic head group and the second cationic head group are present in the same concentration. In some embodiments, the concentration (mg of cationic head group / mg of scaffold material) of the first cationic head group and the second cationic head group are present at a weight ratio of about 10: 1 to about 1: 10, about 1 :8 to about 8:1, about 5: 1 to about 1 :5, about 3: 1 to about 1 :3, about 1 :2 to about 2: 1, or about 1 : 1.

[0115] For example, in one embodiment, the first cationic headgroup is ^NCHoCHnCHnCH© o and the second cationic headgroup is triethylammonium In another embodiment, the cationic head group comprisesfirst cationic head group and tributylammonium as a second cationic head group. In such embodiments, the linker is an aliphatic linker (i.e., -CH2-). In such embodiments, the functionalized resin is porous (e.g., microporous). In other embodiments, the functionalized resin with such head groups is in the form of a gel. In such embodiments, the scaffold material is a crosslinked styrene-based polymer (e.g., poly(styrene-Co-divinylbenzene). In such embodiments, the first and second cationic head group are present in a weight ratio of about 1: 1.

[0116] In particular embodiments, the functionalized resins disclosed herein are macroporous resins or a gel resin. In such embodiments, the cationic head group can be selected from 2,4 lutidinium, 4-terbutyl pyridinium, tributyl ammonium, or combinations thereof. In some embodiments, the functionalized resins disclosed herein is a macroporous resin with 2,4 lutidinium as a cationic head group. In another embodiment, the functionalized resin disclosed herein is a microporous resin with 4-terbutyl pyridinium as a cationic head group. In another embodiment, the functionalized resin disclosed herein contains poly(styrene-Co-divinylbenzene) as a scaffold material comprising 2,4-lutidinim as a cationic head group. In another embodiment, the functionalized resin disclosed herein contains poly(styrene-Co-divinylbenzene) as a scaffold material comprising tributyl ammonium as a cationic head group. In another embodiment, thefunctionalized resin disclosed herein contains poly(styrene-Co-divinylbenzene) as a scaffold material comprising 2,4-lutidinim as a first cationic head group and tributyl ammonium as a second cationic head group. In such embodiments, the 2,4-lutidinim and tributyl ammonium cationic head groups are present in a weight ratio of about 1: 1.

[0117] In some embodiments, the functionalized resins disclosed herein will adsorb a higher concentration of PFAS contaminants compared to commercially available materials currently in use to treat PFAS contaminated water. For example, in some embodiments, the disclosed functionalized resins adsorb higher concentrations of PFAS contaminants compared to commercially available resin. Exemplary commercially available resins include, but are not limited to, DOW PSR2+ (poly(styrene-co-divinylbenzene) gel resin functionalized with tri-A-butyl amine to afford a quaternary amine as a head group), CalRes2301 (poly(styrene-co-divinylbenzene) macroporous resin with tributylamine functional groups) and Purolite’s PFA694E (poly(styrene- co-divinylbenzene gel resin functionalized with various amino groups). In some embodiments, the disclosed functionalized resins adsorb higher concentrations of short chain PFAS contaminants. In some embodiments, the disclosed functionalized resins have high cumulative PFAS removal.C. METHODS OF PREPARING THE FUNCTIONALIZED RESIN

[0118] The subject matter described herein also comprises methods of preparing the disclosed functionalized resin. In one embodiment, the method disclosed herein employs an Sn2 reaction mechanism to prepare the disclosed functionalized resin, which generally requires a nucleophilic reagent and an electrophilic reagent.

[0119] In some embodiments, the nucleophilic reagent is a heterocycle. In some embodiments, the heterocycle contains at least one heteroatom selected from the group consisting of nitrogen (N), oxygen (O), and sulfur (S). In some embodiments, the heterocycle contains a single N atom. In some embodiments, the heterocycle contains N and O. In some embodiments, the heterocycle contains N and S. In some embodiments, the heterocycle contains, two N atoms. In some embodiments the heterocycle contains no more than one or two heteroatoms. In some embodiments, the heterocycle is a heterobiaryl. In some embodiments, the heterocycle contains at least one N atom and is referred to as nitrogen-containing heterocycle. In some embodiments, the heterocycle is aromatic, e.g., a heteroaryl.

[0120] In some embodiments, the heterocycle is a compound of Formula (I-A) or (I-B):Formula (I-A) Formula (I-B) wherein n is 1 or 2; m is an integer selected from 0, 1, 2, 3 and 4;X is selected from CR2, NR3, S, N and O; andRi, R2 and R3, in each instance, are -H, substituted or unsubstituted (Ci-Ce) alkyl or substituted or unsubstituted benzyl.[001211 In some embodiments, n is 1 in Formula (I-A). In some embodiments, n is i and m is 0 in Formula (I-A). In some embodiments, n is 1, m is 0 and X is NR3 in Formula (I-A). In some embodiments, n is 1, m is 0 and X is O in Formula (I-A). In some embodiments, n is 1, m is 0 and X is S in Formula (I-A). In some embodiments, n is 1, m is 0 and X is N 3 in Formula (I-A), wherein R3 is unsubstituted (Ci-Ce) alkyl (e.g., -CH3). In some embodiments, n is 1, m is 0 and X is NR3 in Formula (I-A), wherein R3 is unsubstituted benzyl. Exemplary heterocycle of Formula(I-A) include:

[0122] In some embodiments, n is 2 in Formula (I-A). In some embodiments, n is 2 and X is CR2 or NR3 in Formula (I-A). In some embodiments, n is 2 and X is CR2 in Formula (I-A). In some embodiments, n is 2 and X is CR2 in Formula (I-A), wherein R2 is -H. In some embodiments, n is 2, X is CR2, and m is 0, 1, or 2 in Formula (I-A), wherein R2 is -H. In some embodiments, n is 2, X is CR2, and m is 0 or 2 in Formula (I-A), wherein R2 is -H. In some embodiments, n is 2, X is CR2, and m is 0 in Formula (I-A), wherein R2 is -H. In some embodiments, n is 2, X is CR2, andm is 2 in Formula (I-A), wherein R2 is -H. In some embodiments, n is 2, X is CR2, and m is 2 in Formula (I-A), wherein R2 is -H and each Ri is independently selected from a substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is 2, X is CR2, and m is 2 in Formula (I-A),wherein R2 is -H and each Ri is -CH3. Exemplary heterocycle of Formula (I-A) include:

[0123] In some embodiments, n is 2 and X is CR2 in Formula (I-A), wherein R2 is substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is 2, m is 0 or 1 and X is CR2 in Formula (I-A), wherein R2 is substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is 2, m is 0 and X is CR2 in Formula (I-A), wherein R2 is substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is 2, m is 1 and X is CR2 in Formula (I-A), wherein R2 is substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is 2, m is 1 and X is CR2 in Formula (I-A), wherein Ri and R2 are independently selected from substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is 2, m is 1 and X is CR2 in Formula (I-A), wherein Ri and R2 are -CH3. In some embodiments, n is 2, m is 0 and X is CR2 in Formula (I-A), wherein R2 is -CH3 or -C(CH3)3Exemplary heterocycle of Formula (I-A) include:, ,

[0124] In some embodiments, n is 2 and X is N in Formula (I-A). In some embodiments, n is 2, m is 0, 2, or 4, and X is N in Formula (I-A). In some embodiments, n is 2, m is 0 and X is N in Formula (I-A). In some embodiments, n is 2, m is 2, and X is N in Formula (I-A), wherein Ri is substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is 2, m is 4, and X is N in Formula (I-A), wherein Ri is substituted or unsubstituted (Ci-Ce) alkyl. Exemplary heterocycle ofT F7ormu 1la Z (TI-A A)V inc 1lu Ade

[0125] In some embodiments, n is 1 in Formula (I-B). In some embodiments, n is 1 and X is NR3, S or O. In some embodiments, n is 1 and X is NR3. In some embodiments, n is 1 and X is NR3, wherein R3is substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is 1 and X is NR3, wherein R3is -CH3. In some embodiments, n is i and X is S. In some embodiments, n is iand X is O. Exemplary heterocycle of Formula (I-B) include:

[0126] In some embodiments, n is 2 in Formula (I-B). In some embodiments, n is 1 and X is CR2 or NR3. In some embodiments, n is 2 in Formula (I-B). In some embodiments, n is 1 and X is CR2 or NR3, wherein R2 and R3, in each instance, are -H or substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is i and X is CR2, wherein R2 is -H or substituted or unsubstituted (Ci-Ce) alkyl. In some embodiments, n is 1 and X is NR3, wherein R3, in each instance, are -H or substituted or unsubstituted (Ci-Ce) alkyl.

[0127] In some embodiments, the electrophilic reagent of the disclosed method is a resin comprising a scaffold material as already described above. In some embodiments, the resin is functionalized with a leaving group. Exemplary leaving groups include, but are not limited to halogens (Br, Cl, I, and / or F) and / or sulfonate esters (mesylate, tosylate, brosylate, nosylate, tritiate, etc.).

[0128] Thus, the methods disclosed herein for preparing a compound of Formula (I) comprises: contacting a resin functionalized with a leaving group with nitrogen-containingheterocycle in a polar aprotic solvent to afford a reaction mixture; and filtering the reaction mixture to obtain the compound as disclosed herein.

[0129] In some embodiments, the polar aprotic solvent is acetonitrile, dichloromethane, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, hexamethylphosphoramide, sulfolane, pyridine and a combination thereof. In some embodiments, the polar aprotic solvent is dimethylformamide.

[0130] In some embodiments, the contacting step is carried out at room temperature. In some embodiments, the contacting step is carried out at elevated temperatures (i.e., above 25 °C; room temperature). Elevated temperatures can range from about 30 °C to about 150 °C, from about 40°C to about 120 °C, from about 50 °C to about 120 °C, from about 60 °C to about 100 °C, from about 70 °C to about 90 °C, or from about 75 °C to about 85 °C. In some embodiments, the elevated temperature is about 80 °C.

[0131] In some embodiments, the contacting step is carried out for a certain period of time. In some embodiments, the contacting step is carried out for at least about 1 hour, at least about 2 hours, at least about 5 hours, at least about 10 hours, at least about 12 hours, at least about 24 hours, or at least about 48h. In addition, or in the alternative, the contacting step is carries out for no more than about 72 hours, no more than about 48 hours, no more than about 24 hours, no more than about 12 hours, or no more than about 6 hours.

[0132] In some embodiments, the above method further comprises exposing the resin functionalized with a leaving group with another (i.e. a second) nitrogen-containing heterocycle as disclosed herein. This exposing step can occur either before, during, or after the contacting step of the above-described method to obtain a functionalized resin comprising two different cationic head groups. Likewise, the exposing step can be further expanded to include two or more additional nitrogen-containing heterocycle to obtain a multi-functionalized resin containing more than 2 different cationic head groups. It would be understood by a skilled artisan that the amount for each nitrogen-containing heterocycle used in this method can vary depending on the concentration for each cationic head group present in the functionalized resin of Formula (I).

[0133] Another aspect of the disclosure is directed towards methods of preparing a functionalized resin, wherein the nucleophile is a heterocycle as described above immobilized on a resin containing a scaffold material as described above. The electrophile in this particular method is a (C1-C12) alkyl group substituted with a leaving group (LG) as described above (e.g., halogen or sulfonate). Exemplary (C1-C12) alkyl groups include, but are not limited to, CH3(LG), CH3CH2(LG), CH3CH2CH2(LG), etc.

[0134] Thus, in some embodiments the method comprises: contacting a heterocycle immobilized on a resin as disclosed herein with a (C1-C12) alkyl group substituted with a leaving group in a polar aprotic solvent to afford a reaction mixture; and filtering the reaction mixture to obtain the compound as disclosed herein.

[0135] In some embodiments, the obtained compound for this method is a compound according to Formula (II) as disclosed herein.

[0136] In some embodiments, the (C1-C12) alkyl group can optionally be further substituted with one or more additional substituents as described above.

[0137] In some embodiments, the above method further comprises exposing the heterocycle immobilized on a resin with another (i.e. a second) (C1-C12) alkyl group substituted with a leaving group as disclosed herein. This exposing step can occur either before, during, or after the contacting step of the above-described method to obtain a functionalized resin comprising two different cationic head groups. Likewise, the exposing step can be further expanded to include two or more (C1-C12) alkyl group substituted with a leaving group to obtain a multi-functionalized resin containing more than 2 different cationic head groups. It would be understood by a skilled artisan that the amount for each (C1-C12) alkyl group substituted with a leaving group used in this method can vary depending on the concentration for each cationic head group present in the functionalized resin of Formula (II).D. METHODS OF USING THE FUNCTIONALIZED RESINS

[0138] The functionalized resin described herein are useful for removing per and polyfluorinated alkyl compounds and / or substances (PFAS) (also referred to as “PFAS contaminants”) from water by capturing the per- and polyfluorinated alkyl compounds with the cationic head group of the functionalized resin. In an embodiment, the method further comprises the step of removing the functionalized resin comprising the captured per-and polyfluorinated alkyl compound from the water. In some embodiments, the per-and polyfluorinated alkyl compounds can be captured with the functionalized resin by absorbing and / or adsorbing onto the functionalized resin. In some embodiments, the per-and polyfluorinated alkyl compounds can be removed with the functionalized resin in some other manner generally known in the art. In a further embodiment, the method comprises the step of separating the sorbed per-and polyfluorinated alkyl compound from the functionalized resin.

[0139] Thus, in a particular embodiment, the method disclosed herein is a method of removing per-and polyfluorinated alkyl compounds and / or substances (PFAS) from a PFAS contaminated water supply, the method comprising: a) contacting the PFAS contaminated water supply with a compound according to Formula (II) to form a mixture, wherein Formula (II) is:R-L-C(Formula (II) wherein R is a resin scaffold material selected from the group consisting of crosslinked polymers, modified carbon, modified clay, modified cellulose, modified silica, or a combination thereof;L is an aliphatic linker, an aromatic linker, or an oligoether linker;C is a cationic head group according to Formula (A) or (B):Formula (A) Formula (B) wherein n is 1 or 2; m is an integer selected from 0, 1, 2, 3 and 4;X is selected from CR2, NR3, S, N and O; andRi, R2 and R3, in each instance, are -H, substituted or unsubstituted (Ci-Ce) alkyl or substituted or unsubstituted benzyl; and b) adsorbing one or more PFAS contaminants present in the mixture onto the compound of Formula (II).

[0140] In some embodiments, prior to performing the methods described herein, the water has a concentration of the perfluorinated alkyl compound from about 0.5 ng / L to about 5 mg / L, from about 0.5 ng / L to about 4 mg / L, from about 0.5 ng / L to about 3 mg / L, from about 0.5 mg / L to about 2 mg / L, from about 0.5 ng / L to about 1 mg / L, from about 0.5 ng / L to about 750 pg / L, from about 0.5 ng / L to about 500 pg / L, from about 0.5 ng / L to about 250 pg / L, from about 0.5 ng / L to about 100 pg / L, from about 0.5 ng / L to about 1 pg / L, or from about 0.5 ng / L to about 750 ng / L. In some embodiments, the water has a concentration of the perfluorinated alkyl compound from about 0.1 ng / L to about 500 pg / L, from about 0.1 ng / L to about 250 pg / L, from about 0.5 ng / L to about 100 pg / L, from about 0.5 ng / L to about 1 pg / L, from about 0.5 ng / L to about 750 ng / L, from about 1 ng / L to about 500 ng / L from about 10 ng / L to about 250 ng / L or from about 10 ng / L to about 100 ng / L. In some embodiments, the water has a concentration of the perfluorinated alkyl compound from about 1 pg / L to about 5 mg / L, from about 1 pg / L to about 3 mg / L, from about 1 pg / L to about 1 mg / L, from about 1 pg / L to about 0.5 mg / L, from about 1 pg / L to about 0.1 mg / L, from about 1 pg / L to about 750 pg / L, from about 1 pg / L to about 500 pg / L, from about 1 pg / L to about 250 pg / L, from about 1 pg / L to about 100 pg / L, from about 1 pg / L to about 50 pg / L, from about 1 pg / L to about 25 pg / L, from about 1 pg / L to about 10 pg / L, or from about 1 pg / L to about 5 pg / L. In some embodiments, the water has a concentration of the polyfluorinated alkyl compound of less than about 5 mg / L, about 4 mg / L, about 3 mg / L, about 2 mg / L, about 1 mg / L, about 0.5 mg / L, about 250 pg / L, about 100 pg / L, about 10 pg / L, about 1 pg / L, or about 750 ng / L.

[0141] In an embodiment, prior to performing the methods described herein, the water has a concentration of the polyfluorinated alkyl compound from about 0.1 ng / L to about 500 ng / L, 0.5 ng / L to about 500 ng / L, from about 1 ng / L to about 300 ng / L, from about 10 ng / L to about 250 ng / L, from about 15 ng / L to about 200 ng / L, from about 20 ng / L to about 150 ng / L, from about 25 ng / L to about 125 ng / L, from about 30 ng / L to about 100 ng / L, or from about 35 ng / L to about 70 ng / L. In some embodiments, the water has a concentration of the polyfluorinated alkyl compound from about 0.05 ng / L to about 200 ng / L, from about 0.05 ng / L to about 100 ng / L, from about 0.05 ng / L to about 50 ng / L, from about 0.05 ng / L to about 25 ng / L, from about 0.05 ng / L to about 20 ng / L, from about 0.05 ng / L to about 15 ng / L, from about 0.05 ng / L to about 10 ng / L, from about 0.05 ng / L to about 5 ng / L, or from about 0.05 ng / L to about 2 ng / L. In some embodiments, the water has a concentration of the polyfluorinated alkyl compound from about 1 ng / L to about 200 ng / L, from about 1 ng / L to about 150 ng / L, from about 1 ng / L to about 100 ng / L, from about 1 ng / L to about 80 ng / L, from about 1 ng / L to about 70 ng / L, from about 1 ng / L to about 50 ng / L, from about 1 ng / L to about 25 ng / L, or from about 1 ng / L to about 10 ng / L. In some embodiments, the water has a concentration of the polyfluorinated alkyl compound from about 1 ng / L to about 300 ng / L, from about 5 ng / L to about 250 ng / L, from about 10 ng / L to about 225 ng / L, from about 15 ng / L to about 200 ng / L, from about 20 ng / L to about 200 ng / L, from 25 ng / L to about 175 ng / L, from about 40 ng / L to about 150 ng / L, or from about 50 ng / L to about 125 ng / L. In some embodiments, the water has a concentration of the polyfluorinated alkyl compound ranging from about 20-200 ng / L as an upper limit to about 0.05-10 ng / L as a lower limit. In some embodiments, the water has a concentration of the polyfluorinated alkyl compound of less than about 500 ng / L, about 450 ng / L, about 400 ng / L, about 350 ng / L, about 300 ng / L, about 275 ng / L, about 250 ng / L, about 225 ng / L, about 200 ng / L, about 175 ng / L, about 150 ng / L, about 125 ng / L, about 100 ng / L, about 75 ng / L, about 50 ng / L, about 25 ng / L, about 10 ng / L or less than about 1 ng / L.

[0142] In some embodiments, the polyfluorinated alkyl compounds and / or substances (PFAS) comprise short chain PFAS contaminants, long chain PFAS contaminants, or a combination thereof. Exemplary short chain PFAS contaminants include, but are not limited to, hexafluoropropylene-dimer acid (HFPO-DA, GenX), perfluoro-2-methoxyaacetic acid (PFMOAA), perfluorobutanoic acid (PFBA), perfluorobutanesulfonic acid (PFBS),perfluoropentanoate (PFPeA), and perfluorohexanoic acid (PFHxA). In such embodiments, the short chain PFAS are generally referred to as carboxylic acids with equal to or less than 6 perfluorocarbon atoms and sulfuric acid with less than 6 perfluorocarbon atoms. Exemplary long chain PFAS contaminants include, but are not limited to, perfluorohexane sulfonic acid (PFHxS), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and perfluorononanoic acid (PFNA). In such embodiments, the long chain PFAS are equal to or greater than 7 perfluorocarbon atoms for carboxylic acids but equal to or greater than 6 perfluorocarbon atoms for sulfuric acids.

[0143] In some embodiments, the polyfluorinated alkyl compounds and / or substances (PFAS) is selected from a group consisting of PFOA, PFOS, PFNA, GenX, PFHxS, PFBS and combinations thereof.

[0144] In an embodiment, the methods disclosed herein can be performed in any body of water. For example, the body of water can be a natural body of water, such as a lake, pond, stream, ocean, aquifer, or a manmade body of water, such as a treatment plant, pool, or dam. In one embodiment, the method is performed with nanopure water. In another embodiment, the method is performed with simulated natural water. In another embodiment, the method is performed with settled natural water. In another embodiment, the method is performed with well water. In another embodiment, the method is performed with industrial wastewater. In another embodiment, the method is performed with wastewater. In another embodiment, the method is performed with leachate water. In another embodiments, the water has already undergone a purification treatment. In another embodiment, the water is from any stage in a water treatment plant. In some embodiments, the water was pre-treated with an osmotic system. In some embodiments, the water was pre-treated with a different granular sorbent such as granular activated carbon, ion exchange resins, or other specialty sorbent.

[0145] In an embodiment, the method disclosed herein comprises a functionalized resin with at least one cationic functional group as disclosed herein. For example, in some embodiments, the method comprises a functionalized resin with a first cationic head group and a second cationic head group as described above.

[0146] In some embodiments, the method disclosed herein comprises two or morefunctionalized resins in the form of particles that are mixed together in a homogenous manner. In a particular embodiment, the method disclosed herein comprises two functionalized resins, a first functionalized resin and a second functionalized resin in certain amounts as described above.

[0147] In an embodiment, the method disclosed herein can remove per-and polyfluorinated alkyl compounds from the water in varying amounts. In some embodiments, the per-and polyfluorinated alkyl compounds being removed from the water are targeted per-and polyfluorinated alkyl compounds and / or non-targeted per-and polyfluorinated alkyl compounds. Here, targeted per-and polyfluorinated alkyl compounds are compounds that are specifically targeted by the functionalized resin to be removed from the water. Thus, non-targeted per-and polyfluorinated alkyl compounds are compounds that were not necessarily intended to be removed from the water with the functionalized resin but were removed nonetheless. The amount of targeted and non-targeted per-and polyfluorinated alkyl compounds can vary. In some embodiments, the amount of targeted per-and polyfluorinated alkyl compounds being removed from the water is greater than the amount of non-targeted per-and polyfluorinated alkyl compounds. In some embodiments, the amount of non-targeted per-and polyfluorinated alkyl compounds is greater than the amount of targeted per-and polyfluorinated alkyl compounds. In some embodiments, the methods disclosed herein can remove per-and polyfluorinated alkyl compound(s) in an amount of from about 1% to about 99%. In some embodiments, the methods disclosed herein can remove at least about 1%, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99% of the per-and polyfluorinated alkyl compound (e.g., targeted and / or non-targeted per- and perfluorinated alkyl compounds) from the water. In addition, or in the alternative to, the method disclosed herein can remove per-and polyfluorinated alkyl compounds (e.g., targeted and / or non-targeted per-and perfluorinated alkyl compounds) from the water in an amount of less about 99%, less than about 95%, less than about 90%, less than about 85%, less than about 80%, less than about 75%, less than about 70%, less than about 65%, less than about 60%, less than about 55%, less than about 50%, less than about 45%, less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less thanabout 10%, less than about 5%, less than about 3%, less than about 1%, less than about 0.1%, less than about 0.01%, or less than about 0.0001%.

[0148] In an embodiment, the per-and polyfluorinated alkyl compound is dissolved in the water prior to performing the method.

[0149] In some embodiments, the contacting step in the above method is carried out in a container, which can be made of any material. Examples of a container are basins, contactors, pressure vessels, flasks, eppendorfs, vials, tubes, columns, etc. In some embodiments, the container is enclosed. In some embodiments, the container is open to the atmosphere.

[0150] In some embodiments, the above method comprises contacting the functionalized resin with the PFAS contaminated water for a certain period of time, which can vary. In some embodiments, the functionalized resin is in contact with the PFAS contaminated water for at least about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, about 12 hours, about 13 hours, about 14 hours, or at least about 20 hours. In some embodiments, the functionalized resin is in contact with the PFAS contaminated water for about 3 hours or less, about 2 hours, or less, about 1 hours or less, about 45 minutes or less, about 30 minutes or less, about 20 minutes or less, about 10 minutes or less, about 5 minutes or less, about 3 minutes or less, about 1 minute or less, about 30 seconds or less, about 20 seconds or less, about 10 seconds or less, or about 5 seconds or less.

[0151] During the contacting step the functionalized resin is mixed with the water to form a mixture. Any means of mixing can be used such as shaking, stirring and / or rotating of the container wherein the contacting step takes place. Such means would be considered mechanical mixing. Other mean of mixing would include hydraulic, sonicating, etc. During the contacting step the functionalized resin may be packed in a column while the PFAS contaminated water is exposed to the functionalized resin inside the column, e.g., the PFAS contaminated water is added into the packed column at a certain rate. PFAS contaminants become adsorbed or absorbed onto / into the functionalized resin as the PFAS contaminated water moves through the packed column either by gravity and / or by force, e.g., applying pressure by using air or some other suitable gas to push the PFAS contaminated water through the packed column.

[0152] In one aspect, the method further comprises the step of removing the functionalized resin comprising the absorbed per-and polyfluorinated alkyl compound(s) from the water. As such, the removed per-and polyfluorinated alkyl compound(s) are no longer present in the water, either as dissolved in the water or as absorbed in the functionalized resin. Removing the functionalized resin comprising the absorbed per-and polyfluorinated alkyl compound(s) (a compound of Formula (III)) can be done using techniques that would be apparent to a person skilled in the art. For example, the functionalized resin comprising the absorbed per-and polyfluorinated alkyl compound(s) can be removed from the water using removal techniques selected from settling, floatation, skimming, and filtration, where the functionalized resin comprising the absorbed per- and polyfluorinated alkyl compound(s) is filtered from the water but is not limited to these removal techniques. Additional removal techniques, for example, could also comprise the use of resin products that use a magnetic core to separate the functionalized resin comprising the absorbed per- and poly fluorinated alkyl compound(s) with a magnet from the water (eg., https: / / www.ixomwatercare.com / equipment / miex-magnetic-ion-exchange-systems). In another embodiments, the removal techniques are simply to allow the resin to settle at the bottom of the container (e.g., a tank) to be removed from the water[00153J In another aspect, the functionalized resin is in the form of particles and packed as a bed in a flow through column where water containing the per-and polyfluorinated alkyl compound is filtered through the pack bed to remove the per-and polyfluorinated alkyl compound. In such an embodiment, the bed volume of water containing the per-and polyfluorinated alkyl compound (i.e., PFAS contaminated water) to be filtered can vary. In some embodiments, the bed volume of water containing the polyfluorinated alkyl compound to be filtered is more than about 100, about 1,000, about 10,000, about 100,000, about 150,000, about 200,000, or more than 250,000 the bed volumes of the flow through column. In such an embodiment, minimal breakthrough of PFAS occurs. In such embodiments, the extent of breakthrough can vary. In some embodiments, less than about 90%, about 80%, about 75%, 50%, about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%, about 5%, or about 1% breakthrough of PFAS occurs.

[0154] In one aspect, the method further comprises the step of separating the absorbed per-and polyfluorinated alkyl compound from the functionalized resin. As such, the functionalized resin is regenerated and can be used again to absorb more per-and polyfluorinated alkyl compound (i.e.,PFAS contaminants). In some embodiments, the functionalized resin is regenerated by contacting the resin with an aqueous organic solution or an aqueous solution with no organic solvent. In some embodiments, the aqueous organic solution contains dissolved salt or mixtures of salts. In some embodiments, the salts comprise inorganic salts, such as, but not limited to, an alkali metal salt. In some embodiments, the salt is sodium chloride. In some embodiments, the salt is a sulfate salt. In some embodiments, the salt is an organic salt, such as, but not limited, to ammonium acetate. Additional exemplary salts include sodium bromide, sodium acetate, sodium hydroxide, sodium carbonate, iron sulfate, and / or sodium bicarbonate. In an embodiment, the aqueous organic solution contains at least about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or at least about 95% of an organic solvent. In some embodiments, the organic solvent is polar (e g., alcohols such as methanol, ethanol, denatured ethanol, isopropanol, butanol, iso-butanol, acetonitrile, etc.). In some embodiments the organic solvent is not polar (e.g., acetone, dimethyl sulfoxide, etc.). In some embodiments, the functionalized resin is regenerated by contacting the resin (a compound of Formula (III)) with an aqueous solution, which contains only water as a solvent.[00155J In one aspect, the functionalized resin can be regenerated from 1 to 100 times, such as from 1 to 50 times, or from 1 to 25 times.

[0156] The amount of adsorbed PFAS contaminants released from the functionalized resin during regeneration step can vary. In some embodiments, the amount of adsorbed PFAS contaminants released from the functionalized resin (i.e., a compound of Formula (III)) is at least 1%, least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 98% of PFAS adsorbed onto the functionalized resin. In addition, or in the alternative, the amount of adsorbed PFAS contaminants released from the functionalized resin (i.e., a compound of Formula (III)) is at most about 5%, at most about 10%, at most about 15%, at most about 20%, at most about 25%, at most about 30%, at most about 35%, at most about 40%, at most about 50%, at most about 60%, at most t about 70%, at most about 80%, at most about 90%, at most about 95%, or at most about 98% of PFAS adsorbed onto the functionalized resin.

[0157] In some embodiments, the functionalized resins employed in the methods disclosed herein can adsorb a higher concentration of PFAS contaminants compared to commercially available materials currently in use to treat PFAS contaminated water. For example, in some embodiments, the methods disclosed herein employing the disclosed functionalized resins can adsorb higher concentrations of PFAS contaminants compared to PFAS contaminant removal methods using commercially available gel resin DOW PSR2+ or using commercially available macroporous resin CalRes 2301. In some embodiments, the disclosed methods using functionalized resins as disclosed herein adsorb higher concentrations of short chain PFAS contaminants compared to PFAS removal methods employing commercially available resins, e.g., DOW PSR2+ or CalRes 2301. In such embodiments, the disclosed methods are able to remove higher concentrations of GenX.

[0158] In summary, the current disclosure allows for the preparation of functionalized resin with multiple cationic head groups, which can be combined in a manner as to modulate specific PF AS adsorption and / or absorption. Not to be bound by theory but it is believed that cationic head groups can be “matched” to specific PF AS contaminants based on their adsorption preferences and / or efficiencies. Furthermore, providing different loading of each cationic head group within the functionalized resin would allow to customize functionalized resins for different water matrices. Furthermore, it is believed that having soft aromatic cations as cationic head groups can promote desorption of PFAS in the presence of organic solvent and brine solutions thereby making these materials regenerable and reusable.E. Articles of Manufacture

[0159] In another aspect, described herein are articles of manufacture, for example, a “kit,” containing the one or more functionalized resins and a column or a filter. The kit comprises a container comprising the one or more functionalized resins. The column is designed to hold the one or more functionalized resins. When a filter is used as part of a kit, the kit may further contain additional components that aid in the filtering of the one or more functionalized resins from the water being treated (e.g., a container to collect the filtered, purified water, etc.). In some embodiments, the kit may include additional filtering materials that can be used to filter the water. Such exemplary additional filtering materials include activated carbon (i.e., in a granular form)and / or one or more ion exchange resins. These additional filtering materials can be employed in filtering water either before or after contact with the functionalized resin, or they can be mixed within the functionalized resin. For kits that contain such additional filtering materials, the kit may further contain additional components that aid in the filtering of the water being treated (e.g., a container to collect the filtered, purified water, etc.). The kit advantageously can contain premeasured amounts of the one or more functionalized resins (and additional filtering materials if applicable), for example, in amounts set forth elsewhere herein. The kit may further comprise a label or package insert, on or associated with the container. The term “package insert” is used to refer to instructions that can contain usage and warnings concerning the use of the components. Suitable containers for inclusion in the kit include, for example, bottles, vials, etc. The container may be formed from a variety of materials such as glass or plastic.E. PREPARATION AND OPTIMIZATION OF EXEMPLARY FUNCTIONALIZED RESINS

[0160] A series of functionalized resins (FRs) made from crosslinked polymers that contained a cationic head group bound to the resin (typically a chloride) were prepared. Of those, two classes of FRs with different crosslink densities and porosities were explored, as resin architecture is known to influence PFAS sorption capacity and kinetics.42The first, commonly referred to as geltype resins, has low crosslinking density and no permanent porosity. The second, commonly referred to as macroporous resins, have a higher crosslink density and permanent porosity. The resins were functionalized with the heterocycle of interest through an SN2 reaction between the nucleophilic nitrogen and the electrophilic chloride using an adapted literature procedure.1Briefly, PS beads were suspended in DMF (40 g beads / L solvent) and stirred for 1 hour. Then, the heterocycle of interest was added to the reaction, and the mixture was heated to 80 °C for 24 to 48 hours. The product was filtered, washed with an organic solvent, and dried in vacuo.

[0161] A library of FRs was synthesized by systematically varying the heterocycle (Fig. 1) to tune the steric bulk and electronics of the resulting cations.

[0162] Additionally, FRs containing 1 : 1 mixtures of functional groups, such as N- butylimidazole and triethylamine (FR-nBu-imid-EtsN) and 2,4-lutidine and tributylamine (FR- 2,4-Lut-Bu3N) were synthesized to understand the potential synergistic effects of mixed functional groups on PFAS sorption. Fourier-transform infrared spectroscopy was used to confirmaddition of the heterocycle. The resulting FRs also demonstrated a lower glass transition temperatures relative to the starting material as measured by differential scanning calorimetry, which provide additional evidence for functionalization (Table 1). The lowering of glass transition temperature demonstrates that functional groups were added to the polymer network that occupied a larger free volume than the base resin.

[0163] Table 1. Glass transition temperature of select FRs.

[0164] Batch Test Results: To understand the performance ofthe FRs forPFAS removal from water, the FRs with a size range between 75 and 125 um were subjected to batch equilibrium sorption experiments in simulated natural water containing a mixture of short chain and long chain PFAS spiked to a concentration of Ipg / L each. To prepare the water matrix, deionized water was spiked with 100 mg / L sodium chloride, then FR (10 mg / L) was added and stirred 3 hours. Next, the solution was spiked with PFAS. After 21 hours of stirring, an aliquot was removed and submitted for Liquid Chromatography-Mass Spectrometry (LC-MS) analysis to determine the removal of PFAS analytes relative to controls without FR. Experiments were conducted in duplicate. For comparison, a FR made with triethylamine (FR-EtsN) was synthesized to evaluate how a resin with a ‘hard’ ammonium group would compare. Additionally, a commercial ion exchange resin (Dow PSR2+) was tested under the same conditions.

[0165] Most FRs made with soft cations demonstrated efficient PFAS sorption. FR-Ox and FR-Th notably, were not efficient PFAS removal sorbents. However, FR-nMe-imid, FR-nBu- imid, FR-pyr, and FR-2,4-Lut out-performed the commercial resin (PSR2+) and the control FR- EtsN with respect to long-chain PFAS (PFHxS, PFHpA, PFOA, PFOS, PFNA) removal. With respect to short-chain PFAS (PFMOAA, PFBA, PFBS, PFPeA, PFHxA), the results were varied, as PSR2+ demonstrated superior removal of PFMOAA and PFBA, two ultrashortchain PFAS.However, FR-pyr demonstrated 91% GenX removal, whereas PSR2+ only removed 54% of GenX in this experiment, and FR-EfeN removed 61%. GenX, a short-chain, branched PFAS, is challenging to remove using commercial sorbents. FR-nMe-imid and FR-nBu-imid demonstrated 76% and 84% GenX removal, respectively. Finally, mixed functional group resins FR-nBu-imid-EbN and FR-2,4-Lut-Bu3N demonstrated similar performance to their counterparts FR-nBu-imid and FR-2,4-Lut. Sorbents containing 2,4-lutidine demonstrated higher short-chain PFAS removal, specifically of short-chain PFAS PFMOAA, than other FRs. However, a slight decrease in long-chain PFAS sorption was observed (94% PFHpA removal by FR-2,4- Lut versus 88% removal by FR-nBu-imid-EbN. These results highlight the influence of cation structure on resin performance and demonstrate the excellent performance of FRs with soft cations for removal of challenging PFAS from simulated natural water (Fig. 2; Table 2).

[0166] Table 2. Batch equilibrium sorption of PFAS by FRs after 21 hours. [NaCl] = 200 mg / L, [PFAS]0 = lug / L each. Average of duplicate experiments shown. PSR2+: Dow PSR2+ commercial ion exchange resin.

[0167] Packed Bed Results: Next, FR-nBu-imid was analyzed in a mini-Rapid Small Scale Column Test (mini-RSSCT) using a real-world sample of settled conventional surface water, which was provided by the Orange County (North Carolina) Water and Sewer Authority. Notably, this water sample contained ppt-levels of numerous PFAS, including PFOA (18 ppt), PFOS (21 ppt), perfluorobutanesulfonic acid (PFBS, 3 ppt) and perfluorohexanesulfonic acid (PFHxS, 5 ppt). The water sample was used without additional PFAS spiking.

[0168] Mini-RSSCTs can probe long- term sorbent performance in a packed bed column geometry.43 45Compared to the batch reactors used for initial screening described above, these flow-through, packed bed column reactors provide a closer representation of the fdter columns used in a real -world deployment scheme. Column diameter and sorbent granule size will be similar to those in our previous work,46’47determined by following the commonly used constant-diffusion approach45-48to mimic behavior in full-scale processes. In this experiment, water was flowed through a packed bed of FR-nBu-imid over two weeks, which resulted in 435,000 bed volumes of continuous operation.

[0169] The ratio of each PFAS in the effluent relative to the influent is given by the term “breakthrough.” Long-chain perfluorinated sulfonic acids PFHxS and PFOS demonstrated little breakthrough until roughly 250,000 bed volumes, which correlates to nearly two years of real- world use by first approximation. PFOA and short-chain PFBS surpassed 10% breakthrough much earlier (50,000 and 110,000 bed volumes, respectively). This initial flow-through packed bed result indicates that the FRs are efficient PFAS removal sorbents in practical remediation scenarios suchas large-scale water treatment facilities (Fig. 3; Table 3).

[0170] Table 3. Mini-RSSCT leveraging FR-nBu-imid as the granular sorbent. Settled Conventional water, Orange County, North Carolina.

[0171] Impact of Bead Morphology: The results given in Figs. 1-3 are for gel-type ion exchange poly(styrene-co-divinylbenzene) resins without permanent porosity. Macroporous resins with permanent porosity may demonstrate improved PFAS sorption in varied water matrices, in particular those with higher organic ion levels. To that end, four FRs from macroporous poly(styrene-co-divinylbenzene) resins with / V-butylimidazole, pyridine, 4- / c77-butylpyridine and2,4-lutidine nucleophiles, respectively, were prepared to yield Macro-FR-nBu-imid, Macro-FR- pyr, Macro-FR-4-tBupyr, and Macro-FR-2,4-Lut. In simulated water containing 1000 ng / L PFAS and 200 mg / L NaCl, these macroporous FRs outperformed their gel FR counterparts with respect to short-chain PFAS removal (Fig. 4; Table 4). The macroporous FRs demonstrated varied PFAS sorption relative to their gel counterparts. In particular, Macro-FR-2,4-Lut outperformed FR-2,4-Lut with respect to short-chain PFAS sorption, in particular for PFMOAA and PFBA. Not to be bound by theory, but it is believed that macroporous functionalized resins provide a larger surface area to adsorb PFAS contaminants not only on the surface of the resin but also within the pores of the resin, whereas functionalized resins in the form of a gel can only adsorb PFAS contaminants on the surface of the functionalized resin.

[0172] A selection of macroporous FRs was then evaluated in spiked settled conventional water from an N.C. water treatment plant (Fig. 5; Table 5). The macroporous FRs out-performed gel FRs and commercial PSR2+ for PFAS removal, particularly of short-chain PFAS PFHxA, GenX, and PFMOAA. This selectivity could be due to varied pore sizes in macroporous resins, which facilitate binding of smaller short-chain PFAS into pores which are too small for long-chain PFAS or humic acids. This in turn creates a synergistic effect with the soft acid / base interaction, resulting in highly selective PFAS remediation materials.

[0173] Table 4. Removal of PFAS from water. [PFAS]0 = 1 ug / L. [NaCl] = 200 mg / L. Results shown are averages of duplicate experiments, t = 21 hr.

[0174] Table 5. Removal of PFAS from spiked settled conventional water. [PFAS]o = lug / L. Results shown are averages of duplicate experiments, t = 21 hr. PSR2+: Dow PSR2+ commercial ion exchange resin.

[0175] Regeneration of Functionalized Resins- FRs Macro-FR-2,4-Lut and FR-2,4-Lut were subjected to batch regeneration studies by the following procedure. Briefly, sorbent (50 mg / L) was added to a cellulose teabag and suspended in deionized water spiked with PFAS (1,000 ng / L each PFOA, PFOS, PFHxA, PFHxS, GenX, and PFMOAA) and isolate of Suwanee River natural organic matter (NOM, 50 mg / L). The solutions were stirred for 21 hours, after which point the tea bags containing sorbent were removed. The solution was then analyzed by LC-MS to determine the extent of PFAS sorption by the sorbents. Subsequently, the teabags of sorbent were suspended in 10% sodium chloride solution in water, and the solution was stirred for 1 hour. The concentration of PFAS in the sodium chloride solution was then determined by LC-MS. Regenerability therefore determined as the percent release of PFAS into the NaCl solution by eachsorbent, based on the calculated sorption of PFAS during the initial experiment in spiked water. The results are shown in Fig. 6 and Table 6.[001761 Table 6. Sorbent regenerability as measured by PFAS release in 10% NaCl solution. FRs were first stirred in water containing NOM (50 mg / L) and PFAS ([PFAS]o = 1000 ng / L each). After 21 hours, sorbents were transferred to 10% NaCl solution and stirred 1 hr. PFAS release was determined using LC-MS. PSR2+: Dow PSR2+ commercial ion exchange resin.CalRes 2301 : Calgon CalRes 2301 commercial ion exchange resin.

[0177] Both Macro-FR-2,4-Lut and FR-2,4-Lut demonstrated comparable regenerability as commercial sorbents PSR2+ and CalRes 2301 for long-chain PFAS PFOA. However, results were varied for other PFAS. Macro-FR-2,4-Lut released a greater fraction of sorbed PFHxA than the other sorbents, and both Macro-FR-2,4-Lut and FR-2,4-Lut released a higher fraction of sorbed GenX than the commercial sorbents.

[0178] This library of soft cationic FRs demonstrates potential as a class of PFAS remediation sorbents from natural water matrices. Multiple FRs out-performed commercial sorbents for challenging PFAS analyte removal. In packed-bed experiments, FR-nBu-imid demonstrated efficient removal of relevant PFAS.

[0179] Packed Bed Results: Next, Macro-FR-4-tBupyr was analyzed in a mini-Rapid Small Scale Column Test (mini-RSSCT) using a real-world sample of biofilter effluent, which wasprovided by the Cape Fear Public Utility Authority (North Carolina). Notably, this water sample was spiked with 100 ppt each of numerous PFAS, including PFOA, PFOS, PFHxA, PFHxS, GenX, and PFMOAA. In this experiment, water was flowed through a packed bed of Macro-FR-4-tBupyr over five days, which resulted in -165,000 bed volumes of continuous operation.

[0180] Perfluorinated sulfonic acids, PFHxS and PFOS, demonstrated little breakthrough until roughly 73,000 bed volumes, which correlates to nearly seven months of real -world use by first approximation. PFOA, PFHxA, GenX, and PFMOAA surpassed 10% breakthrough earlier at <42,000, <36,000, <36,000, and <9,500 bed volumes, respectively. Macro-FR-4-tBupyr also outperformed a commercial sorbent, CalRes 2301, at removing PFMOAA; PFMOAA surpassed 10% breakthrough in Macro-FR-4-tBupyr and CalRes 2301 at <9,500 and -2,400 bed volumes, respectively. This initial flow-through packed bed result indicates that the FRs are efficient PFAS removal sorbents in practical remediation scenarios such as large-scale water-treatment facilities(Table 7; Table 8)

[0181] Table 7. RSSCT leveraging Macro-FR-4-tBupyr as the granular sorbent. Biofilter effluent from a surface water treatment plant, New Hanover County, North Carolina.

[0182] Table 8. Comparison in PFMOAA breakthrough between CalRes 2301 and Macro 4- tBupyr in RSSCT. Biofilter effluent from a surface water treatment plant, New Hanover County, North Carolina.Results: Resins evaluated at pilot drinking water Pilots were run at contact time of 2.0 hydraulic loading per minute per column diametera bed depth of 48.1 inches. Gel-type (Gel-FR-2,4-Lut-Bu3N) and macroporous (Macro-FR-4-tBupyr) novel sorbents were analyzed in pilot-scale columns treating surface water biofilter effluent at the Sweeney WaterTreatment Plant in Wilmington, North Carolina. This biofilter effluent contained ppt-levels of numerous PFAS, including PFOA (4-10 ppt), PFOS (5-10 ppt), PFHxA (4-10 ppt), PFHxS (3- 10 ppt), PFPrA (10-40 ppt), and PFMOAA (2-30 ppt). These columns have been running in continuous operation for >200,000 bed volumes. In Gel-FR-2,4-Lut-Bu3N, PFOA, PFHxA, PFPrA, and PFMOAA surpassed 10% breakthrough at <130,000, <104,000, <8,000, and <11,000 bed volumes, respectively. There has not been any significant breakthrough of either PFOS nor PFHxS (Table 9). Macro-FR-4-tBupyr saw earlier breakthrough of all PFAS species for this water source (Table 10). Gel-FR-2,4-Lut-Bu3N outperformed CalRes 2301 at removing PFHxA seeing 10% breakthrough after higher bed volumes, whereas Macro-FR-4-tBupyr was comparable to CalRes 2301 at removing PFHxA (Table 11).

[0184] Table 9. Pilot leveraging Gel-FR-2,4-Lut-Bu3N as the granular sorbent. Biofilter effluent in a surface water treatment plant, New Hanover County, North Carolina.

[0185] Table 10. Pilot leveraging Macro-FR-4-tBupyr as the granular sorbent. Biofilter effluent in a surface water treatment plant, New Hanover County, North Carolina.

[0186] Table 11. Comparison in PFHxA breakthrough between CalRes 2301, Gel-FR-2,4- Lut-Bu3N, and Macro-FR-4-tBupyr in pilot tests. Biofilter effluent in a surface water treatment plant, New Hanover County, North Carolina.

[0187] Macroporous (Macro-FR-2,4-Lut and Macro-FR-4-tBupyr) novel sorbents were analyzed in pilot-scale columns treating raw groundwater at the Richardson Water Treatment Plant in Wilmington, North Carolina. This untreated groundwater contained ppt-levels of numerous PFAS, including PFOA (0.5-2 ppt), PFOS (0.5-3 ppt), PFHxA (0.2-2.5 ppt), PFHxS (0.5-2.5 ppt), PFPrA (16-71 ppt), and PFMOAA (11-210 ppt). These columns have been running in continuous operation for >200,000 bed volumes. The cumulative removal of these sorbents for PFMOAA (measured as micrograms of PFAS per liter of sorbent) was measured at two different time points and compared to CalRes 2301 (FIG. 8). At thirty days, CalRes 2301 had a cumulative removal of 634.9 (pg PFMOAA / L sorbent), Macro-FR-2,4-Lut of 736.4, and Macro-FR-4-tBupyr of714.1. After 100 days, the cumulative removal ofPFMOAAby CalRes 2301 decreased to 202.2,indicating that PFMOAA desorbed from CalRes 2301 as competing contaminants were continuously introduced. The cumulative removal of Macro-FR-2,4-Lut and Macro-FR-4-tBupyr over that time increased to 1,048.7 and 983.3, respectively, indicating that these two sorbents continued to remove PFMOAA from the water.

[0188] Particular embodiments of the subject matter described herein include:

[0189] 1 A compound according to Formula (I):R-L-CFormula (I) wherein R is a resin scaffold material selected from the group consisting of styrene- based polymers and acrylic-based polymers;L is a substituted or unsubstituted (C1-C5) alkyl linker;C is a cationic head group according to Formula (A) or (B):Formula (A) Formula (B) wherein n is 1 or 2; m is an integer selected from 0, 1, 2, 3 and 4;X is selected from CR2, NR3, S, N and O; andRi, R2 and R3, in each instance, are -H, substituted or unsubstituted (Ci-Ce) alkyl or substituted or unsubstituted benzyl.

[0190] 2. The compound according to embodiment 1, wherein n is 1.

[0191] 3. The compound according to embodiment 1 or 2, wherein m is 0.

[0192] 4. The compound according to any one of the preceding embodiment, wherein X isNR3 or N.

[0193] 5. The compound according to embodiment 4, wherein C is a cationic head group according to Formula (A.l) or Formula (B.l):Formula (A. l) Formula (B. l) wherein X is S, O, or NR3; andR3, in each instance, is (Ci-Ce) alkyl or benzyl.

[0194] 6. The compound according to any one of the preceding embodiments, wherein the cationic head group is selected from:

[0195] 7 The compound according to embodiment 1, wherein n is 2.

[0196] 8 The compound according to embodiment 7, wherein X is CR2 or N.

[0197] 9. The compound according to embodiment 8, wherein C is a cationic head group according to Formula (A.2) or (A.3):Formula (A.2) Formula (A.3) wherein m is 0, 1, 2, 3, or 4; andRi and R2, in each instance, are -H or (Ci-Ce) alkyl.

[0198] 10. The compound according to embodiment 9, wherein in Formula (A.2) m is 0, 1 or2.

[0199] 11. The compound according to embodiment 9 or 10, wherein in Formula (A.2) R2 is-H.

[0200] 12. The compound according to embodiment 9, wherein in Formula (A.2) m is 0 or 1; and R2is -CH3or -C(CH3)3.

[0201] 13. The compound according to embodiment 9, wherein in Formula (A.3) m is 0, 2, or 4.

[0202] 14. The compound according to any one of embodiment 9-13, wherein Ri is -CH3.

[0203] 15. The compound according to any one of the preceding embodiments, wherein the cationic head group is selected from:

[0204] 16. The compound according to any one of the preceding embodiments, wherein the linker is -CH2-.

[0205] 17. The compound according to any one of the preceding embodiments, wherein the resin scaffold material is a styrene-based polymer.

[0206] 18. The compound according to any one of the preceding embodiments, wherein the styrene-based polymer is a copolymer of styrene and divinylbenzene.

[0207] 19. The compound according to any one of the preceding embodiments, wherein the polymer is crosslinked with a crosslinking density of from about 0.1% to about 20%.

[0208] 20. The compound according to any one of the preceding embodiments, wherein the resin is porous.

[0209] 21. The compound according to any one of the preceding embodiments, wherein the resin is in the form of a gel.

[0210] 22. The compound of embodiment 20 or 21, wherein the resin comprises a surface area of at least 0.001 m2 / g.

[0211] 23. The compound of embodiment 21, wherein the resin comprise a surface are of less than 100,000 m2 / g.

[0212] 24. The compound according to any one of the preceding embodiments, wherein the resin comprises a surface area of from about 0.001 m2 / g to about 5000 m2 / g.

[0213] 25. The compound according to any one of the preceding embodiments, wherein the resin comprises resin particles with a mean diameter of from about 5 pm to about 2,000 pm.

[0214] 26. The compound according to embodiment 25, wherein the mean diameter ranges from about 100 pm to about 900 pm.

[0215] 27. The compound according to embodiment 25, wherein the mean diameter ranges from about 200 pm to about 1200 pm.

[0216] 28. The compound according to any one of the preceding embodiments, wherein the resin comprises a pore volume of from about 0.01 cm3 / g to about 0.5 cm3 / g.

[0217] 29. A method of removing PFAS from a PFAS contaminated water supply, the method comprising: a) contacting the PFAS contaminated water supply with a compound according to Formula (II) to form a mixture, wherein Formula (II) is:R-L-C(Formula (II) wherein R is a resin scaffold material selected from the group consisting of crosslinked polymers, modified carbon, modified clay, modified cellulose, modified silica, or a combination thereof;L is an aliphatic linker, an aromatic linker, or an oligoether linker;C is a cationic head group according to Formula (A) or (B):Formula (A) Formula (B) wherein n is 1 or 2; m is an integer selected from 0, 1, 2, 3 and 4;X is selected from CR2, NR3, S, N and O; andRi, R2 and R3, in each instance, are -H, substituted or unsubstituted (Ci- Ce) alkyl or substituted or un substituted benzyl;b) adsorbing of one or more PFAS contaminants present in the mixture onto the compound of Formula (I).[002181 30. The method according to embodiment 29, wherein the one or more PFAS contaminants in the purified water supply are reduced in an amount of about 1 to about 99%.

[0219] 31. The method according to embodiment 29 or 30 wherein the one or more PFAS contaminants reduced in the purified water supply comprises short chain PFAS contaminants, long chain PFAS contaminants or a combination thereof.

[0220] 32. The method according to embodiment 29, wherein the one or more PFAS contaminants being reduced are short chain PFAS contaminants selected from the group consisting of PFMOAA, PFBA, PFBS, PFPeA, PFHxA, GenX, PFPrA and a combination thereof.

[0221] 33. The method according to embodiment 29, wherein the one or more PFAS contaminants being reduced are long chain PFAS contaminants selected from the group consisting of PFHxS, PFHpA, PFOA, PFOS, PFNA, and a combination thereof.

[0222] 34. The method according to any one of embodiments 29-33, wherein the contacting step comprises mechanical mixing of the compound of Formula (II) and the PFAS contaminated water supply in a container.

[0223] 35. The method according to any one of embodiments 29-33, wherein the contacting step comprises adding the PFAS contaminated water supply into a column packed with the compound of Formula (II).

[0224] 36. The method according to any one of embodiments 29-35 further comprising filtering the mixture to obtain a purified water supply as an effluent.

[0225] 37. The method according to any one of embodiments 29-36, further comprising releasing the bound PFAS from the PFAS bound functionalized resin to regenerate the compound according to formula (II).

[0226] 38. The method according to embodiment 37, wherein the PFAS boundfunctionalized resin is exposed to a salt solution and / or an aqueous organic solvent.

[0227] 39. The method according to embodiment 38, wherein the salt solution is selected from the group consisting of sodium chloride, sodium bromide, sodium acetate, sodium carbonate, sodium bicarbonate, sodium hydroxide, iron sulfate, and a combination thereof.

[0228] 40. The method according to embodiment 38 or 39, wherein the aqueous organic solvent is selected from the group consisting of methanol, ethanol, denatured ethanol, isobutanol, acetonitrile and a combination thereof.

[0229] 41. The method according to any one of embodiments 37-40, wherein at least 20% of bound PFAS is released from the PFAS bound functionalized resin.

[0230] 42. The method according to any one of the preceding embodiments, wherein n is 1.

[0231] 43. The method according to any one of the preceding embodiments, wherein m is 0

[0232] 44. The method according to any one of the preceding embodiments, wherein X isNR3.

[0233] 45. The method according to any one of the preceding embodiments, wherein C is a cationic head group according to Formula (A.1) or Formula (B.1):Formula (A.1) Formula (B. l) wherein X is S, O, orNR3; andR3is substituted or unsubstituted (C1-C5) alkyl or substituted or unsubstituted benzyl.

[0234] 46. The method according to any one of the preceding embodiments, wherein the cationic head group is selected from:

[0235] 47. The method according to any one of the preceding embodiments, wherein n is 2.

[0236] 48. The method according to embodiment 47, wherein X is CR2.

[0237] 49. The method according to embodiment 48, wherein C is a cationic head group according to Formula (A.2) or (A.3):Formula (A.2) Formula (A.3) wherein Ri and R2, in each instance, are -H or (C1-C5) alkyl.

[0238] 50. The method according to embodiment 49, wherein in Formula (A.2) m is 0, 1 or2.

[0239] 51. The method according to embodiment 49 or 50, wherein in Formula (A.2) R2 is -H.

[0240] 52. The method according to embodiment 49, wherein in Formula (A.2) m is 0 or 1; and R2is -CH3or -C(CH3)3.

[0241] 53. The method according to embodiments 49, wherein in Formula (A.3) m is 0, 2, or4.

[0242] 54. The method according to any one of embodiments 49-53, wherein Ri is -CH3.

[0243] 55. The method according to any one of the preceding embodiments, wherein the cationic head group is selected from:

[0244] 56. The method according to any one of the preceding embodiments, wherein the linker is a substituted or unsubstituted (Ci-Ce) alkyl linker.[00245J 57. The method according to any one of the preceding embodiments, wherein the linker is -CH2-.

[0246] 58. The method of any one of the preceding embodiments, wherein the aromatic linker contains at least one substituted or unsubstituted phenyl moiety and / or at least one substituted or unsubstituted benzyl moiety.

[0247] 59. The method of any one of the preceding embodiments, wherein the linker is an oligoether linker according to Formula (A):-[-O-(Ci-Ci2) alkyl-]n-Formula (A) wherein n is an integer from about 1 to about 100.

[0248] 60. The method according to any one of the preceding embodiments, wherein the resin scaffold material is a styrene-based polymer.

[0249] 61. The method according to any one of the preceding embodiments, wherein the stryrene-based polymer is a copolymer of styrene and divinylbenzene.

[0250] 62. The method according to any one of the preceding embodiments, wherein the polymer is crosslinked with a crosslinking density of from about 0.1% to about 20%.

[0251] 63. The method according to any one of the preceding embodiments, wherein the resin comprises a surface area of from about 0.001 m2 / g to about 100,000 m2 / g.

[0252] 64. The method according to any one of the preceding embodiments, wherein the resin comprises a pore volume of from about 0.01 cm3 / g to about 0.5 cm3 / g.

[0253] 65. The method according to any one of the above embodiments, wherein the aqueous organic solvent is selected from the group consisting of methanol, ethanol, denatured ethanol, isobutanol, acetonitrile and a combination thereof.

[0254] 66. The method according to any one of the above embodiments, wherein at least20% of bound PFAS is released from the PFAS bound functionalized resin.

[0255] 67. A method of making a compound according to embodiment 1, the method comprising: contacting a scaffold resin material with a nitrogen-containing heterocycle in a polar aprotic solvent to afford a reaction mixture; and filtering the reaction mixture to obtained the compound according to embodiment 1.

[0256] 68. The method according to embodiments 67, wherein the scaffold resin material is functionalized with a leaving group.

[0257] 69. The method according to embodiments 67 or 68, further comprising exposing the scaffold resin material with an additional nitrogen-containing heterocycle.F. EXAMPLES

[0258] The following preparations and examples are given to enable those skilled in the art tomore clearly understand and to practice the present invention. They should not be considered as limiting the scope of the invention, but merely as being illustrative and representative.

[0259] Example 1 - General Synthesis of FRs:

[0260] A. Properties of Polystyrene Resins

[0261] The starting polystyrene resins were either spherical or ground bulk materials containing between 0.5 % and 20 % divinylbenzene as a crosslinker and between 0.5 and 5 mmol / g functionalization with a leaving group, typically chloride, another halide, or other good leaving group. The resins could be gel in nature, microporous, mesoporous, or macroporous. The chloride is attached to the bead through a linker at the meta or para position of a styrene unit, typically through a methyl group. The linker between the polystyrene bead and the leaving group could be different from a methyl group, including longer alkyl linkers, ether or polyether linkers, perfluorinated linkers, or others. The resin size could be between 30 um and 1.5 mm.

[0262] A representation of such a resin is:

[0263] A styrenic backbone comprised of a copolymer of styrene, (chloromethyl)styrene, and divinylbenzene is shown, wherein The divinylbenzene forms covalent crosslinks with polymer chains (represented by the squiggly line to reduce complexity).

[0264] B. Procedure

[0265] Functionalized resins (FRs) were synthesized according to an adapted literature procedure.1Briefly, chloromethylated poly(styrene-co-divinylbenzene) spheres were suspended in / VA'-dimethylformamide (DMF) and stirred gently. After 1 hour, a solution of the nucleophile ofinterest (3 eq. relative to chloromethyl groups) in DMF was added, and the reaction was heated to 80° C. After 24-48 hours, the reaction was cooled, solids were filtered to remove solvent, and the resulting sorbent was washed with ethanol / water solutions. The resulting FRs were analyzed via Fourier Transform Infrared Spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC), then submitted for performance testing in batch or column tests. The FRs could be used as whole beads, sieved, or ground, then sieved, for analysis in batch and column tests.

[0266] Functionalized resins could also be synthesized through the copolymerization of styrene, divinylbenzene, and vinyl monomers such as 2-vinylpyridine, 2-vinylimidazole, or others, followed by subsequent quaternization to install permanent charge.

[0267] Example 2: Sorbent performance relative to commercial resin CalRes 2301

[0268] Macro-FR-4tBupyr was evaluated in a mini-Rapid Small Scale Column Test (mini- RSSCT) in settled conventional groundwater from Wilmington, North Carolina. Mini-RSSCTs can probe long-term sorbent performance in less than two weeks. In this experiment, water was flowed through a packed bed of either CalRes 2301 (Calgon Carbon Corporation commercial macroporous resin) or Macro-FR-4tBupyr over roughly 87,000 bed volumes. Although long and short-chain PFAS are all analytes of interest in eastern N.C., short-chain PFAS PFMOAA is particularly challenging to remove and is typically among the first analytes to break through to the effluent water. Therefore, PFMOAA breakthrough is a key driver of sorbent changeout in this municipal drinking water system.

[0269] In the influent, PFMOAA was present at roughly 7 parts-per-trillion (ppt). Detection of PFMOAA by Liquid Chromatography with tandem Mass Spectrometry (LC-MS / MS) is defined as 2 ppt, or roughly 30 % breakthrough (Fig. 7). CalRes 2301 demonstrated PFMOAA breakthrough (2 ppt) at roughly 6,000 bed volumes, while Macro-FR-4tBupyr performed roughly three times better, reaching 2 ppt PFMOAA breakthrough at roughly 20,000 bed volumes. The improved performance of the novel sorbent for short-chain PFAS removal is clear and may translate to longer sorbent bed lives in municipal treatment scenarios targeting short-chain PFAS.

[0270] Table 1. Percent Breakthrough versus bed volumes of water treated for PFMOAA removal. Source: 7 ppt PFMOAA, Sweeney Water Treatment Plant, Wilmington, N.C. Dataaccompanies Fig. 7.

Claims

What is claimed is:

1. A compound according to Formula (I):R-L-CFormula (I) wherein R is a resin scaffold material selected from the group consisting of styrene-based polymers and acrylic-based polymers;L is a substituted or unsubstituted (C1-C5) alkyl linker;C is a cationic head group according to Formula (A) or (B):Formula (A) Formula (B) wherein n is 1 or 2; m is an integer selected from 0, 1, 2, 3 and 4;X is selected from CR2, NR3, S, N and O; andRi, R2 and R3, in each instance, are -H, substituted or unsubstituted (Ci-Ce) alkyl or substituted or unsubstituted benzyl.

2. The compound according to claim 1, wherein n is 1.

3. The compound according to claim 2, wherein m is 0.

4. The compound according to claim 3, wherein X is NR3 or N.

5. The compound according to claim 4, wherein C is a cationic head group according to Formula (A.1) or Formula (B.l):Formula (A.1) Formula (B.l) wherein X is S, O, or NR3; andR3, in each instance, is (Ci-Ce) alkyl or benzyl.

6. The compound according claim 5, wherein the cationic head group is selected from:

7. The compound according to claim 1, wherein n is 2.

8. The compound according to claim 7, wherein X is CR2 or N.

9. The compound according to claim 8, wherein C is a cationic head group according to Formula (A.2) or (A.3):Formula (A.2) Formula (A.3)wherein m is 0, 1, 2, 3, or 4; andRi and R2, in each instance, are -H or (Ci-Ce) alkyl.

10. The compound according to claim 9, wherein in Formula (A.2) m is 0, 1 or 2.

11. The compound according to claim 10, wherein in Formula (A.2) R2 is -H.

12. The compound according to claim 9, wherein in Formula (A.2) m is 0 or 1; and R2 is -CH3 or -C(CH3)3.

13. The compound according to claim 9, wherein in Formula (A.3) m is 0, 2, or 4.

14. The compound according to claim 9, wherein Ri is -CH3.

15. The compound according to claim 9, wherein the cationic head group is selected from:

16. The compound according to claim 1, wherein the linker is -CH2-.

17. The compound according to claim 1, wherein the resin scaffold material is a styrene-based polymer.

18. The compound according to claim 17, wherein the styrene-based polymer is a copolymer of styrene and divinylbenzene.

19. The compound according to claim 1, wherein the resin is porous.

20. The compound according to claim 1, wherein the resin is in the form of a gel.

21. The compound of claim 19, wherein the resin comprises a surface area of at least 0.001 m2 / g.

22. The compound of claim 20, wherein the resin comprises a surface area of at least 0.001 m2 / g.

23. The compound according to claim 1, wherein the resin comprises resin particles with a mean average diameter of from about 5 pm to about 2,000 pm.

24. The compound according to claim 23, wherein the mean average diameter of the resin particle ranges from about 100 pm to about 900 pm.

25. The compound according to claim 23, wherein the mean average diameter of the resin particle ranges from about 200 pm to about 1200 pm.

26. The compound according to claim 1, wherein the resin comprises a pore volume of from about 0.01 cm3 / g to about 0.50 cm3 / g.

27. A method of removing PFAS from a PFAS contaminated water supply, the method comprising: a) contacting the PFAS contaminated water supply with a compound according to Formula (II) to form a mixture, wherein Formula (II) is:R-L-C(Formula (II) wherein R is a resin scaffold material selected from the group consisting of crosslinked polymers, modified carbon, modified clay, modified cellulose, modified silica, or a combination thereof;L is an aliphatic linker, an aromatic linker, or an oligoether linker;C is a cationic head group according to Formula (A) or (B):Formula (A) Formula (B) wherein n is 1 or 2; m is an integer selected from 0, 1, 2, 3 and 4;X is selected from CR2, NR3, S, N and O; andRi, R2 and R3, in each instance, are -H, substituted or unsubstituted (Ci-Ce) alkyl or substituted or unsubstituted benzyl; b) adsorbing of one or more PF AS contaminants present in the mixture onto the compound of Formula (II).

28. The method according to claim 27, wherein the one or more PFAS contaminants in the purified water supply are reduced in an amount of about 1 to about 99%.

29. The method according to claim 28, wherein the one or more PFAS contaminants reduced in the purified water supply comprises short chain PFAS contaminants, long chain PFAS contaminants or a combination thereof.

30. The method according to claim 27, wherein the one or more PFAS contaminants being reduced are short chain PFAS contaminants selected from the group consisting of PFMOAA, PFBA, PFBS, PFPeA, PFHxA, GenX, PFPrA and a combination thereof.

31. The method according to claim 27, wherein the one or more PFAS contaminants being reduced are long chain PFAS contaminants selected from the group consisting of PFHxS, PFHpA, PFOA, PFOS, PFNA, and a combination thereof.

32. The method according to claim 27, wherein the one or more PFAS contaminants being reduced are selected from the group consisting of PFOA, PFOS, PFNA, GenX, PFHxS and PFBS.

33. The method according to claim 28, wherein the contacting step comprises mechanical mixing of the compound of Formula (II) and the PFAS contaminated water supply in a container.

34. The method according to claim 28, wherein the contacting step comprises adding the PFAS contaminated water supply into a column packed with the compound of Formula (II).

35. The method according to claim 28 further comprising filtering the mixture to obtain a purified water supply as an effluent.

36. The method according to claim 28, further comprising releasing the bound PFAS from the PFAS bound functionalized resin to regenerate the compound according to formula (II).

37. The method according to claim 36, wherein the PFAS bound functionalized resin is exposed to a salt solution and / or an aqueous organic solvent.

38. The method according to claim 37, wherein the salt solution is selected from the group consisting of sodium chloride, sodium bromide, sodium acetate, sodium carbonate, sodium bicarbonate, sodium hydroxide, iron sulfate, and a combination thereof.

39. The method according to claim 37, wherein the aqueous organic solvent is selected from the group consisting of methanol, ethanol, denatured ethanol, isobutanol, acetonitrile and a combination thereof.

40. The method according to claim 28, wherein n is i .

41. The method according to claim 40, wherein m is 0.

42. The method according to claim 41, wherein X is NR3.

43. The method according to claim 42, wherein C is a cationic head group according to Formula (A.1) or Formula (B.l):Formula (A. l) Formula (B.l) wherein X is S, O, or NR3; andR3 is substituted or unsubstituted (C1-C5) alkyl or substituted or unsubstituted benzyl.

44. The method according to claim 43, wherein the cationic head group is selected from:

45. The method according to claim 28, wherein n is 2.

46. The method according to claim 45, wherein X is CR2.

47. The method according to claim 46, wherein C is a cationic head group according to Formula (A.2) or (A.3):Formula (A.2) Formula (A.3) wherein Ri and R2, in each instance, are -H or (C1-C5) alkyl.

48. The method according to claim 47, wherein in Formula (A.2) m is 0, 1 or 2.

49. The method according to claim 48, wherein in Formula (A.2) R2 is -H.

50. The method according to claim 47, wherein in Formula (A.2) m is 0 or 1; and R2 is -CH3 or - C(CH3)3.

51. The method according to claim 47, wherein in Formula (A.3) m is 0, 2, or 4.

52. The method according to claim 51, wherein Ri is -CH3.

53. The method according to claim 47, wherein the cationic head group is selected from:

54. The method according to claim 28, wherein the linker is a substituted or unsubstituted (Ci-Ce) alkyl linker.

55. The method according to claim 54, wherein the linker is -CH2-.

56. The method according to claim 28, wherein the aromatic linker contains at least one substituted or unsubstituted phenyl moiety and / or at least one substituted or unsubstituted benzyl moiety.

57. The method according to claim 28, wherein the linker is an oligoether linker according to Formula (A):-[-O-(Ci-C 12) alkyl-]n-Formula (A) wherein n is an integer from about 1 to about 100.

58. The method according to claim 57, wherein the resin scaffold material is a styrene-based polymer.

59. The method according to claim 58, wherein the stryrene-based polymer is a copolymer of styrene and divinylbenzene.

60. The method according to claim 59, wherein the polymer is crosslinked with a crosslinking density of from about 0.1% to about 20%.

61. The method according to claim 59, wherein the resin is at least about 0.001 m2 / g.

62. The method according to claim 61, wherein the resin comprises a pore volume of from about 0.01 cm3 / g to about 0.5 cm3 / g.

63. A method of making a compound according to claim 1, the method comprising: contacting a scaffold resin material with a nitrogen-containing heterocycle in a polar aprotic solvent to afford a reaction mixture; and filtering the reaction mixture to obtained the compound according to claim 1.

64. The method according to claim 63, wherein the scaffold resin material is functionalized with a leaving group.

65. The method according to claim 63, further comprising exposing the scaffold resin material with an additional nitrogen-containing heterocycle.

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