NZ794040A - Charge-bearing cyclodextrin polymeric materials and methods of making and using same - Google Patents

Abstract

The present disclosure relates to a porous polymeric material comprising a plurality of cyclodextrins crosslinked with a plurality of aryl diisocyanate crosslinkers, wherein one or more of the plurality of cyclodextrins are bound to a linker of formula (I) as shown in the abstract drawing, as well as related methods of purifying a fluid sample.

Description

The present disclosure s to charge-bearing polymeric materials and methods of their use for purifying fluid samples from micropollutants, such as anionic micropollutants.

NZ 794040 —BEAEMNG EXTRlN PGL‘thERlC h/lATERlALS AND h/lli'l‘lrlGDS 0F hlAKlNG AND USlNG SAhllij Racheround mmnmunmm {twill} Organic niicropollutants (MPs) are present in water resources at ng L"1 to pg L—1 concentrations as a consequence of human activitiesl’2 Concerns about their negative effects on human health3"7 and the environmentg‘m motivate the development of logies that remove lvll?’s more effectively."16 MPs span a wide variety of physiocheniical ties including surface charge, size, and chemical functionality. Charged Ml’s can he cationic, anionic, or zwitterionic and are typically difficult to remove in the presence of complex matrix constituents like natural organic matter (NOM) using conventional adsorption methods like activated carbon.

Of the anionic h/lPs, PFASs t a particular environmental prohleni because of their resistance to hiodegradation and correlation to negative health effects. PFASs have been used in the ations of thousands of consumer goodsl and are present in aqueous foam ations used to suppress aviation fires in training scenarios. ""9 As a result, they have contaminated surface and ground waters near thousands of ts and, military installations.20 ln 2016, Hu and coworkers showed that at least 6 million Americans were served drinking water contaminated with PFASS at or above the US EPAs 20l6 health advisory limit for pertluorooctanoic acid (PFOA) and pertluorooctanesulfonic acid (PFOS) of 70 ng liil.21 PFASs have been linked to cancers,3 liver damage,4 thyroid disease5 and other health problems.6 {lllll‘tZ} Contaminated water systems are typically rernediated with granular activated carbon (GAG), but its modest affinity for PFASS, particularly short chain derivatives, makes it an expensive and stop~gap solution."24 in recent reports, 14’13 it was discovered that alent interactions and the ostatics of functional groups influence PFAS affinity to adsorbents, For example, a ation of fluorophilic interactions of the crosslinlter and a lower concentration of anionic d functional groups in decafluorohiphenyldinlred CDPs led to high PFOA and PFOS removal from water. in contrast, CDPs crosslinked by epichlorohydrin exhibited inferior FFAS l.25 {(3893} Adsorption processes can be employed to remove specific contaminants or contaminant s from fl uids like air and water. Activated carbons (A (Is) are the most widespread sorhents used to remove organic pollutants, and their efficacy s primarily from their high surface areas, nanostructured pores, and hydrophobicity. However, no single type ofAC removes all contaminants well, particularly anionic h/ll’s. Because of their poorly defined structure and binding site variation, optimal adsorption selectivities require empirical screening at new installations, precluding rational design and, improvement. Furthermore, regenerating spent AC is energy intensive (heating to Siltlngt‘it‘i" C or other energy intensive ures) and does not restore full performance. AC also has a slow pollutant uptake rate, achieving its uptake equilibrium in hours to days, such that more rapid contaminant removal requires excess sorbent.

Finally, AC can perform poorly for many emerging contaminants, ularly those that are relatively hilic.

{Wild} An alternative adsorbent material can he made from ric cyclodextrin materials produced from insoluble polymers of odextrin (B—CD), which are toroidal macrocyeles comprised of seven glucose units whose al cavities are e of binding organic compounds. Ei—CD is an inexpensive and sustainably produced monomer derived from cornstarch that is used extensively to formulate and stabilize pharmaceuticals, flavorants, and fragrances, as well as within chiral chromatography stationary phases. lnsoluhle fi—CD polymers have been formed by crosslinlsing with epichlorohydrin and other reactive compounds, and e well defined binding sites and high ation constants, lnsoluhle Ei—CD polymers crosslirtked with epichlorohydrin have been investigated as alternatives to AC for water cation, hut their low surface areas result in interior sorhent performance relative to ACs. {(3895} Thus there is a need for new sorbents that address the deficiencies ofAC and the like and which will provide more effective sorption and/or sequestration properties for MPs (such as anionic MPs). Th ere is a need for an adsorbent that provides rapid anionic MP extraction, high total uptake, and facile regeneration and reuse procedures. This invention meets those needs, Summary } in some embodiments, the present disclosure provides a porous polymeric material comprising a plurality of cyclodextrins crosslinlred with a plurality of crosslinlss comprising formula (l): wherein A is an aiyl or neteioaryl nieiety; each R1 is. independently selected from the group cdnsisting ofH C1—C6 alkyl, C1—C3 halnalkyh aryl, lietei‘daiyl? ~CF3, —SOiH, —CN, "N02, ~NH2 ~NCOfi ~C(O)2R3, —C(O)N(R3)2, and — each R2 is ndently H, —0H, —O~nietai cation, al,kyl., aryi, netematyl, ~SHfi —S—nietal catidn, —S~aikyl, "C(OhH, er ~C(O)NH2; each R3 is. independently —H, —C1'C6 allay}? —C1'C3 haloalliyi, —atyle —C(O)N(Ra)(Rb), —C(O)R", —C02RC, R"‘)(RbL or —SOR‘, and each Ra and Rb is independently H or C1—C6 alkyl. each W is ndently a, bond, an alkylene group, an arylene greup, a hetemarylene gmup, —O-eiylene-, ~(Cl-{23a—aiylene—, rylene~, ~Nlri-erylene~, ~S—aiyletie—, —O~ neteioeiylene-, 23a—hetemaryleneg —SQ2—heteraeen/letie-, —NH-l’ieteroeiylene-, ~S— AK J-k N 0""(CHzla‘Z‘ neteieeiylene-, ---(---O»—--(CH2)a—--)x---, ---t---NH—--(Cl-12)) »---(»-—S»—-—(Ci—igi), , c c H A.\N/LN—utcnzni' _ . or H H wherein a 15 0-100 and x. is. l—lOtl, and each aryiene 0t heteroai’ylene tneiety can be substituted or unsubstituted; each Z is a, eatieiue moiety or an anionic moiety; each L is independently a linking moiety selected from the group consisting of MO -—S-—- —N—, C1-C6 substituted or unsubstituted alkylene, C1—C3 lialoalkyleiie, O Q O C} O 8 . O G AK JLx /* A'\, [J‘K /* /L\ X fi 0 G E RAG/‘2‘ A\O/U\*, {i .Jk A A a a and E g a 7 3 7 , A’ is a covalent bond to A; Z’ is a covalent bond; to Z; * is a covalent bond to g; ‘3 is a point of ment to the plurality of cyclodextrin carbon atoms; X is GUS; y: is lnzflj, yz is lull; and ys is 04.

{NEW} in some embodiments, the crosslinks of the porous ric material se formula (ll): wherein yz is l or 2; and X is l or 2. {titlllS} in some embodiments, the porous polymeric material of the present disclosure comprises a plurality of linkers of formula (ill); %) H H N N .. . 0%?!" R4 ' R4 03 (iii) wherein one R4 is ---l-l and one R4 is v--—Me.

{M1399} in some embodiments, the present disclosure provides a supported porous polymeric material comprising porous particles affixed to a solid substrate, n said porous particles comprise a ity of cyclodextrin moieties with a plurality of crosslinks comprising formula (u (in, or out {Wild} in some embodiments, the present disclosure provides a method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous ric material or the supported porous polymeric material of the present disclosure whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is ed by the porous polymeric material. lilllllll ln some embodiments, the present disclosure provides a method of ng one or more compounds from a fluid sample or determining the presence or absence of one or more compounds in a fluid sample comprising: a) contacting the sample with the porous polymeric material or the supported porous polymeric material of the present disclosure for an incubation period; b) separating the porous polymeric material or supported porous polymeric material after the incubation period from the sample; and c) g the porous polymeric material or supported porous polymeric al separated in step b), or contacting the porous polymeric al or supported porous polymeric material separated in step b) with a. solvent, y releasing at least a portion of the compounds from the porous polymeric material or ted porous ric material; and d l) optionally isolating at least a portion of the compounds released in step c); or d2) determining the presence or absence of the compounds ed in step c} wherein the presence of one or more compounds correlates to the presence of the one or more compounds in the sample. {@912} ln some embodiments, the present disclosure provides an article of manufacture comprising the porous polymeric material or the supported porous polymeric al of the present disclosure Briefflescrl tion of the Brawin s {Wlft} Fig. l shows a comparison of PFAS uptalre capability of polymers of the present disclosure at 0.5 hours (top) and 48 hours (bottom).

{WM} Fig. 2 shows a comparison between two choline de—modified 'l‘FNuCDF polymers and a {3—CD—l‘Dl polymer for PFOA uptalre (top) and PFGS uptake ni). {8815} Fig. 3 shows a 1H NMR spectrum for B—(iD—TDl polymer (top) and fluCD (bottom).

{W16} Fig. 4 shows the change in the 1H NMR spectrum of fiatCDu'l‘Dl polymer upon addition ofTth).

{W17} Fig. 5 shows a comparison of various l"l)l polymers made with different p— CDYFDE molar equivalents.

{W18} Fig. 6 shows a comparison of choline chloride—modified BuCD—E‘Dl polymers made with ent molar equivalents of choline de.

{W19} Fig. 7 shows choline—chloride modified B—CD—TFN uptake studies performed with methylene blue (top) and methyl orange (bottom).

{W20} Fig. 8 shows MO uptake isotherms for modified 'l‘FNucDF polymers with l5 (top) and 3.0 (middle) equivalents of choline chloride, and unmodified 'l‘F‘NuCDF (bottom). Dots represent the experimental data points and straight lines are the fitted curves using a Langmuir model. {8821} Fig. 9 shows EPA uptake rms for modified 'l‘FNuCDF polymers with l5 (top) and 3.0 (middle) equivalents of choline chloride, and unmodified ’lFN~CDl’ (bottom). Dots represent the experimental data points and straight lines are the fitted curves using a Langmuir model.

{W22} Fig. l0 shows a 1H NMR spectrum of a choline chloride—modified fluCD—TDE r made with l:6:l molar equivalents of fi—CD:TDl:choline chloride.

{W23} Fig. ll shows a comparison of a choline deumodified ButjDu'l‘Dl polymer and a ll" CDJI‘Dl polynier.

{W24} Fig. l2 shows a comparison between three choline chloride—modified p—(ID—TDl polymers with different choline de loading amounts.

{W25} Fig. l3 shows FFOA uptake of e chloride—modified fi—CD—TDI polymers. {9926} All documents cited herein are incorporated by reference in their entirety for all purposes to the same extent as if each individual document was specifically and individually indicated to be orated by reference. {(130327} As used above, and hout this disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings. If a term is missing, the tional term as lrnown to one slrilled in the art controls. {9928} As used herein, the terms "including," "containing," and "comprising" are used in their open, nonmliniiting sense. {8829} The articles "a" and "an" are used in this disclosure to refer to one or more than one t: 1'.c to at least one) of the grammatical obj ect of the article. By way of example, "an element" means one element or more than one element. {(130330} The term "and/or" is used in this disclosure to mean either "and" or "or" unless indicated otherwise. {(130331} To provide a more concise description, some of the tative expressions given herein are not qualified with the term "about". lt is tood that, whether the term "about" is used explicitly or not, every quantity given herein is meant to refer to the actual given value, and it is also meant to refer to the approximation to such given value that would reasonably be inferred based on the ordinary slrill in the art, including equivalents and approximations due to the mental and/or measurement conditions for such given value. Whenever a yield, is given as a tage, such yield refers to a mass of the entity for which the yield is given with respect to the maximum amount of the same entity that could he obtained under the particular stoichioinetric conditions. Concentrations that are given as percentages refer to mass , unless indicated differently. {(3932} The term, adsorbent or adsorh is used to refer to compositions or methods of the present disclosure to refer to solid materials as described herein which remove contaminants or pollutants, typically but not exclusively organic les, from a fluid medium such as a. liquid (eg, water) or a gas (eg, air or other commercially useful gases such as nitrogen, argon, helium, carbon dioxide, anesthesia gases, etc). Such terrns do not imply any specific physical mechanism (e.g adsorption vs. absorption). {8833} The term "cyclodextrin" includes any of the lrnown cyclotlextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, ally, alphaucyclodextrin, beta~ cyclodextrin, gamniaucyclodextrin and/or their derivatives and/or mixtures thereof. The alpha— cyclodextrin consists of six glucose units, the hetaucyclodextrin consists of seven glucose units, and the gamma—cyclodextrin consists of eight glucose units arranged in donut-shaped rings. The specific coupling and conformation of the glucose units give the cyclodextrins rigid, l molecular structures with hollow interiors of specific s. The "lining" of each internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms, therefore, this surface is fairly hydrophobic. The unique shape and physicalnchernical properties of the cavity enable the cyclodextrin molecules to ahsorb (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity. {0934} Unless otherwise stated, the terms "crosslinlrer" or "crosslinlr" or r" refer to a monomer capable of reacting with or forming a covalent linkage between one or more extrins or polymers, For example, if the crosslinher reacts at the end of a polymer chain, it may covalently react with one cyclodextrin moiety of the polymer (eg. via the glycosiilic oxygen of the cyclocl extrin), The inlrer may or may not, further react with other monomers or cyclorlextrin units or polymer chains to, for example, extend a polymer chain or link two or more polymer chains together, For example the crosslinker may he hound to l, 2, 3, or 4+ rs or extrin units or polymers, {9935} The term "cationic moiety" refers to a group which carries a positive charge (eg, +l +2, etc), for example, ammonium, mono~, di— or triallrylamrnonium, diallrylsulfonium and triallrylphosphonium, {9936} The term ic moiety" refers to a group which carries a negative charge (eg —l , ~2, etc), for example, phosphate, carhoxylate, alkoxide, and sulfate.

} As used herein, "alkyl" means a straight chain or branched ted chain having from 1 to ill carbon atoms. Representative saturated alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, Z-niethyl-l ~propyl, 2-methyl~2-propyl, yl~l ~hutyl, 3— methyl—l—hutyl, 2-methyl~3~hutyl, 2,2-dimethyld l, 2~inethyl—l ~pentyl, 3-methyl~l ~pentyl, llamethylulupentyl, Emmethyl—Zupentyl, 3—inethyl~2—pentyl, 4uniethyl—2uperi'tyl, methyl—l_ hutyl, 3,3—dimethylulubutyl, Zuetliyl—l—butyl, hutyl, isobutyl, t—hutyl, n—pentyl, isopentyl, neopentyl, n—hexyl and the like, and longer alkyl groups, such as lieptyl, and oetyl and the like.

An allryl group can be unsubstituted or substituted. Allryl groups containing three or more carbon atoms may be straight, or branched. As used herein, "lower alhyl" means an alkyl having from l to 6 carbon atoms.

{Wild} The term "alkylene" refers to straight~ and branched~chain alltylene groups. Typical alkylene groups include, for example, ene ("CHz—L ethylene ("Cl'elzCHM , propylene (~ CH2CH2CH2-) n— ne H2CH2CH2n) , isopropylene ("CHtZCHfiCHH , , seo~butylene (—CH(CH2CH3)CH2U) and the like. {9&39} The term "hydroxyl" or "hydroxy" means an OH group; {9949} It should also he noted that any carbon as well as heteroatorn with unsatisfied valences in the text, schemes, examples and Tables herein is assumed to have the sufficient number of hydrogen atom(s) to satisfy the yalenees. {hilt-ll} The term "halo" or en" refers to fluorine, ne, bromine, or iodine. {9942} The term "oyano" as used herein means a substituent having a carbon atom joined to a nitrogen atom by a triple bond, in, GEN. {@943} The term "amine" or "amino" as used herein means a substituent containing at least one nitrogen atom. Specifically, NH; —NH(allryl) or arnino, "NtZallrylh or dialkylamino, amide, oarboxainide, urea, and sulfarnide suhstituents are included, in the term "aniino". {tilled} Unless otherwise specifically defined, the term "aryl" refers to , aromatic hydrocarbon groups that have l to 3 aromatic rings, including monooyelic or hicyclic groups such as phenyl, biphenyl or naphthyl. Where containing two aromatic rings (bioyelic, eta), the aromatic rings of the aryl group may be joined at a single point (eg, biphenyl), or fused (gig, naplithyl). Furthermore, in the context of the present disclosure, the term aryl is taken to refer to two aryl rings joined by a short linker suelt as —CH2—, CR2— (where R can be H, alltyl, etc), 4302—, —SO~, ~NR— (where R can be H, alkyl, etc), or —O—; for example, aryl may refer to methylene yl or oxybisphenyl respectively). The aryl group may be optionally tuted by one or more substituents, eg, l to 5 tuents, at any point of attachment. The substituents WO 68104 2020/018149 can themselves be optionally substituted. Furtherinere when containing twe fused rings the aryl groups herein defined may have an unsaturated er partially ted ring fused with a fully saturated ring. Exemplary ring systems all these aryl groups include, hut are net limited to, phenyl, hiphenyl, naphthyl, anthraeenyl, phenalenyl, phenanthrenyl, indanyl, indenyl, tetrahydrenaphthalenyl, ydrobenzeannulenyl, and the like. {8345} Unless otherwise specifically defined, "heternaryl" means a nionoyalent nioneeyclie er polycyclic aromatic radical nf 5 to 18 ring atoms or a polycyclic aromatic radical, containing one or more ring aterns selected, from N, 0, er S, the remaining ring atonis being C.

Heterearyl as herein d also means a polycyclic (eg, hieyclic) heternaromatic group wherein the heternatorn is ed from N, O, or S. The aromatic radical is optionally tuted independently with one or more tuents descrihed herein. The suhstituents can themselves be optinnally substituted. Examples include, but are not d to, benzethiophene, furyl, thienyl, pyrrelyl, pyridyl, pyrazinyl, pyrazelyl, pyridazinyl, pyrimidinyl, iinidazelyl, isexazelyl, exazelyL exadiazolyl, pyrazinyl, indnlyl, tliieplieri~2~ylfi quinelyl, henzepyranyl, isothiazolyl, thiazolyl, thiadiazolyl, thieneEfi,2—blthinphene? triazelyl, triazinyl, imidazofi ,2- hjpyrazelyl, furanfi~clpyridinyl? iniidazofl ,2malpyridinyl, in,daznlyl., pyrroloflfi—e]pyridinyl, ofi,2melpyridinyl, pyrazele[3,4~e]pyridinyl, henzeimidazelyl, thi,eno{3.,2—tt]pyridinyl, thienanfi~c}pyridinyl., thieneflfi~blpyridinyl, henzethiazolyl, indolyl, indolinyl, indolinonyl, dihydrobenzethiophenyl, dihydrnbenzefuranyl, ’uran, chromanyl, thinehromanyl, tetrahydrnquinulinyl, dihydrnbenzothiazine, ohenzoxanyl, inyl, ianmnolmyl? if» napl'ithyridinyl, henmlde}isequinolmyl, EdfihHl filnaphthyridmyl, thieneQfil3h3yrazinyl , quinazolinyl, tetramlell,5~a}pyridinyl, [l 72,4]triazololélfi—a]pyridinyl, isoindolylg pyrreloflfi—h}pyridinyl, ofi,4—hlpyridinyl, pyrrolofiQ—blpyridinyl, imidaznlfi,4~ hlpyridinyl, pyrrololl ,Z—alpyrimidinyl, tetrahydropyrrololl ,Z—alpyrimidinyl, 3,4—dihydrn—ZH~ lAZ-pyrrelopgl—hlpyrirnidme? dihenzeEhfl}thiophene, pyridirnzone, furol3,Z—cjpyridinyl, l‘urelZfinelpyridmyl, illupyridQESAuhjlLilithiazmyl, henzeexazelyl, henzeisexazelyl, furanfi— hjpyridinyl, benzothiephenyl, l,5—naphthyridinyl, fure[3,2—hlpyridine, E:l,2,4}triazele{l,5~ ailpyridinyl, henzo [1,2,3]triazolyl, irnidazoll,Zualpyrimidinyl, {l,2,4:Etriazele{4,3—hjpyridazinyl, benzele] { l ,2,5 lthiadiazolyl, henzole}{1,2,5}oxadiazele, l ,3 —dihydrta—2ll~lien;:ta{idliniidazoluflone 3,4—dihydro—Zl-lupyrazolol:l ,Sub} [: l ,2] exazinyl, 4,5,6,7_tetrahydropy razeloll ,S—alpyridinyl, thiazelel5,4—djthiazolyl, iniidazolefiuhlll ,3,4:§thiadiazelyl, thierio[2,3— jpyrrelyl, 3l-luindolyl, and derivatives thereof. Furthermore when ning two fused rings the heteroaryl groups herein defined may have an unsaturated or partially saturated ring fused with a fully saturated ring. {8346} cal ranges, as used herein, are intended to include sequential integers unless indicated otherwise. For example, a range expressed as "from O to 5" would include 0, l, 2, 3, 4 and 5. {8847} The present disclosure es porous t: e. g. porous or mesoporous), typically high surface area cyclodextrin polymeric materials (PuCDPs), as well as methods of making and using these materials. The P—CDPs are comprised of insoluble polymers of cyclodextrin, which is an inexpensive, sustainably produced macrocycle of glucose. The cyclodextrin polymers are crosslinked with linking groups as bed herein. The polymers of cyclodextrin are comprised of extrin moieties that are derived from cyclodextrins. The cyclodextrin nioiety'(s) can he derived from naturally occurring cyclodextrins (eg, Cir, 33-, and 7—, comprising 6, 7, and 8 glucose units, respectively) or synthetic cyclodextrins. The cyclodextrin moiety has at least one —0— bond d from an —OH group on the cyclodextrin from which it is d.

The cyclodextrin moieties can comprise 3—20 glucose units, including 3, 4, 5, 6, ‘7, 8, 9, l0, ll, l2, l3, l4, l5, l6, l7, 18, l9, and 20 glucose units, inclusive of all ranges therehetween, In, many ments, the cyclodextrin moieties are derived from starch, and comprise 6—9 glucose units, The polymeric materials may comprise two or more different cyclodextrin moieties. ln particular ments, the P—CDP is comprised of insoluble polymers of ll~cyclodextrin (BED), lull/43} The P—CDP can also comprise cyclodextrin derivatives or modified cyclodextrins, The tives of cyclodextrin consist mainly of molecules wherein some of the OH groups are converted to OR groups, The cyclodextrin tives can, for example, have one or more additional moieties that provide additional functionality, such as desirable solubility behavior and affinity characteristics, Examples of suitable cyclodextrin derivative materials include methylated cyclodextrins (eg, RAMEB, randomly methylated ll—cyclodextriris), hydroxyalkylated cyclodextrins (e, g, hydroxypropyl—ll—cyclodextrin and hydroxypropyl—y— cyclodextrin), acetylated cyelodextrins (e, g, acetyl—y—cyclodextrin), ve cyclodextrins (eg, chlorotriaziriyh{tCD}, branched cyclodextriris (eg, glucosyl~B~cyelodextrin and maltosyl-fi— cyclodextrin), utyl—ll—cyclodextrin, and sulfated cyclodextrins. For example, the cyclodextrin nioiety further comprises a moiety that binds (eg, with specificity) a metal such as arsenic, cadrhium, copper, or lead. {111149} The P—CDP can also se cyclodextrin derivatives as disclosed in US Pat. No. 6,881,712 including, e.g., cyclodextrin derivatives with short chain alkyl groups such as methylated cyclodextrihs, and ethylated extrihs, wherein R is a methyl or an ethyl group; those with hy droxyalhyl substituted groups, such as hydroxypropyl cyclodextrihs and/or hydroxyethyl cyclodextrins, wherein R is a —CH2—CH{OH)—CF13 or a "CH2CHz—0H group; branched extrins such as inaltose—honded cyclodextrins; cationic cyclodextrins such as those containing 2—hydroxyn3n(dimethylarnino)propyl ether, wherein R is CH2—CH(OH)— CH2—N(CH3)2W’thl’l is cationic at low pH; quaternary ammonium, e.g, 2nhydroxy—3~ (trinrethylannnonio)propyl ether chloride groups, n R is CH2—CH(OH)—CH22— NYCHsfiCl"; anionic cyclodextrins such as carboxyniethyl cyclodextrins, cyclodextrin sulfates, and extrin succinylates; ainphoteric cyclodextrins such as carhoxyniethyl/quaternary ammonium cyclodextrins; cyclodextrins wherein at least one glucopyranose unit has a 3—6— anhydro—cyclonialto structure, eg, the mono~3~6~anhydrocyclodextrins, as sed in "Optimal Performances with Minimal Chemical Modification of Cyclodextriris", 1:7. DiedainivPilard and B, Perly, The 7th International Cyclodextrin Symposium Abstracts, April 1994, p, 49 said nces being incorporated herein by reference; and mixtures thereof. Other cyclodextrin derivatives are disclosed in US. Pat. No. 3,426,011, rter et a1, issued Fe‘o~ 4, 1969; US Pat. Nos. 257; 3,453,258; 3,453,259; and 260, all in the names ot‘l’arnierter et al, and all issued Jul. 1, 1969; US. Pat. No. 3,459,731, Gramera et al, issued Aug. 5, 1969; US. Pat, No. 3,553,191, Parrnerter eta1., issued Jan. 5, 1971; US. Pat. No. 3,565,887, Parrnerter et al, issued Feb, 23, 1971; US. Pat. No, 4,535,152, Szeitli et a1, issued Aug~ 13, 1985; US Pat. No~ 008, Hirai et al, issued Oct. 7, 1986', US. Pat. No, 4,678,598, Ogino eta1., issued Jul. 7, 1987; US. Pat. No. 4,638,058, Brandt et a1, issued Jan 20, 1987; and US Pat. No~ 4,746,734, 'l‘sucliiyania et a1, issued May 24, 1988, all of said patents heing incorporated herein hy {1111511} In some embodiments, the present disclosure provides a porous polymeric material comprising a plurality of extrins crossliiilO ~ wherein each R3 is as defined above, i .

WO 68104 {8852} ln accordance with certain embodiments of the present disclosure, each W is independently a bond, an allrylehe group (e g. 3:14:10, Gin—{720, or (infirm), an arylene group, a heteroarylene group, uO—arylene—, —((Ill2)a—arylene~, —S()2_arylene—, uNl-l—aryleneu, —S~arylene_, ~ Ouheteroarylene—, —(Cliz)a~heteroarylene~, —S()2_heteraoarylene—, —Nl—luheteroarylene—, —S— arylene—, ( G (CHM ). , ( NH (Cflzh )a or , ( S (CHM ). whereinais 0—100 and X is l—lOO, and each arylene or arylene moiety can be substituted or unsubstituted. The term "arylene" refers to a bivalent group d from an aryl group (as described herein, including phenyl, hiphenyl, naphthyl, etc.) by removing hydrogen atoms from two ring carbons For example, an arylene can include a phenyl in which the two valencies are ed in an orthon or para- orientation. For polycyclic arylenes, the two valencies can be on the same ring, , meta: or on different rings. Arylenes can be derived from any aromatic rings bed herein, and, can be substituted or tituted. Similarly, the term oarylene" refers to a bivalent group d from a heteroaryl group (as described herein, including furyl, pyridyl, etc.) by removing hydrogen atoms from two ring atoms (whi ch can be carbon or heteroatoms). The valencies can be on the same ring or rent rings (in the case of polycyclic heteroaromatics) and can be on any two ring atoms. Heteroarylenes can be derived from any heteroaromatic rings described herein, and can be substituted or unsubstituted. Thus in some embodiments, each W is a bond (re, a covalent bond). In other embodiments, each W is an alliylene group. For example, each W may be, methylene {*CE‘IT‘), ethylene (—CllzCl-lz—) , propylene (~Cll2{:ll2(:ll2—) , isopropylene (—ClfiQCl-lfiCl-lr) n— butylene (—CHzCl-lgCl:lzCl-l2—) and the , , sec~butylene (—Cl-l2(Cl-l2Cl—ls)CH2—) like, in some embodiments, each ’W is methylene (—Cl—lr), ln some embodiments, each W is an arylene group (phenylene). in some ments, each W is a heteroarylene group , pyridyl). in some embodiments, each W is ~O—arylene— (-Q—phenylene), In some embodiments, each W is —(Cl5l2)a—arylene— (—Cliz—phenylene). in some embodiments, each W is —S{)2uaryleneu (~ SQzuplienylene). lh some embodiments, each W is "NH—arylene uphenylene). ln some embodiments, each W is —S~arylene~ (:uSuplienylene). lh some embodiments, each W is a hetei'oarylene group ene, pyridylene). in some embodiments, each W is ~0uheteroarylene— (—()~pyridinylene:i. ln some embodiments, each W is —(Cl-lgh—heteroarylene— (—Cl-lz— pyridinylene}. ln some embodiments, each W is SOz—heteroarylehe— (—SQz—pyridinylene). in some embodiments, each W is uNl-l—heteroaryleneu (éNli—pyi‘idinylene). in some embodiments, each W is nS—heteroarylene~ ("S—pyridinylene). ln some embodiments, Wis —(O—CH2—CH2)x—.

. . \N/Ekomtmizla"? ln some embodiments, Wis --—O-—-~Cl-l2-—-Cl-l2-—-~._ _ _ , , in some embodiments, W is H where A" is a covalent bond to A and Z’ is a covalent bond to 2;. ln some emhcdimehts, Wis AKN/LLOAV, 2’ } In some embodiments, each instance of uW-Z is talten together to form --Cl-l'2---CHz—-- hel(R)3+~ In some embodiments, each instance of ---W»—--Z is talten together to form »-—O»---Cl-l2---Cl-lzm- NtMelf. lh some embodiments, each instance of --—-‘W—-—Z is taken together to form {<2 Omii N Me‘( )3 } In some emhodiments, each L is a linking moiety. ln some embodiments, each L is independently a linking moiety selected from the group consisting ell-Om, -S-, --N»--, o o o it a Nhe» notN fit it JL a ,, , i N N O O H H Ai 4:) O * H H and 7 7 :1 7 7 7 sNiNa 3‘ H H where A’ is a nt bond to A and * is a covalent hand to 3 (which as descrihed herein represents a point of attachment to the plurality of cyclodextriri carbon atoms). In some embodiments, eacli L is independently "O"- ln certain embodiments, when each L is Q A\N’Jl\O/k Q A'\ /U\ /* )L» I’ll independently O Q H AF 0 or --,--—O the oxygen atom maybe a , , glycosidic oxygen from the ity of cyclodextrins of the porous polymeric material or" the t disclosure. For example, in some ments, when each L is independently "0 the oxygen atom is a glycosidic oxygen atom from the plurality of cyclodextrins of the porous polymeric material of the present disclosure. {9955} ln some embodiments, A is an aryl or heteroaryl moiety. in some embodiments, A is an aryl moiety. For example, A may be phenyl, hiphenyl, naplithyl, anthracenyl, phehalenyl, phenantlireriyl, indanyl, indenyl, tetrahydronaphthalehyl, or tetrahydrobenzoannulenyl. in some ments, A is a heterearyl moiety. For example, A may be benzethmphene, furyl, thieiiyl, pyrrelyl, pyridyl, pyrazmyl, pyrazolyl, pyridezinyl, pyrimidiriyl, elyl, isoxazelyl, exazolyl, exadiezelyl, pyreziiiyl, l, thiephenuZuyl, quinolyl, benzopyranyl, isothiazelyl, thiazolyl, tliiadiazelyl, thiene{3,2~b}thi0phene, triazolyl, triazinyl, ell,Z—blpyrezelyl, furolZfinelpyridmyl, imidazofl,Z—alpyridinyl, indezolyl, pyi'relo{2,3—clpyridiiiyl, pyrrolol’fifin clpyridinyl, pyramleBAnclpyridii‘iyl, benzeimidazolyl, tliienol’i,2nelpyridmyl, thienolZfin idinyl, llfinblpyridiiiyl, hiazelyl, indelyl, indolinyl, indoliiionyl, dihydrobenzethiophenyl, diliydi'ehenzofuranyl, benzofuran, chromanyl, thieehremanyl, tetrahyquuinelmyl, (lihydi'ebenzothiazme, dihydrobenzoxanyl, quiriolinyl, isequmolmyl, 1,6" iiaphthyridmyl, benzeldefisequmolmyl, pyridoHfi—blll,6lnaplithyridmyl, thiene[2,3— blpyrazinyl, quinazolmyl, tetrazelell,SUaEpyridinyl, [l,2,4]triazolo[4,3"alpyridmyl, isomdolyl, pyrmloflfi~blpyridiiiyl, pyrmlolS,sil—bjpyridmyl, pyrrolofi,2—33}pyridinyl, imidazelidm blpyridinyl , pyrrel cl l ,Z—a}pyrimidinyl, tetrahydropyrrol0[ l ,Z—alpyrimldmyl , 3 ,4—diliydi‘0—2H~ lVapyrmlofl,l-bjpyrimidme, di,ben,zo[b,d}thiophene, n~2~one, ,2—ttlpyridiriyl, furo[2,3—c}pyridmyl, lH~pyrid0[3,4—b}{l ,d-lthiazmyl, benzooxazelyl, benzeisexazolyl, ful‘£)[2,3' blpyridinyl, beiizothmpheiiyl, LS-nephthyridinyl, furo[3,2—b}pyridine, [l,2,4]triazole{l,5~ alpyi‘idinyl, benze [1,2,3]trlazolyl, imldazofi,Z—ajpyrimldiriyl, }triazolo[4,3—blpyi‘idazinyl, benzeEeHl liiatliazolyl, bends][1,2,5]0xadiazole, l,3~dihydre-2H~benze[dfimidazelflwne 3,4—dihyer—erl~pyi'eml0il,SJD} [l ,2} oxazinyl, 4,5,6,7—tetral’iydmpyrazeloEl ,S-alpyridinyl, tl’iiamlol5,4—dlthiazolyl, imidazelll—b}{l,3,4}thiediazelyl, thienoEZS~lijpyrmlyl, or 3l-l—indolyl.

In some embodiments, A is selected from the group eensisting of phenyl, riaplitliyl, pyridyl, l3enzol'iii'ei'iyl, pyrazinyl, pyridazmyl, pyrin'iiclinyl, triazinyl, ine, benzexemle, bei'imtl’iiamle, lH-benzimidazole, isequmeline, quinazoline, quirioxeline, pyrrole, , bipheiiyl, pyrenyl, and anthracenyl. in some embedimen‘ts, A is phenyl. in some embodiments, A is an aryl er earyl ring system as described in US Patent No. 9,855,545, which is hereby incorporated by reference in its entirety. {8356} En some embodiments, A is the pelymerizatiori preduct 0f commercially available cliiseeyanates. For example, in some embedimen‘ts, A is the pelymerizatien product of commercially available eryl diiseeyenates including but net limited to 2,4—toluene diisecyariete, 2,6—t0luene cliiseeyanate, 4,4’~metliylene diphenyl cliiseeyanate, 2,4’umethylene diphenyl yanete, l,3—bis(iseeyanatemetliylflienzene, l (l misocyanetoul arnetliyletliyl)benzene, 3,3’udichiore—4,4"—diisocyanatou1,1’uhiphenyi, 3,3‘udinrethyimlifi‘—hiphenyiene diisocyanate, 4,45 iphenyi isocyanate), 1,3—phenyiene diisocyanate, 1,4—phenyiene diisocyanate, 4—chioro—6_ methy1u1,3~phenylene diisecyanate, and l"chlorornethyi—Z,4ndiisocyanatohenzene. in some embodiments, A is where the wavy hne represents any of the suhstituents attached to A as d herein. In sonre ©/O\.m140 embodiments? A is or where the wavy hne represents any of the substituents ed to A as defined herein. In some the Me where the wavy hne represents any of the substituents attached to A as defined, herein, the —Me, —C1, and —CH2—Cl groups bound to the aryl ring in the preceding structures corresponds to R} groups, and the — CEL— and —C(Me)2— groups hound to the aryi ring correspond to L groups. In some where the wavy hne represents any of the substituents attached to A as defined herein, and the Me and ---CE groups bound to the aryE ring in the preceding structures corresponds to R1 groups. {@857} The porous polymeric material of the present discios ure comprises a phrrahty of cyeiodextrins with a pturality of crosshnks comprising a (I). The ty of extrins of the present disclosure may he any cyeiodextrin containing from six to twelve WO 68104 glucose units. For example, in some ments, the plurality of cyclodextrins of the present disclosure are selected from the group consisting of odextrin, B—cyclodextrin, y— cyclodextrin, and combinations thereof In some embodiments, each cyclodextrin is a it cyclodextrin. {8858} The R‘1 groups of the plurality of crosslinks sing a (I) are each R1 is independently selected from the group consisting of H, C1—C6 alkyl, (ii—Ca haloalkyl, aryl, heteroaiyl, (To, -S()3l-l, ---CN, ~NO2, ~Nl-l2, —NCO, —C(0)2R3, (R3)z, and »---halogen. In certain embodiments, each R] is independently selected from the group consisting ofl-l, (Ii—Cs , CiuCi lialoalkyl, aryl, heteroaryl, 4:? ’3, "803E, —--CN, —N{)2, , —NCO, —C(0)2R3, u C(O)N(R3)2, and --——lialogen. ln certain embodiments, 0—8 R1 groups are present on the plurality of crossliiilrs comprising formula (l). For example, 0, l, 2, 3, 4, 5, 6, 7, or 8 R} groups are present on each of the individual crosslinlrs comprising formula (1). lt is understood that any positions of A not substituted with R], R3, uW—Z or ML" will be unsubstituted or have one or more H atoms as required to satisfy the valency of that on. As will be appreciated by a skilled artisan, the number of R1 groups on each of the individual crosslinlrs of formula (i) may vary throughout the porous polymeric material of the present disclosure. For example, when Rl is —l§' and the polymerized porous material of the present ion is exposed to reactants capable of substitution (eg. choline chloride), the —F groups on some crosslinks will be substituted, whereas in other crosslinlrs, the —F groups may be effectively shielded from the reactants and thus not react. Accordingly, a porous polymeric material of the present disclosure may have multiple linking groups of formula (I) present, and each individual linlring group may independently have 0—8 (eg. l, 2, or 3) R1 groups. {@939} ln some embodiments, the porous polymeric material of the present disclosure may be characterized as having, on average, a fractional number of R1, R2, JWnZ or —L— groups in each crosslmking group This fractional number of substituents can be calculated by dividing the total number of such groups by the total number of crosslinhs in the porous polymeric material. For example, if half of the crosslinlring groups are functionalized with a —O—CH2—CH2—N(Me)3l group (e.g where W is a —0—CH2—CHz— and Z is —N(Me)3), then the average number (or fraction) of —CH2—N(Me)il groups corresponding to ~W—Z per crosslinking group is 05.

For R1, the fractional number of such groups includes values of about 0, about 0. l, about 0.2, about 0.3, about 04, about 0.5, about 0.6, about 07, about 08, about 09, about 1.0, about 1.1, about 1.2, about 1.3, about 14, about 1.5, about 1.6, about 17, about 1.8, about 1.9, about 2.0, about 2.1, about 22, about 2.3, about 2.4, about 25, about 2.5, about 27, about 2.8, about 2.9, about 3.0, about 3.1, about 3.2, about 3.3, about 3.4, about 35, about 3.6, about 3.7, about 38, about 3.9, about 4.0, about 4.1, about 4.2, about 4.3, about 44, about 4.5, about 4.6, about 4.7, about 4,8. about 4.9, about 5.0, about 5.1, about 5.2, about 5.3, about 5.4, about 5.5, about 5.6, about 5.7, about 5.8, about 5.9, about 6.0, about 6.1, about 6.2, about 6.3, about 6.4, about 6.5, about 6.6, about 6.7, about 6.8, about 6.9, about 7.0, about 7.1, about 7.2, about 7.3, about 7.4, about 7.5, about 7.6, about 7.7, about 7.8, about 7.9, or about 8.0, inc1usive of a11 ranges between any of these va1ues. For R2, the fractiona1 number of such groups 1es va1ues of about 0, about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 11, about 1.2, about 1.3, about 14, about 1.5, about 1.6, about 1.7, about 1.13, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 24, about 25, about 2.5, about 2.7, about 2.8, about 29, about 3.0, about 3.1, about 32, about 3.3, about 34 about 3. 5, about 3.6, about 3.7, about 313, about 3.9, or about 4.0, ino1usive of a11 ranges between any ot‘tbese va1ues.

For ~W—Z, the fractiona1 number of such groups ino1udes va1ues of about 10, about 11, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 113, about 1.9, about 2.0, about 2.1, about 22, about 2.3, about 2.4, about 25, about 2.5, about 2.7, about 28, about 2.9, about , about 3.1, about 32, about 33, about 3.4, about 35, about 3.6, about 3.7, about 38, about 3.9, or about 4.0, ine1usive of a11 ranges between any of these va1ues. For »---1...~, the fractionaE number of such groups ino1udes va1ues of about 1.0, about 11, about 1 .2, about 1.3, about 14, about 1.5, about 16, about 1.7, about 1.8, about 19, about 2.0, about 21, about 22, about 2.3, about 24, about 2.5, about 25, about 27, about 2.8, about 29, about 3.0, about 3.1, about 3.2, about 3.3, about 34, about 3.5, about 3.6, about 37, about 3.8, about 3.9, or about 4.0, ino1usive of a11 ranges between any of these va1ues. {0060} Each R3 is independenfly 11, , "()umeta1 , a11 For example, 0, l, 2, 3, or 4 R) groups are t on the plurality of crosslinks comprising formula (l). As will be appreciated by a skilled artisan, the number of R) groups on each of the individual plurality of linking groups comprising formula (l) may vary by each individual linking group throughout the porous polymeric material of the present sure. Accordingly, a porous polymeric material of the present disclosure may have le linking groups of formula (l) present, and each individual linking group may independently have eg. 0, l, 2, 3, or 4 R3 groups.

When there are more than one R2 groups on the plurality of ng groups of formula (I), the R2 groups may be the same or different. For example, in some embodiments, one or more R2 group is —Ovmetal cation and one or more R2 group is —0H. {earn} Each R3 is independently —H, —Cl-C6 alhyl, —Ci—C3 haloall {W69} in various embodiments, the porous polymeric material of the present sure is prepared by inlring cyclodextrins of the same structure with crosslinkers of the same structure. in some embodiments, the porous polymeric material of the present disclosure is ed by crosslinlring cyclodextrins of the same structure with two, three, four, or more different crosslinlrers, In various embodiments, the porous polymeric material of the present disclosure is prepared by crosslmlring two, three, or four ent cyclodextrins (ie, having different structures) with crosslinlrers of the same structure In some embodiments, the porous polymeric material of the present disclosure is prepared by crosslinlring two, three, or four different cyclodextrins with two, three, four, or more different crosslinkers. } lo some embodiments, some of the crosslinlrs of the porous polymeric material do not include a cationic or anionic moiety (re, corresponding to group "Z" of formula (1)). In such embodiments, the porous polymeric material comprises a plurality of erosslinkers of formula (I) and a plurality of crosslinlrers haying a structure similar to that of formula (l), except that there is no cationic or anionic moiety corresponding to group "Z". So, for example, such crosslinlrers lacking a cationic or anionic moiety can have any of the crosslinlrer structures described in US Patent No. l0,086,360, herein orated by reference for all purposes, including, for example a plurality of crosslinkers of the following structure (a): WO 68104 regime/i \ structure l:a ll or the following structure (b): structure (b), or a combination of structures (a) and (b) (where X in ure (h) is 0,, l, 2, 3, or 4). In such embodiments of porous ric materials having crosslihlrers of structure (a) arid/or structure (b), such materials also include charged crosslmlrers of formula (l) as described herein, {9971} In still other ments, the porous polymeric materials of the present disclosure comprise a plurality of cationic crosslihlrers of the following structure (c): structure (c) (where X' is a pharmaceutically acceptable anionic oounterion such as C l ). {9972} In still other embodiments, the porous polymeric materials of the present disclosure comprise a plurality of cationic ihlrers of the following structure (cl): structure (d) (where x in ure (cl) is 0, l, 2, 3, or 4; and; X" is a pharniaceutically acceptable anionic counterion such as Cl"). {(130373} ln still other embodiments, the porous ric als of the present disclosure comprise a plurality of cationic crosslinkers of structure (c) and a plurality of cationic crosslinkers of structure (cl). As described herein, any crosslinkers of the present disclosure having an aromatic halide group can be modified to proyide a d moiety, for example by reaction with choline chloride under suitable conditions as described herein. {8874} In other embodiments, the porous polymeric materials of the t disclosure comprise a plurality of anionic crosslirrkers of the following ure (e): fiat; i :2 2 at yo «3 structure (e).

Ellll’75l 'l'he cationic counterion for structure (e) (depicted as Na? can alternatively be any other pharmaceutically acceptable cationic counterion such as, without limitation, H+ or {0076} ln yet other embodiments the porous polymeric materials of the present disclosure comprise a plurality of c crosslinkers of the following structure (f2): structure (f) (where x in structure (f) is Oa l2 2., 3 or 4)" {0077} In still other embodiments, the porous polymeric materials of the present disclosure comprise a ity of cationic crosslinlrers of structure (e) and a plurality of ic crosslinlrers of structure (itm {0078} in some embodiments, the present disclosure provides a porous polymeric material comprising a plurality of cyclodextrin moieties crosslinlced by one or more polyisocyanates. in some embodiments, the plurality of cyclodextrins are fi—cyclodextrin. lii some embodiments, the one or more polyisocyanates are aiyl diisocyanates including but not limited to SEA—toluene diisocyanate, 2,6—toluerie diisocyanate, 4,4’~methylerie iyl diisocyanate, 2,4’~methylerie diphenyl diisocyanate, 1,3"his(isocyanatomethyl)benzene, 1,3-bis(l—isocyanato—l _ methylethyDbenzene, 3,3’"dichloronit-A’—diisocyanato~l,l’m‘oiphenyl, 3,3'mdimethy1nclfl’n biphenylene diisocyanate, 4,4’—oxybis(phenyl isocyanate), 1,3—phenylene diisocyanate, L4" ene yanate, 4—ch1oro—6—methy1nl,3—plienylene diisocyanate, and inclilorornethylmléln diisocyanatobenzene, and combinations thereof. ln some embodiments, the aryl diisocyanate is 2,4-toluene diisocyanate in some embodiments, the one or more polyisoeyanates are aliphatic diisocyanates including but not limited to 4,4"—diisocyanato—methylenedicyclohexane (Hlvl‘fll), hexamethylene diisocyanate (EDI), isopliorone diisoeyanate , l_.~lysine diisocyanate (LEI), trimethylhexametliylene diisocyanate (TREE, l,3—bis(i,soeyanatomethyl)cyclohexane, 1,4— diisocyanatobutane, hyl—l ,6~diisocyanatohexane, 1,6—dii socyanato—2,2,4—trimethylhexane, transd ,4—cyelohexylene diisocyanate, l,8-diisocyanatooctane, 1,12—diisocyana‘tododecane, and combinations thereof in some en'ibodiinents, the plurality of cyclodextrins are B-cyclodextrin and the one or more polyisocyanates are Z,4~toluene diisocyanates, in some embodiments, the porous polymeric material has a er—Emmetb’l‘eller (BET) surface area of about 10 mz/g to 2000 rnz/g. For example, in some embodiments, the porous ric al has a BET e area of about l0 m2.«’g, 20 m2/g, 30 in2/g, 40 i'nZ/g, 50 ir12/’g, 75 inZ/g, 100 mz/g, 150 nil/g, zoo ng, 250 ng, soo mW’g, 350 mW/g, 400 nit/g, 450 ng soc ng, 550 ng one ng, 650 m2/’g, 700 rnz/g, 750 rh2/’g, 800 inZ/g, 850 mQ/g, 900 mZ/g, 950 Mg, lOOO rnz/g, 1050 rh2/’g, 1100 inZ/g, l150 inZ/g, 1200 mQ/g, 1250 mZ/g, l300 m2,/g,', 1350 mz/g, 1400 inZ/g, 1450 mQ/g, 1500 m2/’g, 1550 rnz/g, 1600 inZ/g, 1650 in2/'g, l700 mZ/g, 1750 mZ/g, l 800 rnz/g, 1850 , 1900 inz/g, 1950 mZ/g to about 2000 mQ/g, including all integers and ranges tlierebetween. ln some embodiments, the porous polymeric material has an amine content from about 0 mmol/g to about 1.0 minol/g. ln some embodiments, the porous polymeric material has an amine content from about 0.1 mniol/g to about 1.0 nimol/g. in some embodiments, the porous polymeric material has an amine content from about 0.15 mmo1/g to about 0.35 mmol/g. For examp1e, in some embodiments, the amine content may be about 0.15 nimol/g, about 0.16 mmol/g, about 0.17 mmo1/g, about 0.18 mmol/g, about 0.19 mmol/g, about 0.20 mmol/g, about 0.21 nimol/g, about .22 mmol/g, about 0.23 mmol/g, about 0.24 mmol/g, about 0.25 mmol/g, about 0.26 mmol/g, about 0. 27 mmol/g, about 0.28 mmol/g, about 0.29 mmol/g, about 0.30 mmol/g, about 0.31 mmol/g, about 0.32 mmol/g, about 0.33 mmol/g, about 0.34 mmol/g, and about 0.35 mmol/g including all ranges therebetween Without being bound by any particular theory, it was ered that by using asnis CD (re. undrietl) in the polymer synthesis, the resulting polymer had a higher amine content than similar polymers described in the prior art, which lerl to higher affinity for some ollutants such as PFASs. {00791 In certain embodiments, the molar ratio of oyclodextrin to linking groups of formula (1), (11), or (111) ranges from about 1:1 to about 1:31, wherein X is three times the average number of glucose subunits in the cyelodextrin. 1n certain embodiments, the molar ratio of extrin to linking groups of formula (I), (11), or (111) is about 1:6. 1n certain embodiments, the molar ratio of extrin to linking groups of formula (1) (11,), or (111) is about 1:5, 1n certain embodiments, the molar ratio of cyclodextrin to linking groups of a (1), (11), or (111) is about 1:11. 1n n embodiments, the molar ratio of extrin to linking groups of formula (1), (11), or (111) is about l :3. in certain embodiments, the molar ratio of cyelodextrin to linking groups of formula (1), (11), or (111) is about 1:2. 1n various ments, the molar ratio of cyclodextrin moieties to aryl eross1inl Examples of t materials include cellulose (eg, cellulose ), carbon—based materials such as activated carbon, graphene oxide, and oxidized carbon materials, silica, alumina, natural or synthetic polymers, and natural or synthetic polymers modified to include surface hydroxyl . One of shill in the art will recognize that any material with mechanical or other ties suitable to act as a support, which can covalently bond to the porous polymeric material, or can serve as a suitable support al if the porous polymeric material is adhesively bonded to the support via a suitable binder material. In an ment, the composition is in the form a membrane or a column packing al. In an embodiment, the support is a fiber (eg a cellulose, nylon, polyolet‘in or polyester fiber). to an embodiment, the support is a porous ulate material (eg, porous silica and porous alumina} In an embodiment, the t is a woven or non~woven fabric. In an embodiment, the t is a t (such as a protective garment) or a surgical or medical drape, dressing, or sanitary article. {(3981} in some embodiments, the P~CDP may be grafted or bonded (eg chemically or mechanically bonded) onto a support to provide an adsorbent where the particle size and morphology are well-controlled to give ideal flow characteristics The term "mechanical bonc " refers to a bond formed between two materials by pressure, ultrasonic attachment, and/or other mechanical bonding process without the intentional application of heat, such as mechanical entanglement. The physical entanglement and wrapping of mi crofibrils to hold in place micron— sized particulate matter is a prime example of a mechanical bond. The term mechanical bond does not comprise a bond formed using an adhesive or al grafting. ln some embodiments, the PuCDl’ may be grafted or bonded {eg or mechanically bonded) onto a support to / 5 chemically provide an adsorbent where the particle size and morphology are further engineered (e.g by granulation or milling) to e particles with a ontrolled size and morphology to give ideal flow characteristics. {8882} The P—CDP—support complex may be prepared by a variety of methods, including conventional grafting methods. As used herein, the term "grafting" refers to covalently attaching lLCDl’s to a substrate surface through coupling reactions between one or more functional groups on the ECU? and one or more functional groups on the ate. in some embodiments, grafting includes an "in situ" process as bed herein in which cyclodextrins, linking groups of the present disclosure, and a substrate having surface bound nucleophiles (eg, hy dross/ls) are reacted together such that the linking groups of the present sure reacts with the yl groups of the cyclodextrins and the e nucleophiles of the substrate, forming a P—CDP which is lly bonded via one or more linking groups of the present sure to the substrate. The ate having e hound nucleophiles include, but are not limited to hydroxyls (such as niicrocrystalline cellulose), amines, phosphines, and thiols. {9983} In some embodiments, "grafted" P—CDl’~support complexes are prepared by first synthesizing the l’~CDPs in a dedicated al reactor with adequate control of the reaction conditions and material purification to produce optimized P-CDP particles. The PnCDPs are then chemically reacted with a suitably functionalized substrate. For example, a substrate functionalized with carboxylic acid groups (or activated fornis f such as acid halides, anliydrides, etc. known in the art) can react with one of more hydroxyls on the P—CD‘P to form an ester bond with the substrate. Alternatively, the P~CDP can be appropriately functionalized (eg, by selection of a functionalized cyclodextrin as described herein) of by a subsequent modification of the P—CDP such that it can react with suitable functional groups on the substrate.

Any suitable reaction chemistries can be contemplated, such as reactions between carboxylic acids (and tives thereof) and hydroxyls to form ester bonds, reactions between carboxylic acids (and derivatives th ereof) and amine groups to form amide bonds, ons between isocyanates and alcohols to make urethanes, reactions between isocyanates and amines to make ureas, reactions between cyclic carbonates and amines to make urethanes, reactions between thiols and alhenes or alkynes to make tl'iioethers, reactions between epoxides and amine groups, photochemical reactions between acrylates, niethacrylates, thiols etc, and olefins, and so forth.

The reactive functional groups described herein can be on either of the 9—510? or substrate provided the reaction forms a covalent bond between the substrate and the PACE? For example, of the ve functional groups are hydroxyls and carboxylic acids (forming an ester bond after reaction), the hydroxyl groups can be present on the PuCDP and the carbonyl groups on the substrate or viceuversa. {8884} in other embodiments, the substrate can be coated with a "primer" having reactive functional groups as described above. The primer adheres to the surface of the substrate, and under suitable conditions can react with a suitably functionalized P433? to for a covalent bond between the P—CDP and the primer. {8885} The P—CDP particles may be engineered to achieve specific particle sizes. in some embodiments, the P—CDP is produced in the form of crosslinlred particles which may require r reduction in size leg, for the purposes of forming stable dispersions or slurries, or in providing optimal flow characteristics). A variety of means that are readily apparent to a skilled artisan can be employed to reduce the particle size of the l’nCDP such as grinding or milling.

Grinding and milling can be employed to create smaller particles with sizes less than l micron.

Typical milling operations can be used by a skilled artisan and include both wet and dry milling. g can be employed through a variety of s including, but not limited to: ball mill, autogeneous mill, SAG mill, pebble mill, rod mill, Buhrstone mill, tower mill, vertical shaft impactor mill, and the like. g media includes, but is not limited to: metals, silicates, and other inorganic materials in various form factors including, rods, balls, and irregular shapes. In some embodiments, the milling is performed on dry RC1")? powder material in a dry process to produce a finer dry powder or on wet aqueous slurries of the P—CDP powder with or without emulsifying agents to produce a finer particulate dispersion. Eniulsifying agents may be used and are readily apparent to a skilled artisan, including, but not d to: small molecule and polymeric surfactant compounds with nonionic, anionic, or cationic character. A skilled artisan will appreciate that using fine particulate form factors will enable a variety ofbenefits, such as ( l) more stable aqueous dispersions that remain homogeneous over time by resisting separation, (2) enable a high loading of al by weight in the dispersion with values of 50% by weight or higher, (3) produce ulate matter that can be evenly coated or d to s substrates, surfaces, fibers, yarns, s and the like to produce a finished material with l perceptible s in "hand," and (4) produce dispersions that are stable to dilution and blending with other emulsions or solutions such as s, surfactants, wetting agents, or softeners. in some embodiments, the final particle diameter es Granulation may also he conducted in fluidized beds or via spray drying techniques. ln each case, the ECU? particle are combined with the aqueous or solvent borne mixture containing the binder compounds and the mechanical or physical ion is conducted at a ied shear for a determined number of cycles. The resultant particles will display a step growth change in their average diameters and can also display a changed polydispersity. The physical properties of these granules depend on the binder selected, the crosslinlring chemistry, and the physical process used in their granulation. These larger granular particles will be suitable for packed bed column filtration commonly employed for water filtration and industrial separations. {8888} ln some embodiments, the present disclosure es a stable aqueous dispersion comprising P—CDP particles. ln some embodiments, the 1’—CDP particles of the present disclosure, which can be used in such stable aqueous dispersions are from about l pm to about 150 urn. For e, the PCB? particles are from about l, 2, 3, 4, 5, 6, 7, 8, 9, l0: ll, l2, 13, 14515,l6,l7,l8,19,20,2l,22523,24,25,26,27,28,29,3O,3l§32,33,34,35,36,37,38,39, 40,41,42,43,44,45,46,47,48,49,50,Sl,52,53,54,55,56,57,58,59,6u,ol,62,63,64,65, 6$,69,70,7l,72,73,74,75,76,77,78,79,80,8l,82,83,84,85,86,87,88,89,9u,9l, 92,93,94,95,96§97,98,99,l00,101,192,l03,104,105,l06,107,108,l99,llu,lll,ll2, ll3,ll4,l15,llo,ll7,118,119,120,12l,l22,123,124,l25,l26,127,128,l29,130,13h 132,133,l34,l35,136,l37,l38,l39,l40,l4l,142,143,l44,l45,l46,l47,l48,149,n3 about lSO pm A stable aqueous dispersion may be used in "grafting" applications. For e, the stable aqueous dispersion may be used in applications with chemical binders or fibrillating fibers for mechanical loading and binding, and incorporation into thermally—bonded particulate d forms and into solution processed polymer form factors. {9989} The P—CDP materials of the present disclosure can also be prepared on a support material (alternatively termed a "substrate"), for example covalently bonded, adliesiyely bonded, or mechanically attached to a support such as a fibrous substrate. The t material can be any material that has one or more groups (e. g, hydroxyl or amino, thiol, or phosphine, or other group as described herein) that can form an interaction (e,g a covalent or mechanical bond) with a crosslinlring agent or cyclodextrin. For example, one end ofa crosslinking agent (e.g the linking groups of Formulas (1), (11), and/or (111)) is covalently bound to the ate material and another end of the crosslinking agent is covalently bound to a cyclodextrin glucose unit or a reactive center on modified cyclodextrin (such as an acid halide or ted ester bound to the extrin). lt is desirable that the support material not dissolve (e.g to an observable extent by, for example, visual inspection, gravimetric methods, or spectroscopic s) under use conditions, for e in aqueous media. Examples of support materials include, but are not limited to, microcrystalline cellulose, cellulose nanocrystals, polymer materials (e.g acrylate materials, methacrylate materials, styrenic materials (eg, polystyrene), polyester materials, nylon materials, and combinations thereof or inorganic materials (eg, silicates, silicones, metal oxides such as alumina, titania, zirconia, and hafnia, and combinations thereof). ln various examples, the polymer materials are olymers, mers, or resins (eg, resins comprising polymeric als). The support material may be hydroxyl or amino containing polymer beads or irregular particles. The t material can be in the form a fiber (cg, pulps, short cut, staple fibers, and continuous filaments), fiber bundles (e.g., yarn — both spun and uous filament), fiber mats (eg, nonwovens — both staple and continuous nt), fabrics (eg, lrnits, woven, nonwovens), membranes tog, films, spiral wound, and hollow fibers, cloth, particulate leg, a powder), or a solid surface. in some embodiments, the fibrous substrate is a cellulosic substrate. Cellulosic substrates can comprise any suitable form of ose, such as cellulose derived from plant sources such as wood pulp (eg, paper or paper fibers), cotton, regenerated cellulose, modified cellulosics such cellulose esters and/or ethers, and the like, starch, polyvinyl alcohols and derivatives thereof. The cellulosic substrate can be in the form of a fabric, such as a woven or nonwoven fabric, or as , films, or any other suitable shape, particularly shapes that provide high surface area or porosity. In a particular embodiment, the P— CDP materials of the present disclosure are bonded to , for example, a cellulosic fiber or a fabric, such as cotton. {(3899} In addition to the substrates listed in the preceding paragraph, the substrate may include any of the following: polyvinylamine, polyethylenimine, proteins, proteirnbased fibers (cg, wool), an and amine-bearing cellulose derivatives, polyarnide, vinyl de, vinyl acetate, polyurethane, melamine, polyirnide, polystyrene, polyacryl, polyamide, acrylate butadiene styrene (ABS), Barnox, PVC, nylon, EVA, PET, cellulose nitrate, cellulose acetate, mixed cellulose ester, lfone, polyether sulfone, polyvinylidene fluoride (PVDF) or trafluoroethylene (PFTE or Teflon R), polyethylene, polypropylene, polycarbonate, phosphine or thiol functional materials, and ne or combinations thereof. The ate may also consist of silicon or silicon oxide, or glass leg. as fibres). Suitable materials further e textiles or synthetic or natural fiberubased materials. The material may exhibit any form or shape and may for instance be in the form of a sheet, bead, granule, rod, fiber, foam or tube, and may be rigid, flexible or elastic. {$091} If necessary, the material surface may be activated by any method known in the art, such as known surface activation techniques, including for instance corona ent, oxygen , argon plasina, ive plasma hromination, chemical grafting, allyl chemistry, chemical vapour deposition (CVD) of reactive groups, plasma activation, sputter coating, etching, or any other known technique. For ce in the case of a glass surface, such an tion is usually not ed as such a surface is herein considered already activated. The purpose of the activation of the surface is to provide for a surface suitable for the covalent attachment of a surface—modifying functionality or (directly) of a primer polymer. Following its optional activation, the surface may he further functionalized. The e of the onalization of the surface is to provide for functional group suitable for the covalent attachment of a prencoat polymer. {9992} The skilled artisan is well aware of the various possibilities of ing polymers to optionally activated surfaces. These techniques generally involve the introduction of amino, silane—, thiol—, hydroxyl~ and/or epoxy-functionalities to the e, and the subsequent attachment thereto of the polymer. [9993} The onalizati on may also comprise the introduction of spacers or linker to the surface for the attachment of the primer polymer to the surface at a predetermined distance. A suitable spacer is for instance an alkylation by reacting the surface with for instance aininoalkylsilane. [9994} The P—Cf)? may he hound to the ate via the linking groups of the present disclosure (eg. via a hydroxyl or amino group of the linking group). A c‘linlrer moiety" refers to the intervening atoms between the P—CDP and substrate. The terms "linker" and "linking moiety" herein refer to any moiety that connects the ate and PCT)? to one another, The linking moiety can he a covalent bond or a chemical functional group that directly connects the P—CDP to the substrate. The linking moiety can contain a series of covalently bonded atoms and their substituents which are collectively referred to as a linlting group. in some embodiments, linking moieties are characterized by a first covalent bond or a chemical functional group that bonds the P~CDP to a first end of the linlter group and a second covalent bond or chemical functional group that bonds the second end of the linker group to the substrate. The first and second functionality, which independently may or may not be present, and the linker group are collectively referred to as the linker moiety. The linker moiety is defined by the linking group, the first functionality if present and the second functionality if present. In certain embodiments, the linker moiety contains atoms interposed between the P—CDP and substrate, ndent of the source of these atoms and the reaction sequence used to synthesize the coniugate. In some embodiments, the linker moiety is an aryl moiety as described herein. In some embodiments, the linker has one or more of the following functionalities: multifunctional isocyanate (cg, a diisocyanate), epoxy, ylic acid, ester, activated ester, cyanuric chloride, cyanuric acid, acid chloride, halogen, liydroxyl, amino, thiol, and phosphine {0095} In some embodiments, the ECU? is grafted or bonded onto microcrystalline cellulose (CMC). CMC is available in a variety of median particles sizes from about l0 — about 500 um ing about l0 pin, 20 um, 45 ttm, 50 pm, 65 pm, 75 um, l00 uni, lSO um, l80 itin, l90 pm, 200 pm, 225 um, 250 pm, 275 pm, 300 pm, 325 um, 350 um, 375 pm, 400 um, 42:3 pm, 450 pm, 475 um, and about 500 um and all particle sizes tlierebetween, In some embodiments, I’uCDP is d or bonded onto CMC having a median particle size of about 50 um. In one example, CMC is commercialized as Avicelm, In other embodiments, the P—CDP is grafted or bonded onto a polymeric substrate other than cellulose, as described herein, in which the surface is treated to produce surface functional groups as disclosed herein, such as hydroxyl groups. {00%} In some embodiments, the P~CDP—substrate complex (eg, a P—CDP inked with an aryl linker of formula (l)~CMC substrate complex) has a r thickness tie, the thickness of the porous P—CDP particles on the surface of the substrate) of between about l nm to about 2000 nm. For example, P—CDP—substrate complex has a r thickness of about l, 2, 3, 4, 5, 6, 7, 8, 9, l0, 20, 30, 40, 50, 60, 70 , 80, 90, l00, l50, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, l000, l050, ll00, ll50, L200, l250, I300, I350, l400, l450, l500, l550, l600, l650, l700, l750, l300, l850, l900, l950, to about 2000 nm. In some embodiments, P—CDP—substrate complex has a polymer thickness or" less than 1000 nrn. In some embodiments, P—CDP—substrate complex as a r thickness of about 800 nm. As will be readily apparent to a skilled artisan, a having a lower thickness (eg, less than l000 nm} will allow for faster kinetics to absorb inants, for example aqueous contaminants. {0097} In some embodiments, the PuCDP—substrate complex (eg a P—CDP inked with an aryl linker or" formula (1)4)th substrate complex) has a contaminant adsorption capacity of up to 500 mg contaminant/g CD. For example, the adsorption capacity may be up to about l, 2, 3,4,5,6,7,8,9,10,15,20,25,30,35,40,45,SO,55,60,65,70,75,80,85,90,95,100,lOS, ,120,125,130,l35,l40,l45,l50,155,160,165,l70,l75,180,l85,190,195,200, 210,220,230,24o,250,260,270,zso,2ao,300,310,320,330,34o,350,3eo,37o,3so,390, 400, till), 420, 430, 440, 45G, 460, 470, 480, 490, to about 590 mg contaminant/g Cl). in some embodiments, the adsorption capacity is up to about 200 mg contaminant/g Cl). ln some embodiments, the contaminant is an anionic mieropollutant (eg. PFASS). In some embodiments, the cyclodextrin is B—cyclodextrin. ln some embodiments, the linking groups are the linking groups of Formulas (I), (ll), and/or (Ill). {9998} ln some embodiments, the lLCDP—substrate complex (eg, a P—CDP crosslinked with an aryl linlter of formula (l)~Cl\/lC ate complex) has an equilibrium contaminant adsorption capacity of up to Sill) mg contaminant/g Cl). For example, the equilibrium adsorption capacity maybe up to about l, 2, 3, 4, 5, 6, 7, 8, 9, ll), l5, 20, 25, 30, 35, 40, 45, 5t), 55, 60, 65, '70, '75, 9o,95,ioo,ios,iio,iis,izo,i25,iso,135,14o,i45,iso,155,ieo,165,17o,i75, iso,iss,ieo,i95,200,2io,220,230,2ao,250,260,27o,2so,290,3oo,sio,320,330,340, sso,3eo,370,3so,390,aoo,4io,420,430,44o,450,4eo,47o,4so,490,aiaeautsooing inant/g CD. In some embodiments, the equilibrium adsorption capacity is up to about 200 mg contaminant/g Cl?~ In some embodiments, the contaminant is an anionic- ollutant (eg~ . ln some embodiments, the cyclodextrin is ll—cyclodextrin. in some en'ibodiinents, the lii'ikiiig groups are the linking groups of Formulas (l), (ll), arid/or (lll). {(3899} In some ments, the P~CDP—substrate complex (eg, a P—CDP crosslinked with an aryl linlter of formula (DEB/h: substrate complex) has a relaxation time of less than 2 minutes, As will be appreciated by a skilled artisan, where processes with high tion times slowly reach equilibrium, while processes with small relaxation times adapt to equilibrium quickly. ln some embodiments, the contaminant is an anionic i'nicropolhitai'it (eg. PFASs). ln some embodiments, the cyclodextrin is B-cyclodextrin. ln some embodiments, the linking groups are the linking groups of Formulas (I), (ll), or (ill). {lllllllll} ln some embodiments, any of the P-CDP materials disclosed herein are grafted or bonded onto CMC directly or via a linlter group as defined . ln some in'ients, the P- CDP is homogenously distributed on the CMC e. in some embodiments, the aryl linker is WO 68104 an aryl linker of formula (l). ln some embodiments, the aryl linker is a linking groups of Formula (ll). in some embodiments, the aryl linker is a linking groups ot‘li'ormula (ill). ln some embodiments, the median particle size is about 50 pm. hi other embodiments, the median particle size is from about 1 about 250 am. {98191} CMC can also be distinguished by a particle shape known to impact flow characteristics among other things. A nonulimiting list of particle shapes es cal (round—shaped), rod— shaped, and needle—like. Particles can also be described as flat, flat and elongated, or be characterized by their aspect ratio. ln some embodiments, the CMC has a spherical le shape. In some embodiments, the CMC is present in the form of agglomerates of smaller CMC particles. Such CMC agglomerates can have particle sizes in the range of 200 um up to about 2 mm. For example, the particle sizes of CMC agglonierates can be about 200 um, about 300 um, about 400 pm, about 500 pm, about 600 urn, about 700 um, about 800 um, about 900 um, about 1 mm, about 1.2 mm, about l3 mm, about 'l.4 mm, about l5 mm, about 1.6 mm, about l7 mm, about 1.8 mm, about l9 mm, or about 2 mm, inclusive of all ranges therebetween. litltlllliZl ln some embodiments, the ECU? is grafted or bonded onto CMC via a linking groups of Formula (1). ln some embodiments, the ECU? is grafted or bonded onto CMC via a linking groups of a (la). ln some embodiments, the P—CDP is grafted or bonded onto CMC via a linking groups ot‘Formula (ll). In some embodiments, the RC1")? is grafted or bonded onto CMC via a linking group of Formula (Ill), {@9193} ln some embodiments, P~CDP of the present disclosure is grafted or bonded onto CMC via an aryl linker, and the aryl linker is hoinogen ously distributed on the CMC crystal In some embodiments, the median particle size is about 100 nm, lttttll‘ldl In addition to the use of CMC as illustrated , examples of other potential support materials include those materials described above, such as activated carbon, graphene oxide, as well as silica and alumina. {99195} ln some embodiments, it is desirable that the supported P~CDP materials disclosed herein (e,g a P—CDP crosslinked with an aivl linker of a (ll—CMC substrate complex) are in the form of particles having a narrow dispersity of particle sizes. ln some embodiments, the particle size distribution has a low ve span of about 5 or less, where relative span is defined WO 68104 by the ratio (D90—DiG}/’D50, where D90, D50, and Die are, tively the diameters at which 90%, 50%, and 10% of the particles in the distribution have a smaller diameter. Suitable spans are no more than 5, 4.5, 4, 3.5, 3, 2.5, 2, l, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.l, including all ranges tlierebetween. {00106} In other various embodiments, the PuCDP may be grafted or bonded onto cellulose nanocrystais (CN Cs). CNCs are the crystalline regions of cellulose mici'ofibrils obtained after mechanical, chemical, and enzyme treatments. Depending on the source and, preparation method, CNCs are available with lengths ranging front about lml000 nni and, widths ranging from about 3-50 nm, inclusive of all values therehetween. For example, the CNCs have a length of about l, 2, 3, 4, 5, 6, 7, 8, 9, l0, l5, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, '70, '75, 80, 85, 90, 95, ion, l50, zoo, 250, 3m, 350, 400, 450, soc, 550, eon, 6.50, 700, 750, see, 850, sec, 95a, to about 1000 nrn. The CNCS have a Width of about 3, 4, 5, 6, '7, 8, 9, l0, ll, l2, 13, 14, l5, l6, l7, is, 19, 20, 2t, 22, 23, 24, 25, 2e, 27, 2s, 29, so, 31, 32, 33, 34, 35, 36, 37 3s, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or about 50, In some ments, the P~CDP~CNC substrates may he 2- 3 times the size (length, and width) as the unbound CNCs. The CNCs are further characterized by aspect ratio values (LCD) ranging from about 2~l 00 (George, J, et at, Cellulose nanoorystals: synthesis, ional ties, and applications, .Z‘v’anotechnofogu Science andApplications. 206045—54). For example, the CNCs have an aspect ratio of about 2, 5, l 0, 15, 20, 25, 30, '35, 40, 45, so, 55, no, 65, 7o, 75, so, as, so, 95, too, 105, no, its, 120, i25, l30, i35, 140, MS, 150, L55, ieo, res, i7o, i75, iao, 135, l90, l95,01‘l00. {00107} In some embodiments, the P~CDP is grafted or bonded onto (INC via the g groups are the linking groups offinmulas (l), (ll), and/oi (ill) as described herein. ln some embodiments, the P-CDP is d or bonded onto CMC via a g groups of Formula (I). In some embodiments, the P~CDP is gratted or bonded onto CMC via a linking groups of Formula (II). in some embodiments, the P—CDP is grafted or bonded onto CMC via a linking groups of Formula (111). {00108} In some embodiments, P~CDP is grafted or bonded onto CNC via a linker, and the linker is homogenously distributed on the CNC crystal. In some embodiments, the median particle size is about 100 nm. {@8199} (INC can also be distinguished by particle shape known to impact flow characteristics among other things. A nonulimiting list of particle shapes includes spherical (round—shaped), rod— shaped, and needle—like. Particles can also be described as flat, flat and elongated, or be characterized by their aspect ratio. In some ments, the CNC has an aspect ratio of between about 5 to about lQQ. For examples, the aspect ratio may be about 5, l0, l5, 20, 25, 30, , 40, 45, 50, 55, 60, 65, '70, 75, 80, 85, 9t), 95 to about lt‘it‘i. In some embodiments, the CNC aspect ratio is about 20—25. In some embodiments, the CNCs are needle—like. In some embodiments, the CNC is present in the form of agglomerates of smaller CNC particles. Such CNC agglomerates can have le sizes which are 5400 times larger than the sizes of the individual particles, depending on the sizes and number of the particles constituting the aggregates.

{Willi} In some embodiments, the substrate is a fabric or fiber. , in some embodiments, the present disclosure provides a composition comprising a I’nCDP grafted or bonded (e. g, chemically or mechanically) to a fiber. In some embodiments, the PCB? is grafted or bonded onto a fiber yia the linker of formulas (I), (II), and/or (III), as described herein. In some ments, the fiber is a nonwoyen fiber. In some embodiments, the present disclosure provides a composition comprising a P—CI)P grafted or bonded (eg chemically, adhesively, or mechanically) to a fabric. In some ments, the P—CDP is grafted or bonded onto a fabric via the linker of formulas (I), (II), or (III), {titlllll Fibers suitable for use include, but are not limited to fibers comprising any of the polyi'ners disclosed herein, for example fibers made from highly oriented rs, such as gel— spun ultrahigh molecular weight polyethylene fibers (e.g, SPECTRA® fibers from ell Advanced Fibers of Morristowri, Nl and DYNEMA® fibers from DSIVI High mance Fibers Co of the Netherlands), melt-spun polyethylene fibers (eg, CERTRANG?) fibers from Celanese Fibers of Charlotte, NC), melt~spun nylon fibers (eg, high tenacity type nylon 6,6 fibers from Invista of Wichita, Kans), melt—spun polyester fibers (e.g high tenacity type hylene terephthalate fibers from lnyista of Wichita, Kans.), and sintered polyethylene fibers (eg, ’l‘ENSYLONfii‘) fibers from l'l‘S of Charlotte, NC). Suitable fibers also include those made from rigidurod polymers, such as pic rod polymers, heterocyclic rigid~rod polymers, and thermotropic liquid—crystalline polymers. Suitable fibers also include those made from regenerated ose including reactive wet spun Viscose rayon (Viscose from Birla of lndia or Lenzing of Austria}, cuproaniinoniurn based ray on (Cupro® Bernberg,‘ from Asahi Kasei of Japan), or air gap spun froni Nit/{MO solvent ('l'encelfi's) from Lenzing of Austria). Suitable fibers made from lyotropic rigidurod polymers include d fibers, such as polylpu plienyleneterephthalainide) fibers (egg, KE’VLARGE fibers from DuPont of Wilmington, Del. and ONd‘) fibers from in of Japan) and fibers made from a l:l copolyterephthalaniide of 3,4’"dianiinodiphenylether and pnphenylenedianiine (cg, 'l'ECHNORA® fibers front 'l'eiiin of lapan). Suitable fibers made from heterocyclic rigidmrod polymers, such as pnphenylene lieterocyclics, include poly(pnphenylenen2,6-benzobisoxazole) fibers (PEG fibers) (cg.

ZYLON® fibers from 'l'oyobo of Japan), polytpnphenylenenf/l,ombenzobisthiazole) fibers (PBZT fibers), and, polylZfi—diimidazold,5—b:4",5’—e}pyridinylene—l,4—(2,5nrliliydroxy)phenylene} fibers (PIPE) fibers) (ego, M5® fibers from DuPont of Wilmington, Del). Suitable fibers made from therinotropic mcrystalline polymers include poly(o—hydroxy~2~napthoic acid—coalit— hydroxybenzoic acid) fibers (erg, VECTRAN® fibers from Celanese of Charlotte, NC).

Suitable fibers also include carbon , such as those made from the high temperature pyrolysis of rayon, polyacrylonitrile (eg, OPF® fibers from Dow of Midland, Mich), and mesoniorphic hydrocarbon tar (eg, THORNEL® fibers from Cytec of Greenville, SC). In certain possibly preferred embodiments, the yarns or fibers of the textile layers comprise fibers selected from, the group consisting of gel—spun ultrahigh molecular weight polyethylene fibers, rnelt~spun polyethylene fibers, melt—spun nylon fibers, melt—spun polyester fibers, sintered polyethylene fibers, aramid fibers, PEG fibers, PBZT fibers, PIPE) fibers, poly'(6—hydroxy—2— ic acid—co—d—hydroxybenzoic acid) fibers, carbon fibers, and combinations thereof~ 2} The P—CDP materials of the t sure can be d to such fibers by means of a suitable binder polymer as described , or chemically bonded to such fibers by functional izing the surface of the fibers as described herein (cg, surface oxidation to produce surface hydroxyl groups) and either forming the P—CDP in situ on the fiber surface, or by reacting a suitably functionalized P—CDP directly with the functionalized fiber surface, or indirectly Via a r moiety as bed herein. {98113} The fibers may be converted to nonwoyens (either before or after ment of the P— 010?) by different bonding methods. Continuous fibers can be formed into a web using ry standard spunbond type technologies while staple fibers can be formed into a web using industry standard carding, airlaid, or d technologies. Typical bonding methods include: calendar (pressure and heat), thru—air heat, mechanical entanglement, hydrodynamic entanglement, needle punching, and chemical bonding and/or resin bonding. The ar, thru—air heat, and chemical bonding are the preferred bonding methods for the starch polymer fibers. lly bendable fibers are required for the pressurized heat and thru—air heat bonding methods.

{Mill/l} The fibers of the present invention may also be bonded or ed with other synthetic or natural fibers to make nonwoven articles. The synthetic or natural fibers may be blended, together in the forming process or used in discrete layers. Suitable synthetic fibers include fibers made from polypropylene, polyethylene, polyester, polyacrylates, and, copolymers thereof and mixtures thereof. Natural fibers include cellulosic fibers and tives thereof.

Suitable cellulosic fibers include those derived from any tree or vegetation, including od fibers, softwood fibers, hemp, and, cotton. Also included are fibers made from processed natural cellulosic resources such as rayon. {titlllfil The fibers of the present invention may be used to make nonwovens, among other suitable articles. Nonwoven articles are defined as articles that contains greater than l5% of a plurality of fibers that are uous or non—continuous and physically and/or chemically attached to one another. The nonwoyen may be combined with onal noriwoyens or films to produce a layered product used either by itself or as a ent in a complex, combination of other als. Preferred articles are disposable, nonwoven articles. The resultant products may find use in filters for air, oil and water; textile fabrics such as rniero fiber or breathable fabrics having ed moisture and odor absorption and softness of wear; electrostatieally charged, structured webs for collecting and ng dust and ants, medical textiles such as al drapes, wound dressing, bandages, dermal patches, textiles for absorbing water and oil for use in oil or water spill clean—up, etc" The es of the present invention may also e disposable nonwovens for hygiene and medical applications to absorb off~odors Hygiene applications include such items as wipes; diapers, particularly the top sheet or baclr sheet; and feminine pads or products, particularly the top sheet. {lllll 16} The yarns or fibers of the textile layers can have any suitable weight per unit length (cg denier). Typically, the fibers have a weight per unit length of about l to about 50 denier per filament (l to about 50 g per 9000 meters). The yarns contain a plurality of filaments from l0 to about 5000. {98117} ln some ments, the PuCDP is adhesively bound to a substrate such as a fiber or fabric Via a binder. ln some embodiments, the P—CDP is coated on a substrate such as a fiber or fabric via a . in some embodiments, the P—CDP is bound to or coated on a substrate such as a fiber or fabric via a binder by ucing the surface to stable aqueous dispersions of the P— CDP particles in conjunction with s. 'l'he P—CDP particle dispersion may be l~50% by weight and a polymeric binder al may be present in an emulsion or solution in l~50% by weight. For example, the P—CDP particle dispersion may be present at about 1, 2, 3, 4, 5, 6, 7, 8, 9,10,ll,12,13,l4,l5,l6,l7,l8,l9, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 3l, 32, 33, 34, , 36, 3'7, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or about 50% by weight. The polymeric binder material may be present in an emulsion or solution at about l, 2, 3, 4, 5, 6, 7, 8, 9, l0, ll, 12, i3, l4, l5, l6, 17, is, l9, 2o, 21, 22, :23 :24, 25, 2e, 27, 2s, 29, 3o, 31, 3:2 33, 34, 35, 36,, 37, 38, 39, 40, 4l or about 50 % by weight. onal auxiliary , 42, 43, 44, 4-5, 4-6, 47, 48, 49, agents can be used as minor components by weight to control the wetting by the substrate (wetting agent), solution foaming or de—foarning, softening agent for substrate hand, and/or catalyst for binder curing. {99118} A variety of coating techniques known in the art can be applied, such as: dip and squeeze, solution g, foam g, or spraying of the formulated on onto the substrate of interest. Substrates include, but are not limited to: woven, knit or nonwoyen s, continuous filament yarns, spun yarns, spun fibers, wood surfaces, and thermoplastic surfaces.

In some embodiments, upon application of the formulated solution to the substrate, the combined system will be dried to remove the water solvent at which time an even film of P—CDP particles mixed with polymeric binder will be present During the drying process, the binder material present as an emulsified polymer will llow together and hecorne a continuous phase. Depending on the choice of hinder, the P—CDP particles may be held in place through mechanical means or adhesion to the binder continuous phase only, or additional covalent linkages could be present if a cure—able binder is selected. Such covalent linkages could extend the underlying substrate which would further increase the lity of the P—CDP particle coating. {99119} As will be readily apparent to a skilled artisan, the resultant PuCDl’ le filin conforms to the underlying substrate and is durable to physical abrasion, and washing such that the article can be deployed. Furthermore, if the P—CDP les have access to the aqueous or vapor phase within the coating, they will demonstrate the same selective and high affinity small molecule adsorption characteristics as the monolithic particles. Such form factors can be converted into filter cartridges, d filters, nonwoven needlepunched filters, hygienic ens, and apparel.

{M13129} A variety of binders known to a skilled artisan may he used in the context of the present disclosure, such as any of those disclosed in US Patent Publication No. 20l4/Ol78457 Al, which is hereby incorporated by reference in its entirety. Suitable hinders include, but are not limited to, latex binders, isocyanate hinders (eg, d isocyanate s), acrylic binders (eg, ic acrylic binders), polyurethane s (eg, aliphatic polyurethane binders and polyether based polyurethane binders), epoxy hinders, urea/formaldehyde resins, inelarnine/fornialdehyde resins, nylalcohol (PvOH) resins (disclosed in US Patent No. ,496,649, which is hereby incorporated by reference in its entirety) and crosslinked forrns thereof, poly—ethylenevinylalcohol (EvOH) and crosslinked forms thereof, polym ethylenevinylacetate (EVA), starch and starch derivatives, cellulose ether tives, and ose ester derivatives, Small molecule, ric or inorganic inhing agents could be used additionally including formaldehyde, glyoxal, diisocyanates, diepoxides, and/or sodiuni orate, and combinations thereof. {(39121} ln some embodiments, the P—CDP particles are mechanically bound to a surface, such as a fibrillating fiber Fibrillating fibers are used to create high surface area, extended networks which can wrap around and entrap particulate matter. Fibers such as fibrillating polyolefin (such as Mitsui Fybrel®), fibrillating regenerated cellulose (such as Lenzing TencelTM) or fibrillating acrylic (such as Sterling Fibers CFFTM) are deployed in wet laid processes to create specialty papers which excellent mechanical properties, good wet strength, and the ability to hold particulate matter (US Patent No. 4,565,727, which is hereby incorporated by reference in its ty), Onxy Specialty Papers, l-lelsa Corporation, and others. in particular, powdered activated carbon particles with diameters greater than 5 microns have been loaded into specialty carbon papers that are deployed in liquid and vapor filtration applications such as point of use water filters or cabin air filters, {hill 22} ln the paper rnahing process, an aqueous sion or slurry blend of short cut fibers (such as wood pulp, polyester, nylon, or polyolel’in), fibrillating fibers (such as Fyhrel®, 'llencell‘M, or CFF’E‘M), and particle powder al are mixed (eg, under high shear). This mixture can then be rapidly passed through a nonwoven mesh or screen to deposit a wet laid nonwoven web. This web is dried (eg, in hot air oven or on heated rolls) to remove the water carrier. r g may be achieved through cold or hot calendaring either in flat format or with a patterned roll to produce the bonded lty paper. The particulate powder used can be a dispersion of P—CDP particulates of defined particle size. Particulate size can be set Via grinding and milling techniques as defined previously. The particulate loading in the finished nonwoven can he as high as 60% by weight. The particulate can be used alone or blended with other particulate such as ed activated carbon. Additional chemical binders, such as those described herein, may be used to alter or enhance the properties of the paper and will be applied as one skilled in the art. {bulls} The resultant powder loaded papers are le to a high loading of KGB? adsorbent particles in a convenient paper filter form factor for water and/or air filtration. The paper can be used in the flat form, cut into a variety of shapes, or pleated and bonded into a filter media cartridge. lilllllZK-ll in some embodiments, the PCB? particles are mechanically led in yarn leg, continuous filament yarn). In some embodiments, the P—CDP particles are mechanically entangled in continuous filament yarn. As will be readily apparent to a skilled artisan, a special subset of yarn finishing enables the mechanical binding of particulate matter within a continuous filanient yarn in some circumstances. When a yarn leg, uous filament) comprised of multiple nts of a typical synthetic polymer such as polyethyleneterephthalate (PET) or polyamide (nylon 6 or nylon 6,6) that bears n'iicrofibrilla‘ting tendencies on each filament surface, there exists the ility to incorporate particulate within the yarn bundles. The P— CDP particles of the present sure can be incorporated into the yarn in a variety of ways One non—limiting example is to apply a dispersion of the P—CDP particles of interest via dip coating or oil roll application onto a moving yarn bundle during the false twist texturing process. ln this s, the filaments are mechanically ted via twisting, first in one direction followed by the opposite direction. After the first twisting, the filaments are individualized and void space is presented within the yarn . The dispersion solution is applied at this point within the process after which the bundles are twisted back to the standard orientation and the yarn heated to dry the on. This process enables the application of dispersion particles within the yarn bundles that are held in place by the continuous nts and microfibrils emanating from the uous filament surface. Such approaches have been used to apply various micron sized particles to continuous nt yarns, including microcapsules (US Patent Publication No. EGGS/0262646 Al which is hereby incorporated by reference in its entirety), metallic silver inieroparticles (US Patent Publication No. 20l5/036l595 Al which is hereby orated by reference in its entirety), and (US Patent Publication No. 2006/0067965 Al, which is hereby incorporated, by reference in its entirety) other functional particles to synthetic fiber yarn bundles. These textured and particle loaded yarns may then be processed through typical means to create knit and woven fabrics for use in apparel, upholstery, medical, displays, or other uses. {99125; In some embodiments, the PSI)? particles are incorporated, into thermally—bonded, particulate pressed forms. A common form factor for powdered absorbent al is in thermally/"bonded pressed forms. Such form factors can contain as high as 95% by weight lb CDP particles, with the addition of fibrillating fibers (Fybrelfil), 'l'encel"M, or Cll‘FTM), sometimes inorganic materials such as attapulgite clays, and y an organic binder material (most typically cellulose esters and similar derivatives) to create a porous composite structure with adequate mechanical strength and particulate holding efficiency for medium pressure tion applications such as faucet filters and refrigerator filters (US Patent Nos 5,488,02l and 8,l6’7, l 4i both of which are hereby incorporated by reference in their entireties). {£39126} P—CDP dry particles or dispersion can be used in place of or blended with other ent als to form such a composite ent P—CDP particulate—containing forms as bed above In such embodiments, the solid dry components may be dry blended, optionally including dry P-CDP particles and organic binder powder with or without inorganic clays and/or fibrillating fibers, If an aqueous dispersion of P—CDP particles is used, they may be diluted with water and added to the mixture. Water is added (egg in 80~l 50 wt%) and the mixture is blended (eg under high shear) to create a plastic al. This n'iaterial may be formed into the desired form factor, dried and cured at temperatures ranging from l25 to 250 "C.

This final form factor presents the PCB? ent particles in a form factor common to and useful for point of use water filters, {99127} in some ments, the P~CDP particles are incorporation into solution processed polyiner form s. A, variety of means are available to produce filter membrane materials.

For example, via solution cast films or extrude hollow fibers of membrane polymers where controlled coagulation creates a condensed film of lled pore size. ln some embodiments, a polymer such as cellulose acetate ved in a water miscible organic solvent such as NMP, DMSQ, or 'l‘llF is used. This solution can be cast as a film into a water bath which causes rapid coagulation of the cellulose acetate polymer and densification of the film. These films may be processed on roll to roll equipment and many layers are wrapped to create a spiral wound ne filter for use in filtration, ultranfiltration, gas tion, or reverse osmosis applications. In place of cellulose acetate, common polymers used include polyamides, polyolefins, polysulfones, polyetliersulfones, polyvinylidene fluoride, and similar engineered thernioplastics. It is also possible to extrude hollow fibers into the aqueous on to create membrane fibers through the phase inversion process that are ltnown as hollow—fiber membranes commonly used for dialysis, reverse osmosis, and desalination applications. ionizer in some embodiments, the PnCDP particle matter is incorporated into membrane material to enhance the mance of the membrane materials. For example, it is possible to have present in the aqueous coagulation bath a small quantity of P—CDP particle sion that will become incorporated into the dense portions or porous ns of the membrane during the phase inversion process. A, second manner to incorporate the PCB? particles into the membrane is the incorporation of a small amount of wellvdispersed particles into the organic solution of the membrane polymer that become encapsulated in the membrane ing coagulation. Through each of these methods? the production of P-CDP loaded polymer forms may be enabled. in various ments, such as micro—filtration, ultra-filtration, and reverse osmosis, the P—CDP particle incorporation acts to enhance the n'iicropollutant val of the membrane system. {@0129} in some ments, the PCB? particles are incorporated into melt extruded th ermoplastics (cg fibers and molded parts). Having access to small diameter dry powder P~ CDP particle material of low polydispersity enables its incorporation into melt processed polymer forms including fibers and molded parts. Typical thermoplastics of use include polyethyleneterephthalate, co—polyesters, polyolefins, and ides. Typical extrusion temperatures are between 250—300 "C and therefore l’uCDP le stability to those temperatures either under air (most preferred) or inert atmosphere is required. Single or twin— screw extrusion is used to blend and mix the powdered material at elevated temperatures under WO 68104 shear with the thermoplastic in up to five weight percent. Once adequately mixed, the d components can be extruded through small round or otherwise shaped orifices and drawn to produce fibers bearing the particulate matter linear densities ranging from l to 20 denier per filament. A common le added to most thermoplastic fibers is titanium dioxide added to whiten and deluster the fiber. The l’nCDP particles will be added in a similar fashion. ln the most ideal embodiment, the l’nCDP particles will migrate to the surface of the fibers and bloom due to their higher surface energy such that a portion of the particles are t and accessible by the vapor or liquid phase. in other embodiments, instead of extruding the polymer melt through small orifices, it can be blow molded or otherwise melt processed to produce a plastic part. This plastic part will also bear the PnCDP particles that bloom to the surface and become active for the removal of small molecule micropollutants leg. anionic ) from the vapor and liquid phase. illl} The P—CDP of the present disclosure can be supported or formed into a variety of shapes (or formmfactors) suitable for various applications. For example, the P—CDP materials of the present disclosure can be in the form of powders, granules, formed into discs, eg, in a cellulosic al such as paper or other non—woven forms, or ed or pressed into various shapes suitable for, eg, filtration, water treatment, sample absorption, etc. as described herein, {@9131} While it is not unknown to provide adsorbents in a. supported form, it is important that the methods used to affix the adsorbent to the ate or support are sufficiently robust so as to withstand the use conditions. Further, the means of attachment to the substrate should not interfere with or block the adsorption mechanism of the ent. The adsorbents sed herein can be attached to supports, as described herein, so that the resulting performance characteristics are only minimally affected by the attachment . in various embodiments, the supported polymeric materials of the present invention provide performance characteristics which are at least 50% of the same performance teristic which would be provided by the same composition of adsorbent prepared without a support material (based on equivalent amounts of the adsorbent) when measured under identical conditions. So for example a porous material grafted to microcrystalline cellulose (eg, a l’uCDP crosslinked with an aryl linker of formula (l)_Ch/lC substrate complex) may have at least 50% of one or more of a particular performance characteristic found in unsupported porous material tested under the same conditions. {98132} in some embodiments, the performance characteristic can be the amount of uptake rption capacity) of a particular pollutant, measured as the milligrams of pollutant adsorbed per gram P—CDP le under particular conditions. ln other embodiments, the performance characteristic can be the equilibrium adsorption capacity (tie), defined as discussed herein as: our," qt? m gmax CQKL+1 wherein qmm (mg pollutant/g adsorbent) is the maximum adsorption capacity of the t for a particular pollutant at equilibrium, K1, (mol‘l) is the equilibrium constant and (:8 (mid) is the pollutant tration at equilibrium {99133} ln still other embodiments, the performance characteristic is the rate at which equilibrium adsorption of a pollutant is reached (rate of equilibrium adsorption for a particular ent. This rate can be expressed as the time required for a supported or unsupported RC1")? of the present disclosure to reach equilibrium for a particular adsorbed species (or pollutant), } ln still other embodiments, the performance characteristic is the rate at which competing adsorbents sequester pollutants. Competing adsorbents may he unsupported P—CDPs as described herein, or other agents, such as activated carbons (powdered or granular), ion- exchange resins, and specialized resins used for solid—phase niicroextraction (eg, HEB), {(38135} For any of these performance characteristics disclosed above, the performance of the supported P—CDP ot‘ the present disclosure is at least about 50%, 60%, 70%, 80%, 90%, WOO/E), l20%, 140%, least, {80%, 2009/9, 220%, 2a %, zoos/ii, 280%, 300%, 350%, 4a %, 450%, 500% or greater, inclusive of all values, ranges, and subranges therebetween compared to unsupported P~CDP of the same composition, tested under essentially the same ions, eg, with the same pollutant, temperature, pressure, exposure time, etc, 6} The performance characteristics of the t disclosure can be measured, for example based on bisphenol A or PFASs or another suitable specie as sed herein, by a variety of methods which will be readily apparent to a skilled artisan. For example, the contaminant may be ed at initial concentrations of EPA or another suitable specie g from l ppb (or l microgram/L or 5 nM) to l ppt (or l g/L or 5 rnM} in any aqueous sample, including but not limited to ing water, wastewater, ground water, aqueous extracts from contaminated soils, landfill leachates, purified water, or other waters containing salts, or other organic matter. The pl-l may be range from 0—l4. For example, the pl-l may be 0, l, 2, 3, 4, 5, t3, 7, 8, 9, l0, ll, l2, WO 68104 13, or l4, inclusive of all ranges therebetween. The performance characteristics may be measured substantially as described herein (eg, in Examples l and 2), with routine modifications (such as temperature and re) also being envisioned. } in some embodiments, the present disclosure provides an article of manufacture sing one or more P—CDl’s or one or more P—CDlLsuhstrate complexes of the present disclosure. {98138} ln an embodiment, the article of manufacture is tive equipment. in an embodiment, the article of cture is clothing. For example, the article of manufacture is clothing comprising one or more P—CDPs or one or more P—CDl’nsubstrate complexes of the present disclosure leg, clothing such as a uniform at least partially coated with the porous polymeric al or. composition). In another example, the article is filtration medium comprising one or more P—CDPs or one or more P—CDl’nsuhstrate complexes of the present disclosure. The filtration medium can be used as a gas mask filter. in an embodiment, the article is a gas mash comprising the filtration medium. In some embodiments, the article is an extraction device. {99139} In another embodiment, the article is a solid phase microphase (Si’lvfl'i) tion device comprising one or more PUCDPs or one or more P—CDl’nsubstrate complexes of the t sure, where the P—CDPs or PmCDPeubstrate complexes is the extracting phase the device } ln another embodiment, the article is a device for a solidmphase extraction of polar and semi,~polar organic molecules. The device comprises one or more P~CDPs or one or more P- CDP~suhstrate complexes of the present disclosure instead oflllB media (hydrophilic/lipophilic balanced). The article with the one or more P—CDPs or one or more P~CDP~suhstrate complexes outperforms the Hill media. ll} ln another embodiment, the article is a device for liquid filtration of polar and semi— polar organic molecules. The. device comprises one or more RCDPS or one or more Fvlelll substrate complexes of the iresertt disclosure adhered within a fibrous web (as disclosed in US.

Patent No. 7,655,l l 2., which is hereby incorporated by reference in its entirety). Other embodiments include the device comprising P-CDP powders fused via thermoplastic hinder WO 68104 polymer to create porous monolithic filtration media (as disclosed in US Patent No. 4,753,728, which is hereby orated by reference in its entirety). {98142} The P—CDP als of the present disclosure, in the various forms and form factors disclosed herein ding supported and unsupported P—CDP materials) can be used in any application in which it is desirable to separate compounds (eg anionic or cationic MPs) from a fluid l:gases such as air, liquids such as water, aqueous beverages, biological fluids, etc). The l)— CDP materials can be used to "trap" or adsorb desired species for further analysis or quantification (eg, in analytical testing for environmental pollutants in air or water), to separate mixtures (eg, in a chromatographic separation), or to isolate desirable or valuable species which are present as a dilute form in a fluid. in some embodiments, the P—CDP materials of the present disclosure can be used to purify a fluid (eg, by removing rable or noxious impurities), or can be used to isolate desirable compounds from a mixture or dilute fluid solution. ltltllclizll ln some embodiments, the present disclosure provides a method of removing one or more nds (eg. anionic MPs) from a fluid sample or determining the ce or absence of one or more compounds in a fluid sample sing: a) contacting the sample with the porous polymeric material of the present disclosure or the supported porous polymeric material of the present disclosure for an incubation ; b) separating the porous polymeric material or supported porous polymeric material after the incubation period from the sample; and c) heating the porous polymeric material or supported porous polymeric material separated in step b), or contacting the porous ric al or supported porous polymeric material separated in step b) with a solvent, thereby releasing at least a portion of the compounds from the porous polymeric material or supported porous polymeric material; and dl) optionally isolating at. least a portion of the compounds released in step c), or d2) determining the ce or absence of the nds released in step c), wherein the presence of one or more compounds ates to the presence of the one or more compounds in the sample, in some embodiments, the one or more cyclodextrin moieties are li—cyclodextrin moieties, in some embodiments, said ining is carried out by gas chromatography, liquid chrornatography, supercritical fluid tography, or mass spectrometry. in some embodiments, said contacting is by flowing the aqueous phase across, over, around, or through the supported porous polymeric material. in some embodiments, the s sample is contacted with the l’uCDPusubstrate complex under static conditions for an incubation period and after the incubation period the aqueous sample is separated from the porous polymeric al. In some embodiments, the sample is a food and the compounds are le organic compounds. In some embodiments, the aqueous sample is drinlring water, wastewater, ground water, s extracts from contaminated soils, or landfill leachates. In some ments, the sample is a perfume or fragrance and the nds are volatile organic compounds. In some embodiments, the compounds are anionic micropollutants, heavy , and/or dyes. In some embodiments, the compounds are anionic MPs, such as PFASs (eg. polyfluorinated alhyl compounds and/or perfluorinated allryl compounds). ln some embodiments, the PEASs are PFOA and/or l’FOS. 339144} In an embodiment, a method of purifying an aqueous sample comprising one or more organic compounds is provided, the method comprising contacting the aqueous sample with the porous polymeric material of the present disclosure or the supported porous polymeric material of the present disclosure such that, for example, at least St‘i‘Z/o to at least 99% of the one or more pollutants is bound to one or more of the cyclodextrin (cg, ficyclodextrin) moieties of the porous polymeric material. For example, the aqueous sample is flowed across, around, or through the porous polymeric material. in another example, the aqueous sample contacted with the porous polymeric material or the supported porous polymeric material under static conditions for an incubation period and after the incubation period the aqueous sample is separated (e. g, by tion) from the porous polymeric material. The method can be used to purify aqueous samples such as drinking water, wastewatei', ground water, aqueous extracts from contaminated soils, and landfill leachates, In some embodiments, the organic compounds are anionic lVlPs, such as PFASs.

{MIME} In an embodiment, a method of determining the presence or e of compounds (eg, anionic MPs) in a sample comprises: a) contacting the sample with the porous polymeric material of the present disclosure or the supported porous polymeric material of the t disclosure for an incubation period (eg, l minute or less, 5 minutes or less, or l0 minutes or less); b) isolating the complex from a) from the sample; and c) heating the complex material from b) or contacting the complex from b) with a solvent (eg, methanol) such that at least part of the compounds are then released by the porous material; and d) determining the presence or e of any nds, n the presence of one or more compounds correlates to the presence of the one or more compounds in the sample, or isolating (e.g by tion) the nds. For example, the determining (eg, analysis) is carried out by gas chromatography or mass spectrometry. For example, the sample is a food or beverage (eg, mill<, wine, fruitjuice {e.g., orange juice, appleiuice, and grapeiuice), or an alcoholic beverage (eg, beer and spirits)) and the nds are volatile organic compounds. The porous polymeric material or supported porous polymeric material can be the extracting phase in a solid phase microextraction {SPF/1E) device. In some embodiments, the organic compounds are anionic lit/3’s, such as PFASs. } in an embodiment, a method for removing compounds (eg, c compounds) from a sample comprises: a) contacting the sample with the porous polymeric material of the present disclosure or the supported porous polymeric material of the present disclosure for an incubation period such that at least some of the compounds are tered in the polymer; b) isolating complex from a) from the ; c) heating the complex from b) or contacting the complex from b) with a solvent (cg, methanol) such that at least part of the compounds are released by the porous polymeric material; and d) optionally, isolating at least a portion of the nds. ln some embodiments, the compounds are anionic N 3‘s, such as l’FASs. {99147} Ayariety of compounds can be involved (cg, sequestered, detected, and/or isolated) in the s. The compounds can he organic nds. The compounds can be ble compounds such as tlayorants leg, compounds that impact the palatability of foods) or ceutical compounds (or pharmaceutical intermediates), contaminants leg, PCBs, PBAs, etc), and/or adulterants In some embodiments, the compounds are anionic lit/[P5, such as PPASs. ln some embodiments, the compounds are anionic MPs selected from the group consisting of brozil, zone, diolotenac, ioxynil, ketoprot‘en, naproxen, sulfamethoxazole, warfarm, 2,4—dichlorophenoxyacetic acid, clol’ibric acid, fen, 2—methyl—4—chlorophenoxyacetic acid, mecoprop, yalsartan, perthrorobutanoic acid, perlluorobutane sult‘onic acid, pertluoropentanoic acid, perlluoropentane sulfonic acid, peril uorohexanoic acid, pertluorohexane sulfonic acid, peril uoroheptanoic acid, peril uoroheptane sult‘onic acid, pertluorooctanoic acid, peril uorooctane sull’onic acid, perl'luorononanoic acid, pertluorononane sulfonic acid, perthrorodecanoic acid, periluorodecane sulfonic acid, periluoroundecanoic acid, periluorododecanoic acid, perlluorotridecanoic acid, perl'luorotetradecanoic acid, 2,3,3,3—tetrailuoro—Z— tluoropropoxy) propanoate, and combinations thereof. {@8148} The cyclodextrins are chiral. in an embodiment, a chiral compound is sequestered, detected, and/or isolated. in an embodiment, a chiral column (eg, a preparative—scale or analytical—scale column is packed with a chiral porous ric material or composition comprising chiral porous polymeric material) is used to te and detect or isolate (or at least significantly enrich the sample in one enantiomer} a single enantiomer of a compound.

{B9149} ln the methods, the porous polymeric material or the supported porous polymeric material can be regenerated {e.g., for reuse in the methods). For, example, the porous polymeric material is regenerated by heating and/or exposure to solvent (e.g ls such as methanol or ethanol, and aqueous es thereof). {@9159} The following examples are provided to illustrate the present disclosure, and should not be construed as limiting thereof.

Example 1: sis ot‘fi—CDETDl polymer } Reagents: 841D: Wacker, Cavarnax W7 (Used as~is); Tolylene—2,4_cliisocyanate ('l'Dl): Sigma Aldrich, 95%, Product # T398533; N,l\l"Dimethylformamide (EMF): Fisher Chemical, Certified ACS grade, Catalogti Dllguél; Water; Deionized (Dl) water from Milli—Q system {@9152} Procedure: fi—CD (60.0 g, 0.0529 rnol, l erg.) was ved in l20 mL EMF in a 500 mL oneuneck round n flask at a magnetic stir rate of 400 rpm and the temperature was set to 80 "C. An oil bath equipped with thermocouple was used for g. After completely dissolving B—CD, 'l'Dl (36.8 g, 0.21l5 mol, 4 eq.) was added subsequently to the flask at 80 0C.

Air bubbles were observed likely due to the presence of water in the on medium. After about 1 min when there was no bubble produced, the flask was capped with a rubber septum.

After 3 h, the reaction was stopped by adding 30 mL of methanol and turning off the heating.

The resulting viscous clear solution was precipitated into 1.2 L methanol to obtain white powder product. After l h stirring, the crude product was filtered under vacuum using a Buchn er funnel.

The filtered polymer powder was transferred back to a 2~L beaker and washed again with 1.5 L DI water \ 2 times and l2 L methanol X 1 time During each cycle the g time was l h.

After final filtration, wet solid product was transferred to an evaporating dish, which was placed into a vacuum oven at 80 °C to yield 726 g dry polymer, lt was observed that starting at a 6 equivalence of Till and above, a hard gel is obtained which is ult to work up. In contrast, TELCD ratios in the range of 2: l—S: 1 provide a powder material upon stopping the reaction with methanoi (Table 1}. These polymers are aiso soiuhie in a variety soiyents such as DIVE but not in water. See Fig. 5 for a r comparison of the polymers of Table 1.

Table 1: Synthesis of DE poiynieis Materiai i Soivent "1" 9(3) Time Yieid Notes SL-E—GGtA 1:4 Anhydrous DMF 80 15 h 58% White powder* ESL-20828 1:fi Anhydrous DMF 80 15 h We Get O()2C 1:8 Anhydrous DMF 80 ’15 31 111a Gei ESL—2002B 1:1(3 Anhydrous DMF 80 16 h We Gei SL—2-004A 1:2 Anhydrous DMF 80 3 h 36% White powder SL—2~004B 1:3 Anhydrous DMF 50 3 h 55% White powder SL004C 1:4 Anhydrous DMF so 3 h 61% White powder SL~2~604D 1:5 Anhydrous one so 3 h 72% White powder SL004E 1:6 Anhydrous DMF 80 3 h We Get *Washed with methanoix1,water x 2, and methanoix1. {(38153} fi~CD—TDI thnnizntion Studies {@9154} The fi~CD—TDI poiymer was thither optimized by checking the soiubihty of BSD (es~is and dried) in reguiar and anhydrous DMF, the i'esuits of which are shown in Table 2. As—is B~CD has a water t in the range of 12— i 4% water.

Table 2: Soivents and iii-CD water coi'itent comparison in the synthesis of DI polymers Solubility test Register DMF Anhydrous EMF Asais £34312) 0.5 giant. 0.5 giant.

Bried sen 0.25 g/mL 0.22 g/mL {99135; As shown in Table 2,, the soiuhiiity of B—CD is icantly affected based on its water content. Consequently, when dried, {LCD is used, the eiizntion can only he carried, out iowei initial concentrations that impact reaction yields. In comparison, the water content of DIVE? is insignificant and therefore has iess impact on the soluhihtyt prompting us to use regular DIX/ll: in the reaction. A comparison of ButiDuTDl polymers made via small and large scale hatches is shown below in Tahle 3.

Table 3: A comparison of {B—(IDJl‘Dl polyrners rnaole via small and large scale batches Material antigen (anhydrous) {Till} (mollL) T ("Cl Time Yield volume SL~1~010A 1:47 4 mL 176 80 3 h 7§% SL—2—003 1:4? 120 ml. 1.78 80 3 h 82% Water t of B—CD used: 111% {99156} lt was previously tood that the use of dried til—CD and anhydrous solvents was critical for nialong polyurethane~type Cl) polymers; however, as described herein, using c‘wet" solvents (also referred to as "regular" solvents) such as EMF and/or as~is Ell—CD, the resulting polymer is structurally different than the polymers described in the literature and are much more effective for PFAS tration, It was surprisingly discovered that using wet/regular ts resulted in partial anate reduction, shown below in Scheme l for TDli Scheme l: Effects of water on isocyanate groups of "fill {(38157} The presence of amine groups into the polymerization reaction is believed to result in the formation of urea linkages in addition to the urethane linkages which result from the crosslinlring of {hill} and TDl under anl'iydrous conditions (eg‘ completely anhydrous conditions). Additionally, the presence offree arnines in the B—CD-TDl polymer are believed to contribute to PFAS removal. The high amine and urea content provides a polyn'ier that is urally ent from the prior art and which is more advantageous for the rernoval of anionic niicropollutants (cg. PEAS). {$19158} Elemental is data shows that final CD:TDl ratio is l:8~l :lO when a feed ratio of lt4 is used, which suggests the presence of excess 'l‘Dl units on cyclodextrins. Additionally, 1H NMR spectroscopy shows the presence of~-—Cl-l3 s resulting from the arnine functionalized phenyl unit (Fig. 3}. Amine groups can be quantified using the 3 peak at ~l.9 ppm that originates from a ‘TDl unit with amine groups on it. The ratio of that integration to total integration of -—-—Cl-l3 pealrs provide the percentage of TDls with amines. Since absolute ‘T‘Dl density can be calculated from the elemental analysis data, the concentration (mmol/g) of amine groups in the polymers can be calculated by correlating Nl‘le and EA data. See Table 4. The 33- CDnTDl polymer additionally tested positive in the chloranil test, r confirming the amine presence.

Table 4: Determination of amine content of meDnTDl polymers made with regular Eli/ll: NEVER integration {based on one pnCD unit} tal Analysis CD:TDl TDHED TDEKBD Sample Cflgttotal) CHglamlne) Amine (0/6; {TDQmmot/‘g {Aminegmmol/g feed ratio ratio ratio SL—1-O‘i0A 114.7 0.15 SL—QnOD'IA 1:4 0.17 Sl_.—2u003 1:4.7 0.16 SL004A 1:2 0.34 SL004B 1:3 0.22 SLmZ-OMC 1.4 3.21 SL—2n004D 1:5 0.16 {88159} The amine—containing SEE—ml polymers were further tested against a panel of l2 PFASs (fig. l} as well as against the binary mixture ot‘l’EOA and PEOS (Fig. 2). The polymer made with 4 eq. oi" TDT (:SL— l —0l 0A) showed 70% removal of PFQA and excellent removal of PFOS (96%} in only 30 min and reached nearly 90% PFQA and l00% PFOS l over 48 h in the panel study. A similar removal performance was also observed when tested for the binary mixture of PFOA and PFOS.

Example 2: Synthesis and PEAS removal activity of fi—Cflmlsocyanate polymers litltlltitl} Following the general ure outlined in example l, isocyanate polymers obtained from 4,4’uMDl were sized and tested for their ability to remove l’FASs. {99161} The polymers of Table 5 were tested for their ability to remove PFASs. All experiments were conducted with l000 ng/L of each of l2 s and l0 mg/L of adsorbent. Control experiments were performed with no adsorbent. These experiments were conducted in triplicate.

Samples were taken at the following times: 0 h, 0.5 h, 9 h, and 48 h. Fig. l shows the results at 0.5 and 48 h, with rs made from 4,4’—MDl and 2,4~‘T‘Dl being particularly effective at PFAS sequestration. Although faster removal lrinetics was observed in the 'l‘Dl polymer (SLul _ 010A), the MDl polymer (SL_0420~3) also had good removal performance over the course of 48 h. Polyrners obtained from 6 eq. of Hill and MDl did not exhibit good removal of either PFOA or PFOS, most lilrely due to the formation of hard gel during their synthesis which renders binding sites inaccessible in the particle.

Table 5: {luCD polymers made with ent isocyanates Polymer inker Cfizisocyanate ratio Sleeved from scrum DA 2,4x-TDl 1:4 230 mesh SL-l -O1OA 2,4--TD! 1:6 80 mesh SLnlnMQO-S 4,4'—l\/lDl 1:4 230 mesh 514—04204 4,4’—MD! 1:6 8-3 mesh Example 3i: Synthesis and PEAS removal activity of choline chloridewmodified fiwCD~TFN polymer l} In this example, positive charges were added onto CD polymers in order to enhance the binding affinity for anionic PFASs Without being hound hy any particular theory it is believed that the presence of phenol groups produced in a side reaction during polymerization results in c charge on the polymer and diminishes the PFOA and PFOS uptake of polymers. This effect was experimentally ohserved in another polymer formulation? P, which demonstrates good removal performance against a hroad range of micropollutants except negatively d ones including PFASs. 'l‘FNuCDP can he produced in vely large scales using tetrafluoroterephthalonitrile (TFN) as the crosslinker Therefore, it was desired to modify the adsorption ties for PFASs by incorporation of positive charges on the polymer backbone. in this example, choline chloride------a quaternary ammonium salt with a hydroxyl group------was chosen as an additive to the polymerization reaction of TEN—(EDP. Choline de can react with TFN just like fi—CD and thus is orated into the polymer, which hereafter will be denoted as TEN—CDPi- (Scheme 2).

Scheme 2: Synthetic overview for e chloride—modified l3—CD—l‘FN polymers H:33""‘((‘ H‘s l l C" -.‘- ,v\~ wmnh< yflguluul F‘ )\ F Hi}f\\fl§;§\ LEE CNS + I \' WW HO : K2593 ‘ F" "\F i7 {3N HzO/DWESO E 60 "C 34:33 TFN Table 6: Synthetic ions and, yields for 'l'li‘NnCDP+ polymers \: followln :—' -:. _ ms. {EPA}.) 2 23 ppm, {Polymerl 1 rng/inL Contact time ‘9 min MO uptake measured under igr’mL. Co time '4 "i h.

Table m/: Porosity comparison for TEN—(I‘D??- polymers Sample Choline Chloride (sq) Surface area (me/g) NEE-$036 3 574 MB-‘t -037 6 19 Table 8: Elemental analysis for ’l7FN~CDP-t-- polymers if; ? Cl Feed equivalents Ratios Sample fi—CD TFN CC C:N N:F N5CE PC: (31:! (mmollg) (mmoiig; tmmolig) M 8-1 —036 7.45 2.23 71.51 3.38 55.98 MEI-M —C-37 71.19 2.73 5.07 1.86 36.44 {W163} Prior to measuring PFAS removal, a comparison of EPA (a neutral molecule) and methyl orange (Mt), a negatively charged dye molecule) uptakes ofTFN-CDP and TFN~CDP-+— was performed. W'liile EPA uptake was not affected, M0 uptake was icantly improved, from ~30% for TFN-CDP to >99% for TFN—CDP-lz As expected, TFN~CDP1~ rs demonstrated significantly less all’imty towards positively charged molecules such as liyleiie blue compared to TFN-CDP (Table 9; Fig. 7). Encouraged by this preliminary data, TFN—CDP—i- was tested for the removal of PFGA and PFGS at environmentally nt concentrations.

Table 9: MI? removal efficiencies of choline chloride ed and unmodified TFN-CDP Sample BRA Methyl Orange Methylene Blue pliant—036 74% 99% 34% M84 ~03? 57% 99% 10% TFN—CDP 80% 30% 160% {sales} Although further experiments are needed to fully characterize the adsorption mechanism, this approach allows one to (l) take advantage of dual binding mechanism (inclusion complex with B—CD and ionic interactions) at the same time in a single material and/or {2) enhance the binding affinity of the inclusion complex through the presence of positive charges in the ty of CD es. Furthermore, TFN—CDP-r is still synthesized in one step and the amount of positive charges incorporated can be easily modified by changing the amount of e chloride used in the reaction. {(130165} Experimental: 1}ij (l g, 0.88l , TEN (l .06 g, 5.286 , lizCGs (2.44 g, l7.62l mniol), choline chloride (0.37 g, 2.643 mmol), and 5.4 mL HzO/DMSO (2:3, v/v') were added to a 20—mL scintillation vial equipped with a magnetic stir bar. The mixture was stirred at 60 °C for 2f: h. Additional solvent (1 mL) was added after the first hour of stirring. After 20 h, 10 mL of water was added and stirred to disperse the polymer for 30 min. After filtering, the crude product was transferred to a centrifuge tube. The sample was washed with hot methanol ("\rllOmL) three times (3 0 min for each cycle). After decanting methanol, Dl water (~30 mL) was added. 1 M HCl was added dropwise while stirring the sample until the pH was stable between 3—4. The crude product was further washed two more times with hot methanol ). The final methanol wash was filtered under vacuum and product was dried at 80 "C overnight. {anion} Testing PFOA and PFOS removal performance — PFAS adsorption experiments were performed to measure the removal performance of ent TFN—CDP+ rs. In an effort to facilitate the ing process for a large number of polymer formulations, tion kinetics were performed using a mixture of l2 PFASs in nanopure water. The understanding of adsorption kinetics is essential as it reveals ation on adsorbent doses and required contact times that are relevant for treatment processes. in addition to providing insights into PFOA and PFOS uptake, this panel study also allowed assessment of performance against other PFASs such as GenX and short- and long~chain PFASs in order to determine broadspectrum PFAS removal capabilities of these polymers. The results ized in Fig. l show the l percentages for each PFAS at 30 mm and 48 h contact times. These experiments were conducted in triplicate with ~l pph of each of the 12 PFASS in nanopure water at a polymer loading of l0 mg/L.

Control experiments were also performed with no adsorbent and reported removal percentages are corrected for any losses observed during the control experiments. All polymers were sieved with 230 mesh. {(130167} lmpressively, the two derivatives of TFN—CDP-l- (namely, 1343443363 and MBul ~037 made from 3 and 6, eq. of choline chloride. respectively) demonstrated the best removal performance of all polymers tested, with near complete removal of all l’FASs in the panel. Over min, MB—l—Q37 displayed effective removal of GenX and chain l’FASs, in addition to PFOA and PFOS. presumahly due to its higher quaternary ammonium g (Fig. 2 9 {till 163} After performing initial screening under the panel study, removal assessments were ed to select polymers using a binary mixture of PFOA and PFOS le 10). ln this specific task, all adsorption experiments were conducted with 0.5 pph of PFOA and l pph of PFOS at a polymer loading of lt‘i mg/L. Control experiments were med with no adsorbent and all measurements were done in triplicate. Samples from each solution were taken for is at predetermined time points: 0, 0.5g 2., 4., 8, and 24 h. Polymers selected for these measurements were SL—l—Gl 0A, (TDD, Mild—036 (TFN+CC), and hClB—l —03’7 (TFN+CC). All the polymers tested demonstrated great removal of PFQS over 24 he but SL—l—Ol 0A (Till) and two PWL derivatives displayed high removal (>90%) in only '30 min. As for removal of PFOA, even though Mid—01014 (TDT) showed similar performance to the panel study; l‘vle—l —036 and M84 ~03? formed the other two polymers in terms of both cs and removal capacity over 24 h.

Table l0: Removal data of selected polymers for PFOA (0.5 pph) and PFOS ( l pph) mixture. stud-9199. 2,4-TD! 59% 79% 91% 94% 95% M94 -999 TFN+co 93% 99% 99% 99% 99% MB—t "99? Tern-cc 99% 99% 99% 99% 99% 9A 2,4—TD3 99% 99% 9?% 99% 99% MB—t "999 Tern-cc 99% 97% 99% 99% 99% M94 -99? TFN+co 95% 99% 99% 99% 99% {98169} Micropollutant tion Studies {(130179} $421) is known to form a stable inclusion x with rnicropollutants. EPA and MO were chosen as model compounds to study the uptake of neutral and negatively d micropollutants, respectively, for understanding the adsorption mechanism in choline chloride— modified 'l‘lFNuCDP polyniers. Furthermore, fitting the mi cropollutant adsorption data as a function of concentration to a Langmuir model (Equations l and 2) enables the determination of the thermodynamic parameters of the als tested.

{M13171} 'l'he singleusite Langmuir model that considers homogeneous adsorption surface, is given as qmax ., KL ., Ce 0' ... ‘8 1 + KL . Ce (Equation 1) where qe (mg/Cg) is the amount of MP adsorbed per gram of adsorbent at equilibrium, qmax (mg/g) is the maximum adsorption capacity of adsorbent at saturation, KL (L/mg) is the equilibrium constant and C3 (mg/L or ppm) is the concentration at equilibrium. The dualusite Langmuir model that takes the two ct adsorption sites into account, is given as gmaXJ ‘ K143 ° Co qmaxz ’ K52 ' Ce qe + 1 ’l' Km ‘ Ce 1 + Km " Ce (Equation 2) where qe (mg/g) is the amount ofMP adsorbed per gram of adsorbent at equilibrium, :3."wa and Qmaxo (mg/g) are maximum adsorption capacities of adsorbent for each site at saturation, K[4,1 and Km (L/rng) are equilibrium constants and are {mg/L or ppm) is the concentration at equilibrium. By g the experimental tion data using nonlinear regression, quad and KL parameters can he obtained. Single~site Langmuir model was ined to he suitable for fitting the EPA adsorption data, whereas MO adsorption data were best fitted using the dual~site model. {(130172} For choline chloride—modified ’lFNmCDl’ polymers, rnaximurn M0 capacities (9mm) of 46.6 and 78.8 mg/g were found for polymers made with l5 and 3.0 equivalents of e chloride, respectively, for the first adsorption site (Table l I, Fig. 8). The second tion site (aiming) displayed rnaximurn e capacities of 37.3 and 33.0 nig/g, both of which are quite WO 68104 similar to the maximum capacity of unmodified TFNuCDP (grim 37.6 mg/g). This data, as well as similarities hetween K1; and K12 values, suggests that the second adsorption site in choline chlorideuniodilied TEN—CD? polymers is associated with MG adsorption within the CD cavity.

The comparison between K1.,1 and K112 values also indicates a significantly er first adsorption site which likely originates from the ction of c MO molecules with quaternary ammonium sites. BPA adsorption data were fitted using a singlemsite Langmuir model and similar K1 values were determined, for all three polymers, indicating the presence of similar adsorption site for a l molecule. Maximum EPA capacities of llZl and, l00.l nig/g were found for the two choline chlorideunodified CDP polymers and a capacity of l06.l mg/g was determined for the unmodified NnCDl’ (Table ll; Fig. 9). Notably, these saturation uptake values are in good agreement with the density of CD sites in these polymers. This observation also suggests that EPA adsorption occurs within the cavity of CDs.

Table l l: Langmuir fitting parameters for EPA and MO tion ECDl EN‘I Gale. rima for Sale. qnnx for Calotmal Sampie MP qmw Km om: Km a? (mmmrsl. lmmellgl. [CDllmaisl [Mime/s)+ qmaxlms/al MB051 (15 en CC) M0 46.6 27.9 37.3 0.37 0.0828 0 48 0.15 157 49 206 [Via-1036 (3 en CC}, MO 78.8 54.4 33.0 0.19 0.9970 0.37 0,63 121 205 327’ ., [CD] (talc. qmax for Cale. total Qmax KL R" lmmnllsl, {Wilma-'91. . 11W (mo/st TFN-CDF‘ MO 37.6 0.02 0.9828 0.51 167’ 107 M84051 (1.5 on GO) EPA 112.1 0.10 0.9711 0.48 109 109 M81036 (3 eq (:0) EPA 100.5 0.09 0.9651 0.37 84 84 TFN-CDP BF’A 106.1 0.14 0.9714 0.51 118 116 Example 4: Synthesis and PEAS removal activity of choline chloride—modified fimCD—Tlll polymer {00173} finCl) (2 g, 1.76 rnmol, l eq.) was dissolved, in 5 mL l? in a 20 mL llation vial equipped with a magnetic stir bar at a stir rate of 400 rpm and a temperature of 80 "C. 4 g Choline chloride was dissolved, in 110 mL DMSO at 80 °C to achieve a concentration of 0.4 g/inL.

A variety of stoichiornetric ratios of choline chloride solution ((03075 ntL, 0.1230 g, 0.5 eat), (0.6l50 , 0.2460 g, l, on), (09225 niL, 0.369 g, 1.5 eq.) or (1.2300 nil..., 0.492 g, 2 eq.)) was added to the B—Cl) solution at 80 °C, After mixing for 5 min at 80 0C, toluene diisocyanate (2.94— 'lBl, l.84l7 g, l057 mmol, 6 ed.) was added suhsequently. Air bubbling was observed after the diisocyanate on, presumably due to the moisture in the reaction system. After about l min when huhhling suhsided, the vial was . After 3 h, the reaction was stopped by adding l0 rnL of methanol and turning off the heating. White powder product precipitated out after methanol addition. The mixture was transferred to a 50 ml; polypropylene centrifuge tube. After fuging, the solvent was decanted and the crude product was washed with water (4t) mL X 2 times), and methanol (40 ml; X 2 times). ln each wash cycle, the mixture was stirred for 30 min and followed by centrifuge. In the final cycle, the product in methanol was filtered under vacuum and dried at 80 °C overnight. Fig. l0 shows a 1ll NMR spectrum of a choline chloridenmodified B—CD—TDI polymer made with l:6:l molar equivalents of B—Cl):'l'l)l:choline chloride in 5 mL of DMF at 80 0C for 3 hours. The ance of urethane and urea groups at 775—96 ppm indicates successful incorporation of choline chloride into the polymer. The following chemical shifts are also found in thelH l‘leR spectrum: 6.75—7.75 ppm (protons from the aromatic ring in TDD; 556 pm (protons from ~OH groups that are attached to C2 and C3 in SSE); 4,8 -5 ppm ns that are ed to Cl in 5431)); 4.25—4.75 ppm (protons from ~08 groups that are attached to err in BmCD); All ppm (protons from —O~CH2— groups in choline chloride); 3.5—4 ppm (protons that are attached to CZ~C6 in B~CD); 3.3—3.5 ppm (protons from ; 3.18.2 ppm (protons from €83 groups in choline chloride); 2.5 ppm (DMSO); l.9~2.l ppm (protons from — CH3 groups in TDl); Peaks noted with star are from residual solvent. Fig. ll shows a comparison of a choline chloride—modified B-CD—TDE polymer and a DI polymer, with the key difference being the broad peak centered around 3, l3 ppm. Sharp pealrs at all ppm and 3.l ~32 ppm originates from unreacted choline chloride. Fig. 12 shows a comparison between three choline cl'iloride-modit‘ied BwCD-TDI polymers with different choline chloride loading amounts, which supports the position that with increasing amount of e chloride, the pealr intensity ses at 3. l 3 ppm. {98174} in accordance with the synthetic procedure outlined above, a y of rs were made with varying stoichiometric equivalents as shown below in Table l2. Furthermore, the polymers were tested for their PFOA uptalre. The results show that by orating choline chloride into a ButiD—E‘Dl polymer, cationic charge can he added to the polymer in a controlled fashion, resulting in PFQA uptake increasing from 70% to 99% when compared to Shul u0l 0A polymer ('lahle l2). See also Fig. l3.

Tabie 12: Synthesis of ehoiine ehiorideuniedified uTDi polymers . fi—CDfithc PFDA Meterinfl Seivent Ti013) Time YBEM. Notes ratio " SL—Z-DO4E 1:61) DMF 80 3 h n/a We Get SL—2-005A 1.6.0.5. , a DMF 50 3 h n/a ma ESL—$0053 1:621 DMF 80 3 h 73% 98% SL—Z—GOfiC i:6:t.5 DMF 80 3 h 73% 99% ESL—243050 1:652 DMF 80 3 h 60% 99% *500 not PFOAHOGG pot PFOS, 10 mg/L r loading at 05 h.

EQUIVALENTS {WWSE While the present invention has been described in coniunetien with the specific enibediinents set forth above, niany alternatives modifications and other variations thereef will be apparent to these of Ordinary skiii in the art. Ail such aiternatives, inedifications and variations are ed to faii within the spirit and scope 0f the present invention References (:1) Richardson, S. 11.; Ferries, '1‘. A. Anal. Chem. 21118, 90, 398—428. 1:2) Carpenter, C. M. G; Hel‘oling, D. E Environ. Sci. o]. 21118, 52, 196. 1:3) Barry, V. Winquist, A. Steenlend, 14;. Environ. Health Pcrspcci. 2111.3, 121, 1313—1318. 1:4) (13110, V; Leonardi, G; Geiiser, B, Lopez—Espinose, MAJ; e, S. 1.; Karlsson, L; Diicatnian, A M.; F1etcher, '1". Enir-‘iron. Health Pei/aspect. 21112, 1211, 655—660. (51 Meizer, 113.; Rice, N; Dep1edge, M. 151.; Henley, W. E; Galloway, '1‘. S. emu-on. Health Perispeci. 211111, 118, 686—692.

De‘Witt, 1. C. Dietert, R. R, Ed; Mo1ecu1ar and1ntegratiye logy; Springer International Publishing: Chem, 2015.

DiainaritimKandarakis, F.; Bourguignon, 1:11; Giuclice, L. C; Hauser, 11.;1’1'ins, G. S; Soto, A. M.; Zoeller, R. T, Gore, A C. Endocr. Rev. 211119, 30, 293—342.

Vajda, A M.; Berber, L. 11.; Gray, .1. L.; Lopez, 13‘. M.; Woodling, .1. 11.; Norris, D. O.

Environ. Sci. Technol. , 42, 3497—3414. "fetteault, G. R; Bennett, C. 1.; Shires, K; Knight, 13.; Servos, M. R; McMaster, M. E.

Aqua; onicoi. 21111, [04, 278—290.

Gegné, F.; Bouchard; 13.; Andre; C; Farcy, F... Fournier; M. Comp. m. Physiol. — C Toxicol. col. 21111, 153; 99—106.

Alsbaiee, A; Smith, 11. 1.; Xian, L; Ling, Y; Helbhng, D. F; Dichtel, 1V. R. Nature 21116, 529, 1911—1911.

AlzatemSaanhez, 1). M.; Smith, 11. 1.; Alsbaiee; A. Hinestroza, 1. F.; Dichtel; W. R. Chem.

M'tiicr. 21116, 28, 8340—83416.

Ling, Y; Klenies, M. 1.; Kim, 1...; Alsbaiee, A; Dichtel, W. R; ng, D. F Environ.

Sci. chnnoi. 21117, 5], 7590—7598.

Xian, L.; Ling; Y; ee, A; Li; C; Helbling, F). F..; Dichte}; ‘W. R. J. Am. Chem. Soc. 2017, 1:19, 7689—7692. 1i, W; Xiao, L.; Ling, Y; Ching, C; Matsumotc; M; Bisbcy; R. F.; Heibiing, D. F, Dichtel; W. R. J. Am. Chem. Soc. 21118; 141), 12677—12681.

Klemes, M. 1.; Ling; Y; Chiapesco, M; Alshaice, A; Helbiing, D. F..; Dichtei; W. R- Chem. Sci. 21118; 9, 8883—8889.

Li, C; Klemes; M. 1.; Dich‘tei, W. R; 11e1bhng, D. F. J. Chroniaiogr. A 21118, 154']; 52— D’Agostino; L. A; Mahiiry; S. A. Environ. Sci. Techno]. 21117, 51, 13603—13613.

Barzernfianson; K. A; Roberts, S C; Choyke, S; Oetjen; K; McAlces; A; Riddell; N; McCrindle, R; Ferguson, F. L; Higgins, C. 13.; Field, 1. A. Environ. Sci. chnnoi. 21117, 51, 2047—2057.

Breysse, P. N. U.S Dcparicmcni ofHealin andHuman Services." Agencyjor beic Substances and Disease Registry: libxicologicai profiiejor roailqvis. 2018.

Hu, X. C; Andrews, 11. Q; Lindstrorii, A 8.; Britten, '1‘. A; Schaider, L. A; Grandiean, 13.; riii, R; Cerigrian, C. C, Blurn, A; Balan, S. A; et al. Environ. Sci. Technol.

Len. 21116, 5’, 344--—~350.

Kannen, K; Corsoiini, S; Felaiidysz, 1.; enn, G; r, 14;. S; Loganaihari, B. (1;; Mohd, M. A; Olivero, 1.; Van Wouwe, N, Yang, 1. 1-1.; et a}. Environ. Sci. Techno]. 211114, 38, 4489—4495.

Sun, M.; Areva1o, E; Strynar, M.; roni, A; Richardson, 1%.; Kearns, B; Pickett, A; Smith, C; , D. R. U. n. Sci. l. Leif. 21116, 3, 415—419. <24) zier, C; Beerendmk, E, ScholteuVemendaai, P; DEE Voogt, P. Envimn, Sci.

Technai. 2912, 46, 1708"} '7} 5. <25) Kim, L, (Thing, C; Ling, Y; Nasiri, M; Klames, M. 1.; Reineke, T. M; Heibhng, D. E; Dichtei, W. R. (Submitted i0 Chem. Ali/farm". December 2018) ZGEQ, 1~-—9. (26:: Mason, C. R; Maynard—Adam, L; 1-ieard, K. W. 3.; Satflmis, 8., Budd, P. Ms, Friess, K; Land, 1%.; do, B, Clarizia, G; Jansen, I. C. Afacmmaiecuies 2614, 4 7, 1921—1029. (27> Vojkovsk, T. Pept. Res, 1993, 8, 236—237. <28) Mafik, 3.; Song, A; Lam, K. S. I’éiraizedmn Left. 2993, 44, 4319—432(). (29) Buckley, 1).; Henbegt, H. B; Slade, P. J; Chem, SOC, 1957, 4891, 4891. 6 (J1

Claims (17)

CLAIMS :

1. A porous ric material comprising a plurality of cyclodextrins crosslinked with a plurality of aryl diisocyanate crosslinkers, wherein one or more of the plurality of cyclodextrins are bound to a linker of formula (I): wherein A is an aryl moiety; each R1 is independently selected from the group consisting of H, C1-C6 alkyl, C1-C3 haloalkyl, aryl, heteroaryl, -CF3, -SO3H, –CN, -NO2, -NH2, -NCO, -C(O)2R3, -C(O)N(R3)2, and – halogen; each R2 is independently H, -OH, al cation, alkyl, aryl, heteroaryl, -SH, –S-metal cation, –S-alkyl, H, or -C(O)NH2; each R3 is ndently –H, –C1-C6 alkyl, –C1-C3 haloalkyl, –aryl, −C(O)N(Ra)(Rb), −C(O)Rc, −CO2Rc, −SO2N(Ra)(Rb), or −SORc, and each Ra and Rb is independently H, or C1-C6 alkyl; each W is independently a bond, an alkylene group, an arylene group, a heteroarylene group, -O-arylene-, -(CH2)a-arylene-, rylene-, -NH-arylene-, -S-arylene-, -O- heteroarylene-, -(CH2)a-heteroarylene-, -SO2-heteraoarylene-, -NH-heteroarylene-, -S- heteroarylene-, –(–O–(CH2)a–)x–, –(–NH–(CH2)a–)x–, –(–S–(CH2)a–)x–, , or , wherein a is 0-100 and x is 1-100, and each arylene or heteroarylene moiety can be substituted or unsubstituted; each Z is –N(Me)3+; each L is ; A’ is a covalent bond to A; Z’ is a covalent bond to Z; * is a covalent bond to ; is a point of attachment to the plurality of cyclodextrin carbon atoms; x is 0-8; y1 is 1-4; y2 is 1-4; and y3 is 0-4.

2. The porous polymeric material of claim 1, n each instance of –W–Z is taken er to form .

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

4. The porous polymeric material of claim 1, wherein x and y3 are each 0.

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

6. The porous polymeric material of claim 5, wherein the aryl diisocyanate crosslinker is 4,4-methylene diphenyl diisocyanate, the aryl moiety is and x and y3 are each 0.

7. The porous ric material of claim 6, wherein each instance of –W–Z is taken together to form .

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

9. The porous ric material of claim 8, wherein the linker comprising formula (I) has the following structure , wherein the oxygen atom denoted with the * is a glycosidic oxygen from one of the plurality of cyclodextrins.

10. A method of purifying a fluid sample sing one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 9, whereby at least 50 wt. % of the total amount of the one or more ants in the fluid sample is adsorbed by the porous ric material.

11. The porous polymeric material of claim 5, wherein the aryl diisocyanate crosslinker is toluene 2,4-diisocyanate, the aryl moiety is and x and y3 are each 0.

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

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

14. The porous polymeric al of claim 13, wherein the linker comprising formula (I) has the following structure or wherein the oxygen atom denoted with the * is a glycosidic oxygen from one of the plurality of cyclodextrins.

15. A method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 14, whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material.

16. The porous polymeric material of claim 1, wherein the polymer has a surface area from about 10 m2/g to about 2,000 m2/g.

17. A method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous ric al of claim 1, whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material. fix;a? fix? '1‘ - ‘~ :3}: