NZ794040B2 - 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

CHARGE—BEARENG EXTRIN POLYEIERIC lVlATEREALS AND lVlE’l‘lrlGDS 0F hlAKlNG AND USING SAhlE Bachvround mmnmunmm {8001} Organic micropollutants (Dy/ilk) 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 pment of technologies that remove lVIPS more effectively."—16 MPs span a wide variety of physiochemical properties ing surface charge, size, and chemical functionality. Charged MP3 can he cationic, anionic, or zwitterionic and are typically difficult to remove in the presence of x matrix constituents like natural organic matter (NOB/l) using conventional adsorption s like activated carbon.

Of the anionic MPs, PFASS present a particular environmental problem because of their resistance to hiodegradation and correlation to negative health effects. PFASS have been used in the formulations of nds of consumer goodsj and are present in aqueous foam formulations used to suppress aviation fires in training scenarios. ""9 As a result, they have contaminated surface and ground waters near nds of ts and, military installations.20 In 2016, Hu and coworkers showed that at least 6 million Americans were seived ng water contaminated with PFASS at or above the US EPAs 2016 health advisory limit for per?uorooctanoic acid (PFOA) and per?uorooctanesulfonic acid (PFOS) of 70 ng If?" PFASs have been linked to cancers,3 liver damage,4 thyroid disease5 and other health problems." {coin} Contaminated water s are typically remediated with granular activated carbon (GAC), but its modest affinity for PFASS, particularly short chain derivatives, makes it an expensive and stop~gap solution."24 In recent reports, 14’1" it was discovered that noncovalent interactions and the electrostatics of functional groups influence PFAS affinity to adsorbents, For example, a combination of ?uorophilic interactions of the crosslinker and a lower concentration of anionic d functional groups in deca?uorobiphenyhlinked CDPs led to high PFOA and PFOS removal from water. In contrast, CDPs crosslinked by epichlorohydrin exhibited or PEA S removal. 25 {WEB} Adsorption processes can be employed to remove specific contaminants or contaminant classes from fluids like air and water. ted carbons (A Cs) are the most widespread sorbents used to remove organic pollutants, and their efficacy derives primarily from their high surface areas, nanostructured pores, and hydrophobicity. r, no single type ofAC removes all contaminants well, particularly anionic MPs. Because of their poorly defined ure and binding site variation, optimal adsorption selectivities require empirical ing at new installations, precluding al design and, improvement. Furthermore, regenerating spent AC is energy intensive (heating to 500900" C or other energy intensive procedures) and does not restore full performance. AC also has a slow pollutant uptake rate, achieving its uptake brium in hours to days, such that more rapid contaminant removal requires excess sorbent.

Finally, AC can perform poorly for many ng inants, particularly those that are relatively hydrophilic. {@904} An alternative adsorbent material can be made from polymeric cyclodextrin materials produced from insoluble polymers of odextrin (Li—CD), which are toroidal niacrocycles comprised of seven glucose units whose internal cavities are capable of binding organic compounds. B—CD is an inexpensive and sustainably produced monomer derived from cornstarch that is used extensively to formulate and stabilize pharmaceuticals, ?avorants, and fragrances, as well as within chiral chromatography stationary phases. Insoluble ?—CD polymers have been formed by crosslinking with orohydrin and other reactive compounds, and feature well defined g sites and high association constants, lnsoluble B—CD polymers crosslinked with epichlorohydrin have been investigated as alternatives to AC for water purification, but their low surface areas result in inferior sorbent performance ve to A Cs. {@605} 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 ent that provides rapid anionic MP extraction, high total , and facile regeneration and reuse procedures. This invention meets those needs, Summary {@906} In some embodiments, the present disclosure provides a porous polymeric material comprising a plurality of extrins crosslinked with a plurality of crosslinks comprising formula (I): wherein A is an aryl or heteroaryl moiety; each R1 is independently selected from the group consisting ofH C1—C6 alkyl, C1—C3 haloalkyl, aryl, hetei‘earyl, —CF3, —SO.3H, —CN, —N02, —NH2 —NCO, —C(O)2R3, —C(O)N(R3)2, and — halogen; each R2 is independently H, —OH, ta1 cation, alkyl, aryl, ary], —SH, —S—nietal cation, —S—a1kyl, —C(_O)2H, or —C(O)NH2; each R3 is independently —H, —C1—C6 alkyl, —C1—C3 haloalkyl, —aryl, (Ra)(_Rb), —C(_O)RC, —CO2RC, —SO2N(R"‘)(Rb), or —SOR", and each R21 and Rb is independently H, or C1—C6 alkyl. each W is independently a, bend, an alkylene group, an arylene group, a heteroarylene group, —O-arylene-, ~(Cl-12)a—a,rylene—, —SO2—ar'ylene-, ~NH-arylene~, ~S—aryler1e—, —O— heteroarylene-, ~(Cl-{2)a—heteroa,rylene—, —SO2—heteraoarylene-, —NH-heteroarylene-, ~S— AK J-k N 0""(CHzla‘Z‘ arylene-, ---t---O»---(CHz)a—--)x---,, ---t---NH—--(Cl-12)a---)x---, (QWIIsz, , , H N"(CH2)3~Z' H . _ . or H wherein a 15 0—100 and x is 1—100, and each arylene or heteroarylene moiety can be substituted or uns ubsti‘tuted; each Z is a, GatiOI’llC moiety or an anionic moiety; each L is independently a linking moiety selected from the group ting of —---—O -—-,S-—- —N—, Cl-C6 substituted or tituted alkylene, C1—C3 haloalkylene, O O O C) O 8 . O 0 AK JL /* A'\, A /* iii 0 Q E [CV/LI)" A\O/U\*, If; ./U\ A 3%.: A A ill a and m a , ’ 3 7 , ; A’ is a covalent bond to A; Z’ is a covalent bond to Z; * is a covalent bond to E; 4 is a point of attachment to the plurality of cyclodextrin carbon atoms; x is 0mg; y: is 14; yz is 14; and 373 is 04. {0907} in some embodiments, the crosslinks of the porous polymeric material comprise formula (II): wherein ya. is l or 2; and X is l or 2. {@908} In some embodiments, the porous polymeric material of the t disclosure comprises a plurality of linkers of formula (111); %----O H H N N .. . OWIL/ R4 ' R4 03 wherein one R4 is ---l-I and one R4 is wMe. {0009} In some embodiments, the present sure es a supported porous polymeric material comprising porous particles affixed to a solid substrate, wherein said porous particles comprise a plurality of cyclodextrin moieties with a plurality of crosslinks comprising formula (I), (H), or 00). {0010} 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 ?uid sample is adsorbed by the porous polymeric material. }0011} In some embodiments, the present disclosure provides a method of removing one or more compounds from a ?uid sample or determining the presence or absence of one or more compounds in a fluid sample comprising: a) contacting the sample with the porous ric material or the supported porous polymeric al of the present disclosure for an incubation period; b) separating the porous polymeric material or supported porous polymeric al after the tion period, from the sample; and c) heating the porous polymeric material or ted porous ric material separated in step b), or contacting the porous polymeric material or supported porous polymeric material separated in step b) with a solvent, thereby ing at least a portion of the compounds from the porous polymeric material or supported porous polymeric 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 released in step 0), wherein the ce of one or more compounds ates to the presence of the one or more compounds in the sample. {0012} In some embodiments, the present disclosure provides an article of manufacture comprising the porous polymeric material or the supported porous ric material of the present disclosure, Brief?escrl tion of the Drawin s {0013} Fig. 1 shows a comparison of1?FAS uptake capability of polymers of the present disclosure at 0.5 hours (top) and 48 hours (bottom). {0014} Fig. 2 shows a comparison between two choline chloride—modified TFNuCDP polymers and a DI polymer for PFOA uptake (top) and PFOS uptake (bottom). {0015} Fig. 3 shows a 11-1 NMR spectrum for B—CD—TDI polymer (top) and {LCD (bottom). {0016} Fig. 4 shows the change in the 11-1101le spectrum of LluCDuTDl polymer upon addition ofD20. {0017} Fig. 5 shows a comparison of various Bu(ID~'1"DI polymers made with different B— CD:TDI molar equivalents. {0018} Fig. 6 shows a ison of choline chloride—modified BuCD—TDI polymers made with different molar equivalents of choline chloride. {0019} Fig. 7 shows choline—chloride modified B—CDJFFN uptake studies performed with ene blue (top) and methyl orange (bottom). {0020} Fig. 8 shows MO uptake isotherms for modified TFN_CDP polymers with 15 (top) and 3.0 (middle) equivalents of choline chloride, and unmodified TFN "CDP (bottom). Dots represent the experimental data points and straight lines are the fitted curves using a Langmuir model. {0021} Fig. 9 shows BPA uptake isotherms for modified P polymers with 1.5 (top) and 3.0 (middle) lents of choline chloride, and unmodified ’1FNmCDP (bottom). Dots represent the experimental data points and ht lines are the fitted curves using a Langmuir model. {0022} Fig. 10 shows a 11-1 NMR spectrum of a choline chloride—modified DI r made with 1:6:1 molar equivalents of B—CDTDLcholine chloride. {0023} Fig. 11 shows a comparison of a choline chlorideumodified BuCDuTDl polymer and a {in CD~TDI polymer. {0024} Fig. 12 shows a comparison between three choline chloride—modified B—CD—TDI polymers with different choline de loading amounts. {0025} Fig. 13 shows PFOA uptake of choline chloride—modified B—CD—TDI polymers. {0026} 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. {0027} As used above, and throughout 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 known to one d in the art controls. 0028 As used herein, the terms "includin, " "containin, " and "corn rising" are used in their , ._ 7 ._ 7 L/ , , open, nonmliniiting sense. {8029} The articles "a" and "an" are used in this disclosure to refer to one or more than one (126., 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. {0030} The term "and/or" is used in this disclosure to mean either "and" or "or" unless indicated otherwise. {0031} To provide a more concise description, some of the quantitative sions given herein are not qualified with the term "about". it is understood that, r 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 ed based on the ordinary skill in the art, including equivalents and approximations due to the experimental and/or measurement conditions for such given value. Whenever a yield, is given as a percentage, 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 be obtained under the particular stoichiometric conditions. trations that are given as percentages refer to mass ratios, unless indicated differently. {0032} The term adsorbent or adsorb is used to refer to compositions or methods of the t disclosure to refer to solid materials as described herein which remove contaminants or pollutants, typically but not exclusively organic molecules, 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, esia gases, etc). Such terms do not imply any specific physical mechanism (e.g tion vs. absorption). {8033} The term "cyclodextrin" includes any of the known cyclodextrins such as unsubstituted extrins containing from six to twelve glucose units, especially, alphaucyclodextrin, beta~ cyclodextrin, gammaucyclodextrin and/or their derivatives and/or es f. The alpha— cyclodextrin consists of six glucose units, the betaucyclodextrin consists of seven glucose units, and the gamma—cyclodextrin consists of eight glucose units ed in shaped, rings. The specific coupling and mation of the glucose units give the extrins rigid, conical molecular structures with hollow interiors of ic volumes. The "lining" of each internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms; therefore, this surface is fairly hydrophobic. The unique shape and physicalnchemical properties of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules or parts of organic les which can fit into the cavity. {0034} Unless otherwise stated, the terms "crosslinker" or "crosslink" or "linker" refer to a monomer capable of reacting with or forming a covalent linkage between one or more cyclodextrins or polymers, For example, if the crosslinker reacts at the end of a polymer chain, it may covalently react with one cyclodextrin moiety of the polymer (eg. via the glycosidic oxygen of the cyclod extrin), The crosslinker may or may not further react with other rs or cyclodextrin units or polymer chains to, for example, extend a polymer chain or link two or more polymer chains together, For example the crosslinker may be bound to l, 2, 3, or 4+ monomers or cyclodextrin units or polymers {0035} The term "cationic moiety" refers to a group which carries a positive charge (erg, +1, +2, etc), for example, ammonium, mono~, di— or trialkylamrnonium, lsulfonium and trialkylphosphonium, {llll??l The term "anionic moiety" refers to a group which carries a negative charge (eg —l, ~2, etc), for example, phosphate, carboxylate, alkoxide, and e. {@377} As used herein, "alkyl" means a straight chain or branched saturated chain having from 1 to 10 carbon atoms. Representative saturated alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-n'1ethyl-l-propyl, 2-methyl~2-propyl, 2-methyl~l ~butyl, 3— rnethyl—l—butyl, 2-methyl~3~butyl, 2,2-dimethyhl ~propyl, 2~rnethyl—l ~pentyl, 3-methyl~l ~pentyl, 4umethylulupentyl, Emmethyl—Zupentyl, 3—methyl~2—pentyl, 4uniethyl—2upentyl, 2,2—dimetl1yl—l_ butyl, 3,3—dimetl1ylulubutyl, Zuethyl—l—butyl, butyl, yl, t—butyl, n—pentyl, isopentyl, neopentyl, n—hexyl and the like, and longer alkyl , such as heptyl, and octyl and the like.

An alkyl group can be unsubstituted or substituted. Alltyl groups containing three or more carbon atoms may be straight, or branched. As used herein, "lower alkyl" means an alkyl having from 1 to 6 carbon atoms. {@938} The term "alkylene" refers to straightm and branched~chain alkylene groups. l alkylene groups include, for example, methylene ("Cl-1r), ethylene ("CH2CH2n) , propylene (~ CH2CH2CH2-) n— butylene (—CHzCH2CH2CH2n) , isopropylene ("CH(CH3)CH2U) , , sec~butylene (—CH(CH2CH3)CH2-) and the like. {0939} The term "hydroxyl" or "hydroxy" means an OH group; {0040} It should also be noted that any carbon as well as heteroatom with unsatisfied valences in the text, schemes, examples and, Tables herein is d to have the sufficient number of hydrogen atom(s) to y the valences. {0941} The term "halo" or "halogen" refers to fluorine, chlorine, e, or iodine. {0042} The term "cyano" as used herein means a substituent having a carbon atom joined to a nitrogen atom by a triple bond, 12.6., CEN'. {0043} The term "amine" or "amino" as used herein means a tuent containing at least one nitrogen atom. Specifically, Nl-lz, l{y1) or alkylamino, "N(all car’boxamide, urea, and, sulfamide substituents are included, in the term "amino". {9944} Unless otherwise specifically defined, the term "aryl" refers to cyclic, aromatic hydrocarbon groups that have 1 to 3 aromatic rings, ing monocyclic or bicyclic groups such as phenyl, biphenyl or naphthyl. Where containing two aromatic rings (bicyclic, etc), the aromatic rings of the aryl group may be joined at a single point (eg biphenyl), or fused (Lag, naphthyl), Furthermore, in the t of the present disclosure, the term aryl is taken to refer to two ar‘yl rings joined by a short linker such as —CH2—, CR2— (where R can be H, alkyl, etc), 4302—, —SO~, ~NR— (where R can be H, alkyl, etc), or —O—; for e, aryl may refer to methylene diphenyl or oxyhisphenyl respectively). The aryl group may be optionally substituted by one or more substituents, 6.5;, l to 5 substituents, at any point of attachment. The substituents can themselves be optionally tuted. Furthermore when containing two fused rings the aryl groups herein d may have an unsaturated or partially saturated ring fused with a fully saturated ring. Exemplary ring systems of these aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, anthracenyl, phenalenyl, phenanthrenyl, indanyl, indenyl, tetrahydronaphthalenyl, tetrahydrobenzoannulenyl, and the like. {0045} Unless otherwise specifically defined, "heteroaryl" means a nlonoyalent monocyclic or polycyclic aromatic radical of 5 to 18 ring atoms or a clic aromatic l, containing one or more ring heteroatoms selected from N, O, or S, the remaining ring atoms being C.

Heteroaryl as herein defined also means a polycyclic (eg, bicyclic) heteroaromatic group wherein the oatoni is selected from N, O, or S. The aromatic radical is optionally substituted independently with one or more tuents described herein. The substituents can themselves be optionally substituted. Examples include, but are not limited to, benzothiophene, furyl, tliienyl, pyrrolyl, pyridyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrimidinyl, iniidazolyl, isoxazolyl, oxazolyL oxadiazolyl, nyl, indolyl, thioplien~2~yl? quinolyl, benzopyranyl, isothiazolyl, thiazolyl, azolyl, thieno[3,2—b]thiophcne., triazolyl, triazinyl, imidazo? ,2- b]pyrazolyl, furo[2,3~c]pyridinyl., imidazo? ,2ma]pyridinyl, indazolyL pyrrolo[2.,3—c]pyridinyl, pyrrolo[3,2mc]pyridinyl, pyrazolo[3,4mc]pyridinyl, benzoimidazolyl, thieno[3.,2—c]pyridinyl, thieno[2,3~c]pyridinyl., thieno[2,3~b]pyridinyl, benzothiazolyl, indolyl, indolinyl, indolinonyl, dihydrobenzothiophenyl, dihydrobenzofuranyl, benzofuran, chromanyl, thiochromanyl, ydroquinolinyl, dihydrobenzothiazine, dillydrobenzoxanyl, quinolinyl, nolinyl, l,6~ napl'ithyridinyl, benzo[de}isoquinolinyl, pyrido[4,3—b][l ,6]naphthyridinyl, thieno[2,3- b]pyrazinyl, quinazolinyl, tetrazolo?,5~a]pyridinyl, [l 72,4}triazolo[4,3—a}pyridinyl, isoindolyl, o[2,3—b]pyridinyl, o[3,4—b]pyridinyl, pyrrolo[3,2—b]pyridinyl, imidazo[5,4~ dinyl, pyrrolo[l ,Z—ajpyrimidinyl, tetrahydropyrrolo[l ,Z—alpyrimidinyl, 3,4—dihydro—Zl—L lAZ-pyrrolo[27l—b]pyrimidineg dibenzo[l’3,d}thiophene, pyridin~2~one, furo[3,Z—cjpyridinyl, furo[2,3"clpyridinyl, lllupyrido§:3,4ubj[1,4:E'thiazinyl, benzooxazolyl, benzoisoxazolyl, furo[2,3— bjpyridinyl, benzothiophenyl, 1,5—naphtliyridinyl, furo[3,2—bjpyridine, Eil,2,4]triazolo[l,5~ dinyl, benzo [1,2,3]triazolyl, imidazo?,Zua]pyrimidinyl, 3:],2,4:Etriazolo{4,3—bjpyridazinyl, l)enzo{c] [ l ,2,5 ]thiadiazolyl, benzoiic][1,2,5]oxadiazole, 1,3 —dihydro—2H~benzo{idlimidazolu2mone, 3,4—dihydro—ZI-lupyrazolo3:l ,Sub] [: l ,2] yl, 4,5,6,’7utetrahydropy razolo[l ,5—a]pyridinyl, thiazoloii5,4—djtliiazolyl, imidazo[2,l_b]§:l ,3,4:§thiadiazolyl, thieno[2,3— ]pyrrolyl, 3l-luindolyl, and derivatives thereof. Furthermore when containing two fused rings the aryl groups herein defined may have an rated or partially saturated ring fused with a fully saturated ring. {0046} Numerical ranges, as used herein, are ed to include sequential rs unless indicated otherwise. For example, a range expressed as "from O to 5" would include 0, l, 2, 3, 4 and 5. {8047} The present disclosure provides porous (eg microporous 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 nsive, sustainably produced macrocycle of glucose. The extrin polymers are crosslinked with linking groups as described herein. The polymers of cyclodextrin are comprised of cyclodextrin es that are derived from cyclodextrins. The cyclodextrin moiety(s) can be derived from naturally occurring cyclodextrins (eg, to, [3-, and 7—, comprising 6, 7, and 8 glucose units, respectively) or synthetic cyclodextrins. The cyclodextrin moiety has at least one —0— bond derived from an —OH group on the cyclodextrin from which it is derived.

The cyclodextrin moieties can comprise 3—20 e units, including 3, 4, 5, 6, ‘7, 8, 9, l0, ll, 12, l3, l4, l5, l6, 1’7, 18, 19, and 20 glucose units, inclusive of all ranges therebetween, In many ments, the cyclodextrin moieties are derived from starch, and se 6—9 glucose units, The polymeric materials may comprise two or more different cyclodextrin moieties. In particular embodiments, the P—CDP is sed of insoluble polymers of B~cyclodextrin (B~CD), {till/48} The P—CDP can also comprise cyclodextrin derivatives or ed cyclodextrins, Tlie derivatives of cyclodextrin consist mainly of les wherein some of the OH groups are converted to OR groups, The cyclodextrin derivatives can, for example, have one or more additional moieties that provide additional functionality, suclr as desirable lity behavior and affinity characteristics, Examples of suitable cyclodextrirr derivative materials include methylated cyclodextrins (cg, RAMEB, randomly methylated ?—cyclodextrins), hydroxyalkylated cyclodextrins (e, g, hydroxypropyl—B—cyclodextr‘in and bydroxypr'opyl—y— cyclodextrin), acetylated cyclodextrins (e, g, acetyl—y—cyclodextr'ii'r), reactive cyclodextrirrs (cg, chlorotriazinyhB~CD), branched cyclodextrins (eg, glucosyl~B~cyclodextrin and yl-?— cyclodextrin), sulfohutyl— B—cyclodextrin, and sulfated cyclodextrins. For example, the cyclodextrin moiety further comprises a moiety that binds (eg, with specificity) a metal such as arsenic, m, copper, or lead. {@049} The P—CDP can also se cyclodextrin tives as disclosed in US. Pat. No. 6,881,712 including, e.g cyclodextrin derivatives with short chain alkyl groups such as ated cyclodextrins, and ethylated cyclodextrins, wherein R is a methyl or an ethyl group, those with hy droxyalkyl substituted groups, such as hydroxypropyl extrins and/or hydroxyethyl cyclod extrins, wherein R is a —CH2—CH(OH)—CH3 or a "CHzCHz—OH group; branched cyclodextrins such as maltose—bonded cyclodextrins; cationic cyclodextrins such as those containing 2—hydroxyn3"(dimethylamino)propyl ether, wherein R is CH2—CH(OH)— CH2—N(CH3)2which is cationic at low pH; quaternary ammonium, e.g, 2nhydroxy—3~ (trimetliylammonio)propyl ether de groups, wherein R is CH2—CH(OH)—CH2— N‘KCHQsCl"; anionic cyclodextrins such as carboxymetliyl extrins, cyclodextrin sulfates, and cyclodextrin succinylates; ainplioteric cyclodextrins such as carboxymethyl/quaternary ammonium cyclodextrins; cyclodextrins n at least one glucopyranose unit has a 3—6— anliydro—cyclomalto structure, e,g the mono~3~6~anhydrocyclodextrins, as disclosed in "Optimal Performances with Minimal Chemical Modi?cation of exti‘ins", F. DiedainivPilard and B, Perly, The 7th International Cyclodextrin Symposium Abstracts, April 1994, p, 49 said references being incorporated herein by reference; and mixtures thereof. Other cyclodextrin derivatives are disclosed in US. Pat. No. 3,426,011, Parmerter et al., issued Feb~ 4, 1969; US Pat. Nos. 257; 3,453,258; 3,453,259; and 3,453,260, all in the names of Parmerter et al., and all issued Jul. 1, 1969, US. Pat. No. 3,459,731, Gramera et al, issued Aug. 5, 1969, US. Pat, No. 3,553,191, Parmerter et al., issued Jan. 5, 1971; US. Pat. No. 3,565,887, Parmerter et al, issued Feb, 23, 1971', US. Pat. No, 4,535,152, Szejtli et al., issued Aug~ 13, 1985; US Pat. No~ 008, Hirai et al, issued Oct. 7, 1986', US. Pat. No, 4,678,598, Ogino et al., issued Jul. 7, 1987; US. Pat. No. 4,638,058, Brandt et al., issued Jan 20, 1987; and US Pat. No~ 4,746,734, Tsuchiyama et al., issued May 24, 1988, all of said patents being incorporated herein by reference. {0050} In some ments, the present disclosure provides a porous polymeric material comprising a plurality of cyclodextrins crosslinked with a plurality of crosslinks comprising formula (I): wherein A is an aryl or heteroaryl moiety; each R1 is independently selected from the group consisting ofH C1—C6 alkyl, C1—C3 haloalkyl, aryl, hetei‘earyl, —CF3, —SO.3H, —CN, —N02, —NH2 —NCO, —C(O)2R3, —C(O)N(R3)2, and — halogen; each R2 is independently H, —OH, —O—nieta1 cation, alkyl, aryl, heteroary], —SH, tal cation, —S—a1kyl, —C(_O)2H, or —C(O)NH2; each R3 is independently —H, —C1—C6 alkyl, —C1—C3 kyl, —aryl, —C(O)N(Ra)(_Rb), —C(_O)RC, —CO2RC, —SO2N(R"‘)(Rb), or —SOR", and each R21 and Rb is independently H, or C1—C6 alkyl. each W is independently a, bend, an alkylene group, an arylene group, a heteroarylene group, —O-arylene-, 2)a—a,rylene—, —SO2—ar'ylene-, ~NH-arylene~, ~S—aryler1e—, —O— heteroarylene-, ~(Cl-{2)a—heteroa,rylene—, —SO2—heteraoarylene-, —NH-heteroarylene-, ~S— AK J-k N 0""(CHzla‘Z‘ heteroarylene-, ---t---O»---(CHz)a—--)x---,, ---t---NH—--(Cl-12)a---)x---, z, , , H N"(CH2)3~Z' H . _ . or H wherein a 15 0—100 and x is 1—100, and each arylene or heteroarylene moiety can be substituted or uns ubsti‘tuted; each Z is a, GatiOI’llC moiety or an anionic moiety; each L is ndentiy a linking moiety seiected from the group consisting of --,--—O -—-,S-—- A'\ A /* —N—, C1-C6 substituted or unsubstituted alkyiene, C1—C3 haloaikylene, O O O C) A l 0 AF\ l /* Al\f A /;:< l Unix iii 0 0 c J six E )" A\OJJ\* if:l a and m a , ’ 3 7 , ; A’ is a covalent bond to A; Z’ is a covalent bond to Z; * is a covalent bond to E; 4 is a point of attachment to the plurality of cyciodextrin carbon atoms; x is 0mg, yi is 14;, yz is 14, and ya is 04 {0951} Each Z is a cationic moiety or an anionic moiety. For example, in some embodiments, each Z is a cationic moiety. in certain ments, each cationic moiety is independently — N(R3)3+, —l)(R3)3+, —S(R3)z+, or —I-Iete1'oaryi+ wherein each R3 is ndently —H, —Ci-Ci; alkyi, —C1nC3 haloalkyl, —a1yl, —C(O)N(R§‘)(Rb), —C(0)R", —C02Rc, —SO7.N(R*)(R""), or 430R", and each Ra and R" is independently H, or C1—C6 alkyl. For e, in some embodiments, each cationic moiety is —N(R3)3’*' where each R3 is H or C1—C5 alkyl. Accordingly, in some embodiments, each cationic moiety is is —]T‘J(1Vle)3+ or is —I\U—l3+, In some embodiments, each cationic moiety is is —N(Me)3+. In some embodiments, each cationic moiety is independently ~ Heteroaryll, A variety of charged heteroaryls are contemplated in the context of the present disclosure and are readily apparent to a skilled artisan, For example, in some embodiments, — Heteroaryl+ may refer to pyridinium, pyrrolidinium, imidazoiium, lium, tetrazolium, and the like. In some embodiments, each Z is an anionic moiety. in certain ments, each hog?i Gui—Oioggigg Ooi""_/8,\ \\ O 0 ii a; . . i . 3 amomcrnoretyis OR (E) Q 0 $0 R3 F3 7 9 a a 3 3 ’01, 1—90 ~ wherein each Rj is as defined above~, , . {8052} In ance with certain ments of the present disclosure, each W is independently a bond, an alkylene group (e. g. CkClO, (Ito—(720, or Czo~Cioo), an arylene group, a heteroarylene group, uO—arylene—, —(CI-Iz)a—arylene~, arylene—, uNH—aryleneu, —S~arylene_, ~ Ouheteroarylene—, —(CH7.)a~heteroarylene~, —S()2_hetera0arylene—, —NI—Iuheter0arylene—, —S— arylene—, ( O (CH2)a )x ( NH (CI-12):: )x or ( S , (CH2)a )x whereinais 0—100 , , and X is 1—100, and each arylene or heteroarylene moiety can be substituted or tituted. The term "arylene" refers to a bivalent group d from an aryl group (as described herein, including phenyl, biphenyl, 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 he on the same ring, , meta: or on ent rings. Arylenes can be derived from any aromatic rings described herein, and, can be substituted or unsubstituted. Similarly, the term "heteroarylene" refers to a bivalent group derived from a heteroaryl group (as described herein, including furyl, pyridyl, etc.) by removing hydrogen atoms from two ring atoms (which can be carbon or heteroatoms). The ies can be on the same ring or different rings (in the case of polycyclic heteroaromatics) and can be on any two ring atoms. Heteroarylenes can be derived from any hetei‘oaromatic rings described herein, and can be substituted or unsubstituted. Thus in some embodiments, each W is a bond (ie. a covalent bond). In other embodiments, each W is an ne group. For example, each W may be, methylene (4312-), ne (—CHzCI-Iz—) , propylene (~CII2CIIIz(III2—) , isopropylene (—CH(CI-Is)CI—Iz~) n— butylene (—(fIIzCHgCI:IzCI-Ig—) and the , , sec~butylene (—(IIIz(CI-I'2CI13)CII2—) like. In some embodiments, each W is methylene (—CHz~). In some embodiments, each W is an arylene group (phenylene). In some embodiments, each W is a heteroarylene group (furyl, pyridyl). In some ei'nbodiments, each W is ~O—arylene— enylene). In some embodiments, each W is —(CHz)a—arylene— phenylene). In some embodiments, each W is —SOzuaryleneu (~ SOzuphenylene). In some embodiments, each W is "NH—arylene~ (—NHuphenylene). In some embodiments, each W is —S~arylene~ (:uSuphenylene). In some embodiments, each W is a heteroarylene group ene, pyridylene). In some embodiments, each W is ~0uheteroarylene— (—O~pyridinylene). In some embodiments, each W is —((II-Izh—heteroaryiene— (—CI-Iz— pyridinylene). In some embodiments, each W is SOz—heteroarylene— (—SOz—pyridinylene). In some embodiments, each W is uNI-I—heteroaryleneu ("NH—pyridinylene). In some embodiments, each W is nS—heteroarylene~ ("S—pyridinylene). In some embodiments, Wis —(O—CH2—CH2)x—.

. . \NJLOmrcnna—Z‘ In some embodiments, Wis --—O-—--CI-I2-—-CI-Iz-—-~._ _ _ . , In some embodiments, W is H where A" is a covalent bond to A and Z’ is a covalent bond to Z;. In some embodiments, W is ARM/LLO/Nvr {@653} In some embodiments, each ce of -W-Z is taken together to form ---O»—--CI-Iz--- II-Izm- N(R)3+~ In some embodiments, each instance of ---W»—--Z is taken together to form »-—O»---CI-Iz---CI-I2—-- N(Me)3+. In some embodiments, each instance of ----W—--~Z is taken together to form A i N (M623 {0054} In some embodiments, each L is a Iii'iking moiety. In some embodiments, each L is independently a linking moiety selected from the group consisting of—-O»——, -S--, --N»--, o o o o A\N/l\0/, a , o 0 AK JL /* AWDJL / N A/* I3"\\ ,lk OOH HAiooa, AmJL A and, 7 7 :1 7 ANJSLNA S H H where A’ is a covalent bond to A and * is a nt bond to 3 (which as described herein represents a point of attachment to the ity of extrin carbon atoms). In some embodiments, each L is independently "O"- In certain embodiments, when each L is O O A'\ JJ\ /* A\N’J‘ko/* A /* independently O O H A' O or O, the oxygen atom may be a , , idic oxygen from the plurality of cyclodextrins of the porous polymeric material of the present disclosure. For example, in some embodiments, when each L is independently "O the oxygen atom is a glycosidic oxygen atom from the plurality of extrins of the porous polymeric material of the present disclosure. {0055} In some embodiments, A is an aryl or heteroaryi moiety. In some embodiments, A is an aryl moiety. For example, A may be plienyl, biphenyl, naphthyi, cenyl, phenalenyi, phenanthrenyi, indanyl, indenyl, tetrahydronaphthalenyi, or tetrahydrobenzoannulenyi. In some embodiments, A is a heteroai'yl moiety. For example, A may be benzothiophene, furyl, thieiiyl, pyrrolyl, pyridyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrimidinyl, imidazolyl, isoxazolyl, oxazolyl, oxadiazolyl, pyrazinyl, indolyl, thiophenuZuyl, quinolyl, benzopyranyl, isothiazolyl, lyl, tliiadiazolyl, thieno[3,2~b:{thiophene, triazolyl, triazinyl, imidazo[l,2—b]pyrazolyl, fliro[2,3nc]pyridinyl, imidazo[l,2—a]pyridinyl, indazolyl, pyrrolo[2,3—c]pyridinyl, pyrrolo[3,2n c]pyridinyl, lo[3,4mc]pyridinyl, benzoimidazolyl, thienoIS,2nc]pyridinyl, thieno[2,3n c]pyridinyl, thieno[2,3nb]pyridinyl, benzothiazolyl, indolyl, nyl, nonyl, dihydrobenzothiophenyl, dihydrobenzofuranyl, benzofuran, chromanyl, thiochromanyl, tetrahydroquinolinyl, dihydrobenzothiazine, dihydrobenzoxanyl, inyl, isoquinolinyl, 1,6" naphthyridinyl, benzo[de]isoquinolinyl, pyrido[4,3—b][l,6]naphthyridinyl, thieno[2,3— b]pyrazinyl, quinazolinyl, tetrazolo[l,5ma]pyridinyl, [l,2,4]triazolo[4,3na]pyridinyl, isoindolyl, pyrrolo[2,3~b]pyridinyl, pyrrolo[3,4—b]pyridinyl, pyrrolo[3,Z—b]pyridinyl, imidazo[5,4~ b]pyridinyl, pyrrolo[l,2—a]pyi‘imidinyl, tetrahydropyrrolo[ l ,2—a]pyrimidinyl, 3,4—dihydi‘o—2H~ l93mpyrrolo[2,l-b]pyrimidine, dibenzo[b,d]thiophone, pyridin~2~one, furo[3,2—c]pyridinyl, ,3—c]pyridinyl, lH~pyrido[3,4—b][l,4]thiazinyl, benzooxazolyl, benzoisoxazolyl, fui‘o[2,3m b]pyridinyl, benzothiophenyl, 1,5-naphthyridinyl, furo[3,2—b]pyi‘idine, [l,2,r-'l]ti"iazolo[l,5~ a]pyi‘idinyl, benzo [1,2,3]triazolyl, o[l,2—a]pyrimidinyl, [l,2,4]triazolo[4,3—b]pyi‘idazinyl, benzo[c][l ,2,5]thiadiazolyl, benzo[c][1,2,5]oxadiazole, l ,3~dihydro-2H~benzo[d]imidazol~2~one, 3,4—dihydro—ZI:I~pyrazolo[l,5~b] [l ,2] oxazinyl, 4,5,6,7—tetrahydropyrazolo[ l ,5-a]pyridinyl, thiazolo[5,4—d]thiazolyl, imidazo[2,l—b][l,3,4]thiadiazolyl, thieno[2,3-b]pyrrolyl, or ndolyl.

In some embodiments, A is selected from the group consisting of phenyl, naphthyl, pyridyl, benzofurai'iyl, pyrazinyl, zinyl, dinyl, triazinyl, quinolinc, benzoxazole, benzothiazole, lH-benzimidazole, noline, oline, quinoxaline, pyrrole, indole, bipheiiyl, pyrenyl, and anthracenyl. In some embodiments, A is phenyl. In some embodiments, A is an aryl or heteroaryl ring system as described in US Patent No. 9,855,545, which is hereby incorporated by reference in its ty. {0056} In some embodiments, A is the polymerization product of commercially available diisocyanates. For example, in some embodiments, A is the polymerization product of commercially available aryl diisocyanates including but not limited to luene diisocyanate, 2,6—toluene diisocyanate, 4,4’~methylene diphenyl diisocyanate, 2,4’umethylene diphenyl yanate, l,3—bis(isocyanatomethyl)benzene, l,3—bis(l misocyanatoul ametliylethyl)benzene, 3,3’udichloro—4,4’—diisocyanatoul,l’ubiphenyl, 3,3‘udiniethyl~4,4‘—biphenylene diisocyanate, 4,45 oxyhis(phenyl isocyanate), 1,3—phenylene diisocyanate, 1,4—phenylene yanate, 4—Cliloro—6u methylul,3~phenylene diisocyanate, and l"chlorometliyl—Z,4ndiisccyanatohenzene. In some embodiments, A is where the wavy line represents any of the substituents attached to A as defined herein. In some "{"§ )140 enrbodirnentg A is or where the wavy line represents any of the substituents attached to A as defined . In some lite Me where the wavy line ents any of the substituents attached to A as defined, herein, the —Me, —Cl, and —CI-l2—Cl groups bound to the aryl ring in the ing structures corresponds to Rj groups, and the — CI-L— and —C(Me)2— groups bound to the aiyl ring correspond to L groups. In some where the wavy line represents any of the substituents attached to A as defined herein, and the Me and ---Cl groups bound to the aryl ring in the preceding structures ponds to R1 groups. {@657} The porous polymeric material of the present disclosure comprises a plurality of cyclodextrins with a plurality of crosslinks comprising formula (I). The plurality of cycledextrins of the present disclosure may be any cyclodextrin containing from six to twelve glucose units. For example, in some embodiments, the plurality of cyclodextrins of the present disclosure are selected from the group consisting of tx—cyclodextrin, odextrin, y— cyclodextrin, and combinations thereof, In some embodiments, each cyclodextrin is a B~ cyclodextrin. {9658} The R‘1 groups of the plurality of crosslinks ‘lSll’lg a (I) are each R1 is independently selected from the group ting of H, C1—C6 alkyl, Ci—C3 kyl, aryl, beteroaryl, —CF3, -S()3I-l, ---CN, ~N02, ~NI-Iz, —NCO, —C(())2R3, (R3)2, and »---halogen. In certain embodiments, each R1 is ii'idependently selected from the group consisting of H (Ii—Cs alkyl, C1"C3 haloalkyl, aryl, heteroaryl, _C ’3, "8031-1, —--CN, —NO2, uNI-Iz, —NCO, —C(())2R3, u C(O)N(R3)2, and ----l1alogen. In certain embodiments, 0—8 R1l groups are present on the plurality of crosslinks comprising formula (l). For example, 0, l, 2, 3, 4, 5, 6, 7, or 8 RI groups are present on each of the individual crosslinks comprising formula (I). it is understood that any positions of A not substituted with R], R3, uW—Z or -—--Lu will be unsubstituted or have one or more H atoms as required to y 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 R1 is —l5' and the polymerized porous material of the present invention is exposed to reactants capable of substitution (eg. choline chloride), the —F groups on some crosslinks will be substituted, s in other crosslinhs, 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 linking group may independently have 0—8 (eg. 1, 2, or 3) R1 groups. {0059} In some embodiments, the porous polymeric material of the present disclosure may be terized as having, on average, a fractional number ofR R2, —WnZ or —L— groups in each crosslinking group, This fractional number of substituents can be calculated by dividing the total number of such groups by the total number of crosslinks in the porous polymeric material. For example, if half of the crosslinking groups are functionalized with a —O—CH’2—Clrl'g—l’xl?lv/l',e)3+ group (eg, where W is a —CH2— and Z is 3), then the average number (or fraction) of —O—CH2—CH2—N(Me)3+ groups corresponding to ~Vv7—Z per crosslinking group is 05.

For R1, the fractional number of such groups includes values of about 0, about 0.1, about 0.2, about 0.3, about 04, about 0.5, about 0.6, about 07, about 0.8, about 09, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, 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 32, about 3.3, about 3.4, about 3.5, about 3.6, about 3.7, about 3.8, about 39, about 4.0, about 41, about 4.2, about 4.3, about 44, about 4.5, about 4.6, about 47, about 4,8. about 49, about 5.0, about 5.1, about 52, about 5.3, about 5.4, about 5.5, about 5.6, about 5.7, about 58, about 59, about 6.0, about 61, about 62, about 6.3, about 6.4, about 65, about 6.6, about 67, about 6.8, about 6.9, about 70, about 7.1, about 7.2, about 7.3, about 7.4, about 7.5, about 7.6, about '77, about 7.8, about 7.9, or about 8.0, inclusive of all ranges between any of these values. For R2, the fractional number of such groups includes values of about 0, about 0.1, about 0.2, about 03, about 0.4, about 05, about 06, about 0.7, about 0.8, about 09, about 1.0, about 11, about 1.2, about 1.3, about 14, about 1.5, about 1.6, about 1.7, about 1.8 about 1.9, about 2.0, about 21, about 2.2, about 2.3, about 24, about 25, about 2.5, about 27, about 28, 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 38, about 3.9, or about 4.0, inclusive of all ranges between any of these values.

For ~W—Z, the fractional number of such groups includes values of about 10, about 11, about 1.2, about 1.3, about 14, about 1 .5, about 1.6, about 17, about 18, about 1.9, about 20, about 2.1, about 22, about 2.3, about 2.4, about 25, about 2.5, about 2.7, about 28, about 29, about , about 3.1, about 3.2, about 33, about 3.4, about 3.5, about 3.6, about 3.7, about 3.8, about 3.9, or about 4.0, inclusive of all ranges between any of these values. For »---I...~, the fractional number of such groups includes values 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 2.1 about 22, about 2.3, about 24, about 2.5, about 2. 5, about 27, about 2.8, about 2.9, 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, inclusive of all ranges between any of these values. {0060} Each R3 is ndently H, —O1—l, "()umetal cation, alkyl, aryl, ai'yl, —Sl:l, "Sn metal cation, ----Sualkyl, —C(())2H, or —C(O)N1-12. In some embodiments, each R2 is 1:1. in some embodiments, each R3 is —OH. in some embodiments, each R2 is ~O—1’1‘iet2tl . in some embodiments, each 112 is alkyl. In some embodiments, each R2 is aryl (eg, substituted or unsubstituted phenyl or naphthyl). In some embodiments, each R2 is aryl (egg, substituted or unsubstituted 5— or @membered hetei'oaryl rings with one, two, or three ring heteroatoms selected from the group consisting of O, S, or N). In some embodiments, each R2 is —SH. In some ments, each R2 is --——Sumetal cation. In some embodiments, each R2 is ---S_alli:yl. In accordance with embodiments of the present disclosure, there may be 1, 2, 3, or 4 I12 .

For example, 0, l, 2, 3, or 4 R) groups are present on the plurality of inks comprising formula (I). As will be appreciated by a d, artisan, the number of R) groups on each of the individual plurality of linking groups comprising formula (I) may vary by each individual linking group throughout the porous polymeric al of the present sure. Accordingly, a porous polymeric material of the present disclosure may have multiple linking groups of formula (_I) present, and each individual linking group may independently have e.g. 0, I, 2, 3, or 4 R3 groups.

When there are more than one R2 groups on the plurality of linking 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 —OH. {moi} Each R3 is independently —I-I, —C1-C6 alkyl, —C1—C3 haloalkyl, —aryl, —C(O)N(Ra)(Rb), —C(O)RC, —COzRF, —SOzN(Ra)(Rb), 0]" —SORC, and each Ral and Rb is independently H, or C1—C6 alkyl. In some embodiments, each R? is Me. In some embodiments, each R3 is H. When R3 is aryl, the aryl may be, for example, a substituted or unsubstituted phenyl or naplithyl, {(3962} In ceitain embodiments, x, is 14. For example, x may be I, 2, 3, or 4. In some embodiments, x, is l or 2 and R1 is —F. {(3963} In ceitain embodiments, yi is L4, For example, y I may be l, 2, 3, or 4. In some embodiments, yi is 12. {(3964} In ceitain embodiments, yz is l or 2. {0065} In certain embodiments, ys is O or I. {seen} In ceitain embodiments, the porous polymeric material of the t disclosure comprises a plurality of extrins crosslinked with a plurality of crosslinks comprising formula. (II): wherein yz is l or 2; and x is l or 2. In some embodiments, yz is 2 and x is I. In some embodiments, each cyclodextrin is odextrin. {0067} In certain embodiments, the porous polymeric material of the t disclosure comprises a plurality of linkers of formula (III): E—O H N . N Ow l / Y N c c l@ 9 R4 . R4 Ci (III) {@968} wherein one R4 is —I—I and one R4 is —Me. In some embodiments, each cyclodextrin is [S—cyclodextrin. {@969} In various embodiments, the porous polymeric material of the present disclosure is prepared by crosslinking extrins of the same structure with crosslinkers of the same ure. In some embodiments, the porous polymeric al of the present disclosure is prepared by crosslinking cyclodextrins of the same ure with two, three, four, or more different inkers In various embodiments, the porous polymeric material of the present disclosure is prepared by inking two, three, or four different cyclodextrins (ie, having different structures) with crosslinkers of the same structure In some embodiments, the porous polymeric material of the present disclosure is prepared by crosslinking two, three, or four different extrins with two, three, four, or more different crosslinkers. {0070} In some embodiments, some of the crosslinks of the porous polymeric material do not include a cationic or anionic moiety (i,e., corresponding to group "Z" of formula (I)). In such embodiments, the porous polymeric material comprises a plurality of crosslinkers of formula (I) and a ity of crosslinkers having a structure r to that of formula (I), except that there is no cationic or anionic moiety corresponding to group "Z". So, for example, such crosslinkers lacking, a cationic or anionic moiety can have any of the crosslinker structures described in US, Patent No. 10,086,360, herein incorporated by reference for all purposes, including, for example a plurality of crosslinkers of the following structure (a): tag51104 \ ure l:a ll or the following structure (b): structure (b), or a combination of structures (a) and (b) (where x in structure (b) is 0,, l, 2, 3, or 4). In such embodiments of porous polymeric materials having crosslinkers of ure (a) and/or structure (b), such materials also include charged crosslinkers of formula (I) as described herein, {M371} In still other embodiments, the porous polymeric materials of the present disclosure comprise a plurality of cationic crosslinkers of the following structure (c): structure (0) (where X' is a pharmaceutically acceptable anionic counterion such as Cl ).

{M372} In still other embodiments, the porous polymeric als of the present disclosure comprise a ity of ic crosslinkers of the following structure (d): structure (d) Where x in structure d is O, l, 2, 3, or 4, and X" is a 10harniaceuticallv acce table anionic s P counterion such as Cl"). {0073} In still other embodiments, the porous polymeric materials of the present sure comprise a plurality of cationic crosshnkers of structure (c) and a plurality of cationic nkers of structure (d). As described , any crosslinkers of the present disclosure having an aromatic halide group can be modified to provide a charged moiety, for example by reaction with choline chloride under suitable conditions as described herein. {8074} In other embodiments, the porous polymeric materials of the present disclosure comprise a plurality of anionic crossiinkers of the following structure (6): (3* Va w; ure (e).

E9975] The cationic counterion for ure (e) (depicted as Na+) can atively be any other pharmaceutically acceptable cationic counterion such as, without limitation, H+ or In yet other embodiments, the porous polymeric materials of the present disclosure comprise a plurality of anionic crosslmkers of the following structure (f): structure (f) (where X in structure (f) is 0, l, 2, 3 or 4), {0077} In still other embodiments, the porous polymeric als of the present disclosure comprise a plurality of cationic crosslinkers of structure (e) and a plurality of cationic crosslinkers of structure (it)m {0078} In some embodiments, the present disclosure provides a porous polymeric material comprising a plurality of cyclodextrin moieties crosslinlred by one or more polyisocyanates. In some embodiments, the ity of cyclodextrins are B—cyclode’xtrin. In some ments, the one or more polyisocyanates are aiyl diisocyanates including but not limited to 2,4—toluene diisocyanate, 2,6—toluene diisocyanate, 4,4’~methylene diphenyl diisocyanate, ethylene diphenyl diisocyanate, 1,3"bis(isocyanatomethyl)benzene, l,3-bis(1—isocyanato—ln inetliylethyl)benzene, 3,3’"dichloron4,4’—diisocyanato~1,1’mbiphenyl, 3,3'mdimethyln4,4’n ylene diisocyanate, 4,4’—oxybis(phenyl isocyanate), 1,3—phenylene diisocyanate, 1,4" plienylene diisocyanate, ro—6—methyln1,3—plienylene diisocyanate, and lncliloromethylml?n diisocyanatobenzene, and combinations thereof. In some embodiments, the aryl diisocyanate is 2,4-toluene diisocyanate In some embodiments, the one or more polyisooyanates are aliphatic diisocyanates including but not limited to 4,4"—diisocyanato—methylenedioyclohexane (HMDI), hexamethylene diisocyanate (HDI), isophorone yanate , Lmlysine diisocyanate (LDI), trimethylhexametliylene diisocyanate (TIVIDI), s(i,soc-yanatomethyl)cyclohexane, 1,4— diisocyanatobutane, trimethyl—l ,6~diisocyanatohexane, 1,6—dii socyanato—2,2,4—trimethylhexane, transd ,4—cyclohexylene yanate, 1,8-diisocyanatooctane, l,l2—diisocyanatododecane, and combinations thereof, In some embodiments, the plurality of cyclodextrins are S-cyclodextrin and the one or more polyisocyanates are luene diisocyanates In some embodiments, the porous ric material has a Brunauer—Emmetheller (BET) surface area of about 10 mZ/g to 2000 m2/g. For example, in some embodiments, the porous polymeric material has a BET surface area of about l0 tog/g, 20 mz/g, 30 rnZ/g, 40 mZ/g, 50 mZ/g, 75 m2/g, 100 mQ/g, l50 1112/g, 200 rnZ/g, 250 mZ/g, 300 mz/g, 350 n12/g, 400 mZ/g, 450 mZ/g 500 mZ/g, 550 mZ/g, 600 mZ/g, 650 mZ/g, 700 mZ/g, 750 rn2/’g, 800 mZ/g, 850 n12/g, 900 mZ/g, 950 nil/g, 1000 m2,«’g, 1050 rn2/’g, 1100 rnZ/g, 1150 mZ/g, 1200 n12/g, 1250 mZ/g, 1300 mZ/g, 1350 m2/g, 1400 mZ/g, 1450 n12/g, 1500 mZ/g, 1550 mZ/g, 1600 mZ/g, 1650 rn2/'g, 1700 mZ/g, 1750 , 1800 m2,«’g, 1850 rn2/’g, 1900 rnZ/g, 1950 mz/g to about 2000 n12/g, including all integers and ranges therebetween. In some embodiments, the porous polymeric material has an amine content from about 0 nimol/g to about 1.0 mmol/g. In some embodiments, the porous polymeric material has an amine content from about 0.1 mmol/g to about 1.0 mmol/g. In some embodiments, the porous polymeric material has an amine content from about 0.15 mmol/g to about 0.35 mmol/g. For example, in some embodiments, the amine content may be about 0.1 5 mmol/g, about 0.16 mmol/g, about 0.17 mmol/g, about 0.18 mmol/g, about 0.19 , about 0.20 mmol/g, about 0.21 mmol/g, about .22 mmol/g, about 0.23 mmol/g, about 0.24 mniol/g, about 0.25 rnmol/g, about 0.26 rnmol/g, about 0. 27 nimol/g, about 0.28 mmol/g, about 0.29 mmol/g, about 0.30 rnmol/g, about 0.31 mmol/g, about 0.32 , 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 discovered that by using asnis CD (ie. undrietl) in the polymer synthesis, the resulting polymer had a higher amine content than similar rs described in the prior art, which led to higher affinity for some niicropollutants such as PFASS. {00791 In certain ments, the molar ratio of cyclodextrin to linking groups of formula (I), (11), or (_111) ranges from about 1:1 to about 1:X, wherein X is three times the e number of glucose subunits in the cyclodextrin In certain embodiments, the molar ratio of cyclodextrin to linking groups of formula (I), (II), or (III) is about 1:6 In certain embodiments, the molar ratio of cyclodextrin to linking groups of formula (I) (II), or (III) is about 1:5~ In ceitain embodiments, the molar ratio of cyclodextrin to linking groups of formula (I), (II), or (III) is about 1:4. In certain embodiments, the molar ratio of cyclodextrin to linking groups of formula (I), (II), or (III) is about 1 :3. In certain embodiments, the molar ratio of cyclodextrin to linking groups of a (I), (II), or (111) is about 1 :2. In various embodiments, the molar ratio of extrin moieties to aryl crosslinking moieties is about 1:1 to about 1:24, including about 1:1, about 1115, about 1:2, about 1:25, about 1:3, about 1 :35, about 1:4, about 1 :45, about 1:5, about 1:55, about 1:6, about 1 :65, about 1 :7, about 1:75, about 1:8, about 1:85, about 1:9, about 1:95, about 1:10, about 1:105, about 1:11, about 1:115, about 1:12, about 1:125, about 1:13, about 1:135, about 1:14, about 1:145, about 1:15, about 1:155, about 1:16, about 1:165, about 1:17, about 1:175, about 1:18, about 1:185, about 1:19, about 1:195, about 1:20, about 1:205, about 1:21, about 1:215, about 1:22, about 1:225, about 1:23, about 1:235, or about 1:24, including all ranges of ratios therebetween. In an ment, the molar ratio of cyclodextrin moieties to aryl crosslinking es is about 1:25 to about 1:10. 10080} In some embodiments, a composition according to the present disclosure comprises one or more porous polymeric materials of the present disclosure and one or more support materials, where the porous polymeric material is bound (e.g covalently, adhesively, or mechanically bonded as described herein) to the support material. For example, in some embodiments, the composition comprises porous ric materials comprising a plurality of cyclodextrins crosslinked with a plurality of crosslinks comprising formulatil), and/or (II), and/or (HI).

Examples of support materials include cellulose (eg, cellulose fibers), carbon—based materials such as activated carbon, graphene oxide, and oxidized carbon materials, silica, alumina, natural or tic polymers, and natural or synthetic polymers modified to e surface hydroxyl groups. One of skill 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 material if the porous polymeric material is adhesively bonded to the support via a suitable binder material. In an embodiment, the composition is in the form a membrane or a column packing material. In an embodiment, the support is a fiber (eg. a cellulose, nylon, polyolefin or polyester fiber). In an embodiment, the support is a porous particulate material (eg, porous silica and porous alumina), In an embodiment, the support is a woven or non~woven fabric, In an embodiment, the support is a t (such as a tive garment) or a surgical or medical drape, dressing, or sanitary article. {0081} In some embodiments, the P~CDP may be grafted or bonded (eg chemically or mechanically bonded) onto a support to provide an ent where the particle size and logy are well-controlled to give ideal flow characteristics The term nical boni " refers to a bond formed n two als by pressure, ultrasonic attachment, and/or other mechanical g process without the intentional application of heat, such as mechanical entanglement. The physical entanglement and wrappii'ig 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 chemical grafting. In some embodiments, the RED? may be grafted or bonded (cg, chemically or ically bonded) onto a t to provide an adsorbent where the le size and morphology are further engineered (e.g by granulation or milling) to e particles with a wellucontrolled size and morphology to give ideal flow characteristics. {8082} 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 P~CDPs to a substrate surface through coupling reactions between one or more functional groups on the P~CDP and one or more onal groups on the ate. In some embodiments, grafting includes an "in situ" process as described herein in which cyclodextrins, g groups of the present disclosure, and a substrate having surface bound nucleophiles (eg, by dro'xyls) are reacted together such that the linking groups of the present disclosure reacts with the hydroxyl groups of the cyclodextrins and the surface nucleophiles of the ate, forming a P—CDP which is partially honded via one or more linking groups of the present sure to the substrate. The substrate having surface hound nucleophiles include, but are not limited to hydroxyls (such as microcrystalline cellulose), amines, phosphines, and, thiols. {0083} In some embodiments, "grafted" P—CDl’~support complexes are prepared by first synthesizing the s in a dedicated chemical reactor with te control of the reaction conditions and material purification to e optimized P-CDP les. The PnCDPs are then chemically reacted with a suitably functionalized substrate. For example, a substrate onalized with carboxylic acid groups (or activated fornis thereof such as acid halides, anliydrides, etc. known in the ant) can react with one of more hydroxyls on the P—CDP 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 le reaction chemistries can be contemplated, such as reactions between carboxylic acids (and derivatives thereof) and hydroxyls to form ester bonds, reactions between carboxylic acids (and derivatives thereof) and amine groups to form amide bonds, reactions between nates and ls to make urethanes, reactions between isocyanates and amines to make ureas, reactions between cyclic carbonates and amines to make urethanes, reactions n thiols and alkenes or alkynes to make thioethers, reactions between epoxides and amine groups, photochemical reactions between acrylates, niethacrylates, thiols etc, and olefins, and so forth.

The ve functional groups described herein can be on either of the P—CDP or substrate provided the reaction forms a covalent bond between the substrate and the PuCDP. For example, of the reactive functional groups are yls and carboxylic acids (forming an ester bond after reaction), the hydroxyl groups can be present on the PuCDP and the carboxyl groups on the substrate or viceuversa. {8084} 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 ate, and under suitable conditions can react with a suitably functionalized PuCDP to for a nt bond between the P—CDP and the primer. {8085} The P—CDP particles may be engineered to achieve specific particle sizes. In some embodiments, the P—CDP is ed in the form of crosslinked particles which may require further reduction in size (e.g., for the es of forming stable dispersions or slurries, or in providing optimal flow characteristics). A variety of means that are readily nt to a d n can be employed to reduce the particle size of the PnCDP such as grinding or g.

Grinding and milling can be employed to create smaller particles with sizes less than 1 micron.

Typical milling operations can be used by a skilled artisan and include both wet and dry milling.

Milling can be employed through a y of methods 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. Milling media includes, but is not limited to: metals, silicates, and other inorganic materials in various form s including, rods, balls, and irregular shapes. In some embodiments, the milling is performed on dry PmCDP 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. Emulsifying agents may be used and are readily apparent to a skilled artisan, including, but not limited to: small molecule and polymeric surfactant compounds with ie, anionic, or ic character. A skilled artisan will appreciate that using fine particulate form factors will enable a variety ofbenefi ts, such as ( l) more stable aqueous dispersions that remain homogeneous over time by resisting separation, (2) enable a high loading of material by weight in the dispersion with values of 50% by weight or higher, (3) e particulate matter that can be evenly coated or applied to various substrates, surfaces, fibers, yarns, fabrics and the like to produce a finished material with minimal perceptible changes in "hand," and (4) produce sions that are stable to dilution and blending with other emulsions or ons such as binders, surfactants, wetting agents, or softeners. In some embodiments, the final particle diameter es <1 micron, l_5 micron, 5— micron, lOml 5 micron, and 15—20 micron, or ranges therebetween. {8086} If larger particle sizes are desired, the composition may be granulated to form agglomerates of larger le size. Thus, in some embodiments, granules (cg, self~supporting es) are produced from PuCDP particle powders of various sizes. Broadly, this process will transform P—CDP particle powders in the size regimes ranging from lu3O microns to granules in excess of 100 microns, 200 microns, 300 microns, and larger. This process may be achieved via granulation techniques common to the pharmaceutical ry (Htmd'book Qmenuiarian ogy, Ed. Parikh, D. NI, 2005:. Taylor & Francis Group) in which the powders are bound together via physical and/or chemical means in batch or continuous modes. In the simplest form, particles of the P—CDP are blended mechanically with a fluid (cg, aqueous) mixture ning an adhesive binder — typically a synthetic, seminsynthetic, or natural polymer. Suitable semi" tic polymers that can be used include cellulose ethers, specifically ethylcellulose, methylcellulose. hydroxypropylcellulose, carboxymethylcellulose, starch and starch derivatives, and others. Suitable fully synthetic polymers such as polyvinylpyrrolidone or polyethylene glycol can be used. Other le binders include sizes and other coatings used in the textile ry and paper industries including polyamide amine epichlorohydrin (FAB) or polymeric glyoxal crosslinkers, nylalcoliol, and starch~based sizes. In order to create robust granules which are resistant to dissolution in water or other solvents, further covalent crosslinking may be facilitated via the addition of small molecule crosslinkers such as glyoxal, formaldehyde, diisocyanate, and/or diepoxide functionalities. In addition to covalent crosslinking electrostatic agglomeration of polyelectrolytes can also be utilized as a binding motif in which cationic polyelectrolytes form suitable ve properties when blended with anionic polyelectrolytes in the presence of P-CDP powders and/or support structures. Polyca‘tions can comprise those commonly used for flocculation including, but not limited to polydiallyldimethylammoniurn chloride (polyDADh/IAC), acidic polyethyleneimine, and rylamides. Polyanions can se those commonly used for flocculation including, but not limited to sodium polyacrylate, sodium polystyrene sulfonate, and polyvinylsulfonate. {@687} Mechanical ng during the granulation may be ed via low shear processes such as rotary drum mixing or overhead ical stirring. As will be readily apparent to a skilled artisan, the stirring rate and total length of stirring time effects the granule size. ation may also be ted in fluidized beds or via spray drying techniques. In each case, the PuCDP particle are combined with the aqueous or solvent borne mixture containing the binder compounds and the mechanical or physical agitation is conducted at a specified shear for a determined number of cycles. The resultant les will display a step growth change in their e 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 rial separations. 1111188} In some embodiments, the present disclosure provides a stable aqueous dispersion comprising P—CDP particles. In some embodiments, the P—CDP particles of the present disclosure, which can be used in such stable aqueous dispersions are from about 1 um to about 150 pm. For example, the PnCDP particles are from about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 2o, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 4s, 49, 5o, 51, 52, 53, 54, 55, 56, 57, 58, 59, so, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75:, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 9s, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113,114, 115,116, 117,118, 119,120,121,122, 123,124,125,126,127,128, 129,130,131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, to about 150 pm, A stable aqueous dispersion may be used in "grafting" ations. For example, the stable aqueous dispersion may be used in applications with chemical s or fibrillating fibers for mechanical loading and binding, and incorporation into thermally—bonded particulate pressed forms and into solution processed polymer form factors. {1111891 The P—CDP materials of the present disclosure can also be prepared on a support material (alternatively termed a "substrate"), for example covalently bonded, adhesively bonded, or mechanically attached to a support such as a fibrous substrate~ The support material can be any material that has one or more groups (e, g, hydroxyl or ainino, thiol, or phospl'iine, or other group as described herein) that can form an interaction (e, g, a covalent or mechanical bond) with a crosslinking agent or cyclodextrin. For example, one end ofa inking agent (e.g the linking groups of Formulas (1), (11), and/or (111)) is covalently bound to the substrate 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 activated ester bound to the cyclodextrin). It is desirable that the support al not ve (eg to an observable extent by, for example, 'visual tion, gravimetric methods, or spectroscopic methods) under use conditions, for example in aqueous media. Examples of t materials e, but are not d to, rystalline cellulose, ose nanocrystals, polymer materials (eg, acrylate materials, methacrylate materials, styrenic materials (e.g., polystyrene), ter materials, nylon materials, and combinations thereof or inorganic materials (eg silicates, silicones, metal oxides such as alumina, titania, zirconia, and hafma, and combinations thereof). In various examples, the polymer als are homopolymers, copolymers, or resins (e.g., resins sing polymeric als). The support material may be hydroxyl or amino containing polymer beads or irregular particles. The support material can be in the form a fiber (eg, pulps, short cut, staple fibers, and continuous nts), fiber bundles (e.g, yarn — both spun and uous filament), fiber mats (cg, nonwovens — both staple and continuous filament), fabrics (cg, knits, woven, ens), membranes (e.g, films, spiral wound, and hollow fibers, cloth, particulate (e.g., a powder), or a solid surface. In some embodiments, the fibrous substrate is a cellulosic substrate. Cellulosic ates can comprise any suitable form of cellulose, such as cellulose derived from plant sources such as wood pulp (e.g., 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 fibers, 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 t disclosure are bonded to fibers, for example, a cellulosic fiber or a fabric, such as cotton. {@690} In addition to the ates listed in the preceding paragraph, the substrate may include any of the following: polyvinylamine, polyethyleniinine, proteins, protein~based fibers (cg, wool), chitosan and amine-bearing cellulose derivatives, polyamide, vinyl chloride, vinyl acetate, polyurethane, melamine, polyirnide, polystyrene, polyacryl, ide, acrylate ene styrene (ABS), Barnox, PVC, nylon, EVA, PET, cellulose nitrate, cellulose e, mixed ose ester, lfone, polyether sulfone, polyvinylidene fluoride (PVDF) or polytetr'afluoroethylene (PFTE or Teflon R), polyethylene, polypropylene, polycarbonate, phosphine or thiol functional materials, and silicone or combinations thereof. The substrate may also consist of silicon or silicon oxide, or glass (eg. as ofibres). Suitable materials further include textiles or synthetic or natural fiberubased als. 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.

E0091] If necessary, the material surface may be activated by any method known in the art, such as known surface activation techniques, ing for instance corona treatment, oxygen , argon , selective plasma bromination, chemical grafting, allyl chemistry, chemical vapour deposition (CVD) of reactive groups, plasma activation, sputter coating, g, or any other known technique. For ce in the case of a glass surface, such an activation is y not required as such a surface is herein considered already activated. The e 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. ing its optional activation, the surface may be further functionalized. The purpose of the functionalization of the surface is to e for functional group suitable for the covalent attachment of a prencoat polymer. {0092} The skilled artisan is well aware of the various possibilities of attaching polymers to optionally activated es. These techniques generally involve the introduction of amino«, silane—, thiol—, hydroxy1~ and/or epoxy-functionalities to the surface, and the subsequent attachment thereto of the polymer.

The ?inctionalizati 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 aminoalkyl silane.

The P—CDP may be bound to the substrate via the linking groups of the present disclosure (eg. via a hydroxyl or amino group of the linking group). A "linker moiety" refers to the intervening atoms between the P—CDP and substrate. The terms "linker" and ng moiety" herein refer to any moiety that connects the substrate and P~CDP to one another, The linking moiety can be 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 ed to as a linking group. In some embodiments, g moieties are characterized by a first covalent bond or a chemical functional group that bonds the P~CDP to a first end of the linker 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 ns atoms osed between the P—CDP and substrate, independent of the source of these atoms and the reaction sequence used to size the conjugate. 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: unctional isocyanate (e.g., a diisocyanate), epoxy, carboxylic acid, ester, activated ester, cyanuric chloride, cyanuric acid, acid chloride, halogen, liydroxyl, amino, thiol, and phosphine. {0095} In some embodiments, the PnCDP is grafted or bonded onto microcrystalline cellulose (CMC). CMC is available in a variety of median particles sizes from about 10 — about 500 um including about 10 um, 20 um, 45 um, 50 pm, 65 um, 75 um, 100 um, 150 pm, 180 pm, 190 pm, 200 pm, 225 pm, 250 pm, 275 pm, 300 pm, 325 pm, 350 pm, 375 um, 400 pm, 425 pm, 450 pm, 475 um, and about 500 um and all particle sizes therebetween, In some embodiments, PuCDP is grafted 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 , in which the surface is treated to produce surface functional groups as disclosed herein, such as hydroxyl groups. {0096} In some embodiments, the P~CDP—substratc complex (eg, a P—CDP crosslinked with an aryl linker of formula (I)~CI\/IC substrate complex) has a polymer ess (ie, the ess 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 polymer thickness of about 1, 2, 3 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70 , 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, l050, IlOO, IlSO, I200, 1250, 1300, I350, I400, i450, 1500, 1550, 1600, 1650, i700, 1750, 1800, 1350, i900, i950, to about 2000 nm. In some embodiments, P—CDP—substi'ate complex has a polymer ess of less than 1000 nm. In some embodiments, P—CDP—substrate x as a polymer thickness of about 800 nm. As will be readily apparent to a skilled artisan, a having a lower ess (eg, less than 1000 nm) will allow for faster kinetics to absorb contaminants, for example aqueous contaminants. {0097} In some embodiments, the PuCDP—substrate complex (eg, a P—CDP crosslinked with an aryl linker of formula (1:)uCMC substrate complex) has a contaminant tion capacity of up to 500 mg contaminant/g CD. For example, the adsorption capacity may be up to about 1, 2, 3,4,5,6,7,8,9,10,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90,95,100,105, 110,115,120,125,130,135,140,145,150,155,160,165,170,175,180,185,190,195,200, 210,220,230,240,250,260,270,280,290,300,310,320,330,340,350,360,370,380,390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, to about 500 mg contaminant/g CD. In some ments, the adsorption capacity is up to about 200 mg contaminant/g Cl). In some embodiments, the contaminant is an anionic micropollutant (e. g. PFASs). In some embodiments, the cyclodextrin is [?—cyolodextrin. In some embodiments, the linking groups are the linking groups of Formulas (I), (II), and/or (III). {0098} In some embodiments, the l’~CDl’—substrate complex (e.g, a P—CDP crosslinked with an aryl linker of a C substrate complex) has an equilibrium inant adsorption capacity of up to 500 mg contaminant/g CD. For example, the equilibrium adsorption capacity may be up to about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65:, 70, '75, 80,85,90,95,100,105,l10,115,120,l25,l30,135,140,145,150,155,l60,165,170,175, 180,185,l90,l95,200,2]0,220,230,240,250,260,270,280,290,300,3l0,320,330,340, 350,360,370,380,390,400,410,420,430,440,450,460,47o,480,49o,u3abouisooing inant/g CD. In some embodiments, the equilibrium adsorption capacity is up to about 200 mg contaminant/g CD. In some embodiments, the contaminant is an anionic mieropollutant (eg . In some embodiments, the cyclodextrin is [l—cyelodextrin. In some embodiments, the linking groups are the linking groups of Formulas (I), (II), and/or (Ill). {6699} In some embodiments, the substrate complex (e.g, a P—CDP crosslinked with an aryl linker of formula (l)~Cl,\/IC ate complex) has a relaxation time of less than 2 minutes, As will be appreciated by a d artisan, where processes with high relaxation times slowly reach brium, while processes with small relaxation times adapt to equilibrium quickly. In some embodiments, the contaminant is an anionic: i'nieropollutai'it (e.g PFASs). In some embodiments, the eyelodextrin is B-cyclodextrin. In some embodiments, the linking groups are the linking groups of Formulas (I), (II), or (III). {@0100} In some embodiments, any of the P-CDP materials disclosed herein are grafted or bonded onto CMC directly or via a linker group as defined herein. In some embodiments, the P- CDP is homogenously distributed on the CMC surface. In some embodiments, the aryl linker is an aryl linker of formula (I). In some embodiments, the aryl linker is a linking groups of Formula (II). In some embodiments, the aryl linker is a linking groups of Formula (111). In some embodiments, the median particle size is about 50 pm. In other embodiments, the median le size is from about 1 about 250 pm. {08101.} CMC can also be guished by a le shape known to impact flow characteristics among other things. A miting list of particle shapes includes spherical (round—shaped), rod— shaped, and —like. Particles can also be described as flat, flat and elongated, or be characterized by their aspect ratio. In some embodiments, the CMC has a spherical particle shape. In some embodiments, the CMC is present in the form of agglomerates of smaller CMC particles. Such CMC agglomerates can have le sizes in the range of 200 pm up to about 2 mm. For example, the particle sizes of CMC agglomerates can be about 200 um, about 300 um, about 400 pm, about 500 um, about 600 um, about 700 um, about 800 um, about 900 um, about 1 mm, about 1.2 mm, about 1.3 mm, about 14 mm, about 1.5 mm, about 1.6 mm, about 1.7 mm, about 1.8 mm, about 1.9 mm, or about 2 mm, inclusive of all ranges therebetween. 300102} In some embodiments, the PnCDI’ is grafted or bonded onto CIVIC via a linking groups of Formula (I). In some embodiments, the PnCDI’ is grafted or bonded onto CIVIC via a linking groups of Formula (la). In some embodiments, the P—CDP is grafted or bonded onto CMC via a linking groups ofFormula (II). In some embodiments, the RCMP is grafted or bonded onto CMC via a linking group of Formula (III), 3} In some embodiments, P~CDP of the present disclosure is grafted or bonded onto CMC via an aryl linker, and the aryl linker is homogenously buted on the CMC l In some embodiments, the median particle size is about 100 nm {M3104} In addition to the use of CMC as illustrated herein, examples of other potential support materials include those materials described above, such as activated carbon, graphene oxide, as well as silica and alumina. {(10105} In some embodiments, it is desirable that the supported P~CDP materials disclosed herein (eg, a P—CDP crosslinked with an aryl linker of formula (I)~CMC ate complex) are in the form of particles having a narrow dispersity of particle sizes. In some embodiments, the paiticle size distribution has a low relative span of about 5 or less, where relative span is defined by the ratio (Dim—Dioy'Dm, where D90, D50, and 1310 are, respectively 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, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 01, including all ranges tlierebetween.

} In other various embodiments, the PuCDP may be d or bonded onto cellulose nanocrystals (CN Cs). CN Cs are the cry stalline regions of cellulose mierofibrils obtained after mechanical, al, and enzyme treatments. Depending on the source and, preparation method, CNCs are available with lengths ranging from about 1,1000 nm and, widths ranging from about 350 nni, inclusive of all values therebetween. For example, the CNCs have a length of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, '75, 80, 85, 90, 95, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, to about 1000 nm. The CNCS have a Width of about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, I5, 16, 17, 18, 19, 20, 21, 22, 2 , 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or about 50, In some embodiments, the P~CDP~CNC substrates may be 2- 3 times the size (length and width) as the unbound CNCs. The CNCs are further characterized by aspect ratio values (LID) ranging from about 2~100 e, I, et al., Cellulose nanoorystals: synthesis, functional properties, and applications, ,z‘v’anotechnoiogyg Science airszpplz’mtz‘ons, 2015;845—54), For example, the CNCs have an aspect ratio of about 2, 5, 10, 15, 20, 25, 30, '35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 9o, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160,165, 170, 175,180, 185, 190, 195, or 100. {00107} In some embodiments, the PCB? is grafted or bonded onto CNC via the linking groups are the g groups ofFormulas (I), (ll), and/or (III) as described herein. In some embodiments, the P-CDP is grafted or bonded onto CIVIC via a linking groups of Formula (I). In some embodiments, the P~CDP is d or bonded onto CMC via a linking groups of a (II). In some embodiments, the P—CDP is grafted or bonded onto CMC via a linking groups of Formula (HI). {00108} In some embodiments, P~CDP is grafted or bonded onto CNC via a linker, and the linker is l'1omogenously distributed on the CNC crystal. In some ments, the median particle size is about 100 nm. {88109} CNC can also be distinguished by particle shape known to impact flow characteristics among other things. A nonulimiting list of particle shapes es cal —shaped), rod— shaped, and —like. Particles can also be described as ?at, flat and elongated, or be characterized by their aspect ratio. In some embodiments, the CNC has an aspect ratio of between about 5 to about 100. For examples, the aspect ratio may be about 5, IO, 15, 20, 25, 30, , 40, 45, 50, 55, 60, 65, '70, 75, 80, 85, 90, 95 to about 100. 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 erates of smaller CNC particles. Such CNC agglomerates can have particle sizes which are 5~l00 times larger than the sizes of the individual particles, ing on the sizes and number of the particles constituting the aggregates. {00111)} In some embodiments, the substrate is a fabric or fiber. Thus, in some embodiments, the present disclosure provides a composition comprising a PnCDP grafted, or bonded, (e. g, chemically or mechanically) to a fiber. In some embodiments, the P~CDP is grafted or bonded onto a fiber Via the linker of formulas (I), (II), and/or (III), as described herein. In some embodiments, the fiber is a nonwoyen fiber. In some embodiments, the present disclosure provides a composition comprising a P—CDP grafted or bonded (eg chemically, vely, or mechanically) to a fabric. In some embodiments, the RCMP is grafted or bonded onto a fabric via the linker of formulas (I), (II), or (HI), {00111} Fibers suitable for use include, but are not limited to fibers comprising any of the rs disclosed herein, for example fibers made from highly oriented polymers, such as gel— spun ultrahigh molecular weight polyethylene fibers (e.g, SPECTRA® fibers from Honeywell Advanced Fibers of tovv'n, NI and DYNEMA® fibers from DSM High Performance Fibers Co~ of the Netherlands), melt-spun polyethylene fibers (eg, CERTRANG’S) fibers from Celanese Fibers of Charlotte, NC), melt~spun i'iylon fibers (_ e~g high tenacity type nylon 6,6 fibers from Invista of Wichita, Kans), melt—spun polyester fibers (e.g high tenacity type polyethylene terephthalate fibers from Invista of Wichita, Kans.), and sintered polyethylene fibers (eg, ’I‘ENSYLONQ‘) fibers from ITS of Charlotte, NC.) Suitable fibers also include those made from rigidurod polymers, such as lyotropic rigidmrod polymers, heterocyclic rigid~rod polymers, and therrnotropic liquid—crystalline polymers. Suitable fibers also include those made from rated cellulose including ve wet spun Viscose rayon (Viscose from Birla of lndia or Lenzing of Austria), cuproammonium based ray on (Cupro® Bemberg from Asahi Kasei of Japan), or air gap spun from M‘s/[MO t ('I'encel® from Lenzing of Austria). Suitable fibers made from lyotropic rigidurod polymers include aramid fibers, such as poly(pu phenyleneterephthalamide) fibers tog, GE fibers from DuPont of Wilmington, Del. and ’1"ML\RON® fibers from Teijin of Japan) and fibers made from a 1:1 copolyterephthalamide of 3,4’mdianiinodiphenylether and pnphenylenediamine (eg, 'l'ECHNORA® fibers from Teijin of Japan). Suitable fibers made from heterocyclic rigidmrod polymers, such as pnphenylene heterocyclics, include nphenylenen2,6-benzobisoxazole) fibers (PBO fibers) (eg, ZYLON® fibers from Toyobo of , poly(pnphenylenen2,6~benzobisthiazole) fibers (PBZT fibers), and, poly[2,6—diimidazo[4,5—b:4",5’—e]pyridinylene—l,4—(2,5ndihydroxy)phenylene] fibers (PIPE fibers) (eg, MS® fibers from DuPont of gton, Del). Suitable fibers made from therinotropic vcrystalline polymers include poly(6—hydroxy~2~napthoic acid—coali— hydroxybenzoic acid) fibers (eg, VECTRAN® fibers from Celanese of Charlotte, NC.) Suitable fibers also include carbon fibers, such as those made from the high temperature pyrolysis of rayon, polyacrylonitrile (e.g., OPP® fibers from Dow of Midland, Mich), and mesomorphic hydrocarbon tar (eg, THORNEL® fibers from Cytec of Greenville, SC.) In n possibly preferred embodiments, the yarns or fibers of the textile layers comprise fibers ed from the group consisting of gel—spun ultrahigh molecular weight polyethylene fibers, rnelt~spun polyethylene , melt—spun nylon fibers, pun polyester fibers, sintered polyethylene fibers, aramid fibers, PBO fibers, PBZT fibers, PIPD fibers, poly(6—hydroxy—2— napthoic acid—co—4—hydroxybenzoic acid) , carbon fibers, and combinations tl’iereof. {00112} The P—CDP materials of the present disclosure can be adhered to such fibers by means of a suitable binder polymer as described herein, or chemically bonded to such fibers by functionalizing the surface of the fibers as described herein (eg, surface oxidation to produce e 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 linker moiety as described herein. {00113} The fibers may be converted to nonwovens (either before or after attachment of the P— CDP) by ent bonding methods. Continuous fibers can be formed into a web using industry standard spunbond type technologies while staple fibers can be formed into a web using industry standard carding, airlaid, or wetlaid technologies. Typical bonding methods e: calendar (pressure and heat), thru—air heat, mechanical entanglement, ynamic entanglement, needle punching, and chemical g and/or resin bonding. The calendar, ir heat, and chemical bonding are the red bonding s for the starch polymer fibers. 'l‘hermally bondable fibers are required for the pressurized heat and thru—air heat bonding methods. {00114} The fibers of the t invention may also be bonded or combined with other synthetic or natural fibers to make nonwoven articles. The synthetic or natural fibers may be blended er in the forming s or used in discrete layers. Suitable synthetic fibers include fibers made from polypropylene, polyethylene, polyester, polyacrylates, and copolymers thereof and mixtures thereof. l fibers include cellulosic fibers and derivatives thereof.

Suitable cellulosic fibers include those d from any tree or vegetation, including hardwood fibers, softwood fibers, hemp, and, cotton. Also included are fibers made from processed natural osic resources such as rayon.

} 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 15% of a plurality of fibers that are continuous or non—continuous and ally and/or chemically attached to one another. The nonwoven may be combined with additional nonwovens or films to e a l' jered product used either by itself or as a component in a complex, combination of other materials. Preferred articles are disposable, nonwoven articles. The resultant products may find use in filters for air, oil and water; textile fabrics such as micro fiber or breathable fabrics having improved moisture and odor absorption and softness of wear; electrostatically charged, structured webs for collecting and removing dust and pollutants; medical textiles such as surgical drapes, wound dressing, bandages, dermal s; textiles for absorbing water and oil for use in oil or water spill clean—up, etc. The articles of the present ion may also include disposable nonwovens for hygiene and medical applications to absorb off~odors Hygiene applications include such items as wipes; diapers, particularly the top sheet or back sheet; and feminine pads or products, particularly the top sheet. {00116} 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 1 to about 50 denier per filament (l to about 50 g per 9000 meters). The yarns contain a plurality of filaments from 10 to about 5000. {08117} In some embodiments, the PuCDP is adhesively bound to a substrate such as a fiber or fabric via a binder. In some embodiments, the P—CDP is coated on a substrate such as a fiber or fabric via a binder. In some embodiments, the P—CDP is bound to or coated on a substrate such as a fiber or fabric via a binder by introducing the surface to stable aqueous dispersions of the P— CDP particles in conjunction with binders. The P—CDP particle dispersion may be 1~50% by weight and a polymeric binder material may be present in an emulsion or solution in 1~50% by weight. For example, the P—CDP particle dispersion may be present at about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 2o, 21, 22, 23, 24, 25, 26, 27, 23, 29, 30, 31, 32, 33, 34 , 36, 5'7, 58, 59, 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 1, 2, 5, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 2o, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 3,1 32, 33, 34, 35, 36, 37, 38, '39, 40, 41 or about 50 % by weight. Additional auxiliary , 42, 43, 44, 45, 46, 47, 48, 49, agents can be used as minor components by weight to control the wetting hy the substrate (wetting agent), solution foaming or de—foaming, softening agent for ate hand, and/or catalyst for binder .

} A variety of g techniques known in the art can be applied, such as: dip and squeeze, solution casting, foam coating, or spraying of the formulated solution onto the ate of interest. ates include, but are not limited to: woven, knit or nonwoven fabrics, 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 1oinder will be present, During the drying process, the binder material present as an emulsified polymer will flow together and become a continuous phase. Depending on the choice of binder, the P—CDP particles may be held in place h mechanical means or on to the binder continuous phase only, or additional nt linkages could be present if a cure—able binder is ed. Such covalent linkages could extend the underlying substrate which would r increase the durability of the P—CDP particle coating. {00119} As will be readily apparent to a d artisan, the resultant PuCDP particle film 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 particles have access to the s 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, pleated filters, nonwoven needlepunched filters, hygienic nonwovens, and apparel. {00120} A variety of binders known to a skilled artisan may be used in the context of the present disclosure, such as any of those sed in US Patent ation No. 20l4/Ol7845'7 Al, which is hereby incorporated by reference in its entirety. Suitable binders include, but are not limited to, latex binders, isocyanate binders (e.g, blocked isocyanate s), acrylic binders (e.g, nonionrc acrylic binders), polyurethane binders (e.g, tic ethane binders and polyether based polyurethane binders), epoxy binders, urea/formaldehyde resins, melamine/formaldehyde resins, polyvinylalcohol (PvOH) resins (disclosed in US Patent No. ,496,649, which is hereby incorporated by reference in its ty) and crosslinked forms thereof, poly—ethylenevinylalcohol (EvOH) and crosslinked forms thereof, polym ethylenevinylacetate (EVA), starch and starch tives, cellulose ether derivatives, and ose ester derivatives, Small molecule, polymeric or inorganic crossliiiking agents could be used additionally including formaldehyde, glyoxal, diisocyanates, diepoxides, and/or sodium tetraborate, and combinations thereof. {00121} In some embodiments, the P—CDP particles are mechanically bound to a surface, such as a fibrillating fiber Fibrillatiiig 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®), fihrillating regenerated cellulose (such as Lenzmg TM) or fibrillating acrylic (such as Sterling Fibers CFFTM) are deployed in wet laid processes to create lty 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 entirety), Onxy Specialty , Helsa 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.

} In the paper making process, an aqueous dispersion or slurry blend of short cut fibers (such as wood pulp, polyester, nylon, or polyolefin), fibrillating fibers (such as Fybrel®, ’llencelTM, or , and particle powder material are mixed (eg, under high shear). This mixture can then be rapidly passed through a nonwoyen mesh or screen to t a wet laid nonwoven web. This web is dried (eg, in hot air oven or on heated rolls) to remove the water carrier. Further bonding may be achieved through cold or hot calendaring either in flat format or with a patterned roll to e the bonded specialty paper. The particulate powder used can be a sion 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, nonwoyen can be as high as 60% by weight. The particulate can be used alone or blended with other particulate such as powdered activated carbon. Additional chemical binders, such as those described herein, may be used to alter or enhance the ties of the paper and will be applied, as one skilled in the art. {@9123} The ant powder loaded, papers are le to a high loading of P~CDP adsorbent particles in a ient 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 bended into a filter media {00124} In some embodiments, the PnCDP particles are ically entangled in yarn (eg, continuous filament yarn), In some ments, the P—CDP particles are mechanically entangled in uous filament yarn. As will be readily apparent to a skilled artisan, a special subset of yarn finishing s the mechanical binding of particulate matter within a continuous filament yarn in some circumstances. When a yarn (eg, continuous filament) comprised of multiple filaments of a l synthetic polymer such as polyethyleneterephthalate (PET) or polyamide (nylon 6 or nylon 6,6) that bears n'iicrofibrillating tendencies on each filament surface, there exists the possibility to incorporate particulate within the yarn bundles. The P— CDP particles of the present disclosure can be incorporated into the yarn in a variety of ways.

One non—limiting example is to apply a sion 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.

In this process, the filaments are rnecl'ianically separated 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 bundle. 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 solution. This process enables the application of dispersion particles within the yarn bundles that are held in place by the continuous filaments and microfibrils emanating from the continuous filament surface. Such approaches have been used to apply s niicron sized particles to continuous filament yarns, ing apsules (US Patent ation No. 2005/0262646 Al which is hereby incorporated by reference in its entirety), metallic silver microparticles (US Patent Publication No. 361595 Al which is hereby incorporated by reference in its entirety), and (US Patent Publication No. 2006/0067965 A1, 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. {00125} In some embodiments, the l’~CDP particles are incorporated into thermally—bonded, particulate pressed forms. A common form factor for powdered absorbent material is in therniallynbonded pressed forms. Such form factors can contain as high as 95% by weight P~ CDP particles, with the addition of fibrillating fibers (Fybrel®, 'I'encelTM, or CFFTM), sometimes inorganic materials such as attapulgite clays, and finally an organic binder material (most typically cellulose esters and similar derivatives) to create a porous composite structure with te mechanical strength and particulate g efficiency for medium pressure filtration applications such as faucet filters and refrigerator filters (US Patent Nos, 5,488,021 and 8,167,141, both of which are hereby incorporated by reference in their entireties) {W126} P—CDP dry particles or sion can be used in place of or blended with other adsorbent materials to form such a composite adsorbent P—CDP paiticulate—containing forms as described above~ In such embodiments, the solid dry components may be dry blended, optionally ing dry P-CDP particles and organic binder powder with or without inorganic clays and/or fibrillating fibers, If an aqueous dispersion of P—CDP les is used, they may be diluted with water and added to the mixture. Water is added (e~g in 80~l 50 wt%) and the mixture is blended (eg under high shear) to create a c material. This material may be formed into the desired form factor, dried and cured at temperatures ranging from 125 to 250 "C.

This final form factor presents the P~CDP ent particles in a form factor common to and useful for point of use water filters, } In some embodiments, the P~CDP particles are incorporation into solution processed polymer form factors. 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 controlled pore size. In some embodiments, a polymer such as cellulose acetate dissolved in a water miscible organic solvent such as NMP, DMSO, or THF 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 membrane filter for use in micro—filtration, ultranfiltration, gas filtration, or reverse osmosis ations. In place of cellulose acetate, common polymers used include polyamides, polyolefins, polysulfones, polyethersulfones, nylidene fluoride, and similar engineered thermoplastics. It is also possible to extrude hollow fibers into the aqueous solution to create membrane fibers through the phase inversion process that are known as hollow—fiber membranes commonly used for dialysis, reverse osmosis, and desalination applications. {@9128} In some embodiments, the PnCDP particle matter is incorporated into ne material to enhance the performance of the membrane als. For example, it is possible to have present in the aqueous coagulation bath a small quantity of P—CDP le dispersion that will become incorporated into the dense portions or porous portions of the membrane during the phase ion process. A, second manner to incorporate the P~CDP particles into the membrane is the incorporation of a small amount of wellvdispersed particles into the c solution of the membrane polymer that become encapsulated in the membrane following coagulation. Through each of these methods? the production of P-CDP loaded polymer forms may be d. In various embodiments, such as micro—filtration, filtration, and reverse osmosis, the P—CDP particle incorporation acts to enhance the n'iicropollutant ren'ioval of the membrane . {@6129} In some embodiments, the PCT)? les are orated into melt extruded th er'rnoplastics (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 thermoplasti cs of use e polyethyleneterephthalate, co—polyesters, polyolefins, and ides. Typical extrusion temperatures are between 0 "C and therefore PuCDP particle 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 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 1 to 20 denier per filament. A common particle added to most thermoplastic fibers is titanium dioxide added to whiten and deluster the fiber. The PnCDP particles will be added in a similar fashion. In the most ideal embodiment, the PnCDP particles will migrate to the e of the fibers and bloom due to their higher surface energy such that a n of the particles are present 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 ECU? particles that bloom to the surface and become active for the removal of small molecule micropollutants (eg. anionic Will’s) from the vapor and liquid phase.

} 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, e.g in a cellulosic material such as paper or other non—woven forms, or extruded or pressed into various shapes le for, e.g., filtration, water treatment, sample absorption, etc. as described herein. {@0131} While it is not unknown to provide adsorbents in a ted form, it is ant that the methods used to affix the adsorbent to the substrate or support are sufficiently robust so as to withstand the use conditions. r, the means of attachment to the substrate should not interfere with or block the adsorption mechanism of the adsorbent. The adsorbents disclosed herein can be attached to ts, as described herein, so that the resulting performance characteristics are only minimally affected by the attachment method. in various embodiments, the ted polymeric materials of the present invention provide mance characteristics which are at least 50% of the same performance characteristic 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 PuCDP crosslinked with an aryl linker of formula (um/K: substrate x) may have at least 50% of one or more of a particular mance teristic found in unsupported porous material tested under the same conditions. {00132} In some embodiments, the performance characteristic can be the amount of uptake l:adsorption ty) of a particular pollutant, measured as the milligrams of pollutant adsorbed per gram P—CDP particle under particular ions. In other ments, the performance characteristic can be the equilibrium adsorption capacity (qe), defined as discussed herein as: C910" qt? m Limax CIQKVL+1 wherein qmax (mg pollutant/g ent) is the maximum adsorption capacity of the sorbent for a particular pollutant at equilibrium, KL (mol‘j') is the brium constant and Ce (inM) is the pollutant tration at equilibrium {00133} In 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 adsorbent. This rate can be expressed as the time required for a supported or unsupported PmCDP of the present disclosure to reach equilibrium for a particular adsorbed species (or pollutant), {00134} In still other embodiments, the mance 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 ted carbons (powdered or ar), ion- exchange resins, and specialized resins used for solid—phase n'iicroextraction (eg, I-ILB) {00135} For any of these mance characteristics disclosed above, the performance of the supported P—CDP of the present disclosure is at least about 50%, 60%, 7004:, 80%, 90%, l0t %, 120%, 140%, 160%, 180954;, 200%, 220%, 240%, 260%, 280%, 300%, 350%, 400%, 450%, 500% or greater, inclusive of all values, ranges, and subranges therebetween compared to unsupported P~CDP of the same ition, tested under essentially the same conditions, eg, with the same pollutant, temperature, pressure, re time, etc, {00136} The performance teristics of the present disclosure can be measured, for example based on bisphenol A or PFASs or another suitable specie as disclosed herein, by a variety of methods which will be readily apparent to a skilled artisan. For example, the contan'iinant may be measured at initial concentrations of EPA or another suitable specie g from 1 ppb (or l microgram/L or 5 nM) to l ppt (or 1 g/L or 5 leI) in any aqueous sample, including but not limited to drinking water, wastewater, ground water, s extracts from contaminated soils, landfill leachates, purified water, or other waters containing salts, or other organic matter. The pH may be range from 0—14. For example, the pH may be 0, l, 2, 3, 4, 5, 6, 7, 8, 9, 10, ll, 12, 13, or 14, inclusive of all ranges therebetween. The performance characteristics may be measured substantially as described herein (eg, in Examples 1 and 2), with routine cations (such as temperature and pressure) also being envisioned. {00137} In some embodiments, the present disclosure provides an article of manufacture comprising one or more P—CDPs or one or more P—CDP~substrate xes of the present disclosure. {08138} In an embodiment, the article of manufacture is protective ent. In an embodiment, the article of manufacture is clothing. For example, the article of manufacture is clothing comprising one or. more P—CDPs or one or rrrore P—CDPnsubstrate complexes of the present disclosure (eg, clothing such as a uniform at least partially coated with the porous polymeric material or. composition). In another e, the article is filtration medium comprising one or more P—CDPs or one or more substrate complexes of the present disclosure. The filtration medium can be used as a gas mask filter. In an embodiment, the article is a gas mask comprising the filtration medium In some embodiments, the article is an tion device. {00139} In another embodiment, the article is a solid phase microphase (SPl‘i/IE) extraction device comprising one or more BCDPS or one or rrrore P—CDPnsubstrate complexes of the present disclosure, where the P—CDPs or substrate complexes is the extracting phase the device } In 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— bstrate complexes of the present disclosure instead ofHIB media (hydrophilic/lipophilic balanced). The article with the one or more P—CDPs or one or more P~CDP~substrate complexes outperforms the HLB media {(36141} In another embodiment, the article is a device for liquid filtration of polar and semi— polar organic molecules. The device comprises one or more l‘nCD‘Ps or one or more FvCBll substrate cmnplexes of the t disclosure adhered within a fibrous web (as disclosed in US.

Patent No. l 12., which is hereby incorporated by reference in its ty). Other embodiments e the device comprising P-CDP powders fused via thermoplastic binder 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). {00142} The P—CDP materials of the present disclosure, in the various forms and form factors disclosed herein (including supported and unsupported P—CDP materials) can be used in any application in which it is desirable to te compounds (eg, anionic or cationic MP5) from a fluid {gases such as air, liquids such as water, aqueous beverages, biological fluids, etc). The P— CDP materials can be used to "trap" or adsorb desired species for further analysis or quantification (e. g, in analytical testing for environmental pollutants in air or water), to te mixtures (e.g, 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 sure can be used to purify a fluid (eg, by removing undesirable or noxious impurities), or can be used to isolate desirable compounds from a e or dilute fluid solution. 300143} In some embodiments, the present disclosure es a method of removing one or more compounds (eg. anionic MP5) 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 of the present disclosure or the supported porous polymeric material of the present disclosure for an incubation period; b) ting 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 material separated in step b), or contacting the porous polymeric material or supported porous polymeric al ted in step b) with a solvent, thereby ing at least a portion of the nds from the porous polymeric material or supported porous polymeric material; and dl) optionally isolating at least a, portion of the compounds ed in step c), or d2) determining the presence or absence of the compounds released in step 0), 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 [i—cyclodextrin moieties, In some ments, said determining is carried out by gas chromatography, liquid chromatography, supercritical fluid cl'iromatography, or mass spectrometry. In some embodiments, said contacting is by ?owing the aqueous phase across, over, around, or through the supported porous polymeric material. In some embodiments, the aqueous sample is contacted with the PuCDPusubstrate x under static conditions for an incubation period and after the incubation period the aqueous sample is separated from the porous polymeric material. ln some embodiments, the sample is a food and the compounds are volatile organic compounds. In some embodiments, the aqueous sample is drinking water, wastewater, ground water, aqueous extracts from contaminated soils, or ll leachates. In some embodiments, the sample is a perfume or fragrance and the compounds are volatile organic compounds. ln some embodiments, the compounds are anionic micropollutants, heavy metals, and/or dyes. In some embodiments, the compounds are anionic MPs, such as PFASS (eg. polyfluorinated alkyl compounds and/or perfluorinated alkyl compounds). In some ments, the PFASs are PFOA and/0r PFOS. {00144} 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 sure or the supported porous polymeric material of the present disclosure such that, for example, at least 50% to at least 99% of the one or more ants is bound to one or more of the cyclodextrin (eg, B~cyclodextrin) moieties of the porous polymeric al. For example, the s sample is flowed across, around, or through the porous polymeric material. In another e, 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 filtration) from the porous polymeric material. The method can be used to purify aqueous samples such as drinking water, ater, ground water, aqueous extracts from contaminated soils, and landfill leachates. In some embodiments, the organic compounds are anionic MP3, such as PFASs. {00145} In an ment, a, method of determining the presence or absence of compounds (eg, anionic MPs) in a sample comprises: a) contacting the sample with the porous polymeric material of the present sure or the supported porous polymeric al of the present disclosure for an incubation period (eg, 1 minute or less, 5 minutes or less, or 10 minutes or less); b) isolating the complex from a) from the sample; and c) heating the x material from b) or contacting the complex from h) with a t (eg, methanol) such that at least part of the compounds are then released by the porous material; and d) determining the presence or absence of any compounds, wherein the presence of one or more compounds correlates to the presence of the one or more compounds in the sample, or isolating (eg, by filtration) the compounds. For example, the determining (e.g analysis) is carried out by gas chromatography or mass spectrometry. For e, the sample is a food or beverage (eg, milk, wine, fruit juice (cg, orangejuice, applejuice, and grapeiuice), or an alcoholic beverage (eg, beer and spirits)) and the compounds are volatile organic compounds. The porous polymeric material or supported porous polymeric material can be the extracting phase in a solid phase microextraction (SPlViE) device. In some embodiments, the or’ranic corn ounds are anionic NOSb such as PFASs. {00146} In an embodiment, a method for removing compounds (eg, organic compounds) from a sample comprises: a) contacting the sample with the porous polymeric material of the present disclosure or the supported porous ric al of the present sure for an incubation period such that at least some of the compounds are sequestered in the polymer; b) isolating x from a) from the sample; c) heating the complex from b) or ting 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 compounds.

In some embodiments, the compounds are anionic 1V ' )s, such as PFASs. {00147} Avariety of compounds can be involved (cg, sequestered, detected, and/or isolated) in the methods. The nds can be organic compounds. The compounds can be desirable compounds such as tlavorants (cg, compounds that impact the palatability of foods) or pharmaceutical compounds (or pharmaceutical intermediates), contaminants (cg, PCBs, PEAS, etc), and/or adulterants In some embodiments, the compounds are anionic MPs, such as PFASs.

In some embodiments, the compounds are anionic MPs selected from the group consisting of rozil, oxybenzone, diclofenac, ioxynil, ketoprot‘en, naproxen, sulfamethoxazolc, warfarin, 2,4—dichlorophenoxyacetic acid, ric acid, ibuprofen, Z—metl'iyl—4—chlorophenoxyacetic acid, mecoprop, valsartan, pertluorobutanoic acid, perfluorobutane ic acid, peril uoropemanoic acid, per?uoropentane sulfonic acid, rohexanoic acid, pertluorohexane sulfonic acid, pcr?uoroheptanoic acid, periluoroheptane sulfonic acid, pertluorooctanoic acid, peril tane sulfonic acid, per?uorononanoic acid, pertluorononane sulfonic acid, pertluorodecanoic acid, perfluorodecane sulfonic acid, periluoroundccanoic acid, orododecanoic acid, perfluorotridecanoic acid, per?uorotetradecanoic acid, 2,3,3,3—tetral‘luoro—Z— (heptafluoropropoxy) propanoate, and combinations thereof. {00148} The cyclodextrins are chiral. In an embodiment, a chiral compound is sequestered, detected, and/or isolated. In an embodiment, a chiral colunm (eg, a preparative—scale or ical—scale column is packed with a chiral porous polymeric al or composition comprising chiral porous polymeric material) is used to separate and detect or isolate (or at least significantly enrich the sample in one enantiomer) a single enantiomer of a nd. {00149} In the s, 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 alcohols such as methanol or ethanol, and aqueous mixtures thereof). {00150} The following es are provided to illustrate the present disclosure, and should not be construed as limiting thereof.

Example 1: Synthesis of?—CDETDI polymer {00151} Reagents: BuCD; er, CavamaX W7 (Used as~is); Tolylene—2,4_diisocyanate (1131): Sigma Aldrich, 959/6, Product # 139853; N,N"Dimethylformarnide (EMF): Fisher Chemical, Certified ACS grade, Catalog# D1194; Water; Deionized (D1) water from Q system {00152} Procedure: {3—0) (60.0 g, 0.0529 mol, 1 eq.) was dissolved in 120 rnL Dh/[F in a 500 mL oneuneek round bottom 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 heating. After completely dissolving B—CD, TDI (368 g, 0.2115 mol, 4 eq.) was added subsequently to the flask at 80 °C.

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 1 h stirring, the crude product was ed 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 D1 water \ 2 times and 1.2 L methanol X 1 time During each cycle the washing time was 1 h.

After final filtration, wet solid product was transferred to an ating dish, which was placed into a vacuum oven at 80 °C to yield 726 g dry polymer. lt was ed that starting at a 6 equivalence of TDI and above, a hard gel is obtained which is difficult to work up. In contrast, TULCD ratios in the range of 2:1—5: 1 provide a powder material upon stopping the reaction with ol (Table 1). These polymers are also soluble in a variety solvents such as Dis/IF but not in water. See Fig. 5 for a further comparison of the polymers of Table 1.

Table 1: Synthesis of ?—CD—TDI polymers Material B—fggng Solvent 'l' PC) Time Yield Notes SL-2—001A 1:4 ous DMF 80 16 h 58% White powder* SL-—2—002E§ he ous DMF 80 16 h n/a Gel SL-Z-DOZC 1:8 Anhydrous DMF 80 13 h n/a Gel SL—2—002D 1:10 Anhydrous DMF 80 16 h n/a Gel SL004A 1:2 Anhydrous DMF 80 3 h 36% White powder SL-2~004B 1:3 Anhydrous DMF 80 3 h 55% While powder SL004C 1:4 Anhydrous DMF 80 3 h 61% White powder SL~2~004D 1:5 Anhydrous DMF so 3 h 72% White powder SL004E 1:5 Anhydrous DMF 80 3 h n/a Gel *Washed with methanol x 1, water x 2, and methanol x 1. {@6153} B~CD—TDT Optimization Studies {@0154} The B~CD—TDI polymer was r zed by checking the solubility of B~CD (as~is and dried) in regular and anhydrous DMF, the results of which are shown in Table 2.. As—is B~CD has a water con tent in the range of 12—14% water.

Table 2: Solvents and B-CD water content comparison in the synthesis of B-CD—TDI rs Solubility test Regular DMF Anhydrous DMF As-ls fi-CD 0.5 g/mL 0‘5 g/mL Dried 33—00 0.25 g/mL 0.22 g/mL {00155} As shown in Table 2,, the solubility of B—CD is significantly affected based on its water t. Consequently, when dried, ?nCD is used, the polymerization can only be carried out lower initial concentrations that impact reaction yields. In comparison, the water content of DMF is insignificant and therefore has less impact on the solubility? ing. us to use regular Dh/[F' in the reaction. A comparison of TDl polymers made via small and large scale batches is shown below in Table 3.

Table 3: A comparison of [3411331)] rs made via small and large scale batches Material ?nfgi'lm (anhydrous) {TDl} (motlL) T ("C) Time Yield volume SL~1~01OA 1:4] 4 ml. 176 80 3 h 79% SL—2—003 1:4] 120 mL 1.78 80 3 h 82% Water content of B—CD used: 14% {00156} It was previously understood that the use of dried li—CD and anhydrous solvents was al for making polyurethanetype CD polymers; however, as described , using c‘wet" solvents (also referred to as "regular" solvents) such as DMF and/or as~is li—CD, the resulting polymer is structurally different than the polymers described in the literature and are much more effective for PFAS sequestration, It was surprisingly ered that using wet/regular solvents resulted in partial isocgranate reduction, shown below in Scheme l for TDlr Scheme 1: Effects of water on nate groups of TDL NCO NCO {@6157} 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 crosslinking of B~CD and TD] under anhydrous conditions (eg completely anhydrous conditions). Additionally, the presence of free amines in the ?—CD-TDI polymer are believed to contribute to PFAS removal. The high amine and urea content provides a polymer that is structurally different from the prior art and which is more advantageous for the l of anionic micropollutants {eg PFAS). {00158} Elemental analysis data shows that final CD:TDl ratio is l:8~l :10 when a feed ratio of 1:4 is used, which suggests the presence of excess TD] units on cyclodextrins. Additionally, 1H Nl‘s/[R oscopy shows the presence ofv—"Cl-{a protons resulting from the amine functionalized phenyl unit (Fig. 3). Amine groups can be quantified using the "(31-13 peak at ~19 ppm that originates from a T‘Dl unit with amine groups on it. The ratio of that integration to total integration of ----C1-13 peaks provide the percentage of TDTs with amines. Since absolute TDT density can be calculated from the elemental analysis data, the concentration (mmol/g) of amine groups in the polymers can be calculated by correlating NTVIR and EA data. See Table 4. The B- CDnTDl polymer additionally tested positive in the chloranil test, further confirming the amine presence.

Table 4: Determination of amine content of BmCDnTDl polymers made with regular Dlva NMR integration (based on one BnCD unit) Elemental Analysis CD:TDl TDl:CD TDE:CD Sample (3H1 (total) CH3 ) Amine ("M [T1311 mmoiig {Amine} mmoi/g feed ratio ratio ratio SL—1-0‘10A 114.7 0.15 SL—QnOO'lA 1:4 0.17 Sim—$003 1:4.7 p.16 04A 1:2 0.34 SL004B 1:3 0.22 SLm2-004C 1.4 0.21 SL—2n004D 1:5 0.16 {00159} The amine—eontaining B~CD—TD1 polymers were further tested against a panel of 12 PFASs (Fig. l) as well as against the binary mixture ofPlJOA and Pli'OS (Fig. 2). The polymer made with 4 eq. of TDI —010A) showed 709/5 removal of PFOA and ent removal of PFOS (96%) in only 30 min and reached nearly 90% PFOA and 100% PFOS removal 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: sis and PFAS removal activity of isocyanate polymers {00160} Following the general procedure ed in example 1, B~CDuisocyanate polymers obtained from 4,4’uMD1 were synthesized and tested for their y to remove PFASS. {00161} The polymers of Table 5 were tested for their ability to remove PFASs. All experiments were conducted with 1000 ng/L of each of 12 PFASs and 10 mg/L of ent. Control experiments were performed with no ent. These experiments were conducted in triplicate.

Samples were taken at the following times: 0 h, 0.5 h, 9 h, and 48 h. Fig. 1 shows the results at 0.5 and 48 h, with polymers made from 4,4’—MDI and 2,4~TDT being particularly effective at PFAS sequestration. Although faster removal kinetics was observed in the TDT polymer (SLul _ 010A), the MDT polymer (SL_O420~3) also had good removal performance over the course of 48 h. Polymers obtained from 6 eq. of TDI and MDl did not exhibit good removal of either PFOA or PFOS, most likely due to the formation of hard gel during their synthesis which s binding sites inaccessible in the particle.

Table 5: {LCD rs made with different isocyanates Polymer Crossllnker CDzlsocyanate ratio Sleeved from SL--D1OA 2,4x-TDl 1:4 230 mesh SL-‘l -010A 2,4--TDl 1 :6 80 mesh 8Ln1n0420-3 4,4'—MDl 1:4 230 mesh SL—1—0420—4 4,4’—MDl 1:6 80 mesh Example 3: Synthesis and PEAS removal activity of choline chloridewmodi?ed BICD~TFN polymer {@6162} In this example, positive charges were added onto CD polymers in order to enhance the binding affinity for c PFASs~ Without being bound by any particular theory it is believed that the presence of phenol groups produced in a side reaction during polymerization results in anionic charge on the polymer and diminishes the PFOA and PFOS uptake of polymers. This effect was experimentally observed in r r formulation? P, which demonstrates good removal performance against a broad range of micropollutants except negatively charged ones including PFASs. TFNuCDP can be produced in relatively large scales using tetra?uoroterephthalonitrile (TFN) as the inker. Therefore, it was desired to modify the adsorption properties for PFASs by incorporation of positive s on the r 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 chloride can react with TFN just like 6—01) and thus is incorporated into the polymer, which hereafter will be d as TEN—CDP+ (Scheme 2).

Scheme 2: Synthetic overview for choline chloride—modified B—CD—TFN polymers Table 6: Synthetic ions and yields for TFN-CDP+ rs ß-CD TFN TFN-CDP+ BPA MO Sample ß-CD TFN K2CO3 CC Yield [B-CD] [CC] Uptake Uptake Sample Name ß-CD eq.Name eq. eq. TFN eq. eq. K2CO3 eq. CC eq.eq. Yield (%)(%) Crosslinker:CD Crosslinker:CD [ß-CD] (mmol/g)(mmol/g) [CC] (mmol/g)(mmol/g) BPA Uptake (%)(%) (%) MO Uptake (%) MB 036 MB036 11 6 6 20 20 33 8181 5.5 5.5 0.37 0.37 0.63 0.63 74 74 >99% >99% MB 037 MB037 11 6 6 20 20 66 7474 5.6 5.6 0.35 0.35 0.96 0.96 67 67 >99% >99% *CC: Choline chloride. BPA uptake measured under following conditions: [BPA]0 = 23 ppm, er] = 1 mg/mL, Contact time = 1 min. MO uptake measured under following conditions: [MO]0 = 10 ppm, er] = 1 mg/mL, t time = 1 h.

Table 7: Porosity comparison for TFN-CDP+ polymers Sample Choline de (eq) Surface area (m2/g) MB036 3 574 MB037 6 19 Table 8: Elemental analysis for TFN-CDP+ polymers C F Cl Feed equivalents Ratios TFN:CD Sample (mmol/g) (mmol/g) (mmol/g) ß-CD TFN CC C:N N:F N:Cl F:Cl C:Cl ratio MB036 1 6 3 7.45 2.23 7.51 3.36 55.98 5.49 35.2 2.1 0.63 MB037 1 6 6 7.19 2.73 5.07 1.86 36.44 5.64 35.1 1.8 0.96 Prior to measuring PFAS removal, a comparison of BPA (a neutral molecule) and methyl orange (MO, a negatively charged dye molecule) uptakes of TFN-CDP and TFNCDP + was performed. While BPA uptake was not affected, MO uptake was significantly improved, from ~30% for TFN-CDP to >99% for TFN-CDP+. As expected, TFN-CDP+ polymers demonstrated significantly less affinity towards positively charged molecules such as methylene blue compared to P (Table 9; Fig. 7). Encouraged by this preliminary data, TFN-CDP+ was tested for the removal of PFOA and PFOS at environmentally relevant concentrations.

Table 9: MP removal efficiencies of choline de modified and unmodified TFN-CDP Sample BPA Methyl Orange Methylene Blue MEN—036 74% 99% 34% NIB-14337 57% 99% 10% TFN—CDP 80% 30% 10 % {@0164} Although further experiments are needed to fully characterize the adsorption mechanism, this approach allows one to (1) take advantage of dual binding mechanism sion complex with B—CD and ionic ctions) at the same time in a single material and/or (2) e the binding affinity of the ion complex through the presence of positive charges in the vicinity of CD cavities. Furthermore, TFN—CDP-t- 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. {00165} Experimental: BuCD (l g, 0.881 mmol), TEN (l .06 g, 5.286 nimol), K2C03 (2.44 g, 17.621 mmol), 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 2t) h. Additional solvent (1 mL) was added after the first hour of stirring. After 20 h, 10 UL of water was added and stirred to se the polymer for 30 min. After filtering, the crude product was transferred to a centrifuge tube. The sample was washed with hot methanol (~40mL) three times (3 0 min for each cycle). After decanting methanol, DI 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 (~4t‘iinL). The final methanol wash was ed under vacuum and product was dried at 80 °C overnight. {@0166} Testing PFOA and PFOS l performance — PFAS adsorption experiments were performed to measure the removal performance of ent TFN—CDP+ polymers. In an effort to facilitate the screening process for a large number of polymer formulations, adsorption kinetics were performed using a mixture of 12 PFASs in nanopure water. The understanding of adsorption kinetics is essential as it reveals information on adsorbent doses and required contact times that are relevant for treatment processes. In addition to ing ts into PFOA and PFOS uptake, this panel study also allowed assessment of performance against other PFASS such as GenX and short- and lorig~chain PFASs in order to determine hroad~spectrum PFAS removal capabilities of these polymers. The results summarized in Fig. l show the removal percentages for each PFAS at 30 min and 48 11 contact times. These experiments were conducted in triplicate with ~l ppb of each of the 12 PFASs in nanopure water at a polymer loading of 10 mg/L. l 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. {00167} Impressively, the two derivatives of 'I‘FN—CDP-l- (namely, 84344336 and MBul ~O37 made from 3 and 6 eq. of choline chloride. respectively) trated the best removal performance of all polymers , with near complete removal of all PFASS in the panel. Over min. MB—l—O37 displayed effective removal of GenX and short~chain , in addition to PTFOA and PTFOS. presumably due to its higher quaternary ammonium loading (Fig. 2 i {@9168} After performing initial screening under the panel study, l assessments were narrowed to select polymers using a binary mixture of PFOA and PFOS (Table 10). In this specific task, all adsorption experiments were conducted with 0.5 ppb of PFOA and 1 ppb of PTFOS at a polymer g of 10 mg/L. Control experiments were performed with no adsorbent and all measurements were done in triplicate. Samples from each on were taken for analysis at predetermined time points: 0, 0.5g 2., 4., 8, and 24 h. rs selected for these measurements were ST..-—l—010A(TDT), NIB-L036 (TFN+CC), and TVlB—l —037 (TFN+CC). All the polymers tested demonstrated great removal of PFOS over 24 he but SL—l—Ol 0A (TDT) and two TFNmCDP+ derivatives displayed high removal (>90%) in only '30 min. As for removal of PFOA, even though ST_.~l—010A (TDT) showed similar performance to the panel study? MB—l—036 and MB~l ~03? formed the other two rs in terms of both kinetics and removal capacity over 24 h.

Table l0: Removal data of selected polymers for PFOA (0.5 ppb) and PFOS ( 1 ppb) mixture.

SL-‘l —91 9A 2,4-TD! 56% 76% 81% 84% 85% tee—1-099 TFN+co 93% 98% 99% 99% 99% memes? TFN+oc 98% 99% 99% 99% 99% SL4 -91 9A 2,4—TDT 90% 96% 97% 98% 98% madness TFN+oc 98% 97% 98% 98% 98% tee—1-097 TFN+co 95% 98% 98% 99% 99% {00169} ollutant Adsorption Studies {00170} B~CD is known to form a stable inclusion complex with micropollutants. EPA and MO were chosen as model compounds to study the uptake of neutral and vely charged micropollutants, respectively, for understanding the adsorption mechanism in choline chloride— modified TFNuCDP polymers. Furthermore, fitting the mi cropollutant adsorption data as a function of concentration to a Langmuir model (Equations 1 and 2) enables the determination of the thermodynamic ters of the materials tested. {00171} The singleusite Langmuir model that considers homogeneous adsorption surface, is given as Clmax ., KL ., Ce a ... ‘6' 1 + KL . Ce (Equation 1) where qe (mg/g) is the amount of MP adsorbed per gram of adsorbent at brium, qmax (mg/g) is the maximum tion capacity of adsorbent at saturation, KL (L/mg) is the equilibrium constant and C6 (mg/L or ppm) is the concentration at equilibrium. The dualusite Langmuir model that takes the two distinct tion sites into account, is given as gmaxd ‘ KAI ° C6 qmax,2 ’ K142 ' Ce q8 + 1 + Km ‘ Ce 1 + Km " Ce (Equation 2) where qe (mg/g) is the amount ofMP adsorbed per gram of adsorbent at equilibrium, qmax,1 and qmax,2 (mg/g) are maximum tion capacities of adsorbent for each site at saturation, K[4,1 and Km (L/mg) are equilibrium constants and Ce (mg/L or ppm) is the concentration at equilibrium. By fitting the experimental adsorption data using nonlinear regression, grim and KL parameters can be obtained. Single~site Langmuir model was determined to be suitable for fitting the EPA adsorption data, whereas MO adsorption data were best fitted using the dual~site model. {00172} For choline chloride—modified ’lFNmCDP polymers, m MO capacities (Qmam') of 46.6 and 78.8 mg/g were found for polymers made with 1.5 and 3.0 equivalents of choline chloride, respectively, for the first adsorption site (Table 11, Fig. 8). The second adsorption site (9mm) displayed m uptake capacities of 37.3 and 33.0 nig/g, both of which are quite similar to the maximum capacity of unmodified 'l‘FNuCDP (Qmax 37.6 mg/g). This data, as well as rities between K1. and K12 values, ts that the second adsorption site in e chlorideumodified 'I’EN—CDP polymers is associated with MG adsorption within the CD .

The comparison between Km and K112 values also indicates a significantly er first tion site which likely originates from the interaction of anionic MO molecules with quaternary ammonium sites. EPA 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 neutral molecule. Maximum BPA capacities of 112.1 and, 100.1 mg/g were found, for the two choline chloridemmodified, 'l‘FN—CDP polymers and a capacity of 106.1 mg/g was ined for the unmodified TFNnCDP (Table 11; Fig. 9). Notably, these saturation uptake values are in good agreement with the density of CD sites in these rs. This observation also suggests that EPA adsorption occurs within the cavity of CD5.

Table l l: I_.angmuir fitting parameters for EPA and MO adsorption [CD] [N‘] Cats. (m x3 for Cale. qnnx for Cale. total Sampie MP Q'maxn Km 01mm Km R2 (mmt?rgl. (mmoilgl. [CDllmgigl [Nng/g)+ qmaxlme/gl MB051 (15 eq CC) MO 46.6 27.9 37.3 0.3.7 0.9828 0 48 0.15 157 49 206 1148-1036 (3 eq CC}, MO 78.8 54.4 33.0 0.19 0.9970 0.37 0,63 121 205 327’ ., [CD] Cale. qmax for Cale. total Q'max KL R" (mmttllgl, [CD] (mg-'91. ~ «rm (me/Q) TFN-CDF‘ MO 37.6 0.02 0.9828 0.51 167’ 16'? MB051 (1.5 eq (30) EPA 112.1 0.10 0.9711 0.48 109 109 "43.1.0355 (3 eq CC) BPA 100.6 0.09 0.9651 0.37 84 84 TFN-CDP BPA 106.1 0.14 0.9714 0.51 116. 116 Example 4: Synthesis and PEAS removal activity of choline chloride—modified BmCD—TDI polymer {00173} BnCl) (2 g, 1.76 mmol, 1 eq.) was dissolved, in 5 mL DMF in a 20 mL scintillation vial equipped with a magnetic stir bar at a stir rate of 400 rpm and a temperature of 80 0C. 4 g Choline chloride was dissolved, in 10 mL DMSO at 80 °C to achieve a concentration of 0.4 g/mL.

A variety of stoichiometric ratios of choline chloride solution ((03075 mL, 0.1230 g, 0.5 eq.), (0.6150 ml..., 0.2460 g, 1 eq.), (0.9225 mL, 0.369 g, 1.5 eq.) or (1.2300 ml..., 0.492 g, 2 eq.)) was added to the B—CD solution at 80 °C, After mixing for 5 min at 80 °C, toluene diisocyanate (2.4— TDI, 1.8417 g, 10.57 nimol, 6 eq.) was added uently. Air bubbling was observed after the yanate addition, presumably due to the moisture in the on system. After about 1 min when ng subsided, the vial was . After 3 h, the reaction was stopped by adding 10 mL 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 centrifuging, the solvent was decanted and the crude product was washed with water (40 mL X 2 times), and methanol (40 mL X 2 times). In 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. 10 shows a 1H NMR spectrum of a choline chloridenmodified B—CD—TDI polymer made with l:6:l molar equivalents of B—CD:TDT:choline chloride in 5 mL of UMP at 80 0C for 3 hours. The appearance of urethane and urea groups at 775—95 ppm indicates successful incorporation of e chloride into the polymer. The following chemical shifts are also found in thelH BWTR spectrum: 6.75—7.75 ppm (protons from the aromatic ring in TDI); 5545 pm (protons from ~OH groups that are attached to C2 and C3 in B~CD); ~48 ~5 ppm (protons that are attached to Cl in B~CD); 4.25—4.75 ppm (protons from ~OH groups that are attached to C6 in BmCD); 4,1 ppm (protons from —O~CH2— groups in choline chloride); 3.5—4 ppm (protons that are attached to C2~C6 in B~CD); 3.3—3.5 ppm (protons from water); 3.162 ppm (protons from —CH3 groups in choline chloride); 2.5 ppm (DMSO); 1.92,] ppm (protons from — CH3 groups in TDI); Peaks noted with star are from residual solvent. Fig. 11 shows a comparison of a choline chloride—modified B-CD—TDI polymer and a EB—CD-TDI polymer, with the key difference being the broad peak centered around 3.13 ppm. Sharp peaks at 41 ppm and 3.1-32 ppm originates from unreacted choline chloride. Fig. 12 shows a comparison between three choline de-modifi ed TDI polymers with different choline chloride loading amounts, which supports the position that with increasing amount of choline chloride, the peak; intensity ses at 3.13 ppm. {011174} In accordance with the synthetic procedure outlined above, a variety of polymers were made with g iometric equivalents as shown below in Table 12. Furthermore, the polymers were tested for their PFOA uptake. The results show that by incorporating choline de into a DI polymer, cationic charge can he added to the polymer in a lled fashion, resulting in PFOA uptake increasing from 70% to 99% when compared to SL_1 _010A polymer (Table 12). See also Fig. 13.

Table 12: Synthesis of choline chlorideuniodified BmCDuTDI rs . .

. DE:CC PFOA Materia? Soivent T( C)0 Time Yield Notes ratio uptake" SL—2-004E 1:6:0 DMF 80 3 h n/a n/a Ge! SL—2-005A 1.6.0.5. , a DIVIF 80 3 h n/a n/a SL—Z—OOSB 1:621 DMF 80 3 h 73% 98% SL—Z—OOBC 1:65:15 DMF 80 3 h 73% 99% SL—Z—OOSD 1:6:2 DMF 80 3 h 60% 99% *500 ppt PFOAHOOO ppt PFOS, 10 mg/L polymer loading at 05 h.

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Claims (17)

CLAIMS :

1. A porous polymeric material comprising a plurality of cyclodextrins crosslinked with a plurality of aryl diisocyanate crosslinkers, n one or more of the plurality of cyclodextrins are bound to a linker of formula (I): 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, -O-metal cation, alkyl, aryl, heteroaryl, -SH, –S-metal cation, –S-alkyl, H, or -C(O)NH2; each R3 is independently –H, –C1-C6 alkyl, –C1-C3 haloalkyl, –aryl, (Ra)(Rb), or -SO2N(Ra)(Rb), and each Ra and Rb is independently H, or C1-C6 alkyl; each W is ndently a bond, an alkylene group, an arylene group, a heteroarylene group, -O-arylene-, -(CH2)a-arylene-, -SO2-arylene-, -NH-arylene-, -S-arylene-, -O- heteroarylene-, -(CH2)a-heteroarylene-, -SO2-heteroarylene-, -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; 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 al of claim 1, n each instance of –W–Z is taken together to form .

3. The porous polymeric material of claim 1, wherein each extrin is selected from the group consisting of a-cyclodextrin, ß-cyclodextrin, ?-cyclodextrin, and combinations thereof.

4. The porous polymeric material of claim 1, wherein x is 0-8; y3 is 0-4; and R1 and R2 are each independently H or C1-C6 alkyl.

5. The porous polymeric material of claim 1, wherein the aryl moiety is , , , , , , , , , , , , , , , , , , , or , wherein represents any of the substituents attached to A in formula (I).

6. The porous polymeric material of claim 5, wherein the aryl diisocyanate inker is 4,4’-methylene diphenyl diisocyanate; the aryl moiety is ; x is 0-8; y3 is 0-4; R1 and R2 are each independently H or C1-C6 alkyl; and represents any of the substituents attached to A in formula (I).

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

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

9. The porous polymeric material of claim 8, wherein the linker comprising formula (I) has the following structure , wherein the oxygen atom denoted with the * is a idic 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 pollutants in the fluid sample is adsorbed by the porous polymeric material.

11. The porous polymeric material of claim 5, wherein the aryl diisocyanate crosslinker is e 2,4-diisocyanate; the aryl moiety is ; represents any of the substituents attached to A in formula (I); x is 0-8; y3 is 0-4; R1 and R2 are each independently H or C1-C6 alkyl; each W is -NH-heteroarylene-, -S-heteroarylene-, –(–O–(CH2)a–)x’–, –(–NH–(CH2)a–)x’–, –(–S– (CH2)a–)x’–, , or ; a is 0-100; x’ is 1-100; Z’ is a covalent bond to Z; and Z is –N(Me)3+.

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 ßcyclodextrin.

14. The porous ric material of claim 13, wherein the linker comprising formula (I) has the following ure 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 sing 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 ric material of claim 1, wherein the porous polymeric material 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 polymeric material of claim 1, whereby at least 50 wt. % of the total amount of the one or more ants in the fluid sample is adsorbed by the porous polymeric material. EX £12: AER“: ““ :9“ ?x h;1... E33? rw 99 x a... 3 i t“) 2 m arm 0‘) 21‘; A639 35.139 «rd-'- a; ‘s toiti R: 3:173.. “9 13-1: .~ \, kit ‘1‘ ‘9 toiti thiti fiat Esta Ev? ii? *5 IA: " 3Q: m. 2*}; 35:25. ‘6‘ 9 h; w“!