Granulation of Lithium-Ion Sieves Using Biopolymers: A Review.

The high demand for lithium (Li) relates to clean, renewable storage devices and the advent of electric vehicles (EVs). The extraction of Li ions from aqueous media calls for efficient adsorbent materials with various characteristics, such as good adsorption capacity, good selectivity, easy isolation of the Li-loaded adsorbents, and good recovery of the adsorbed Li ions. The widespread use of metal-based adsorbent materials for Li ions extraction relates to various factors: (i) the ease of preparation via inexpensive and facile templation techniques, (ii) excellent selectivity for Li ions in a matrix, (iii) high recovery of the adsorbed ions, and (iv) good cycling performance of the adsorbents. However, the use of nano-sized metal-based Lithium-ion sieves (LISs) is limited due to challenges associated with isolating the loaded adsorbent material from the aqueous media. The adsorbent granulation process employing various binding agents (e.g., biopolymers, synthetic polymers, and inorganic materials) affords composite functional particles with modified morphological and surface properties that support easy isolation from the aqueous phase upon adsorption of Li ions. Biomaterials (e.g., chitosan, cellulose, alginate, and agar) are of particular interest because their structural diversity renders them amenable to coordination interactions with metal-based LISs to form three-dimensional bio-composite materials. The current review highlights recent progress in the use of biopolymer binding agents for the granulation of metal-based LISs, along with various crosslinking strategies employed to improve the mechanical stability of the granules. The study reviews the effects of granulation and crosslinking on adsorption capacity, selectivity, isolation, recovery, cycling performance, and the stability of the LISs. Adsorbent granulation using biopolymer binders has been reported to modify the uptake properties of the resulting composite materials to varying degrees in accordance with the surface and textural properties of the binding agent. The review further highlights the importance of granulation and crosslinking for improving the extraction process of Li ions from aqueous media. This review contributes to manifold areas related to industrial application of LISs, as follows: (1) to highlight recent progress in the granulation and crosslinking of metal-based adsorbents for Li ions recovery, (2) to highlight the advantages, challenges, and knowledge gaps of using biopolymer-based binders for granulation of LISs, and finally, (3) to catalyze further research interest into the use of biopolymer binders and various crosslinking strategies to engineer functional composite materials for application in Li extraction industry. Properly engineered extractants for Li ions are expected to offer various cost benefits in terms of capital expenditure, percent Li recovery, and reduced environmental footprint.

Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate Removal.

The fabrication of chitosan (CH) biocomposite beads with variable copper (Cu2+) ion doping was achieved with a glutaraldehyde cross-linker (CL) through three distinct methods: (1) formation of CH beads was followed by imbibition of Cu(II) ions (CH-b-Cu) without CL; (2) cross-linking of the CH beads, followed by imbibition of Cu(II) ions (CH-b-CL-Cu); and (3) cross-linking of pristine CH, followed by bead formation with Cu(II) imbibing onto the beads (CH-CL-b-Cu). The biocomposites (CH-b-Cu, CH-b-CL-Cu, and CH-CL-b-Cu) were characterized via spectroscopy (FTIR, 13C solid NMR, XPS), SEM, TGA, equilibrium solvent swelling methods, and phosphate adsorption isotherms. The results reveal variable cross-linking and Cu(II) doping of the CH beads, in accordance with the step-wise design strategy. CH-CL-b-Cu exhibited the greatest pillaring of chitosan fibrils with greater cross-linking, along with low Cu(II) loading, reduced solvent swelling, and attenuated uptake of phosphate dianions. Equilibrium and kinetic uptake results at pH 8.5 and 295 K reveal that the non-CL Cu-imbibed beads (CH-b-Cu) display the highest affinity for phosphate (Qm = 133 ± 45 mg/g), in agreement with the highest loading of Cu(II) and enhanced water swelling. Regeneration studies demonstrated the sustainability and cost-effectiveness of Cu-imbibed chitosan beads for controlled phosphate removal, whilst maintaining over 80% regenerability across several adsorption-desorption cycles. This study offers a facile synthetic approach for controlled Cu2+ ion doping onto chitosan-based beads, enabling tailored phosphate oxyanion uptake from aqueous media by employing a sustainable polysaccharide biocomposite adsorbent for water remediation by mitigation of eutrophication.

A Review on the Design and Hydration Properties of Natural Polymer-Based Hydrogels.

Hydrogels are hydrophilic 3D networks that are able to ingest large amounts of water or biological fluids, and are potential candidates for biosensors, drug delivery vectors, energy harvester devices, and carriers or matrices for cells in tissue engineering. Natural polymers, e.g., cellulose, chitosan and starch, have excellent properties that afford fabrication of advanced hydrogel materials for biomedical applications: biodegradability, biocompatibility, non-toxicity, hydrophilicity, thermal and chemical stability, and the high capacity for swelling induced by facile synthetic modification, among other physicochemical properties. Hydrogels require variable time to reach an equilibrium swelling due to the variable diffusion rates of water sorption, capillary action, and other modalities. In this study, the nature, transport kinetics, and the role of water in the formation and structural stability of various types of hydrogels comprised of natural polymers are reviewed. Since water is an integral part of hydrogels that constitute a substantive portion of its composition, there is a need to obtain an improved understanding of the role of hydration in the structure, degree of swelling and the mechanical stability of such biomaterial hydrogels. The capacity of the polymer chains to swell in an aqueous solvent can be expressed by the rubber elasticity theory and other thermodynamic contributions; whereas the rate of water diffusion can be driven either by concentration gradient or chemical potential. An overview of fabrication strategies for various types of hydrogels is presented as well as their responsiveness to external stimuli, along with their potential utility in diverse and novel applications. This review aims to shed light on the role of hydration to the structure and function of hydrogels. In turn, this review will further contribute to the development of advanced materials, such as "injectable hydrogels" and super-adsorbents for applications in the field of environmental science and biomedicine.

Comparison of the Moisture Adsorption Properties of Starch Particles and Flax Fiber Coatings for Energy Wheel Applications.

The adsorption-desorption behavior of flax fibers (FFs) is reported in this paper. FFs are a potential desiccant material for air-to-air energy wheels, which transfer heat and moisture in building heating, ventilation, and air conditioning (HVAC) systems. The raw FFs sample was subjected to physical modification, followed by complementary material characterization to understand the relationship between its structure and its moisture uptake performance. The surface and textural properties of the modified FFs were determined by gas adsorption (N2, H2O) and gravimetric liquid water swelling studies and further supported by spectroscopic (infrared and scanning electron microscopy) results. A FF-coated small-scale energy exchanger was used to determine the moisture transfer (or latent effectiveness; εl) using single-step and cyclic testing. The FF-coated exchanger had εl values of ∼10 and 40% greater compared to similar exchangers coated with starch particles (SPs) and silica gel (SG) reported in a previous study. The enhanced surface and textural properties, along with the complex compositional structure of FFs and its greater propensity to swell in water, account for the improved performance over SPs. Thus, FFs offer an alternative low-cost, environment-friendly, and sustainable biodesiccant for air-to-air energy wheel applications in buildings. The current study contributes to an improved understanding of the structure-function relationship of biodesiccants for such energy wheel applications.

Flax Biomass Conversion via Controlled Oxidation: Facile Tuning of Physicochemical Properties.

The role of chemical modification of pristine linen fiber (LF) on its physicochemical and adsorption properties is reported in this contribution. The surface and textural properties of the pristine LF and its peroxyacetic acid- (PAF) and chlorite-treated (CF) fiber forms were characterized by several complementary methods: spectroscopy (SEM, TEM, FT-IR, and XPS), thermal analysis (DSC and TGA), gas/water adsorption isotherms, and zeta potential (ξ). The results obtained reveal that the surface charge and textural properties (surface area and pore structure) of the LF material was modified upon chemical treatment, as indicated by changes in the biomass composition, morphology, ξ-values, and water/dye uptake properties of the fiber samples. Particularly, the pristine LF sample displays preferential removal efficiency (ER) of methylene blue (MB) dye with ER ~3-fold greater (ER~62%) as compared to the modified materials (CF or PAF; ER~21%), due to the role of surface charge of pectins and lignins present in pristine LF. At higher MB concentration, the relative ER values for LF (~19%) relative to CF or PAF (~16%) reveal the greater role of micropore adsorption sites due to the contributing effect of the textural porosity observed for the modified flax biomass at these conditions. Similar trends occur for the adsorption of water in the liquid vs. vapour phases. The chemical treatment of LF alters the polarity/charge of the surface functional groups, and pore structure properties of the chemically treated fibers, according to the variable hydration properties. The surface and textural properties of LF are altered upon chemical modification, according to the variable adsorption properties with liquid water (l) vs. water vapor (g) due to the role of surface- vs. pore-sites. This study contributes to an understanding of the structure-adsorption properties for pristine and oxidized flax fiber biomass. The chemical conversion of such biomass yields biomaterials with tunable surface and textural properties, as evidenced by the unique adsorption properties observed for pristine LF and its modified forms (CF and PAF). This study addresses knowledge gaps in the field by contributing insight on the relationship between structure and adsorption properties of such LF biomass in its pristine and chemically modified forms.

Hydration and Sorption Properties of Raw and Milled Flax Fibers.

The physicochemical and hydration properties of mechanically modified flax fibers (FFs) were investigated herein. Raw flax fibers (FF-R) were ball-milled and sieved through mesh with various aperture sizes (420, 210, and 125 µm) to achieve modified samples, denoted as FF-420, FF-210, and FF-125, respectively. The physicochemical and hydration properties of FF-R with variable particle sizes were characterized using several complementary techniques: microscopy (SEM), spectroscopy (FT-IR, XRD, and XPS), thermoanalytical methods (DSC and TGA), adsorption isotherms using gas/dye probes, and solvent swelling studies in liquid H2O. The hydration of FF biomass is governed by the micropore structure and availability of active surface sites, as revealed by the adsorption isotherm results and the TGA/DSC profiles of the hydrated samples. Gravimetric water swelling, water retention values, and vapor adsorption results provide further support that particle size reduction of FF-R upon milling parallels the changes in surface chemical and physicochemical properties relevant to adsorption/hydration in the modified FF materials. This study outlines a facile strategy for the valorization and tuning of the physicochemical properties of agricultural FF biomass via mechanical treatment for diverse applications in biomedicine, energy recovery, food, and biosorbents for environmental remediation.

Water Vapor Adsorption-Desorption Behavior of Surfactant-Coated Starch Particles for Commercial Energy Wheels.

This study reports on the adsorption (dehumidification)-desorption (humidification) behavior of cetylpyridinium bromide (CPB) coated starch particles (SPs), denoted as SP-CPB, as a potential desiccant material for air-to-air energy exchangers. CPB is a cationic surfactant with antibacterial activity that can be used to modify the surface properties of SPs, especially at variable CPB loading levels (SP-CPB0.5, SP-CPB2.5, and SP-CPB5.0, where the numeric suffix represents the synthetic loading level of CPB in mM). The SP-CPB0.5 sample displayed optimal surface area and pore structure properties that was selected for water sorption isotherm studies at 25 °C. The CPB-coated SPs sample (SP-CPB0.5) showed an improved water vapor uptake capacity compared to unmodified starch (SPs) and other desiccant systems such as high amylose starch (HAS15) and silica gel (SG13). Single-step and cyclic water vapor sorption tests were conducted using a small-scale exchanger coated with SP-CPB0.5. The calculated latent effectiveness values obtained from direct measurements using cyclic tests (65.4 ± 2%) agree closely with the estimated latent effectiveness from single-step tests (64.6 ± 2%) at controlled operating conditions. Compared to HAS15- and SG13-coated exchangers, the SP-CPB0.5-coated exchanger performed much better at controlled operating conditions, along with improved longevity due to the CPB surface coating. The presence of CPB did not attenuate the uptake properties of native SPs. Latent effectiveness of SP-CPB0.5-coated exchanger was enhanced (5-30% higher) over that of the SG13- or HAS15-coated exchangers, according to the wheel angular speed. This study reports on a novel and sustainable SP-CPB0.5 material as a promising desiccant coating with tunable uptake and surface properties with potential utility in air-to-air energy exchangers for ventilation systems.

Inclusion Complexes of Melphalan with Gemini-Conjugated ß-Cyclodextrin: Physicochemical Properties and Chemotherapeutic Efficacy in In-Vitro Tumor Models.

ß-cyclodextrin (ßCD) has been widely explored as an excipient for pharmaceuticals and nutraceuticals as it forms stable host-guest inclusion complexes and enhances the solubility of poorly soluble active agents. To enhance intracellular drug delivery, ßCD was chemically conjugated to an 18-carbon chain cationic gemini surfactant which undergoes self-assembly to form nanoscale complexes. The novel gemini surfactant-modified ßCD carrier host (hereafter referred to as 18:1ßCDg) was designed to combine the solubilization and encapsulation capacity of the ßCD macrocycle and the cell-penetrating ability of the gemini surfactant conjugate. Melphalan (Mel), a chemotherapeutic agent for melanoma, was selected as a model for a poorly soluble drug. Characterization of the 18:1ßCDg-Mel host-guest complex was carried out using 1D/2D 1H NMR spectroscopy and dynamic light scattering (DLS). The 1D/2D NMR spectral results indicated the formation of stable and well-defined 18:1ßCDg-Mel inclusion complexes at the 2:1 host-guest mole ratio; whereas, host-drug interaction was attenuated at greater 18:1ßCDg mole ratio due to hydrophobic aggregation that accounts for the reduced Mel solubility. The in vitro evaluations were performed using monolayer, 3D spheroid, and Mel-resistant melanoma cell lines. The 18:1ßCDg-Mel complex showed significant enhancement in the chemotherapeutic efficacy of Mel with 2-3-fold decrease in Mel half maximal inhibitory concentration (IC50) values. The findings demonstrate the potential applicability of the 18:1ßCDg delivery system as a safe and efficient carrier for a poorly soluble chemotherapeutic in melanoma therapy.

Cyclodextrin-Based Polymer-Supported Bacterium for the Adsorption and in-situ Biodegradation of Phenolic Compounds.

Dual function polymer materials with immobilized Sphingobium Chorophenolicum (SpC) bacterium cells are reported herein that undergo tandem adsorption and biodegradation of phenolic compounds. The cross-linked polymer materials contain ß-cyclodextrin (ß-CD) with incremental hexamethylene diisocyanate (HDI) cross-linker at variable mole ratios (X = 1, 3, or 6), denoted as HDI-X systems. The adsorptive uptake properties of the insoluble HDI-X polymers (X = 3 and 6) with various phenolic compounds [pentachlorophenol (PCP), 2,4,6-trichlorophenol (TCP), and 2,4,6-trimethylphenol (TMP)] were studied using batch adsorption isotherms. The molecular selective phenol removal (SR) capacity of the HDI-3 and HDI-6 materials was evaluated by electrospray ionization mass spectrometry (ESI-MS). The results were compared against granular activated carbon (GAC) and native ß-CD, where 1D/2D 1H NMR spectral characterization of the complexes formed between phenolic guests and a soluble polymer (HDI-1) in aqueous solution provide insight on the intermolecular interactions and the role of cross-linking effects. Immobilization of SpC onto HDI-3 was shown to form a composite polymer/bacterium material. The composite system displays synergistic removal effects due to tandem PCP adsorption and SpC biodegradation to yield by-products such as 2,6-dichloro-1,4-hydroquinone (DCHQ). Apoptosis and cytotoxicity of DCHQ were evaluated using three breast cancer cell lines.

Spectroscopic and Thermodynamic Study of Biopolymer Adsorption Phenomena in Heterogeneous Solid-Liquid Systems.

Molecular selective adsorption processes at the solid surface of biopolymers in mixed solvent systems are poorly understood due to manifold interactions. However, the ability to achieve adsorptive fractionation of liquid mixtures is posited to relate to the role of specific solid-liquid interactions at the adsorbent interface. The hydration of solid biopolymers (amylose, amylopectin, cellulose) in binary aqueous systems is partly governed by the relative solvent binding affinities with the biopolymer surface sites, in accordance with the role of textural and surface chemical properties. While molecular models that account for the surface area and solvent effects provide reliable estimates of hydration energy and binding affinity parameters, spectroscopic and thermal methods offer a facile alternative experimental approach to account for detailed aspects of solvation phenomena at biopolymer interfaces that involve solid-liquid adsorption. In this report, thermal and spectroscopic methods were used to understand the interaction of starch- and cellulose-based materials in water-ethanol (W-E) binary mixtures. Batch adsorption studies in binary W-E mixtures reveal the selective solvent uptake properties by the biomaterials, in agreement with their solvent swelling in pure water or ethanol. The nature, stability of the bound water, and the thermodynamic properties of the biopolymers in variable hydration states were probed via differential scanning calorimetry and Raman spectroscopy. The trends in biopolymer-solvent interactions are corroborated by dye adsorption and scanning electron microscopy, indicating that biopolymer adsorption properties in W-E mixtures strongly depend on the surface area, pore structure, and accessibility of the polar surface groups of the biopolymer systems, in agreement with the solvent-selective uptake results reported herein.

Starch Particles, Energy Harvesting, and the "Goldilocks Effect".

This study reports on the unique water vapor adsorption properties of biomass-derived starch particles (SPs). SPs offer an alternative desiccant for air-to-air energy exchangers in heating, ventilation, and air conditioning systems because of their remarkable adsorption-desorption performance. SP15 has a particle diameter (d p) of 15 µm with a surface area (SA) of 2.89 m2/g and a pore width (P w) of 80 Å. Microporous starch particles (SP15) were compared with high amylose starch (HAS15; SA = 0.56 m2/g, d p = 15 µm, P w = 46 Å) and silica gel (SG13; SA = 478 m2/g, d p = 13 µm, P w = 62 Å). Transient water vapor tests were performed using a customized small-scale energy exchanger coated with SP15, HAS15, and SG13. The water swelling (%) for SP15 was ca. 2 orders of magnitude greater with markedly higher (ca. three- and six-fold) water vapor uptake compared to HAS15 and SG13, respectively. At similar desiccant coating levels on the energy exchanger, the latent effectiveness of the SP15 system was much improved (4-31%) over the HAS15 and SG13 systems at controlled operating conditions. SP15 is a unique desiccant material with high affinity for water vapor and superior adsorption properties where ca. 98% regeneration was achieved under mild conditions. Therefore, SPs display unique adsorption-desorption properties, herein referred to as the "Goldilocks effect". This contribution reports on the utility of SPs as promising desiccant coatings in air-to-air energy exchangers for ventilation systems or as advanced materials for potential water/energy harvesting applications.

Physicochemical Properties and the Gelation Process of Supramolecular Hydrogels: A Review.

Supramolecular polysaccharide-based hydrogels have attracted considerable research interest recently due to their high structural functionality, low toxicity, and potential applications in foods, cosmetics, catalysis, drug delivery, tissue engineering and the environment. Modulation of the stability of hydrogels is of paramount importance, especially in the case of stimuli-responsive systems. This review will update the recent progress related to the rational design of supramolecular hydrogels with the objective of understanding the gelation process and improving their physical gelation properties for tailored applications. Emphasis will be given to supramolecular host⁻guest systems with reference to conventional gels in describing general aspects of gel formation. A brief account of the structural characterization of various supramolecular hydrogels is also provided in order to gain a better understanding of the design of such materials relevant to the nature of the intermolecular interactions, thermodynamic properties of the gelation process, and the critical concentration values of the precursors and the solvent components. This mini-review contributes to greater knowledge of the rational design of supramolecular hydrogels with tailored applications in diverse fields ranging from the environment to biomedicine.

Preparation and Characterization of a Polymer-Based "Molecular Accordion".

A urethane-based polymer material, denoted HDI-1, was obtained from the addition reaction of ß-cyclodextrin (ß-CD) with 1,6-hexamethylene diisocyanate (HDI) at the 1:1 mole ratio. In aqueous solution and ambient temperature conditions, HDI-1 adopts a compact (coiled) morphology where the cross-linker units become coiled and are partially self-included in the annular hydroxyl (interstitial) region of ß-CD. As the temperature is raised or as p-nitrophenol (PNP) was included within the ß-CD cavity and the noninclusion sites of the polymer, an extended (uncoiled) morphology was adopted. The equilibrium distribution between the extended and the compact forms of HDI-1 is thermally and chemically switchable, in accordance with the hydration properties and host-guest chemistry of this responsive polymer system. The molecular structure of this water-soluble urethane polymer and its host-guest complexes with PNP were investigated using spectroscopic (Raman, (1)H NMR, induced circular dichroism), dynamic light scattering (DLS), and calorimetric (DSC) methods in aqueous solution at ambient pH, and compared with native ß-CD. This study reports on the unique supramolecular properties of a polymer that resembles a thermally and chemically responsive "molecular accordion".

A 1H NMR Study of Host/Guest Supramolecular Complexes of a Curcumin Analogue with ß-Cyclodextrin and a ß-Cyclodextrin-Conjugated Gemini Surfactant.

Host systems based on ß-cyclodextrin (ßCD) were employed as pharmaceutical carriers to encapsulate a poorly soluble drug, curcumin analogue (NC 2067), in order to increase its water solubility. ßCD was chemically conjugated with an amphiphilic gemini surfactant with the ability to self-assemble and to form nanoscale supramolecular structures. The conjugated molecule, ßCDgemini surfactant (ßCDg), was shown to be a promising drug delivery agent. In this report, its physicochemical properties were assessed in aqueous solution using 1D and 2D 1H NMR spectroscopy. The results showed that the apolar hydrocarbon domain of the gemini surfactant was self-included within the ßCD internal cavity. The host/guest complexes composed of native ßCD or ßCDg with NC 2067 were examined using 1D/2D ROESY NMR methods. The stoichiometry of ßCD/NC 2067 complex was estimated using Job's method via 1H NMR spectroscopy. The binding geometry of NC 2067 within ßCD was proposed using molecular docking and further supported by 1D and 2D ROESY NMR results. Addition of NC 2067 to ßCDg revealed minimal changes to the overall structure of the ßCDg system, in agreement with the formation of a ßCDg/NC 2067 ternary complex.

Nano-Sized Cyclodextrin-Based Molecularly Imprinted Polymer Adsorbents for Perfluorinated Compounds-A Mini-Review.

Recent efforts have been directed towards the design of efficient and contaminant selective remediation technology for the removal of perfluorinated compounds (PFCs) from soils, sediments, and aquatic environments. While there is a general consensus on adsorption-based processes as the most suitable methodology for the removal of PFCs from aquatic environments, challenges exist regarding the optimal materials design of sorbents for selective uptake of PFCs. This article reviews the sorptive uptake of PFCs using cyclodextrin (CD)-based polymer adsorbents with nano- to micron-sized structural attributes. The relationship between synthesis of adsorbent materials and their structure relate to the overall sorption properties. Hence, the adsorptive uptake properties of CD-based molecularly imprinted polymers (CD-MIPs) are reviewed and compared with conventional MIPs. Further comparison is made with non-imprinted polymers (NIPs) that are based on cross-linking of pre-polymer units such as chitosan with epichlorohydrin in the absence of a molecular template. In general, MIPs offer the advantage of selectivity, chemical tunability, high stability and mechanical strength, ease of regeneration, and overall lower cost compared to NIPs. In particular, CD-MIPs offer the added advantage of possessing multiple binding sites with unique physicochemical properties such as tunable surface properties and morphology that may vary considerably. This mini-review provides a rationale for the design of unique polymer adsorbent materials that employ an intrinsic porogen via incorporation of a macrocyclic compound in the polymer framework to afford adsorbent materials with tunable physicochemical properties and unique nanostructure properties.

Characterization and dynamic properties for the solid inclusion complexes of ß-cyclodextrin and perfluorooctanoic acid.

The structural characterization and dynamic properties of solid-state inclusion complexes (ICs) formed between ß-cyclodextrin (ß-CD; host) and perfluorooctanoic acid (PFOA; guest) were investigated using (13)C NMR spectroscopy. The 1:1 and 2:1 host/guest solid-state complexes were prepared using a modified dissolution method to obtain complexes with high phase purity. These complexes were further characterized using differential scanning calorimetry (DSC), FT-IR spectroscopy, powder X-ray diffraction (PXRD), (19)F directpolarization (DP), and (13)C cross-polarization (CP) with magic-angle spinning (MAS) NMR spectroscopy. The (19)F → (13)C CP results provided unequivocal support for the formation of well-defined inclusion compounds. The phase purity of the complexes formed between ß-CD and PFOA were assessed using the (19)F DP NMR technique at variable temperature (VT) and MAS at 20 kHz. The complexes were found to be of high phase purity when prepared in accordance with the modified dissolution method. The motional dynamics of the guest in the solid complexes were assessed using T1/T2/T1ρ relaxation NMR methods at ambient and VT conditions. The relaxation data revealed reliable and variable guest dynamics for the 1:1 versus 2:1 complexes at the VTs investigated. The motional dynamics of the guest molecules involve an ensemble of axial motions of the whole chain and 120° rotational jumps of the methyl (CF3) group at the termini of the perfluorocarbon chain. The axial and rotational dynamics of the guest in the 1:1 and 2:1 complexes differ in distribution and magnitude in accordance with the binding geometry of the guest within the host.

Tunable macromolecular-based materials for the adsorption of perfluorooctanoic and octanoic acid anions.

The sorption properties of tunable urethane-based copolymer materials containing ß-cyclodextrin (ß-CD) were evaluated with perfluorooctanoic acid (PFOA) and octanoic acid (OA) anions in aqueous solutions, respectively. The copolymer materials are herein referred to as macromolecular imprinted materials (MIMs) since their design strategy incorporates a porogen macromolecule (ß-CD) within a cross-linked hexamethylene diisocyanate (HDI) framework. We report the tunable uptake of OA and PFOA anions from aqueous solution with variable adsorption modes, in accordance with the composition of the MIMs. The sorption results with granular activated carbon (GAC) were compared at 295 K and pH values exceeding the pKa values of each adsorbate. The BET and Sips models provided estimates of the monolayer sorption capacity (Qm) and related equilibrium sorption parameters. The Qm value for GAC with PFOA was ~1.4 mmol/g; whereas, a greater Qm value for PFOA (up to 2.6 mmol/g) was observed with the MIMs. GAC displays greater sorption capacity toward PFOA at relatively low Ce values and saturation of the monolayer occurs at Ce~0.5 mM. The MIMs/PFOA system displays monolayer completion at values of Ce~1 mM and multilayer sorption when Ce>1mM. Equilibrium sorption of PFOA onto MIMs occurs at the inclusion sites of ß-CD and interstitial binding sites of the polymeric framework. Surface adsorption of the PFOA anion occurs between the PFOA carboxylate head group and dipolar interstitial domains of the cross-linker framework. The MIMs sorbents display tunable and favorable binding with PFOA and OA anions where the uptake (per mg MIMs) with PFOA was ~5-33% (5 µM-5 mM) and with OA was ~0.5-5% (1-20 mM). The overall sorptive uptake of OA and PFOA anions by the MIMs sorbents meets or exceeds those observed for GAC.

Formation of host-guest complexes of ß-cyclodextrin and perfluorooctanoic acid.

Structural characterization and dynamic properties of solid-state inclusion complexes of ß-cyclodextrin (ß-CD) with perfluorooctanoic acid (PFOA) were investigated by (19)F/(13)C solid-state and (19)F/(1)H solution NMR spectroscopy. The complexes in the solid state were prepared using dissolution and slow cool methods, where thermal analyses (DSC and TGA), PXRD, and FT-IR results provided complementary support that inclusion complexes were formed between ß-CD and PFOA with variable stoichiometry and inclusion geometry. (19)F DP (direct polarization) and (13)C CP (cross-polarization) with magic-angle spinning (MAS) solids NMR, along with (19)F/(1)H solution NMR were used to characterize the complexes in the solid and solution phases, respectively. The dynamics of the guest molecules in the inclusion complexes (ICs) were studied using variable temperature (VT) (19)F DP/MAS NMR experiments in the solid state. The guest molecules were observed to be in several different molecular environments, providing strong evidence of variable host-guest stoichiometry and inclusion geometry, in accordance with the preparation method of the complex and the conformational preference of PFOA. It was concluded from PXRD that ß-CD and PFOA form inclusion complexes with "channel-type" structures. Variable spin rate (VSR) (19)F DP/MAS NMR was used to assess the phase purity of the complexes, and it was revealed that slow cooling resulted in relatively pure phases. In the solution state, (1)H and (19)F NMR complexation-induced chemical shifts (CISs) of ß-CD and PFOA, respectively, provided strong support for the formation of 1:1 and 2:1 ß-CD/PFOA inclusion complexes. The dynamics of the guest molecule in the ß-CD/PFOA complexes in D(2)O solutions were probed using VT (19)F NMR and revealed some guest conformational and exchange dynamics as a function of temperature and the relative concentrations of the host and guest.