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.

The detection and removal of heavy metal species in aquatic environments is of continued interest to address ongoing efforts in water security. This study was focused on the preparation and characterization of aniline grafted chitosan (CS-Ac-An), and evaluation of its adsorption properties with Cu(II) under variable conditions. Materials characterization provides support for the grafting of aniline onto chitosan, where the kinetic and thermodynamic adsorption properties reveal a notably greater uptake (>20-fold) of Cu(II) relative to chitosan, where the adsorption capacity (Qm) of CS-Ac-An was 106.6 mg/g. Adsorbent regeneration was demonstrated over multiple adsorption-desorption cycles with good uptake efficiency. CS-Ac-An has a strong fluorescence emission that undergoes prominent quenching at part per billion levels in aqueous solution. The quenching process displays a linear response over variable Cu(II) concentration (0.05-5 mM) that affords reliable detection of low level Cu(II) levels by an in situ "turn-off" process. The tweezer-like chelation properties of CS-Ac-An with Cu(II) was characterized by complementary spectroscopic methods: IR, NMR, X-ray photoelectron (XPS), and scanning electron microscopy (SEM). The role of synergistic effects are inferred among two types of active adsorption sites: electron rich arene rings and amine groups of chitosan with Cu(II) species to afford a tweezer-like binding modality.

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 β-cyclodextrin (β-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 β-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.

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.

The adsorption mechanisms for model hydrocarbons, 4-nitrophenol (PNP), and naphthalene were studied in a coagulation-based process using a ferric sulfate-lime softening system. Kinetic and thermodynamic adsorption parameters for this system were obtained under variable ionic strength and temperature. An in situ method was used to investigate kinetic adsorption profiles for PNP and naphthalene, where a pseudo-first order kinetic model adequately described the process. Thermodynamic parameters for the coagulation of PNP and naphthalene reveal an endothermic and spontaneous process. River water was compared against lab water samples at optimized conditions, where the results reveal that ions in the river water decrease the removal efficiency (RE; %) for PNP (RE = 28 to 20.3%) and naphthalene (RE = 89.0 to 80.2%). An aluminum sulfate (alum) coagulant was compared against the ferric system. The removal of PNP with alum decreased from RE = 20.5% in lab water and to RE = 16.8% in river water. Naphthalene removal decreased from RE = 89.0% with ferric sulfate to RE = 83.2% with alum in lab water and from RE = 80.2% for the ferric system to RE = 75.1% for alum in river water. Optical microscopy and dynamic light scattering of isolated flocs corroborated the role of ions in river water, according to variable RE and floc size distribution.

The context of this study responds to the need for sorbent technology development to address the controlled removal of inorganic sulfate (SO42-) from saline water and the promising potential of chitosan as a carrier system for organosulfates in pharmaceutical and nutraceutical applications. This study aims to address the controlled removal of sulfate using chitosan as a sustainable biopolymer platform, where a modular synthetic approach was used for chitosan bead preparation that displays tunable sulfate uptake. The beads were prepared via phase-inversion synthesis, followed by cross-linking with glutaraldehyde, and impregnation of Ca2+ ions. The sulfate adsorption properties of the beads were studied at pH 5 and variable sulfate levels (50-1000 ppm), where beads with low cross-linking showed moderate sulfate uptake (35 mg/g), while cross-linked beads imbibed with Ca2+ had greater sulfate adsorption (140 mg/g). Bead stability, adsorption properties, and the point-of-zero charge (PZC) from 6.5 to 6.8 were found to depend on the cross-linking ratio and the presence of Ca2+. The beads were regenerated over multiple adsorption-desorption cycles to demonstrate the favorable uptake properties and bead stability. This study contributes to the development of chitosan-based adsorbent technology via a modular materials design strategy for the controlled removal of sulfate. The results of this study are relevant to diverse pharmaceutical and nutraceutical applications that range from the controlled removal of dextran sulfate from water to the controlled release of chondroitin sulfate.

In the present study, variable forms of pelletized chitosan adsorbents were prepared and their sulfate uptake properties in aqueous solution was studied in a fixed-bed column system. Unmodified chitosan pellets (CP), cross-linked chitosan pellets with glutaraldehyde (CL-CP), and calcium-doped forms of these pellets (Ca-CP, Ca-CL-CP) were prepared, where the removal efficiencies and breakthrough curves were studied. Dynamic adsorption experiments were conducted at pH 4.5 and 6.5 with a specific flow rate of 3 mL/min, fixed-bed height of 200 mm, and an initial sulfate concentration of 1000 mg/L. Breakthrough parameters demonstrated that Ca-CP had the best sulfate removal among the adsorbents, where the following adsorption parameters were obtained: breakthrough time (75 min), exhaust time (300 min), maximum sulfate adsorption capacity (qmax; 46.6 mg/g), and sulfate removal (57%) at pH 4.5. Two well-known kinetic adsorption models, Thomas and Yoon-Nelson, were fitted to the experimental kinetic data to characterize the breakthrough curves. The fixed-bed column experimental results were well-fitted by both models and the maximum adsorption capacity (46.9 mg/g) obtained was for the Ca-CP adsorbent. A regeneration study over four adsorption-desorption cycles suggested that Ca-CP is a promising adsorbent for sulfate removal in a fixed-bed column system.

Binary (Chitosan-Cu(II), CCu) and Ternary (Chitosan-Alginate-Cu(II), CACu) composite materials were synthesized at variable composition: CCu (1:1), CACu1 (1:1:1), CACu2 (1:2:1) and CACu3 (2:1:1). Characterization was carried out via spectroscopic (FTIR, solids C-13 NMR, XPS and Raman), thermal (differential scanning calorimetry (DSC) and TGA), XRD, point of zero charge and solvent swelling techniques. The materials' characterization confirmed the successful preparation of the polymer-based composites, along with their variable physico-chemical and adsorption properties. Sulfate anion (sodium sulfate) adsorption from aqueous solution was demonstrated using C and CACu1 at pH 6.8 and 295 K, where the monolayer adsorption capacity (Qm) values were 288.1 and 371.4 mg/g, respectively, where the Sips isotherm model provided the "best-fit" for the adsorption data. Single-point sorption study on three types of groundwater samples (wells 1, 2 and 3) with variable sulfate concentration and matrix composition in the presence of composite materials reveal that CACu3 exhibited greater uptake of sulfate (Qe = 81.5 mg/g; 11.5% removal) from Well-1 and CACu2 showed the lowest sulfate uptake (Qe of 15.7 mg/g; 0.865% removal) from Well-3. Generally, for all groundwater samples, the binary composite material (CCu) exhibited attenuated sorption and removal efficiency relative to the ternary composite materials (CACu).

Graphene oxide (GO) was cross-linked with chitosan to yield a composite (GO-LCTS) with variable morphology, enhanced surface area, and notably high methylene blue (MB) adsorption capacity. The materials were structurally characterized using thermogravimetric analysis and spectroscopic methods (X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and 13C solid-state NMR) to support that cross-linking occurs between the amine groups of chitosan and the -COOH groups of GO. Equilibrium swelling studies provide support for the enhanced structural stability of GO-cross-linked materials over the synthetic precursors. Scanning electron microscopy studies reveal the enhanced surface area and variable morphology of the cross-linked GO materials, along with equilibrium and kinetic uptake results with MB dye in aqueous media, revealing greater uptake of GO-LCTS composites over pristine GO. The monolayer uptake capacity (Q m; mg g-1) with MB reveals twofold variation for Q m, where GO-LCTS (402.6 mg g-1) > GO (286.9 mg g-1). The kinetic uptake profiles of MB follow a pseudo-second-order trend, where the GO composite shows more rapid uptake over GO. This study reveals that the sorption properties of GO are markedly improved upon formation of a GO-chitosan composite. The facile cross-linking strategy of GO reveals that its physicochemical properties are tunable and versatile for a wider field of application for contaminant removal, especially over multiple adsorption-desorption cycles when compared against pristine GO in its highly dispersed nanoparticle form.

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.