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The rapid detection of contaminants in water resources is vital for safeguarding the environment, where the use of eco-friendly materials for water monitoring technologies has become increasingly prioritized. In this context, the role of biocomposites in the development of a SERS sensor is reported in this study. Grafted chitosan was employed as a matrix support for Ag nanoparticles (NPs) for the surface-enhanced Raman spectroscopy (SERS). Chitosan (CS) was decorated with thiol and carboxylic acid groups by incorporating S-acetyl mercaptosuccinic anhydride (SAMSA) to yield CS-SAMSA. Then, Ag NPs were immobilized onto the CS-SAMSA (Ag@CS-SAMSA) and characterized by spectral methods (IR, Raman, NIR, solid state 13 C NMR with CP-MAS, XPS, and TEM). Ag@CS-SAMSA was evaluated as a substrate for SERS, where methylene blue (MB) was used as a model dye adsorbate. The Ag@CS-SAMSA sensor demonstrated a high sensitivity (with an enhancement factor ca. 10 8 ) and reusability over three cycles, with acceptable reproducibility and storage stability. The Raman imaging revealed a large SERS effect, whereas the MB detection varied from 1-100 μM. The limits of detection (LOD) and quantitation (LOQ) of the biocomposite sensor were characterized, revealing properties that rival current state-of-the-art systems. The dye adsorption profiles were studied via SERS by fitting the isotherm results with the Hill model to yield the ΔG° ads for the adsorption process. This research demonstrates a sustainable dual-function biocomposite with tailored adsorption and sensing properties suitable for potential utility in advanced water treatment technology and environmental monitoring applications.

Adsorption-based treatment of sulfate contaminated water sources present challenges due to its favourable hydration characteristics. Herein, a copper-modified granular chitosan-based biocomposite (CHP-Cu) was prepared and characterized for its sulfate adsorption properties at neutral pH via batch equilibrium and fixed-bed column studies. The CHP-Cu adsorbent was characterized by complementary methods: spectroscopy (IR, Raman, X-ray photoelectron), thermal gravimetry analysis (TGA) and pH-based surface charge analysis. Sulfate adsorption at pH 7.2 with CHP-Cu follows the Sips isotherm model with a maximum adsorption capacity (407 mg/g) that exceeds most reported values of granular biosorbents at similar conditions. For the dynamic adsorption study, initial sulfate concentration, bed height, and flow rate were influential parameters governing sulfate adsorption. The Thomas and Yoon-Nelson models yield a sulfate adsorption capacity (146 mg/g) for the fixed bed system at optimized conditions. CHP-Cu was regenerated over 5 cycles (33 % to 31 %) with negligible Cu-leaching. The adsorbent also displays excellent sulfate uptake properties, regenerability, and sustainable adsorbent properties for effective point-of-use sulfate remediation in aqueous media near neutral pH (7.2). This sulfate remediation strategy is proposed for other oxyanion systems relevant to contaminated environmental surface and groundwater resources., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Orthophosphate (P i ) remediation from effluent serves to address global water security by preventing eutrophication. Herein, chitosan (C), alginate (Alg) and three respective metal systems (Fe 3+ , Al 3+ , Cu 2+ ) were used to prepare binary (BMC) or ternary (TMC) metal composite adsorbents. Their physicochemical properties were analyzed through XPS, IR and TGA, while the adsorption properties of the composites were characterized via adsorption isotherms and single-point experiments in saline environmental water. Al-composites formed Al-O complexes, while Fe- and Cu-composites formed in the presence of the biopolymer backbone FeO(OH) and Cu 2 (OH) 3 NO 3 , respectively. While Al-composites showed the highest bound water fraction (up to 16%), the Cu-composites (Cu-TMC-N, CuC-BMC-N; where N = nitrate) revealed the lowest water content. Alginate-based binary composites showed slightly higher water content, as compared to ternary and binary chitosan composites. Among the four materials (Al-TMC-N, Fe-TMC-N, Cu-TMC-N and CuC-BMC-N), the Al-TMC showed the highest P i selectivity over sulfate, along with high P i removal-% even in a binary mixture (sulfate + orthophosphate) despite the presence of competitive anion species. Upon spiking saline groundwater samples with low P i (5 mg/L) that contains 2060 or 6030 mg/g sulfate, Al-TMC-N showed the highest P i selectivity, followed by Fe-TMC-N. This trend in adsorption of Pi among the various composites is understood based on the HSAB principle for the conditions employed in this study. Removal efficiencies of P i above 60% in Well 1 (ca. 2000 mg/L sulfate) and above 30% in Well 3 (ca. 6030 mg/L sulfate). Herein, environmentally compatible and sustainable composite adsorbents were prepared that reveal selective P i recovery from (highly) saline groundwater that can mitigate eutrophication in aqueous media., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Herein, a natural material including chitosan (CTS) and algae (food-grade algae, FGA) was exploited to attain a bio-adsorbent (CTS/FGA) for enhanced methyl violet 2B dye removal. A study of the FGA loading into CTS matrix showed that the best mixing ratio between CTS and FGA to be used for the MV 2B removal was 50 %:50 % (CTS/FGA; 50:50 w/w). The present study employed the Box-Behnken design (RSM-BBD) to investigate the impact of three processing factors, namely CTS/FGA-(50:50) dose (0.02-0.1 g/100 mL), pH of solution (4-10), and contact time (5-15 min) on the decolorization rate of MV 2B dye. The results obtained from the equilibrium and kinetic experiments indicate that the adsorption of MV 2B dye on CTS/FGA-(50:50) follows the Langmuir and pseudo-second-order models, respectively. The CTS/FGA exhibits an adsorption capacity of 179.8 mg/g. The characterization of CTS/FGA-(50:50) involves the proposed mechanism of MV 2B adsorption, which primarily encompasses various interactions such as electrostatic forces, n-π stacking, and H-bonding. The present study demonstrates that CTS/FGA-(50:50) synthesized material exhibits a distinctive structure and excellent adsorption properties, thereby providing a viable option for the elimination of toxic cationic dyes from polluted water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

This work aims to apply the use of food-grade algae (FGA) composited with chitosan-benzaldehyde Schiff base biopolymer (CHA-BD) as a new adsorbent (CHA-BA/FGA) for methyl violet 2B (MV 2B) dye removal from aqueous solutions. The effect of three processing variables, including CHA-BA/FGA dosage (0.02-0.1 g/100 mL), pH solution (4-10), and contact duration (10-120 min) on the removal of MV 2B was investigated using the Box-Behnken design (BBD) model. Kinetic and equilibrium dye adsorption profiles reveal that the uptake of MV 2B dye by CHA-BA/FGA is described by the pseudo-second kinetics and the Langmuir models. The thermodynamics of the adsorption process (ΔG°, ΔH°, and ΔS°) reveal spontaneous and favorable adsorption parameters of MV 2B dye onto the CHA-BA/FGA biocomposite at ambient conditions. The CHA-BA/FGA exhibited the maximum ability to absorb MV 2B of 126.51 mg/g (operating conditions: CHA-BA/FGA dose = 0.09 g/100 mL, solution pH = 8.68, and temperature = 25 °C). Various interactions, including H-bonding, electrostatic forces, π-π stacking, and n-π stacking provide an account of the hypothesized mechanism of MV 2B adsorption onto the surface of CHA-BA/FGA. This research reveals that CHA-BA/FGA with its unique biocomposite structure and favorable adsorption properties can be used to remove harmful cationic dyes from wastewater.

Herein, a quadruple biomagnetic nanocomposite of cross-linked chitosan-ethylene glycol diglycidyl ether/organo-nanoclay (MCH-EGDE/ORNC) was designed for the uptake of remazol brilliant blue R (RBBR) dye from aqueous environment. The adsorption process was systematically improved via the Box-Behnken design (BBD) to determine the influence of key uptake parameters, including MCH-EGDE/ORNC dosage, pH, and time, on the RBBR removal. The highest RBBR removal of 87.5 % was achieved at the following conditions: MCH-EGDE/ORNC dosage: 0.1 g/100 mL; pH: 4.0; contact time: 25 min. The findings of the kinetics and equilibrium studies revealed an excellent fit to the pseudo-second order and the Freundlich models, respectively. The adsorption capacity of the MCH-EGDE/ORNC for RBBR was found to be 168.4 mg/g, showcasing its remarkable adsorption capability. The present work highlights the potential of MCH-EGDE/ORNC biomaterial as an advanced adsorbent and lays the foundation for future applications in water purification and environmental remediation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Herein, a highly efficient and sustainable adsorbent of cross-linked chitosan-glyoxal/algae biocomposite (CHT-GLX/ALG) adsorbent was developed through an innovative hydrothermal cross-linking method. The CHT-GLX/ALG biocomposite was characterized using several complementary analytical methods that include CHN-O, XRD, FTIR, SEM-EDX, and pH pzc . This new adsorbent, named CHT-GLX/ALG, was utilized for the adsorption of a cationic dye (methyl violet 2B; MV 2B), from synthetic wastewater. The optimization of the dye adsorption process involved key parameters is listed: CHT-GLX/ALG dosage (from 0.02 to 0.1 g/100 mL), pH (from 4 to 10), and contact time (from 20 to 180 min) that was conducted using the Box-Behnken design (BBD). The optimal adsorption conditions for the highest decolorization efficiency of MV 2B (97.02 %) were estimated using the statistical model of the Box-Behnken design. These conditions include a fixed adsorbent dosage of 0.099 g/100 mL, pH 9.9, and a 179.9 min contact time. The empirical data of MV 2B adsorption by CHT-GLX/ALG exhibited favorable agreement with the Freundlich isotherm model. The kinetic adsorption profile of MV 2B by CHT-GLX/ALG revealed a good fit with the pseudo-second-order model. The maximum adsorption capacity (q max ) for MV 2B by CHT-GLX/ALG was estimated at 110.8 mg/g. The adsorption of MV 2B onto the adsorbent can be attributed to several factors, including electrostatic interactions between the negatively charged surface of CHT-GLX/ALG and the MV 2B cation, as well as n-π and H-bonding. These interactions play a crucial role in facilitating the effective adsorption of MV 2B onto the biocomposite adsorbent. Generally, this study highlights the potential of CHT-GLX/ALG as an efficient and sustainable adsorbent for the effective removal of organic dyes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Herein, the polymer nanomatrix of chitosan/SiO 2 (CHI/n-SiO 2 ) was enriched with a π-π electron donor-acceptor system using diaromatic rings of benzil (BEZ) assisted via a hydrothermal process to obtain an effective adsorbent of chitosan-benzil/SiO 2 (CHI-BEZ/n-SiO 2 ). The polymer nanomatrix (CHI/n-SiO 2 ) and the resulting adsorbent (CHI-BEZ/n-SiO 2 ) were applied to remove the anionic acid red 88 (AR88) dye from aqueous media in a comparative mode. Box-Behnken design (BBD) was adopted to optimize AR88 adsorption onto CHI/n-SiO 2 and CHI-BEZ/n-SiO 2 with respect to variables that influence AR88 adsorption (adsorbent dose: 0.02-0.1 g/100 mL; pH: 4-10; and time: 10-90). The adsorption studies at equilibrium were conducted with a variety of initial AR88 dye concentrations (20-200 mg/L). The adsorption isotherm results reveal that the AR88 adsorption by CHI/n-SiO 2 and CHI-BEZ/n-SiO 2 are described by the Langmuir model. The kinetic adsorption profiles of AR88 with CHI/n-SiO 2 and CHI-BEZ/n-SiO 2 reveal that the pseudo-first-order model provides the best fit results. Interestingly, CHI-BEZ/n-SiO 2 has a high adsorption capacity (261.2 mg/g), which exceeds the adsorption capacity of CHI/n-SiO 2 (215.1 mg/g) that relates to the surface effects of SiO 2 and the functionalization of chitosan with BEZ. These findings show that CHI-BEZ/n-SiO 2 represents a highly efficient adsorbent for the removal of harmful pollutants from water, which outperforming the CHI/n-SiO 2 system., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Herein, a novel nanohybrid composite of magnetic chitosan-salicylaldehyde/nanoclay (MCH-SAL/NCLA) was hydrothermally synthesized for removal of azo dye (acid red 88, AR88) from simulated wastewater. Response surface methodology combined with the Box-Behnken design (RSM-BBD) was applied with 29 experiments to assess the impact of adsorption variables, that include A: % NCLA loading (0-50), B: MCH-SAL/NCLA dose (0.02-0.1 g/100 mL), C: pH (4-10), and time D: (10-90 min) on AR88 dye adsorption. The highest AR88 removal (75.16 %) as per desirability function was attained at the optimum conditions (NCLA loading = 41.8 %, dosage = 0.06 g/100 mL, solution pH = 4, and time = 86. 17 min). The kinetic and equilibrium adsorption results of AR88 by MCH-SAL/NCLA reveal that the process follows the pseudo-first-order and Temkin models. The MCH-SAL/NCLA composite has a maximum adsorption capacity (173.5 mg/g) with the AR88 dye. The adsorption of AR88 onto the MCH-SAL/NCLA surface is determined by a variety of processes, including electrostatic, hydrogen bonding, n-π, and n-π interactions. This research revealed that MCH-SAL/NCLA can be used as a versatile and efficient bio-adsorbent for azo dye removal from contaminated wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

An effective hydrothermally prepared chitosan-benzaldehyde/SiO 2 adsorbent (CTA-BZA/SiO 2 ) employed functionalization of a CTA biopolymer with SiO 2 nanoparticles and BZA. CTA-BZA/SiO 2 is an adsorbent that was utilized for the adsorption of an acidic dye (acid red 88, AR88) from synthetic wastewater. The fundamental adsorption variables (A: CTA-BZA/SiO 2 dosage (0.02-0.1 g); B: pH (4-10); and C: duration (10-60)) were optimized via the Box-Behnken design (BBD). The Langmuir and Freundlich isotherms (coefficients of determination R 2  = 0.99) agreed well with empirical data of AR88 adsorption by CTA-BZA/SiO 2 . The pseudo-first-order model showed reasonable agreement with the kinetic data of AR88 adsorption by CTA-BZA/SiO 2 . The maximal AR88 adsorption capacity (q max ) for CTA-BZA/SiO 2 was identified to be 252.4 mg/g. The electrostatic attractions between both the positively charged CTA-BZA/SiO 2 adsorbent and the AR88 anions, plus the n-π, π-π, and H-bond interactions contribute to the favourable adsorption process. This study reveals that CTA-BZA/SiO 2 has the capacity to be a suitable adsorbent for the removal of a wider range of organic dyes from industrial effluents., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In this study, a magnetic chitosan grafted-benzaldehyde (CS-BD/Fe 3 O 4 ) was hydrothermally prepared using benzaldehyde as a grafting agent to produce a promising adsorbent for the removal of acid red 88 (AR88) dye. The CS-BD/Fe 3 O 4 was characterized by infrared spectroscopy, surface area analysis, scanning electron microscopy-energy dispersive X-ray, vibrating sample magnetometry, powder X-ray diffraction, CHN elemental analysis, and point of zero charge (pH PZC ). The Box-Behnken design (BBD) was adopted to study the role of variables that influence AR88 dye adsorption (A: CS-BD/Fe 3 O 4 dose (0.02-0.1 g), B: pH (4-10), and time C: (10-90 min)). The ANOVA results of the BBD model indicated that the F-value for the AR88 removal was 22.19 %, with the corresponding p-value of 0.0002. The adsorption profiles at equilibrium and dynamic conditions reveal that the Temkin model and the pseudo-first-order kinetics model provide an adequate description of the isotherm results, where the maximum adsorption capacity (q max ) with the AR88 dye was 154.1 mg/g. Several mechanisms, including electrostatic attraction, n-π interaction, π-π interaction, and hydrogen bonding, regulate the adsorption of AR88 dyes onto the CS-BD/Fe 3 O 4 surface. As a result, this research indicates that CS-BD/Fe 3 O 4 can be utilized as an effective and promising bio-adsorbent for azo dye removal from contaminated wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Three-dimensional (3D) printed hydrogel scaffolds enhanced with ceramics have shown potential applications for cartilage regeneration, but leaving biological and mechanical properties to be desired. This paper presents our study on the development of chitosan /alginate scaffolds with nano hydroxyapatite (nHA) by combining 3D printing and impregnating techniques, forming a hybrid, yet novel, structure of scaffolds for potential cartilage regeneration. First, we incorporated nHA into chitosan scaffold printing and studied the printability by examining the difference between the printed scaffolds and their designs. Then, we impregnated alginate with nHA into the printed chitosan scaffolds to forming a hybrid structure of scaffolds; and then characterized the scaffolds mechanically and biologically, with a focus on identifying the influence of nHA and alginate for potential cartilage regeneration. The results of compression tests on the scaffolds showed that the inclusion of nHA increased the elastic moduli of scaffolds; while the live/dead assay illustrated that nHA had a great effect on improving attachment and viability of ATCD5 cells on the scaffolds. Also, our results illustrated scaffolds with nHA impregnated in alginate hydrogel enhanced the cell viability and attachment. Furthermore, antibacterial activity of hybrid scaffolds was characterized with results indicating that the chitosan scaffolds had favourable antibacterial ability, which was further enhanced with the impregnated nHA. Taken together, our study has illustrated that chitosan/HA/alginate hybrid scaffolds are promising for cartilage regeneration and the methods developed to create hybrid scaffolds based on 3D printing and impregnating techniques, which can also be extended to fabricating scaffolds for other tissue engineering applications., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Chitosan (chi) and its modified forms as electrospun nanofibers have potential applications in advanced water treatment and biomedicine. Polyethylene oxide (PEO) is an additive commonly used to facilitate the formation of chitosan electrospun fibers because PEO (Mw ≥ 400 kDa) affords chain entanglement that stabilize the electrospinning jet, leading to enhanced formation of chi-based electrospun fibers. Herein, we report on the preparation of chitosan grafted with salicylic acid and its utility to afford improved electrospun fibers with low molecular weight (LMw) PEO (Mw » 100 kDa). A comparison of the interactions between original and grafted chitosan with PEO reveals that stable supramolecular assemblies are established between grafted chitosan and PEO, which provides support that such supramolecular interactions favor formation of chitosan electrospun fibers. Moreover, a porous chitosan electrospun nanofiber was prepared through physical treatment that reveals notably higher (ca. 4-fold) dye uptake than the pristine (unmodified) chitosan electrospun nanofibers., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Phosphorylated chitosan (P-CS) was successfully synthesized using a facile experimental setup of hydrothermal method that was applied to the adsorption of anionic Acid Red 88 (AR88) from aqueous media. The adsorption process obeyed the pseudo-second-order (PSO) kinetic model. In contrast, the adsorption isotherm conformed to the Langmuir model, with the maximum adsorption capacity (q m  = 230 mg g -1 ) at 303 K. Both external and intraparticle diffusion strongly influenced the rate of adsorption. The insights from this study reveal that P-CS could be easily prepared and regenerated for reusability applications. The adsorption mechanism and intermolecular interaction between P-CS and AR 88 were investigated using Fourier transform infrared (FTIR) spectroscopy and calculations via Density Functional Theory (DFT). The key modes of adsorption for the P-CS/AR 88 system are driven by electrostatic attractions, H-bonding, and n-π interactions. The findings herein reveal that P-CS is a promising adsorbent for the removal of anionic dyes such as AR88 or similar pollutants from water., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The context of this study responds to the need for sorbent technology development to address the controlled removal of inorganic sulfate (SO 4 ) 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 Ca 2- ) 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 Ca 2+ 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 Ca 2+ . 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.2+ . 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.

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 ( Q m ) 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.

A systematic experimental study is reported that provides a molecular based understanding of cross-linked chitosan beads and their adsorption properties in aqueous solution containing phosphate dianion (HPO 4 ) species. Synthetically modified chitosan using epichlorohydrin and glutaraldehyde cross-linkers result in surface modified beads with variable hydrophile-lipophile character and tunable HPO 2- uptake properties. The kinetic and thermodynamic adsorption properties of cross-linked chitosan beads with HPO 4 species were studied in aqueous solution. Complementary structure and physicochemical characterization of chitosan beads via potentiometry, Raman spectroscopy, DSC, and dye adsorption measurements was carried out to establish structure-property relationships. The maximum uptake (Q 2- uptake properties. The kinetic and thermodynamic adsorption properties of cross-linked chitosan beads with HPO 4 2- ; whereas, kinetic uptake results for chitosan bead/phosphate systems are relatively rapid (0.111-0.113min m ) with an intraparticle diffusion rate-limiting step. The adsorption process follows a multi-step pathway involving inner- and outer-sphere complexes with significant changes in hydration. Phosphate uptake strongly depends on the composition and type of cross-linker used for preparation of chitosan beads. The adsorption isotherms and structural characterization of bead systems illustrate the role of surface charge, hydrophile-lipophile balance, adsorption site accessibility, and hydration properties of the chitosan bead surface.4 2- at equilibrium was 52.1mgg -1 ; whereas, kinetic uptake results for chitosan bead/phosphate systems are relatively rapid (0.111-0.113min -1 ) with an intraparticle diffusion rate-limiting step. The adsorption process follows a multi-step pathway involving inner- and outer-sphere complexes with significant changes in hydration. Phosphate uptake strongly depends on the composition and type of cross-linker used for preparation of chitosan beads. The adsorption isotherms and structural characterization of bead systems illustrate the role of surface charge, hydrophile-lipophile balance, adsorption site accessibility, and hydration properties of the chitosan bead surface., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The presence of contaminants in wastewater poses significant challenges to water treatment processes and environmental remediation. The use of coagulation-flocculation represents a facile and efficient way of removing charged particles from water. The formation of stable colloidal flocs is necessary for floc aggregation and, hence, their subsequent removal. Aggregation occurs when these flocs form extended networks through the self-assembly of polyelectrolytes, such as the amine-based polysaccharide (chitosan), which form polymer "bridges" in a floc network. The aim of this overview is to evaluate how the self-assembly process of chitosan and its derivatives is influenced by factors related to the morphology of chitosan (flocculant) and the role of the solution conditions in the flocculation properties of chitosan and its modified forms. Chitosan has been used alone or in conjunction with a salt, such as aluminum sulphate, as an aid for the removal of various waterborne contaminants. Modified chitosan relates to grafted anionic or cationic groups onto the C-6 hydroxyl group or the amine group at C-2 on the glucosamine monomer of chitosan. By varying the parameters, such as molecular weight and the degree of deacetylation of chitosan, pH, reaction and settling time, dosage and temperature, self-assembly can be further investigated. This mini-review places an emphasis on the molecular-level details of the flocculation and the self-assembly processes for the marine-based biopolymer, chitosan., Competing Interests: The authors declare no conflict of interest.

A one-pot kinetic uptake study of urea in aqueous solution with various chitosan sorbent materials such as pristine chitosan, cross-linked chitosan with glutaraldehyde from low (C-1) to higher (C-2) glutaraldehyde content, and a Cu(II) complex of a glutaraldehyde cross-linked chitosan material (C-3) is reported herein. The kinetic uptake profiles were analyzed by the pseudo-first order (PFO) and pseudo-second-order (PSO) models, respectively. The uptake rate constant of urea and the sorption capacity (qe) of high molecular weight (HMW) chitosan, C-1, C-2, and C-3 were best described by the PFO model. The uptake rate constant of urea with the various sorbents is listed in ascending order: HMW chitosan

Composite nano-microparticles were prepared in aqueous solution that contain chitosan or modified (carboxymethyl) chitosan with polyanion species such as alginate or tripolyphosphate, respectively. Several types of particles were prepared and characterized by (1)H/(31)P NMR spectroscopy, IR spectroscopy, and DLS. According to DLS, the particle size was observed to increase as the concentration of the aqueous urea solution increased. The average size and polydispersity index (in parentheses) vary and are reported for the chitosan-based particles from 243.0 ± 1 nm (0.28) to 424 ± 14 nm (0.33), according to DLS measurements at ambient conditions. Thus, the particles are herein referred to as nano-microparticles (NMPs) due to the relative size range. The stability of the NMPs is related to the particle composition and the aqueous solution conditions, as evidenced by variable NMP stability on the order of two weeks or more at different ionic strength., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study reports the preparation of chitosan-glutaraldehyde (Chi-Glu) copolymers at modified reaction conditions such as the temperature prior to gelation, pH, and reagent ratios. The chitosan copolymers were characterized using infrared spectroscopy (FT-IR), CHN elemental analysis, and thermal gravimetric analysis (TGA). Evidence of self-polymerized glutaraldehyde was supported by CHN and TGA results. The sorption properties of Chi-Glu copolymers were evaluated in aqueous solutions containing p-nitrophenol at variable pH (4.6, 6.6, and 9.0). The sorption properties of the copolymers correlated with the level of the accessibility of the sorption sites in accordance with the relative cross-linker content. The relative sorption capacity of the Chi-Glu copolymers increases as the level of cross-linking increases. Chitosan displays the lowest sorptive uptake while an optimal sorption capacity was concluded at the 4:1 glutaraldehyde:chitosan monomer mole ratio, in close agreement with the three reactive sites (i.e. OH/NH) per glucosamine monomer. The PNP dye probe was determined to bind to chitosan through an electrostatic interaction due to the increased sorption capacity of the phenolate anion, as evidenced by the change in pH from 4.6 to 9.0., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In this study, chitosan-based copolymers were prepared at various weight ratios of chitosan (C) to glutaraldehyde (G): 1:1 (CG11), 2:1 (CG21), and 3:1 (CG31). The sorption properties of these copolymers were investigated with roxarsone in simulated aquatic conditions at pH 7 in phosphate buffer, similar to that found in poultry litter leachate. The relative sorption capacity (Q(m); mmol/g) of the sorbents are listed in parentheses in descending order: CG11 (1.80)>CG31 (0.945)>CG21 (0.802)>chitosan (0.416). The sorptive properties of the copolymers are comparable to granular activated carbon (GAC), a standard carbonaceous sorbent material, where Q(m)=2.36 mmol/g. The adsorption properties of phenolic adsorbates such as o-nitrophenol, p-nitrophenol, and roxarsone with the CG copolymers and GAC were investigated at various pH and compared with phosphate and carbonate buffer systems., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Chitosan-glutaraldehyde copolymer sorbents were synthesized by reacting variable weight ratios (low, medium, and high) of glutaraldehyde with fixed amounts of chitosan. Two commercially available chitosan polymers with low (L) and high (H) relative molecular weights were investigated. The chitosan-glutaraldehyde (Chi-Glu) copolymer sorbents are denoted as CPL-X or CPH-X where X denotes the incremental level (X=-1, -2, -3) of glutaraldehyde. The copolymers were characterized using FT-IR spectroscopy and TGA. The solid-solution sorption isotherms in alkaline aqueous solution for the copolymers were characterized using absorbance and emission based spectroscopic methods for p-nitrophenol (PNP) and the arsenate oxoanion HAsO4(2-) species, respectively. The Sips isotherm model was utilized to obtain sorption parameters at pH 8.5 and 295K (i.e. sorbent surface area, sorption capacity and removal efficiency) for each copolymer sorbent. The sorbent surface areas for the low molecular weight chitosan copolymers are listed in parentheses (m(2)g(-1)), as follows: CPL-1 (124), CPL-2 (46.7) and CPL-3 (31.6). The high molecular weight chitosan copolymers are as follows: CPH-1 (79.8), CPH-2 (64.7) and CPH-3 (96.3). The removal efficiencies depend on the pH, temperature, and the relative amounts of sorbate and sorbent. The sorbent removal efficiencies for p-nitrophenol ranged between 7.1% and 49%, and the values for H2AsO4(2-) ranged between 31% to 93% for the low and high molecular weight copolymers., (Copyright © 2012 Elsevier Inc. All rights reserved.)

β-Cyclodextrin-chitosan-glutaraldehyde terpolymers were synthesized by reacting variable weight fractions of β-cyclodextrin (β-CD) and chitosan (Chi), with a constant amount of crosslinker (glutaraldehyde). The β-CD:Chi:Glu terpolymer sorbents were characterized by FT-IR spectroscopy and TGA. The solid-solution sorption isotherms in aqueous solution for the copolymers were characterized using two spectroscopic methods (UV-Vis and ICAP-OES) for p-nitrophenol (PNP) and the arsenate oxoanion (HAsO(4)(2-)) at alkaline pH conditions. The Sips isotherm model was utilized to obtain sorption parameters at pH 8.5 and 295 K (i.e. sorbent surface area, sorption capacity and removal efficiency) for each copolymer sorbent. The sorbent surface area estimates for the terpolymers at low (T1), medium (T2), and high (T3) weight fractions of β-CD are listed in parentheses (m(2) g(-1)), as follows: T1 (161), T2 (51.2) and T3 (275). The removal efficiencies are dependent on the relative weight fraction of the polysaccharide components (i.e. β-CD and Chi); whereas the removal efficiencies for p-nitrophenolate ranged between 7.3% and 28%, and H(2)AsO(4)(2-) ranged between 23% and 55%., (Copyright © 2012 Elsevier Inc. All rights reserved.)