Novel High-Performance Functionalized and Grafted Bio-Based Chitosan Adsorbents for the Efficient and Selective Removal of Toxic Heavy Metals from Contaminated Water.

Novel functionalized and/or grafted crosslinked chitosan adsorbents were synthesized and used to remove several toxic heavy metal ions such as nickel, lead, chromium, and cadmium ions from contaminated water. The chitosan biopolymer was functionalized by maleic anhydride (CS_MA) acting also as a crosslinking agent. Glutaraldehyde-crosslinked chitosan (CS_GA) grafted with poly(methyl methacrylate) (CS_MMA) was also synthesized. The synthesized adsorbents were characterized using a variety of analytical techniques such as SEM, TGA, and FTIR, which confirmed their chemical structures and morphology. The adsorption capacity of the adsorbents was analyzed under various conditions of contact time, adsorbent dose, initial concertation, temperature, and pH and evaluated against those of pure chitosan (CS) and the crosslinked chitosan(CS_GA). The ultimate removal conditions were 0.5 g/100 mL adsorbent dose, an initial metal ion concentration of 50 ppm, a temperature of 45 °C, and pH 9. CS_MMA had the highest removal percentages for all metal ions, ranging from 92% to 94%. The adsorption was demonstrated to fit a pseudo-first-order model that followed a Langmuir adsorption isotherm. The results highlight the capacity of the synthesized polymers to efficiently remove major toxic contaminants at low cost from contaminated water, present especially in low-income areas, without harming the environment.

Environmentally safe biopolymer-clay composite for efficient adsorption of ciprofloxacin in fresh and saline solutions.

In alignment with the sustainable development goals (SDGs), recent trends in water management have been directed toward using environmentally friendly bio-based materials for removing contaminants. In this work, we prepared a biocomposite of chitosan (CS) intercalated into acid activated calcium bentonite (Bent). A thermally stable mesoporous CS-Bent composite was prepared with a zeta potential of 15.5 to -34.4 mV in the pH range of 2.22-10. The biocomposite successfully removed up to 99.2% and 50 mg/g of the antibiotic ciprofloxacin HCl (CPX) at pH 5.5 via electrostatic and hydrogen bonding forces. In a multi-component aqueous system of heavy metal and CPX, the composite was more selective to CPX than to the heavy metals and removal of CPX in this system was comparable to that in a single-component system. The composite also maintained its high adsorption efficiency in NaCl solutions which makes it suitable for treating fresh and saline solutions. The combination of CS and bent produced a biodegradable eco-friendly composite characterized with good thermal and surface properties along with efficient and selective adsorption performance.

Impact of the Configurational Microstructure of Carboxylate-Rich Chitosan Beads on Its Adsorptive Removal of Diclofenac Potassium from Contaminated Water.

A novel adsorbent-contaminant system was investigated for its ability to remove a contaminant of emerging concern, diclofenac potassium, from contaminated water. Bio-based crosslinked chitosan beads functionalized with poly(itaconic acid) side chains were examined for their potential to remove the emerging contaminant. To evaluate the impact of the polymeric microstructure on its adsorptive capacity, several adsorbent samples were prepared using different combinations of initiator and monomeric concentrations. Fourier Transform Infrared (FTIR) analysis confirmed the crosslinking of the chitosan chains and the incorporation of the carboxylic groups on the surface of the final chitosan beads. After the grafting copolymerization process, an additional peak at 1726 cm-1 corresponding to the carboxylic C=O groups of the grafted chains appeared, indicating the successful preparation of poly(IA)-g-chitosan. Thermal stability studies showed that the grafting copolymerization improved the thermal stability of the beads. X-ray and Scanning Electron Microscopy confirmed the successful grafting of the itaconic acid on the surface of the beads. The study revealed that the higher the initiator concentration, the greater the number of side chains, whereas the higher the monomeric concentration, the longer the length of these side chains. The adsorption mechanism involved hydrogen bonding to the carboxylic groups of the grafted chains along with n-π* stacking interaction between the amino group of the chitosan and the aromatic rings of diclofenac potassium. The adsorption efficiencies of diclofenac potassium onto the grafted beads were significantly improved compared to the unfunctionalized chitosan beads, reaching values above 90%. The removal efficiency of grafted chitosan increased with an increase in the concentration in the range of 10-30 ppm and then flattened out in the range of 30-50 ppm. The removal efficiencies of 1-50 ppm of DCF ranged between about 75% and 92% for the grafted chitosan and 30-45% for the crosslinked chitosan. Rapid adsorption occurred within 20 min for all grafted sample combinations, and the adsorption kinetics followed a pseudo-second-order model with qe values ranging from 28 to 44.25 g/mg and R2 values greater than 0.9915. The results highlight the potential of grafted chitosan beads in removing emerging contaminants from contaminated water without harming the environment.

Polypyrrole- and Polyaniline-Coated Cotton Fabrics as Efficient Adsorbents for the Pharmaceutical Water Contaminants Diclofenac and Salicylic Acid.

The emerging pharmaceutical contaminants diclofenac (DCF) and salicylic acid (SA) pose potential hazards to humans and living organisms due to their persistence in water environments. In this work, the conductive polymers polypyrrole (PPY) and polyaniline (PANI) were successfully coated on cotton fabrics, as confirmed by FTIR and SEM measurements. The coated fabrics efficiently removed DCF at pH 5.3 and SA at pH 4, with removal efficiencies that exceeded 90% and 70%, respectively. Adsorption was rapid for most of the tested contaminant-fabric systems and reached equilibrium within 20-30 min. The best adsorption performance for both contaminants was shown on the PPY-coated fabrics, which yielded adsorption capacities of about 65 and 21 mg/g for DCF and SA, respectively. This could be explained by molecular modeling simulations, which mostly estimated higher total cohesive energy densities for adsorption on the PPY-coated fabrics than on the PANI-coated ones. The adsorption mechanism involved both coulombic electrostatic attractions and non-coulombic van der Waals and π-π stacking. The fabrics could be reused for three adsorption-desorption cycles. Immobilization of the conductive polymers on cotton fabrics provides a facile method for their handling and collection during adsorption and regeneration cycles while maintaining their multi-functionality in adsorbing different contaminants.

Design and Development of Enhanced Antimicrobial Breathable Biodegradable Polymeric Films for Food Packaging Applications.

The principle of breathable food packaging is to provide the optimal number of pores to transfer a sufficient amount of fresh air into the packaging headspace. In this work, antimicrobial microporous eco-friendly polymeric membranes were developed for food packaging. Polylactic acid (PLA) and polycaprolactone (PCL) were chosen as the main packaging polymers for their biodegradability. To develop the microporous films, sodium chloride (NaCl) and polyethylene oxide (PEO) were used as porogenic agents and the membranes were prepared using solvent-casting techniques. The results showed that films with of 50% NaCl and 10% PEO by mass achieved the highest air permeability and oxygen transmission rate (O2TR) with PLA. Meanwhile, blends of 20% PLA and 80% PCL by mass showed the highest air permeability and O2TR at 100% NaCl composition. The microporous membranes were also coated with cinnamaldehyde, a natural antimicrobial ingredient, to avoid the transportation of pathogens through the membranes into the packaged foods. In vitro analysis showed that the biodegradable membranes were not only environmentally friendly but also allowed for maximum food protection through the transportation of sterile fresh air, making them ideal for food packaging applications.

Tailored-design of electrospun nanofiber cellulose acetate/poly(lactic acid) dressing mats loaded with a newly synthesized sulfonamide analog exhibiting superior wound healing.

To effectively allow for controlled release of a newly synthesized sulfonamide analog, biodegradable poly(lactic acid) nanofibrous dressing mats tailored-designed for maximum wound healing efficacy were developed. The heterocyclic analog, N-(3,4-diamino-7-(benzo [d]thiazol-2-yl)-6-oxo-1H-pyrazolo[4,3-c]pyridin-5(6H)-yl)benzenesulfonamide, has been specifically synthesized to possess superior antibacterial and anti-inflammatory characteristics. Hydrophilic cellulose acetate and/or poly(ethylene oxide) were blended with the hydrophobic PLA to control the hydrophilicity/hydrophobicity ratio for the sustained release of the drug. SEM detected no drug crystals on the surface of the nanofibers confirming the homogeneous dispersion and compatibility of the drug with the nanofibers. BET indicated almost-reversible Type II sorption isotherms. The swelling studies revealed that the presence of hydrogen bonds between the hydroxyl groups of CA with the carbonyl ester groups of PLA limited the ability of CA molecules to leach from the polymer matrix. Water vapor permeability were all determined to be within the range of 15-19 g/m2/h. In-vitro cell viability and cell proliferation studies revealed the superiority of the fabricated dressing mats in terms of its bioactivity and cellular interaction. In-vivo studies confirmed the major improvement in its wound healing capabilities attributed to an enhanced epithelization, anti-inflammation, neo-angiogenesis, fibroplasias and collagen deposition that surpassed that of commercially available ones.

Imide-Based Polymers of Intrinsic Microporosity: Probing the Microstructure in Relation to CO2 Sorption Characteristics.

A range of microporous, imide-based polymers were newly synthesized using two-step poly-condensation reactions of bis(carboxylic anhydride) and various aromatic diamines for CO2 gas capture and storage applications. In this report, we attempted to assess the relative significance of molecular structural aspects through the manipulation of the conformational characteristics of the building blocks of the polymeric structures, the spiro-containing acid anhydride and the aromatic amines, to induce greater intrinsic microporosity and higher surface areas for the resulting solids. Results obtained from this study were thus used to outline a working relationship between the structural diversity of the constructed porous solids and their performance as CO2 sorbents.

New polylactic acid/ cellulose acetate-based antimicrobial interactive single dose nanofibrous wound dressing mats.

New single dose interactive extracellular matrix (ECM) mimicking nanofibrous wound dressings based on polylactic acid (PLA) and cellulose acetate (CA) were developed, characterized and investigated for wound treatment. The antimicrobial agent, thymoquinone (TQ) was selected and incorporated into the scaffolds for preventing common clinical infections, and to accelerate the rate of wound closure and re-epithelialization. The newly fabricated TQ-loaded PLA/CA wound dressings offered many advantages such as mimicking the ECM via the 3D nanofibrous structure, and promoted the cell proliferation due to the hydrophilicity and bioactivity of CA. The wound dressings also prevented the bacterial infection in the early stages due to presence of TQ, and maintained the minimum possible bacterial load in the wound area through the sustained release of the drug for 9days. In vivo assessment demonstrated that TQ-loaded PLA: CA (7:3) scaffolds significantly promoted the wound healing process by increasing re-epithelialization and controlling the formation of granulation tissue. The obtained results suggest that the developed TQ-loaded PLA/CA nanofibrous mats could be ideal for wound dressing applications.

The role of the deformational entropy in the miscibility of polymer blends investigated using a hybrid statistical mechanics and molecular dynamics model.

To fully understand the thermodynamic nature of polymer blends and accurately predict their miscibility on a microscopic level, a hybrid model employing both statistical mechanics and molecular dynamics techniques was developed to effectively predict the total free energy of mixing. The statistical mechanics principles were used to derive an expression for the deformational entropy of the chains in the polymeric blends that could be evaluated from molecular dynamics trajectories. Evaluation of the entropy loss due to the deformation of the polymer chains in the case of coiling as a result of the repulsive interactions between the blend components or in the case of swelling due to the attractive interactions between the polymeric segments predicted a negative value for the deformational entropy resulting in a decrease in the overall entropy change upon mixing. Molecular dynamics methods were then used to evaluate the enthalpy of mixing, entropy of mixing, the loss in entropy due to the deformation of the polymeric chains upon mixing and the total free energy change for a series of polar and non-polar, poly(glycolic acid), PGA, polymer blends.