Innovative biopolyelectrolytes-based technologies for wastewater treatment.

Developing eco-friendly, cost-effective, and efficient methods for treating water pollutants has become paramount in recent years. Biopolyelectrolytes (BPEs), comprising natural polymers like chitosan, alginate, and cellulose, have emerged as versatile tools in this pursuit. This review offers a comprehensive exploration of the diverse roles of BPEs in combating water contamination, spanning coagulation-flocculation, adsorption, and filtration membrane techniques. With ionizable functional groups, BPEs exhibit promise in removing heavy metals, dyes, and various pollutants. Studies showcase the efficacy of chitosan, alginate, and pectin in achieving notable removal rates. BPEs efficiently adsorb heavy metal ions, dyes, and pesticides, leveraging robust adsorption capacity and exceptional mechanical properties. Furthermore, BPEs play a pivotal role in filtration membrane techniques, offering efficient separation systems with high removal rates and low energy consumption. Despite challenges related to production costs and property variability, their environmentally friendly, biodegradable, renewable, and recyclable nature positions BPEs as compelling candidates for sustainable water treatment technologies. This review delves deeper into BPEs' modification and integration with other materials; these natural polymers hold substantial promise in revolutionizing the landscape of water treatment technologies, offering eco-conscious solutions to address the pressing global issue of water pollution.

Process-structure-property relationships of cellulose nanocrystals derived from Juncus effusus stems on Ò¡-carrageenan-based bio-nanocomposite films.

This study investigates the potential of Juncus plant fibers as a renewable source for producing cellulose nanocrystals (CNs) to reinforce polymers. Cellulose microfibers (CMFs) were extracted with a 0.43 ± 0.2 µm diameter and 69 % crystallinity through alkaline and bleaching treatments, then subjected to sulfuric acid hydrolysis, yielding four CN types (CN10, CN15, CN20 and CN30) with distinct physico-chemical properties and aspect ratios (47, 55, 57, and 60). The study assessed the influence of cellulose nanocrystals (CNs), incorporated at different weight percentages (3 %, 5 %, and 8 %), on thermal, transparency, and mechanical properties in k-carrageenan (CA) biocomposite films. The results indicate significant enhancements in these characteristics, highlighting good compatibility between CNs and CA matrix. Particularly noteworthy is the observed substantial improvement in tensile strength at an 8 wt% loading, with values of 23.43 ± 0.83 MPa for neat CA, 33.53 ± 0.83 MPa for CA-CN10, 36.67 ± 0.71 MPa for CA-CN15, 37.65 ± 0.56 MPa for CA-CN20, and 39.89 ± 0.77 MPa for CA-CN30 composites. Furthermore, the research explores the connection between the duration of hydrolysis and the properties of cellulose nanocrystals (CNs), unveiling their influence on the characteristics of nanocomposite films. Prolonged hydrolysis enhances CN crystallinity (CrI), aspect ratio, and surface charge content, consequently enhancing mechanical features like strength and flexibility in these films. These findings demonstrate the potential of Juncus plant fibers as a natural and eco-friendly resource for producing CNs that effectively reinforce polymers, making them an attractive option for diverse applications in the field.

Experimental and theoretical studies on nitrate removal using epichlorohydrin-modified cross-linked chitosan derived from shrimp waste.

Nitrates level in water is a worldwide problem that represents a risk to the environment and people's health; efforts are currently devoted to the development and implementation of new biomaterials for their removal. In this study, chitosan (Ch) from shrimp waste and the related epichlorohydrin-modified crossover chitosan (Ch-EPI) were used to remove nitrates from aqueous solutions. The mechanism of selective nitrate removal was elucidated and validated by theoretical calculations. The physicochemical performance of Ch and Ch-EPI was investigated through the main parameters pH, adsorption capacity, contact time, initial nitrate concentration, coexisting anions, and temperature. The experimental data were fitted to widely used adsorption kinetic models and adsorption isotherms. The maximum percentage of nitrate adsorption was reached at an equilibrium pH of 4.0 at an adsorbent dose of 2.0 g/L after a contact time of 50 min. Competing anion experiments show that chloride and sulfate ions have minimal and maximal effects on nitrate adsorption by Ch-EPI. Experimental adsorption data are best fitted to pseudo-second-order kinetic and isothermal Langmuir models. The maximum adsorption capacities of Ch and Ch-EPI for nitrate removal were 12.0 mg/g and 38 mg/g, respectively.

A Novel Chitosan/Nano-Hydroxyapatite Composite for the Adsorptive Removal of Cd(II) from Aqueous Solution.

A novel polymer bio-composite based on nano-hydroxyapatite (n-Hap) and chitosan (CS) (CS/n-Hap) was synthesized to effectively address toxic cadmium ions removal from water. The composition and structure of CS/n-Hap bio-composite were analyzed through different characterization techniques. XRD patterns affirmed that the crystalline structure of n-Hap remained unaltered during CS/n-Hap synthesis, while FT-IR spectrum sustained all the characteristic peaks of both CS and n-Hap, affirming the successful synthesis of CS/n-Hap. Adsorption studies, including pH, adsorbent dosage, contact time, initial Cd(II) concentration, and temperature, were carried out to explain and understand the adsorption mechanism. Comparatively, CS/n-Hap bio-composite exhibited better Cd(II) adsorption capacity than pristine CS, with an experimental maximum uptake of 126.65 mg/g under optimized conditions. In addition, the kinetic data were well fitted to the pseudo-second-order model, indicating the formation of chemical bonds between Cd(II) and CS/n-Hap during adsorption. Furthermore, the thermodynamic study suggested that Cd(II) adsorption onto CS/n-Hap was endothermic and spontaneous. The regeneration study showed only about a 3% loss in Cd(II) uptake by CS/n-Hap after five consecutive cycles. Thus, a simple and facile approach was here developed to synthesize an eco-friendly and cost-effective material that can be successfully employed for the removal of toxic heavy metal ions from water.

Exploration of multifunctional properties of garlic skin derived cellulose nanocrystals and extracts incorporated chitosan biocomposite films for active packaging application.

For many years, garlic has been used as a condiment in food and traditional medicine. However, the garlic skin, which accounts for 25% of the garlic bulk, is considered agricultural waste. In this study, cellulose nanocrystals (CNCs) and garlic extract (GE) from garlic skin were isolated and used as fillers to manufacture biocomposite films. The films were characterized in terms of UV barrier, thermal, mechanical, biodegradability, and antimicrobial activity. The chitosan-containing films and CNCs have significantly improved the films' tensile strength, Young's modulus, and elongation but decreased the film transparency compared to chitosan films. The combination of the CNCs and GE, on the other hand, slightly reduced the mechanical properties. The addition of CNCs slightly decreased the film transparency, while the addition of GE significantly improved the UV barrier properties. Thermal studies revealed that the incorporation of CNC and GE had minimal effect on the thermal stability of the chitosan films. The degradability rate of the chitosan composite films was found to be higher than that of the neat chitosan films. The antimicrobial properties of films were studied against Escherichia coli, Streptomyces griseorubens, Streptomyces alboviridis, and Staphylococcus aureus, observing that their growth was considerably inhibited by the addition of GE in composite films. Films incorporating both CNCs and GE from garlic skin hold more promise for active food packaging applications due to a combination of enhanced physical characteristics and antibacterial activity.

Comparison of green bio-based cerium/alginate vs. copper/alginate beads: a study of vibrational and thermal properties using experimental and theoretical methods.

Herein, bio-based alginates (Alg) containing metallic beads (Ce and Cu) were synthesized via an alginate cross-linking method, and their properties were studied using experimental techniques combined with theoretical simulations. Materials were characterized through Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscope (SEM) images, to determine the cross-linking structural features, thermal stability, and surface morphology of alginates. Besides, density functional theory (DFT) methods were employed to calculate global reactivity parameters such as HOMO-LUMO gap energies (ΔEH-L), electronegativity (χ), hardness (η), and electrophilic and nucleophilic indicators, using both gas and aqueous media for the study of the complexation process. Among other features, characterization of the thermal properties showed that Alg@Ce and Alg@Cu alginate beads behave differently as a function of the temperature. This behavior was also predicted by the conformation energy differences between Alg@Ce and Alg@Cu, which were found out theoretically and explained with the combined study of the vibrational modes between the carboxylate group with either Ce or Cu. Overall, the reactivity of the Alg@Ce alginate bead was higher than that of the Alg@Cu counterpart, results could be used as a cornerstone to employed the materials here studied in a wide range of applications.

DFT, Monte Carlo and molecular dynamics simulations for the prediction of corrosion inhibition efficiency of novel pyrazolylnucleosides on Cu(111) surface in acidic media.

Five novel pyrazolylnucleosides have been evaluated theoretically for their corrosion inhibition efficiency on the Cu(111) surface in acidic media. DFT calculations were carried out to exhibit the intrinsic properties such as lowest unoccupied (ELUMO) and highest occupied (EHOMO) molecular orbital energies, as well as energy gap (∆E), chemical hardness (η), chemical softness (σ), electronegativity (χ), electrophilicity (ω) and nucleophilicity (ε). The theoretical FT-IR spectra were recorded to indicate the presence of the specific bonds in the studied molecules. The surface interactions between the inhibitor molecules and the metal surface were investigated using molecular dynamics simulations and Monte Carlo (MC) simulations. As a result, we have found that the inhibitor pyrazolylnucleosides 5a-e have strong interactions with Cu(111) surface, and therefore have excellent predictive inhibition power against copper corrosion.

Synthesis and Surface Modification of Small Pore Size Zeolite W for Improving Removal Efficiency of Anionic Contaminants from Water.

The presence of regulated inorganic contaminants in water such as AsO43- and PO43- anions, is becoming a relevant environmental research topic. The harm that these anions cause to human health and the ecosystem have been reported in several works. The adsorption processes using low-cost materials, such as zeolites, have proven to be an option to removal hazardous contaminants from water. The coal fly ash, a waste from thermoelectrical plants, offers a raw pollutant material to synthesis an effective adsorbent (Zeolite W). In this research was studied the removal of arsenic and phosphates anions from water, applying a functionalized by iron and zirconium Zeolite W, which was modified using a fast and efficient process through microwave-assisted method (1 min at 150°C). The obtained Zeolite W did not show significant changes in its structure and morphology. The maximum adsorption capacity (Qm expressed in mg g-1) was found to be 42.31 (Iron-zirconium-zeolite) and 27.82 (Iron-zeolite) for AsO43-, while it reached 50.89 for PO43- using Zirconium-zeolite. Results showed that functionalized zeolites are efficient adsorbents for hazardous anionic species; therefore, it could be useful for aqueous effluents remediation.

Eco-Efficient Green Seaweed Codium decorticatum Biosorbent for Textile Dyes: Characterization, Mechanism, Recyclability, and RSM Optimization.

Biosorption using natural waste has emerged as a potential and promising strategy for removal of toxic dyes from wastewaters in comparison to conventional ones. Herein, the Codium decorticatum alga (CDA) was biologically identified and used as a biosorbent for anionic and cationic dyes from aqueous solutions. SEM analysis showed a rough surface with an irregular edge and shape while hydroxyl, amine, sulfur and carboxyl functional groups were identified using FTIR analysis. TGA/DTG confirmed the stability of CDA and the adsorption process. Batch studies were conducted to investigate the effect of operational factors such as initial pH, biosorbent dosage, temperature, initial concentration, and solid/liquid contact time on the biosorption of crystal violet (CV) and Congo red (CR) dyes. For both CV and CR dyes, the biosorption kinetics was accurately described by the pseudo-second-order model and the Langmuir isotherm was found to be best fitted for equilibrium data. Maximum uptake capacities have attained up to 278.46 mg/g for CV and 191.01 mg/g for CR. The CV and CR dye biosorption mechanism was ultimately manifested through the electrostatic interactions. The regeneration study showed that the CDA presents excellent reuse performance up to four consecutive cycles. The process optimization was performed using the response surface methodology based on Box-Behnken design (RSM-BDD). Accordingly, the optimum predicted removal efficiencies using RSM-BBD for CV and CR were obtained, respectively, at 96.9 and 89.8% using a CDA dose of 1.5 g/L, dye concentration of 20 mg/L, pH of 10 for CV, and pH of 4 for CR. Overall, CDA behaves as an efficient, recyclable, cheap, and eco-friendly adsorbent for cleaning-up of dyed effluents.

Micro- and nano-celluloses derived from hemp stalks and their effect as polymer reinforcing materials.

Fiber-reinforced polymers have emerged as one of the most popular methods to improve the polymers' characteristics owing to their prominent properties. This study aimed to investigate the properties of cellulose microfibers (CMF), cellulose nanocrystals (CNC) and cellulose nanofibrils (CNF) extracted from hemp stalks, then their effect as reinforcement for the PVA-polymer. CMF have been extracted from hemp stalks with a diameter and yield of 16.96 µm and 63 %, respectively. Needle-shaped CNC were obtained from CMF using sulfuric acid hydrolysis at two hydrolysis times, while CNF exhibited a web-like structure obtained using TEMPO-oxidation followed by mechanical treatment. Cellulose derivatives were utilized to develop cellulose-based PVA composites; their transparency, chemical structure, thermal stability and mechanical properties were investigated. The incorporation of nanocellulose demonstrated a significant increase in mechanical properties compared to the neat PVA. The extracted nanocellulose could be used as nanofillers for the preparation of transparent and mechanically strong PVA-based nanocomposites.

Eco-Efficient Biosorbent Based on Leucaena leucocephala Residues for the Simultaneous Removal of Pb(II) and Cd(II) Ions from Water System: Sorption and Mechanism.

Leucaena leucocephala is a potential source of polyphenols widely available in southern Mexico. This work highlights the extraction of polyphenols from Leucaena leucocephala leaves waste (LLEPs) and the evaluation of their efficiency to remove the single and multicomponent Pb(II) and Cd(II) metal ions from aqueous solutions. Batch test conditions were carried out to examine the effects of contact time, initial metal ion concentration, and adsorbent dosage on the biosorption process. The surface textures and the composition of the LLEP biosorbent was characterized using pH of point of zero charge (pHPZC), attenuated total reflectance Fourier transform infrared (ATR-FTIR), and matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry, respectively. Further analysis using ATR-FTIR after adsorption contact of biosorbent was also investigated. The highest Langmuir saturation monolayer adsorption capacity, q m, for the removal of Pb(II) by LLEPs was obtained as 25.51 and 21.55 mg/g in mono- and bimetal solutions, respectively. The pseudo-second-order model provided the best fit for the kinetic data obtained for the removal of Pb(II), Cd(II), and their mixture, and the k2 values depend on the adsorbent mass. This implied that the chemisorption process might be the mechanism of the solute ions-LLEPs interaction in this study. Furthermore, nearly 100% removal of lead and cadmium individually and 95% of their mixture was found using 0.9 g of LLEPs.