A multifunctional biogenic films and coatings from synergistic aqueous dispersion of wood-derived suberin and cellulose nanofibers.

Here, biogenic and multifunctional active food coatings and packaging with UV shielding and antimicrobial properties were structured from the aqueous dispersion of an industrial byproduct, suberin, which was stabilized with amphiphilic cellulose nanofibers (CNF). The dual-functioning CNF, synthesized in a deep eutectic solvent, functioned as an efficient suberin dispersant and reinforcing agent in the packaging design. The nanofibrillar percolation network of CNF provided a steric hindrance against the coalescence of the suberin particles. The low CNF dosage of 0.5 wt% resulted in dispersion with optimal viscosity (208.70 Pa.s), enhanced stability (instability index of <0.001), and reduced particle size (9.37 ± 2.43 µm). The dispersion of suberin and CNF was further converted into self-standing films with superior UV-blocking capability, good thermal stability, improved hydrophobicity (increase in water contact angle from 61° ± 0.15 to 83° ± 5.11), and antimicrobial properties against gram-negative bacteria. Finally, the synergistic bicomponent dispersions were demonstrated as fruit coatings for bananas and packaging for strawberries to promote their self-life. The coatings and packaging considerably mitigated fruit deterioration and improved their freshness by preventing moisture loss and microbial attack. This sustainable approach is expected to pave the way toward advanced, biogenic, and active food packaging based on widely available bioresources.

Pickering Emulsions and Hydrophobized Films of Amphiphilic Cellulose Nanofibers Synthesized in Deep Eutectic Solvent.

Herein, a dual-functioning deep eutectic solvent system based on triethylmethylammonium chloride and imidazole was harnessed as a swelling agent and a reaction medium for the esterification of cellulose with n-octyl succinic anhydride (OSA). The modified or amphiphilic cellulose nanofibers (ACNFs), synthesized using three different OSA-to-anhydroglucose unit molar ratios (0.5:1, ACNF-1; 1:1, ACNF-2; and 1.5:1, ACNF-3), were further converted into nanofibers with degree of substitution (DS) values of 0.24-0.66. The ACNFs possessed a lateral dimension of 4.24-9.22 nm and displayed surface activity due to the balance of hydrophobic and hydrophilic characteristics. The ACNFs made stable aqueous dispersions; however, the instability index of ACNF-3 (0.51) was higher than those of ACNF-1 (0.29) and ACNF-2 (0.33), which was attributed to the high DS-induced hydrophobicity, causing the instability in water. The amphiphilic nature of ACNFs promoted their performance as stabilizers in oil-in-water Pickering emulsions with average droplet sizes of 4.85 µm (ACNF-1) and 5.48 µm (ACNF-2). Self-standing films of ACNFs showed high contact angles for all the tested DS variants (97.48-114.12°), while their tensile strength was inversely related to DS values (ACNF-1: 115 MPa and ACNF-3: 49.5 MPa). Aqueous dispersions of ACNFs were also tested for coating fruits to increase their shelf life. Coatings improved their shelf life by decreasing oxygen contact and moisture loss.

Insights into the role of molar ratio and added water in the properties of choline chloride and urea-based eutectic mixtures and their cellulose swelling capacity.

Eutectic mixtures and deep eutectic solvents (DESs) are promising green media for the pre-treatment of lignocellulose materials. They can be harnessed for the swelling of cellulose and further facilitate cellulose hydrolysis, derivatization, and production of cellulose-based (nano) materials. Several studies indicated that water can take part in the formation of the nanostructure of DES; however, it is still unclear how additional water influences many important properties and functioning of DES, especially when the molar ratio of compounds differs from the eutectic point composition. Here, viscosity, pH, conductivity, solvatochromic and solvatomagnetic solvent parameters, and fiber swelling capacity of choline chloride and urea mixtures demonstrating different molar ratios were investigated in the presence and absence of added water. The participation of water in the formation of molecular clusters with choline chloride and urea was indicated by viscosity, pH, and conductivity measurements. Hydrogen bond acceptor values of aqueous mixtures increased as a function of water content, and the results obtained using both methods were in line, indicating their suitability for the determination of hydrogen bond acidity of aqueous choline chloride-urea mixtures. However, hydrogen bond basicity determined by solvatochromic and magnetic methods exhibited almost opposite trends. The close investigation of the chemical shift of solvatomagnetic probes indicated that the chemical environment of the choline chloride-urea (1 : 2) mixture remained constant until the water content of 30 wt% was in line with previous molecular simulations. When cellulose fibers were treated with mixtures under mixing, the non-ideality of the choline chloride-urea mixture and the absence of water were found to be advantageous; however, aqueous mixtures efficiently increased the diameters of cellulose fibers in the absence of mixing, and water-containing mixtures appeared to be appealing systems for cellulose pretreatments.

High-purity lignin fractions and nanospheres rich in phenolic hydroxyl and carboxyl groups isolated with alkaline deep eutectic solvent from wheat straw.

A combined pretreatment based on alkaline deep eutectic solvent (DES) of K2CO3 and glycerol and sequential acid fractionation was developed to extract reactive lignin from wheat straw biomass. This process exhibited excellent purification performance in lignin isolation, and the lignin fractionated at low pH displayed high reactivity, having hydroxyl and carboxyl groups up to 9.60 and 2.52 mmol/g, respectively. Silica was selectively separated and removed during the precipitation stage, avoiding the "silica interference". Moreover, DES-lignin nanospheres created by self-assembly using lignin fractions obtained by acid precipitation possessed a high zeta potential, large particle size and high content of hydrophilic groups. Overall, the findings related to the dissociation mechanism and fractionation of reactive lignin during alkaline DES pretreatment and the acid sequence precipitation are crucial for facilitating lignin valorization in high-added value products.

Comparison of Lignin Fractions Isolated from Wheat Straw Using Alkaline and Acidic Deep Eutectic Solvents.

This study aims to examine the characteristics of two solid lignin fractions isolated from wheat straw using alkaline and acidic deep eutectic solvents (DESs). The chemical properties and morphological characteristics of the two lignin fractions were evaluated by measuring their purity, elemental composition, molecular weight and particle size distributions, and microstructure. Their chemical structure was evaluated using DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy, GPC (gel permeation chromatography), TGA (thermogravimetric analysis), 13C NMR (nuclear magnetic resonance), 31P NMR, and HSQC NMR. Our findings showed that the lignin isolated using alkaline DESs was less pure and had a smaller particle size, higher molecular weight, and thermal stability compared to the lignin isolated using acidic DESs. Their lignin structure was also determined to be different due to varying selective fractures on the linkages of lignin. These results suggest that the DES treatments could selectively extract lignin from wheat straw with different yields, compositions, morphologies, and structures, which could then provide a theoretical basis for the selection of DESs for specially appointed lignin extraction.

Surface Modification of Cured Inorganic Foams with Cationic Cellulose Nanocrystals and Their Use as Reactive Filter Media for Anionic Dye Removal.

In this work, a surface cationized inorganic-organic hybrid foam was produced from porous geopolymer (GP) and cellulose nanocrystals (CNCs). GPs were synthesized from alkali-activated metakaolin using H2O2 as a blowing agent and hexadecyltrimethylammonium bromide (CTAB) as a surfactant. These highly porous GPs were combined at pH 7.5 with cationic CNCs that had been synthesized from dissolving pulp through periodate oxidation followed by cationization in a deep eutectic solvent. The GP-CNC hybrid foams were employed as reactive filters in the removal of the anionic dye, methyl orange (MO; 5-10 mg/L, pH 7). The effects of a mild acid wash and thermal treatments on the structure, properties, and adsorption capacity of the GPs with CNCs and MO were investigated. The CNCs aligned as films and filaments on the surfaces of the neutralized GPs and the addition of CNCs improved MO removal by up to 84% compared with the reference sample. In addition, CTAB was found to disrupt the attachment of CNCs on the pores and improve adsorption of MO in the GPs with and without CNCs.

Hydrophobic, Superabsorbing Aerogels from Choline Chloride-Based Deep Eutectic Solvent Pretreated and Silylated Cellulose Nanofibrils for Selective Oil Removal.

Superabsorbents are highly appealing materials for use in cleaning up oil and chemical spills. However, the development of a low-cost, highly efficient superabsorbent remains a major challenge. This paper demonstrates a straightforward method of producing a cellulose nanofibril aerogel that is low-cost, ultralight, highly porous, hydrophobic, and reusable superabsorbing cellulose nanofibril aerogel from recycled waste fibers using a simple, environmentally friendly nanofibrillation treatment involving deep eutectic solvent and freeze-drying. Nanofibrillation and hydrophobic modification (silylation) of waste cellulose fibers resulted in nanofibril sponges with ultralow density (0.0029 g/cm3) and high porosity (up to 99.81%) after freeze-drying. These sponges exhibited excellent absorption performances for various oils and organic solvents and were reusable. In particular, the nanofibril aerogels showed selectivity in absorbing marine diesel oil from an oil-water mixture and possessed ultrahigh absorption capacities of up to 142.9 g/g, much higher than those of the commercial absorbent materials (i.e., polypropylene-based material) (8.1-24.6 g/g) that were used as references. The absorbed oil could easily be recovered by means of simple mechanical squeezing. In addition, the nanofibril sponges exhibited excellent reusability, maintaining a high capacity to absorb diesel oil for at least 30 cycles at 71.4-81.0% of capacity compared to a fresh absorbent. The above-mentioned advantages make cellulose nanofibril superabsorbents created from recycled waste cellulose fibers promising material for cleaning oil and chemical spills.

Nanofibrillation of deep eutectic solvent-treated paper and board cellulose pulps.

In this work, several cellulose board grades, including waste board, fluting, and waste milk container board, were pretreated with green choline chloride-urea deep eutectic solvent (DES) and nanofibrillated using a Masuko grinder. DES-treated bleached chemical birch pulp, NaOH-swollen waste board, and bleached chemical birch pulp were used as reference materials. The properties of the nanofibrils after disc grinding were compared with those obtained through microfluidization. Overall, the choline chloride-urea DES pretreatment significantly enhanced the nanofibrillation of the board pulps in both nanofibrillation methods-as compared with NaOH-treated pulps-and resulted in fine and long individual nanofibrils and some larger nanofibril bunches, as determined by field emission scanning electron microscopy and transmission electron microscopy. The nanofibril suspensions obtained from the DES pretreatment had a viscous, gel-like appearance with shear thinning behavior. The nanofibrils maintained their initial crystalline structure with a crystallinity index of 61%-47%. Improved board handsheet properties also showed that DES-treated and Masuko-ground waste board and paper nanocellulose can potentially enhance the strength of the board. Consequently, the DES chemical pretreatment appears to be a promising route to obtain cellulose nanofibrils from waste board and paper.

The effect of seasonal variations on floc morphology in the activated sludge process.

The effect of seasonal variations on floc formation in the activated sludge process (ASP) was studied in a municipal wastewater treatment plant in Finland nearly 16 months. Floc formation was measured with an online optical monitoring device, and results were correlated with the temperature of the upcoming wastewater and the treatment efficiency of the ASP. Results showed that floc formation has a clear, seasonal pattern, with flocs in summer being larger and rounder and having fewer filaments and small particles. In addition, treatment efficiency increased in summer. The study correlated the results of image analysis with the composition (chemical oxygen demand and suspended solids content) and temperature of the wastewater before and after the ASP. Results showed that the composition of upcoming wastewater has no clear correlation with floc morphological parameters. However, the wastewater temperature clearly correlated with floc formation. Results indicated that cold winter conditions enhanced the growth of filamentous bacteria in wastewater, decreasing treatment efficiency. Furthermore, these results confirmed that floc formation has seasonal variations.

Distinctive green recovery of silver species from modified cellulose: mechanism and spectroscopic studies.

The present study aimed to recover precious silver in order to identify the adsorption coupled reduction pathways that determine this process. A combination technique of adsorption and nanocrystallization was used to investigate the recovery of silver species from taurine-cellulose (T-DAC) samples. The non-synthetic route of nanocrystallization yielded spherical zero-valent silver sized ∼ 18 nm. Rate-controlling steps were modeled by adsorption parameters by the best fit of Langmuir capacity (55 mg/g), pseudo-second order curves, and exothermic chemical reactions. The T-DAC was an excellent sorbing phase for the treatment of silver-polluted waters over a broad range of pH (2.1-10.1) and varying ionic strengths (8.5-850 mM, as NaCl), which are the conditions often encountered in industrial and mining effluents. A good recovery of silver (40-65%) was also obtained in the presence of Cd(II), Co(II), Cr(VI), Ni(II), and As(V) at lower or equivalent concentrations with Ag(I), either from individually added metals or from all metal ions mixed together. Desorption was compared with a series of five eluents including complexing agents. In these experiments acidified thiourea yielded 86% desorption of Ag(I). Aqueous silver reduced to metallic silver on the surface of the T-DAC samples, which was confirmed by X-ray photo electron spectroscopy.

Fabrication of cationic cellulosic nanofibrils through aqueous quaternization pretreatment and their use in colloid aggregation.

The aqueous pre-treatment of cellulose with periodate and Girard' reagent T was employed as a novel and promising method to promote nanofibrillation of wood pulp and to obtain cellulosic nanofibrils with cationic functionality (CNFC). To demonstrate the feasibility of CNFCs in particle aggregation, a kaolin clay model suspension was aggregated by the CNFCs. Direct high-pressure homogenization of cationized cellulose resulted in nanofibrils exhibiting typical widths of 10-50 nm and cationic charge densities ranging from 1.10 to 2.13 mequiv.g(-1). The nanofibril suspensions existed in the form of highly transparent gels and possessed cellulose I crystalline structures. All of the CNFCs promoted strong aggregation of kaolin and produced voluminous kaolin-CNFC aggregates with lateral dimensions of several millimeters. Moreover, the CNFCs maintained good aggregation performance through wide pH (3-9) and temperature (25-60 °C) ranges. Thus, CNFCs were shown to be highly potential candidates for replacement of present synthetic soluble flocculation and coagulation aids.