Effect of Lipoxygenase Oxidation on Surface Deposition of Unsaturated Fatty Acids.

We studied the interactions of lipid molecules (linoleic acid, glycerol trilinoleate and a complex mixture of wood extractives) with hydrophilic and hydrophobic surfaces (cellulose nanofibrils (CNFs) and polyethylene terephthalate (PET), respectively). The effect of lipoxygenase treatment to minimize the affinity of the lipids with the given surface was considered. Application of an electroacoustic sensing technique (QCM) allowed the monitoring of the kinetics of oxidation as well as dynamics of lipid deposition on CNF and PET. The effect of the lipoxygenase enzymes (LOX) was elucidated with regards to their ability to reduce the formation of soiling lipid layers. The results pointed to the fact that the rate of colloidal oxidation depended on the type of lipid substrate. The pretreatment of the lipids with LOX reduced substantially their affinity to the surfaces, especially PET. Surface plasmon resonance (SPR) sensograms confirmed the effect of oxidation in decreasing the extent of deposition on the hydrophilic CNF. QCM energy dissipation analyses revealed the possible presence of a loosely adsorbed lipid layer on the PET surface. The morphology of the deposits accumulated on the solids was determined by atomic force microscopy and indicated important changes upon lipid treatment with LOX. The results highlighted the benefit of enzyme as a biobased treatment to reduce hydrophobic interactions, thus providing a viable solution to the control of lipid deposition from aqueous media.

Aminated clay-polymer composite as soil amendment for stabilizing the short- and long-chain per- and poly-fluoroalkyl substances in contaminated soil.

Soils contaminated with per- and poly- fluoroalkyl substances (PFAS) require immediate remediation to protect the surrounding environment and human health. A novel animated clay-polymer composite was developed by applying polyethyleneimine (PEI) solution onto a montmorillonite clay-chitosan polymer composite. The resulting product, PEI-modified montmorillonite chitosan beads (MMTCBs) were characterized as an adsorptive soil amendment for immobilizing PFAS contaminants. The MMTCBs exhibited good efficiency to adsorb the PFAS, showing adsorption capacities of 12.2, 16.7, 18.5, and 20.8 mg g-1 for PFBA, PFBS, PFOA, and PFOS, respectively, which were higher than those obtained by granular activated carbon (GAC) (i.e., an adsorbent used as a reference). Column leaching tests demonstrated that amending soil with 10% MMTCBs resulted in a substantial decrease in the leaching of PFOA, PFOS, PFBA, and PFBS by 90%, 100%, 64%, and 68%, respectively. These reductions were comparable to the values obtained for GAC-modified soil, particularly for long-chain PFAS. Incorporating MMTCBs into the soil not only preserved the structural integrity of the soil matrix but also enhanced its shear strength (kPa). Conversely, adding GAC to the soil resulted in a reduction of the soil's mechanical properties.

Lignin self-assembly phenomena and valorization strategies for pulping, biorefining, and materials development: Part 1. The physical chemistry of lignin self-assembly.

Physical chemistry aspects are emphasized in this comprehensive review of self-assembly phenomena involving lignin in various forms. Attention to this topic is justified by the very high availability, low cost, and renewable nature of lignin, together with opportunities to manufacture diverse products, for instance, polymers/resins, bioplastics, carbon fibers, bio-asphalt, sunscreen components, hydrophobic layers, and microcapsules. The colloidal lignin material, nanoparticles, and microstructures that can be formed as a result of changes in solvent properties, pH, or other adjustments to a suspending medium have been shown to depend on many factors. Such factors are examined in this work based on the concepts of self-assembly, which can be defined as an organizing principle dependent on specific attributes of the starting entities themselves. As a means to promote such concepts and to facilitate further development of nano-scale lignin products, this article draws upon evidence from a wide range of studies. These include investigations of many different plant sources of lignin, processes of delignification, solvent systems, anti-solvent systems or other means of achieving phase separation, and diverse means of achieving colloidal stability (if desired) of resulting self-assembled lignin structures. Knowledge of the self-organization behavior of lignin can provide significant structural information to optimize the use of lignin in value-added applications. Examples include chemical conditions and preparation procedures in which lignin-related compounds of particles organize themselves as spheres, hollow spheres, surface-bound layers, and a variety of other structures. Published articles show that such processes can be influenced by the selection of lignin type, pulping or extraction processes, functional groups such as phenolic, carboxyl, and sulfonate, chemical derivatization reactions, solvent applications, aqueous conditions, and physical processes, such as agitation. Precipitation from non-aqueous solutions represents a key focus of lignin self-assembly research. The review also considers stabilization mechanisms of self-assembled lignin-related structures.

A comprehensive review of chitosan applications in paper science and technologies.

Using environmentally friendly biomaterials in different aspects of human life has been considered extensively. In this respect, different biomaterials have been identified and different applications have been found for them. Currently, chitosan, the well-known derivative of the second most abundant polysaccharide in the nature (i.e., chitin), has been receiving a lot of attention. This unique biomaterial can be defined as a renewable, high cationic charge density, antibacterial, biodegradable, biocompatible, non-toxic biomaterial with high compatibility with cellulose structure, where it can be used in different applications. This review takes a deep and comprehensive look at chitosan and its derivative applications in different aspects of papermaking.

Innovation in lignocellulosics dewatering and drying for energy sustainability and enhanced utilization of forestry, agriculture, and marine resources - A review.

Efficient utilization of forestry, agriculture, and marine resources in various manufacturing sectors requires optimizing fiber transformation, dewatering, and drying energy consumption. These processes play a crucial role in reducing the carbon footprint and boosting sustainability within the circular bioeconomy framework. Despite efforts made in the paper industry to enhance productivity while conserving resources and energy through lower grammage and higher machine speeds, reducing thermal energy consumption during papermaking remains a significant challenge. A key approach to address this challenge lies in increasing dewatering of the fiber web before entering the dryer section of the paper machine. Similarly, the production of high-value-added products derived from alternative lignocellulosic feedstocks, such as nanocellulose and microalgae, requires advanced dewatering techniques for techno-economic viability. This critical and systematic review aims to comprehensively explore the intricate interactions between water and lignocellulosic surfaces, as well as the leading technologies used to enhance dewatering and drying. Recent developments in technologies to reduce water content during papermaking, and advanced dewatering techniques for nanocellulosic and microalgal feedstocks are addressed. Existing research highlights several fundamental and technical challenges spanning from the nano- to macroscopic scales that must be addressed to make lignocellulosics a suitable feedstock option for industry. By identifying alternative strategies to improve water removal, this review intends to accelerate the widespread adoption of lignocellulosics as feasible manufacturing feedstocks. Moreover, this review aims to provide a fundamental understanding of the interactions, associations, and bonding mechanisms between water and cellulose fibers, nanocellulosic materials, and microalgal feedstocks. The findings of this review shed light on critical research directions necessary for advancing the efficient utilization of lignocellulosic resources and accelerating the transition towards sustainable manufacturing practices.

Adsorption of glycinin and ß-conglycinin on silica and cellulose: surface interactions as a function of denaturation, pH, and electrolytes.

Soybean proteins have found uses in different nonfood applications due to their interesting properties. We report on the kinetics and extent of adsorption on silica and cellulose surfaces of glycinin and ß-conglycinin, the main proteins present in soy. Quartz crystal microgravimetry (QCM) experiments indicate that soy protein adsorption is strongly affected by changes in the physicochemical environment. The affinity of glycinin and the mass adsorbed on silica and cellulose increases (by ca. 13 and 89%, respectively) with solution ionic strength (as it increases from 0 to 100 mM NaCl) due to screening of electrostatic interactions. In contrast, ß-conglycinin adsorbs on the same substrates to a lower extent and the addition of electrolyte reduces adsorption (by 25 and 57%, respectively). The addition of 10 mM 2-mercaptoethanol, a denaturing agent, reduces the adsorption of both proteins with a significant effect for glycinin. This observation is explained by the cleavage of disulfide bonds which allows unfolding of the molecules and promotes dissociation into subunits that favors more compact adsorbed layer structures. In addition, adsorption of glycinin onto cellulose decreases with lowering the pH from neutral to pH 3 due to dissociation of the macromolecules, resulting in flatter adsorbed layers. The respective adsorption isotherms fit a Langmuir model and QCM shifts in energy dissipation and frequency reveal multiple-step kinetic processes indicative of changes in adlayer structure.

Oil spills abatement: factors affecting oil uptake by cellulosic fibers.

Wood-derived cellulosic fibers prepared in different ways were successfully employed to absorb simulated crude oil, demonstrating their possible use as absorbents in the case of oil spills. When dry fibers were used, the highest sorption capacity (six parts of oil per unit mass of fiber) was shown by bleached softwood kraft fibers, compared to hardwood bleached kraft and softwood chemithermomechanical pulp(CTMP) fibers. Increased refining of CTMP fibers decreased their oil uptake capacity. When the fibers were soaked in water before exposure to the oil, the ability of the unmodified kraft fibers to sorb oil was markedly reduced, whereas the wet CTMP fibers were generally more effective than the wet kraft fibers. Predeposition of lignin onto the surfaces of the bleached kraft fibers improved their ability to take up oil when wet. Superior ability to sorb oil in the wet state was achieved by pretreating the kraft fibers with a hydrophobic sizing agent, alkenylsuccinic anhydride (ASA). Contact angle tests on a model cellulose surface showed that some of the sorption results onto wetted fibers could be attributed to the more hydrophobic nature of the fibers after treatment with either lignin or ASA.

Holocellulosic fibers and nanofibrils using peracetic acid pulping and sulfamic acid esterification.

Cellulose provides promising alternatives to synthetic plastics to achieve a low carbon footprint and biodegradable materials, which have significant positive impacts on environmental protection and on human health. In this work, sulfated holocellulose fibers and sulfated holocellulose nanofibrils (SHCNFs) are prepared using a combination of delignification with derivatization to achieve high fiber yield, superior recycling performance, and less energy consumption of the final products by means of preserving hemicellulose. Derivatization of the surface with sulfate groups provides a further means to avoid excessive aggregation between adjacent cellulose surfaces. Interestingly, hemicellulose increases the accessibility of holocellulose fibers and reduces the embodied energy during sulfate esterification. The presence of hemicellulose imparts high optical transmittance, mechanical performance (ultimate strength, 390 MPa; Young's modulus, 33 GPa), and recyclability for SHCNFs. This combination of two treatments can unlock the greater potential of cellulose as a sustainable material over its entire life cycle.

Rheological Aspects of Cellulose Nanomaterials: Governing Factors and Emerging Applications.

Cellulose nanomaterials (CNMs), mainly including nanofibrillated cellulose (NFC) and cellulose nanocrystals (CNCs), have attained enormous interest due to their sustainability, biodegradability, biocompatibility, nanoscale dimensions, large surface area, facile modification of surface chemistry, as well as unique optical, mechanical, and rheological performance. One of the most fascinating properties of CNMs is their aqueous suspension rheology, i.e., CNMs helping create viscous suspensions with the formation of percolation networks and chemical interactions (e.g., van der Waals forces, hydrogen bonding, electrostatic attraction/repulsion, and hydrophobic attraction). Under continuous shearing, CNMs in an aqueous suspension can align along the flow direction, producing shear-thinning behavior. At rest, CNM suspensions regain some of their initial structure immediately, allowing rapid recovery of rheological properties. These unique flow features enable CNMs to serve as rheological modifiers in a wide range of fluid-based applications. Herein, the dependence of the rheology of CNM suspensions on test protocols, CNM inherent properties, suspension environments, and postprocessing is systematically described. A critical overview of the recent progress on fluid applications of CNMs as rheology modifiers in some emerging industrial sectors is presented as well. Future perspectives in the field are outlined to guide further research and development in using CNMs as the next generation rheological modifiers.

Crude Wood Rosin and Its Derivatives as Hydrophobic Surface Treatment Additives for Paper and Packaging.

The aim of this work is to obtain better water resistance properties with additives to starch at the size press. A further goal is to replace petroleum-based additives with environmentally friendly hydrophobic agents obtained by derivatization of wood rosin. A crude wood rosin (CWR) sample was methylated and analyzed with gas chromatography-mass spectrometry (GC-MS). Methyl abietate, dehydroabietic acid, and abietic acid were the main constituents of the sample. The crude wood rosin samples were fortified with fumaric acid and then esterified with pentaerythritol. Fortified and esterified wood rosin samples were dissolved in ethanol and emulsified with cationic starch to make them suitable as hydrophobic additives for surface treatment formulations in mixtures with starch. These hydrophobic agents (2% on a dry weight basis in a cationic starch solution) were applied to paperboard, bleached kraft paper, and test liner paper using a rod coater with a target pickup of 3-5 gsm. The solution pickup was controlled by varying the rod number. The amounts of hydrophobic material applied in the preparation of the paper samples were 32.2, 48.6, and 35.1 lb/ton pickup compared to three types of base papers. Basic surface features of fortified and fortified and esterified rosin-treated paper were compared with base paper and paper treated with starch alone. Lower Cobb60 values were obtained for fortified and esterified samples than for linerboard samples that had been surface-sized just by starch. Thus, as novel hydrophobic additive agents, derivatives of CWR can be a green way to increase hydrophobicity while reducing starch consumption in papermaking.

Highly conductive carbon nanotubes and flexible cellulose nanofibers composite membranes with semi-interpenetrating networks structure.

Highly conductive multi-walled carbon nanotubes (MWCNTs) and flexible cellulose nanofibers (CNF) membranes with semi-interpenetrating networks structure were fabricated using the typical paper-making method, which was simple and cost-effective. The Scanning electron microscope (SEM), Fourier-transform infrared (FT-IR), and thermal gravimetric analysis (TGA) were used to estimate the morphology, chemical structure, and thermal stability of the membranes. The mechanical, optical, and electrical properties of the membranes were characterized with a uniaxial tensile testing machine, ultraviolet visible spectroscope, and digital multimeter, respectively. The results indicated that the membranes containing 10 wt% of MWCNTs showed a high conductivity value of 37.6 S/m, and the sheet resistances of the membranes were stable at different bending states. Furthermore, we demonstrated the electrical features of membrane-based capacitive pressure sensors based on CNF/MWCNTs. The proposed method for fabricating CNF/MWCNTs membranes can simplify the production process and have great practical potential in various electronics applications such as touch screens.

Nanocellulose-based multilayer barrier coatings for gas, oil, and grease resistance.

Cellulose derivatives such as cellulose nanofibers (CNF) and cellulose nanocrystals (CNC) have enormous potential to reduce or replace petroleum and fluorochemicals for food and other packaging applications. CNFs have been studied for their excellent oxygen and gas barrier properties; however, their performance rapidly decreases in the presence of moisture and higher humidity. CNCs are less sensitive to moisture due to their highly crystalline nature; however, coatings and films made of CNCs are much more prone to fracture due to their high brittleness. Our work demonstrates a unique composite barrier coating system of CNF and CNC that synergistically enables oil and grease resistance (a kit rating of 11) comparable to fluorochemicals. It also demonstrates a significant increase in air resistance (∼by a factor of about 300), and a reduction in oxygen transmission rate (∼by a factor of about 260) compared to uncoated paper. The improvements in oil and gas barrier properties were evaluated with respect to the molecular, chemical, and structural properties of the developed coatings.

Optimizing the mechanical properties of papers reinforced with refining and layer-by-layer treated recycled fibers using response surface methodology.

Layer-by-layer (LbL) treated recycled fibers were investigated in mixtures with refined pulp relative to the mechanical properties of paper. The LbL treatments were conducted to assemble consecutive cationic and anionic starch layers on the fibers of old corrugated container (OCC) pulp. Fibers zeta potential was measured to examine the success of LbL treatment. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to reveal the differences between treated and untreated fibers surface and network. Subsequently, the LbL-treated fibers were added to the refined OCC pulps. Optimization of paper (60 ± 3 g m-2 basis weight) strength properties including: tensile index, Scott bond (internal bonding), and ring crush test (RCT) was carried out by response surface methodology (RSM). The meaningful change of zeta potential substantiated cationic/anionic starch layers construction. The AFM results showed that the surface of fibers were covered with starch, which was consistent with deposition of polyelectrolyte multi-layers (PEMs). The surfaces of the LbL-treated fibers were rough in comparison with untreated fibers. The optimization of mechanical parameters using RSM indicated that refining time significantly affected the paper's mechanical properties. The property values of 44.5 N.m/g tensile index, 149 J/m2 Scott bond, 32 mN RCT, and 245% strain at break were achieved at optimal conditions of 16 min refining time and the addition ratio of 17.6% LbL treated pulp respectively.

The performance of chitosan with bentonite microparticles as wet-end additive system for paper reinforcement.

In this research, the effect of bentonite micro-particles on the performance of chitosan as a new additive system for improving the dry strengths of acidic papermaking was studied. Chitosan, an abundant carbohydrate biopolymer, in 4 dosages (0, 0.75, 1.25 and 2% based on dry weight of pulp) was applied with bentonite in 4 dosages (0, 0.3, 0.6 and 0.9% based on oven-dry weight of pulp). Although the addition of chitosan up to 0.75% (without bentonite) improved tensile index and burst index, but the addition of more chitosan decreased all mechanical properties in comparison with the control sample. The application of bentonite in combination with chitosan had a significant impact on chitosan performance in mechanical properties. The best results were obtained with 0.3% bentonite consumption. Visual formation ranking had a proper correlation with this obtained results. The micro-kjeldahl indirectly confirmed chitosan retention in the treated paper with chitosan/bentonite.

TEMPO-mediated oxidation of oat ß-D-glucan and its influences on paper properties.

An enhanced bonding agent for papermaking was prepared by selective oxidation of a hemicellulose-rich byproduct of oat processing, which will be identified here by its primary component, ß-D-glucan. The ß-D-glucan was treated sequentially with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and sodium hypochlorite, or alternatively just with sodium hydroxide. When added to a slurry of unbleached softwood kraft fibers, in combination with an optimal dosage of aluminum sulfate, the oxidized ß-D-glucan yielded greater increases in tensile strength and folding endurance in comparison to untreated ß-D-glucan. NaOH treatment also improved dry-strength performance of the ß-D-glucan, except for folding endurance. The improvements were attributed to increased charge density of the treated polyelectrolytes, leading to better distribution and retention on fibers prior to sheet formation. Modified ß-D-glucan also enhanced the strength of recycled sheets when the treated paper was repulped and formed into recycled paper with no further chemical addition.

Water-wettable polypropylene fibers by facile surface treatment based on soy proteins.

Modification of the wetting behavior of hydrophobic surfaces is essential in a variety of materials, including textiles and membranes that require control of fluid interactions, adhesion, transport processes, sensing, etc. This investigation examines the enhancement of wettability of an important class of textile materials, viz., polypropylene (PP) fibers, by surface adsorption of different proteins from soybeans, including soy flour, isolate,glycinin, and ß-conglycinin. Detailed investigations of soy adsorption from aqueous solution (pH 7.4, 25 °C) on polypropylene thin films is carried out using quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). A significant amount of protein adsorbs onto the PP surfaces primarily due to hydrophobic interactions. We establish that adsorption of a cationic surfactant, dioctadecyldimethylammonium bromide (DODA) onto PP surfaces prior to the protein deposition dramatically enhances its adsorption. The adsorption of proteins from native (PBS buffer, pH 7.4, 25 °C) and denatured conditions (PBS buffer, pH 7.4, 95 °C) onto DODA-treated PP leads to a high coverage of the proteins on the PP surface as confirmed by a significant improvement in water wettability. A shift in the contact angle from 128° to completely wettable surfaces (≈0°) is observed and confirmed by imaging experiments conducted with fluorescence tags. Furthermore, the results from wicking tests indicate that hydrophobic PP nonwovens absorb a significant amount of water after protein treatment, i.e., the PP-modified surfaces become completely hydrophilic.

On the surface interactions of proteins with lignin.

Lignins are used often in formulations involving proteins but little is known about the surface interactions between these important biomacromolecules. In this work, we investigate the interactions at the solid-liquid interface of lignin with the two main proteins in soy, glycinin (11S) and ß-conglycinin (7S). The extent of adsorption of 11S and 7S onto lignin films and the degree of hydration of the interfacial layers is quantified via Quartz crystal microgravimetry (QCM) and surface plasmon resonance (SPR). Solution ionic strength and protein denaturation (2-mercaptoethanol and urea) critically affect the adsorption process as protein molecules undergo conformational changes and their hydrophobic or hydrophilic amino acid residues interact with the surrounding medium. In general, the adsorption of the undenatured proteins onto lignin is more extensive compared to that of the denatured biomolecules and a large amount of water is coupled to the adsorbed molecules. The reduction in water contact angle after protein adsorption (by ~40° and 35° for undenatured 11S and 7S, respectively) is explained by strong nonspecific interactions between soy proteins and lignin.

Survey of soy protein flour as a novel dry strength agent for papermaking furnishes.

A series of experiments were conducted on recycled pulp samples for the novel purpose of determining the efficacy of employing soy protein flour to increase the strength of dry paper. Values of short span compression and tensile strength were the prime criteria for comparison based on industrial considerations. Various conditions were considered to uncover effective schemes for applying the soy proteins under industrial-like papermaking conditions including alkaline versus acidic as well as high or low ionic content papermaking conditions. A hybrid system of starch, a dry strength additive currently used in paper furnishes, and soy protein was considered to study the possible existence of any synergistic chemical effects. Results indicated that a 1 part (by mass) soy protein to 3 parts cationic starch hybrid system resulted in the highest strength increase in comparison to solely either the soy protein or the cationic starch as dry strength additives.

Capillary flooding of wood with microemulsions from Winsor I systems.

A new approach based on microemulsions formulated with at least 85% water and minority components consisting of oil (limonene) and surfactant (anionic and nonionic) is demonstrated for the first time to be effective for flooding wood's complex capillary structure. The formulation of the microemulsion was based on phase behavior scans of Surfactant-Oil-Water systems (SOWs) and the construction of pseudo-ternary diagrams to localize thermodynamically stable one-phase emulsion systems with different composition, salinity and water-to-oil ratios. Wicking and fluid penetration isotherms followed different kinetic regimes and indicated enhanced performance relative to that of the base fluids (water, oil or surfactant solutions). The key properties of microemulsions to effectively penetrate the solid structure are discussed; microemulsion formulation and resultant viscosity are found to have a determining effect in the extent of fluid uptake. The solubilization of cell wall components is observed after microemulsion impregnation. Thus, the microemulsion can be tuned not only to effectively penetrate the void spaces but also to solubilize hydrophobic and hydrophilic components. The concept proposed in this research is expected to open opportunities in fluid sorption in fiber systems for biomass pretreatment, and delivery of hydrophilic or lipophilic moieties in porous, lignocellulosics.

Effect of charge asymmetry on adsorption and phase separation of polyampholytes on silica and cellulose surfaces.

The relation between the properties of polyampholytes in aqueous solution and their adsorption behaviors on silica and cellulose surfaces was investigated. Four polyampholytes carrying different charge densities but with the same nominal ratio of positive to negative segments and two structurally similar polyelectrolytes (a polyacid and a polybase) were investigated by using quartz crystal microgravimetry using silica-coated and cellulose-coated quartz resonators. Time-resolved mass and rigidity (or viscoelasticity) of the adsorbed layer was determined from the shifts in frequency (Deltaf) and energy dissipation (DeltaD) of the respective resonator. Therefore, elucidation of the dynamics and extent of adsorption, as well as the conformational changes of the adsorbed macromolecules, were possible. The charge properties of the solid surface played a crucial role in the adsorption of the studied polyampholytes, which was explained by the capability of the surface to polarize the polyampholyte at the interface. Under the same experimental conditions, the polyampholytes had a higher nominal charge density phase-separated near the interface, producing a soft, dissipative, and loosely bound layer. In the case of cellulose substrates, where adsorption was limited, electrostatic and polarization effects were concluded to be less significant.