Periodate oxidation of nanofibrillated cellulose films for active packaging applications.

An alternative packaging material based on cellulose that possesses excellent barrier properties and is potentially useful for active packaging has been developed. Cellulose nanofibril was efficiently and selectively oxidized with sodium periodate generating reactive aldehyde groups. These groups formed hemiacetal and hemialdal bonds during film formation and, consequently, highly transparent, elastic and strong films were created even under moisture saturation conditions. The periodate oxidation treatment additionally decreased the polarity of the films and considerably enhanced their water barrier properties. Thus, the water contact angle of films treated for 3 and 6 h was 97° and 102°, their water drop test value was higher than in untreated film (viz., 138 and 141 min with 3 and 6 h of treatment) and their water vapour transmission rate was substantially better (3.31 and 0.78 g m-2 day-1 with 3 and 6 h, respectively). The presence of aldehyde groups facilitated immobilization of the enzyme laccase, which efficiently captures oxygen and prevents food decay as a result. Laccase-containing films oxidized 80 % of Methylene Blue colorant and retained their enzymatic activity after storage for 1 month and 12 reuse cycles, opening the door to the possible creation of a reusable packaging to replace the single-use packaging.

Composites of cellulose nanocrystals in combination with either cellulose nanofibril or carboxymethylcellulose as functional packaging films.

Cellulose nanocrystals (CNC) were mixed with either cellulose nanofibril (CNF) or carboxymethylcellulose (CMC) in variable proportions (0/100, 20/80, 40/60, 50/50, 60/40, 80/20 and 100/0) to obtain cast films with acceptable barrier and mechanical properties as replacements for food packaging plastics. Both CNF and CMC improved tensile strength, elongation, UV opacity, air resistance, hydrophobicity (WCA-water contact angle), water vapor transmission rate (WVTR) and oxygen impermeability in pure CNC. WVTR and oxygen permeability were strongly dependent on relative humidity (RH). Interestingly, the greatest effect on WVTR was observed at RH = 90% in films containing CMC in proportions above 60%. CMC- and CNF-containing films had oxygen impermeability up to an RH level of 80% and 60%, respectively. The previous effects were confirmed by food packaging simulation tests, where CMC-containing films proved the best performers. The composite films studied were biodegradable-which constitutes a major environmental related advantage-to an extent proportional to their content in CMC or CNF.

Lignin Particles for Multifunctional Membranes, Antioxidative Microfiltration, Patterning, and 3D Structuring.

We introduce a new type of particle-based membrane based on the combination of lignin particles (LPs) and cellulose nanofibrils (CNF), the latter of which are introduced in small volume fractions to act as networking and adhesive agents. The synergies that are inherent to lignin and cellulose in plants are re-engineered to render materials with low surface energy (contact angle measurements) and can be rendered water-resistant with the aid of wet-strength agents (WSAs). Importantly, they are most suitable for antioxidative separation (ABTS•+ radical inhibition): membranes with uniform porous structures (air permeability and capillary flow porosimetry) allow effluent oxidation at 95 mL/cm2, demonstrating, for the first time, the use of unmodified lignin particles in flexible membranes for active microfiltration. Moreover, the membranes are found to be nonfouling (protein adhesion and activity rate). The inherent properties of lignin, including UV radiation blocking capacity (UV transmittance analysis) and reduced surface energy, are further exploited in the development of tailorable and self-standing architectures that are almost entirely comprised of nonbonding LP (solids content as high as 92 w/w%). Despite such composition, the materials develop high toughness (oscillatory dynamic mechanical analysis), owing to the addition of minor amounts of CNF. Multifunctional materials based on thin films (casting), 3D structures (molding), and patterned geometries (extrusion deposition) are developed as a demonstration of the potential use of lignin particles as precursors of new material generation. Remarkably, our observations hold for spherical LPs since a much poorer performance was observed after using amorphous powder, indicating the role of size and shape in related applications.

Particulate Coatings via Evaporation-Induced Self-Assembly of Polydisperse Colloidal Lignin on Solid Interfaces.

Polydisperse smooth and spherical biocolloidal particles were suspended in aqueous media and allowed to consolidate via evaporation-induced self-assembly. The stratification of the particles at the solid-air interface was markedly influenced, but not monotonically, by the drying rate. Cross-sectional imaging via electron microscopy indicated a structured coating morphology that was distinctive from that obtained by using particles with a mono- or bimodal distribution. Segregation patterns were found to derive from the interplay of particle diffusion, interparticle forces, and settling dynamics. Supporting our experimental findings, computer simulations showed an optimal drying rate for achieving maximum segregation. Overall, stratified coatings comprising nano- and microparticles derived from lignin are expected to open opportunities for multifunctional structures that can be designed and predicted on the basis of experimental Péclet numbers and computational order.

Electrochemical Insights on the Hydrophobicity of Cellulose Substrates Imparted by Enzymatically Oxidized Gallates with Increasing Alkyl Chain Length.

In this work, we studied the influence of the alkyl chain length in enzymatically oxidized gallates on the development of hydrophobicity on paper-based materials, and further correlated the obtained effect to the redox mechanism of the enzymatic treatment. Laccase (Lac) enzyme was used to oxidize various members of the gallate homologous series in the presence or not of lignosulfonates (SL) to produce several functionalization solutions (FS), which were subsequently applied to cellulosic substrates. The hydrophobicity of the substrates was then assessed by means of water drop test (WDT) and contact angle (WCA) measurements. Hydrophobicity peaked reaching WDT and WCA values around 5000 s and 130°, respectively, and then decreased with increasing length of the hydrocarbon chain of gallate. Cyclic voltrammetry (CV) was used to study the effect of SL on the redox reactions of several gallates. The intensity of the anodic peak in their voltammograms decreased increasing the chain length of the gallate. The electrochemical behavior of lauryl gallate (LG) differed from that of other gallates. The fact that the voltammetric curves for SL and LG intersected at a potential of 478 mV indicates an enhancing effect of SL on LG oxidation at high potentials (above 478 mV).

A facile and green method to hydrophobize films of cellulose nanofibrils and silica by laccase-mediated coupling of nonpolar colloidal particles.

Hydrophobic particles based on dodecyl 3,4,5-trihydroxybenzoate (LG) were coupled onto the surface of cellulose nanofibrils (CNFs) and silica by treatment with a multicomponent colloidal system (MCS) derived from the laccase-mediated reaction of LG in the presence of a sulfonated lignin (SL). Surface modification upon treatment with MCS was monitored in situ and in real time by quartz crystal microgravimetry. The colloidal stability of MCS and its components in water was followed by measuring space- and time-resolved light transmission and back scattering. The sulfonated lignin increased dispersion stability and reduced the characteristic MCS particle size [from ≈4 to ≈80 nm, according to AFM and dynamic light scattering (DLS)]. It also facilitated the surface enzymatic reaction that led to adsorption and coupling of MCS onto CNFs and silica surfaces. The combined effect of reduced surface energy and surface roughness by MCS treatment produced an increase in water contact angle on CNFs and silica of about 90 and 80°, respectively. Surface pretreatment with chitosan further increased the extent of MCS adsorption on the surfaces. This method represents a sustainable alternative to traditional approaches for cellulose hydrophobization and a step forward in implementing green routes for surface modification.

Application of surface enzyme treatments using laccase and a hydrophobic compound to paper-based media.

A new approach for the hydrophobization of finished cellulosic substrates based on a previously reported enzymatic technique is proposed. Commercial finished paper was hydrophobized by using laccase from Trametes villosa in combination with lauryl gallate (LG) as hydrophobic compound. The efficiency of the method was increased by the use of a lignosulfonate as a natural dispersant to improve the surface distribution of LG on the paper, raise its hydrophobicity and help preserve the enzyme activity. No similar threefold effect from a single compound for the improvement of enzymatic treatments was previously reported. The influence of processing conditions including the LG dose, treatment time and temperature was also examined, resulting in further increased hydrophobicity. Efficient fiber bonding and chemical functionalization were confirmed by thorough washing and Soxhlet extraction of the paper. As shown here for the first time, enzyme treatments have the potential to improve the surface hydrophobicity of paper-based media.