Water stable colloidal lignin-PVP particles prepared by electrospray.

In this study, electrospray deposition has been used as a method to prepare lignin submicron spherical particles. Regularities of electrospraying of lignin solutions in DMSO were revealed. The influence of voltage, distance between electrodes, feed rate, temperature and concentration of lignin solution on the morphology, size and polydispersity of the obtained particles was determined. SEM, IR, TG-DSC, elemental analysis, dynamic light scattering, Zeta potential and nitrogen sorption were used to characterize the particles and to determine their properties. The aqueous colloidal solutions of the submicron particles of lignins from various plant sources were stabilized by preparing the lignin/polyvinylpyrrolidone polymeric complexes.

New lignin-based hybrid materials as functional additives for polymer biocomposites: From design to application.

Within this study, the ZrO2/lignin and ZrO2-SiO2/lignin hybrid materials were obtained for the first time. The mechanical grinding method was used for this purpose. In order to determine the properties of obtained lignin-based hybrids and the components used to produce them, as well as to evaluate the efficiency of their preparation, the authors used such research techniques as scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), elemental analysis, porous structure analysis and thermal stability assessment (TGA/DTG). The next step involved using the components and produced hybrid materials as polymer fillers for poly(methyl methacrylate) (PMMA). The obtained lignin-based hybrid biocomposites have then been thoroughly characterized using gel permeation chromatography (GPC), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and hardness testing. All the conducted tests confirm the possibility of using the obtained bio-based products in practice, within the widely understood construction industry, for producing durable building facades or noise barriers, among others.

A functional lignin-based nanofiller for flame-retardant blend.

Lignin-based flame retardants represent great promising next-generation flame retardants due to their sustainability, unique aromatic structure, and high charring capability. However, their applications are still limited by the compatibility, processability, and efficiency of flame retardancy. Here, a green functional lignin-based nanofiller (lignin-diethylenetriamine/red phosphorus nanoparticles, Lignin-N-P NPs) was prepared by the chemical modification and co-precipitation. After blending with the commercial acrylonitrile butadiene styrene copolymers (ABS), the physical, chemical, and flame retardant properties of the blends reveal that Lignin-N-P NPs/ABS blend has acceptable processability, mechanical properties, and significantly improved thermal stability and fire performance. Its values of peak heat release rate and total heat released per unit area were significantly dropped 67.8% and 77.5%, respectively. This study will initiate a new design for not only flame retardants but also lignin-based materials.

Facile fabrication of transparent lignin sphere/PVA nanocomposite films with excellent UV-shielding and high strength performance.

With the rapid development of human society, more and more concerns are directed to utilization of environment-friendly and biodegradable materials. To meet this demand, we fabricated an environment-friendly poly (vinyl alcohol) (PVA)/lignin nanocomposite films with excellent UV-shielding and visible-transparent performance. The lignin-based nanosphere (LNSs) were prepared via self-assembly and uniformly distributed in the PVA matrix by forming strong hydrogen bonds with PVA matrix. With the introduction of LNSs into PVA matrix, the various performance such as tensile strength, thermal stability, and UV-shielding of PVA/Lignin nanocomposite films were enhanced. Amazingly, the UV-shielding results revealed that UVB (320-275 nm) and UVC (275-200 nm) were completely shielded and UVA (400-320 nm) was mostly shielded with addition of 4 wt% LNSs. Meanwhile, the tensile strength of the nanocomposite film was dramatically enhanced, in which the strength increased from 76 MPa to 112 MPa. Since both lignin and PVA were biodegradable materials, this work provides a simple and valuable method for the preparation of biodegradable and functional films.

Biodegradable and renewable UV-shielding polylactide composites containing hierarchical structured POSS functionalized lignin.

The demand for biodegradable and renewable UV-shielding materials is ever increasing due to the rising concern for the environment. In this paper, biobased lignin was functionalized by polyhedral oligomeric silsesquioxane (POSS) with an epoxy substituent. Then the POSS decorated lignin (lignin-POSS) was mixed with polylactide (PLA) to act as UV-shielding filler by melt compounding. The SEM observation revealed that the presence of POSS contributed to improving the homogeneous dispersion of lignin-POSS in the PLA matrix with good compatibility when the content of lignin-POSS was lower than 5 wt%. The synergistic effects of lignin and POSS endowed PLA composite films with a good balance of UV-shielding ability and transparency in the visible light region. With the addition of 5 wt% lignin-POSS, the PLA composite film absorbed almost all UV irradiation across the entire UV spectrum. In addition, the presence of lignin-POSS could serve as a nucleating agent to increase the degree of crystallinity of PLA. The dynamical rheological tests revealed that the lignin-POSSS reduced the complex viscosity and storage modulus of PLA composites, improving the flowability of PLA composites. This work presents a viable pathway to prepare biodegradable and renewable UV-shielding materials for potential packaging applications.

Agroindustrial Wastes as a Support for the Immobilization of Lipase from Thermomyces lanuginosus: Synthesis of Hexyl Laurate.

As a consequence of intense industrialization in the last few decades, the amount of agro-industrial wastes has increasing, where new forms of valorization are crucial. In this work, five residual biomasses from Maranhão (Brazil) were investigated as supports for immobilization of lipase from Thermomyces lanuginosus (TLL). The new biocatalysts BM-TLL (babaçu mesocarp) and RH-TLL (rice husk) showed immobilization efficiencies >98% and hydrolytic activities of 5.331 U g-1 and 4.608 U g-1, respectively, against 142 U g-1 by Lipozyme® TL IM. High esterification activities were also found, with 141.4 U g-1 and 396.4 U g-1 from BM-TLL and RH-TLL, respectively, against 113.5 U g-1 by TL IM. Results of porosimetry, SEM, and BET demonstrated BM and RH supports are mesoporous materials with large hydrophobic area, allowing a mixture of hydrophobic adsorption and confinement, resulting in hyperactivation of TLL. These biocatalysts were applied in the production of hexyl laurate, where RH-TLL was able to generate 94% conversion in 4 h. Desorption with Triton X-100 and NaCl confirmed that new biocatalysts were more efficient with 5 times less protein than commercial TL IM. All results demonstrated that residual biomass was able to produce robust and stable biocatalysts containing immobilized TLL with better results than commercial preparations.

Porous carboxymethyl cellulose carbon of lignocellulosic based materials incorporated manganese oxide for supercapacitor application.

The present work developed porous carboxymethyl cellulose (CMC) carbon film from lignocellulosic based materials as supercapacitor electrode. Porous CMC carbon films of bamboo (B) and oil palm empty fruit bunch (O) were prepared through simple incipient wetness impregnation method followed by calcination process before incorporation with manganese oxide (Mn2O3). The carbonization produced porous CMC carbon whereby CMCB exhibited higher surface area than CMCO. After Mn2O3 incorporation, the crystallite size of CMCB and CMCO were calculated as 50.09 nm and 42.76 nm, respectively whereas Mn2O3/CMCB and Mn2O3/CMCO composite films were revealed to be 26.71 nm and 35.60 nm in size, respectively. Comparatively, the Mn2O3/CMCB composite film exhibited higher electrochemical performance which was 31.98 mF cm-2 as compared to 24.15 mF cm-2 by Mn2O3/CMCO composite film and both CMC carbon films with fairly stable cycling stability after 1000 charge-discharge cycles. Therefore, it can be highlighted that Mn2O3/CMC composite film as prepared from bamboo and oil palm fruit can potentially become the new electrode materials for supercapacitor application.

MXene/wood-derived hierarchical cellulose scaffold composite with superior electromagnetic shielding.

Electromagnetic-interference (EMI) shielding materials that are green, lightweight, and with high mechanical properties need to be urgently developed to address increasingly severe radiation pollution. However, limited EMI shielding materials are successfully used in practical applications, due to the intensive energy consumption or the absence of sufficient strength. Herein, an environmentally friendly and effective method was proved to fabricate wood-based composites with high mechanical robustness and EMI shielding performance by a MXene/cellulose scaffold assembly strategy. The lignocellulose composites with a millimeter-thick mimic the "mortar-brick" layered structure, resulting in excellent mechanical properties that can achieve the compressive strength of 288 MPa and EMI shielding effectiveness of 39.3 dB. This "top-down" method provides an alternative for the efficient production of robust and sustainable EMI shielding materials that can be used in the fields of structural materials for next-generation communications and electronic devices.

Lignin containing cellulose nanofibers (LCNFs): Lignin content-morphology-rheology relationships.

This study aims to investigate the relationship between lignin content, morphology, and rheology of lignin containing cellulose nanofibers (LCNFs). The morphology and rheology of LCNFs were dominated by lignin content. Lignin content had two-sides on mechanical fibrillation. At high lignin content (23.79 %), reduced efficiency of defibrillation resulted in large LCNFs connecting with lignin patches. LCNF suspensions exhibited low viscosity, weak gel behavior due to infirm fibril network. Small yield stress of 1.14 Pa suggested that fibril network was easily disrupted. At residual lignin of 6.52 %, fibril bundles were sensitive to defibrillation, producing long and flexible LCNFs with high capacity of entanglement. The entangled fibril network had high viscosity and strong gel like behavior. Creep compliance of 0.09 Pa-1 and large yield stress of 4.25 Pa indicated excellent resistance to deformation. The desired rheology can be tailored by lignin content, providing practical guidance on novel rheology-dependent LCNF based materials.

Size-Controlled and Super Long-Term Stable Lignin Nanospheres through a Facile Self-Assembly Strategy from Kraft Lignin.

In diverse fields, much attention has been concentrated on the preparation of lignin nanospheres with various structures. Here we report a facile self-assembly strategy for preparing super long-term stable hollow and solid nanospheres based on lignin fractionation. We found that different lignins obtained at different pHs during fractionation can form nanospheres with different particle sizes and structures. The self-assembled and formation mechanisms of the nanospheres were surveyed by dynamic light scattering (DLS), elemental analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). The analysis results showed that the phenolic hydroxyl groups and the intermolecular π-π interaction play a decisive effect in the formation of nanospheres. This study can not only facilitate the advance of lignin-based nanotechnologies but also provide a broad prospect for the use of black liquor.

Atomic force microscopy imaging of delignified secondary cell walls in liquid conditions facilitates interpretation of wood ultrastructure.

Deep understanding of the physicochemical and structural characteristics of wood at the nanoscale is essential for improving wood usage in biorefining and advancing new high performance materials design. Herein, we use in situ atomic force microscopy and a simple delignification treatment to elucidate the nanoscale architecture of individual secondary cell wall layers. Advantages of this approach are: (i) minimal sample preparation that reduces the introduction of potential artifacts; (ii) prevention of structural rearrangements due to dehydration; (iii) increased accessibility to structural details masked by the lignin matrix; and (iv) possibility to complement results with other analytical techniques without sample manipulation. The methodology permits the visualization of parallel and helicoidally arranged microfibril aggregates in the S1 layer and the determination of lignin contribution to microfibril aggregates forming S2 layers. Cellulose and hemicelluloses constitute the core of the aggregates with a mean diameter of approximately 19 nm, and lignin encloses the core forming single structural entities of about 30 nm diameter. Furthermore, we highlight the implications of sample preparation and imaging parameters on the characterization of microfibril aggregates by AFM.

Structure and morphology of cellulose fibers in garlic skin.

The knowledge of the texture and morphology of cellulose is essential for reliable modelling of cell growth and mechanical resistance of vegetal systems. Microscopic observations on thin layers of the skin of Allium sativum have shown elongated structures (i.e. cellulose fibers) imbedded in a matrix of more or less rounded cells. Examination by an optical polarizing microscope (OPM) has shown an intermittent high and low birefringence along fibers. Transversal regions with a reduced brightness along fibers are expected to contain a higher amount of amorphous lignin, hemicelluloses and waxes, some of which might also be birefringent, but at a much lower degree than cellulose. Scanning electron microscopy (SEM) has also evidenced an alternating growth of the fibers. Moreover, the negative sign of birefringence suggests a parallel orientation of cellulose nanofibrils transversally to the fiber axis. The characteristic modulation of intensity along lignocellulosic fibers can be due to variation of the cellulose concentration or orientation, perhaps caused by circadian cycles of temperature and light during growth. Indeed, imperfect orthogonal light can be totally reflected at the interface between regions with different values of the refractive index, contributing to the optical effect of banding.

Basic understanding of the color distinction of lignin and the proper selection of lignin in color-depended utilizations.

Lignin based materials and chemicals with outstanding sustainability have drawn increasingly attentions. However, the dark color of lignin limits the utilization in color-depended fields. In this work, the factors that influence the color of lignin were investigated and mechanisms were illustrated by GPC, NBO, 2D HSQC, XPS, SEM, and visible light spectrum. It is found that the condensed structures were mainly separated at higher pH due to its high molecular weight and low solubility. The condensation contributes to the conjugation and unsaturation, which resulted in the dark-color of the lignin precipitated at high pH value. The oxidation is not crucial for the color darkening of lignin in drying, it is the micro aggregation that dominantly determined the color degree. The concentration of chromophore was decreased owing to the decrease of bulk density (caused by the alleviation of aggregation), which endowed lignin with the bright seeing macroscopically. Notably, the selection of light-colored lignin needs to be individually considered regarding different use, since the dominating factors that influence the color at solid or solution are totally different. In summary, this work offers guidance for acquiring light-colored lignin and helps people select the light-colored lignin properly regarding utilizations.

Preparation and characterization of high-strength and water resistant lignocelluloses based composites bonded by branched polyethylenimine (PEI).

High-strength and water resistant lignocelluloses based composites (LC) were fabricated using branched polyethylenimine (PEI) as the main bonding agent combined with glutaraldehyde cross-linking reaction and grinding pre-treatment. Physical and mechanical properties of different composites prepared were measured and investigated. It is evident that PEI was efficient in endowing LC with high strength and excellent water resistance. The obtained physical and mechanical properties of LC were complied with the requirement of the Chinese national standard for medium-density fiberboard (MDF). Most notably, the glutaraldehyde cross-linking and grinding pre-treatment could further improve these properties. When 5% PEI and 2.5% glutaraldehyde were incorporated, together with 2-hour grinding treatment, the LC prepared exhibited the optimum modulus of rupture (MOR) 58.1 MPa, modulus of elasticity (MOE) 5077 MPa, internal bonding strength (IB) 2.14 MPa, and thickness swell (TS) 30.2%. The excellent properties obtained could be attributed to the cross-linking effect and Schiff's base addition reaction among lignocelluloses, PEI and glutaraldehyde, which were confirmed by the Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analysis. The high-strength LC prepared in this study is expected to be used as load-bearing material in structural application.

Rice Husk Hydrolytic Lignin Transformation in Carbonization Process.

Lignin processing products have an extensive using range. Because products properties depend on lignin precursor quality it was interesting to study lignin isolated from rice husk being a large tonnage waste of rice production and its structural transformations during carbonization. Lignin isolated by the thermal hydrolysis method with H2SO4 1 wt % solution and its carbonized products prepared under different carbonization conditions were characterized using elemental analysis, IR, TPD-MS, XRD, TEM, and EPR. It was shown lignin degradation takes place over the wide (220-520 °C) temperature range. Silica presenting in lignin affects the thermal destruction of this polymer. Due to the strong chemical bond with phenolic hydroxylic group it decreases an evaporation of volatile compounds and as a result increases the temperature range of the lignin degradation. Rice husk hydrolytic lignin transformations during carbonization occur with generation of free radicals. Their concentration is decreased after condensation of aromatic rings with carbon polycycles formation, i.e., the graphite-like structure. Quantity and X-ray diffraction characteristics of the graphite-like phase depend on carbonization conditions. Morphology of the lignin-based carbonized products is represented by carbon fibers, carbon and silica nanoparticles, and together with another structure characteristics provides prospective performance properties of lignin-based end products.

Real Time and Quantitative Imaging of Lignocellulosic Films Hydrolysis by Atomic Force Microscopy Reveals Lignin Recalcitrance at Nanoscale.

Lignocellulosic biomass is considered as a sustainable source of energy and chemicals, but its recalcitrance to bioconversion still limits its use. In this paper, a strategy based on two aspects was developed to improve our knowledge on the lignin recalcitrance to enzymatic hydrolysis. First, lignocellulosic films of cellulose nanofibrils (CNFs) with increasing content of lignin (up to 40%) were prepared. Thanks to in situ real time Atomic Force Microscopy (AFM) measurements during the hydrolysis and by comparison with biochemical assays, the use of such films allows to fully assess the importance of the lignin content and of the arrangement between CNFs and lignin on the hydrolysis efficiency. In a second time, contrary to other studies by AFM which only followed a specific structure during enzymatic processes mostly on simple systems (CNFs or cellulose nanocrystals), a quantitative analysis of in-situ time-lapse measurements was developed. It enables to accurately address lignocellulosic biomass recalcitrance mechanisms mediated by lignin at nanoscale. Such analysis could pave the way for the use of a quantitative criteria to visualize in situ deconstruction of complex lignocellulosic substrates. Coupling the use of lignocellulosic films and dynamical AFM quantitative analysis to follow the evolution of the structure at nanoscale might lead to an effective targeting of new promising bioconversion strategies.

Ultrastructure and Enzymatic Hydrolysis of Deuterated Switchgrass.

Neutron scattering of deuterated plants can provide fundamental insight into the structure of lignocellulosics in plant cell walls and its deconstruction by pretreatment and enzymes. Such plants need to be characterized for any alterations to lignocellulosic structure caused by growth in deuterated media. Here we show that glucose yields from enzymatic hydrolysis at lower enzyme loading were 35% and 30% for untreated deuterated and protiated switchgrass, respectively. Lignin content was 4% higher in deuterated switchgrass but there were no significant lignin structural differences. Transmission electron microscopy showed differences in lignin distribution and packing of fibers in the cell walls that apparently increased surface area of cellulose in deuterated switchgrass, increasing cellulose accessibility and lowering its recalcitrance. These differences in lignification were likely caused by abiotic stress due to growth in deuterated media.

Bacterial cellulose-lignin composite hydrogel as a promising agent in chronic wound healing.

Lignins and lignin-derived compounds are known to have antibacterial properties. The wound healing agents in the form of dressings produce faster skin repair and decrease pain in patients. In order to create an efficient antimicrobial agent in the form of dressing in the treatment of chronic wounds, a composite hydrogel of bacterial cellulose (BC) and dehydrogenative polymer of coniferyl alcohol (DHP), BC-DHP, was designed. Novel composite showed inhibitory or bactericidal effects against selected pathogenic bacteria, including clinically isolated ones. The highest release rate of DHP was in the first hour, while after 24 h there was still slow release of small amounts of DHP from BC-DHP during 72 h monitoring. High-performance liquid chromatography coupled with mass-spectrometry showed that BC-DHP releases DHP oligomers, which are proposed to be antimicrobially active DHP fractions. Scanning electron microscopy and atomic force microscopy micrographs proved a dose-dependent interaction of DHP with BC, which resulted in a decrease of the pore number and size in the cellulose membrane. The Fourier-transform infrared absorption spectra of the BC-DHP showed that DHP was partly bound to the BC matrix. The swelling and crystallinity degree were dose-dependent. All obtained results confirmed BC-DHP composite as a promising hydrogel for wounds healing.

Laccase-mediated synthesis of lignin-core hyperbranched copolymers.

Lignin, one of the major chemical constituents of woody biomass, is the second most abundant biopolymer found in nature. The pulp and paper industry has long produced lignin on the scale of millions of tons annually as a by-product of the pulping process, and the dawn of cellulosic ethanol production has further contributed to this amount. Historically, lignin has been perceived as a waste material and burned as a fuel for the pulping process. However, recent research has been geared toward developing cost-effective technologies to convert lignin into valuable commodities. Attributing to the polyphenolic structure of lignin, enzymatic modification of its surface using laccases (benzenediol:oxygen oxidoreductases, EC 1.10.3.2) has demonstrated to be highly successful. The current study aims at developing lignin-core hyperbranched copolymers via the laccase-assisted copolymerization of kraft lignin with methylhydroquinone and a trithiol. Based on the physical properties of the resulting material, it is likely that crosslinking reactions have taken place during the drying process to produce a copolymeric network rather than discrete hyperbranched copolymers, with NMR data providing evidence of covalent bonding between monomers. Preliminary thermal analysis data reveals that the copolymeric material possesses a moderate glass transition temperature and exhibits good thermostability, thus may have potential application as a lignin-based thermoplastic. Scanning electron microscopy images confirm the smooth, glossy surface of the material and that it is densely packed. The presented results are a sustainable, ecofriendly, economic method to create an exciting novel biomaterial from a renewable feedstock while further enhancing lignin valorization.

Nitrogen fertilizer application affects lodging resistance by altering secondary cell wall synthesis in japonica rice (Oryza sativa).

Stem mechanical strength is an important agricultural quantitative trait that is closely related to lodging resistance in rice, which is known to be reduced by fertilizer with higher levels of nitrogen. To understand the mechanism that regulates stem mechanical strength in response to nitrogen, we analysed stem morphology, anatomy, mechanical properties, cell wall components, and expression of cell wall-related genes, in two varieties of japonica rice, namely, Wuyunjing23 (lodging-resistant variety) and W3668 (lodging-susceptible variety). The results showed that higher nitrogen fertilizer increased the lodging index in both varieties due to a reduction in breaking strength and bending stress, and these changes were larger in W3668. Cellulose content decreased slightly under higher nitrogen fertilizer, whereas lignin content reduced remarkably. Histochemical staining revealed that high nitrogen application decreased lignin deposition in the secondary cell wall of the sclerenchyma cells and vascular bundle cells compared with the low nitrogen treatments, while it did not alter the pattern of cellulose deposition in these cells in both Wuyunjing23 and W3668. In addition, the expression of the genes involved in lignin biosynthesis, OsPAL, OsCoMT, Os4CL3, OsCCR, OsCAD2, OsCAD7, OsCesA4, and OsCesA7, were also down-regulated under higher nitrogen conditions at the early stage of culm growth. These results suggest that the genes involved in lignin biosynthesis are down-regulated by higher nitrogen fertilizer, which causes lignin deficiency in the secondary cell walls and the weakening of mechanical tissue structure. Subsequently, this results in these internodes with reduced mechanical strength and poor lodging resistance.