Valorization of Kraft Lignin by Fractionation and Chemical Modifications for Different Applications

Abstract Lignin is one of the most abundant biopolymers. Approximately 70 million tons of technical lignin is generated annually, but only little is used for products other than energy. The complexity of lignin hinders full utilization in high-value products and materials. In spite of the large recent progress of knowledge of lignin structure and biosynthesis, much is still not fully understood, including structural inhomogeneity. We made synthetic lignin at different pH’s and obtained structural differences that might explain the structural inhomogeneity of lignin. Technical lignins from the chemical pulping are available in large scale, but the processes result in alterations, such as oxidation and condensation. Therefore, to utilize technical lignin, modifications, such as fractionation and/or chemical modifications are necessary. Fractionation with ceramic membranes is one way to lower the polydispersity of lignin. The main advantage is their tolerance towards high temperature and harsh conditions. We demonstrated that low Mw lignin was extracted from industrially produced LignoBoost lignin aiming: i) to investigate the performance of the membrane over time; ii) to analyze the antioxidant properties of the low Mw lignin. Chemical modification can also improve the properties of lignin. By adding moieties, different properties can be obtained. Amination and methacrylation of kraft lignin were performed, as well as lignin-silica hybrid materials with potential for the adsorption were produced and investigated. Non-modified and methacrylated lignin were used to synthesize lignin-St-DVB porous microspheres to be utilized as a sorbent for organic pollutants. The possibility to substitute styrene with methacrylated lignin was evaluated, demonstrating that interaction between lignin and DVB, and porosity increased. Lignin has certain antibacterial properties. Un-modified and modified (aminated) lignin samples and sphere nanoparticles of lignin were tested for their effect against gram-positive and gram-negative bacteria’s and an injectable hydrogel was developed with encapsulated lignin for being used as an injectable gel for the open wounds. Results demonstrated promising antibacterial efficiency of lignins against gram-positive, more especially better inhibition with aminated lignins against gram-positive and negative bacterium.    SAMMANFATTNING Lignin är en av de mest förkommande biopolymererna och ca 70 miljoner ton av tekniskt lignin produceras årligen, men endast en mindre del används till andra applikationer än energiproduktion. Ett hinder för användning av lignin i mer komplexa produkter och material är dess komplexa struktur. Trotts senare års stora framsteg när det gäller kunskap om ligninets struktur, är mycket alltjämt dåligt förstått, exempelvis angående den strukturella inhomogeniteten hos lignin. Vi har studerat detta genom att göra syntetiskt lignin vid olika pH, och erhöll strukturella skillnader som kan vara en förklaring till den strukturella inhomogeniteten. Tekniska ligniner från kemisk massatillverkning är tillgängliga i stor skala, men processerna resulterar i strukturella modifieringar hos ligninet, såsom oxidationer och kondensationer. Därför är fraktionering och modifiering av tekniskt lignin lämpligt. Fraktionering med hjälp av keramiska membran är ett sätt att minska polydisperiteten hos lignin. Den största fördelen är membranens stora tolerans mot höga temperatur och aggressiva kemikalier. Vi använde filtrering på keramiska membran för att framställa lågmolekylärt lignin från den industriella kvaliteten LignoBoost, för att utvärdera membranens prestanda över tid, och analysera antioxidantegenskaperna hos det lågmolekylära ligninet. Kemisk modifiering kan också användas för att förbättra egenskaperna hos lignin. Genom att koppla på grupper, kan egenskaperna ändras. Amidering och metakrylering av sulfatlignin utfördes liksom tillverkning av lignin-silikon-hybridmaterial, med potential för adsorption, och materialen undersöktes. Omodifierat och metakrylerat lignin användes tillsammans med styren för att syntetisera porösa mikrosfärer som testades som absorbent för organiska föroreningar. Utvärdering visade att metakrylering ökade interaktionen mellan lignin och polystyren och ökade porositeten. Lignin har viss antimikrobiell aktivitet. Omodifierade och amiderade ligninprover och sfäriska nanopartiklar av lignin testades för sin verkan mot gram-positiva och gram-negativa bakterier. Resultaten visade lovande resultat för antimikrobiell aktivitet, och särskilt för amiderade ligniner när det gäller grampositiva bakterier. En injicerbar hydrogel med inkapslat lignin utvecklades också för behandling av öppna sår.    QC 20181122</p

Valorization of Kraft Lignin by Fractionation and Chemical Modifications for Different Applications

Abstract Lignin is one of the most abundant biopolymers. Approximately 70 million tons of technical lignin is generated annually, but only little is used for products other than energy. The complexity of lignin hinders full utilization in high-value products and materials. In spite of the large recent progress of knowledge of lignin structure and biosynthesis, much is still not fully understood, including structural inhomogeneity. We made synthetic lignin at different pH’s and obtained structural differences that might explain the structural inhomogeneity of lignin. Technical lignins from the chemical pulping are available in large scale, but the processes result in alterations, such as oxidation and condensation. Therefore, to utilize technical lignin, modifications, such as fractionation and/or chemical modifications are necessary. Fractionation with ceramic membranes is one way to lower the polydispersity of lignin. The main advantage is their tolerance towards high temperature and harsh conditions. We demonstrated that low Mw lignin was extracted from industrially produced LignoBoost lignin aiming: i) to investigate the performance of the membrane over time; ii) to analyze the antioxidant properties of the low Mw lignin. Chemical modification can also improve the properties of lignin. By adding moieties, different properties can be obtained. Amination and methacrylation of kraft lignin were performed, as well as lignin-silica hybrid materials with potential for the adsorption were produced and investigated. Non-modified and methacrylated lignin were used to synthesize lignin-St-DVB porous microspheres to be utilized as a sorbent for organic pollutants. The possibility to substitute styrene with methacrylated lignin was evaluated, demonstrating that interaction between lignin and DVB, and porosity increased. Lignin has certain antibacterial properties. Un-modified and modified (aminated) lignin samples and sphere nanoparticles of lignin were tested for their effect against gram-positive and gram-negative bacteria’s and an injectable hydrogel was developed with encapsulated lignin for being used as an injectable gel for the open wounds. Results demonstrated promising antibacterial efficiency of lignins against gram-positive, more especially better inhibition with aminated lignins against gram-positive and negative bacterium.    SAMMANFATTNING Lignin är en av de mest förkommande biopolymererna och ca 70 miljoner ton av tekniskt lignin produceras årligen, men endast en mindre del används till andra applikationer än energiproduktion. Ett hinder för användning av lignin i mer komplexa produkter och material är dess komplexa struktur. Trotts senare års stora framsteg när det gäller kunskap om ligninets struktur, är mycket alltjämt dåligt förstått, exempelvis angående den strukturella inhomogeniteten hos lignin. Vi har studerat detta genom att göra syntetiskt lignin vid olika pH, och erhöll strukturella skillnader som kan vara en förklaring till den strukturella inhomogeniteten. Tekniska ligniner från kemisk massatillverkning är tillgängliga i stor skala, men processerna resulterar i strukturella modifieringar hos ligninet, såsom oxidationer och kondensationer. Därför är fraktionering och modifiering av tekniskt lignin lämpligt. Fraktionering med hjälp av keramiska membran är ett sätt att minska polydisperiteten hos lignin. Den största fördelen är membranens stora tolerans mot höga temperatur och aggressiva kemikalier. Vi använde filtrering på keramiska membran för att framställa lågmolekylärt lignin från den industriella kvaliteten LignoBoost, för att utvärdera membranens prestanda över tid, och analysera antioxidantegenskaperna hos det lågmolekylära ligninet. Kemisk modifiering kan också användas för att förbättra egenskaperna hos lignin. Genom att koppla på grupper, kan egenskaperna ändras. Amidering och metakrylering av sulfatlignin utfördes liksom tillverkning av lignin-silikon-hybridmaterial, med potential för adsorption, och materialen undersöktes. Omodifierat och metakrylerat lignin användes tillsammans med styren för att syntetisera porösa mikrosfärer som testades som absorbent för organiska föroreningar. Utvärdering visade att metakrylering ökade interaktionen mellan lignin och polystyren och ökade porositeten. Lignin har viss antimikrobiell aktivitet. Omodifierade och amiderade ligninprover och sfäriska nanopartiklar av lignin testades för sin verkan mot gram-positiva och gram-negativa bakterier. Resultaten visade lovande resultat för antimikrobiell aktivitet, och särskilt för amiderade ligniner när det gäller grampositiva bakterier. En injicerbar hydrogel med inkapslat lignin utvecklades också för behandling av öppna sår.    QC 20181122</p

Valorization of Kraft Lignin by Fractionation and Chemical Modifications for Different Applications

Abstract Lignin is one of the most abundant biopolymers. Approximately 70 million tons of technical lignin is generated annually, but only little is used for products other than energy. The complexity of lignin hinders full utilization in high-value products and materials. In spite of the large recent progress of knowledge of lignin structure and biosynthesis, much is still not fully understood, including structural inhomogeneity. We made synthetic lignin at different pH’s and obtained structural differences that might explain the structural inhomogeneity of lignin. Technical lignins from the chemical pulping are available in large scale, but the processes result in alterations, such as oxidation and condensation. Therefore, to utilize technical lignin, modifications, such as fractionation and/or chemical modifications are necessary. Fractionation with ceramic membranes is one way to lower the polydispersity of lignin. The main advantage is their tolerance towards high temperature and harsh conditions. We demonstrated that low Mw lignin was extracted from industrially produced LignoBoost lignin aiming: i) to investigate the performance of the membrane over time; ii) to analyze the antioxidant properties of the low Mw lignin. Chemical modification can also improve the properties of lignin. By adding moieties, different properties can be obtained. Amination and methacrylation of kraft lignin were performed, as well as lignin-silica hybrid materials with potential for the adsorption were produced and investigated. Non-modified and methacrylated lignin were used to synthesize lignin-St-DVB porous microspheres to be utilized as a sorbent for organic pollutants. The possibility to substitute styrene with methacrylated lignin was evaluated, demonstrating that interaction between lignin and DVB, and porosity increased. Lignin has certain antibacterial properties. Un-modified and modified (aminated) lignin samples and sphere nanoparticles of lignin were tested for their effect against gram-positive and gram-negative bacteria’s and an injectable hydrogel was developed with encapsulated lignin for being used as an injectable gel for the open wounds. Results demonstrated promising antibacterial efficiency of lignins against gram-positive, more especially better inhibition with aminated lignins against gram-positive and negative bacterium.    SAMMANFATTNING Lignin är en av de mest förkommande biopolymererna och ca 70 miljoner ton av tekniskt lignin produceras årligen, men endast en mindre del används till andra applikationer än energiproduktion. Ett hinder för användning av lignin i mer komplexa produkter och material är dess komplexa struktur. Trotts senare års stora framsteg när det gäller kunskap om ligninets struktur, är mycket alltjämt dåligt förstått, exempelvis angående den strukturella inhomogeniteten hos lignin. Vi har studerat detta genom att göra syntetiskt lignin vid olika pH, och erhöll strukturella skillnader som kan vara en förklaring till den strukturella inhomogeniteten. Tekniska ligniner från kemisk massatillverkning är tillgängliga i stor skala, men processerna resulterar i strukturella modifieringar hos ligninet, såsom oxidationer och kondensationer. Därför är fraktionering och modifiering av tekniskt lignin lämpligt. Fraktionering med hjälp av keramiska membran är ett sätt att minska polydisperiteten hos lignin. Den största fördelen är membranens stora tolerans mot höga temperatur och aggressiva kemikalier. Vi använde filtrering på keramiska membran för att framställa lågmolekylärt lignin från den industriella kvaliteten LignoBoost, för att utvärdera membranens prestanda över tid, och analysera antioxidantegenskaperna hos det lågmolekylära ligninet. Kemisk modifiering kan också användas för att förbättra egenskaperna hos lignin. Genom att koppla på grupper, kan egenskaperna ändras. Amidering och metakrylering av sulfatlignin utfördes liksom tillverkning av lignin-silikon-hybridmaterial, med potential för adsorption, och materialen undersöktes. Omodifierat och metakrylerat lignin användes tillsammans med styren för att syntetisera porösa mikrosfärer som testades som absorbent för organiska föroreningar. Utvärdering visade att metakrylering ökade interaktionen mellan lignin och polystyren och ökade porositeten. Lignin har viss antimikrobiell aktivitet. Omodifierade och amiderade ligninprover och sfäriska nanopartiklar av lignin testades för sin verkan mot gram-positiva och gram-negativa bakterier. Resultaten visade lovande resultat för antimikrobiell aktivitet, och särskilt för amiderade ligniner när det gäller grampositiva bakterier. En injicerbar hydrogel med inkapslat lignin utvecklades också för behandling av öppna sår.    QC 20181122</p

Membrane filtration of kraft lignin: Structural charactristics and antioxidant activity of the low-molecular-weight fraction

Lignin, which is the second most abundant biomass component and has carbon-rich phenolic content, is a promising renewable raw material for multiple applications, such as carbon fibers, adhesives, and emulsifiers. To use lignin efficiently, it is important to ensure its purity and homogeneity. As a result, the separation of lignin into fractions with high purity and narrow molecular-weight distributions is likely a prerequisite for several applications. Ultrafiltration using ceramic membranes has many advantages, including enabling direct lignin extraction from Kraft pulp cooking liquors without pH and temperature adjustment. One challenge with membrane filtration using such a system is the potential for reduced membrane performance over time, which is associated with fouling. In this study, LignoBoost Kraft lignin was fractionated using a ceramic membrane with a molecular weight cut-off of 1 kDa. The separation behavior during ultrafiltration fractionation was investigated and the antioxidant properties of the recovered low-molecular-weight (low-MW) lignin samples were evaluated. Using this model system, the permeate fluxes were unstable during the 100 h of membrane operation. However, a decrease in the average MW in the permeate over time was observed. The shift in MW was most pronounced for virgin membranes, while a more stable MW distribution was evident for membranes subjected to multiple cleaning cycles. According to 2D NMR analysis, low-MW lignin that was recovered after 100 h of operation, consisted of smaller lignin fragments, such as dimers and oligomers, with a high content of methoxy-groups. This was confirmed using the size exclusion chromatography method, which indicated an weigh average molecular weight in the range of 450–500 Da. 31P NMR spectroscopy showed that, despite the lower total content of phenolic OH groups, the low-MW sample had a higher proportion of non-condensed phenolic OH groups. The results of the antioxidant tests demonstrated the strong potential of lignin and its low-MW fraction as a natural antioxidant, particularly for lipid-containing systems. The low-MW lignin fraction showed better antioxidant activity than the non-fractionated LignoBoost lignin in the kinetic oxygen radical absorbance capacity (ORAC) test and demonstrated three-fold stronger inhibition of the substrate (fluorescein) than the reference antioxidant Trolox (a water-soluble derivative of vitamin E)

Utilizing native lignin as redox-active material in conductive wood for electronic and energy storage applications

Nanostructured wood veneer with added electroactive functionality combines structural and functional properties into eco-friendly, low-cost nanocomposites for electronics and energy technologies. Here, we report novel conducting polymer-impregnated wood veneer electrodes where the native lignin is preserved, but functionalized for redox activity and used as an active component. The resulting electrodes display a well-preserved structure, redox activity, and high conductivity. Wood samples were sodium sulfite-treated under neutral conditions at 165 degrees C, followed by the tailored distribution of PEDOT:PSS, not previously used for this purpose. The mild sulfite process introduces sulfonic acid groups inside the nanostructured cell wall, facilitating electrostatic interaction on a molecular level between the residual lignin and PEDOT. The electrodes exhibit a conductivity of up to 203 S m(-1) and a specific pseudo-capacitance of up to 38 mF cm(-2), with a capacitive contribution from PEDOT:PSS and a faradaic component originating from lignin. We also demonstrate an asymmetric wood pseudo-capacitor reaching a specific capacitance of 22.9 mF cm(-2) at 1.2 mA cm(-2) current density. This new wood composite design and preparation scheme will support the development of wood-based materials for use in electronics and energy storage.Funding Agencies|Wallenberg Wood Science Center (Knut and Alice Wallenberg Foundation); Karl-Erik Onnesjo Foundation; Treesearch, a collaboration platform for Swedish forest industrial research</p

Assessing the aneurysm occlusion efficacy of a shear-thinning biomaterial in a 3D-printed model

Metallic coil embolization is a common method for the endovascular treatment of visceral artery aneurysms (VAA) and visceral artery pseudoaneurysms (VAPA); however, this treatment is suboptimal due to the high cost of coils, incomplete volume occlusion, poor reendothelialization, aneurysm puncture, and coil migration. Several alternative treatment strategies are available, including stent flow diverters, glue embolics, gelfoam slurries, and vascular mesh plugs-each of which have their own disadvantages. Here, we investigated the in vitro capability of a shear-thinning biomaterial (STB), a nanocomposite hydrogel composed of gelatin and silicate nanoplatelets, for the minimally-invasive occlusion of simple necked aneurysm models. We demonstrated the injectability of STB through various clinical catheters, engineered an in vitro testing apparatus to independently manipulate aneurysm neck diameter, fluid flow rate, and flow waveform, and tested the stability of STB within the models under various conditions. Our experiments show that STB is able to withstand at least 1.89&nbsp;Pa of wall shear stress, as estimated by computational fluid dynamics. STB is also able to withstand up to 10&nbsp;mL&nbsp;s-1 pulsatile flow with a waveform mimicking blood flow in the human femoral artery and tolerate greater pressure changes than those in the human aorta. We ultimately found that our in vitro system was limited by supraphysiologic pressure changes caused by aneurysm models with low compliance