Pilot-Scale Production of Hemicellulose Ethers from Softwood Hemicelluloses Obtained from Compression Screw Pressate of a Thermo-Mechanical Pulping Plant.

Bio-derived materials are becoming increasingly sought-after as a sustainable alternative to petrochemical-derived polymers. In the present pilot-scale study, a hemicellulose-rich compression screw pressate, obtained from the pre-heating stage of thermo-mechanical pulping (TMP) of radiata pine, was purified by treatment with adsorbent resin (XAD7), then ultrafiltered and diafiltered at 10 kDa to isolate the high-molecular weight (MW) hemicellulose fraction (yield 18.4% on pressate solids), and, finally, reacted with butyl glycidyl ether to plasticise the hemicelluloses. The resulting light brown hemicellulose ethers (yield 102% on the isolated hemicelluloses) contained ca. 0.5 butoxy-hydroxypropyl side chains per pyranose unit and had weight- and number-average MWs of 13,000 Da and 7200 Da, respectively. The hemicellulose ethers may serve as raw material for bio-based products such as barrier films.

Tannin-Based Microbicidal Coatings for Hospital Privacy Curtains.

The goal of this study was to develop a sustainable, tannin-based option for silver-based and other current antimicrobial solutions for hospital privacy curtains. Commercial tree-derived tannins were characterized and their in vitro antibacterial properties against Staphylococcus aureus and Escherichia coli were determined. Hydrolysable tannins showed greater antibacterial efficacy than condensed tannins but differences in antibacterial efficacy between any of the tannins could not be attributed to their functional group content or molar mass. Outer membrane disruption was not a significant factor in antibacterial efficacy of tannins against E. coli. In a hospital field study, draw patches coated with hydrolysable tannins and affixed to privacy curtains reduced total bacteria count by 60% over eight weeks compared to their matching uncoated reference sides. In a follow-up laboratory study with S. aureus, very light spraying with water improved contact between bacteria and coating, enhancing the antibacterial effect by several orders of magnitude.

Antimicrobial and Flame-Retardant Coatings Prepared from Nano- and Microparticles of Unmodified and Nitrogen-Modified Polyphenols.

The purpose of this study was to elucidate the structures and functional properties of tannin- and lignin-derived nano- and microparticles and the coatings prepared from them. Nanoparticles prepared from technical lignins and water-insoluble tannin obtained from softwood bark showed large differences in the suspension testing of antibacterial efficacy against methicillin-resistant Staphylococcus aureus (MRSA) bacteria. A common factor among the most effective lignin nanoparticles was a relatively low molar mass of the lignin, but that alone did not guarantee high efficacy. Tannin nanoparticles showed good antibacterial activity both in suspension testing and as coatings applied onto cellulose. The nanoparticles of nitrogen-modified tannin and the small microparticles of nitrogen-modified kraft lignin exhibited promising flame-retardant parameters when applied as coatings on cellulose. These results illustrate the potential of nano- and microsized particles of unmodified and chemically modified polyphenols to provide functional coatings to cellulosic substrates for environments and applications with high hygiene and fire safety requirements.

Improved Fire Retardancy of Cellulose Fibres via Deposition of Nitrogen-Modified Biopolyphenols.

Driven by concerns over the health and environmental impacts of currently used fire retardants (FRs), recent years have seen strong demand for alternative safer and sustainable bio-based FRs. In this paper, we evaluated the potential of nitrogen-modified biopolyphenols as FRs for cellulosic natural fibres that could be used in low-density cellulose insulations. We describe the preparation and characterisation of nitrogen-modified lignin and tannin containing over 10% nitrogen as well as the treatment of cellulose pulp fibres with combinations of lignin or tannin and adsorption-enhancing retention aids. Combining lignin or tannin with a mixture of commercial bio-based flocculant (cationised tannin) and anionic retention chemical allowed for a nearly fourfold increase in lignin adsorption onto cellulosic pulp. The nitrogen-modified biopolyphenols showed significant improvement in heat release parameters in micro-scale combustion calorimetry (MCC) testing compared with their unmodified counterparts. Moreover, the adsorption of nitrogen-modified lignin or tannin onto cellulose fibres decreased the maximum heat release rate and total heat release compared with cellulose reference by 15-23%. A further positive finding was that the temperature at the peak heat release rate did not change. These results show the potential of nitrogen-modified biopolyphenols to improve fire-retarding properties of cellulosic products.

Natural Sunscreens Based on Nanoparticles of Modified Kraft Lignin (CatLignin).

Commercial chemical sunscreens have a high content of synthetic ultraviolet (UV) actives that have caused widespread damage to marine ecosystems and may have adverse health effects in humans. In the present work, safer bio-based sunscreens with lignin UV absorbers were developed to address this issue. Partly demethylated and otherwise altered kraft lignins, the so-called CatLignins with abundant phenolic hydroxyl auxochromes and catechol units, outperformed regular kraft lignins as sunscreen UV absorbers in terms of sun protection factor (UVB-SPF) and UVA-UVB transmittance. Converting lignins to nanoparticles significantly enhanced sunscreen performance. The best lignin sunscreen, containing nanoparticles of hardwood CatLignin, had a UV transmittance of only 0.5-3.8% over the entire UVA-UVB region compared to 2.7-51.1% of a commercial SPF 15 sunscreen. Lignin-based sunscreens are particularly suitable for dark-tinted SPF cosmetics.

Tannins and extracts of fruit byproducts: antibacterial activity against foodborne bacteria and antioxidant capacity.

The shelf life of fresh fish and meat transported over long distances could be extended by using plant-based extracts to control spoilage bacteria. The goals of the present study were to identify plant-based extracts that effectively suppress the main spoilage bacteria of chilled fish and lamb and to assess their antioxidant capacity. The phenolic compounds in wood-based tannins and extracts isolated from byproducts of the fruit processing industry were identified and/or quantified. The total phenol content, but not the flavonoid to total phenol ratio, was strongly associated with higher antibacterial activity against several fish and lamb spoilage bacteria in zone of inhibition and minimum inhibitory concentration assays as well as greater antioxidant capacity in the DPPH (2,2-diphenyl-1-picrylhydrazyl) radical assay. The most promising compounds in both cases, and thus good candidates for antibacterial packaging or antioxidant dietary supplements, were mango seed extract and tannic acid containing mostly polygalloyl glucose type phenols.

Citric acid crosslinking of paper products for improved high-humidity performance.

Fibre crosslinking with polycarboxylic acids can be used to improve certain properties of paper products, including wet tensile and compressive strength. In the present work it was proposed that citric acid (CA) crosslinks the cellulosic fibres of linerboard by self-catalysed esterification of cellulosic hydroxyl groups, which makes an additional catalyst unnecessary. An increase in CA dose or curing temperature increased linerboard compressive strength. In CA-treated corrugated board most of the applied CA was esterified with fibres while some CA thermolysis products were also present. A significant portion of the applied CA was unaccounted for. The deficit was attributed to thermolysis to give volatile anhydrides of unsaturated acids. Under cyclic humidity and static compressive loading, CA-treated corrugated boxes showed a greater than three-fold increase in resistance to compressive creep, showing that CA treatment can be used to extend the lifetime of corrugated boxes used for horticultural produce storage.

Laccase catalyzed covalent coupling of fluorophenols increases lignocellulose surface hydrophobicity.

This work presents for the first time the mechanistic evidence of a laccase-catalyzed method of covalently grafting hydrophobicity enhancing fluorophenols onto Fagus sylvatica veneers. Coupling of fluorophenols onto complex lignin model compounds guaiacylglycerol beta-guaiacyl ether and syringylglycerol beta-guaiacyl ether was demonstrated by LC-MS and NMR. Laccase-mediated coupling increased binding of 4-[4-(trifluoromethyl)phenoxy]phenol (4,4-F3MPP) and 4-(trifluoromethoxy)phenol (4-F3MP) to veneers by 77.1% and 39.2%, respectively. XPS studies showed that laccase-catalyzed grafting of fluorophenols resulted in a fluorine content of 6.39% for 4,4-F3MPP, 3.01% for 4-F3MP and 0.26% for 4-fluoro-2-methylphenol (4,2-FMP). Grafting of the fluorophenols 4,2-FMP, 4-F3MP and 4,4-F3MPP led to a 9.6%, 28.6% and 65.5% increase in hydrophobicity, respectively, when compared to treatments with the respective fluorophenols in the absence of laccase, in good agreement with XPS data.

Adhesion improvement of lignocellulosic products by enzymatic pre-treatment.

Enzymatic bonding methods, based on laccase or peroxidase enzymes, for lignocellulosic products such as medium-density fiberboard and particleboard are discussed with reference to the increasing costs of presently used petroleum-based adhesives and the health concerns associated with formaldehyde emissions from current composite products. One approach is to improve the self-bonding properties of the particles by oxidation of their surface lignin before they are fabricated into boards. Another method involves using enzymatically pre-treated lignins as adhesives for boards and laminates. The application of this technology to achieve wet strength characteristics in paper is also reviewed.