Søren Barsberg

The fluorescence characteristics of furfurylated wood studied by fluorescence spectroscopy and confocal laser scanning microscopy

The fluorescence of furfurylated wood was studied. Furfurylation of wood introduced fluorescent curing products into the cell walls. Fluorescent products were also found in the lumina if high loadings were used and/or if the wood contained cells with small radii. More intense fluorescence was obtained from lignin-rich parts of the compound cell wall (i.e., the middle lamella and the cell corners) than from the secondary cell wall if the wood was impregnated using furfuryl alcohol (FA), while impregnation using small poly(FA) oligomers showed no or only minor differences between different regions. The study also showed that when higher amounts of catalyst were added to the impregnation liquid, a red-shift in the fluorescence from the furfurylated wood was seen, corresponding to an increased conjugation length of conjugated poly(FA) formed within the wood cell wall. Longer conjugation length than within the cell wall was observed for the poly(FA) formed within the lumina. This indicates that the cell wall polymers restrict poly(FA) formation.

Composition of Cypripedium calceolus (Orchidaceae) seeds analyzed by attenuated total reflectance IR spectroscopy: In search of understanding longevity in the ground

UNLABELLED PREMISE OF THE STUDY Orchid seeds are minute and covered with a thin coat, yet they often have a long life after dispersal. They are notorious for low and irregular germination, in nature as well as in vitro. Since orchids are often rare species of conservational and commercial interest, reproduction by seeds is an important concern. The purpose of this study was to learn more about the resilience of these highly specialized seeds and stimulatory processes toward germination. • METHODS We studied testa and embryos of Cypripedium calceolus to identify natural components in intact seeds and the impact of 7 yr in soil in its natural habitat. We also analyzed the effects of Ca(OCl)2, used technically to enhance germination for cultivation in vitro. For the first time with this kind of plant material, we used attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, an ideal method for minute sample sizes and surface selectivity. Thus, we could link treatments with changes in seed surface chemistry. • KEY RESULTS A lignin-like polymer is an essential testa component that undergoes degradation by soil or hypochlorite processes. In both cases, we found a build-up of CaCO3 on the testa, which could interact with lignin to enhance germination. Very minor changes occurred in embryo reserve nutrient content after a long sojourn underground, which supports their continued viability. • CONCLUSIONS We suggest that degradation of lignin and enrichment of the testa surface with CaCO3 are important stimulants of germination both in the habitat and during laboratory sowing.

Fourier Transform Raman Difference Spectroscopy for Detection of Lignin Oxidation Products in Thermomechanical Pulp

Spruce thermomechanical pulp (TMP) was oxidized by the 2,29′-azinobis-3-ethylbenzthiazoline-6-sulfonate cation radical (ABTS•+) in the presence and absence of oxygen. The pulp modification was monitored by Fourier transform (FT) Raman difference spectroscopy and other nondestructive spectroscopic methods. The ABTS•+ oxidative system resulted in modifications very similar to the laccase–ABTS–oxygen system, except for the FT-Raman results, which showed a difference in mechanisms attributed to a difference in produced Raman bands. Oxygen resulted in no oxygen-derived products, but only enhanced the production of a specific Raman band of several oxidation-produced bands. Detailed information on lignin reactions can be obtained from FT-Raman signals.

Modification phenomena of solid-state lignin caused by electron-abstracting oxidative systems.

Oxidative treatments of wood pulp lignin by one-electron-abstracting enzymatic or chemical systems result in modification phenomena which are not fully described in terms of those known from lignin model compound studies. The generation of, e.g., long-lived radicals necessitates nondestructive spectroscopic analysis of the lignin polymer for a proper characterization of these. The present work exposes a complexity of spectroscopic modification phenomena, which has not previously been realized. This is achieved by a laccase-mediator system, where the mediator is an aromatic low-molecular-weight compound, which mediates the electron abstraction between the lignin and the enzyme laccase. It is demonstrated that the modification generated exhibits qualitatively different temporal phases. The mechanisms are partly explained in terms of Marcus electron transfer theory, and it is suggested that these may play a role in the in vivo synthesis and degradation of lignin.

Complex between lignin and a Ti-based coupling agent

Abstract Durability, haptic, and optical appearance of wood are improved by coatings, which are nowadays prepared using environmentally compatible and less health-damaging materials. However, contemporary wood coatings have frequently a shortened service life compared to their traditional predecessors. New coating formulations would have a better performance if the adhesion to wood could be improved. In the present work, the chemical interaction between a titanium-based coupling agent, isopropyl triisostearoyl titanate (titanium agent, TA) and lignin has been studied by means of attenuated total reflectance-fourier transform infrared spectroscopy in combination with first principle predictions based on the density functional theory (DFT). In the infrared spectra, a new band at 1586 cm-1 was identified and the DFT predictions confirmed that the new band is because of the covalent bonds in the form of ether linkages between TA and lignin.

Effect of Fiber Treatment Condition and Coupling Agent on the Mechanical and Thermal Properties in Highly Filled Composites of Sugarcane Bagasse Fiber/PP

This paper reports on a study of highly filled composites of polypropylene (PP) and 75% by weight sugarcane bagasse fiber with and without alkali treatment and with and without coupling agent (SEBS-g-MA). Composites were prepared using a Rheomix600 mixer connected to a HAAKE torque rheometer. The thermal and mechanical behavior of these composites were investigated by thermogravimetry (TGA), differential Scanning Calorimetry (DSC), flexural tests, impact tests and scanning electron microscopy. Scanning electron microscopy (SEM) images taken from sugarcane bagasse fibers showed enhancements in the fibers surface topography after the surface treatment process. The FTIR, TGA and SEM results for the fibers showed that the alkali treatment modified the fiber surface as well as the chemical composition. The impact test results showed a good potential of SEBS-g-MA as coupling agent and impact modifier in highly filled composites, increasing by more than 100% the impact strength of the composite as compared to those without the coupling agent. Scanning electron microscopy showed that addition of coupling agent improved the interfacial adhesion between the fibers and polypropylene.

Assessment of covalent bond formation between coupling agents and wood by FTIR spectroscopy and pull strength tests

Abstract In the focus was the question whether metal alkoxide coupling agents – titanium, silane, and zirconium – form covalent bonds to wood and how they improve coating adhesion. In a previous work, a downshift of the lignin infrared (IR) band ∼1600 cm-1 was shown to be consistent with the formation of ether linkages between lignin and titanium coupling agent. In the present work, changes were found in the attenuated total reflectance-Fourier transform IR (ATR-FTIR) spectra of lignin and wood mixed with silane, and titanium coupling agents, and to a lesser extent for a zirconium coupling agent. This was seen as evidence for covalent bonds between lignin phenolics and the coupling agents. No spectral changes were observed when the coupling agents were mixed with the wood constituents cellulose and hemicellulose. For verification of the results, a modified EN 311 wet adhesion pull strength test was performed with softwood panels painted with a solvent-borne alkyd/acrylic coating. The results revealed an improved adhesion for all tested coupling agents compared to the untreated reference. The spectroscopic and pull test results underline that the presence of the lignin moiety in wood is of central importance for improved wood coating adhesion.