Phenolic residues in spruce galactoglucomannans improve stabilization of oil-in-water emulsions.

HYPOTHESIS: Amphiphilic character of surfactants drives them at the interface of dispersed systems, such as emulsions. Hemicellulose-rich wood extracts contain assemblies (lignin-carbohydrate complexes, LCC) with natural amphiphilicity, which is expected to depend on their chemical composition resulting from the isolation method. Lignin-derived phenolic residues associated with hemicelluloses are hypothesized to contribute to emulsions' interfacial properties and stability. EXPERIMENTS: We investigated the role of phenolic residues in spruce hemicellulose extracts in the stabilization of oil-in-water emulsions by physical and chemical approach. Distribution and changes occurring in the phenolic residues at the droplet interface and in the continuous phase were studied during an accelerated storage test. Meanwhile, the physical stability and lipid oxidation in emulsions were monitored. FINDINGS: Naturally associated lignin residues in GGM act as vehicles for anchoring these hemicelluloses into the oil droplet interface and further enable superior stabilization of emulsions. By adjusting the isolation method of GGM regarding their phenolic profile, their functionalities, especially interfacial behavior, can be altered. Retaining the native interactions of GGM and phenolic residues is suggested for efficient physical stabilization and extended protection against lipid oxidation. The results can be widely applied as guidelines in tailoring natural or synthetic amphiphilic compounds for interfacial stabilization.

Characterisation of volatile organic compounds in stemwood using solid-phase microextraction.

Solid-phase microextraction (SPME), hydrodistillation and dynamic headspace combined with GC and GC-MS were applied and compared for the analysis of volatile organic compounds (VOCs) from coniferous wood. The SPME conditions (type of fibre, size of wood sample, temperature and exposure time) were optimised, and more than 100 VOCs and semi-volatile compounds extracted and identified from the sapwood and heartwood of Norway spruce (Picea abies). The total number of mono- and sesquiterpenes eluted and identified was similar for the SPME and hydrodistillation methods, but more semi-volatile compounds were released by hydrodistillation. By applying dynamic headspace at room temperature, it was possible to analyse only the most volatile compounds. The qualitative composition of VOCs was similar in spruce sapwood and heartwood, although Z-beta-ocimene occurred only in sapwood while fenchol was present only in heartwood. SPME sampling coupled with GC, applied here to the analysis of VOCs released from stemwood of firs for the first time, is a convenient, sensitive, fast, solvent-free and simple method for the determination of wood volatiles. The technique requires much smaller sample amounts compared with hydrodistillation, and the total amount of VOCs extracted and identified is higher than that obtained by hydrodistillation or dynamic headspace. The relative ratios of the main mono- and sesquiterpenes and -terpenoids were similar using the SPME-GC and hydrodistillation methods.

Chromatographic analysis of lignans.

Methods and procedures for analysis of lignans in trees and other plants are reviewed. The importance of cautious sample handling and pretreatment procedures to avoid contamination, loss of sample, and unwanted chemical reactions is discussed. Sequential extraction with a non-polar solvent followed by extraction with acetone or ethanol is recommended to separate the lignans from the plant matrix. An additional step of acid, alkaline, or enzymatic hydrolysis may be necessary for some plant matrixes. Flash chromatography is a convenient method for preparative separation and isolation of pure lignans from raw extracts. TLC is very suitable for qualitative screening of extracts and for monitoring of lignan isolation and purification steps. Trimethylsilyl ethers of lignans can be separated and quantified by GC even in the case of complex mixtures of lignans and other polyphenols, and the lignans can be identified by GC-MS in a routine manner. HPLC on reversed-phase columns is especially suited for analysis of lignans and their metabolites in biological matrixes. The recent development of HPLC-electrospray ionisation (ESI)-iontrap MS (MS(n)) and corresponding techniques with high sensitivity and selectivity has proven valuable in lignan analysis. Lignan enantiomers can be separated on chiral HPLC columns.

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds of Scots pine (Pinus sylvestris) wood. Part I: lipophilic compounds.

The wood resin in Scots pine (Pinus sylvestris) stemwood and branch wood were studied using UV resonance Raman (UVRR) spectroscopy. UVRR spectra of the sapwood and heartwood hexane extracts, solid wood samples and model compounds (six resin acids, three fatty acids, a fatty acid ester, sitosterol and sitosterol acetate) were collected using excitation wavelengths of 229, 244 and 257 nm. In addition, visible Raman spectra of the fatty and resin acids were recorded. Resin compositions of heartwood and sapwood hexane extracts were determined using gas chromatography. Raman signals of both conjugated and isolated double bonds of all the model compounds were resonance enhanced by UV excitation. The oleophilic structures showed strong bands in the region of 1660-1630 cm(-1). Distinct structures were enhanced depending on the excitation wavelength. The UVRR spectra of the hexane extracts showed characteristic bands for resin and fatty acids. It was possible to identify certain resin acids from the spectra. UV Raman spectra collected from the solid wood samples containing wood resin showed a band at approximately 1650 cm(-1) due to unsaturated resin components. The Raman signals from extractives in the resin rich branch wood sample gave even more strongly enhanced signals than the aromatic lignin.

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds in Scots pine (Pinus sylvestris) wood. Part II. Hydrophilic compounds.

Hydrophilic extracts of Scots pine (Pinus sylvestris) heartwood and sapwood and a solid Scots pine knotwood sample were studied by UV resonance Raman spectroscopy (UVRRS). In addition, UVRR spectra of two hydrophilic model compounds (pinosylvin and chrysin) were analysed. UV Raman spectra were collected using 244 and 257 nm excitation wavelengths. The chemical composition of the acetone:water (95:5 v/v) extracts were also determined by gas chromatography. The aromatic and oleophilic structures of pinosylvin and chrysin showed three intense resonance enhanced bands in the spectral region of 1649-1548 cm(-1). Pinosylvin showed also a relatively intense band in the aromatic substitution region at 996 cm(-1). The spectra of the heartwood acetone:water extract showed many bands typical of pinosylvin. In addition, the extract included bands distinctive for resin and fatty acids. The sapwood acetone:water extract showed bands due to oleophilic structures at 1655-1650 cm(-1). The extract probably also contained oligomeric lignans because the UVRR spectra were in parts similar to that of guaiacyl lignin. The characteristic band of pinosylvin (996 cm(-1)) was detected in the UVRR spectrum of the resin rich knotwood. In addition, several other bands typical for wood resin were observed, which indicated that the wood resin in the knotwood was resonance enhanced even more than lignin.

Antibacterial effects of knotwood extractives on paper mill bacteria.

Hydrophilic knotwood extracts from 18 wood species were assessed in disc diffusion and liquid culture tests for antibacterial effects against three species of paper mill bacteria. The Pinus sylvestris, P. resinosa, P. contorta, and P. banksiana extracts decreased or inhibited bacterial growth. The susceptibility order was P. sylvestris > P. resinosa > P. contorta > P. banksiana, correlating with the concentrations of pinosylvin and pinosylvin monomethyl ether in these wood species. Also, Pseudotsuga menziesii and Thuja occidentalis extracts had a small inhibitory effect. The Gram-positive Bacillus coagulans was more susceptible to the extracts than the Gram-negative Burkholderia multivorans and Alcaligenes xylosoxydans. The main components in the Pinus knotwood extracts were pinosylvin monomethyl ether and pinosylvin, suggesting these to be the active components. Therefore, pure pinosylvin, pinosylvin monomethyl ether, and dihydro-pinosylvin monomethyl ether were also tested. All compounds showed antibacterial effects. However, higher concentrations were needed for these pure compounds than for the knotwood extracts. Pinosylvin had stronger antibacterial effects than pinosylvin monomethyl ether. This work shows that knotwood extracts, especially from Pinus species, have a potential for use as natural biocides in papermaking.