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This paper describes the use of a suite of extraction procedures applicable to the assessment of the in vitro toxicity of paper/board samples intended for food-contact applications. The sample is extracted with ethanol, water, or exposed to modified polyphenylene oxide (Tenax®) for fatty, non-fatty and dry food applications, respectively. The water extracts are directly suitable for safety assessment using in vitro bioassays. The ethanol extracts of the paper/board and of the exposed Tenax require pre-concentration to give acceptable sensitivity. This is because the in vitro bioassays can tolerate only a small percentage of added organic solvent before the solvent itself inhibits. The extraction procedures have been selected such that they mimic the foreseeable conditions of use with foods and that they are also fully compatible with the battery of in vitro biological assays for the safety assessment of the total migrate. The application of the extraction protocols is illustrated by the results for one of the many paper/board samples provided by the BIOSAFEPAPER project industrial platform members. The assessment indicated that this sample should not be considered as suitable for use with fatty foodstuffs but was suitable for dry and non-fatty foods. Information subsequently received from the manufacturer revealed that this was a non-food-grade product included in the project to test the capabilities of the bioassay procedures. The selection criteria for the test conditions and the suite of methods developed have been prepared in Comité Européen de Normalisation (CEN) format and is currently being progressed by CEN/TC172 as a European Standard. [ABSTRACT FROM AUTHOR]

Birch chips were subjected to pilot-scale pre-hydrolysis under various sets of conditions to mimic a pre-hydrolysis step in a dissolving pulp process. The process generates residual process liquor, a wood hydrolysate, and the treated chips may be directly utilized in a dissolving process. The wood hydrolysates were rich in xylan and utilized in the production of fully renewable films that provide very good oxygen barrier function and mechanical integrity also at high relative humidity. Membrane filtration had an effect in enriching higher molecular weight fractions from the hydrolysates, but noteworthy, a hydrolysate used in the crude state without any membrane filtration performed just as well as upgraded fractions in forming films providing acceptable tensile properties and a good barrier against oxygen permeation.

A scaled-up prehydrolysis process was elaborated to demonstrate an industrially feasible operation step in a pulping process that generates a valuable side product in addition to the cellulose pulp. The valuable side product is aqueous process liquor, a softwood hydrolysate (SWH) herein produced in 60 L batches, and its components were recovered and utilized as materials. The process parameters were shown to influence the yield, composition, and quality of the obtained hydrolysates. Furthermore, the process conditions were shown to influence the ability of SWHs to form free-standing, foldable films in blends with either microfibrillated cellulose (MFC) or carboxymethyl cellulose (CMC). Films with oxygen permeabilities (OP) as low as 0.35 cm(3) μm day(-1) m(-2) kPa(-1) at 50% relative humidity, were produced from aqueous solutions providing a viable and green alternative to petroleum-based packaging barriers. The OPs were very low regardless of SWH film composition and upgrading conditions, whereas the films' tensile performance was directly controlled by the ratio of SWH to cocomponent.

A new route for the design of renewable hydrogels is presented. The soluble waste from masonite production was isolated, fractionized, and upgraded. The resulting hemicellulose rich fraction was alkenyl-functionalized and used in the preparation of covalently cross-linked hydrogels capable of sustained release of incorporated agents. Said hydrogels showed a Fickian diffusion-based release of incorporated bovine serum albumin. Also, a method for the coating of seeds with hydrogel was developed. The sustained release of incorporated growth retardant agents from the hydrogel coating on rape seeds was shown to enable the temporary inhibition of germination.

Partially depolymerized, water-soluble hemicelluloses were solubilized from flax shive employing hydrothermal microwave treatment and thereafter subjected to ion-exchange chromatography, enzymatic purification and/or size-exclusion chromatography (SEC). The oligo- and polysaccharide fractions thus obtained were characterized with respect to molar mass, molar mass distribution, degree of polymerization (DP) and degree of substitution with acetyl moieties (DSAc) by employing SEC in combination with MALDI-TOF mass spectrometry. The major portion of the water-soluble flax hemicellulose consisted of an O-acetyl-4-O-methylglucuronoxylan exhibiting a DPp value (i.e., peak-average DP) of 28. When the DSAc for this O-acetyl-4-O-methylglucuronoxylan was calculated on the basis of the MALDI-MS spectra obtained without and following deacetylation, a value of 0.7 was obtained. In addition, an O-acetyl-glucomannan (DPp=9, DS=0.4) and minor quantities of small neutral O-acetyl-xylooligosaccharides were also isolated from the mixture of water-soluble hemicelluloses released from the flax shive by microwave treatment.

O-acetylated glucomannans were isolated from aspen and birch wood employing two different procedures and thereafter subjected to carbohydrate analysis by NMR spectroscopy and MALDI mass spectrometry. In one of the isolation procedures, acetone-extracted aspen or birch wood meal was extracted with dimethyl sulfoxide and then with hot water. Fractionation of the hemicellulose-containing extracts by size-exclusion chromatography was subsequently performed. In the other procedure, fractional precipitation with ethanol was used to isolate glucomannans from lyophilized process water produced by mechanical pulping of aspen. The aspen and birch glucomannans are O-acetylated at the C-2 or C-3 position of some of the mannose residues (random distribution), with a degree of acetylation of approx 0.3. In both cases the degree of polymerization was approx 16, indicating that low-molecular mass fractions of the glucomannans in hardwood have been isolated here.

In the present study, hardwood and softwood pulps were characterized by employing Fourier transform infrared photoacoustic spectroscopy (FT-IR-PAS). The pulp samples examined originated from Swedish sulfite and kraft pulp mills, which utilize different cooking processes and modern bleaching technologies. Partial least-squares (PLS) analysis was used to correlate the spectral data obtained with the kappa (K) numbers and carbohydrate compositions of the pulp samples determined by enzymatic hydrolysis and subsequent capillary zone electrophoresis. Using four principal components, the present PLS model based on photoacoustic FT-IR spectra could explain 85% of the variance in the X matrix and 81% of the variance in the Y matrix. The FT-IR-PAS technique in combination with PLS was found to accurately predict the contents of carbohydrates, i.e., xylose, glucose, mannose, arabinose, galactose, and hexenuronic acid residues, as well as the content of lignin measured in terms of K numbers and corrected K numbers of the pulps. From these predictions, the contents of xylan, glucomannan, and cellulose can also be predicted. The content of 4-O-methylglucuronic acid residues is, however, more difficult to predict accurately, using this approach.

Partly depolymerized hemicelluloses isolated from wood chips of spruce and aspen employing microwave treatment were resolved using size-exclusion chromatography (SEC) into oligo- and polysaccharide fractions containing components with a narrow range of sizes, as determined by MALDI mass spectroscopy. The degree of substitution with acetyl moieties (DS) was also calculated on the basis of the MALDI-MS spectra obtained prior to and following deacetylation. For spruce hemicelluloses, the low molecular mass fraction contained small arabino-4-O-methylglucuronoxylan oligosaccharides, with DP values ranging from 4 to approximately 20, separated primarily on the basis of their charge density. The fraction eluted last consisted of an O-acetyl-(galacto)glucomannan polysaccharide of peak-average DP value (DP(p)) 14. The degree of substitution with acetyl groups (DS) decreased with decreasing DP, a value DS of 0.39 being obtained for the fraction with DP(p) 12. For the aspen hemicelluloses, the SEC fractions eluted first contained an acidic O-acetyl-4-O-methylglucuronoxylan polysaccharide with DP ranging from 10 to approximately 28 and an average DS of approximately 0.75. The fractions eluted last consisted of oligosaccharide mixtures composed primarily of small neutral O-acetyl-xylooligosaccharides (DP(p) 6, DS 0.41), together with minor quantities of an O-acetyl-glucomannan.

Spectra of highly acidic oligosaccharides obtained by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) can be greatly enhanced in quality by coating the MALDI probe surface with a film consisting of a perfluorosulfonated ionomer (Nafion) prior to the addition of the sample-matrix mixture. For comparison, three mixtures containing highly acidic oligo- and polysaccharides derived from partial acidic hydrolysis of alginate, pectin, or carboxymethyl cellulose (CMC) were analyzed by employing probes with an uncoated gold surface or a surface coated with a Nafion or nitrocellulose film. The negative ion-mode MALDI spectra of the oligouronates (oligomers containing mannuronic/guluronic and galacturonic acid residues) obtained using uncoated or nitrocellulose-coated probes consisted of a series of broad, multiple peaks. These multiple peaks were assigned to the molecular ions of the nondissociated [M - H]- and partially sodiated [MnNa - H]-, where n = 1, 2, or 3, oligomers. In contrast, the corresponding spectra obtained with Nafion-coated probes contained only a single series of sharp peaks originating from the molecular ions ([M - H]-) of nondissociated oligomers exhibiting chain lengths of as many as approximately 15 uronic acid residues. The Nafion coating was apparently capable of removing the sodium counterions remaining in the deposit of the sample-matrix mixture on the probe, thereby greatly enhancing the signal-to-noise ratios of the peaks in the spectra. In a similar manner, higher quality spectra could also be obtained by using Nafion-coated probes for analysis of the oligouronates and CMC oligomers by positive ion-mode MALDI-MS.

A series of alkyl and alkenyl substituted guaiacols, which comprise a group of biologically and organoleptically active compounds, have been synthesized. Mass spectra and GC retention times for these have been recorded and compared with those obtained for constituents of a weakly acidic fraction of smoke condensate derived from American blend type cigarettes. On the basis of these results, 25 guaiacols have been identified, 18 of which have not been detected in tobacco smoke condensate previously.

Three 3-C-hydroxymethylpentoses with the D-ribo-, D-xylo and L-lyxo-configurations, were synthesised via nitromethane addition for the first two and 1,3-dithiane addition for the last one, to appropriate 3-ulose derivatives. 3-C-Hydroxy-methyl-L-lyxose is identical with a monosaccharide component previously isolated from hydrolysates of the phase I Coxiella burnetii lipopolysaccharide.