抽提物对生物质热裂解机理的影响研究

利用惰性溶剂从生物质中提取得到相应抽提物,在热重红外联用仪上研究了抽提物的热裂解行为,并探讨了其对生物质热裂解的影响。结果表明,因不同种类生物质中木质素结构单元中紫丁香基和愈创木基数量不同,从而导致抽提物成分存在差异,相应的热裂解产物分布也不一致。水曲柳抽提物因含有较多的酚类物质而在热解高温段生成了甲醇和甲烷。相比于原样,抽提残渣反应活化能增加,且主要产物析出时间提前,同时酸类物质和直链烷烃析出量减少,而水、CO2、CO和醛类物质的产量则有所增加。     

Determination of the alkyl- and methoxy-phenolic content in wood extractives by micellar solid-phase microextraction and gas chromatography-mass spectrometry

This work combines the utilization of the micellar media during the extraction step and the focused microwave-assisted extraction followed by the solid-phase microextraction-gas chromatography/mass spectrometry (SPME-GC/MS) to determine the alkyl- and methoxy-phenolic content in wood extractives. The proposed environmental-friendly method is mainly characterized by short analysis times (5 min for the microwaves extraction step) and for avoiding the use of organic solvents. Different surfactants were tried for the extraction process: the cationic surfactant CTAB and the non-ionic surfactants Triton X-100 and POLE, with similar extraction efficiencies (85.5-99.7%). The overall method presents limits of detection in the ng g⁻¹ region for the alkylphenols (from 7 to 150 ng g⁻¹) and in the μg g⁻¹ region for the methoxyphenols (from 0.80 to 22.9 μg g⁻¹). The vanillin was the compound most abundant in the wood extractives studied, with concentrations up to 116.2 mg kg⁻¹.     

The Identification of New Triterpenoids in Eucalyptus globulus Wood

Eight polyhydroxy triterpenoid acids, hederagenin, (4α)-23-hydroxybetulinic acid, maslinic acid, corosolic acid, arjunolic acid, asiatic acid, caulophyllogenin, and madecassic acid, with 2, 3, and 4 hydroxyl substituents, were identified and quantified in the dichloromethane extract of Eucalyptus globulus wood by comparing their GC-retention time and mass spectra with standards. Two other triterpenoid acids were tentatively identified by analyzing their mass spectra, as (2α)-2-hydroxybetulinic acid and (2α,4α)-2,23-dihydroxybetulinic acid, with 2 and 3 hydroxyl substituents. Two MS detectors were used, a quadrupole ion trap (QIT) and a quadrupole mass filter (QMF). The EI fragmentation pattern of the trimethylsilylated polyhydroxy structures of these triterpenoid acids is characterized by the sequential loss of the trimethylsilylated hydroxyl groups, most of them by the retro-Diels-Alder (rDA) opening of the C ring with a π-bond at C12-C13. The rDA C-ring opening produces ions at m/z 320 (or 318) and m/z 278 (or 277, 276, 366). Sequential losses of the hydroxyl groups produce ions with m/z from [M - 90] to [M - 90*y], where y is the number of hydroxyl substituents present (from 2 to 4). Moreover, specific cleavage in ring E was observed, passing from m/z 203 to m/z 133 and conducting other major fragments such as m/z 189.     

Surface characterization of unbleached kraft pulps by means of ESCA

The effect of digestion conditions (amount of effective alkali, digestion time) on the surface compositions of unbleached softwood (Pinus sylvestris) kraft pulp has been investigated by electron spectroscopy for chemical analysis (ESCA). The quantities monitored were the angular dependence of the total O/C ratio, the relative amounts of carbons in different states of oxidation and the adsorption of Al and Ca ions to the carboxyl groups in the surface. Examination of the angular dependence of ESCA intensities shows that the concentration of alkyl carbon is high in a very thin surface layer and that it decreases linearly with decreasing kappa number. The concentration of alkyl carbon is decreased by extraction of the fibres with dichloromethane, but the amount remaining in the surface after extraction still decreases linearly with decreasing kappa number (i.e. it decreases with increasing digestion time). It is suggested that the observed enrichment of alkyl carbon in the outermost surface layers most probably is due to reprecipitation of lignin. In pulp that has not been extracted, there is also strong enrichment of extractives in the surface. This amount increases with increasing effective alkali but is relatively independent of digestion time. ESCA analysis of the Al and Ca bound to the carboxyl groups shows that the amount depends on digestion time; the results are consistent with the notion that the reprecipitated lignin contains carboxyl groups.     

Influence of air plasma treatment at atmospheric pressure on wood extractives

The influence of an atmospheric pressure plasma treatment on wood extractives has been investigated by means of surface energy determination and XPS. Polar and disperse component of the surface energy show only marginal influence of plasma treatment, whereas XPS indicates plasma induced oxidation and degradation of the extractives.     

不同工艺的荔枝核提取物抗氧化活性的比较

分别采用回流提取、热浸提取、微波辅助提取法分离荔枝核活性成分,测定了不同工艺制备的荔枝核提取物抑制油脂氧化以及清除羟基自由基和超氧阴离子自由基的抗氧化活性.结果表明,荔枝核提取物具有较强的抗氧化活性,能够有效地抑制油脂氧化;不同工艺的提取物对油脂抗氧化作用的排序为微波提取物热浸提取物回流提取物.与此同时,荔枝核提取物能够有效地清除羟基自由基,其中微波提取物的半清除率质量浓度(EC50)约为0.76 g/L,热浸提取物的EC50约为0.94 g/L,回流提取物的EC50约为2.0 g/L.此外,荔枝核提取物对超氧阴离子自由基也有一定的清除效果.     

Surface Composition and Surface Energetics of Various Eucalypt Pulps

In this paper we report on our study of the surface chemical composition, surface energy and acid-base characteristics of plantation eucalypt pulps obtained using the kraft, neutral sulphite semichemical (NSSC) and cold soda processes. X-ray photoelectron spectroscopy (XPS) was used to quantify the surface coverages of extractives and lignin. Inverse gas chromatography (IGC) was used to analyse the dispersive component and the acid-base characteristics of the pulp samples. The pulp yield and the total lignin and extractives in the pulp increased in the sequences of kraft, NSSC and cold soda. The relative surface concentrations of extractives and lignin on the pulps (expressed in terms of the ratios of the pulp surface coverage to the total content of these materials in the pulp) did not increase in the same sequence. The relative surface concentrations of lignin and extractives on the kraft pulps were found to be distinctively higher than those of the NSSC and cold soda pulps. The dispersive components of the surface energy of all pulps were similar before extraction, but increased by different degrees after extraction, with that of the cold soda pulp showing the lowest degree of increase. The acid-base characteristics of the pulps were evaluated using the method of acceptor and donor constants described by Schultz and Lavielle and the method of work of adhesion described by Lundqvist and Ödberg. A comparison of these methods has been made. The acidity of all pulps was found to increase after extraction. The degree of increase in pulp acidity is negatively correlated with the surface lignin concentration on the pulps. The low relative acidity of the cold soda pulp is probably associated with its high surface lignin coverage. An experimental model was established to test this hypothesis.     

Behaviour of Extractives in Norway Spruce (Picea abies) Bark during Pile Storage

The current practices regarding the procurement chain of forest industry sidestreams, such as conifer bark, do not always lead to optimal conditions for preserving individual chemical compounds. This study investigates the standard way of storing bark in large piles in an open area. We mainly focus on the degradation of the most essential hydrophilic and hydrophobic extractives and carbohydrates. First, two large 450 m³ piles of bark from Norway spruce (Picea abies) were formed, one of which was covered with snow. The degradation of the bark extractives was monitored for 24 weeks. Samples were taken from the middle, side and top of the pile. Each sample was extracted at 120 °C with both n-hexane and water, and the extracts produced were then analysed chromatographically using gas chromatography with flame ionisation or mass selective detection and high-performance liquid chromatography. The carbohydrates were next analysed using acidic hydrolysis and acidic methanolysis, followed by chromatographic separation of the monosaccharides formed and their derivatives. The results showed that the most intensive degradation occurred during the first 4 weeks of storage. The levels of hydrophilic extractives were also found to decrease drastically (69% in normal pile and 73% in snow-covered pile) during storage, whereas the decrease in hydrophobic extractives was relatively stable (15% in normal pile and 8% in snow-covered pile). The top of the piles exhibited the most significant decrease in the total level of extractives (73% in normal and snow-covered pile), whereas the bark in the middle of the pile retained the highest amount of extractives (decreased by 51% in normal pile and 47% in snow-covered pile) after 24-week storage.     

Fast analysis of relative levels of dehydroabietic acid in papermaking process waters by on-line sample enrichment followed by atmospheric pressure chemical ionisation-mass spectrometry (APCI-MS)

Resin acids are considered to be significant contributors to the toxicity of pulp mill effluents. Traditionally, the analysis of these acids is performed by liquid–liquid extraction followed by gas chromatography. This paper describes a method suitable for monitoring the relative concentration levels of the main resin acid component, dehydroabietic acid (DHAA), in process waters by atmospheric pressure chemical ionisation-mass spectrometry (APCI-MS). This method was further improved, first by testing different precolumns for on-line sample clean-up and then by developing the APCI-MS analysis of the analytes trapped in the precolumn (i.e., solid-phase extraction column). The external standard, internal standard, and response factor methods were compared. The curve profiles of the results obtained with the above determinations were very similar to each other. This finding suggested that the rapid APCI-MS method, using a selected ion monitoring (SIM) technique, is a potential tool for monitoring relative concentration levels of DHAA. The technique is also recommended for rapid and simple monitoring of DHAA as well as of other resin acids, and their derivatives, such as their chlorinated analogues, in various aquatic environmental samples.     

A Comparative Study on the Chemical Composition of the Oriental Spruce Woods <Emphasis Type="Italic">Picea orientalis</Emphasis> from Planted and Natural Forests

The main constituents and cyclohexane extractives of wood obtained from planted and native oriental spruce, P. orientalis, were comparatively investigated. The plantation stand in Belgrad Forest near the city Istanbul is about 1000 km west to the original provenance in northeast Turkey with somewhat different environmental factors. The distribution of the main components and the total extractive contents in the woods were affected insignificantly. Only few differences were notable in the amount of sugar monomers of the main polyoses, mannan and xylan, when the native and planted woods were subject to total hydrolyses. The yield of lipophilic extractives in native and planted woods was almost the same. The composition of lipophilic extractives of the woods, determined after proper derivatization by GC-MS, were also not different qualitatively, but some constituents exhibited quantitative changes. Although the planted wood contained significantly more resin acids, sterols, and alcohols, the natural samples had more unsaturated fatty acids. __________ Published in Kimiya Prirodnikh Soedinenii No. 5, pp. 405–408, September–October, 2005.