Fire-retardant mechanism of fire-retardant FRW by FTIR

The structures of the solid state products formed by the partial combustion of Korean pine wood treated with fire-retardant FRW were analyzed by microscopic FTIR. The volatile pyrolytic products of basswood (Tilia amurensis) specimens treated with FRW and its components guanylurea phosphate and boric acid were analyzed by GC-FTIR. The pyrolytic and charring process, the effects of fire-retardant, and the structural characteristics of the pyrolytic products were discussed. It was concluded that upon heating and by the catalysis of FRW and its decomposition products reactions of wood took place successively, namely the dehydration of polysaccharide, the elimination of acetic acid from hemicellulose, the degradation of polysaccharide, the degradation of lignin, the polymerization of the pyrolytic products of wood, reactions of oxygen-element-elimination of aliphatic polymers and the structural change of the latter to form aromatic structures, and charring. The pyrolysis process of wood was altered and the yield of volatile pyrolytic products was decreased by FRW treatment. __________ Translated from Scientia Silvae Sinicae, 2005, 41(4): 149–154 [译自: 林业科学, 2005, 41(4): 149–154]     

Degradation of a nonphenolic β-O-4 lignin model dimer by horseradish peroxidase with 1-hydroxybenzotriazole

Nonphenolic β-O-4 lignin substructure model dimer, 1,3-dihydroxy-2-(2,6-dimethoxyphenoxy)-1-(4-ethoxy-3-methoxyphenyl)propane (I) was degraded by horseradish peroxidase (HRP) in the presence of hydrogen peroxide and 1-hydroxybenztriazole (HBT). 4-Ethoxy-3-methoxybenzoic acid (II), 1-(4-ethoxy-3-methoxyphenyl)-3-hydroxypropanone (III), 2,3-dihydroxy-1-(4-ethoxy-3-methoxyphenyl)-1-formyloxypropane (IV), 2,3-dihydroxy-1-(4-ethoxy-3-methoxyphenyl)propanone (V), 1-(4-ethoxy-3-methoxyphenyl)-1,2,3-trihydroxypropane (VI), 1-(4-ethoxy-3-methoxyphenyl)-1,2,3-trihydroxypropane-2,3-cyclic carbonate (VII), and 1-(4-ethoxy-3-methoxyphenyl)-1,2,3-trihydroxypropane-1,2-cyclic carbonate (VIII) were identified as degradation products by gas chromatography-mass spectrometry. These degradation products were qualitatively the same as those of substrate I in the laccase/HBT system, but the yield of the products was apparently different. The products catalyzed by the HRP/H₂O₂/HBT system contained large amounts of the aromatic ring cleavage products IV, VII, and VIII compared with those catalyzed by the laccase/HBT system, while the amount of Cα-Cβ cleavage product II is relatively low. These results suggest that the role of HBT is not in a simple one-electron transfer between the enzymes and substrates.     

Thermochemical behavior of Norway spruce (Picea abies) at 180–225 °C

Norway spruce (Picea abies) was heated for 2–8 h in the temperature range 180–225 °C, under a steam atmosphere. The chemical analyses of the treated feedstock samples indicated that during heating (total mass loss 1.5–12.5% of the initial DS) carbohydrates (hemicelluloses and cellulose) were clearly more amenable to various degradation reactions than lignin. In addition, major water-soluble products released from the feedstock material during the treatments were classified into several compound groups and changes in the relative mass portion of these groups were monitored by GC during a separate experiment. Received 20 December 1998     

Comparative pharmacokinetics and tissue distribution study of mono-, and di-caffeoylquinic acids isomers of Ainsliaea fragrans Champ by a fast UHPLC–MS/MS method

Ainsliaea fragrans Champ, as a well-known herb in Traditional Chinese Medicine, was often used in the treatment of gynecological diseases. Caffeoylquinic acids (CQAs) were the bioactive constituents of this plant medicine which primarily contains mono-CQAs (MCQA) and di-CQAs (DCQA). The biosynthesis showed that MCQAs were the precursor of DCQAs. Recent literatures manifested some particular features of DCQAs, different from MCQAs. Therefore it is apparent that a complete and scientific assessment of DCQAs and MCQAs should include not only the DCQAs' pharmacokinetics and distribution but also its degradation products. So an efficient, sensitive rapid resolution liquid chromatography/tandem mass spectrometry (UHPLC–MS/MS) method for the simultaneous determination of the active ingredients in rat plasma and different tissues had been developed and validated. Mass spectrometric detection was performed by selected reaction monitoring mode (MRM) via an electrospray ionization source operating in negative ionization mode. The method was validated in plasma and tissue samples, which showed good linearity over a wide concentration range (r² > 0.99), and obtained lower limit of quantification (LLOQ) was 2.34 ng·mL^− 1 for the analytes in biological samples. The intra- and inter-day assay variability was less than 15%, and the accuracy was between − 8.8% and 5.7%. This study provided the pharmacokinetic profiles and the tissue regional distribution of MCQAs, DCQAs and caffeic acid. The results indicated that the DCQAs isomers were absorbed quickly after oral administration and degradation products MCQAs were mostly found in tissues, not in plasma. Besides, 1,5-DCQA was the prior configuration for the isomerization phenomenon. The small intestine was the main absorption site for DCQAs. Interestingly, the content of the DCQA and MCQA isomers was all high in the ovary and uterus, and some could pass through the barrier between the blood and brain obviously.     

Iron-binding compounds produced by white-rot fungusPhanerochaete sordida YK-624

Iron-binding compounds were isolated from a culture ofPhanerochaete sordida YK-624 and were found to bind to Fe(III) preferentially compared with Fe(II). Two iron-binding compounds were purified to near-homogeneity with gel permeation chromatography. Hydrolysis of the iron-binding compounds with 6N hydrochloric acid gave ninhydrin-negative products. The molecular weight of these compounds was 3–5 kDa. These compounds may play an important role in the reduction of extracellular manganese dioxide to Mn(II) by intracellular ferrireductases for lignin degradation by manganese peroxidase.     

Degradation of lipophilic wood extractive constituents in Pinus sylvestris by the white-rot fungi Bjerkandera sp. and Trametes versicolor

The white-rot fungi Trametes versicolor and Bjerkandera spp. are among the most frequent decomposers of angiosperm wood in forest ecosystems and in wood products in service. Wood extractives have a major impact on wood properties and wood utilization. This work evaluated the ability of two white-rot fungal strains (Bjerkandera sp. strain BOS55 and T. versicolor strain LaVec94-6) to degrade the main lipophilic extractive constituents in Scots pine (Pinus sylvestris L.). The time course of wood decay and wood extractive degradation was monitored in stationary batch assays incubated for eight weeks. The strains tested eliminated high levels of total resin, 34 to 51% in two weeks. Wood triglycerides were the most readily degraded extractive components (over 93% elimination in only two weeks). Free fatty acids and resin acids, which are potential fungal inhibitors, were also rapidly decomposed by the fungal strains. Sterols were used more slowly, nonetheless, the fungal degradation of this extractive fraction ranged from 50 to 88% after four weeks. Received 19 March 1999     

The chemistry of chromated copper arsenate II. Preservative-wood interactions

 The reactions which cause chromated copper arsenate preservative  to fix strongly into wood are reviewed. A number of the mechanisms proposed in the literature appear chemically implausible. A new model is advanced in which the final fixation products are dominated by chromium (III) arsenate, chromium (III) hydroxide, and copper (II)- wood carboxylate complexes. Carboxylate groups should be generated in large numbers in the reduction of chromium (VI) by primary alcohol groups in lignin and carbohydrate fractions, or in the oxidative degradation of lignin. The model is supported by a recent X-ray absorption fine structure analysis. Received: 13 November 1998     

Deforestation and forest degradation monitoring and assessment of biomass and carbon stock of lowland rainforest in the Analanjirofo region, Madagascar

Madagascar is currently developing a policy and strategies to enhance the sustainable management of its natural resources, encouraged by United Nations Framework Convention on Climate Change (UNFCCC) and REDD. To set up a sustainable financing scheme methodologies have to be provided that estimate, prevent and mitigate leakage, develop national and regional baselines, and estimate carbon benefits. With this research study this challenge was tried to be addressed by analysing a lowland rainforest in the Analanjirofo region in the district of Soanierana Ivongo, North East of Madagascar. For two distinguished forest degradation stages: “low degraded forest” and “degraded forest” aboveground biomass and carbon stock was assessed. The corresponding rates of carbon within those two classes were calculated and linked to a multi-temporal set of SPOT satellite data acquired in 1991, 2004 and 2009. Deforestation and particularly degradation and the related carbon stock developments were analysed. With the assessed data for the 3 years 1991, 2004 and 2009 it was possible to model a baseline and to develop a forest prediction for 2020 for Analanjirofo region in the district of Soanierana Ivongo. These results, developed applying robust methods, may provide important spatial information regarding the priorities in planning and implementation of future REDD+ activities in the area.     

Discrimination of Bursaphelenchus xylophilus and Bursaphelencus mucronatus by PCR-RFLP technique

A polymerase chain reaction-restriction fragment length polymorphism analysis was used to discriminate isolates of Bursaphelenchus xylophilus and B. mucronatus. The amplifications of B. xylophilus isolates yielded one fragment of approximately 890 bp and that of B. mucronatus was about 930 bp. Digestion of amplified products of each nematode isolate with five restriction endonucleases revealed the following results: 1) Dra I digestion of the internal transcribed spacer (ITS) products of B. xylophilus populations yielded two fragments of 510 and 380 bp. Dra I could not digest the ITS products of B. mucronatus populations; 2) Sal I could not digest the ITS products of all B. xylophilus populations, but it could digest those of B. mucronatus populations into two fragments, which were 720 and 220 bp; 3) digested products of four B. xylophilus populations by Msp I yielded two fragments of 530 and 360 bp, except GZ02, which could not be digested. B. mucronatus populations yielded three fragments: 340, 290, and 180 bp; 4) all populations of B. xylophilus and B. mucronatus could not be digested by Apa I; 5) digestion of the ITS products of B. xylophilus and B. mucronatus yielded two fragments of 520 and 370 bp, and 530 and 400 bp respectively. The restriction endonucleases Dra I and Sal I could be used to identify B. xylophilus and B. mucronatus. Because the results of digestion of B. xylophilus and B. mucronatus were markedly different, they were very easy to be identified and applied; Msp I and Xho I were not suitable for identification of B. xylophilus and B. mucronatus and Apa I could not identify and distinguish between B. xylophilus and B. mucronatus. __________ Translated from Journal of Nanjing Forestry University, 2005, 30(4): 5–9 [译自: 南京林业大学学报]     

用FTIR法研究木材阻燃剂FRW的阻燃机理

采用FTIR显微分析技术,对FRW阻燃处理红松木材限制燃烧固相产物的结构进行分析;采用GC_FTIR联机分析方法,对经FRW阻燃剂及其主要组分处理的紫椴木材试样的热解挥发性产物进行分析和鉴定;讨论FRW阻燃处理木材的热解炭化过程、阻燃剂的作用以及热解产物的结构特点。结果表明:FRW阻燃木材受热时,随着温度的升高,在FRW及其分解产物的催化下,木材逐步发生聚糖脱水、半纤维素脱乙酸、聚糖降解、木质素降解、木材热解产物聚合、脂肪族聚合物脱氧及芳构化等反应,最终炭化;FRW阻燃剂改变了木材的热解途径,并且显著降低了挥发性有机化合物的生成量。     

Formation and chemical structures of acid-soluble lignin II: reaction of aromatic nuclei model compounds with xylan in the presence of a counterpart for condensation,and behavior of lignin model compounds with guaiacyl and syringyl nuclei in 72% sulfuric acid

To elucidate the formation and chemical structures of water-soluble material in acid-soluble lignin (ASL), lignin aromatic nuclei model compounds of creosol (I) and 5-methoxycreosol (II) were reacted with xylose or xylan in the presence of apocynol as a counterpart for condensation in 72% sulfuric acid (SA). The reaction of I gave mainly condensation product. However, the condensation reaction of II with apocynol was suppressed because of steric hindrance from the methoxyl group, and II yielded a C-xyloside after refluxing in 3% SA together with condensation products. To obtain information on CHCl₃-soluble material in ASL, model compounds of arylglycerol--aryl ethers with guaiacyl (VIII) and syringyl (X) nuclei were treated by the Klason procedure. VIII gave only insoluble polymerized product, while X gave insoluble polymerized product and CHCl₃-soluble low molecular weight products, which were dissolved in 3% SA. These results prove earlier views that water-soluble material in ASL consists of condensation products formed from syringyl lignin and monosaccharide units in hemicellulose. In addition, the CHCl₃-soluble material in ASL appears to be composed of low molecular weight degradation products from SA treatment of Klason lignin with the syringyl nucleus.Part of this report was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001 and at the 47th Lignin Symposium, Fukuoka, October 2002, and was reviewed in Mokuzai Gakkaishi (2002) 48:55–62     

Smith degradation,an efficient method for the preparation of cycloastragenol from astragaloside IV

Cycloastragenol (CA) is the genuine sapogenin of astragaloside IV (ASI). This study focuses on the preparation of CA from ASI. Five hydrolysis methods were compared including H₂SO₄ hydrolysis, HCl hydrolysis, two-phase acid hydrolysis, mild acid hydrolysis, and Smith degradation. Seven hydrolysis products were purified, and five of them were identified as new compounds. The results indicated that Smith degradation was the most effective approach to prepare CA. In contrast, mild acid hydrolysis produced CA at a low yield, accompanied with the artificial sapogenin astragenol. The other three acid hydrolysis methods mainly produced astragenol. Furthermore, the reaction conditions for Smith degradation were optimized as follows: ASI was dissolved in 60% MeOH–H₂O solution, oxidized with 5 equiv. NaIO₄ for 12 h, followed by reduction with 3 equiv. NaBH₄ for 4 h, and finally acidified with 1 M H₂SO₄ at pH 2 for 24 h. Under the optimal conditions, CA could be prepared from ASI at a yield of 84.4%.     

竹浆GIF仿酶漂白木质素降解产物气相色谱-质谱解析

利用气相色谱-质谱联用(GC-MS)方法对GIF仿酶漂白中的木质素降解产物进行了分析,进一步探讨这种仿酶系统对木质素的降解机制.结果显示GIF仿酶处理使竹浆残余木质素进一步氧化降解,降解的主要方式有脱甲基作用、醌型结构的产生和开环、烷基-芳基醚键的开裂、侧链碳-碳连接的氧化断裂等.GC-MS检测所得的降解产物中,含羰基的化合物较多,这是GIF仿酶系统催化氧化的结果.一些醌式结构、共轭羰基和酚类的脱除,也使纸浆因发色基团减少而白度提高.此外,检测出一些糖类降解产物,说明GIF仿酶系统对纸浆碳水化合物有一定的降解作用.     

光催化提高黑荆树单宁与甲醛反应能力研究

为提高黑荆树单宁与甲醛反应能力,以纳米TiO 2为催化剂对黑荆树单宁进行紫外光催化降解。以降解物的甲醛结合量为指标,分析催化剂用量对黑荆树单宁降解产物甲醛反应能力的影响。采用基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)测定黑荆树单宁和具有最大甲醛结合量黑荆树单宁降解产物的分子量和聚合度。采用傅里叶转换红外光谱(FT-IR)对黑荆树单宁及具有最大甲醛结合量黑荆树单宁降解产物的官能团进行表征。结果表明,催化剂用量对降解物甲醛结合量的影响较大,当紫外光功率为400 W、溶液初始质量浓度为60 g/L、反应温度为(35±5)℃、纳米TiO 2添加量为4%(质量分数,以黑荆树单宁质量计)、降解时间为10 h时,降解物的甲醛结合量达到最大值(1.13 g/g),超过了苯酚和间苯二酚的甲醛结合量(0.89 g/g和0.94 g/g),有替代苯酚和间苯二酚与甲醛反应制备木材用胶黏剂的潜能。MALDI-TOF MS分析表明,黑荆树单宁的聚合度和分子量均有明显地下降趋势,降解物分子量分布集中于低分子量部分。FT-IR分析表明,单宁结构中连接棓酰基的醚键、棓儿茶素的苯环骨架、芳醚键、单元间C—C连接键均被破坏。以上结果表明,可通过紫外光催化降解调控黑荆树单宁的化学组成并降低其聚合度和分子量,获得的降解物具有良好的甲醛反应能力。     

The application of a DNA-based identification technique to over-the-counter herbal medicines

Reliable methods to identify medicinal plant material are becoming more important in an increasingly regulated market place. DNA-based methods have been recognised as a valuable tool in this area with benefits such as being unaffected by the age of the plant material, growth conditions and harvesting techniques. It is possible that the methods of production used for medicinal plant products will degrade or remove DNA. So how applicable are these techniques to processed medicinal plant products?A simple PCR-based identification technique has been developed for St. John's Wort, Hypericum perforatum L. Thirteen St. John's Wort products were purchased including capsules, tablets and tinctures. DNA was extracted from each product, and the species specific PCR test conducted.DNA was successfully extracted from all thirteen products, using a fast and efficient modified method for extracting DNA from tinctures. Only four products yielded the full length ITS region (850 bp) due to the quality of the DNA. All of the products tested positive for H. perforatum DNA.DNA-based identification methods can complement existing methods of authentication. This paper shows that these methods are applicable to a wide range of processed products, provided that they are designed to account for the possibility of DNA degradation.     

Antioxidative activity of tree phenolic constituents 1: Radical-capturing reaction of flavon-3-ols with radical initiator

The present work was undertaken from the standpoint of radical-capturing ability with regard to the antioxidative ability of flavonoids, especially flavonols distributed widely in woody plants. In regard to the flavonols, six methyl derivatives were initially prepared from quercetin and its litinoside. Their radical-capturing constants were determined strictly by the stopped-flow spectroscopic method. It was proved that the radical-capturing ability of quercetin mainly involves the vicinal C₃. and C₄, hydroxyl groups and the C₃ hydroxyl group. To clarify the reaction mechanism begun at the C₃ hydroxyl group of quercetin, 5,7,3,4-tetramethylquercetin (TMQ), flavon-3-ol (F30) and so on were treated with 2,2-azo-bis-(2,4-dimethylvaleronitrile) (AMVN). Six products (1–6) containing one depside and its two hydrolytic products, two valeronitrile adducts, and others were isolated from the reaction mixture of TMQ and their structures determined by instrumental analyses. Similarly, F30 gave four products, 7–10, which corresponded to the above products 1–3 and 5 (one depside, its two hydrolytic products, and one adduct), respectively. 3,5,7,3,4-Pentamethylquercetin (PMQ) and flavon-3-O-methylate (F3M) gave no products. The quantitative change of the products with reaction time was determined spectroscopically. An initial reaction pathway for the radical-capturing reaction of flavon-3-ols with AMVN was proposed based on the products and their amounts. The main route — formation of depside and its hydrolytic products via ketohydroperoxide (3) or ketohydroperoxy radical (4) - was similar to that of the oxidation reaction of quercetin with quercetinase and light.Part of this paper was presented at the 46th and 47th annual meetings of the Japan Wood Research Society, Kumamoto and Kouchi, April 1996 and 1997     

Forest management and carbon sequestration in wood products

Wood products are considered to contribute to the mitigation of carbon dioxide emissions. A critical gap in the life cycle of wood products is to transfer the raw timber from the forest to the processing wood industry and, thus, the primary wood products. Therefore, often rough estimates are used for this step to obtain total forestry carbon balances. The objectives of this study were (1) to examine the fate of timber harvested in Thuringian state forests (central Germany), representing a large, intensively managed forested region, and (2) to quantify carbon stocks and the lifetime of primary wood products made from this timber. The analyses were based on the amount and assortments of actually sold timber, and production parameters of the companies that bought and processed this timber. In addition, for coniferous stands of a selected Thuringian forest district, we calculated potential effects of management, as expressed by different thinning regimes on wood products and their lifetimes. Total annual timber sale of soft- and hardwoods from Thuringian state forests (195,000 ha) increased from about 136,893 t C (~0.7 t C ha⁻¹ year⁻¹) in 1996 to 280,194 t C (~1.4 t C ha⁻¹ year⁻¹) in 2005. About 47% of annual total timber harvest went into short-lived wood products with a mean residence time (MRT) < 25 years. Thirty-one per cent of the total harvest went into wood products with an MRT of 25–43 years, and only 22% was used as construction wood and glued wood, products with the longest MRT (50 years). The average MRT of carbon in harvested wood products was 20 years. Thinning from above throughout the rotation of spruce forests would lead to an average MRT in harvested wood products of about 23 years, thinning from below of about 18 years. A comparison of our calculations with estimates that resulted from the products module of the CO2FIX model (Nabuurs et al. 2001) demonstrates the influence of regional differences in forest management and wood processing industry on the lifetime of harvested wood products. To our knowledge, the present study provides for the first time real carbon inputs of a defined forest management unit to the wood product sector by linking data on raw timber production, timber sales and wood processing. With this new approach and using this data, it should be possible to substantially improve the net-carbon balance of the entire forestry sector.     

Potential for greenery from degraded temperate forests to increase income of indigenous women in Chile

There has been much emphasis placed on the economic contribution that non-timber forest products (NTFP) can make to rural livelihoods of people living in or near forests. In this study we focus on the benefits of greenery obtained from two tree species, romerillo (Lomatia ferruginea (Cav.) R. Br.) and avellano (Gevuina avellana Mol.), collected by indigenous women in southern Chile. Trees producing commercial-quality leaves grew in secondary forests dominated by species usually abundant in ecological formations that follow forest degradation. Natural availability of greenery was relatively low (658 and 38 commercial leaves per hectare for romerillo and avellano, respectively) which added to restrictive market conditions resulted in modest financial returns and a contribution to household income of less than 1%. Our results confirm that trade on NTFP does not always lead to significant income generation. Yet, the information provided, represents a basis to explore management alternatives, such as agroforestry schemes, which can potentially expand greenery yield and economic returns.     

Biodegradation of new quaternary ammonium compounds in treated wood by mould fungi

The degradation of seven potential wood preservatives based on imidazolium compounds (ICs) and quaternary ammonium compounds (QACs) with a modified anion structure by mould fungi was determined using soil-block method. Experiments were carried out on Scots pine (Pinus sylvestris L.) wood. Two-phase titration and high-performance liquid chromatography (HPLC) method were used to detect and quantify the degradation products. The performed soil-block tests showed that the ICs and QACs with alkoxymethyl substituents were leached from the experimental wood when in contact with moist soil and revealed their fungal detoxification by mould fungi, especially by Gliocladium roseum. The degree of biological decomposition of new compounds was higher than didecyldimethylammonium chloride and didecylmethylpoli(oxyethyl)ammonium propionate. The observations of the colonization by mould fungi were made using the scanning electron microscope (SEM). Decay of treated wood by mould fungi showed its tolerance to QACs.     

Income and labour productivity of collection and use of indigenous fruit tree products in Zimbabwe

Rural people in Africa periodically rely on wild fruits to supplement their diet and to generate cash income. However, scientific evidence on the economics of using indigenous fruit tree (IFT) products is scarce. The objective of the study was to fill in some of the gaps for which farm-household surveys were conducted in Zimbabwe during 1999–2000. Gross margins and returns to labour in collection, use and sale of products of Uapaca kirkiana (Muell. Arg., Wild Loquat), Strychnos sp. (S. cocculoides (Baker) and S. spinosa (Lam.), Monkey Orange) and Parinari curatellifolia (Planch. ex. Benth., Fever Tree) were compared with other farming activities. A random sample of over three hundred households in the Murehwa Communal and the Takawira Resettlement Areas was interviewed to gather income and expenditure data. Additionally, income, expenditure and labour allocation of 39 households were closely monitored for one year. Results indicated that the majority of rural households benefited from consumption and sale of indigenous (IF), although the extent varied among households. Within the households, children were the main consumers of fruits. Marketing of IF are carried out by women who used the receipts to purchase household goods. While U. kirkiana fruits were more important in generating cash income than others, fruits of P. curatellifoliawere important for home consumption during periods of food shortages. The gross margins for collection of IFT products were lower than for livestock and crop production. However, returns to labour from collection and use of IFT products were considerably greater than from other activities including gardening and livestock rearing. The study indicates that collection of IFT products is an efficient labour allocation strategy in Zimbabwe. This revised version was published online in June 2006 with corrections to the Cover Date.