Delignification of cell walls of <Emphasis Type="Italic">Chamaecyparis obtusa</Emphasis> during alkaline nitrobenzene oxidation

To clarify the behavior of whole lignins in wood cell walls during alkaline nitrobenzene oxidation, the delignification process from cell walls in normal and compression woods of Chamaecyparis obtusa Endl. (Cupressaceae) was observed using ultraviolet and transmission electron microscopies. The lignin content conspicuously decreased to around 10% after 35min in normal wood. The lignin content in compression wood finally leveled off at aroumd 10% after 50min. In gel filtration of oxidation products in ethyl acetate, a high molecular weight fraction was prominent in extracts from the early stage of the reaction. As the oxidation progressed, the high molecular weight fraction became less prominent in both normal and compression wood. Changes in the weights of cell wall residues during reaction indicated that approximately half of the components other than lignin were also removed from the cell walls. This shows that the majority of lignin with relatively high molecular weight is removed from the cell walls together with polysaccharides in the early stage of the reaction and that further oxidative degradation occurs in solution in later stages. Only a small amount of the lignin with low molecular weight could be analyzed by gas chromatography.Parts of this report were presented at the 47th (Kochi, April 1997) and 48th (Shizuoka, April 1998) Annual Meetings of the Japan Wood Research Society, and at the Lignin Symposium, Sapporo, October 1997     

Determination of nitrobenzene oxidation products by GC and1H-NMR spectroscopy using 5-iodovanillin as a new internal standard

The nitrobenzene oxidation method was modified to obtain more reproducible data and more structural information about lignin, not only by gas chromatography (GC) but also by proton nuclear magnetic resonance (¹H-NMR) spectroscopy for quantitative determination of the oxidation products and to simplify the procedures. The nitrobenzene oxidation mixture was directly extracted after acidification without preextraction of by-products. The direct extraction made the extractive step easy and gave reproducible data. 5-Iodovanillin was selected as a new internal standard. The reason for this selection was that 5-iodovanillin did not exist in the nitrobenzene oxidation products from any plant species and had an aldehyde group whose peak did not overlap with the other aldehyde peaks on an¹H-NMR spectrum. Thus, the use of 5-iodovanillin enabled us to quantifyp-hydroxybenzaldehyde, vanillin, and syringaldehyde in oxidation products on the basis of¹H-NMR analysis as well as GC. Furthermore, more information about the condensed structure of lignin was derived by comparing the¹H-NMR and GC analyses.Part of this work was presented at the 42nd Annual Meeting of the Lignin Symposium, Sapporo, October 1997     

Semi-quantitative method to evaluate the α-carbonyl content in lignin

A method to estimate the content of -carbonyl structures in lignin was developed. This method consists of two successive treatments: NaBD₄ treatment of pulp to reduce an -carbonyl structure in lignin, and nitrobenzene oxidation. NaBD₄ was used to convert an -carbonyl structure to a deuterium-labeled hydroxymethine structure. The ratio of D-vanillin [(HO)(H₃CO)C₆H₃CDO] to H-vanillin [(HO)(H₃CO)C₆H₃CHO] or that of their syringyl analogues obtained by nitrobenzene oxidation was used as the measure of the content of -carbonyl structure. Model experiments demonstrated that when sodium hydroxide was used as alkali for the nitrobenzene oxidation, the retention of deuterium at the side chain -position was very low due to the displacement of deuterium with hydrogen by an unknown reaction mechanism. In order to depress this unexpected displacement, the reaction conditions of the nitrobenzene oxidation were modified. The modified nitrobenzene oxidation employs 0.5mol/l of lithium hydroxide as a reaction medium instead of 2.0mol/l sodium hydroxide. By this modification, this method could successfully trace the formation and the degradation of the -carbonyl structure in milled wood lignins.This paper was presented in part at the 11th International Symposium on Wood and Pulping Chemistry, Nice, France, June 2001 and at the 46th Lignin Symposium, Kyoto, Japan, November 2001     

不同林分下土壤活性有机碳库研究

采样分析常绿阔叶林、马尾松林和人工杉木林不同层次土壤的活性有机碳含量。结果表明 :常绿阔叶林土壤微生物量碳和易氧化态碳含量高于马尾松与杉木林土壤 ,杉木林土壤水溶性碳含量相对较低。从不同层次看 ,土壤微生物量碳、易氧化态碳含量均随着土层深度加深而递减。水溶性碳、微生物量碳和易氧化态碳占总有机碳的比率分别波动在 0 31%～ 1 18%、0 90 %～ 2 5 1%和 7 0 3%～ 2 9 5 2 %之间 ,其中 ,土壤水溶性碳占总有机碳比率为马尾松林 >常绿阔叶林 >人工杉木林 ,易氧化态碳占总有机碳比率常绿阔叶林明显高于马尾松林和杉木林。不同土壤水溶性有机碳占总有机碳比率随剖面从上到下均表明出上升趋势 ,而易氧化态碳占总有机碳比率随剖面加深有规律地下降。土壤有机碳总量与各活性碳之间以及各类活性碳之间相关性均达到极显著水平。     

Biochemical and histopathological studies to assess chronic toxicity of triazophos in blood, liver and brain tissue of rats

Triazophos, O,O-diethyl-1-H-1,2,4-triazol-3-yl phosphorothioate, (TZ) is an organophosphorus pesticide which is extensively used in agriculture for controlling insect pests. Except a FAO/WHO report no study has investigated its short-term toxicity with respect to its potential to cause biochemical and histopathological alterations. The present study was designed to identify the effect of TZ at different doses (1.64, 3.2 and 8.2 mg/kg) on the oxidative stress parameters in blood as well as organs involved in xenobiotic metabolism (liver and brain) following chronic exposure for 90 days. Moreover, the study also delineates the effect of TZ on the histo-architecture of these organs. The results indicated a dose dependent induction (p < 0.001) of oxidative stress, as evident by increased malondialdehyde (MDA) level and compromised antioxidant defense including glutathione S transferase (GST) activity, glutathione (GSH) content and ferric reducing ability of plasma (FRAP) in blood, and increased MDA level with concomitantly decreased GSH content in tissues, following chronic exposure to TZ. The ratio of MDA: FRAP in blood was found to be increased following chronic exposure to TZ and may serve as a suitable indicator of severity of oxidative damage. Onset of such biochemical alterations is one of the early adaptive responses to TZ exposure which leads to histopathological alterations in terms of diffuse fatty changes expanding from mid-zonal area to whole lobule in liver. However, increased oxidative stress did not bring any morphological alteration in brain. The present study concludes that induction of oxidative stress, leading to subsequent histopathological alterations in liver, is an important mechanism underlying the TZ induced chronic toxicity.     

Exogenously applied hexaconazole ameliorates salinity stress by inducing an antioxidant defense system in Brassica napus L. plants

The ability of hexaconazole (HEX) to ameliorate salinity stress was studied in canola plants (Brassica napus L.). Canola seedlings were subjected to sodium chloride (NaCl) treatment. A treatment with 200 mM NaCl reduced growth parameters, chlorophyll content and protein content as well as increased the proline (Pro) content in canola plants. In addition, NaCl stress increased the endogenous, nonenzymatic antioxidants and the activity of antioxidant enzymes, such as peroxidase (POX; EC 1.11.1.7), superoxide dismutase (SOD; EC 1.15.1.1) and catalase (CAT; EC 1.11.1.6). When these plants were treated with a combination of NaCl and 50 mg L⁻¹ HEX, the inhibitory effects of NaCl stress were decreased by increasing the root growth, shoot growth, dry weight (DW), chlorophyll content, protein content and antioxidant enzyme activity by ameliorating the salinity injury. These results suggested that HEX has an important role in the enhancement of plant antioxidant systems and resistance to salinity in canola plants.     

木质素电氧化的影响因素研究

木质素是天然高分子聚合物，具有一定的化学反应惰性。本文率先研究草类木质素在膜助电解时的电化学氧化作用。其结果表明：膜助电解对黑液中的有机物具有一定的氧化作用，能使木质素中的芳环被氧化而打开；同时木质素的氧化作用与施加的电压、阳极的电极材料等因素有关。通过对木质素氧化产物结构的进一步研究，可为木质素的电化学改性提供了新的方法。     

Chemopreventive efficacy of lycopene on 7,12-dimethylbenz[a]anthracene-induced hamster buccal pouch carcinogenesis

The chemopreventive efficacy of lycopene on 7,12-dimethylbenz[a]anthracene (DMBA)-induced hamster buccal pouch (HBP) carcinogenesis was examined using lipid peroxidation, reduced glutathione (GSH), glutathione peroxidase (GPx), glutathione S-transferase (GST) and glutathione reductase (GR) as biomarkers of chemoprevention. Twenty four male Syrian hamsters were divided into four groups of six animals each. The right buccal pouches of the animals in group 1 were painted with a 0.5% solution of DMBA in liquid paraffin three times a week. The animals in group 2 were painted with DMBA as in group 1 and in addition received 2.5 mg/kg body weight lycopene orally three times a week on days alternate to DMBA application. Group 3 animals received lycopene as in group 2. Animals in group 4 received neither DMBA nor lycopene and served as control. The hamsters were killed after an experimental period of 14 weeks. Biochemical measurements were carried out in tumour and normal tissues. All hamsters painted with DMBA alone for 14 weeks developed well-differentiated squamous cell carcinomas. Diminished lipid peroxidation in the oral tumour tissue was accompanied by a significant increase in the levels of GSH, GPx, GST and GR. Administration of lycopene significantly suppressed DMBA-induced oral carcinogenesis as revealed by the absence of carcinomas. The results of the present study suggest that lycopene may exert its chemopreventive effects by modulating lipid peroxidation and enhancing the activities of the enzymes in the glutathione redox cycle.     

芥子酸甲酯氧化偶合合成二聚体酯的研究

在单锅中探讨了以芥子酸为底物,经酯化和氧化偶合两步反应合成芥子酸甲酯二聚体酯的方法.研究结果表明,此合成方法操作简便,反应条件温和(室温反应),无须分离中间体,且产率较高(收率高达66.58%).还探讨了时间、原料比、催化剂的用量等对一锅法产率的影响及氧化偶合机理.     

Changes in Protein Oxidation,Water-Holding Capacity,and Texture of Bighead Carp (Aristichthys Nobilis) Fillets Under Chilled and Partial Frozen Storage

This study aimed to evaluate the contribution of protein oxidation to the changes in the water-holding capacity (WHC) and texture of bighead carp (Aristichthys nobilis) fillets under chilled and partial frozen storage (4°C and ?3°C). The results indicated that less protein oxidation occurred to fillets at ?3°C than at 4°C, which was reflected by the higher value of salt-soluble protein contents (SSP), total sulfhydryl content (SH), Ca²⁺-ATPase activity, lower water-soluble protein contents (WSP), total disulfide content (SS), and surface hydrophobicity (So-ANS). However, the fillets had better WHC and texture at 4°C, as well as lower drip loss and higher centrifugal loss, hardness, and springiness. A significant linear relationship existed between protein oxidation parameters with WHC and texture characteristics for fillets under both types of storage, but the process of freezing and then thawing, instead of protein oxidation, was the main factor affecting the texture and WHC of fillets at ?3°C.