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     

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.     

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。     

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。     

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     

Growth of four tree species managed as hedgerows in response to liming on an acid soil in West Sumatra,Indonesia

A hedgerow intercropping study was conducted for 7 years in West Sumatra, Indonesia on an acid and highly Al-saturated soil to determine growth and yield responses of tree hedgerows and upland rice and cowpea intercrops. Three tree species,Paraserianthes falcataria, Calliandra calothyrsus, andGliricidia sepium and a no-tree control were planted at three lime rates with low annual fertilizer inputs of 20 kg P and 50 kg K ha^–1.Paraserianthes andCalliandra grew vigorously, whileGliricidia grew poorly and was replaced after four years withFlemingia macrophylla. After four years,Paraserianthes yields declined due to tree mortality, probably due to intensive pruning.Calliandra andFlemingia were well adapted to intensive pruning (4 to 6 times per year). Gliricidia growth was especially limited by low soil Ca availability and high soil acid saturation.Calliandra andFlemingia yields increased with liming only in the last several years of the study whileParaserianthes did not respond to lime. The species can be tentatively ranked in response to lime as:Gliricidia > Calliandra > Flemingia > Paraserianthes.     

基于不同回收方法的肌浆蛋白对鲢鱼糜冻融稳定性的影响

为研究不同回收方法的肌浆蛋白对鲢鱼糜冻融稳定性的影响,分别通过加热法、酸偏移法和酸偏移-耦合壳聚糖絮凝法回收鲢鱼糜漂洗液中的肌浆蛋白,并将其添加至鱼糜中,测定鱼糜冻融循环过程中蛋白质冷冻变性、脂肪氧化及凝胶品质的指标。结果显示:添加不同方法回收的肌浆蛋白均能抑制鲢鱼糜冻融循环过程中盐溶性蛋白含量、Ca²⁺-ATPase活性和总巯基含量的下降以及表面疏水性的上升,其中加热法回收的肌浆蛋白抑制鱼糜蛋白质冷冻变性的效果最显著,经过9次冻融后仍能够对鱼糜蛋白质变性起到抑制效果。蛋白质羰基含量测定结果显示,肌浆蛋白的添加可以抑制鱼糜冻融循环过程中蛋白质氧化现象。而与空白组鱼糜相比,添加不同回收处理的肌浆蛋白的鱼糜,其硫代巴比妥酸值（TBARs）和pH值并没有显著变化。此外,随着冻融循环次数的增加,鱼糜凝胶品质会发生严重劣化,其中添加酸偏移-耦合壳聚糖絮凝处理的肌浆蛋白的鱼糜始终保持较好的凝胶质构性能。     

Effects of grape seed extract on meat color and premature browning of meat patties in high-oxygen packaging

This study investigated the effects of grape seed extract (GSE) on fresh and cooked meat color and premature browning (PMB) in ground meat patties (85% beef and 15% pork back fat) packaged under high-oxygen modified atmospheres (HiOx-MAP).  The GSE was added to patties at concentrations of 0, 0.10, 0.25, 0.50 and 0.75 g kg^–1.  This study evaluated the surface color, pH, lipid oxidation, and total viable counts (TVC) of raw patties, and the internal color and pH of patties cooked to a temperature of 66 or 71°C over 10-day storage at 4°C.  Compared with the control (0 g kg^–1 GSE), GSE improved the color stability (P<0.05) and significantly inhibited the lipid and myoglobin oxidation of raw patties from day 5 to 10, but GSE had no effect (P>0.05) on TVC.  Patties containing 0.50 and 0.75 g kg^–1 GSE cooked to 66°C exhibited greater (P<0.05) interior redness than the control and reduced the PMB of cooked patties in the late storage stage.  These results suggested that 0.50 and 0.75 g kg^–1 GSE can improve fresh meat color and minimize PMB of HiOx-MAP patties.     

铁碳复合材料活化过氧化氢吸附-氧化萘的机理

为探讨不同铁源对铁碳复合材料结构及其吸附-氧化萘污染的影响,分别以硫酸亚铁、氯化铁、硝酸铁、纳米零价铁和纳米四氧化三铁为铁源,葡萄糖为碳源,采用水热-碳热法合成了铁碳复合材料。采用比表面积测试、红外光谱仪、X射线衍射仪和电化学工作站分别测定材料的比表面积和孔结构、表面官能团、晶体结构和氧化还原能力,同时通过动力学实验研究不同复合材料吸附和活化过氧化氢氧化萘的效果。结果表明：Fe₂SO₄@C、FeCl₃@C和Fe（NO₃） ₃@C因较小的孔体积或较高的表面含氧官能团含量,而对萘的吸附去除率较低,且无法对萘的氧化起到活化作用。而nFe⁰@C和nFe₃O₄@C的孔体积较大,且生成结构态亚铁[Fe（Ⅱ）]和碳化三铁（Fe₃C）活性物质,可通过吸附和活化过氧化氢氧化去除萘,其中nFe₃O₄@C对萘的去除效果最好,去除率达到63.7%。研究表明,使用固态铁源制备的铁碳复合材料,具有较低的极性、较大的孔体积以及结晶较好的铁活性物质,在萘污染水体修复中具有较大应用潜力。