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.     

遮荫下2种热带树苗叶片光合特性和抗氧化酶系统对自然降温的响应

选取 2种遮荫条件下 (8%、2 5 %全光照 )西双版纳地区热带雨林上层树种滇南红厚壳和中层树种玉蕊的幼苗 ,测定了雨季末自然降温过程中 2种植物叶片光合特性、抗氧化酶 (SOD、CAT、APX)活性、丙二醛 (MDA)含量的变化。研究结果表明 :低温使 2种植物单位面积叶绿素含量和净光合速率明显下降 ,生长在中等光强下的幼苗比低光强下的幼苗下降的比率大 ,滇南红厚壳比玉蕊下降的比率大。在降温初期 ,即从 10月到 12月初 ,2种光强下 2种植物SOD和APX活性上升 ,CAT活性出现波动 ,黎明光化学效率和MDA含量基本没有变化 ,光合机构没有受到氧化破坏。 12月末 ,中等光强下滇南红厚壳黎明光化学效率降低 ,SOD和APX活性有所下降 ,MDA含量显著上升 ;而低光强下的滇南红厚壳和 2种光强下玉蕊SOD和APX活性仍在上升 ,MDA含量变化较小。这表明 ,2种光强下 2种热带树苗是以不同的方式响应自然降温 ,低温对中等光强下的植物比低光强下的影响大 ,上层树种滇南红厚壳受到的影响比中层树种玉蕊大。同时 ,根据降温过程中抗氧化酶活性和MDA含量的变化 ,大致可将西双版纳热带雨林幼苗对低温的响应分为 2个阶段 ,即第 1阶段为低温适应阶段 ,抗氧化酶活性上升 ,光合机构没有受到明显的氧化破坏 ;第 2阶段 ,中等光强下滇南红厚壳抗氧化酶     

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     

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。     

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。     

Pigmentation, carotenoids, lipid peroxides and lipid composition of skin of red porgy (Pagrus pagrus) fed diets supplemented with different astaxanthin sources

A feeding experiment was carried out to determine the efficiency of different commercial sources, chemical forms and levels, of dietary astaxanthin, to appropriately pigment the red porgy (Pagrus pagrus) skin. According to this, total carotenoid content, profiles and chemical forms present in the skin were determined. In order to establish the potential for antioxidant protecting role of astaxanthin supplemented diets, peroxide levels and lipid composition of skin were also determined.

Red porgy alevins were fed six dietary treatments in triplicate; a basal diet (B) without carotenoids; two diets (N25 and N50) formulated to supply either 25 or 50 mg kg^− 1 of an esterified source of astaxanthin (Haematococcus pluvialis, NatuRose™); two diets (CP25 and CP50) with either 25 or 50 mg kg^− 1 of unesterified astaxanthin (Carophyll® Pink); and a positive control diet (B + S) proved as a successful pigmenting-diet in previous experiences (B + S, 88% basal diet:12% frozen shrimp) [Cejas, J., Almansa, E., Tejera, N., Jerez, S., Bolaños, A., Lorenzo, A., 2003. Effect of dietary supplementation with shrimp on skin pigmentation and lipid composition of red porgy (P. pagrus) alevins. Aquaculture 218, 457–469].

All fish fed carotenoid supplemented diets displayed a pink-coloured skin after 4 months of feeding in contrast to the greyish appearance displayed by fish fed the basal diet not supplemented with carotenoids (B). Furthermore, astaxanthin diesters were the major carotenoid in the skin of pink fish. A second carotenoid, tentatively identified as tunaxanthin diester, was also detected. The best results in terms of skin natural reddish hue, total carotenoid and astaxanthin contents were found by using the esterified forms of dietary astaxanthin (N25, N50 and B + S). Interestingly, the lowest levels of lipid peroxides were found in the fish fed these three treatments. However, no effect of treatment on lipid composition was found. In conclusion, red porgy alevins are able to efficiently utilise dietary natural or synthetic astaxanthin, and deposit this pigment in its esterified form to acquire an acceptable pink-coloured skin compared to that of the wild fish.     

Effects of high‐fat and high‐carbohydrate diets on fat and carbohydrate oxidation and plasma metabolites in healthy cats

High‐fat (HF) or high‐carbohydrate (HC) diets (30% fat, 18.9% carbohydrate; HF and 10% fat, 46.3% carbohydrate; HC) and lengths of adaptation were investigated in cats (Felis catus; 10 ± 2 months, 3.6 ± 0.3 kg). Cats randomly received each treatment for 14 days in a crossover design with a 14‐day washout period between each diet. Three 22‐h indirect calorimetry studies were conducted after acute (day 0), semichronic (day 4) and chronic (day 13) dietary exposure. Blood samples were collected after a 24‐h fast on days 1, 5 and 14. When cats consumed the HC and HF diet, oxidation of the restricted nutrient exceeded intake while oxidation of the nutrient in excess matched intake. Mean max energy expenditure (EE) of cats consuming the HF and HC diet were 107 and 102 kcal/kg^0.67/day and occurred at a mean of 4 and 12 h post‐feeding respectively. Maximal fat (0.90 g/h) and carbohydrate (carbohydrate; 1.42 g/h) oxidation were attained at 26 min and 10.4 h post‐feeding respectively. The changes observed in macronutrient oxidation and EE suggest that cats adapt whole‐body nutrient metabolism in response to changes in dietary macronutrient content, but may require longer than 14 day to adapt to a macronutrient that is present at a lower concentration in the diet.