Synthesis and imidization of poly(amic methyl ester)s

The synthesis and characterization of a series of poly(amic methyl ester)s from five aromatic dianhydrides and a diamine, 4,4'-oxydianiline (ODA), are described. These poly(amic ester)s are obtained by the low-temperature polycondensation from dianhydrides derived diester-diacyl chlorides and ODA in DMAc solution with the inherent viscosities in the 0.5-0.9 dL/g range. These precursors are readily soluble in aprotic solvents. A detailed thermal study of the imidization process is presented, based on dynamic and isothermal TGA measurements, FTIR spectroscopy, and dynamic mechanical analysis. (C) 1997 John Wiley & Sons, Inc.

CHARACTERISTICS OF FATTY ACID METHYL ESTERS (FAMEs) AND ENZYMATIC ACTIVITIES IN SEDIMENTS OF TWO EUTROPHIC LAKES

Enzymatic activities and fatty acid methyl esters (FAMEs) in the sediments of two eutrophic lakes in Wuhan city were investigated. The results showed phosphatase and dehydrogenase activities in the lotus zone and plant floating bed zone were significantly lower than those in other sites, and urease activity was the highest where microorganism agents were put in. Fatty acid group compositions indicated the predominance of aerobic bacteria in the surface sediments in shallow lakes. The ratios of FAMEs specific for bacteria and Gram-positive bacteria exibited significant differences between the two lakes. The results of trans to cis indicated that the microorganisms in Lake Yuehu could adapt themselves to environmental stress better. The enzymatic activities and FAMEs showed differences in different sites, indicating that ecological restoration measures and environmental conditions could affect lake sediment to some extent. But the monitoring, work would be done in series to exactly evaluate the effect of the remediation measures.

Lipase-catalyzed synthesis of biodiesel from acid oil in fixed bed reactor

Acid oil, which is a by-product in vegetable oil refining, mainly contains free fatty acids (FFAs) and acylglycerols and is a feedstock for production of biodiesel fuel now. The transesterification of acid oil and methanol to biodiesel was catalyzed by immobilized Candida lipase in fixed bed reactors. The reactant solution was a mixture of acid oil, water, methanol and solvent (hexane) and the main product was biodiesel composed of fatty acid methyl ester (FAME) of which the main component was methyl oleate. The effects of lipase content, solvent content, water content temperature and flow velocity of the reactant on the reaction were analyzed. The experimental results indicate that a maximum FAME content of 90.18% can be obtained in the end product under optimum conditions. Most of the chemical and physical properties of the biodiesel were superior to the standards for 0(#) diesel (GB/T 19147) and biodiesel (DIN V51606 and ASTM D6751).

酸化油固定床酶法合成生物柴油研究

酸化油是油脂工业中以皂脚、油脚经酸化处理得到的产品。它的主要成分是游离脂肪酸及中性油，是生产脂肪酸的重要原料，但生产过程中有水解废水的产生，若将其直接排放，既污染了环境又浪费了资源。生物柴油的主要成分是脂肪酸甲酯（fatty acid methyl ester，FAME）。它具有原料丰富而且可再生、可生物降解、无毒、不含芳香烃、二氧化硫等污染物、燃烧排放低、闪点高、运输储存安全等特点。作为石化柴油的潜在替代能源，生物柴油因其独特的优越性和现实的需求越来越受到关注。利用酸化油生产生物柴油不仅可以缓解生物柴油原料不足问题，还可解决酸化油所带来的环境问题。

The convertion of acid oil to biodiesel by use of immobilized Candida lipase absorbed on textile cloth was studied in a fixed bed reactor, which can not only reduce the environmental pollution of acid oil, but also produce a substitute for petroleum diesel. The acid oil mixed with methanol was pumped into three fixed bed reactors in series, and the methanol was added with the molar flow rate same as the acid oil in each reactor. The effects of enzyme content, solvent content, water content, flow rate of reactant and temperature on the enzymatic reaction were analyzed. The result of orthogonal experiments indicates that the optimal transesterification can be performed under the following conditions： immobilized lipase content in acid oil, 20% ; hexane content in acid oil, 10% ; water content in acid oil, 10%, reaction temperature, 50 ℃ ; and flow rate of reactant, 0.08 g/rain. Under these conditions, the FAME content of 90.18% in the product is obtained. The immobilized lipase can be reused with relatively stable activity after glycerol being removed from the surface. By refining, most of the chemical and physical properties of biodiesel will meet the American and Germany biodiesel standards and exceed the Chinese standard of 0^# petroleum diesel except for carbon residue, density and kinematic viscosity.

酸化油固定床酶法合成生物柴油研究

以固定化的假丝酵母酶为催化剂，在三段式固定床反应器内，醇油摩尔比为1：1，采用分级流加甲醇的方式，将高酸值的酸化油转化为生物柴油，探讨了酶量、溶剂量、水量、温度、反应液流速等与产物中甲酯含量的关系。正交实验结果表明，反应的最适条件为酶用量、溶剂量、水量分别为油重的15％、10％、10％，反应液流速为0.8g·min^-1，温度为45℃，在此条件下，产物中甲酯含量达到了90．18％。

生物柴油转化效果测定方法的研究

生物柴油的生产原料、催化剂、工艺流程等存在多样化特点，为比较各种方法的优劣，需要建立一种适宜、通用的测定方法。通过分析国内外相关测定方法，提出以气相色谱测定反应产物，十七碳脂肪酸甲酯为标准物，内标法计算反应转化率和产率的方法。

Synthesis of biodiesel from waste cooking oil using immobilized lipase in fixed bed reactor

Waste cooking oil (WCO) is the residue from the kitchen, restaurants, food factories and even human and animal waste which not only harm people's health but also causes environmental pollution. The production of biodiesel from waste cooking oil to partially substitute petroleum diesel is one of the measures for solving the twin problems of environment pollution and energy shortage. In this project, synthesis of biodiesel was catalyzed by immobilized Candida lipase in a three-step fixed bed reactor. The reaction solution was a mixture of WCO, water, methanol and solvent (hexane). The main product was biodiesel consisted of fatty acid methyl ester (FAME), of which methyl oleate was the main component. Effects of lipase, solvent, water, and temperature and flow of the reaction mixture on the synthesis of biodiesel were analyzed. The results indicate that a 91.08% of FAME can be achieved in the end product under optimal conditions. Most of the chemical and physical characters of the biodiesel were superior to the standards for 0(#)diesel (GB/T 19147) and biodiesel (DIN V51606 and ASTM D-6751).

Production and characterization of biodiesel from tung oil

The feasibility of biodiesel production from tung oil was investigated. The esterification reaction of the free fatty acids of tung oil was performed using Amberlyst-15. Optimal molar ratio of methanol to oil was determined to be 7.5:1, and Amberlyst-15 was 20.8wt% of oil by response surface methodology. Under these reaction conditions, the acid value of tung oil was reduced to 0.72mg KOH/g. In the range of the molar equivalents of methanol to oil under 5, the esterification was strongly affected by the amount of methanol but not the catalyst. When the molar ratio of methanol to oil was 4.1:1 and Amberlyst-15 was 29.8wt% of the oil, the acid value decreased to 0.85mg KOH/g. After the transesterification reaction of pretreated tung oil, the purity of tung biodiesel was 90.2wt%. The high viscosity of crude tung oil decreased to 9.8mm(2)/s at 40 degrees C. Because of the presence of eleostearic acid, which is a main component of tung oil, the oxidation stability as determined by the Rancimat method was very low, 0.5h, but the cold filter plugging point, -11 degrees C, was good. The distillation process did not improve the fatty acid methyl ester content and the viscosity.

Production of biodiesel from soapstock using an ion-exchange resin catalyst

The feasibility of biodiesel production from soapstock containing high water content and fatty matters by a solid acid catalyst was investigated. Soapstock was converted to high-acid acid oil (HAAO) by the hydrolysis by KOH and the acidulation by sulfuric acid. The acid value of soapstock-HAAO increased to 199.1 mg KOH/g but a large amount of potassium sulfate was produced. To resolve the formation of potassium sulfate, acid oil was extracted from soapstock and was converted to HAAO by using sodium dodecyl benzene sulfonate (SDBS). The maximum acid value of acid oil-HAAO was 194.2 mg KOH/g when the mass ratio of acid oil, sulfuric acid, and water was 10:4:10 at 2% of SDBS. In the esterification of HAAO using Amberylst-15, fatty acid methyl ester (FAME) concentration was 91.7 and 81.3% for soapstock and acid oil, respectively. After the distillation, FAME concentration became 98.1% and 96.7% for soapstock and acid oil. The distillation process decreased the total glycerin and the acid value of FAME produced a little.

西藏胡黄连和鸡矢藤的化学成分及黄芪多糖的提取工艺研究

本论文由四部分组成，前三部分为实验论文，第四部分为文献综述。第一、二部分分别报道了中药西藏胡黄连和鸡矢藤的化学成分研究结果。从两种药用植物中共分离和鉴定了32个化学成分，其中3个为新化合物。第三部分为黄芪多糖的提取工艺研究。第四部分概述了近年来植物多糖的研究进展。 第一章为西藏胡黄连化学成分研究。通过正、反相硅胶柱层析等分离方法从药用植物西藏胡黄连（Picrorhiza scrophulariiflora Pennell）的根茎中共分离纯化出7个化合物。运用MS、1H-NMR、13C-NMR、DEPT、HSQC和HMBC等现代谱学方法，结合理化分析对这些化合物的结构进行了分析鉴定。7个化合物中有两个是酚性的葡萄糖苷类成分：西藏胡黄连酚苷D (1)、4-O-β-D-(6-O-vanilloyl glucopyranosyl) vanillic acid (6)；四个苯乙基苷类化合物：plantamajoside (2)、plantainoside D (3)、西藏胡黄连苷A (4) 和西藏胡黄连苷F (5)；一个苯基小分子化合物：香豆酸甲酯 (7)。其中化合物1和5未见文献报道，确定为新化合物；化合物3为首次从该种植物中分到。 第二章为鸡矢藤化学成分研究。从鸡矢藤（Paederia scandense (Lour) Merrill）全草中分离出25个化合物，通过理化常数和波谱数据鉴定了它们的结构。25个化合物中包括一个蒽醌类成分：茜根定-1-甲醚 (1)；两个香豆素：异东莨菪香豆素 (2)和5-羟基-8-甲氧基吡喃香豆素 (3)；两个香豆素-木脂素化合物：臭矢菜素 B (4)和臭矢菜素 D (5)；一个木脂素：异落叶松树脂醇 (6)；两个黄酮：diadzein (7)和蒙花苷 (8)；三个三萜类化合物：齐墩果酸 (9)、乌苏酸 (10)和 3-O-β-D-吡喃葡萄糖基乌苏烷 (11)；三个甾体及其糖苷：b-谷甾醇 (12)、胡萝卜苷 (13)和(24R)-豆甾-4-烯-3-酮 (14)；六个小分子化合物：对羟基苯甲酸 (15)，咖啡酸 (16)，香豆酸 (17)，丁烯二酸 (18)，3,5-二甲氧基-4-羟基苯甲酸(19)，咖啡酸-4-O-β-D-吡喃葡萄糖苷(20)；五个环烯醚萜类化合物：鸡矢藤苷 (21)，鸡矢藤酸 (22)，鸡矢藤酸甲酯 (23)，saprosmoside E (24)和paederoside B (25)。其中化合物25未见文献报道，为新化合物。化合物1～8、11、14、15～20为首次从该化合物中分离得到。同时对鸡矢藤中环烯醚萜类化合物做了高效液相-串联质谱(HPLC-MSn)分析，探讨了这类化合物的质谱裂解规律。 第三章为黄芪多糖的提取工艺研究。首先确定了黄芪多糖含量的测定方法，并进行了方法学验证；其次探讨了黄芪中黄芪多糖的提取工艺，确定以酶法-Sevag法联用来去除黄芪多糖中的蛋白质，可使其提取物中黄芪多糖总含量达到70％以上。 第四章为近年来植物多糖的研究进展。主要包括植物多糖的提取纯化、多糖的定性定量检测方法、多糖的结构分析和多糖的药理活性。 This dissertation consists of four parts. The first and second parts reports the studies on the chemical constituents of medicinal plants of Picrorhiza Scrophulariiflora and Paederia scandens. The third part is about the extract technique of Astragalan Polysaccharide (APS). The last part reviews the progress of the studies on plant polysaccharides. 　 The first chapter is about the chemical constituents of P. Scrophulariiflora which is widely used as an important medicine to treat various immune-related diseases. A new phenyl glycoside, scrophenoside D (1) and a new phenylethyl glycoside, scroside F (5), together with five known compounds, plantamajoside (2), plantainoside D (3), scroside A (4), 4-O-β-D-(6-O-vanilloylglucopyranosyl) vanillic acid (6); and methyl-p-coumarate (7) were isolated from the stems of P. scrophulariiflora. Their structures were elucidated by spectroscopic and chemical methods. The second chapter is about the chemical constituents of medicinal herb of P. scandens. Twenty-five compounds were isolated and purified by normal and reversed phase silica gel column chromatography. By physicochemical properties and spectral analysis, their structures were identified as rubiadin-1-methylether (1), isoscopoletin (2), 5-hydroxyl-8-methoxyl-coumarin (3), cleomiscosin B (4), cleomiscosin D (5), isolariciresinol (6), diadzein (7), linarin (8), oleanolic acid (9), ursolic acid (10), 3-O-β-D-glucopyranosyloxyl-ursane (11), b-sitosterol (12), b-daucosterol (13), (24R)-stigmast-4-ene-3-one (14), p-hydroxyl-benzoic acid (15), caffic acid (16), coumaric acid (17), trans-butenedioic acid (18), 3,5-dimethoxyl-4-hydroxylbenzoic acid (19), caffeic acid 4-O-β-D-glucopyranoside (20), paederoside (21), paederosidic acid (22), paederosidic acid methyl ester (23), saprosmoside E (24), paederoside B (25). Among them, compound 25 is a new compound. Compounds 1～8、11、14、15～20 were isolated from this plant for the first time. Futhermore, we studied the HPLC-MSn analysis and investigation of fragmentation behavior of the sulfur-containing iridoid glucosides. The third chapter is about the extracting process of Astragalan Polysaccharide (APS). The method of the content determination is built. The optimum condition of extraction of polysaccharides from Radix Astragali is defined and the more effective way to remove protein is combined enzyme method with Sevag method, by which the content of polysaccharides extract can be up to 70%. The last part is a review of the research progress of the plant polysaccharides, which includes its extraction, isolation, purification, determination, structure analysis, and pharmacology.

尼泊尔水东哥、水麻、木姜冬青和青荚叶的化学成分研究

活性筛选中发现尼泊尔水东哥 (Saurauia napaulensis DC.) 树皮95%乙醇提取物具有α-淀粉酶抑制活性、水麻(Debregeasia orientalis) 枝叶95%乙醇提取物显示血管紧张素转化酶(ACE)抑制活性、青荚叶(Helwingia japonica (Thunb.) Dieter.) 95%乙醇提取物的中小极性部分显示蛋白酪氨酸磷酸酯酶(PTP)1B抑制活性。为全面了解它们的成分及相关活性成份，主要运用硅胶柱层析方法从这三个植物分离得到39个化合物，通过波谱分析或与已知品对照的方法对其进行了鉴定。对木姜冬青(Ilex litseaefolia Hu et Tang)的成分做了进一步的研究，取得了如下结果。 1. 从尼泊尔水东哥树皮的95%乙醇提取物分离并鉴定12个化合物： auranamide、aurantiamide benzoate、齐墩果酸、β-谷甾醇、β-胡萝卜甙、乌苏酸、2α,3α-二羟基-12-烯-28-乌苏酸、2α,3β,24-三羟基-12-烯-28-乌苏酸、(2S,3S,4R,10E)-2-[(2'R)-2' -hydroxytetracosanoylamino] -10-octadecene -1,3,4-triol、 2α,3α,24-三羟基-12-烯-28-齐墩果酸、2α,3β-二羟基-12-烯-28-乌苏酸和2α,3α,24-三羟基-12-烯-28-乌苏酸。 2. 从水麻枝叶的95%乙醇提取物分离并鉴定了18个化合物：棕榈酸、二十烷酸、二十烷酸甲酯、β-谷甾醇、Monogynol A、桦木酸、Hederagenin、β-胡萝卜甙、18αH-19(29)-烯-3-酮-乌苏烷、3，4-开环-20(30)-烯-乌苏烷-3-酸、Pomolic acid，表儿茶素、儿茶素、槲皮素、槲皮素-3-O-β-D-吡喃葡萄糖苷、紫丁香苷、紫丁香酚苷和山萘酚-3-O-芸香糖。儿茶素、槲皮素和槲皮素-3-O-β-D-吡喃葡萄糖苷为具有ACE抑制活性的成分。 3. 从木姜冬青95%乙醇提取物的乙酸乙酯部分分离并鉴定了5个化合物： 2-O-β-D-吡喃葡萄糖-6,2´-二羟基-4,4´-二香草酰氧甲基-1,1´-二苯醚（冬青苷）和四个已知化合物：七叶内酯、香草酸、3,4-二甲氧基苯乙酸和vanilloylcalleryanin。冬青苷为新化合物。 4. 从青荚叶95%乙醇提取物的中小极性部分分离并鉴定了9个化合物：β-谷甾醇、β-胡萝卜苷、羽扇豆醇、桦木醇、桦木酸、棕榈酸甘油酯、桂皮酸、6αH-4-烯-3-酮-豆甾醇和6βH-4-烯-3-酮-豆甾醇。 5. 对1985-2006年间天然二苯醚类化合物及活性研究进展进行综述. The in vitro test indicated that the 95% ethanolic extract of the barks of Saurauia napaulensis DC showed α-amylase inhibitory activity, the 95% ethanolic extract of the whole plants of Debregeasia. orientalis showed angiotensin converting enzyme (ACE) inhibitory activity and some fractions of the 95% ethanolic extract of the aerial parts of Helwingia japonica showed protein tyrosine phosphatase (PTP)1B inhibitory activity. In order to investigate components and active compounds of the three plants, they were chemically studied mainly using. Thirty-nine compounds were isolated predominantly by column chromatography identified by spectral methods or comparing them with authentic samples. Further investigation of Ilex litseaefolia Hu et Tang was carried out. Major results are as follows: 1. Twelve compounds were isolation from the 95% ethanolic extract of the barks of S. napaulensis DC. They were identified as auranamide, aurantiamide benzoate, oleanolic acid, β-sitosterol, β-daucosterol, ursolic acid, 2α,3α-dihydroxyurs-12-en-28-oic acid, 2α,3β,24-trihydroxyurs-12-en-28-oic acid, (2S,3S,4R,10E)-2-[(2'R)-2'-hydroxytetracosanoyl amino]-10-octadecene-1,3,4-triol, 2α,3α,24 -trihydroxyolean-12-en-28-oic acid, 2α,3β-dihydroxyurs-12-en-28-oic acid, and 2α,3α,24-trihydroxyurs-12-ene-28-oic acid, respectively, by spectral methods or comparing them with authentic samples. 2. Eighteen compounds were isolation from the 95% ethanolic extract of the whole plants of D. orientalis. They were identified as palmitic acid, henicosanoic acid, henicosanoic acid methyl ester, β-sitosterol, monogynol, betulinic acid, hederagenin, β-daucosterol, 18αH-urs-20(30)-en-3-one, 3,4-seco-urs-20(30)-en-3-oic acid, pomolic acid, (-)-epicatechin, (+)-catechin, quercetin, quercetin 3-O-β-D-glucopyranoside, syringin, syringiaresinol digloside and kaempferol-3-O-rutinose. (+)-Catechin, quercetin and quercetin 3-O-β-D-glucopyranoside were the ACE inhibitory active components. 3. Further phytochemical investigation of the ethyl acetate parts of 95% ethanolic extract of the whole plant of I. litseaefolia afforded 2-O-β-D-glucopyranose-4,4´-di-vanilloyloxymethyl-2,6´-dihydroxy-1,1´-diphenyl ether (ilexiside), esculetin, vanillic acid, 3,4-dimethoxybenzylacetic acid and vanilloylcalleryanin. Ilexiside was new compound. 4. Nine compounds were isolation from the 95% ethanolic extract of the whole plant of H. japonica: β-sitosterol, β-daucosterol, lupeol, betulin, betulinic acid, glycerol monopalmitate, cinnamic acid, stignast-4-en-6β-3-one and stignast-4-en-6α-3-one 5.Diphenyl ether compounds from nature between 1985-2006 were summarized.