非水介质中脂肪酶催化亚麻酸油醇酯合成的研究

已知脂肪酶（ＥＣ３．１．１．３）在非水体系中能够催化合成脂肪族、芳香族和其它多种多样的酯类．这些反应中的大多数都是以链较长的脂肪酸为底物．其中一类反应是高级脂肪酸和脂肪醇合成酯蜡的酯化反应．合成的酯蜡用途广泛,可以用在化工、纺织、医药、日化、食品等工业中．利用传统的化学法合成酯蜡,需要在高温高压及强酸条件下进行反应,副反应多,产物的分离纯化困难,生产成本高,且对于长链脂肪酸和醇的反应难度增大．利用脂肪酶水解反应的逆反应酯化反应合成酯蜡的方法,具有反应条件温和,产物的分离纯化容易等优点,能够弥补化…     

磷钨酸（盐）催化苯甲酸与正癸醇和鲸蜡醇酯化反应的研究

磷钨酸（盐）催化苯甲酸与正癸醇和鲸蜡醇酯化反应的研究司宗兴孙亚秋汪海涛（中国农业大学应用化学系北京１０００９４）长链化合物是一类具有广泛杀虫、杀菌和植物生长调节活性的化合物。在长链醇的酯化反应中，由于醇部分碳原子数目多，亲酯性增加，溶解度在极性溶剂中...     

二-(2-羟基-5-长链烷基苯基)-甲烷的合成

以脂肪酸、苯酚为原料, 经酰化反应、酯化反应、Fries重排、黄鸣龙还原等步骤, 得到正构长链烷基酚, 再与多聚甲醛在酸性催化剂下进行缩合反应, 生成二-(2-羟基-5-长链烷基苯基)-甲烷, 用核磁共振氢谱和碳谱、红外光谱和元素分析对产物进行了结构鉴定. 据上述反应路线, 以工业品壬基酚和多聚甲醛为原料, 合成出了二-(2-羟基-5-壬基苯基)-甲烷, 并对其工艺条件进行了研究. 结果表明, 选用草酸作催化剂, 烷基酚和甲醛物质的量比为2∶1, 130 ℃反应4 h, 产物产率达到60%, 且反应转化率和选择性分别为63%和95%.     

血浆中极长链脂肪酸的毛细管气相色谱分析

建立了血浆中极长链脂肪酸毛细管气相色谱法，并用于测定了１０例正常人和４例临床拟诊为肾上腺白质营养不良（ＡＬＤ）病人血浆中极长链脂肪酸，其中一例肯定了ＡＬＤ的临床诊断。     

检测饲料、蛋黄及鸡肝中长链饱和及不饱和脂肪酸的毛细管气相色谱法

探索检测饲料、蛋黄和鸡肝中长链饱和、单烯及多烯键脂肪酸的前处理步骤,样品匀浆后,用氯仿－丙酮混合溶剂提取,以氢氧化钾－甲醇酯化反使生成相应的脂肪酸甲 酯,再转溶于异辛烷中,采用不分流进样技术注入气相色谱仪中,经毛细管柱分离,用火焰离子化检测器检测。应用该法能检测出含量较低、具有生理活性意义但易于氧化的ｗ－３长链多烯键脂肪酸,如二十碳五烯酸（ＥＰＡ）、二十二碳五烯酸（ＤＰＡ）、二十二碳六烯酸（ＤＨＡ）。     

疏水性全氟烷基磺酰亚胺固体酸催化酯化与Pechmann缩合

通过溶剂热的方法,成功制备一类具有良好疏水性和强酸性的高分子,聚二乙烯苯-对苯乙烯磺酰基全氟丁基磺酰亚胺(记作H-PDVB-0.3-SSFAI).用于催化水相中长链脂肪酸的酯化反应,可获得88%转化率(24 h);在直接酯化反应体系中,转化率最高能达到95%~96%(5~6 h);催化短链的乙酸和己酸的酯化反应,伯醇和环己醇都能顺利进行,其中,环己醇转化率87%~92%(4 h).催化剂能循环使用至少7次.在无溶剂条件下用于催化另一类酯化反应Pechmann缩合,制备7-羟基香豆素,能在140℃高温下循环使用4次,平均产率约90%.H-PDVB-0.3-SSFAI的良好疏水性、强酸性和丰富多孔性,是影响其催化效率的关键.     

Brφnsted酸性离子液体催化合成长链脂肪酸甲酯

本文合成了以1-丁基-3-甲基咪唑为阳离子,HSO4-、H2PO4-和BF4-为阴离子的Brφnsted酸性离子液体,并以长链脂肪酸与甲醇的酯化反应考察了这些Brφnsted酸性离子液体的催化性能。实验结果表明,1-丁基-3-甲基咪唑硫酸氢根鎓盐([bmim][HSO4])离子液体具有很高的催化活性,当n(醇)∶n(酸)∶n(离子液体)=6∶1∶0.25,反应温度为70℃,不分水酯化反应2h,长链脂肪酸甲酯的产率可达到93.4%以上,选择性达到100%;且产物酯与离子液体分离容易;离子液体经干燥处理后可以循环使用5次以上,催化活性没有明显降低。     

介孔分子筛SBA-15-SO3H催化合成油酸甲酯

在成功合成出含磺酸基的介孔分子筛SBA-15-SO3H的基础上，用于油酸与甲醇的酯化反应，考察该催化剂的催化性能，结果表明：在高级脂肪酸的酯化反应中，SBA-15-SO3H催化剂的活性高于沸石分子筛，与等摩尔数的硫酸的活性接近。考察了反应条件对SBA-15-SO3H催化剂性能的影响，得到油酸与甲醇酯化反应的最佳条件：反应温度60 ℃，甲醇与油酸的原料比为2∶1（摩尔），催化剂与原料比为1.5∶35（重量）。最后对催化剂的稳定性进行了考察，反应结果认为该催化剂在重复使用过程中活性未发生明显变化，反应前后的XRD分析结果认为，SBA-15-SO3H具有较高的水热稳定性。     

气相色谱-质谱法测定油炸薯条和食用油中反式脂肪酸

脂肪酸通常指长链羧酸,碳原子数大于12的一系列饱和脂肪酸和不饱和脂肪酸;反式脂肪酸(TFAs)是指含有反式构型双键的一类不饱和脂肪酸的总称。绝大多数天然不饱和脂肪酸以顺式构型存在,但在特殊条件下,如光、热、催化剂或加氢反应     

微波诱导活性炭提载PTSA催化合成酯

通过对不同无机载体提载ＰＴＳＡ催化剂同微波的偶合作用及其用于催化羧酸酯化反应活性的研究,发现活性炭提载ＰＴＳＡ催化剂是用于微波诱导催化羧酸酯化反应的最佳经济。研究了１７种羧酸酯化反应,所有反应均可在１ｍｉｎ内完成,并具有较高的收率。     

Synthesis and Characterization of 2, 3-Dihydroxypropylcellulose

Water-soluble 2,3-dihydroxypropylcellulose (DHPC) was successfully synthesized by the reaction of 3-chloro-1,2-propanediol with alkali cellulose in dioxane, or with glycidol in acetone. DHPC from the glycidol reaction was shown to have better solubility and yield. DHPC made from cotton wool and glycidol possesses the highest intrinsic visocisty (up to 4.05 dL/g). Quantitative ¹³ C-NMR analysis was utilized to estimate the molar substitution and degree of substitution of the resulting DHPC. Since the ratios of molar substitution to degree of substitution were found to be 2 or less, the substituents on the cellulose probably consist of monomer, dimer, or trimer of the alkylation agents used. Above the critical concentration of DHPC, the solution viscosity was found to be increased tremendously upon treating with boric acid under basic conditions.     

Partial Carbamoylation of Cellulose Microspheres:a New Method to Prepare Adsorbents for Liquid Chromatography简

Micron-sized cellulose microspheres were prepared through sol-gel method using NaOH/urea solution to dissolve cellulose, then cross-linked by 1,6-hexanylene diisocyanate （HDI）, toluene 2,4-diisocyanate （TDI） and 1,4-phenylene diisocyanate （PDI）, respectively. The reaction conditions for partial modification of the microspheres were studied. The degree of substitution （DS） in cellulose was controlled by adjusting the reaction conditions. HDI-crosslinked microspheres were partially modified with phenyl isocyanate to obtain chiral stationary phases （CSPs）. The CSPs of a lower degree of crosslinking （DC） showed better chiral recognition ability than those of a higher DC. Meanwhile the CSPs prepared by pre- modification exhibited better chiral recognition ability than those prepared by pre-crosslinking.     

Structural analysis of polymer-brush-type cellulose β-ketoesters by molecular dynamics simulation

The reason for anomalous NMR patterns of cellulose β-ketoesters, which were prepared by reaction between cellulose and ketene dimers having long alkyl chains (AKDs) under homogeneous conditions using a cellulose solvent system, was studied by molecular dynamics simulation. Cellulose/AKD β-ketoester models with degree of substitution (DS) 2.0 and degree of polymerization (DP) 5, 10, 20 or 40, and cellulose/fatty acid ester models with DS 3.0 and DP 5, 10, 20 or 40 were assembled in the simulation. The calculated results were compared with those obtained by NMR and conformation analyses of the actually prepared cellulose derivatives. The molecular dynamics simulation data showed that the average velocities of anhydroglucose units in cellulose/AKD β-ketoesters were approximately one tenth of those in cellulose/fatty acid esters. Thus, cellulose chains in the cellulose/AKD β-ketoesters are extremely restricted in motion by the β-ketoester substituents. The solid-like behavior of cellulose chains in cellulose/AKD β-ketoesters in solution state is, therefore, explainable by strong restriction in motion of cellulose chains by long, branched and bulky substituents introduced into cellulose hydroxyls in high densities via β-ketoester bonds.     

Synthesis of Cellulose Long-Chain Esters in 1-Butyl-3-methylimidazolium Acetate: Structure-Property Relations

In this study, we prepared cellulose long-chain esters homogeneously in 1-butyl-3-methylimidazolium acetate, using cotton linter as the raw material, long-chain fatty acid as the esterification agent and paratoluensulfonyl chloride as the co-reactant. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction were used to characterize the product. The maximum degree of substitution was found to be 1.53 when the molar ratio of cellulose, lauric acid and paratoluensulfonyl chloride was 1 : 6 : 6, provided that the reaction temperature was 60°C and the reaction time was 24 h. The mechanical property of the free-film made of cellulose laurate was also tested. It was found that the toughness of cellulose laurate was much better than that of cellulose acetate.     

Synthesis of cellulose benzoates under homogeneous conditions in an ionic liquid

The ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a reaction medium was studied for the synthesis of cellulose benzoates by homogeneous acylation of dissolved cellulose with benzoyl chlorides in the absence of any catalysts. Cellulose benzoates with a degree of substitution (DS) in the range from about 1 to 3.0 were accessible under mild conditions. The DS of cellulose derivatives increased with the increase of the molar ratio of benzoyl chloride/anhydroglucose unit (AGU) in cellulose, reaction time, and reaction temperature. Benzoylation of cellulose with some 4-substituted benzoyl chlorides including 4-toluoyl chloride, 4-chlorobenzoyl chloride and 4-nitrobenzoyl chloride was also readily carried out under mild conditions. Furthermore, regioselectively substituted mixed cellulose esters were synthesized in this work. All products were characterized by means of FT-IR, ¹H-NMR, and ¹³C-NMR spectroscopy. In addition, at the end of benzoylation of cellulose, the ionic liquid AmimCl was easily recycled. When the recycled AmimCl was used as the reaction media, the cellulose benzoate with a similar DS was obtained under comparable reaction conditions.     

The synthesis and thermotropic behaviour of an ethyl cellulose derivative containing azobenzene-based mesogenic moieties

An ethyl cellulose derivative containing azobenzene-based mesogenic moieties was prepared by the reaction of 4-methoxyazobenzene-4'-oxyacetic acid and ethyl cellulose by esterification in the presence of N,N' -dicylcohexylcarbodiimide and 4-dimethylaminopyridine. Its chemical structure and liquid crystalline properties were characterized by FTIR, 1 H NMR, POM, DSC and WAXD. The degree of substitution of the cellulose backbone by the azobenzene-based mesogenic moieties is 0.9. The polymer is thermotropic and exhibits liquid crystalline behaviour over the temperature range 125-172°C.     

Phenoxyhydroxypropylhydroxyethylcellulose—new amphiphilic cellulose derivative

A new amphiphilic cellulose derivative phenoxyhydroxypropylhydroxyethylcellulose of substitution degree up to 0.67 was synthesized by reaction of water-soluble hydroxyethylcellulose with 2,3-epoxypropylphenylether in the presence of sodium hydroxide as a catalyst. The chemical composition of the derivative was confirmed by means of UV, IR- and ¹³C-NMR-spectroscopy. The derivatives with substitution degree up to 0.12 are soluble in water and water–alcohol mixtures. With increasing substitution degree, the polymers lose their water solubility, but still dissolve in water–alcohol mixtures. All products are soluble in aprotic solvents. The effect of the reaction conditions, such as temperature and molar ratios of reaction components, on both the reaction rate and degree of substitution was investigated.     

Carboxymethylation of Bacterial Cellulose

The carboxymethylation of bacterial cellulose (BC) was studied under typical heterogeneous reaction conditions. It was found that the BC possesses a significantly lower reactivity compared to wood cellulose converted under comparable conditions. Moreover, water-solubility of carboxymethyl cellulose (CMC) obtained from BC appears at rather high degree of substitution of about 1.5 although a nearly statistical functionalization pattern was analyzed by HPLC. Obviously, the nano-structure of BC is important for the reactivity and the properties of the synthesized CMC like water-solubility.     

Studies on regioselective acylation of cellulose with bulky acid chlorides

The regioselective esterification of cellulose by reaction with bulky acyl halides including pivaloyl chloride, adamantoyl chloride and 2,4,6-trimethylbenzoyl chloride was studied. Functionalization conditions to achieve a given degree of substitution (DS) and the resulting ester substitution pattern were described in detail. One- and two-dimensional NMR spectroscopy techniques were used to confirm the structure of the esters obtained. We compared the effects on substitution of using different esterifying reagents and solvent systems including DMAc/LiCl, DMSO/TBAF, and ionic liquids (ILs).     

Interactions of ionic liquids with polysaccharides 9. Hydroxyalkylation of cellulose without additional inorganic bases

Water-soluble hydroxyalkyl cellulose with a molar degree of substitution of up to 2.79 was prepared under completely homogeneous reaction conditions in various ionic liquids without addition of inorganic bases. In acetate containing solvents the IL acts as a catalyst. The substitution patterns of the cellulose ethers were analyzed by ¹³C NMR spectroscopy, ¹H NMR spectroscopy after peracetylation and GLC/MS after permethylation and depolymerization. A diminished tendency towards the formation of side chains compared to heterogeneously prepared hydroxyalkyl celluloses in the presence of inorganic bases was found.