Enzymatic esterification of glycerol II. Lipase-catalyzed synthesis of regioisomerically pure 1(3)-rac-monoacylglycerols

Regioisomerically pure 1(3)-rac-monoacylglycerols are conveniently prepared in high yields (>75%) and in multigram quantities by enzymatic esterification of glycerol in the presence of various lipases(Chromobacterium viscosum, Rhizopus delemar, Rhizomucor miehei) with a variety of different acyl donors, such as free fatty acids, fatty acid alkyl esters, vinyl esters and triacylglycerols, as well as natural fats and oils. All reactions are carried out in aprotic organic solvents with low water content, namelyn-hexane, diethyl ether, tBuOMe or mixtures of these solvents. Essential for the success of these transformations were the following two factors. First, the creation of an artificial interphase between the solvent-immiscible hydrophilic glycerol and the hydrophobic reaction medium by its adsorption onto a solid support. Second, a facile system for the separation of the desired monoacylglycerol from the reaction mixture, coupled with the continuous recycling of acyl donor and undesirable by-products.     

Interpenetrating polymer networks based on polyol modified castor oil polyurethane and poly(2‐ethoxyethyl methacrylate): Synthesis,chemical, mechanical,thermal properties,and morphology

Interpenetrating polymer networks (IPNs) of glycerol modified castor oil polyurethane (GC‐PU) and poly(2‐ethoxyethyl methacrylate) poly(2‐EOEMA) were synthesized using benzoyl peroxide as initiator and ethylene glycol dimethacrylate (EGDM) as crosslinker. GC‐PU/poly (2‐EOEMA) interpenetrating polymer networks were obtained by transfer molding. The novel GC‐PU/poly (2‐EOEMA) IPNs are found to be tough films. These IPNs are characterized in terms of their resistance to chemical reagents thermal behavior (DSC, TGA) and mechanical behavior, including tensile strength, Young's modulus, shore A hardness, and elongation. The morphological behavior was studied by scanning electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1029–1034, 2004     

Enzymatic esterification of glycerol I. Lipase-catalyzed synthesis of regioisomerically pure 1,3-sn-diacylglycerols

Regioisomerically pure 1,3-sn-diacylglycerols are conveniently prepared in high yields (>80%) and in large quantities by enzymatic esterification of glycerol in the presence of various 1,3-selective lipases(Chromobacterium viscosum, Rhizopus delemar, Rhizomucor miehei) and a variety of different acyl donors like free fatty acids, fatty acid alkyl esters and vinyl esters. All reactions are carried out in aprotic organic solvents of low water content, namelyn-hexane, diethyl ether or tBuOMe. The creation of an artificial interphase between the solvent-immiscible hydrophilic glycerol and the hydrophobic reaction media by the adsorption of glycerol onto a solid support prior to use was essential for the success of these transformations. The effects of reaction conditions and the regioselectivities of the lipases on the product yields are described in detail.     

Continual conversion of free fatty acid in rice bran oil to triacylglycerol by immobilized lipase

Rice bran oil containing 30–50% free fatty acid was continually converted to an oil containing more than 75% of triacylglycerol (TG) by means of immobilized lipase. The reaction was carried out at 60°C for 24 h with dehydration and reactant mixing by dry nitrogen flow under a positive nitrogen atmosphere. Enzymatic TG synthesis with evaporation by heating was not suitable because of the increasing peroxide value of the oil. Part of this article was presented at the annual meeting of the Japan Oil Chemists' Society at Sendai, Japan, October, 16, 1990.     

活性炭固载钛酸异丙酯催化剂的制备

研究了新型固载钛酸异丙酯催化剂的制备方法，该催化剂活性高，选择性好，可成为绿色酯化工艺用催化剂。     

活性炭负载Ti(SO_4)_2催化合成丙二酸二丁酯的研究

首次以活性炭负载硫酸钛 (Ti(SO4) 2 /C)作催化剂 ,合成丙二酸二丁酯 ,此催化剂活性高 ,选择性好 ,易分离 ,不腐蚀设备 ,反应时间短 ,是一种环境友好催化剂。考察了影响酯化反应的条件 ,获得优化工艺条件如下 :Ti(SO4) 2 负载量 2 0 % ,丙二酸 0 2mol,正丁醇 0 6mol,催化剂 0 8g ,反应温度 15 0℃ ,反应时间 90min ,丙二酸的转化率 94 %以上     

Promotional effect of hydroxyl on the aqueous phase oxidation of carbon monoxide and glycerol over supported Au catalysts

Gold particles supported on carbon and titania were explored as catalysts for oxidation of CO or glycerol by O₂ at room temperature in liquid-phase water. Although Au/carbon catalysts were not active for vapor phase CO oxidation at room temperature, a turnover frequency of 5 s⁻¹ could be achieved with comparable CO concentration in aqueous solution containing 1 M NaOH. The turnover frequency on Au/carbon was a strong function of pH, decreasing by about a factor of 50 when the pH decreased from 14 to 0.3. Evidently, a catalytic oxidation route that was not available in the vapor phase is enabled by operation in the liquid water at high pH. Since Au/titania is active for vapor phase CO oxidation, the role of water, and therefore hydroxyl concentration, is not as significant as that for Au/carbon. Hydrogen peroxide is also produced during CO oxidation over Au in liquid water and increasing the hydroxyl concentration enhances its formation rate. For glycerol oxidation to glyceric acid (C₃) and glycolic acid (C₂) with O₂ (1–10 atm) at 308–333 K over supported Au particles, high pH is required for catalysis to occur. Similar to CO oxidation in liquid water, H₂O₂ is also produced during glycerol oxidation at high pH. The formation of the C-C cleavage product glycolic acid is attributed to peroxide in the reaction.     

水相酶促酯化法拆分dl－薄荷醇的连续操作

对影响脂肪酶活性、稳定性和对映选择性的因素，如有机溶剂和反应温度等首先进行了优化。其次，使用悬浮于环已烷的粉末状游离脂肪酶（ＣａｎｄｉｄａｃｙｌｉｎｄｒａｃｅａｌｉｐａｓｅＯＦ３６０）作生物催化剂，成功地构建了一个高效的非水相游离酶连续搅拌釜反应器。当使用高度反应性的丙酸酐作为薄荷醇的酰基给体，进行连续的酶促对映选择性酯化反应时，醇的转化率在两周内可保持４０％以上，所生成酯的光学纯度超过９５％ｅ．ｅ。但是，当使用相应的游离丙酸（而不是酸酐）作酰基给体时，薄荷醇的转化率在连续操作开始后迅速下降，表明使用酸酐时的生产力要比使用游离酸时高。最后，对底物溶液的浓度和流速进行了进一步优化；同时对反应器系统的含水量进行了监测，并通过对酸酐料液的浓度或流速进行微调的方法，有效地将有机溶液相的水分浓度控制在一定的范围（２～４ｍｍｏｌ／Ｌ）之内，结果，ｄｌ－薄荷醇对映选择性连续酯化反应非常稳定地运行了两个月之久（转化率４７～３５％，光学纯度９５～９８％ｅ．ｅ．），酶反应器的半衰期超过２００天。     

蒙脱土负载［C14mim］+有机阳离子催化合成柠檬酸三丁酯

通过咪唑基离子液体和蒙脱土在甲苯溶液中的离子交换反应，将热稳定性高的咪唑基有机阳离子［C₁₄mim］⁺交换吸附进入蒙脱土片层间，制备了蒙脱土负载的有机阳离子固体催化剂［C₁₄mim］⁺/MMT。利用XRD和TGA对催化剂的结构与性能进行了表征和测定，研究了蒙脱土负载有机阳离子固体催化剂的催化性能，初步考察了其稳定性及再次使用效率。研究结果表明，［C₁₄mim］⁺/MMT在合成无毒增塑剂柠檬酸三丁酯的酯化反应中表现出较高的催化活性，可循环使用。与未负载的C₁₄mimBF₄相比，［C₁₄mim］⁺/MMT具有催化活性高、稳定性好和易分离的特点。     

响应面法优化甘油歧化产1,3-丙二醇菌培养基的研究

以甘油为原料,在单因素试验的基础上,利用响应面法研究了(NH4)2HPO4、K2HPO4/KH2PO4、pH值对1,3-丙二醇产量的影响,得到二次多项式回归模型.结果表明:回归模型能很好地反映各因素水平与响应值之间的关系,同时得出这3因素的最佳用量为(NH4)2HPO42.76 g/L、K2HPO4/KH2PO4(质量比1∶1)3.98 g/L、pH值7.58,此时1,3-丙二醇理论产量为28.702 g/L,实际产量为27.597 g/L,比优化前提高了19.02%.