【作者】 俞晓峰；

【导师】 蒋惠亮；

【作者基本信息】 江南大学 ， 应用化学， 2008， 硕士

【摘要】 1,4-二棕榈酰羟脯氨酸(1,4-Dipalmitoyl Hydroxyproline),作为胶原蛋白主要组成成分之一的羟脯氨酸衍生物,是一种化妆品中有效的抗皱抗衰老添加剂。本文以肖顿·鲍曼(Schotten·Banmamm)缩合反应法对酰氯进行氨解和醇解制备1,4-二棕榈酰羟脯氨酸,并探索1,4-二棕榈酰羟脯氨酸的非水相酶催化反应。1.首先制备了用于酯化和酰胺化的棕榈酰氯,通过对反应物摩尔比、反应时间和反应温度因素进行了考察,得到制备棕榈酰氯反应的适宜条件为:反应摩尔比n(酸):n(三氯化磷)=1:2、反应温度70-80℃、反应时间3 h。2.用肖顿·鲍曼缩合反应对棕榈酰氯进行了氨解和醇解,制备得到了1,4-二棕榈酰羟脯氨酸。通过单因素实验考察了各因素对制备二棕榈酰羟脯氨酸的影响。得到了反应条件为:以丙酮为有机溶剂,反应pH为8~9,有机溶剂(指丙酮)体积分数为50%,反应温度为15℃,原料摩尔比n(羟脯氨酸) : n(棕榈酰氯)=1: 2.4,反应时间为4 h。此条件下,反应转化率可达98.13%,产率可达60%。为了得到最佳的反应条件,运用了正交设计和响应面分析手段对实验进行优化。结果表明,对于二棕榈酰羟脯氨酸的产率,影响因素顺序为:原料摩尔比>反应温度>丙酮体积分数>反应时间。得到的最佳反应条件为有机溶剂体积分数为55%,反应温度为15℃,原料摩尔比为n(羟脯氨酸) : n(棕榈酰氯)=1:2.5,反应时间为5 h。采用三因素三水平的响应面分析法,建立了反应的二次多项式数学模型,并以1,4-二棕榈酰羟脯氨酸的产率为响应值作响应面和等高线,考察了反应温度、有机溶剂体积分数和原料摩尔比对产率的影响。得出了反应拟合方程,其反应的最佳工艺条件为:有机溶剂体积分数为55%,反应温度为15℃,原料摩尔比为n(羟脯氨酸) : n(棕榈酰氯)=1:2.5。此条件下,产率可达58.26%。3.考察了1,4-二棕榈酰羟脯氨酸的非水相酶合成反应。对酶种类、有机溶剂、加酶量和加水量等因素进行的比较实验,可知Lipolase脂肪酶和Savinase蛋白酶对催化效果较好;在疏水性溶剂异辛烷中转化率较大;加酶量增加转化率有适当的增加;必要加水量在1-2%下较为合适,在水量过少或过多的情况下都容易导致酶失活而使转化率降低。更多还原

【Abstract】 1,4-dipalmitoyl hydroxyproline, plant-derived lipid agent consisting of hydroxyproline (natural amino acid) & palmitic acid, is anti-aging agent which can be applied to cosmetics. This experiment focused on the synthesis of 1,4-dipalmitoyl hydroxyproline by Schotten Banmamm condensation reactions, and studied the non-aqueous enzyme catalysis.1.Firstly, palmitoyl chloride used in esterification and amidation, By studying of the influencing facts such as molar ratio of materials, the time, temperature in detail, the optimum reaction conditions were obtained as follows: molar ratio of materials was 1:2, reaction temperature was 70-80℃, reaction time was 3 h.2.1,4-dipalmitoyl hydroxyproline was obtained by Schotten Banmamm condensation reactions. The different influencing factors of reaction were studied. Then the reaction conditions were obtained as follows: volume ratio of acetone was 50%, molar ratio of materials was 1:2.5, pH=8~9, reaction temperature was 15℃, reaction time was 4 h. The conversion of reaction had reached to 98.13 % under the optimal conditions, and the yield 60%. Orthogonal design and Response surface methodology were used in the experiment for optimum condition. The experimental results show that the molar ratio of materials had the largest effect, the second was reaction temperature, third was volume ratio of acetone and reaction time had the least effect. And the optimum reaction conditions were obtained as follows: volume ratio of acetone was 55%, molar ratio of materials was 1:2.5, reaction temperature was 15℃, reaction time was 5 h. By using the three-level-three-factor response surface methodology, a quadratic polynomial mathematical model was established. The influences of the reaction temperature, volume ratio of organic agent and the molar ratio of materials were investigated by determining the yield as the response. The optimum reaction conditions were obtained as follows: volume ratio of acetone was 55%, reaction temperature was 15℃, molar ratio of materials was 2.5. And in these conditions, the yield reaches 58.26%.3.In order to study the non-aqueous enzyme catalysis, the influencing factors were investigated. The results show that the catalysis effects of Lipolase lipase and Savinase albuminuria are better than others; Conversion of reaction, much bigger in isooctane, will increase by adding of enzyme. And the optimum water content is 1~2%.更多还原