【作者】 王锡元；

【导师】 王建新；

【作者基本信息】 江南大学 ， 应用化学， 2007， 硕士

【摘要】 本论文主要研究了酪氨酸酶激活剂补骨脂素及其复配物对酪氨酸酶的协同激活性能,以及酪氨酸酶抑制剂芒柄花苷的合成、优化及其对酪氨酸酶抑制性能和抗氧化性能测试。酪氨酸酶是产生黑色素的主要限速酶,通过激活或抑制酪氨酸酶的活性可促进毛发和皮肤黑素的生成或抑制,达到乌发或皮肤增白的目的。在化妆品原料的研究过程中,酪氨酸酶作为性能测试试剂起着重要的作用。中药补骨脂细粉经75 %的乙醇提取得到补骨脂素,其HPLC纯度为99 %。将补骨脂素配制成不同的浓度,用紫外-可见光分光光度法进行酪氨酸酶激活性能的检测,当浓度为0.03 mg/mL时,最高激活率为44.9 %。选择对酪氨酸酶都有一定激活作用的不同添加助剂Cu²⁺、Fe²⁺、Mn²⁺、Zn²⁺和半胱氨酸、咖啡因、人参皂苷等与补骨脂素复配,结果显示Cu²⁺、Mn²⁺、Zn²⁺和半胱氨酸与补骨脂素都有不同程度协同激活效应。采用单因素法将Cu²⁺、Mn²⁺、Zn²⁺和半胱氨酸同时与补骨脂素复配,测定其对酪氨酸酶的激活率,当Cu²⁺浓度为0.1 mg/mL、Mn²⁺浓度为0.05 mg/mL、Zn²⁺浓度为0.1 mg/mL、半胱氨酸浓度为0.05 mg/mL,加入量均为0.3 mL时,对酪氨酸酶激活率最高为104.3 %。因此,补骨脂素及其复配物可以作为促进黑色素生成的物质在化妆品或药物中使用。采用脱氧安息香路线两步法合成芒柄花素,以芒柄花素和四乙酰溴代葡萄糖为原料,采用固-液和液-液两种不同的相转移催化合成芒柄花苷。通过对比产率等因素,最终确定采用液-液相转移催化体系。并采用正交试验进行优化,收率可达64.8 %。分离得到的中间体四乙酰芒柄花苷及产物芒柄花苷的HPLC纯度分别为98.27 %和98.36 %。采用紫外-可见光分光光度法测定芒柄花苷对酪氨酸酶活性的抑制性能。结果表明:0.05 mg/mL时,芒柄花苷对酪氨酸酶最大抑制率为51.7 %。同时采用紫外-可见光分光光度法,测定了芒柄花苷对超氧自由基的抑制率。结果表明:在1 mg/mL时,芒柄花苷对超氧自由基的最大抑制率为45.2 %。因此芒柄花苷可以作为美白剂和抗衰老成分在化妆品中使用。更多还原

【Abstract】 The synergistic activation on tyrosinase of psoralen cooperated with substrates, and the synthesis and optimization of ononin, as well as inhibition activity on tyrosinase and antioxidant activity were primarily studied in this thesis .Tyrosinase is a major enzyme, which controls the speed of melanin biosynthesis, the generating of hair and skin melanin, which is the key factor to black hair and whiten skin, can be promoted or prohibited by activating or inhibiting the tyrosinase. Tyrosinase plays a vital role in selecting cosmetic materials as a reagent.Psoralen was extacted by 75% ethanol water solution from Chinese traditional medicine psoralen . UV-Vis spectrophotometry method was selected to study the tyrosinase avtivity of psoralen which was in different concentration. The highest activation can be 44.9% when the concentration is 0.03 mg/mL . Different additives which can activate the tyrosinae , such as Cu²⁺、Fe²⁺、Mn²⁺、Zn²⁺and cysteine、affein、panaxcoside were selected to cooperate with psoralen to study the synergistic activation on tyrosinase . It indicated that Cu²⁺、Mn²⁺、Zn²⁺and cysteine were the right substances.Single factor method was selected to study the synergistic activation on tyrosinase of psoralen cooperated with all the right substances together, the highest activation can be 104.3 % , when the the concentration of Cu²⁺、Mn²⁺、Zn²⁺and cysteine was 0.1 mg/mL, 0.05 mg/mL, 0.1 mg/mL, 0.05 mg/mL respectively . Psoralen and the complex were proved to be a good additive to promote melanin biosynthesis in cosmetics and medicines .α-D-acetobromoglucose was used as sugar donor and formononetin,which was prepared by Deoxybenzoin route ,was used as nucleophilic reagent to synthesize ononin. Two Phase Transfer Catalysis （PTC） systems-solid-liquid PTC （SLPTC） system and liquid-liquid PTC （LLPTC） system were used to synthesize ononin. By comparing the yields, LLPTC system was selected and the highest yield can be 64.8 % by orthogonal experimentation. acetyl-ononin and ononin was isolated the HPLC purity can be 98.27 % and 98.36 % respectively.By using UV-Vis spectrophotometry method to determine the inhibitory rates of ononin and formononetin against tyrosinase and superoxide radical, it was found that the highest inhibitory rate of ononin against superoxide radical is lower than this of formononetin. The inhibitory rate can reach 45.2 % at the concentration of 1 mg/mL. And the inhibitory rate of ononin against tyrosinase can reach 51.7 % when the concentration is 0.05 mg/mL,. So ononin can be used in cosmetics as natural safe skin-lightening and anti-aging agent.更多还原