Page 165 - 《精细化工》2021年第10期
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第 10 期              王舒舒，等:  响应面优化褶皱假丝酵母脂肪酶催化合成木质甾醇油酸酯                                   ·2095·


            程中没有观察到任何化学催化合成法中常见的脱                                  novel virtual tracking tool[J]. Nutrients, 2019, 11: 1-13.
                                                               [2]   HE W S, PAN R  R, LI  L  L,  et al. Combined lowering effect of
            水、氧化等副产物的生成。CUI 等              [12] 报道 Ylip 脂肪         phytosterol esters and tea extracts on  lipid profiles in SD rats[J].
                                                                   Food Science and Technology Research, 2018, 24(5): 875-882.
            酶催化甾醇油酸酯合成过程中水活度的控制对反应                             [3]   DENG Q  C, YU  X, XU J Q,  et al. Single frequency intake of
            有着重要的影响；霍振宇等             [17] 报道 Lipozyme 435 脂        a-linolenic acid rich phytosterol esters attenuates atherosclerosis risk
                                                                   factors in hamsters fed a high  fat diet[J]. Lipids in Health and
            肪酶催化没食子酸植物甾醇酯合成的过程中分子筛                                 Disease, 2016, 15: 1-8.
            的添加对甾醇的酯化率提升十分明显。本文在最佳                             [4]   SONG L H, ZHAO X G, OUYANG P L, et al. Combined effect of
                                                                   n-3 fatty acids and phytosterol esters on alleviating hepatic steatosis
            工艺条件下进行了添加 0.4 nm 分子筛（10 g/L）的                         in non-alcoholic fatty liver disease subjects: A double-blind
                                                                   placebo-controlled clinical trial[J]. British Journal of Nutrition, 2020,
            10 倍放大验证实验，与文献报道不同的是，分子筛                               123(10): 1148-1158.
                                                               [5]   MENG X H, PAN Q Y, YANG T K. Synthesis of phytosteryl esters
            脱 水剂的添加对酯化反应影响不大，转化率为                                  by using alumina-supported zinc oxide (ZnO/Al 2O 3) from
            91.52%。按 1.2.2 节进行纯化处理，得到木质甾醇油                         esterification production of phytosterol with patty acid[J]. Journal of
                                                                   the American Oil Chemists' Society, 2011, 88(1): 143-149.
            酸酯，HPLC 纯度达到 98.73%。HE 等            [14] 报道的无      [6]   PAN D J (潘丹杰), ZHANG B (张斌), JIANG X J (蒋晓杰), et al.
            催化剂合成植物甾醇酯中，来源于油酯脱臭馏出物                                 Application of novel supported catalyst in  synthesis  process  of
                                                                   phytosterol ester[J]. CHINA Oils and Fats (中国油脂), 2017, 42(3):
            的植物甾醇（质量分数 93.35%）中 β-谷甾醇质量分                           59-63.
                                                               [7]   ROBLES M S, BARRAULT J, VALANGE S. Selective synthesis of
            数 42.68%、豆甾醇质量分数 23.38%、菜籽甾醇质                          phytosterol esters from natural sterols and fatty  methyl  esters over
            量分数 1.93%、菜油甾醇质量分数 25.36%。在油酸                          Mg-containing solid catalysts[J]. Comptes Rendus Chimie, 2011,
                                                                   14(7): 656-662.
            和植物甾醇的物质的量比 3∶1、反应温度 220  ℃、                       [8]   DONG L (董玲), ZHENG M M (郑明明), GUO P M (郭萍梅), et al.
                                                                   Advance in lipase-catalyzed synthesis of  phytosterol  esters[J].
            反应时间 4 h 时，总转化率为 99.1%，其中 β-菜油                         CHINA Oils and Fats (中国油脂), 2012, 37(6): 58-62.
            甾醇、豆甾醇和 β-谷甾醇的活性最高，转化率分别                           [9]  ZHAO Y  (赵岩), TANG G S (唐国胜), HOU Y Y (侯莹莹), et al.
                                                                   Research on synthesis technology of phytosterol esters[J]. Journal of
            为 99.5%、99.5%和 99.1%，而菜籽甾醇的转化率为                        Food Safety and  Quality (食品安全质量检测学报), 2015,  6(2):
                                                                   585-590.
            80.9%。本文所使用的木质甾醇包含的各种甾醇与现                          [10]  ME T T  (么婷婷), XIN J  Y (辛嘉英), WANG Y  (王艳), et al.
            有文献报道中脱臭馏出物来源的植物甾醇含量差别                                 Synthesis of phytosterol esters catalyzed by lipase[J].  Chemical
                                                                   Engineer (化学工程师), 2016, 30(9): 4-9.
            较大，且催化活性存在差异，其中 β-谷甾醇、豆甾                           [11]  JIANG S T (姜绍通)，ZHENG H  J (郑海杰)，PANG M (庞敏).
                                                                   Lipase-catalyzed synthesis and characterization of  phytosterol
            醇优先转化，转化率分别为 99.7%和 99.6%，而菜                           esters[J]. Journal of Food Science (食品科学), 2012, 33(6): 78-82.
            油甾醇和菜籽甾醇的转化率分别为 82.3%和 83.4%。                      [12]  CUI  C X, GUAN N,  XING  C,  et al. Immobilization of  Yarrowia
                                                                   lipolytica  lipase  Ylip2  for the biocatalytic synthesis  of  phytosterol
            与之前文献报道的诸多酶法合成植物甾醇酯方法相                                 ester in a water activity controlled reactor[J]. Colloids and Surfaces
                                                                   B: Biointerfaces, 2016, 146: 490-497.
            比较   [10-13] ，采用本文的优化合成工艺可以在较少催                    [13]  CHOI N, CHO H J, KIM H, et al. Preparation of phytosteryl ester
            化剂、较短时间内得到更高的转化率。                                      and simultaneous enrichment of stearidonic acid via lipase-catalyzed
                                                                   esterification[J]. Process Biochemistry, 2017, 61: 88-94.
                                                               [14]  HE B Q, DENG  T, LI J X,  et al. An innovative auto-catalytic
            3   结论                                                 esterification for the production of phytosterol esters: Experiment
                                                                   and kinetics[J]. RSC Advances, 2014, 4(119): 64319-64327.
                                                               [15]  YANG F M (杨福明), MA Y (马莺). Simultaneous determination of
                 在所考察的 10 种常见商品化脂肪酶中，CRL                           phytosterols and phytosterols by HPLC[J]. Journal of Food Science
            催化木质甾醇油酸酯合成的性能最好，正己烷是优                                 (中国粮油学报), 2017, 32(6): 134-138, 145.
                                                               [16]  YU D Y, WANG T, CHEN J, et al. Enzymatic esterification of rice
            选的反应介质。在单因素实验的基础上，通过响应                                 bran oil and phytosterol in supercritical CO 2[J]. Journal of Food
                                                                   Processing and Preservation, 2019, 43(9):14066.
            面实验设计对合成工艺进行了优化，建立了拟合性                             [17]  HUO Z Y (霍振宇), REN M X (任明星), JIA C S (贾承胜), et al.
            良好的回归模型方程，得到了一个二阶模型来预测                                 Sythesis of galloyl phytosterol esters[J]. CHINA Oils and Fats (中国
                                                                   油脂), 2016, 41(2): 65-69.
            转化率与酶添加量、底物物质的量比、反应温度和                             [18]  ZHANG X Y, YU J, ZENG A W. Optimization and modeling for the
                                                                   synthesis of sterol esters from deodorizer distillate by lipase-
            反应时间的关系。该模型模拟出 CRL 催化合成木质                              catalyzed esterification[J]. Biotechnology and Applied Biochemistry,
            甾醇油酸酯的优化工艺条件，实验证实了模型预测                                 2017, 64(2): 270-278.
                                                               [19]  CHEN K,  ARNOLD F H. Engineering new catalytic activities in
            工艺的精准性。经过修正得到的脂肪酶催化合成木                                 enzymes[J]. Nature Catalysis, 2020, 3(3): 203-213.
                                                               [20]  SANCHEZ M J M, HAMON V, THOMAS D, et al. Modulation of
            质甾醇油酸酯的最优工艺参数为：酶添加量为木质                                 lipase hydrolysis and synthesis reactions  using carbohydrates[J].
            甾醇质量的 10%，油酸与木质甾醇的物质的量比为                               Biochimica et Biophysica Acta, 1991, 1078(3): 345-350.
                                                               [21]  YU M (于敏), JIANG Z H (蒋振华), REN L W (任立伟),  et al.
            3.8∶1，反应温度为 46  ℃，反应时间为 28 h，转化                        Study on preparation of phytosterol esters[J]. Food and Drug (食品
            率为 91.56%±0.25%。论文研究内容可为木质甾醇酯                          与药品), 2014, 16(1): 1-5.
                                                               [22]  SHANG C  Y, LI W  X, ZHANG R F.  Immobilization  of  Candida
            的绿色、高效合成提供有价值的参考。                                      rugosa lipase on ZnO nanowires/macroporous silica composites for
                                                                   biocatalytic synthesis of phytosterol  esters[J]. Materials Research
                                                                   Bulletin, 2015, 68: 336-342.
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