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第 4 期                          张光杰,等:  不同环糊精对角鲨烯的包合作用                                    ·707·


            对角鲨烯有更大的包合常数有关。                                    度的升高而增加,且随着温度的升高,5 种环糊精
            2.4   包合过程中热力学参数                                   的包合常数及增溶因子均不同程度地增大,其中
                 根据 1.2.5 所述方法计算包合过程中的热力学                      55 ℃下 γ-环糊精的 K 值及增溶因子均为最大值。热
            参数即焓值(ΔH)、熵值(ΔS)及吉布斯自由能(ΔG),                       力学参数表明,5 种环糊精的包合反应均为自发的
            结果如表 3 所示。                                         吸热反应,且均为无序化程度升高的熵增加的过程。
                                                               温度升高有利于包合反应进行,且熵增加是角鲨烯
                   表 3    不同环糊精包合反应的热力学参数                      分子进入环糊精空腔的主要驱动力。可为进一步研
            Table  3    Thermodynamic  parameters  of  inclusion  reaction
                    by different cyclodextrins                 究环糊精包合角鲨烯的分子机制及对角鲨烯性能的
             环糊精种类       T/K   ΔH/(J/mol) ΔS/〔J/(Kmol)〕ΔG/(J/mol)  影响提供依据及参考。
                        298.15                    13573.4
              α-环糊精     313.15   41010.4  183.1   16319.5     参考文献:
                        328.15                    19065.7     [1]   Tsujimoto M. A highly unsaturated hydrocarbon in shark liver oil[J].
                                                                   Journal of Industrial Engineering Chemistry, 1916, 8(10): 889-896.
                        298.15                    17414.5     [2]   Batista I, Nunes M. Characterisation of shark liver oils[J]. Fisheries
              β-环糊精     313.15   9281.1    89.5   18757.6         Research, 1992, 14(4): 329-334.
                                                               [3]   Wang Jun (王军), Weng Youzhu (翁幼竹), Su Yongquan (苏永全), et
                        328.15                    20100.7
                                                                   al.  Isolation  and  determination  of  squalene  from  the  liver  of
                        298.15                    17430.2         cetorhinus maximus in fujian coastal[J]. Journal of Xiamen University:
              γ-环糊精     313.15   11310.8   96.4   18876.2         Natural Science (厦门大学学报:自然科学版), 2002, 41(4): 506-508.
                                                               [4]   Zhang Guangjie (张光杰), Yang Liling (杨利玲), Yuan Chao (袁超),
                        328.15                    20322.1         et al. Research progress on development and application of squalene
                        298.15                    13749.9         [J]. Cereals & Oils (粮食与油脂), 2017, 30(12):7-10.
             羟丙基-β-环           47904.6    206.8                [5]   Chen Xuebing (陈学兵), Shi Xuanming (史宣明), Zhao Shuna (赵抒
                糊精      313.15                    16851.8         娜),  et al.  Progress  of  squalene  extraction  from  vegetable  oils[J].
                        328.15                    19953.6         China Oils and Fats (中国油脂), 2013, 38(11): 72-75.
                                                               [6]   Grażyna W, Przemysław H, Jerzy G. Separation of squalene and oil
                        298.15                    13732.8
               甲基-β-           37564.8    172.1                    from Amaranthus seeds by supercritical carbon dioxide[J]. Separation
               环糊精      313.15                    16313.6         and Purification Technology, 2013, 110(1): 39-43.
                        328.15                    18894.4     [7]   Zhang Guangjie (张光杰), Du Lei (杜磊), Yuan Chao (袁超), et al.
                                                                   Research progress on bioactivity and application of triterpenoids[J].
                                                                   Cereals & Oils (粮食与油脂), 2017, 30(10): 1-5.
                 如表 3 所示,不同温度下 5 种环糊精的 ΔH 为                    [8]   Villers. Squalene olive oil and hypothesis[J]. Cancer Epidemol, 1997,
                                                                   889(1): 193-203.
            正值,表明包合反应为吸热反应,ΔS 为正值,表明                           [9]   Zhao  Yancheng  (赵炎成).  The  combination  of  eight  treasures-the
            包合过程是无序化程度升高的熵增加的过程。由热                                 food therapy health care function of squalene[J]. Oriental Diet-Therapy
                                                                   and Health Care (东方食疗与保健), 2006, 4(11): 6-7.
            力学第二定律可得,当环糊精的空腔容纳疏水性客                             [10]  Subramanian  S,  Thiruvengadam  D,  Bhakthavatchalam  M,  et al.
            体分子前需要脱去水壳,此时会释放结合水,进而                                 Effect of squalene on cyclophosphamide-induced toxicity[J]. Clinica
                                                                   Chimica Acta, 2006, 364(1): 335-342.
            被客体分子所取代,这个过程会引起熵的正变,说                             [11]  Yang Yunshang (杨云裳), Shi Gaofeng (史高峰), Lu Runhua (鲁润
                                                                   华). Effect of cyclodextrins on the solubility of flavonol veronicafolin
            明疏水作用在整个包合过程中起着重要作用。此外,                                in water[J]. Chinese Journal of Applied Chemistry (应用化学), 2004,
            该过程是吸热反应,但客体分子与环糊精空腔内壁                                 21(11): 1191-1192.
                                                               [12]  Honjo  M,  Iwamoto  C,  Arima  H.Squalene/cyclodextrin  clathrate
            之间通过范德华力和分子间氢键力的相互作用是放                                 pseudorotaxane: JP2009269829[P]. 2009-11-19.
                                                               [13]  Fu Song (付松), Xiang Shixue (向仕学). Determination of squalene
            热反应。在此实验中,熵增加期间吸收的热量可能                                 in  health  foods  by  gas  chromatography-mass  spectrometry[J].
            大于主-客体络合反应释放的热量,从而导致正焓                                 Chinese Journal of Health Laboratory Technology (中国卫生检验杂
                                                                   志), 2003, 13(6): 717.
            值。负吉布斯自由能值表明包合物形成是一个自发                             [14]  Higuchi  T,  Connors  K.  A  phase-solubility  techniques.  Advances  in
                                                                   analytical  chemistry  and  instrumentation[M].  Jonh  Wiley  &  Sons,
            过程   [19] ,ΔG 随着温度的升高而呈负增加,表明温                         INC, 1965: 117-212.
            度的升高增加了形成包合物的自发倾向。温度升高                             [15]  Tao  F,  Hill  L,  Peng  Y,  et al.  Synthesis  and  characterization  of
                                                                   β-cyclodextrin  inclusion  complexes  of  thymol  and  thyme  oil  for
            也是增加无序化(熵增加)的过程。因此,从能量                                 antimicrobial  delivery  applications[J].  LWT-Food  Science  and
                                                                   Technology, 2014, 59(1): 247-255.
            变化可以推断,无序化增加(熵增加)是角鲨烯分                             [16]  Rakmai  J,  Cheirsilp  B,  Mejuto  J,  et al.  Physico-chemical
            子进入环糊精空腔的主要驱动力。                                        characterization  and  evaluation  of  bio-efficacies  of  black  pepper
                                                                   essential  oil  encapsulated  in  hydroxypropyl-beta-cyclodextrin[J].
                                                                   Food Hydrocolloid, 2017(65): 157-164.
            3    结论                                            [17]  Fang Haiyan (方海燕). Study on inclusion complexation of insoluble
                                                                   drugs with β-cyclodextrin and its derivatives[D]. Changsha: Central
                                                                   south university (中南大学), 2014.
                 应用相溶解度法,研究在不同浓度、温度下 α-                        [18]  Huang Yingxi (黄莹玺),  Li Pingpin (李瓶娉), Yin Shanshan (银杉
                                                                   杉 ),  et al.  Preparation  and  characterization  of  Tamoxifen
            环糊精、β-环糊精、γ-环糊精、羟丙基-β-环糊精、                             hydroxypropyl-β-cyclodextrin  inclusion  complex[J].  West  China
            甲基-β-环糊精对角鲨烯的包合作用。由相溶解图可                               Journal  of  Pharmaceutical  Sciences  (华西药学杂志),  2014,  29(5):
                                                                   503-506.
            判断在此实验条件下所绘制的 5 种环糊精的相溶解                           [19]  Karathanos V, Mourtzinos I, Yannakopoulou K, et al. Study of the
                                                                   solubility, antioxidant activity and structure of inclusion complex of
            图均为 A L 型。角鲨烯的溶解度随环糊精的浓度与温                             vanillin with β-cyclodextrin[J]. Food Chemistry, 2007, 101(2): 652-658.
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