不同环糊精对角鲨烯的包合作用
|
摘要
角鲨烯是一种含有6个非共轭双键的直链三萜,其生理功能显著,但因水溶性及稳定性较差,限制了其应用。采用相溶解度法,在25、40和55℃下,考察了α-环糊精、β-环糊精、γ-环糊精、羟丙基-β-环糊精及甲基-β-环糊精对角鲨烯的包合作用,绘制相溶解图并计算包合过程中的热力学参数。结果表明:各相溶解图均为AL型,且γ-环糊精的包合效果及增溶效果最为显著。γ-环糊精对角鲨烯的包合常数(K)最大可达1778.0860 L/mol,最大可将角鲨烯的溶解度增大至原来的309.0935倍。包合过程中的热力学参数焓变(ΔH)及熵变(ΔS)均为正值,而吉布斯自由能(ΔG)均为负值,表明包合过程为吸热的自发反应,且无序化增加(熵增加)是环糊精空腔包封角鲨烯分子的主要驱动力。
Squalene is a linear triterpenoid with six non-conjugated double bonds. Its physiological function is remarkable, but its application is limited due to its poor water solubility and stability. The interactions between squalene and different cyclodextrins, including α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin,hydroxypropyl-β-cyclodextrin and methyl-β-cyclodextrin were studied by phase solubility method at different temperatures(25, 40 and 55 ℃). The phase dissolution diagrams were plotted and the thermodynamic parameters during the inclusion process were calculated. The results showed that all phase dissolving diagrams were AL type. The inclusion effect and solubilization effect of γ-cyclodextrin were the most remarkable. The inclusion constant K of γ-cyclodextrin for squalene was up to 1778.0860 L/mol, and the solubility of squalene increased to 309.0935 times. The thermodynamic parameters enthalpy change(ΔH) and entropy change(ΔS) of the inclusion process were both positive values, while Gibbs free energy(ΔG) were both negative values, indicating that the inclusion process was an endothermic spontaneous reaction, and the increase of disorder(entropy increase) was the main driving force for the encapsulation of squalene molecules in cyclodextrin cavities.
Squalene is a linear triterpenoid with six non-conjugated double bonds. Its physiological function is remarkable, but its application is limited due to its poor water solubility and stability. The interactions between squalene and different cyclodextrins, including α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin,hydroxypropyl-β-cyclodextrin and methyl-β-cyclodextrin were studied by phase solubility method at different temperatures(25, 40 and 55 ℃). The phase dissolution diagrams were plotted and the thermodynamic parameters during the inclusion process were calculated. The results showed that all phase dissolving diagrams were AL type. The inclusion effect and solubilization effect of γ-cyclodextrin were the most remarkable. The inclusion constant K of γ-cyclodextrin for squalene was up to 1778.0860 L/mol, and the solubility of squalene increased to 309.0935 times. The thermodynamic parameters enthalpy change(ΔH) and entropy change(ΔS) of the inclusion process were both positive values, while Gibbs free energy(ΔG) were both negative values, indicating that the inclusion process was an endothermic spontaneous reaction, and the increase of disorder(entropy increase) was the main driving force for the encapsulation of squalene molecules in cyclodextrin cavities.
引文
[1]Tsujimoto M.A highly unsaturated hydrocarbon in shark liver oil[J].Journal of Industrial Engineering Chemistry,1916,8(10):889-896.
[2]Batista I,Nunes M.Characterisation of shark liver oils[J].Fisheries Research,1992,14(4):329-334.
[3]Wang Jun(王军),Weng Youzhu(翁幼竹),Su Yongquan(苏永全),et al.Isolation and determination of squalene from the liver of cetorhinus maximus in fujian coastal[J].Journal of Xiamen University: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),et al.Research progress on development and application of squalene[J].Cereals&Oils(粮食与油脂),2017,30(12):7-10.
[5]Chen Xuebing(陈学兵),Shi Xuanming(史宣明),Zhao Shuna(赵抒娜),et al.Progress of squalene extraction from vegetable oils[J].China Oils and Fats(中国油脂),2013,38(11):72-75.
[6]Gra?yna W,Przemys?aw H,Jerzy G.Separation of squalene and oil from Amaranthus seeds by supercritical carbon dioxide[J].Separation and Purification Technology,2013,110(1):39-43.
[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.
[8]Villers.Squalene olive oil and hypothesis[J].Cancer Epidemol,1997,889(1):193-203.
[9]Zhao Yancheng(赵炎成).The combination of eight treasures-the 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.
[10]Subramanian S,Thiruvengadam D,Bhakthavatchalam M,et al.Effect of squalene on cyclophosphamide-induced toxicity[J].Clinica Chimica Acta,2006,364(1):335-342.
[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 in water[J].Chinese Journal of Applied Chemistry(应用化学),2004,21(11):1191-1192.
[12]Honjo M,Iwamoto C,Arima H.Squalene/cyclodextrin clathrate pseudorotaxane:JP2009269829[P].2009-11-19.
[13]Fu Song(付松),Xiang Shixue(向仕学).Determination of squalene in health foods by gas chromatography-mass spectrometry[J].Chinese Journal of Health Laboratory Technology(中国卫生检验杂志),2003,13(6):717.
[14]Higuchi T,Connors K.A phase-solubility techniques.Advances in analytical chemistry and instrumentation[M].Jonh Wiley&Sons,INC,1965:117-212.
[15]Tao F,Hill L,Peng Y,et al.Synthesis and characterization ofβ-cyclodextrin inclusion complexes of thymol and thyme oil for antimicrobial delivery applications[J].LWT-Food Science and Technology,2014,59(1):247-255.
[16]Rakmai J,Cheirsilp B,Mejuto J,et al.Physico-chemical characterization and evaluation of bio-efficacies of black pepper essential oil encapsulated in hydroxypropyl-beta-cyclodextrin[J].Food Hydrocolloid,2017(65):157-164.
[17]Fang Haiyan(方海燕).Study on inclusion complexation of insoluble drugs withβ-cyclodextrin and its derivatives[D].Changsha:Central south university(中南大学),2014.
[18]Huang Yingxi(黄莹玺),Li Pingpin(李瓶娉),Yin Shanshan(银杉杉),et al.Preparation and characterization of Tamoxifen hydroxypropyl-β-cyclodextrin inclusion complex[J].West China Journal of Pharmaceutical Sciences(华西药学杂志),2014,29(5):503-506.
[19]Karathanos V,Mourtzinos I,Yannakopoulou K,et al.Study of the solubility,antioxidant activity and structure of inclusion complex of vanillin withβ-cyclodextrin[J].Food Chemistry,2007,101(2):652-658.
[2]Batista I,Nunes M.Characterisation of shark liver oils[J].Fisheries Research,1992,14(4):329-334.
[3]Wang Jun(王军),Weng Youzhu(翁幼竹),Su Yongquan(苏永全),et al.Isolation and determination of squalene from the liver of cetorhinus maximus in fujian coastal[J].Journal of Xiamen University: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),et al.Research progress on development and application of squalene[J].Cereals&Oils(粮食与油脂),2017,30(12):7-10.
[5]Chen Xuebing(陈学兵),Shi Xuanming(史宣明),Zhao Shuna(赵抒娜),et al.Progress of squalene extraction from vegetable oils[J].China Oils and Fats(中国油脂),2013,38(11):72-75.
[6]Gra?yna W,Przemys?aw H,Jerzy G.Separation of squalene and oil from Amaranthus seeds by supercritical carbon dioxide[J].Separation and Purification Technology,2013,110(1):39-43.
[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.
[8]Villers.Squalene olive oil and hypothesis[J].Cancer Epidemol,1997,889(1):193-203.
[9]Zhao Yancheng(赵炎成).The combination of eight treasures-the 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.
[10]Subramanian S,Thiruvengadam D,Bhakthavatchalam M,et al.Effect of squalene on cyclophosphamide-induced toxicity[J].Clinica Chimica Acta,2006,364(1):335-342.
[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 in water[J].Chinese Journal of Applied Chemistry(应用化学),2004,21(11):1191-1192.
[12]Honjo M,Iwamoto C,Arima H.Squalene/cyclodextrin clathrate pseudorotaxane:JP2009269829[P].2009-11-19.
[13]Fu Song(付松),Xiang Shixue(向仕学).Determination of squalene in health foods by gas chromatography-mass spectrometry[J].Chinese Journal of Health Laboratory Technology(中国卫生检验杂志),2003,13(6):717.
[14]Higuchi T,Connors K.A phase-solubility techniques.Advances in analytical chemistry and instrumentation[M].Jonh Wiley&Sons,INC,1965:117-212.
[15]Tao F,Hill L,Peng Y,et al.Synthesis and characterization ofβ-cyclodextrin inclusion complexes of thymol and thyme oil for antimicrobial delivery applications[J].LWT-Food Science and Technology,2014,59(1):247-255.
[16]Rakmai J,Cheirsilp B,Mejuto J,et al.Physico-chemical characterization and evaluation of bio-efficacies of black pepper essential oil encapsulated in hydroxypropyl-beta-cyclodextrin[J].Food Hydrocolloid,2017(65):157-164.
[17]Fang Haiyan(方海燕).Study on inclusion complexation of insoluble drugs withβ-cyclodextrin and its derivatives[D].Changsha:Central south university(中南大学),2014.
[18]Huang Yingxi(黄莹玺),Li Pingpin(李瓶娉),Yin Shanshan(银杉杉),et al.Preparation and characterization of Tamoxifen hydroxypropyl-β-cyclodextrin inclusion complex[J].West China Journal of Pharmaceutical Sciences(华西药学杂志),2014,29(5):503-506.
[19]Karathanos V,Mourtzinos I,Yannakopoulou K,et al.Study of the solubility,antioxidant activity and structure of inclusion complex of vanillin withβ-cyclodextrin[J].Food Chemistry,2007,101(2):652-658.