响应面试验优化羟丙基-β-环糊精包合植物甾醇的水溶性改性工艺
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摘要
为增加植物甾醇(phytosterol,PS)的水溶性,拓宽其在食品领域中的应用,本研究采用羟丙基-β-环糊精(hydroxypropyl-β-cyclodextrin,HP-β-CD)对植物甾醇进行包合,达到增大其水溶性的目的。采用差热扫描分析、傅里叶红外光谱和X射线衍射对包合后的产物进行检测。同时,采用单因素和响应面试验对包合工艺进行优化,得到最佳包合工艺为HP-β-CD与PS物质的量比4.27∶1、包合温度47℃、包合时间11.93 h,得到的包合率为96.57%。考虑到实际操作的便利,将其修正为:HP-β-CD与PS物质的量比4.30∶1、包合温度47℃、包合时间12 h,并在此修正条件下进行3次平行实验,其平均包合率为97.25%。结果表明在包合状态下,经改造后的PS在37℃水中的溶解度得到了大幅度提高,达到了8.31 mg/m L,是其原来(0.027 mg/m L)的307.90倍。
In this study, phytosterol(PS) was included with hydroxypropyl-β-cyclodextrin(HP-β-CD) to improve its solubility and thereby broaden the range of its application in the food industry. The inclusion complex was tested by differential scanning calorimetry(DSC), Fourier transform infrared(FT-IR) spectroscopy and X-ray diffraction. The inclusion process was optimized using response surface methodology. The optimum conditions obtained were as follows: molar ratio between PS and HP-β-CD, 4.27:1; temperature, 47 ℃; and inclusion time, 11.93 h, yielding an inclusion rate of 96.57%. However, to improve operating convenience, these parameters were modified as 4.30:1, 47 ℃, and 12 h, respectively. Triplicate experiments carried out under these conditions gave an average inclusion rate of up to 97.25%. At 37 ℃, the water solubility of HP-β-CD/PS clathrate reached an average of 8.31 mg/m L, which was 307.90 times of its original solubility(0.027 mg/m L).
In this study, phytosterol(PS) was included with hydroxypropyl-β-cyclodextrin(HP-β-CD) to improve its solubility and thereby broaden the range of its application in the food industry. The inclusion complex was tested by differential scanning calorimetry(DSC), Fourier transform infrared(FT-IR) spectroscopy and X-ray diffraction. The inclusion process was optimized using response surface methodology. The optimum conditions obtained were as follows: molar ratio between PS and HP-β-CD, 4.27:1; temperature, 47 ℃; and inclusion time, 11.93 h, yielding an inclusion rate of 96.57%. However, to improve operating convenience, these parameters were modified as 4.30:1, 47 ℃, and 12 h, respectively. Triplicate experiments carried out under these conditions gave an average inclusion rate of up to 97.25%. At 37 ℃, the water solubility of HP-β-CD/PS clathrate reached an average of 8.31 mg/m L, which was 307.90 times of its original solubility(0.027 mg/m L).
引文
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[24]GERUO A,WAHR J,ZHONG S.Computations of the viscoelastic response of a 3-D compressible earth to surface loading:an application to glacial isostatic,adjustment in Antarctica and Canada[J].Geophysical Journal International,2013,192(2):557-572.DOI:10.1093/gji/ggs030.
[25]GE Y,WEI B,WANG S,et al.Optimization of anthraquinone dyes decolorization conditions with response surface methodology by Aspergillus[J].Korean Chemical Engineering Research,2015,53(3):327-332.DOI:10.9713/kcer.2015.53.3.327.
[26]胡奕俊,徐妍,马超,等.联苯菊酯-β-环糊精包合物的制备及其光谱研究[J].农药学学报,2010,12(3):92-96.DOI:10.3969/j.issn.1008-7303.2010.03.16.
[27]CHARUMANEE S,OKONOGI S,SIRITHUNYALUG J,et al.Effect of cyclodextrin types and co-solvent on solubility of a poorly water soluble drug[J].Scientia Pharmaceutica,2016,84(4):694-704.DOI:10.3390/scipharm84040694.
[28]代金玲.苯乙酮-β-环糊精包合物的制备及其紫外吸收光谱研究[J].科学技术与工程,2011,11(28):6934-6935.DOI:10.3969/j.issn.1671-1815.2011.28.032.
[29]YUHSIN T,HSIEHHO T,WU C P,et al.Preparation,characterisation and activity of the inclusion complex of paeonol withβ-cyclodextrin[J].Food Chemistry,2010,120(3):837-841.DOI:10.1016/j.foodchem.2009.11.024.
[30]BAI L,ZHAO Q,WANG J,et al.Mechanism study on p H-responsive cyclodextrin capped mesoporous silica:effect of different stalk densities and the type of cyclodextrin[J].Nanotechnology,2015,26(16):165704.DOI:10.1088/0957-4484/26/16/165704.
[2]吕晓玲,温娟,陶东川,等.植物甾醇及其环糊精包合物对高血脂小鼠降血脂实验研究[J].食品工业科技,2011,32(9):393-395.DOI:10.13386/j.issn1002-0306.2011.09.010.
[3]YUE M E,JIANG T F,SHI Y P.?Fast?determination?of?flavonoids?in?Hippophae rhamnoides and its medicinal preparation by capillary zone?electrophoresis?using?dimethyl-beta-cyclodextrin?as?modifier[J].?Talanta,2004,62(4):695-699.DOI:10.1016/j.talanta.2003.09.024.
[4]陈鑫涛,王罗新,蔡静平,等.环糊精在聚合反应中的应用研究进展[J].天津工业大学学报,2010,29(6):54-57.DOI:10.3969/J.ISSN.1671-024X.2010.06.015.
[5]SCHUCHERT A,MUTO C,MAOUNIS T,et al.Lead complications,device infections,and clinical outcomes in the first year after implantation of cardiac resynchronization therapy-defibrillator and cardiac resynchronization therapy-pacemaker[J].EP Europace,2013,15(1):71-76.DOI:10.1093/europace/eus247.
[6]CENSI R,GIGLIOBIANCO M R,DUBBINI A,et al.New nanometric solid dispersions of glibenclamide in neusilin?UFL2[J].Aaps Pharmscitech,2016,17(5):1-9.DOI:10.1208/s12249-015-0457-z.
[7]DI C M,STEIN P C,SKALKOBASNET N,et al.Solubilization of ibuprofen withβ-cyclodextrin derivatives:energetic and structural studies[J].Journal of Pharmaceutical&Biomedical Analysis,2011,55(3):446-451.DOI:10.1016/J.JPBA.2011.02.022.
[8]SZENTE L,SZEJTLI J.Cyclodextrins as food ingredients[J].Trends in Food Science and Technology,2004,15(3/4):137-142.DOI:10.1016/J.TIFS.2003.09.019.
[9]REKHARSKY M V,INOUE Y.Thermodynamics of cucurbituril complexation in aqueous solutions[J].Netsu Sokutei,2007,34(5):232-243.DOI:10.11311/JSCTA1974.34.232.
[10]雍国平,李光水.β-环糊精包合物的结构研究[J].高等学校化学学报,2000,21(7):1124-1126.DOI:10.3321/J.ISSN:0251-0790.2000.07.040.
[11]宋占军,刘炳玉,钱小红,等.应用光谱分析技术研究碘与β-环糊精结合物的结构特征[J].光谱学与光谱分析,2001,21(5):603-606.DOI:10.3321/J.ISSN:1000-0593.2001.05.008.
[12]LI N,ZHANG Y H,WU Y N,e t a l.I n c l u s i o n c o m p l e x o f trimethoprim withβ-cyclodextrin[J].Journal of Pharmaceutical&Biomedical Analysis,2005,39(3/4):824-829.DOI:10.1016/j.jpba.2005.05.011.
[13]余德顺.β-环糊精包埋技术及研究进展[J].重庆理工大学学报(自然科学版),2010,24(11):44-49.DOI:10.3969/j.issn.1674-8425-B.2010.11.009.
[14]GEBREMARIAM M M,ZARNKOW M,BECKER T.Effect of drying temperature and time on alpha-amylase,beta-amylase,limit dextrinase activities and dimethyl sulphide level of teff(Eragrostis tef)malt[J].Food and Bioprocess Technology,2013,6(12):3462-3472.DOI:10.1007/s11947-012-1025-0.
[15]LOFTSSON T,BREWSTER M E.Pharmaceutical applications of cyclodextrins:effects on drug permeation through biological membranes[J].Journal of Pharmacy and Pharmacology,2011,63(9):1119-1135.DOI:10.1111/j.2042-7158.2011.01279.x.
[16]B E T T I N E T T I G P,S O R R E N T I M S,F E R R A R I F,e t a l.Assessment of solid-state interactions of naproxen with amorphous cyclodextrin derivatives by DSC[J].Journal of Pharmaceutical&Biomedical Analysis,2002,30(4):1173-1179.DOI:10.1016/S0731-7085(02)00421-1.
[17]ROCHA B A,RODRIGUES M R,BUENO P C P,et al.Preparation and thermal characterization of inclusion complex of Brazilian green propolis and hydroxypropyl-β-cyclodextrin[J].Journal of Thermal Analysis and Calorimetry,2012,108(1):87-94.DOI:10.1007/s10973-011-1713-4.
[18]张境,刘万毅,张霞.β-环糊精-苯甲酰二茂铁缩氨基硫脲包合物特征及微环境效应研究[J].光谱学与光谱分析,2006,26(3):517-521.DOI:10.3321/J.ISSN:1000-0593.2005.10.009.
[19]AMMAR H O,SALAMA H A,GHORAB M,et al.Formulation and biological evaluation of glimepiride-cyclodextrin-polymer systems[J].International Journal of Pharmaceutics,2006,309(1/2):129-138.DOI:10.1016/j.ijpharm.2005.11.024.
[20]LI W,LU B,SHENG A,et al.Spectroscopic and theoretical study on inclusion complexation of beta-cyclodextrin with permethrin[J].Journal of Molecular Structure,2010,981(1/2/3):194-203.DOI:10.1016/j.molstruc.2010.08.008.
[21]周阳.植物甾烷醇油溶性及水溶性的改性研究[D].无锡:江南大学,2013:34-35.
[22]PARLAK O,ZORBA O,KURT S.Modelling with response surface methodology of the effects of egg yolk,egg white and sodium carbonate on some textural properties of beef patties[J].Journal of Food Science&Technology,2014,51(4):780-784.
[23]YU Z J,FISHER K C,WHEELWRIGHT B M,et al.PVMirror:a new concept for tandem solar cells and hybrid solar converters[J].Photovoltaics IEEE Journal of Photovoltaics,2015,5(6):1791-1799.DOI:10.1109/JPHOTOV.2015.2458571.
[24]GERUO A,WAHR J,ZHONG S.Computations of the viscoelastic response of a 3-D compressible earth to surface loading:an application to glacial isostatic,adjustment in Antarctica and Canada[J].Geophysical Journal International,2013,192(2):557-572.DOI:10.1093/gji/ggs030.
[25]GE Y,WEI B,WANG S,et al.Optimization of anthraquinone dyes decolorization conditions with response surface methodology by Aspergillus[J].Korean Chemical Engineering Research,2015,53(3):327-332.DOI:10.9713/kcer.2015.53.3.327.
[26]胡奕俊,徐妍,马超,等.联苯菊酯-β-环糊精包合物的制备及其光谱研究[J].农药学学报,2010,12(3):92-96.DOI:10.3969/j.issn.1008-7303.2010.03.16.
[27]CHARUMANEE S,OKONOGI S,SIRITHUNYALUG J,et al.Effect of cyclodextrin types and co-solvent on solubility of a poorly water soluble drug[J].Scientia Pharmaceutica,2016,84(4):694-704.DOI:10.3390/scipharm84040694.
[28]代金玲.苯乙酮-β-环糊精包合物的制备及其紫外吸收光谱研究[J].科学技术与工程,2011,11(28):6934-6935.DOI:10.3969/j.issn.1671-1815.2011.28.032.
[29]YUHSIN T,HSIEHHO T,WU C P,et al.Preparation,characterisation and activity of the inclusion complex of paeonol withβ-cyclodextrin[J].Food Chemistry,2010,120(3):837-841.DOI:10.1016/j.foodchem.2009.11.024.
[30]BAI L,ZHAO Q,WANG J,et al.Mechanism study on p H-responsive cyclodextrin capped mesoporous silica:effect of different stalk densities and the type of cyclodextrin[J].Nanotechnology,2015,26(16):165704.DOI:10.1088/0957-4484/26/16/165704.