β-环糊精与香芹酮形成常数的测定及其包合物的制备及表征
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摘要
通过固相微萃取-气相色谱-质谱联用(solid phase micro-extraction-gas chromatography-mass spectrometer,SPME-GC-MS)法测定了β-环糊精在溶液中对香芹酮的保留率及两者之间的形成常数,并用冷冻干燥法制备了β-环糊精与香芹酮的包合物,采用扫描电镜(scanning electron microscopy,SEM)、红外光谱(infrared spectrum,IR)、X-衍射(X-ray diffraction,XRD)及热重分析(thermogravimetric analysis,TGA)对包合物进行结构表征。结果表明,香芹酮与β-环糊精在水溶液中形成了1∶1的包合物,且两者之间的形成常数为1 066. 7 mol~(-1)。冷冻干燥法制备的包合物的包合率为75. 04%,SEM以及XRD分析结果都表明,β-环糊精在包合前后,其晶体形态发生了变化; IR和TG结果证明β-环糊精与香芹酮形成了包合物。由此得出,β-环糊精适合包埋香芹酮,可以提高香芹酮的热稳定性,从而使香芹酮的应用更加广泛。
The retention rate of carvone in β-cyclodextrin solution and the formation constant between these two compounds were determined by SPME-GC-MS. The inclusion complex of β-cyclodextrin and carvone was prepared by freeze-drying method,and it was characterized by scanning electron microscopy(SEM),infrared spectroscopy(IR),X-ray diffraction(XRD) and thermogravimetric analysis(TGA). The results showed that carvone and β-cyclodextrin formed an inclusion complex in a ratio of 1∶ 1 in aqueous solution,and the formation constant was 1 066. 7 mol~(-1). Moreover,the encapsulation efficiency of the complex was 75. 04%,and SEM and XRD showed that the crystal morphology of β-cyclodextrin changed before and after inclusion. Furthermore,IR and TGA also showed that β-cyclodextrin and carvone formed an inclusion complex. Therefore,it can be concluded that β-cyclodextrin is suitable for embedding carvone to improve its thermal stability,which will be beneficial for broadening the application of carvone.
The retention rate of carvone in β-cyclodextrin solution and the formation constant between these two compounds were determined by SPME-GC-MS. The inclusion complex of β-cyclodextrin and carvone was prepared by freeze-drying method,and it was characterized by scanning electron microscopy(SEM),infrared spectroscopy(IR),X-ray diffraction(XRD) and thermogravimetric analysis(TGA). The results showed that carvone and β-cyclodextrin formed an inclusion complex in a ratio of 1∶ 1 in aqueous solution,and the formation constant was 1 066. 7 mol~(-1). Moreover,the encapsulation efficiency of the complex was 75. 04%,and SEM and XRD showed that the crystal morphology of β-cyclodextrin changed before and after inclusion. Furthermore,IR and TGA also showed that β-cyclodextrin and carvone formed an inclusion complex. Therefore,it can be concluded that β-cyclodextrin is suitable for embedding carvone to improve its thermal stability,which will be beneficial for broadening the application of carvone.
引文
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[21]WANG X,LUO Z,XIAO Z.Preparation,characterization,and thermal stability ofβ-cyclodextrin/soybean lecithin inclusion complex[J].Carbohydrate Polymers,2014,101:1 027-1 032.
[22]马君义,张继,王宝生,等.百里香油β-环糊精包合物的制备与表征[J].食品与发酵工业,2012,38(3):95-99.
[23]MENEZES P P,SERAFINI M R,QUINTANS-JU'NIOR LJ,et al.Inclusion complex of(-)-linalool andβ-cyclodextrin[J].Journal of Thermal Analysis and Calorimetry,2014,115(3):2 429-2 437.
[24]YANG Zujin,XIAO Zuobing,JI Hongbing.Solid inclusion complex of terpinen-4-ol/β-cyclodextrin:Kinetic release,mechanism and its antibacterial activity[J].Flavour and Fragrance Journal,2015,30(2):179-187.
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[26]ABARCA R L,RODRGUEZ F J,GUARDA A,et al.Characterization of beta-cyclodextrin inclusion complexes containing an essential oil component[J].Food Chemistry,2016,196:968-975.
[2]钟瑞敏,王羽梅,曾庆孝,等.芳香精油在食品保藏中的应用性研究进展[J].食品与发酵工业,2005,31(3):93-98.
[3]GONG L,LI T,CHEN F,et al.An inclusion complex of eugenol intoβ-cyclodextrin:Preparation,and physicochemical and antifungal characterization[J].Food Chemistry,2016,196:324-330.
[4]ASTRAY G,MEJUTO J C,MORALES J,et al.Factors controlling flavors binding constants to cyclodextrins and their applications in foods[J].Food Research International,2010,43(4):1 212-1 218.
[5]CIOBANU A,LANDY D,FOURMENTIN S.Complexation efficiency of cyclodextrins for volatile flavor compounds[J].Food Research International,2013,53(1):110-114.
[6]KFOURY M,AUEZOVA L,GREGE-GERGES H,et al.Cyclodextrin,an efficient tool for trans-anethole encapsulation:Chromatographic,spectroscopic,thermal and structural studies[J].Food Chemistry,2014,164:454-461.
[7]DECOCK G,FOURMENTIN S,SURPATEANU G,et al.Experimental and theoretical study on the inclusion compounds of aroma components withβ-cyclodextrins[J].Supramolecular Chemistry,2006,18(6):477-482.
[8]MAZZOBRE F M,DOS SANTOS C I,DEL-PILAR-BUERA,M.Solubility and stability ofβ-cyclodextrin-terpineol inclusion complex as affected by water[J].Food Biophysics,2011,6(2):274-280.
[9]LI Jiajia,MAN Dong,LIU Yanlong,et al.Effect of food emulsifiers on aroma release[J].Molecules,2016,21(4):511.
[10]LADAA T I,LEE C M,COATES J T,et al.Cosolvent effects of alcohols on the Henry’s law constant and aqueous solubility of tetrachloroethylene[J].Chemosphere,2001,44(5),1 137-1 143.
[11]BLACH P,FOURMENTIN S,LANDY D,et al.Cyclodextrins:A new efficient absorbent to treat waste gas streams[J].Chemosphere,2008,70(3),374-380.
[12]FOURMENTIN S,OUTIRITE M,BLACH P,et al.Solubilisation of chlorinated solvents by cyclodextrin derivatives.A study by static headspace gas chromatography and molecular modelling[J].Journal of Hazardous Materials,2007,141(1),92-97.
[13]LANDY D,FOURMENTIN S,SALOME M,et al.Analytical improvement in measuring formation constants of inclusion complexes betweenβ-cyclodextrin and phenolic compounds[J].Journal of Inclusion Phenomena and Macrocyclic Chemistry,2000,38(1-4),187-198.
[14]张扬,周裔彬,曹胜男,等.β-和γ-环糊精与丁酸乙酯包合物的制备及结构表征[J].食品与发酵工业,2014,40(9):34-38.
[15]曹胜男.α-、β-环糊精包合丙酸乙酯和戊酸复合物的制备、表征及其释放动力学研究[D].合肥:安徽农业大学,2015.
[16]王艳丽,袁超,刘亚伟.肉桂精油/羟丙基-β-环糊精包合物的表征及成分分析[J].中国食品添加剂,2018(11):56-61.
[17]李萍,舒展,申晓霞,等.超声波法制备八角茴香油-β-环糊精微胶囊及其表征分析[J].食品科学,2017,38(4):243-249.
[18]GUIMARES A G,OLIVEIRA M A,DOS-SAN-TOSALVES R D S,et al.Encapsulation of carvacrol,a monoterpene present in the essential oil of oregano,withβ-cyclodextrin,improves the pharmacological response on cancer pain experimental protocols[J].Chemico-Biological Interactions,2015,227:69-76.
[19]曹胜男,张扬,金姗姗,等.β-环糊精丙酸乙酯包合物的制备及表征[J].食品工业科技,2015,36(20):124-127;132.
[20]张扬.β-、γ-环糊精与丁酸乙酯、己醛、己醇包合物的制备、表征及释放动力学的研究[D].合肥:安徽农业大学,2015.
[21]WANG X,LUO Z,XIAO Z.Preparation,characterization,and thermal stability ofβ-cyclodextrin/soybean lecithin inclusion complex[J].Carbohydrate Polymers,2014,101:1 027-1 032.
[22]马君义,张继,王宝生,等.百里香油β-环糊精包合物的制备与表征[J].食品与发酵工业,2012,38(3):95-99.
[23]MENEZES P P,SERAFINI M R,QUINTANS-JU'NIOR LJ,et al.Inclusion complex of(-)-linalool andβ-cyclodextrin[J].Journal of Thermal Analysis and Calorimetry,2014,115(3):2 429-2 437.
[24]YANG Zujin,XIAO Zuobing,JI Hongbing.Solid inclusion complex of terpinen-4-ol/β-cyclodextrin:Kinetic release,mechanism and its antibacterial activity[J].Flavour and Fragrance Journal,2015,30(2):179-187.
[25]ZHU Xiashi,PING Wenhui.Optimization ofβ-cyclodextrin cross-linked polymer for monitoring of quercetin[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2014,132:38-43.
[26]ABARCA R L,RODRGUEZ F J,GUARDA A,et al.Characterization of beta-cyclodextrin inclusion complexes containing an essential oil component[J].Food Chemistry,2016,196:968-975.