蜂蜜酚类化合物的色谱分析及其电喷雾质谱裂解途径的研究
|
摘要
本论文采用高效液相色谱-电化学检测法(HPLC-ECD)和高效液相色谱-电喷雾质谱法(HPLC-ESI-MS),建立了蜂蜜酚类化合物的色谱分析新方法,并采用量子化学理论,计算解析了4种黄酮类化合物的质谱裂解过程。全文共分五章,作者的主要工作有以下几点:
1.建立了蜂蜜中苯酚和百里酚的HPLC-DAD-ECD分析新方法。两种酚类化合物在电化学检测器上的检出限分别为2.0ng/g和12.5ng/g,与紫外检测器相比,检出限分别低400和800倍。该方法无需对蜂蜜样品进行富集处理即可进行定量分析,具有样品处理简单,测定时间短,误差来源少等优点。
2.通过对色谱柱、流动相、工作电压以及分离条件的筛选和优化,建立了同时测定柑橘蜜中咖啡酸、p-香豆酸、阿魏酸和橙皮素等4种酚类化合物的HPLC-ECD新方法。实验表明:4种酚类化合物的线性相关系数均大于0.9993,回收率在98.9%～100.3%之间,相对标准偏差(RSD)在1.1%～1.8%范围内。与传统方法比较,该方法简便、快速、准确、灵敏度高。
3.建立了快速、准确测定向日葵蜜中没食子酸、咖啡酸、p-香豆酸、阿魏酸、杨梅酮、槲皮素、山奈酚和高良姜素等8种酚类化合物的HPLC-DAD-ECD分析新方法,且8种酚类化合物的电化学检测器的检出限在1.0×10~(-3)μg/mL～2.9×10~(-3)μg/mL之间,均低于紫外检测器的检出限(3.1×10~(-2)μg/mL～9.7×10~(-2)μg/mL)。
4.依据密度泛函理论,采用高斯(Gaussian)程序中的ROB3LYP/6-311++G(2d,2p)∥B3LYP/6-31G(d)方法,研究了芹菜素、白杨素、山奈酚和高良姜素等4种黄酮类化合物的电喷雾质谱裂解过程。通过计算上述化合物在裂解过程中各碎片离子的单点能、零点振动能和键断裂能,推导得出了芹菜素、白杨素、山奈酚和高良姜素的质谱裂解途径。
In this thesis,high performance liquid chromatography with electrochemical detection (HPLC-ECD) and electrospray ionization tandem mass spectrometry(HPLC-ESI-MS) are used in the analysis of phenolic compounds in Chinese honey,and quantum chemistrycalculation method is applied to analyze the fragmentation pathways of four flavonoid compounds.The thesis consists of five chapters,the main contributions are summarized and presented as follows:
1.A simple and rapid method for the determination of phenol and thymol in honey by high performance liquid chromatography using combined electrochemical detection with diode array detection(HPLC-ECD-DAD) has been established.The limit of detections(LODs) for phenol and thymol are determined to be 2.0 ng/g and 12.5 ng/g,respectively.The sensitivity detected by ECD is 400-800 folds higher than that obtained by DAD.The method simplifies the sample treatment,decreases the determination time,reduces the error origins and makes samples be analyzed directly without enrichment.
2.The HPLC-ECD method for the determination of four kinds of phenolic compounds (caffeic acid,p-coumaric acid,ferulic acid,hesperetin) in Chinese citrus honey by testing the chromatographic column,mobile phase,potential and separation condition has been founded. The experiment results indicate that the four phenolic compounds show good linearity (r＞0.9993),with the recoveries ranging from 98.9%to 100.3%and RSDs from 1.1%to 1.8%. This method is more simple,rapid,accurate and sensitive compared with the traditional methods.
3.The rapid and accurate method for the simultaneous separation and determination of eight phenolic compounds,including gallic acid,caffeic acid,p-coumaric acid,ferulic acid, myricetin,quercetin,kaempferol and galangin in Chinese sunflower honey by HPLC-ECD-DAD has been established.The detection limits of the eight phenolic compounds by ECD range from 1.0×10~(-3)μg/mL to 2.9×10~(-3)μg/mL,much lower than that by DAD(3.1×10~(-2) μg/mL to 9.7×10~(-2)μg/mL).
4.The fragmentations of apigenin,chrysin,galangin and kaempferol are analyzed by ESI-MS and Gaussian program on the basis of Density Functional Theory(DFT) at ROB3LYP/6-311 ++ G(2d,2p)//B3LYP/6-31G(d) level.The single-point energy(SPE), zero-point vibrational energy(ZPVE) and bond dissociation energy(BDE) are calculated in order to deduce the detail fragmentation pathways.
1.建立了蜂蜜中苯酚和百里酚的HPLC-DAD-ECD分析新方法。两种酚类化合物在电化学检测器上的检出限分别为2.0ng/g和12.5ng/g,与紫外检测器相比,检出限分别低400和800倍。该方法无需对蜂蜜样品进行富集处理即可进行定量分析,具有样品处理简单,测定时间短,误差来源少等优点。
2.通过对色谱柱、流动相、工作电压以及分离条件的筛选和优化,建立了同时测定柑橘蜜中咖啡酸、p-香豆酸、阿魏酸和橙皮素等4种酚类化合物的HPLC-ECD新方法。实验表明:4种酚类化合物的线性相关系数均大于0.9993,回收率在98.9%～100.3%之间,相对标准偏差(RSD)在1.1%～1.8%范围内。与传统方法比较,该方法简便、快速、准确、灵敏度高。
3.建立了快速、准确测定向日葵蜜中没食子酸、咖啡酸、p-香豆酸、阿魏酸、杨梅酮、槲皮素、山奈酚和高良姜素等8种酚类化合物的HPLC-DAD-ECD分析新方法,且8种酚类化合物的电化学检测器的检出限在1.0×10~(-3)μg/mL～2.9×10~(-3)μg/mL之间,均低于紫外检测器的检出限(3.1×10~(-2)μg/mL～9.7×10~(-2)μg/mL)。
4.依据密度泛函理论,采用高斯(Gaussian)程序中的ROB3LYP/6-311++G(2d,2p)∥B3LYP/6-31G(d)方法,研究了芹菜素、白杨素、山奈酚和高良姜素等4种黄酮类化合物的电喷雾质谱裂解过程。通过计算上述化合物在裂解过程中各碎片离子的单点能、零点振动能和键断裂能,推导得出了芹菜素、白杨素、山奈酚和高良姜素的质谱裂解途径。
In this thesis,high performance liquid chromatography with electrochemical detection (HPLC-ECD) and electrospray ionization tandem mass spectrometry(HPLC-ESI-MS) are used in the analysis of phenolic compounds in Chinese honey,and quantum chemistrycalculation method is applied to analyze the fragmentation pathways of four flavonoid compounds.The thesis consists of five chapters,the main contributions are summarized and presented as follows:
1.A simple and rapid method for the determination of phenol and thymol in honey by high performance liquid chromatography using combined electrochemical detection with diode array detection(HPLC-ECD-DAD) has been established.The limit of detections(LODs) for phenol and thymol are determined to be 2.0 ng/g and 12.5 ng/g,respectively.The sensitivity detected by ECD is 400-800 folds higher than that obtained by DAD.The method simplifies the sample treatment,decreases the determination time,reduces the error origins and makes samples be analyzed directly without enrichment.
2.The HPLC-ECD method for the determination of four kinds of phenolic compounds (caffeic acid,p-coumaric acid,ferulic acid,hesperetin) in Chinese citrus honey by testing the chromatographic column,mobile phase,potential and separation condition has been founded. The experiment results indicate that the four phenolic compounds show good linearity (r＞0.9993),with the recoveries ranging from 98.9%to 100.3%and RSDs from 1.1%to 1.8%. This method is more simple,rapid,accurate and sensitive compared with the traditional methods.
3.The rapid and accurate method for the simultaneous separation and determination of eight phenolic compounds,including gallic acid,caffeic acid,p-coumaric acid,ferulic acid, myricetin,quercetin,kaempferol and galangin in Chinese sunflower honey by HPLC-ECD-DAD has been established.The detection limits of the eight phenolic compounds by ECD range from 1.0×10~(-3)μg/mL to 2.9×10~(-3)μg/mL,much lower than that by DAD(3.1×10~(-2) μg/mL to 9.7×10~(-2)μg/mL).
4.The fragmentations of apigenin,chrysin,galangin and kaempferol are analyzed by ESI-MS and Gaussian program on the basis of Density Functional Theory(DFT) at ROB3LYP/6-311 ++ G(2d,2p)//B3LYP/6-31G(d) level.The single-point energy(SPE), zero-point vibrational energy(ZPVE) and bond dissociation energy(BDE) are calculated in order to deduce the detail fragmentation pathways.
引文
[1]Amoros M.,Lurton E.,Boustie J.,et al.Comparison of the Anti-herpes Simplex Virus Activities of Propolis and 3-methylbut-2-enyl caffeate[J].Journal of Natural Products,1994,64:235-240
[2]Katirciogul H.,Mercan N.Antimicrobial Activity and Chemical Compositions of Turkish Propolis from Different Regions[J].African Journal of Biotechnology,2006,5:1151-1153
[3]Kahkonen M.P.,Hopia A.I.,Vuorela H.J.,et al.Antioxidant Activity of Plant Extracts Containing Phenolic Compounds[J].Journal Agricultural and Food Chemistry,1999,47:3954-3962
[4]Li H.B.,Wong C.C.,Cheng K.W.,et al.Antioxidant Properties in Vitro and Total Phenolic Contents in Methanol Extracts from Medicinal Plants[J].LWT-Food Science and Technology,2008,41:385-390
[5]Sanchez-Moreno C.Methods Used to Evaluate the Free Radical Scavenging Activity in Foods and Biological Systems[J].Food Science Technology International,2002,8:121-137
[6]Yao L.H.,Jiang Y.M.,Singanusong R.T.,et al.Phenolic Acids in Australian Melaleuca,Guioa,Lophostemon,Banksia and Helianthus Honeys and their Potential for Floral Authentication[J].Food Research International,2005,38:651-658
[7]Schuster B.,Herrmann K.Hydroxybenzoic and Hydroxycinnamic Acid Derivatives in Soft Fruits[J].Phytochem,1985,24:2761-2764
[8]刘琳.多酚化合物的高效液相色谱-安培检测方法研究[D].陕西:西北大学,2006
[9]Silva E.M.,Souza J.N.S.,Rogez H.,et al.Antioxidant Activities and Polyphenolic Contents of Fifteen Selected Plant Species from the Amazonian Region[J].Food Chemistry,2007,101:1012-1018
[10]Hagen S.F.,Borge G.I.A.,Bengtsson G.B.,et al.Phenolic Contents and Other Health and Sensory Related Properties of Apple Fruit(Malus domestica Borkh.,cv.Aroma):Effect of Postharvest UV-B Irradiation[J].Postharvest Biology and Technology,2007,45(1):1-10
[11]Zheng J.B.,Suo Z.R.,Liu L.Simultaneous Determination of Four Phenolic Compounds and Tanshione ⅡA in Guanxintong Tablets by LC Using Combined Electrochemical Detection and DAD [J].Chromatographia,2006,63:39-44
[12]刘琳,索志荣,郑建斌.高效液相色谱-二极管阵列检测-电化学检测联用技术同时测定三精双黄连口服液中四种化合物[J].色谱,2006,3:247-250
[13]梁艳,于世峰,陈卫军,等.色谱分析法在蜂蜜农药残留测定中的研究进展[J].中国蜂业,2008,59(6):12-14
[14]李福娟,蔡文生,邵学广.反相高效液相色谱法分离测定烟草中9种多酚类化合物[J].色谱,2007,25(4):564-568
[15]Kumazawa S.,Hamasaka T.,Nakayama T.Antioxidant Activity of Propolis of Various Geographic Origins[J].Food Chemistry,2004,84:329-339
[16]Cabanero A.I.,Recio J.L.,REZ R.R.Liquid Chromatography Coupled to Isotope Ratio Mass Spectrometry:A New Perspective on Honey Adulteration Detection[J].Journal Agricultural and Food Chemistry,2006,54:9719-9727
[17]Huang Z.L.,Wang B.W.,Eaves D.H.,et al.Phenolic Compound Profile of Selected Vegetables Frequently Consumed by African Americans in The Southeast United States[J].Food Chemistry,2007,103:1395-1402
[18]Radovic B.S.,Goodacre R.,Anklam E.Contribution of Pyrolysis-Mass Spectrometry(Py-Ms) to Authenticity Testing of Honey[J].Journal of analytical and pyrolysis,2001,60:79-87
[19]Duenasa M.,Hernandeza T.,Estrella I.,et al.Phenolic Composition and Antioxidant Activity of Mocan Seeds(Visnea mocanera L.f)[J].Food Chemistry,2003,82:373-379
[20]Fang Z.X.,Zhang M.,Wang L.X.HPLC-DAD-ESIMS Analysis of Phenolic Compounds in Bayberries(Myrica rubra Sieb.et Zucc.)[J].Food Chemistry,2007,100:845-852
[21]Volpi N.,Bergonzini G.Analysis of Flavonoids from Propolis by On-line HPLC-Electrospray Mass Spectrometry[J].Journal of Pharmaceutical and Biomedical Analysis,2006,42:354-36
[22]Maksimovic Z.,Malencic D.,Kovacevic N.Polyphenol Contents and Antioxidant Activity of Maydis Stigma Extracts[J].Bioresource Technology,2005,96:873-877
[23]Singleton V.L.,Orthofer R.,Lamuela-Raventos R.M.Analysis of Total Phenols and Other Oxidation Substrates and Antioxidants by Means of Folin-Ciocalteau Reagent[J].Methods of Enzymology,1999,299:152-178
[24]D'Arcy B.R,Rintoul G.B.,Rowland C.Y.Composition of Australian Honey Extractives.1.Norisoprenoids,Monoterpenes,and Other Natural Volatiles from Blue Gum(Eucalyptus leucoxylon)and Yellow Box(Eucatlypus melliodora) Honeys[J].Journal Agricultural and Food Chemistry,1997,45:1834-1843
[25]Castro-Vazquez L.,Draz-Maroto M.C.,Perez-Coello M.S.Aroma Composition and New Chemical Markers of Spanish Citrus Honeys[J].Food Chemistry,2007,103:601-606
[26]Corbella E.,Cozzolino D.Classification of The Floral Origin of Uruguayan Honeys by Chemical and Physical Characteristics Combined with Chemometrics[J].LWT,2006,39:534-539
[27]Ferreres F.,Garcia-Viguera C.,Tomas-Lorente F.,et al.Hesperetin:A Marker of the Floral Origin of Citrus Honey[J].Journal of the Science of Food and Agriculture,1993,61:121-123
[28]Gheldof N.,Wang X.F.,Engeseth N.J.Identification and Quantification of Antioxidant Components of Honeys from Various Floral Sources[J].Journal of Agricultural and Food Chemistry,2002,50:5870-5877
[29]单丽娜,谭洪涛,陈洪.分光光度法测定蜂胶中总黄酮质量分数的不确定度[J].江西化工,2006,3:122-123
[30]庆伟霞.几种天然黄酮类化合物的电化学检测方法研究[D].河南:河南大学,2007
[31]Jia Z.S.,Tang M.C.,Wu J.M.The Determination of Flavonoid Contents in Mulberry and Their Scavenging Effects on Superoxide Radicals[J].Food Chemistry,1999,64:555-559
[32]Carmona M.,Sanchez A.M.,Ferreres F.,et al.Identification of the Flavonoid Fraction in Saffron Spice by LC/DAD/MS/MS:Comparative Study of Samples from Different Geographical Origins[J].Food Chemistry,2007,100:445-450
[33]赵霖.蜂蜜代糖,有益健康[J].科学养生,2006,1:25
[34]杨玉凤,李小玲,刘剑霞,等.固体蜂蜜加工技术[J].中小企业科技,2006,2:47
[35]赵建军.蜂蜜[J].中华实用中西医杂志,2001,14(8):1918
[36]王文静.洋槐蜂蜜HPLC指纹图谱的研究[D].重庆:西南大学,2008
[37]Francisco A.,Isabel M.,Federico F.HPLC Flavornoid Profiles as Markers for the Botanical Origin of European Unifloral Honeys[J].Journal of Science and Food Agricultural,2001,81:485-496
[38]陈兰珍,叶志华,赵静,蜂蜜品种鉴别技术研究进展[J].食品科学,2008,29(3):494-498
[39]曹炜,陈卫军,宋纪蓉.不同种类蜂蜜总酚酸含量测定和抗氧化作用的研究[J].食品科学,2005,26(1):48-51
[40]Mohamed A.M.,Ali A.M.,Molham A.H.Antioxidant Activities and Total Phenolics of Different Types of Honey[J].Nutrition Research,2002,22:1041-1047
[41]苟小锋,曹炜,索志荣.荞麦蜜酚酸含量的高效液相色谱测定及其抗氧化作用的研究[J].食品科学,2004,25(10):254-258
[42]Martos I.,Ferreres F.,Yao L.,et al.Flavonoids in monospecific Eucalyptus honeys from Australia[J].Journal of Agricultural and Food Chemistry,2000,48:4744-4748
[43]Andrade P.,Ferreres F.,Gil M.I.,et al.Determination of Phenolic Compounds in Honeys with Different Floral Origin by Capillary Zone Electrophoresis[J].Food Chemistry,1997,60(1):79-84
[44]Yao L.H.,Jiang Y.M.,D'Arcy,B.R.,et al.Quantitative High-Performance Liquid Chromatography Analyses of Flavonoids in Australian Eucalyptus Honeys[J].Journal of Agricultural and Food Chemistry,2004,52:210-214
[45]Fiorani M.,Accorsi A.,Blasa M.,et al.Flavonoids from Italian Multifloral Honeys Reduce the Extracellular Ferricyanide in Human Red Blood Cells[J].Journal of Agricultural and Food Chemistry,2006,54:8328-8334
[46]Liang Y.,Cao W.,Chen W.J.,et al.Simultaneous Determination of Four Phenolic Components in Citrus Honey by High Performance Liquid Chromatography Using Electrochemical Detection[J].Food Chemistry,2009,114:1537-1541
[47]Roderick J.W.,Kevin R.M.,Kerry L.A.Antibacterial Phenolic Components of New Zealand Manuka Honey[J].Food Chemistry,1999,64:295-301
[48]Alissandrakis E.,Tarantilis P A,Harizanis P C,et al.Aroma Investigation of Unifloral Greek Citrus Honey Using Solid-phase Microextraction Coupled to Gas Chromatographic-Mass Spectrometric Analysis[J].Food Chemistry,2007,100:396-404
[49]Ferreres F.,Amparo Blazquez A.,Gil M.I.,et al.A Separation of Honey Flavonoids by Micellar Electrokinetic Capillary Chromatography[J].Journal of Chromatography A,1994,669:268-274
[50]Yao L.H.,Dattaa N.,Tomas-Barberan F.A.,et al.Flavonoids,Phenolic Acids and Abscisic Acid in Australian and New Zealand Leptospermum Honeys[J].Food Chemistry,2003,81:159-168
[51]Tomas-Barberan F.A.,Martos I.,Ferreres F.,et al.HPLC Flavonoid Profiles as Markers for the Botanical Origin of European Unifloral Honeys[J].Journal of the Science of Food and Agriculture,2001,81:485-496
[52]Zheng J.B,Liu X.X.,Zhou Y.Z.,et al.Simultaneous Determination of Five Phenolic Compounds in Dried Flowers by High Performance Liquid Chromatography Using Combining Electrochemical Detection with Diode Array Detection[J].Chromatographica,2007,65:707-712
[53]Shui G.H.,Peng L.L.An Improved Method for the Analysis of Major Antioxidants of Hibiscus Esculentus Linn[J].Journal of Chromatography A,2004,1048:17-24
[54]李启隆,胡劲波.电分析化学[M].北京:北京师范大学出版社,2007:467-470
[55]云自厚,欧阳津,张晓彤.液相色谱检测方法(第二板)[M].北京:化学工业出版社,2006:113-137
[56]刘晓莉.十一种酚类化合物的高效液相色谱测定方法研究[D].陕西:西北大学,2008
[57]刘晓星,温普红,郑建斌.高效液相色谱—二极管阵列—电化学联用技术测定八角莲中3种成分的含量[J]_药物分析杂志,2005,25(12):1547-1549
[58]索志荣,曹炜,秦海燕,等.葡萄酒中7种酚酸的色谱电化学分析[J].高等学校化学学报,2005,26(8):1424-1427
[59]Yu X.Y.,Xu X.,Chen Z.ESI-MS and Theoretical Study on the Coordination Structures and Reaction Modes of the Diperoxovanadate Complexes Containing Histidine-like Ligands[J].International Journal of Mass Spectrometry,2008,269:138-144
[60]李宇航,戴海学,李晓蓉,等.葛根素的电喷雾电离裂解规律解析[J].质谱学报,2007,28(4):224-228
[61]Zayed M.A.,Fahmey M.A.,Hawash M.A.,et al.Mass Spectrometric Investigation of Buspirone Drug in Comparison with Thermal Analyses and MO-Calculations[J].Spectrochimica Acta Part A,2007,67:522-530
[62]Bythell B.J.,Barofsky D.F.,Pingitore F.,et al.Backbone Cleavages and Sequential Loss of Carbon Monoxide and Ammonia from Protonated AGG:A Combined Tandem Mass Spectrometry,Isotope Labeling,and Theoretical Study[J].Journal of the American Society for Mass Spectrometry,2007,18:1291-1303
[63]Castro-Vazquez L.,Diaz-Maroto M.C.,Perez-Coello M.S.Aroma Composition and New Chemical Markers of Spanish Citrus Honeys[J].Food Chemistry,2007,103:601-606
[64]D'Arcy B.R.,Rintoul G.B.,Rowland C.Y.,et al.Composition of Australian Honey Extractives.1. Norisoprenoids,Monoterpenes,and Other Natural Volatiles from Blue Gum(Eucalyptus leucoxylon)and Yellow Box(Eucalyptus melliodora) Honeys[J].Journal of Agricultural and Food Chemistry,1997,45:1834-1843
[65]Beales K.E.,Betteridge K.,Colegate S.,et al.Solid-Phase Extraction and LC-MS Analysis of Pyrrolizidine Alkaloids in Honeys[J].Journal of Agricultural and Food Chemistry,2004,52:6664-6672
[66]Martos I.,Cossentini M.,Ferreres F.,et al.Flavonoid Composition of Tunisian Honeys and Propolis[J].Journal of Agricultural and Food Chemistry,1997,45:2824-2829
[67]陈卫军.酚类化合物抗氧化机理分析及新型抗氧化剂合成思路的理论研究[D].陕西:西北大学,2007
[68]孙少芳.槲皮素-铬(Ⅲ)离子络合物结构及抗氧化性的理论与实验研究[D].陕西:西北大学,2008
[69]廖沐真.量子化学从头计算方法[M].北京:清华大学出版社,1984:26-33
[70]梁文平.新世纪的物理化学[M].北京:科技出版社,2004:108-119
[71]陈念贻.计算化学及其应用[M].北京:北京师范大学出版社,292-321
[72]许海棠.高效液相色谱-质谱法在中成药分析中的应用研究[D].广西:广西大学,2008
[73]Jones R.O.,Gunnarsson O.The Density Functional Formalism,it's Application and Propects[J].Review of Modern Physics,1989,61:689
[74]Yuan L.F.,Yang J.L.,Li Q.X.,et al.A First-Principles Study of Acetylene and it's Evolution Products on Cu(001)[J].Journal of Chemical Physics,2002,116:3104
[75]Dai B.,Dong K.W.,Yang J.L.,et al.Excited States of 3d Transition Metal Monoxides[J].Journal of Chemical Physics,2003,118:9608
[76]Li Z.Y.,Yang J.L.,Hou J.G.,et al.Inorganic Electrode:Theoretical Study on Structural and Electronic Properties[J].Journal of the American Chemical Society,2003,125:6050
[77]Frisch M.J.,Trucks G.W.,Schlegel H.B.,et al.GAUSSIAN 03(B.05)[S].Pittsburgh:Gaussian,Inc.,PA,2003
[1]查玉兵,陈美,王晓芳,等.农药残留分析技术研究进展[J].安徽农业科学,2007,35(23):7252-7253.7256
[2]刘爱红,张琳.农药残留与食品安全[J].安徽农业科学,2007,35(13):4017-4018
[3]2001/110/EC.Council Directive 2001/110/EC Relating to Honey[S].Europe,2001
[4]美国食品与药物管理部门.农药允许量.(http://www.cfsan.fda.gov)
[5]Gyorik M.,Herpai Z.,Szecsenyi I.,et al.Rapid and Sensitive Determination of Phenol in Honey by High-Performance Liquid Chromatography with Fluorescence Detection[J].Journal of Agricultural and Food Chemistry,2003,51(18):5222-5225
[6]Bogdanov S.,Imdorf A.,Kilchenmann V.Residues in Wax and Honey after Apilife VAR Treatment[J].Apidologie,1998,29:513-524
[7]Gyorik M.,Herpai Z.,Szecsenyi I.,et al.Rapid and Sensitive Determination of Phenol in Honey by High-Performance Liquid Chromatography with Fluorescence Detection[J].Journal of Agricultural and Food Chemistry,2003,51(18):5222-5225
[8]Takeba K.,Matsumoto M.,Shida Y.,et al.Determination of Phenol in Honey by Liquid Chromatography with Amperometric Detection[J].Journal of the Association of Official Analytical Chemists,1990,73(4):602-605
[9]Nozal M.J.,Bemal J.L.,Jimenez J.J.,et al.Extraction of Thymol,Eucalyptol,Mtography with Flame Ionization Detection[J].Journal of Chromatography A,2002,954:207-215
[10]蜂蜜中苯酚残留量的测定方法.液相色谱法.蜂产品标准汇编.北京:中国标准出版社,2003:299-305
[1]Corbella E.,Cozzolino D.Classification of the Floral Origin of Uruguayan Honeys by Chemical and Physical Characteristics Combined with Chemometrics[J].LWT,2006,39:534-539
[2]Tewari J.C.,Imdayaraj J.M.K.Floral Classification of Honey Using Mid-Infrared Spectroscopy and Surface Acoustic Wave Based z-Nose Sensor[J].Journal of Agricultural and Food Chemistry,2005,53:6955-6966
[3]Alissandrakisa E.,Dafererab D.,Tarantilisb P.A.,et al.Ultrasound-assisted Extraction of Volatile Compounds from Citrus Flowers and Citrus Honey[J].Food Chemistry,2003,82:575-582
[4]Martos I.,Ferreres F.,Yao L.,et al.Flavonoids in Monospecific Eucalyptus Honeys from Australia[J]. Journal of Agricultural and Food Chemistry, 2000, 48: 4744-4748
[5] Ferreres F., Tomas-Barberan F. A., Soler C., et al. A Simple Extractive Technique for Honey Flavonoid HPLC Analysis [J]. Apidologie, 1994, 25(1): 21-30
[6] Tomas-Barberan F. A., Martos I., Ferreres F., et al. HPLC Flavonoid Profiles As Markers for the Botanical Origin of European Unifloral Honeys [J]. Journal of the Science of Food and Agriculture, 2001,81:485-496
[7] Xie M. X., Xu X. Y., Wang Y. D. Interaction between Hesperetin and Human Serum Albumin Revealed by Spectroscopic Methods [J]. Biochimica Biophysica Acta, 2005, 1724: 215-224
[8] Wilcox L. J., Borradaile N. M., Dreu L. E., et al. Secretion of Hepatocyte ApoB is Inhibited by the Flavonoids, Naringenin and Hesperetin, via Reduced Activity and Expression of ACAT2 and MTP [J]. Journal of Lipid Research, 2001, 42: 725-734
[9] Jin Y. R., Han X. H., Zhang Y. H., et al. Antiplatelet Activity of Hesperetin, A Bioflavonoid, Is Mainly Mediated by Inhibition of PLC-γ2 Phosphorylation and Cyclooxygenase-1 Activity [J]. Atherosclerosis, 2007, 194: 144-152
[10] Scholz E.P., Zitron E., Kiesecker C., et al. Orange Flavonoid Hesperetin Modulates Cardiac hERG Potassium Channel via Binding to Amino Acid F656 [J]. Nutrition, Metabolism & Cardiovascular Diseases, 2007, 17: 666-675
[11] Yao L. H., Jiang Y. M., Singanusong R. T., et al. Phenolic Acids and Abscisic Acid in Australian Eucalyptus Honeys and their Potential for Floral Authentication [J]. Food Chemistry, 2004, 86: 169-177
[12] Martos I., Cossentini M., Ferreres F., et al. Flavonoid Composition of Tunisian Honeys and Propolis[J]. Journal of Agricultural and Food Chemistry, 1997,45: 2824-2829
[13] Gheldof N., Wang X. F., Engeseth N. J. Identification and Quantification of Antioxidant Components of Honeys from Various Floral Sources [J]. Journal of Agricultural and Food Chemistry, 2002, 50: 5870-5877
[14] Yao L. H., Jiang Y. M., Singanusong R. T., et al. Phenolic Acids in Australian Melaleuca, Guioa, Lophostemon, Banksia and Helianthus Honeys and Their Potential for Floral Authentication [J]. Food Research International, 2005, 38: 651-658.
[15] Castro-Vazquez L., Draz-Maroto M. C., Perez-Coello M. S. Aroma Composition and New Chemical Markers of Spanish Citrus Honeys [J]. Food Chemistry, 2007, 103: 601-606
[16]Alissandrakis E.,Tarantilis P.A.,Harizanis P.C.,et al.Aroma Investigation of Unifloral Greek Citrus Honey Using Solid-phase Microextraction Coupled to Gas Chromatographic-mass Spectrometric Analysis[J].Food Chemistry,2007,100:396-404
[17]Tananaki C.,Thrasyvoulou A.,Giraudel J.L.,et al.Determination of Volatile Characteristics of Greek and Turkish Pine Honey Samples and Their Classification by Using Kohonen Self Organising Maps [J].Food Chemistry,2007,101:1687-1693
[18]Gonzalez Paramas A.M.,Gomez Barez J.A.,Marcos C.C.,et al.HPLC-Fluorimetric Method for Analysis of Amino Acids in Products of the Hive(honey and bee-pollen)[J].Food Chemistry,2006,95:148-156
[19]Patsias J.,Papadopoulou M.E.Development of An Automated On-line Solid-phase Extraction -high-performance Liquid Chromatographic Method for the Analysis of Aniline,Phenol,Caffeine and Various Selected Substituted Aniline and Phenol Compounds in Aqueous Matrices[J].Journal of Chromatography A,2000,904:171-188
[20]Vanbeneden N.,Delvaux F.,Delvaux F.R.Determination of Hydroxycinnamic Acids and Volatile Phenols in Wort and Beer by Isocratic High-Performance Liquid Chromatography Using Electrochemical Detection[J].Journal of Chromatography A,2006,1136:237-242
[21]Ferreres F.,Garcia-Viguera C.,Tomás-Lorente F.,et al.Hesperetin:A Marker of the Floral Origin of Citrus Honey[J].Journal of the Science of Food and Agriculture,1993,61:121-123
[22]D'Arcy B.R.Antioxidants in Australian Floral Honeys-Identification of Health-enhancing Nutrient Components[M].Australia:Rural Industries Research and Development Corporation,2005:37-42
[23]索志荣.液相色谱电化学检测方法及其应用[D].西安:西北大学,2007
[1]Al-Mamary M.,Al-Meeri A.,AI-Habori M.Antioxidant Activities and Total Phenolics of Different Types of Honey[J].Nutrition Research,2002,22:1041-1047
[2]D'Arcy B.R.Antioxidants in Australian Floral Honeys-Identification of Health-Enhancing Nutrient Components[M].Australia:Rural Industries Research and Development Corporation,2005:37-42
[3]Tomás-Barberán F.A.,Martos I.,Ferreres F.,et al.HPLC Flavonoid Profiles as Markers for the Botanical Origin of European Unifloral Honeys[J].Journal of the Science of Food and Agriculture,2001,81:485-496
[4] Ferreres F., Andrade P., Tomas-Barberan F. A. Natural Occurrence of Abscisic Acid in Heather Honey and Floral Nectar [J]. Journal of Agricultural and Food Chemistry, 1996,44: 2053-2056
[5] Martos I., Ferreres F., Yao L., et al. Flavonoids in Monospecific Eucalyptus Honeys from Australia [J]. Journal of Agricultural and Food Chemistry, 2000,48: 4744-4748
[6] Andrade P., Ferreres F., Gilb M. I., et al. Determination of Phenolic Compounds in Honeys with Different Floral Origin by Capillary Zone Electrophoresis [J]. Food Chemistry, 1997, 60(1): 79-84
[1]陈兰慧,金莲姬,苏忠民,等.乌头碱类生物碱电喷雾串联质谱行为及碎片离子稳定性的量子化学计算[J].高等学校化学学报,2005,26:2340-2344
[2]叶勇,曹立峰,牛明玉,等.三聚毗咯/丝组缀合物的电喷雾电离质谱裂解规律研究[J].质谱学报,2006,27(4):203-208
[3]Yu X.Y.,Xu X.,Chen Z.ESI-MS and Theoretical Study on The Coordination Structures and Reaction Modes of The Diperoxovanadate Complexes Containing Histidine-like Ligands[J].Intemational Joumal of Mass Spectrometry,2008,69:138-144
[4]Bythell B.J.,Barofsky D.F.,Pingitore F,et al.Backbone Cleavages and Sequential Loss of Carbon Monoxide and Ammonia from Protonated AGG:A Combined Tandem Mass Spectrometry,Isotope Labeling,and Theoretical Study[J].Journal of American Society of Mass Spectrometry,2007,18: 1291-1303
[5]Ye Y.,Cao L.F.,Niu M.Y.,et al.ESI-MS Fragmentation Pathways of N-methylpyrrole Polyamide /peptide Conjugates[J].International Journal of Mass Spectrometry,2006,253:141-145
[6]Kebarle P.J.A Brief Overeview of the Present Status of the Mechanisms Involved in Electrospray Mass Spectrometry[J].Mass Spectrospray,2000,35:804-817
[7]陈耀祖.有机质谱原理及应用[M].北京:科学出版社,2000,191-194
[8]Simoneit N.,Bernd R.T.A Review of Current Applications of Mass Spectrometry for Biomarker/Molecular Tracer Elucidations[J].Mass Spectrometry Reviews,2005,24(5):719-765
[9]Fabre N.,Rustan I.,Hoffmann E.,et al.Determination of Flavone,Flavonol,and Flavanone Aglycones by Negative Ion Liquid Chromatography Electrospray Ion Trap Mass Spectrometry[J].Journal of American Society of Mass Spectrometry,2001,12:707-715
[10]Luo Y.R.Handbook of Bond Dissociation Energies in Organic Compounds[M].Florida:CRC Press,Boco Raton,FL,2003:1-20
[2]Katirciogul H.,Mercan N.Antimicrobial Activity and Chemical Compositions of Turkish Propolis from Different Regions[J].African Journal of Biotechnology,2006,5:1151-1153
[3]Kahkonen M.P.,Hopia A.I.,Vuorela H.J.,et al.Antioxidant Activity of Plant Extracts Containing Phenolic Compounds[J].Journal Agricultural and Food Chemistry,1999,47:3954-3962
[4]Li H.B.,Wong C.C.,Cheng K.W.,et al.Antioxidant Properties in Vitro and Total Phenolic Contents in Methanol Extracts from Medicinal Plants[J].LWT-Food Science and Technology,2008,41:385-390
[5]Sanchez-Moreno C.Methods Used to Evaluate the Free Radical Scavenging Activity in Foods and Biological Systems[J].Food Science Technology International,2002,8:121-137
[6]Yao L.H.,Jiang Y.M.,Singanusong R.T.,et al.Phenolic Acids in Australian Melaleuca,Guioa,Lophostemon,Banksia and Helianthus Honeys and their Potential for Floral Authentication[J].Food Research International,2005,38:651-658
[7]Schuster B.,Herrmann K.Hydroxybenzoic and Hydroxycinnamic Acid Derivatives in Soft Fruits[J].Phytochem,1985,24:2761-2764
[8]刘琳.多酚化合物的高效液相色谱-安培检测方法研究[D].陕西:西北大学,2006
[9]Silva E.M.,Souza J.N.S.,Rogez H.,et al.Antioxidant Activities and Polyphenolic Contents of Fifteen Selected Plant Species from the Amazonian Region[J].Food Chemistry,2007,101:1012-1018
[10]Hagen S.F.,Borge G.I.A.,Bengtsson G.B.,et al.Phenolic Contents and Other Health and Sensory Related Properties of Apple Fruit(Malus domestica Borkh.,cv.Aroma):Effect of Postharvest UV-B Irradiation[J].Postharvest Biology and Technology,2007,45(1):1-10
[11]Zheng J.B.,Suo Z.R.,Liu L.Simultaneous Determination of Four Phenolic Compounds and Tanshione ⅡA in Guanxintong Tablets by LC Using Combined Electrochemical Detection and DAD [J].Chromatographia,2006,63:39-44
[12]刘琳,索志荣,郑建斌.高效液相色谱-二极管阵列检测-电化学检测联用技术同时测定三精双黄连口服液中四种化合物[J].色谱,2006,3:247-250
[13]梁艳,于世峰,陈卫军,等.色谱分析法在蜂蜜农药残留测定中的研究进展[J].中国蜂业,2008,59(6):12-14
[14]李福娟,蔡文生,邵学广.反相高效液相色谱法分离测定烟草中9种多酚类化合物[J].色谱,2007,25(4):564-568
[15]Kumazawa S.,Hamasaka T.,Nakayama T.Antioxidant Activity of Propolis of Various Geographic Origins[J].Food Chemistry,2004,84:329-339
[16]Cabanero A.I.,Recio J.L.,REZ R.R.Liquid Chromatography Coupled to Isotope Ratio Mass Spectrometry:A New Perspective on Honey Adulteration Detection[J].Journal Agricultural and Food Chemistry,2006,54:9719-9727
[17]Huang Z.L.,Wang B.W.,Eaves D.H.,et al.Phenolic Compound Profile of Selected Vegetables Frequently Consumed by African Americans in The Southeast United States[J].Food Chemistry,2007,103:1395-1402
[18]Radovic B.S.,Goodacre R.,Anklam E.Contribution of Pyrolysis-Mass Spectrometry(Py-Ms) to Authenticity Testing of Honey[J].Journal of analytical and pyrolysis,2001,60:79-87
[19]Duenasa M.,Hernandeza T.,Estrella I.,et al.Phenolic Composition and Antioxidant Activity of Mocan Seeds(Visnea mocanera L.f)[J].Food Chemistry,2003,82:373-379
[20]Fang Z.X.,Zhang M.,Wang L.X.HPLC-DAD-ESIMS Analysis of Phenolic Compounds in Bayberries(Myrica rubra Sieb.et Zucc.)[J].Food Chemistry,2007,100:845-852
[21]Volpi N.,Bergonzini G.Analysis of Flavonoids from Propolis by On-line HPLC-Electrospray Mass Spectrometry[J].Journal of Pharmaceutical and Biomedical Analysis,2006,42:354-36
[22]Maksimovic Z.,Malencic D.,Kovacevic N.Polyphenol Contents and Antioxidant Activity of Maydis Stigma Extracts[J].Bioresource Technology,2005,96:873-877
[23]Singleton V.L.,Orthofer R.,Lamuela-Raventos R.M.Analysis of Total Phenols and Other Oxidation Substrates and Antioxidants by Means of Folin-Ciocalteau Reagent[J].Methods of Enzymology,1999,299:152-178
[24]D'Arcy B.R,Rintoul G.B.,Rowland C.Y.Composition of Australian Honey Extractives.1.Norisoprenoids,Monoterpenes,and Other Natural Volatiles from Blue Gum(Eucalyptus leucoxylon)and Yellow Box(Eucatlypus melliodora) Honeys[J].Journal Agricultural and Food Chemistry,1997,45:1834-1843
[25]Castro-Vazquez L.,Draz-Maroto M.C.,Perez-Coello M.S.Aroma Composition and New Chemical Markers of Spanish Citrus Honeys[J].Food Chemistry,2007,103:601-606
[26]Corbella E.,Cozzolino D.Classification of The Floral Origin of Uruguayan Honeys by Chemical and Physical Characteristics Combined with Chemometrics[J].LWT,2006,39:534-539
[27]Ferreres F.,Garcia-Viguera C.,Tomas-Lorente F.,et al.Hesperetin:A Marker of the Floral Origin of Citrus Honey[J].Journal of the Science of Food and Agriculture,1993,61:121-123
[28]Gheldof N.,Wang X.F.,Engeseth N.J.Identification and Quantification of Antioxidant Components of Honeys from Various Floral Sources[J].Journal of Agricultural and Food Chemistry,2002,50:5870-5877
[29]单丽娜,谭洪涛,陈洪.分光光度法测定蜂胶中总黄酮质量分数的不确定度[J].江西化工,2006,3:122-123
[30]庆伟霞.几种天然黄酮类化合物的电化学检测方法研究[D].河南:河南大学,2007
[31]Jia Z.S.,Tang M.C.,Wu J.M.The Determination of Flavonoid Contents in Mulberry and Their Scavenging Effects on Superoxide Radicals[J].Food Chemistry,1999,64:555-559
[32]Carmona M.,Sanchez A.M.,Ferreres F.,et al.Identification of the Flavonoid Fraction in Saffron Spice by LC/DAD/MS/MS:Comparative Study of Samples from Different Geographical Origins[J].Food Chemistry,2007,100:445-450
[33]赵霖.蜂蜜代糖,有益健康[J].科学养生,2006,1:25
[34]杨玉凤,李小玲,刘剑霞,等.固体蜂蜜加工技术[J].中小企业科技,2006,2:47
[35]赵建军.蜂蜜[J].中华实用中西医杂志,2001,14(8):1918
[36]王文静.洋槐蜂蜜HPLC指纹图谱的研究[D].重庆:西南大学,2008
[37]Francisco A.,Isabel M.,Federico F.HPLC Flavornoid Profiles as Markers for the Botanical Origin of European Unifloral Honeys[J].Journal of Science and Food Agricultural,2001,81:485-496
[38]陈兰珍,叶志华,赵静,蜂蜜品种鉴别技术研究进展[J].食品科学,2008,29(3):494-498
[39]曹炜,陈卫军,宋纪蓉.不同种类蜂蜜总酚酸含量测定和抗氧化作用的研究[J].食品科学,2005,26(1):48-51
[40]Mohamed A.M.,Ali A.M.,Molham A.H.Antioxidant Activities and Total Phenolics of Different Types of Honey[J].Nutrition Research,2002,22:1041-1047
[41]苟小锋,曹炜,索志荣.荞麦蜜酚酸含量的高效液相色谱测定及其抗氧化作用的研究[J].食品科学,2004,25(10):254-258
[42]Martos I.,Ferreres F.,Yao L.,et al.Flavonoids in monospecific Eucalyptus honeys from Australia[J].Journal of Agricultural and Food Chemistry,2000,48:4744-4748
[43]Andrade P.,Ferreres F.,Gil M.I.,et al.Determination of Phenolic Compounds in Honeys with Different Floral Origin by Capillary Zone Electrophoresis[J].Food Chemistry,1997,60(1):79-84
[44]Yao L.H.,Jiang Y.M.,D'Arcy,B.R.,et al.Quantitative High-Performance Liquid Chromatography Analyses of Flavonoids in Australian Eucalyptus Honeys[J].Journal of Agricultural and Food Chemistry,2004,52:210-214
[45]Fiorani M.,Accorsi A.,Blasa M.,et al.Flavonoids from Italian Multifloral Honeys Reduce the Extracellular Ferricyanide in Human Red Blood Cells[J].Journal of Agricultural and Food Chemistry,2006,54:8328-8334
[46]Liang Y.,Cao W.,Chen W.J.,et al.Simultaneous Determination of Four Phenolic Components in Citrus Honey by High Performance Liquid Chromatography Using Electrochemical Detection[J].Food Chemistry,2009,114:1537-1541
[47]Roderick J.W.,Kevin R.M.,Kerry L.A.Antibacterial Phenolic Components of New Zealand Manuka Honey[J].Food Chemistry,1999,64:295-301
[48]Alissandrakis E.,Tarantilis P A,Harizanis P C,et al.Aroma Investigation of Unifloral Greek Citrus Honey Using Solid-phase Microextraction Coupled to Gas Chromatographic-Mass Spectrometric Analysis[J].Food Chemistry,2007,100:396-404
[49]Ferreres F.,Amparo Blazquez A.,Gil M.I.,et al.A Separation of Honey Flavonoids by Micellar Electrokinetic Capillary Chromatography[J].Journal of Chromatography A,1994,669:268-274
[50]Yao L.H.,Dattaa N.,Tomas-Barberan F.A.,et al.Flavonoids,Phenolic Acids and Abscisic Acid in Australian and New Zealand Leptospermum Honeys[J].Food Chemistry,2003,81:159-168
[51]Tomas-Barberan F.A.,Martos I.,Ferreres F.,et al.HPLC Flavonoid Profiles as Markers for the Botanical Origin of European Unifloral Honeys[J].Journal of the Science of Food and Agriculture,2001,81:485-496
[52]Zheng J.B,Liu X.X.,Zhou Y.Z.,et al.Simultaneous Determination of Five Phenolic Compounds in Dried Flowers by High Performance Liquid Chromatography Using Combining Electrochemical Detection with Diode Array Detection[J].Chromatographica,2007,65:707-712
[53]Shui G.H.,Peng L.L.An Improved Method for the Analysis of Major Antioxidants of Hibiscus Esculentus Linn[J].Journal of Chromatography A,2004,1048:17-24
[54]李启隆,胡劲波.电分析化学[M].北京:北京师范大学出版社,2007:467-470
[55]云自厚,欧阳津,张晓彤.液相色谱检测方法(第二板)[M].北京:化学工业出版社,2006:113-137
[56]刘晓莉.十一种酚类化合物的高效液相色谱测定方法研究[D].陕西:西北大学,2008
[57]刘晓星,温普红,郑建斌.高效液相色谱—二极管阵列—电化学联用技术测定八角莲中3种成分的含量[J]_药物分析杂志,2005,25(12):1547-1549
[58]索志荣,曹炜,秦海燕,等.葡萄酒中7种酚酸的色谱电化学分析[J].高等学校化学学报,2005,26(8):1424-1427
[59]Yu X.Y.,Xu X.,Chen Z.ESI-MS and Theoretical Study on the Coordination Structures and Reaction Modes of the Diperoxovanadate Complexes Containing Histidine-like Ligands[J].International Journal of Mass Spectrometry,2008,269:138-144
[60]李宇航,戴海学,李晓蓉,等.葛根素的电喷雾电离裂解规律解析[J].质谱学报,2007,28(4):224-228
[61]Zayed M.A.,Fahmey M.A.,Hawash M.A.,et al.Mass Spectrometric Investigation of Buspirone Drug in Comparison with Thermal Analyses and MO-Calculations[J].Spectrochimica Acta Part A,2007,67:522-530
[62]Bythell B.J.,Barofsky D.F.,Pingitore F.,et al.Backbone Cleavages and Sequential Loss of Carbon Monoxide and Ammonia from Protonated AGG:A Combined Tandem Mass Spectrometry,Isotope Labeling,and Theoretical Study[J].Journal of the American Society for Mass Spectrometry,2007,18:1291-1303
[63]Castro-Vazquez L.,Diaz-Maroto M.C.,Perez-Coello M.S.Aroma Composition and New Chemical Markers of Spanish Citrus Honeys[J].Food Chemistry,2007,103:601-606
[64]D'Arcy B.R.,Rintoul G.B.,Rowland C.Y.,et al.Composition of Australian Honey Extractives.1. Norisoprenoids,Monoterpenes,and Other Natural Volatiles from Blue Gum(Eucalyptus leucoxylon)and Yellow Box(Eucalyptus melliodora) Honeys[J].Journal of Agricultural and Food Chemistry,1997,45:1834-1843
[65]Beales K.E.,Betteridge K.,Colegate S.,et al.Solid-Phase Extraction and LC-MS Analysis of Pyrrolizidine Alkaloids in Honeys[J].Journal of Agricultural and Food Chemistry,2004,52:6664-6672
[66]Martos I.,Cossentini M.,Ferreres F.,et al.Flavonoid Composition of Tunisian Honeys and Propolis[J].Journal of Agricultural and Food Chemistry,1997,45:2824-2829
[67]陈卫军.酚类化合物抗氧化机理分析及新型抗氧化剂合成思路的理论研究[D].陕西:西北大学,2007
[68]孙少芳.槲皮素-铬(Ⅲ)离子络合物结构及抗氧化性的理论与实验研究[D].陕西:西北大学,2008
[69]廖沐真.量子化学从头计算方法[M].北京:清华大学出版社,1984:26-33
[70]梁文平.新世纪的物理化学[M].北京:科技出版社,2004:108-119
[71]陈念贻.计算化学及其应用[M].北京:北京师范大学出版社,292-321
[72]许海棠.高效液相色谱-质谱法在中成药分析中的应用研究[D].广西:广西大学,2008
[73]Jones R.O.,Gunnarsson O.The Density Functional Formalism,it's Application and Propects[J].Review of Modern Physics,1989,61:689
[74]Yuan L.F.,Yang J.L.,Li Q.X.,et al.A First-Principles Study of Acetylene and it's Evolution Products on Cu(001)[J].Journal of Chemical Physics,2002,116:3104
[75]Dai B.,Dong K.W.,Yang J.L.,et al.Excited States of 3d Transition Metal Monoxides[J].Journal of Chemical Physics,2003,118:9608
[76]Li Z.Y.,Yang J.L.,Hou J.G.,et al.Inorganic Electrode:Theoretical Study on Structural and Electronic Properties[J].Journal of the American Chemical Society,2003,125:6050
[77]Frisch M.J.,Trucks G.W.,Schlegel H.B.,et al.GAUSSIAN 03(B.05)[S].Pittsburgh:Gaussian,Inc.,PA,2003
[1]查玉兵,陈美,王晓芳,等.农药残留分析技术研究进展[J].安徽农业科学,2007,35(23):7252-7253.7256
[2]刘爱红,张琳.农药残留与食品安全[J].安徽农业科学,2007,35(13):4017-4018
[3]2001/110/EC.Council Directive 2001/110/EC Relating to Honey[S].Europe,2001
[4]美国食品与药物管理部门.农药允许量.(http://www.cfsan.fda.gov)
[5]Gyorik M.,Herpai Z.,Szecsenyi I.,et al.Rapid and Sensitive Determination of Phenol in Honey by High-Performance Liquid Chromatography with Fluorescence Detection[J].Journal of Agricultural and Food Chemistry,2003,51(18):5222-5225
[6]Bogdanov S.,Imdorf A.,Kilchenmann V.Residues in Wax and Honey after Apilife VAR Treatment[J].Apidologie,1998,29:513-524
[7]Gyorik M.,Herpai Z.,Szecsenyi I.,et al.Rapid and Sensitive Determination of Phenol in Honey by High-Performance Liquid Chromatography with Fluorescence Detection[J].Journal of Agricultural and Food Chemistry,2003,51(18):5222-5225
[8]Takeba K.,Matsumoto M.,Shida Y.,et al.Determination of Phenol in Honey by Liquid Chromatography with Amperometric Detection[J].Journal of the Association of Official Analytical Chemists,1990,73(4):602-605
[9]Nozal M.J.,Bemal J.L.,Jimenez J.J.,et al.Extraction of Thymol,Eucalyptol,Mtography with Flame Ionization Detection[J].Journal of Chromatography A,2002,954:207-215
[10]蜂蜜中苯酚残留量的测定方法.液相色谱法.蜂产品标准汇编.北京:中国标准出版社,2003:299-305
[1]Corbella E.,Cozzolino D.Classification of the Floral Origin of Uruguayan Honeys by Chemical and Physical Characteristics Combined with Chemometrics[J].LWT,2006,39:534-539
[2]Tewari J.C.,Imdayaraj J.M.K.Floral Classification of Honey Using Mid-Infrared Spectroscopy and Surface Acoustic Wave Based z-Nose Sensor[J].Journal of Agricultural and Food Chemistry,2005,53:6955-6966
[3]Alissandrakisa E.,Dafererab D.,Tarantilisb P.A.,et al.Ultrasound-assisted Extraction of Volatile Compounds from Citrus Flowers and Citrus Honey[J].Food Chemistry,2003,82:575-582
[4]Martos I.,Ferreres F.,Yao L.,et al.Flavonoids in Monospecific Eucalyptus Honeys from Australia[J]. Journal of Agricultural and Food Chemistry, 2000, 48: 4744-4748
[5] Ferreres F., Tomas-Barberan F. A., Soler C., et al. A Simple Extractive Technique for Honey Flavonoid HPLC Analysis [J]. Apidologie, 1994, 25(1): 21-30
[6] Tomas-Barberan F. A., Martos I., Ferreres F., et al. HPLC Flavonoid Profiles As Markers for the Botanical Origin of European Unifloral Honeys [J]. Journal of the Science of Food and Agriculture, 2001,81:485-496
[7] Xie M. X., Xu X. Y., Wang Y. D. Interaction between Hesperetin and Human Serum Albumin Revealed by Spectroscopic Methods [J]. Biochimica Biophysica Acta, 2005, 1724: 215-224
[8] Wilcox L. J., Borradaile N. M., Dreu L. E., et al. Secretion of Hepatocyte ApoB is Inhibited by the Flavonoids, Naringenin and Hesperetin, via Reduced Activity and Expression of ACAT2 and MTP [J]. Journal of Lipid Research, 2001, 42: 725-734
[9] Jin Y. R., Han X. H., Zhang Y. H., et al. Antiplatelet Activity of Hesperetin, A Bioflavonoid, Is Mainly Mediated by Inhibition of PLC-γ2 Phosphorylation and Cyclooxygenase-1 Activity [J]. Atherosclerosis, 2007, 194: 144-152
[10] Scholz E.P., Zitron E., Kiesecker C., et al. Orange Flavonoid Hesperetin Modulates Cardiac hERG Potassium Channel via Binding to Amino Acid F656 [J]. Nutrition, Metabolism & Cardiovascular Diseases, 2007, 17: 666-675
[11] Yao L. H., Jiang Y. M., Singanusong R. T., et al. Phenolic Acids and Abscisic Acid in Australian Eucalyptus Honeys and their Potential for Floral Authentication [J]. Food Chemistry, 2004, 86: 169-177
[12] Martos I., Cossentini M., Ferreres F., et al. Flavonoid Composition of Tunisian Honeys and Propolis[J]. Journal of Agricultural and Food Chemistry, 1997,45: 2824-2829
[13] Gheldof N., Wang X. F., Engeseth N. J. Identification and Quantification of Antioxidant Components of Honeys from Various Floral Sources [J]. Journal of Agricultural and Food Chemistry, 2002, 50: 5870-5877
[14] Yao L. H., Jiang Y. M., Singanusong R. T., et al. Phenolic Acids in Australian Melaleuca, Guioa, Lophostemon, Banksia and Helianthus Honeys and Their Potential for Floral Authentication [J]. Food Research International, 2005, 38: 651-658.
[15] Castro-Vazquez L., Draz-Maroto M. C., Perez-Coello M. S. Aroma Composition and New Chemical Markers of Spanish Citrus Honeys [J]. Food Chemistry, 2007, 103: 601-606
[16]Alissandrakis E.,Tarantilis P.A.,Harizanis P.C.,et al.Aroma Investigation of Unifloral Greek Citrus Honey Using Solid-phase Microextraction Coupled to Gas Chromatographic-mass Spectrometric Analysis[J].Food Chemistry,2007,100:396-404
[17]Tananaki C.,Thrasyvoulou A.,Giraudel J.L.,et al.Determination of Volatile Characteristics of Greek and Turkish Pine Honey Samples and Their Classification by Using Kohonen Self Organising Maps [J].Food Chemistry,2007,101:1687-1693
[18]Gonzalez Paramas A.M.,Gomez Barez J.A.,Marcos C.C.,et al.HPLC-Fluorimetric Method for Analysis of Amino Acids in Products of the Hive(honey and bee-pollen)[J].Food Chemistry,2006,95:148-156
[19]Patsias J.,Papadopoulou M.E.Development of An Automated On-line Solid-phase Extraction -high-performance Liquid Chromatographic Method for the Analysis of Aniline,Phenol,Caffeine and Various Selected Substituted Aniline and Phenol Compounds in Aqueous Matrices[J].Journal of Chromatography A,2000,904:171-188
[20]Vanbeneden N.,Delvaux F.,Delvaux F.R.Determination of Hydroxycinnamic Acids and Volatile Phenols in Wort and Beer by Isocratic High-Performance Liquid Chromatography Using Electrochemical Detection[J].Journal of Chromatography A,2006,1136:237-242
[21]Ferreres F.,Garcia-Viguera C.,Tomás-Lorente F.,et al.Hesperetin:A Marker of the Floral Origin of Citrus Honey[J].Journal of the Science of Food and Agriculture,1993,61:121-123
[22]D'Arcy B.R.Antioxidants in Australian Floral Honeys-Identification of Health-enhancing Nutrient Components[M].Australia:Rural Industries Research and Development Corporation,2005:37-42
[23]索志荣.液相色谱电化学检测方法及其应用[D].西安:西北大学,2007
[1]Al-Mamary M.,Al-Meeri A.,AI-Habori M.Antioxidant Activities and Total Phenolics of Different Types of Honey[J].Nutrition Research,2002,22:1041-1047
[2]D'Arcy B.R.Antioxidants in Australian Floral Honeys-Identification of Health-Enhancing Nutrient Components[M].Australia:Rural Industries Research and Development Corporation,2005:37-42
[3]Tomás-Barberán F.A.,Martos I.,Ferreres F.,et al.HPLC Flavonoid Profiles as Markers for the Botanical Origin of European Unifloral Honeys[J].Journal of the Science of Food and Agriculture,2001,81:485-496
[4] Ferreres F., Andrade P., Tomas-Barberan F. A. Natural Occurrence of Abscisic Acid in Heather Honey and Floral Nectar [J]. Journal of Agricultural and Food Chemistry, 1996,44: 2053-2056
[5] Martos I., Ferreres F., Yao L., et al. Flavonoids in Monospecific Eucalyptus Honeys from Australia [J]. Journal of Agricultural and Food Chemistry, 2000,48: 4744-4748
[6] Andrade P., Ferreres F., Gilb M. I., et al. Determination of Phenolic Compounds in Honeys with Different Floral Origin by Capillary Zone Electrophoresis [J]. Food Chemistry, 1997, 60(1): 79-84
[1]陈兰慧,金莲姬,苏忠民,等.乌头碱类生物碱电喷雾串联质谱行为及碎片离子稳定性的量子化学计算[J].高等学校化学学报,2005,26:2340-2344
[2]叶勇,曹立峰,牛明玉,等.三聚毗咯/丝组缀合物的电喷雾电离质谱裂解规律研究[J].质谱学报,2006,27(4):203-208
[3]Yu X.Y.,Xu X.,Chen Z.ESI-MS and Theoretical Study on The Coordination Structures and Reaction Modes of The Diperoxovanadate Complexes Containing Histidine-like Ligands[J].Intemational Joumal of Mass Spectrometry,2008,69:138-144
[4]Bythell B.J.,Barofsky D.F.,Pingitore F,et al.Backbone Cleavages and Sequential Loss of Carbon Monoxide and Ammonia from Protonated AGG:A Combined Tandem Mass Spectrometry,Isotope Labeling,and Theoretical Study[J].Journal of American Society of Mass Spectrometry,2007,18: 1291-1303
[5]Ye Y.,Cao L.F.,Niu M.Y.,et al.ESI-MS Fragmentation Pathways of N-methylpyrrole Polyamide /peptide Conjugates[J].International Journal of Mass Spectrometry,2006,253:141-145
[6]Kebarle P.J.A Brief Overeview of the Present Status of the Mechanisms Involved in Electrospray Mass Spectrometry[J].Mass Spectrospray,2000,35:804-817
[7]陈耀祖.有机质谱原理及应用[M].北京:科学出版社,2000,191-194
[8]Simoneit N.,Bernd R.T.A Review of Current Applications of Mass Spectrometry for Biomarker/Molecular Tracer Elucidations[J].Mass Spectrometry Reviews,2005,24(5):719-765
[9]Fabre N.,Rustan I.,Hoffmann E.,et al.Determination of Flavone,Flavonol,and Flavanone Aglycones by Negative Ion Liquid Chromatography Electrospray Ion Trap Mass Spectrometry[J].Journal of American Society of Mass Spectrometry,2001,12:707-715
[10]Luo Y.R.Handbook of Bond Dissociation Energies in Organic Compounds[M].Florida:CRC Press,Boco Raton,FL,2003:1-20