【作者】 梁艳；

【导师】 曹炜；

【作者基本信息】 西北大学 ， 应用化学， 2009， 硕士

【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^-3μg/mL～2.9×10^-3μg/mL之间,均低于紫外检测器的检出限(3.1×10^-2μg/mL～9.7×10^-2μg/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。更多还原

【Abstract】 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^-3μg/mL to 2.9×10^-3μg/mL,much lower than that by DAD(3.1×10^-2 μg/mL to 9.7×10^-2μg/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.更多还原