Tuberoso Carlo I G, Bifulco Ersilia, Jerković Igor, Caboni Pierluigi, Cabras Paolo, Floris Ignazio
Dipartimento di Tossicologia, Università di Cagliari, via Ospedale 72, 09124 Cagliari, Italy.
J Agric Food Chem. 2009 May 13;57(9):3895-900. doi: 10.1021/jf803991j.
During the liquid chromatographic study of the phenolic fraction of monofloral honeys was detected in the asphodel honey ( Asphodelus microcarpus Salzm. et Viv.) chromatogram a distinctive peak not detected in other monofloral honeys such as Arbutus unedo L., Hedysarum coronarium , Eucalyptus spp., and Galactites tomentosa . After thin layer chromatography (TLC) purification and characterization by NMR and LC-MS/MS, the compound was identified as methyl syringate (MSYR) and confirmed against an original standard. Levels of MSYR were measured in honeys of 2005, 2006, and 2007 by HPLC-DAD analysis. Level determination of MSYR was repeated in 2008 for 2006 and 2007 honeys to evaluate chemical stability of this phenolic compound. Levels of MSYR measured 1 year after the sampling did not show significant statistical differences (p < 0.05). The stability of MSYR was also confirmed by 12 asphodel honey samples collected in 2005 that showed amounts of methyl syringate comparable with those found in fresh honey. For the evaluation of MSYR origin, samples of nectars were collected from flowers and the content of MSYR was measured. Levels of MSYR in honeys are originated from the nectar with an average contribution of the nectar to the honey of 80%. Melissopalinological analysis did not allow the attribution of the honey monofloral origin because levels of asphodel pollen were <6% for all analyzed samples. Previously reported levels of MSYR for robinia, rape, chestnut, clover, linden blossom, dandelion, sunflower, thyme, manuka, and fir honeys were <5 mg/kg. For this reason, a minimum level of 122.6 mg/kg for MSYR in asphodel honeys can be considered as a chemical marker and, unlike the melissopalynological analysis, can be used for the origin attribution and to evaluate the percent of asphodel nectar in the honey.
在对单花蜂蜜酚类成分的液相色谱研究中,在水仙蜂蜜(小果水仙Asphodelus microcarpus Salzm. et Viv.)的色谱图中检测到一个在其他单花蜂蜜(如草莓树蜂蜜、冠状岩黄芪蜂蜜、桉属植物蜂蜜和绒毛奶子花蜂蜜)中未检测到的独特峰。经薄层色谱(TLC)纯化以及核磁共振(NMR)和液相色谱-串联质谱(LC-MS/MS)表征后,该化合物被鉴定为丁香酸甲酯(MSYR),并与原始标准品进行了对照确认。通过高效液相色谱-二极管阵列检测(HPLC-DAD)分析测定了2005年、2006年和2007年蜂蜜中MSYR的含量。2008年对2006年和2007年的蜂蜜重复进行了MSYR含量测定,以评估这种酚类化合物的化学稳定性。采样1年后测定的MSYR含量未显示出显著的统计学差异(p < 0.05)。2005年采集的12个水仙蜂蜜样品也证实了MSYR的稳定性,这些样品中丁香酸甲酯的含量与新鲜蜂蜜中的相当。为了评估MSYR的来源,从花朵中采集了花蜜样品并测定了MSYR的含量。蜂蜜中MSYR的含量源自花蜜,花蜜对蜂蜜的平均贡献为80%。由于所有分析样品中水仙花粉的含量均<6%,因此蜜源花粉学分析无法确定蜂蜜的单花来源。先前报道的刺槐、油菜、板栗、三叶草、椴树花、蒲公英、向日葵、百里香、麦卢卡和冷杉蜂蜜中MSYR的含量<5 mg/kg。因此,水仙蜂蜜中MSYR的最低含量122.6 mg/kg可被视为一种化学标志物,与蜜源花粉学分析不同,它可用于确定蜂蜜的来源并评估蜂蜜中水仙花蜜的百分比。