CQM/UMa-Centro de Química da Madeira, Centro de Ciências Exactas e da Engenharia, Universidade da Madeira, Campus Universitário da Penteada, Funchal, Portugal.
J Sep Sci. 2012 Sep;35(17):2282-96. doi: 10.1002/jssc.201200244. Epub 2012 Jul 17.
Hop (Humulus lupulus L., Cannabaceae family) is prized for its essential oil contents, used in beer production and, more recently, in biological and pharmacological applications. In this work, a method involving headspace solid-phase microextraction and gas chromatography-mass spectrometry was developed and optimized to establish the terpenoid (monoterpenes and sesquiterpenes) metabolomic pattern of hop-essential oil derived from Saaz variety as a mean to explore this matrix as a powerful biological source for newer, more selective, biodegradable and naturally produced antimicrobial and antioxidant compounds. Different parameters affecting terpenoid metabolites extraction by headspace solid-phase microextraction were considered and optimized: type of fiber coatings, extraction temperature, extraction time, ionic strength, and sample agitation. In the optimized method, analytes were extracted for 30 min at 40°C in the sample headspace with a 50/30 μm divinylbenzene/carboxen/polydimethylsiloxane coating fiber. The methodology allowed the identification of a total of 27 terpenoid metabolites, representing 92.5% of the total Saaz hop-essential oil volatile terpenoid composition. The headspace composition was dominated by monoterpenes (56.1%, 13 compounds), sesquiterpenes (34.9%, 10), oxygenated monoterpenes (1.41%, 3), and hemiterpenes (0.04%, 1) some of which can probably contribute to the hop of Saaz variety aroma. Mass spectrometry analysis revealed that the main metabolites are the monoterpene β-myrcene (53.0 ± 1.1% of the total volatile fraction), and the cyclic sesquiterpenes, α-humulene (16.6 ± 0.8%), and β-caryophyllene (14.7 ± 0.4%), which together represent about 80% of the total volatile fraction from the hop-essential oil. These findings suggest that this matrix can be explored as a powerful biosource of terpenoid metabolites.
啤酒花（蛇麻草，大麻科）以其精油含量而备受推崇，用于啤酒生产，最近又用于生物和药理学应用。在这项工作中，开发并优化了一种涉及顶空固相微萃取和气相色谱-质谱的方法，以确定萨兹品种啤酒花精油的萜类（单萜和倍半萜）代谢组学模式，旨在探索这种基质作为新型、更具选择性、可生物降解和天然产生的抗菌和抗氧化化合物的强大生物来源。考虑并优化了影响顶空固相微萃取萜类代谢物提取的不同参数：纤维涂层类型、萃取温度、萃取时间、离子强度和样品搅拌。在优化的方法中，分析物在样品顶空以 50/30μm 二乙烯基苯/羧基/聚二甲基硅氧烷涂层纤维在 40°C 下萃取 30 分钟。该方法允许鉴定总共 27 种萜类代谢物，占萨兹啤酒花精油挥发性萜类成分的 92.5%。顶空组成主要由单萜（56.1%，13 种化合物）、倍半萜（34.9%，10 种）、含氧单萜（1.41%，3 种）和半萜（0.04%，1 种）组成，其中一些可能有助于萨兹品种啤酒花的香气。质谱分析表明，主要代谢物是单萜 β-月桂烯（占总挥发性部分的 53.0±1.1%）和环状倍半萜 α-葎草烯（16.6±0.8%）和 β-石竹烯（14.7±0.4%），它们共同代表了从啤酒花精油中提取的总挥发性部分的约 80%。这些发现表明，这种基质可以作为萜类代谢物的强大生物源进行探索。
