天然木材中气味活性成分的化学感官表征及其结构-气味关系

Rahil Ghadiriasli, Prof. Dr. Andrea Büttner, Prof. Dr. Monika Pischetsrieder
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引用次数: 0

摘要

活树及其获得的木材在人类的日常生活中以建筑材料、家具或日常用品的形式发挥着突出的作用。木制品散发的香气成分对人类的心理生理活动有强大的影响,已被用于心理、精神和身体的治疗。木材香气可以在室内环境中使用,以促进放松和释放压力的效果。目前的研究是为了确定两种不同类型的木材,即橡木和香松木的单个木材气味及其成分。长期以来,橡木一直被用于成熟和陈酿过程中,作为在橡木桶中发酵或陈酿的副产品,赋予酒精饮料和醋香气和风味。一些研究针对改性和热处理橡木的香气成分,但只有很少的信息,构成天然和生橡木的香气活性化合物。香松木(Pinus cembra L.),也被称为花冠松、瑞士松或石松,有一种突出而持久的香气,据报道可以缓解压力,并广泛用于芳香疗法。然而,产生这种独特香气的气味剂尚未被全面揭示。因此,本论文的主要目的是通过基于人类感官评价和多维气相色谱和质谱技术的组合化学分析方法来表征影响气味的物质,并加深对天然橡木和独特的香松木气味的认识。此外,本文还试图深入了解这两种木材的形成途径和气味来源及其应用。这些气味剂大多由醛、酸、内酯、一系列萜烯(主要是单萜和倍半萜)和几种含有酚类核心部分的气味活性化合物组成。比较了所有木材样品的气味特征,确定了有效的气味剂,并通过应用稳定同位素稀释法(SIDA)对两种木材样品(橡木和香柏木样品)的选定气味剂进行了量化。气味活性值(oav)是基于在水中确定的气味阈值(OTs)计算的。本文的第二部分研究了不同地理区域和气候条件对不同木材样品气味的影响。本研究的重点是阐明来自德国、奥地利和匈牙利的几种天然橡木样品的气味特征。特别考虑到目前与气候变化有关的挑战对林业部门的影响,从而涉及到各自的区域条件,并进行了统计解释。以香柏木为例,通过主成分分析(PCA)和对获得的数据进行统计解释,确定和评估了奥地利和意大利不同地理林区的影响。通过混合天然存在浓度的主要气味活性化合物的重组实验显示,模型混合物与各自原生木材样品的整体气味非常一致。此外,还阐明了木材中代表性物质类别的结构气味关系。具体来说,研究了愈创木酚的气味印象,以及选择的结构相关的气味剂,如烷基化、烯基化、甲氧基化和卤化愈创木酚衍生物。所有被研究的化合物都引起了典型的烟熏味、香草味和/或丁香味的印象。烟熏味主要由愈创木酚、酚和甲酚组成,在葡萄酒、威士忌、烟熏火腿、奶酪或披萨等烘焙食品和饮料中都能闻到。此外,研究表明,烷基化和卤化愈创木酚和酚的气味特性表明,烟熏味对每个人来说都是不一样的,每个人都能感受到不同的气味。总的来说,愈创木酚及其烷基化、烯基化和甲氧基化衍生物的气味阈值研究表明,没有特定的取代基对OT产生显著和普遍的影响。然而,取代基在羟基上的位置似乎对OT有影响。所得数据可用于所研究化合物的鉴定和分析。此外,该结果还有助于理解化合物的结构和气味相关性,这一问题尚未完全解决。最后,采用气相色谱-嗅觉法(GC-O)对桶陈酒样品进行分析,发现桶陈酒中存在典型的泥土味异味。 在这些葡萄酒中检测到2-甲基异冰片醇(2-MIB),尽管这些葡萄酒样品已经有7年的历史了,而且之前所有的研究都表明这种物质在葡萄酒中是不稳定的,而且必须。合成了2-MIB的降解产物,关于它们的气味,这些脱水产物被发现是无味的。为了研究这种矛盾的情况,我们从初始浓度升高开始,分析了葡萄酒和模型溶液中2-MIB的稳定性。因此,尽管2-MIB的浓度随着时间的推移大大降低,但在陈年葡萄酒中仍能检测到它,并能引起泥土味。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Chemo-sensory characterization of odor-active constituents in native woods and their structure-odor relationship

The living tree and its obtained wood have played a prominent role in human everyday life in the form of building material and furniture, or in products of daily use. The aroma components emanating from wood-based products have a powerful influence on human Psychophysiological activity and have been used for mental, spiritual and physical healing. The wood aroma can be used in the indoor environment to foster relaxation and stress release effects. The current study was conducted to determine the individual wood odor and its constituents in two diverse types of woods, namely Oak wood and cembran pine wood.

Oak wood has been used since long during the maturation and aging process imparting aroma and flavor in alcoholic beverages and vinegar as by-products that have been either fermented or aged in oak barrels. Several investigations targeted the aroma composition of modified and heat-treated oak wood, but only little information about aroma-active compounds constituting the native and raw oak wood is available. The Cembran pine wood (Pinus cembra L.), also known as Arolla pine, Swiss pine, or Stone pine, has a prominent and long-lasting aroma that has been reported to relieve stress and that is widely used in aromatherapy. However, the odorants responsible for this distinctive aroma are not yet comprehensively revealed. Therefore, the main objective of this thesis was to characterize the impacting odorants and to deepen the knowledge about native oak wood and unique Cembran pine wood odor by applying a combinatory chemo-analytical approach based on human-sensory evaluations and multidimensional gas chromatographic and mass spectrometric techniques. Furthermore, it was tried in this thesis to gain deeper insights into formation pathways and odor sources in these two types of wood and their applications. Most of these odorants comprised aldehydes, acids, lactones, a series of terpenes, mostly mono- and sesquiterpenes, and several odor-active compounds containing a phenolic core moiety. The odor profiles of all wood samples were compared, the potent odorants were determined, and selected odorants of both types of wood samples (oak and Cembran wood samples) were quantified by application of stable isotope dilution assays (SIDA). Odor activity values (OAVs) were calculated based on the odor threshold (OTs) determined in water.

The second part of this thesis dealt with the investigation of the effects of different geographical regions and pedoclimatic conditions on the odor of different wood samples. This study focused on elucidating the smell profiles of several natural oak samples from Germany, Austria, and Hungary. Particular consideration is given to view the current challenges associated with climate change on the forestry sector, and thus concerning the respective regional conditions, and underwent statistical interpretation. In the case of Cembran wood, the influence of different geographical forest regions in Austria and Italy was determined and evaluated by means of principal component analysis (PCA) and statistical interpretation of obtained data. Recombination experiments by mixing the dominant odor-active compounds in their naturally occurring concentrations revealed a good agreement of the model mixtures with the overall smell of the respective native wood samples.

In addition, the structure odor relationships in representative substance classes of wood were elucidated. Specifically, the smell impressions of guaiacol and selected structurally related odorants such as alkylated, alkenylated, methoxylated and halogenated guaiacol derivatives were studied. All investigated compounds elicited characteristic smoky, vanilla-like, and /or clove-like smell impressions. Smoky smells, primarily comprising guaiacols, phenols and cresols, are enjoyed in diverse foods and beverages such as wine, whiskey, smoked ham, cheese, or baked goods such as pizza. Furthermore, the studies indicated that the odor properties of alkylated and halogenated guaiacols and phenols demonstrated the smoky smells are not the same for everyone and can be differently perceived in individual humans. Overall, the odor threshold investigation of guaiacol and its alkylated, alkenylated, and methoxylated derivatives showed that no specific substituent caused a significant and universal effect on OT. However, the positioning of the substituents to the hydroxyl function seems to have an impact on OT. Obtained data could be used to identification and analysis of the investigated compounds. Furthermore, the results can also be avail in understanding the structure and the odor correlation of compounds, which is still not fully resolved.

Finally, to investigate the wine off-odors, barrel-aged wine samples were analyzed by gas chromatography-olfactometry (GC-O), with regards to the presence of the typical earthy-smelling off-odor. The 2-methylisoborneol (2-MIB) was detected in these wines, although the wine samples were seven years old and all the previous studies showed that this substance is unstable in wine and must. Degradation products of 2-MIB were synthesised, and with regard to their odor, these dehydration products were found to be odorless. To investigate this paradoxical situation, 2-MIB stability was analyzed in wine and model solutions, starting with an elevated initial concentration. Therefore, it was concluded that although 2-MIB concentration greatly decreased with time it still can be detected in old wines and can induce the earthy off-odor.

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