湖南油樟的化学类型

对湖南省的油樟（Cinnamomum longepaniculatum (Gamble)N.Cho ex H.W.Li）资源作了调查。用色谱、色谱/质谱联用方法鉴定了油樟叶精油的43个化学成分,依主含成分不同可将其划分为6个不同的化学类型。其中,主含甲基丁香酚、龙脑、樟脑、芳樟醇和倍半萜烯的5个化学类型为首次在油樟中发现。     

不同化学型樟树的RAPD分析

用RAPD标记技术分析了30个不同化学型樟树〔Cinnamomum camphora(L.)Presl〕样本的遗传关系。14个引物共扩增出170个位点,其中多态位点161个,多态性位点百分率达94.71%,特异位点有15个。聚类结果显示,当λ=13时,30个樟树样本被分为4类,即芳樟型(主成分为芳樟醇)、脑樟型(主成分为樟脑)、桉樟型(主成分为1,8-桉叶油素)和黄樟型(主成分为黄樟醇),表明不同化学型樟树样本间的遗传关系与其叶精油的主成分有一定的相关性。     

香桂叶精油成份的研究

本文报道香桂叶精油化学成份的分离鉴定和含量测定。运用减压分馏、柱层析、薄层色谱、气相色谱和红外光谱等方法分离鉴定了3个单萜烯——α—蒎烯(1.28%)、莰烯(0.17%)和对-聚伞花素(0.14%);5个含氧单萜化台物——1,8-桉叶素(0.85%)、芳樟醇(14.35%)、α-松油醇(0.22%)、黄樟油素(69.70%)和丁香酚(4.20%);2个醛类化合物——壬醛(0.16%)和癸醛(0.40%);2个倍半萜烯——β-丁香烯(0.11%)和β-甜没药烯(0.05%);1个倍半萜含氧化合物——橙花叔醇(0.75%)等13个成份。另外,还测定了不同月份的植物精油主要成份的含量变化。     

精油化学成份研究方法发展概况

精油由于来源不同(各种类植物和不同的器官),其化学组成差异很大,而且大都非常复杂。它们基本组成包括脂肪类、芳香族,单萜和倍半萜等类化合物,也包含一些含氮和含硫的化合物。这些种类的化合物中有烃类及其含氧化合物,如醇、醛酮、酸、酯、内酯、醚、酚、环氧化合物等。然而精油的主要组成大都是以单萜、倍半萜和它们的含氧化合物为主。     

植物萜类合酶研究进展

随着植物中许多有价值的萜类化合物被发现和应用于人类生活 ,萜类生物合成途径的研究倍受重视。萜类合酶催化单萜、倍半萜和二萜生物合成 ,即分别催化GPP、FPP和GGPP形成单萜、倍半萜和二萜。本文叙述了近年来在植物萜类合酶催化机理、克隆策略和萜类生物工程的研究进展     

松毛虫狭颊寄蝇对被害马尾松针叶挥发物的触角电位反应

松毛虫狭颊寄蝇Carcelia matsukarehaeShima是我国松毛虫Dendrolimus punctatus(Walke)的重要天敌。通过对被害马尾松(Pinus massonianaLamb.)针叶挥发性物质的提取、鉴定以及对松毛虫狭颊寄蝇的电生理测定,结果表明,大多数的挥发性物质,包括绿叶性挥发物以及松针特有的单萜、氧化单萜和倍半萜,对雌蝇均有明显的电生理活性,其中以顺-3-己烯-1-醇最高,长叶烯最低。雌蝇对4大类挥发性物质的平均相对触角电位反应值,以绿叶性挥发物为最高,其余依次为单萜、氧化单萜和倍半萜。     

云南不同产地臭灵丹精油化学成分及抗菌活性

采用水蒸气蒸馏的方法,对采自云南4个不同地区（昆明,丽江,普洱,新平）的臭灵丹叶子进行挥发油提取,并利用GC MS和GC FID气相色谱联用技术分析其化学组成,分别从中鉴定出39、37、33、44个化合物。鉴定的化合物各占挥发油总量的9332% (昆明)、8057% (丽江)、9224% (普洱)和9385% (新平)。研究结果表明,采自这四个地区植物样品提取所得挥发油化学组成不尽相同：昆明产臭灵丹挥发油富含芳香族化合物(3806%);而从丽江和普洱样品中获得的挥发油化学成分以倍半萜（分别为1989%和4465%）和氧化倍半萜（分别为4085%和3511%）为主;非氧化单萜和非氧化倍半萜化合物（分别为4223%和3325%）则是新平产臭灵丹挥发油的主要化合物类型。同时,对这些不同产地的臭灵丹挥发油也进行了抗菌活性测试。从以上实验研究结果推测环境差异是影响臭灵丹挥发油化学组成差异的重要因素,而不同的化学组成可能是导致4种样品抗菌敏感程度不同的原因。     

遮阴对柠檬香茅中萜类化合物及其合成酶基因影响研究

为获取柠檬香茅(Cymbopogon citratus)中萜类化合物及其合成酶基因信息,以正常生长及遮阴下的柠檬香茅嫩叶为材料,进行代谢组学和转录组学结合q RT-PCR验证分析。代谢组分析结果表明,柠檬香茅所含萜类共23种,包括单萜4种、倍半萜4种、二萜8种、三萜3种和四萜4种。在遮阴下,柠檬香茅的二萜类银杏内酯C和四萜类虾青素相对含量更高。转录组测序结果表明,单萜生物合成涉及4类合成酶的24个基因,二萜生物合成涉及11类合成酶的49个基因,倍半萜和三萜生物合成涉及12类合成酶的58个基因,其中6类合成酶的8个基因在遮阴下的相对表达量显著提高,而前萘二烯加氧酶(c64786.0)基因正好相反。q RT-PCR分析表明,遮阴下4个FPKM值差异明显的萜类合成酶基因表达的变化趋势与转录组测序结果一致,但不同合成酶基因的差异表达量存在差异。因此,柠檬香茅所含4类共23种萜类化合物由27类合成酶共131个基因编码而来,不同光照强度影响9个合成酶基因的表达和2种萜类化合物含量。     

植物萜类合酶研究进展

随着植物中许多有价值的萜类化合物被发现和应用于人类生活,萜类生物合成途径的研究倍受重视。萜类合酶催化单萜、倍半萜和二萜生物合成,即分别催化GPP、FPP和GGPP形成单萜、倍半萜和二萜。本文叙述了近年来在植物萜类合酶催化机理、克隆策略和萜类生物工程的研究进展。     

鱼腥草挥发油化学成份的研究

本文报道用气相色谱-质谱联用,结合成份系统分离和薄层析,对国产鱼腥草挥发油成份进行了研究,鉴定了4个单萜烯——α-蒎烯(α-pinene)、莰烯(camphene)、月桂烯(myrcene)和 d-柠檬烯(d-liraonene);2个含氧单萜化合物——芳樟醇(linalool)和乙酸龙脑酯(bornylacetate);1个倍半萜——丁香烯(caryophyllene);3个醛酮化合物——甲基正壬基酮(2-undecanone)、癸酰乙醛(decanoyl acetaldehyde)和月桂醛(dodecanaldehyde)等10个成份。其中莰烯、乙酸龙脑酯和丁香烯系首次在鱼腥草中发现。研究证明,我国广东产鱼腥草全草挥发油的成份与国外报道的日本产鱼腥草地上部分挥发油有较大的差别。癸酰乙醛、芳樟醇、α-蒎烯和甲基正壬基酮为挥发油中的抗菌有效成份。     

A chemometric interpopulation study of the essential oils of Cistus creticus L. growing in Crete (Greece)

The chemical composition of the essential oils of twenty-five populations of Cistus creticus subsp. creticus L. from the island of Crete (Greece) and their interpopulation variability were analysed in detail by GC-MS. 142 compounds were identified representing an average of 56.8-89.8% of the oil composition. The components are represented here by homologous series of monoterpenes, oxygenated monoterpenes, sesquiterpenes, oxygenated sesquiterpenes, diterpenes, labdane diterpenes, aldehydes, alkanes, esters, fatty acids, ketones, and others. Labdane diterpenes were detected and identified in the essential oils and have been found in high percentage composition. The results from the chemical analysis of the essential oils were submitted to chemometric cluster analysis in order to detect some pattern distribution and to identify which constituents can differentiate the groups of individuals. Two main chemotypes (clusters) were well differentiated; the first deals with eight populations of West Crete and the second with the rest of the populations. Cluster analysis based on labdane type diterpenes patterns, proved to be the best chemotype for the examined populations among the other chemical groups.     

Chemical classification of the essential oils of the Iranian Salvia species in comparison with their botanical taxonomy

The essential oils of eight Salvia species collected from different localities in Iran were analyzed by gas chromatography/mass spectrometry (GC/MS). The analytical results were compared with those previously published for related Iranian sage species in order to identify chemical markers for these species. Salvia eremophila, S. hypoleuca, and S. reuteriana are endemic, while S. atropatana, S. chloroleuca, S. santolinifolia, S. aegyptiaca, and S. macrosiphon also grow wild in neighboring countries. We categorized the Iranian Salvia species into four main chemotypes according to their essential-oil constituents: those which are dominated by 1) monoterpenes, 2) mono- and sesquiterpenes, or 3) sesquiterpenes as the major constituents, and 4) those containing low-molecular-weight acids, aldehydes, and esters, and green-leaf volatiles (GLVs). Likely due to the chemical diversity of different Salvia chemotypes, this categorization was supported by principal component analysis (PCA) for the group sampled here, but not for the values reported in the literature. We identified the following chemical markers: α-pinene, β-pinene, 1,8-cineol, linalool, and borneol in monoterpene-rich species, or β-caryophyllene, germacrene D, bicyclogermacrene, spathulenol, and caryophyllene oxide in sesquiterpene-rich species. Among these, α-pinene, β-caryophyllene, and germacrene D are the most common and abundant in the Salvia species investigated. In accordance with their close biological taxonomy, the chemical similarity of the essential oils of S. santolinifolia and S. eremophila is so high that we may consider them chemically identical.     

Variation in Terpene and Linear‐Chain Hydrocarbon Content in Yarrow (Achillea millefolium L.) Germplasm from the Rhaetian Alps,Italy

Yarrow (Achillea millefolium L.) is a herbaceous species common in the Alpine region of Europe and used in folk medicine since antiquity. Its organs are rich in monoterpenes and sesquiterpenes, two subclasses of plant terpenoids with relevant ecological significance, which were reported as valuable markers for the traceability of mountain dairy products. The variability in chemical composition of yarrow germplasm may be related with its genetic diversity, accounting for possible differences in medical properties, and supporting its use as a specific territorial marker. Aim of this work was to assess the leaf chemical composition of 16 yarrow populations collected at altitudes exceeding 1600 m in three valleys of the Rhaetian Alps, Italy, and jointly evaluated in a lowland site. The most abundant compounds detected generally differed from those of the germplasm from other countries. A trend of valley‐specific pattern of composition was evident. However, the variability among individual populations was even more remarkable, regardless of their valley of origin. The concentrations of sesquiterpene hydrocarbons, oxygenated monoterpenes, and oxygenated sesquiterpenes discriminated the populations in multivariate analysis. A few prevailing chemotypes were characterized, which differed from those previously reported in the literature. The geographic isolation from other germplasms, and the local ecotypization, likely originated a chemically distinct gene pool.     

侧柏树干的超临界CO_2萃取物组分分析及双条杉天牛的EAG反应

利用超临界CO2萃取法和索氏提取法分别提取侧柏Platycladus orientalis(L.)的韧皮部和木质部挥发物,经GC/MS分析其成分,结果表明:超临界CO2萃取物中检测到的21种组分中以倍半萜烯及其氧化物为主,没有检测到单萜类物质;索氏提取法检测到23种组分,韧皮部中检测到的组分以高沸点的树脂酸和二萜等为主,单萜烯和倍半萜及其氧化物含量较低;木质部中以倍半萜烯及其氧化物为主。将不同提取样品进行双条杉天牛Semanotus bifasciatus(Motschulsky)的触角电位反应,结果表明:2种方法的萃取物均能引起天牛的EAG反应,但以超临界萃取物引起的EAG反应较强,且与索氏提取物的反应值差异显著。罗汉柏烯和雪松醇可能是侧柏植物中引诱双条杉天牛的重要活性组分。     

Intensive sampling identifies previously unknown chemotypes,population divergence and biosynthetic connections among terpenoids in Eucalyptus tricarpa

Australian members of the Myrtaceae produce large quantities of ecologically and economically important terpenes and display abundant diversity in both yield and composition of their oils. In a survey of the concentrations of leaf terpenes in Eucalyptus tricarpa (L.A.S. Johnson) L.A.S. Johnson & K.D. Hill, which were previously known from few samples, exceptional variability was found in composition. The aim was to characterize the patterns of variation and covariation among terpene components in this species and to use this information to enhance our understanding of their biosynthesis. There were marked discontinuities in the distributions of numerous compounds, including the overall proportions of mono- and sesquiterpenes, leading us to delineate three distinct chemotypes. Overall, positive covariation predominated, but negative covariation suggested competitive interactions involved in monoterpene synthesis. Two groups of covarying monoterpenes were found, each of which was positively correlated with a group of sesquiterpenes and negatively correlated with the alternate sesquiterpene group. These results imply substantial cross-talk between mono- and sesquiterpene biosynthesis pathways. However, only those compounds hypothesized to share final carbocation intermediates or post-processing steps were strongly positively correlated within chemotypes. This suggests that the broader patterns of covariation among groups of compounds may result from co-regulation of multiple biosynthetic genes, controlling the complex terpene profiles of the chemotypes of Eucalyptus.     

Induced volatiles in elicitor-treated and rice blast fungus-inoculated rice leaves

The volatiles released from elicitor (copper chloride, jasmonic acid, UV, L-methionine and chitosan oligomer)-treated and rice blast fungus-inoculated rice leaves were collected by the solid-phase microextraction technique and analyzed by GC-MS. (Z)-3-Hexen-1-ol, monoterpenes, methyl salicylate, and sesquiterpenes were identified as elicitor-induced volatiles by a comparison of their GC retention times and mass spectra with those of authentic compounds. The different elicitors resulted in some qualitative and quantitative differences in the production of volatiles. Monoterpenes and sesquiterpenes were identified as the rice blast fungus-induced volatiles.     

Genetic and Metabolite Diversity of Sardinian Populations of Helichrysum italicum

Background

Helichrysum italicum (Asteraceae) is a small shrub endemic to the Mediterranean Basin, growing in fragmented and diverse habitats. The species has attracted attention due to its secondary metabolite content, but little effort has as yet been dedicated to assessing the genetic and metabolite diversity present in these populations. Here, we describe the diversity of 50 H. italicum populations collected from a range of habitats in Sardinia.

Methods

H. italicum plants were AFLP fingerprinted and the composition of their leaf essential oil characterized by GC-MS. The relationships between the genetic structure of the populations, soil, habitat and climatic variables and the essential oil chemotypes present were evaluated using Bayesian clustering, contingency analyses and AMOVA.

Key results

The Sardinian germplasm could be partitioned into two AFLP-based clades. Populations collected from the southwestern region constituted a homogeneous group which remained virtually intact even at high levels of K. The second, much larger clade was more diverse. A positive correlation between genetic diversity and elevation suggested the action of natural purifying selection. Four main classes of compounds were identified among the essential oils, namely monoterpenes, oxygenated monoterpenes, sesquiterpenes and oxygenated sesquiterpenes. Oxygenated monoterpene levels were significantly correlated with the AFLP-based clade structure, suggesting a correspondence between gene pool and chemical diversity.

Conclusions

The results suggest an association between chemotype, genetic diversity and collection location which is relevant for the planning of future collections aimed at identifying valuable sources of essential oil.     

Phytochemical diversity of Origanum vulgare L. subsp. vulgare (Lamiaceae) from Austria

This investigation was aiming at the phytochemical characterisation of Origanum vulgare subsp. vulgare from Austria. To study the qualitative and quantitative composition of essential oil compounds 374 individual plants were analysed via GC. The volatiles of Austrian O. vulgare subsp. vulgare were found to be complex mixtures of 53 mono- and sesquiterpenes. Among the sesquiterpenes β-caryophyllene, germacrene D, E-E-α-farnesene, germacrene D-4-ol and caryophyllene oxide were frequently present in higher amounts. The monoterpenes were mainly made up of sabinyl-compounds [mainly sabinene (up to 48.4%) and cis-sabinene hydrate (up to 57.8%)] and/or cymyl-compounds [mainly p-cymene (up to 49.7%), γ-terpinene (up to 21.5%) and carvacrol (up to 32.9%)] that were accompanied by usually smaller amounts of bornyl-compounds and acyclic compounds. Some exceptional (in O. vulgare rare) chemotypes were detected. The essential oil content of Austrian O. vulgare subsp. vulgare ranged between 0.1 and 1.8%. The content of rosmarinic acid was analysed by HPLC and ranged from 0.6 mg/g dry mass up to 37.2 mg/g dry mass. No arbutin could be detected in the analysed populations.     

Foliar and cortex oleoresin variability of silver fir (Abies alba Mill.) in Albania

Terpene composition of needle and cortical oleoresin from lateral shoots were analyzed by GC/MS for four Silver fir (Abies alba Mill.) populations scattered in natural species range in Albania. More than sixty compounds were detected in the needle oleoresin, which was characterized by a high content of alpha-pinene, camphene, beta-pinene, limonene and bornyl acetate. Three monoterpenes, alpha-pinene, beta-pinene and limonene, and two sesquiterpenes, beta-caryophyllene and germacrene D, comprised the majority of cortical oleoresin. The terpene composition differences among the populations that led to the recognition of two chemotypes. The needle oleoresin from the provinces of Puka, Bulqiza and Llogara were characterised by high amounts of beta-pinene, camphene and alpha-pinene and low amounts of limonene, while that from Drenova had high amounts of beta-pinene and limonene. A similar pattern was found in the cortical oleoresin with the exception of camphene that was a minor contributor. Geographical and seasonal variation between the populations was, also, investigated. Multivariate analysis of both needle and cortical oleoresin separated Drenova (southeastern population) from the other sites. When both major monoterpenes and sesquiterpenes were considered four chemical profiles could be attributed. Based on their chemical profiles, the populations can be divided into two groups: Populations with high content of beta-pinene and alpha-pinene but a low content of limonene (Puka, Bulqiza and Llogara), typical of most of A. alba populations in all its distribution range. Population with a high content of limonene and a moderate content of beta-pinene and alpha-pinene (Drenova).     

鸭儿芹根、茎、叶挥发油的化学成分

采用水蒸气蒸溜法提取其根、茎、叶中的挥发油,利用GC-MS联用仪对其化学成分进行分析,以归一化法计算各个化学成分的相对含量.鸭儿芹根挥发油中共分离出11个峰,鉴定出11种化合物,占总离子峰的98.61％,主要成分为α-芹子烯、γ-芹子烯等;茎中共分离出25个峰,鉴定出25种化合物,占总离子峰的100.00％,主要成分为...