7种松树挥发物分析及其主要萜烯类物质对红脂大小蠹行为选择的影响

入侵种红脂大小蠹在我国逐渐向北扩散至内蒙古和辽宁等地.同时在林间发现,相对于油松Pinus tabuliformis,其更偏好危害樟子松Pinus sylvestris var.mongolica.本文主要分析我国7种松树挥发性物质以及新发生地红脂大小蠹对其中主要物质的行为选择.本研究采用动态顶空采样法和气相色谱——质谱联用技术(GC-MS),对7种松树树干木段挥发性有机化合物(VOCs)进行采集和分析,包括油松、樟子松、华山松Pinus armandii、白皮松Pinus bungeana、马尾松 Pinus massoniana、红松 Pinus koraiensis和落叶松 Larix gmelinii.在此基础上参考以往研究中与红脂大小蠹行为相关的化合物,选择树种挥发物中7种主要烯烃类化合物:(1R)-(+)-α-蒎烯、(+)-3-蒈烯、(-)-β-蒎烯、月桂烯、(S)-(-)-柠檬烯,萜品油烯和莰烯,通过自制十通道行为仪器进行嗅觉反应试验,分析红脂大小蠹在不同浓度的化合物刺激下的行为选择反应.GC-MS结果表明,7种松树树干释放化合物中共包含烯烃类、醇类、酮类、醛类、酯类、酸类、烷烃和芳香烃8类化合物在内的54种化合物,其中烯烃类化合物相对含量最高.主成分分析及聚类分析结果表明,红脂大小蠹以往偏好寄主油松与新偏好寄主樟子松的挥发物相似度最高,(+)-3-蒈烯为其特有的挥发性物质,莰烯含量高于其他树种;4种受害寄主树种(油松、樟子松、白皮松和华山松)挥发性物质相似,均含有高比例的α-蒎烯,同时有β-蒎烯、柠檬烯、萜品油烯.选择上述6种化合物及月桂烯(华山松、白皮松中共有的萜烯类化合物)进行行为选择反应.结果显示,受害寄主树种中含有β-蒎烯以及油松、樟子松中的特征性挥发物质(+)-3-蒈烯对雌虫具有明显的吸引作用,低浓度(-)-柠檬烯(10-4mg/mL)对雄虫具有吸引作用;低浓度(10-4mg/mL)月桂烯对雌虫以及中浓度(10-2mg/mL)莰烯对雌雄成虫具有刺激性.综上所述,本研究证明了红脂大小蠹的寄主选择行为趋性与寄主树干挥发物的组成和含量有关.本试验结果将有助于理解植物挥发物对红脂大小蠹偏好寄主选择的影响,并进一步开发红脂大小蠹的引诱剂和趋避剂以应用于其防治.     

云南切梢小蠹对初侵害云南松挥发物的电生理和行为反应

云南切梢小蠹Tomicus yunnanensis(Kirkendall and Faccoli)是一种蛀害云南松Pinus yunnanensis的本土害虫.为深入了解其寄主选择机制,用顶空动态法和浸提法分别提取了初侵染云南松针叶和松脂的挥发性化合物,并用气相色谱-质谱联用技术(GC-MS)、气相色谱-昆虫触角电位测量系统(GC-EAD)、生测法鉴定和筛选了对云南切梢小蠹具有活性功能的成分.结果表明:云南松针叶和松脂中共有18种化合物,均为萜烯类物质,但两者化学成分的构成有显著差异.针叶中单萜类占99.98％,主要是 α-蒎烯(80.82％)、β-蒎烯(8.78％)、D-柠檬烯(4.77％)、莰烯(2.86％)和β-月桂烯(1.42％),而松脂以单萜类和双萜类为主,前者以α-蒎烯(21.38％)、3-蒈烯(21.42％)和异松油烯(2.78％)为主要成分,后者仅有长叶松酸(51.13％)一种.云南切梢小蠹对α-蒎烯、β-蒎烯、3-蒈烯、γ-萜品烯和4-烯丙基苯甲醚有触角电位反应,其中α-蒎烯、3-蒈烯和γ-萜品烯具引诱作用,4-烯丙基苯甲醚和β-蒎烯则为驱避功能.研究可为开发植物源引诱剂或与性信息素结合进行种群监测和诱杀提供科学依据.     

外来入侵害虫红脂大小蠹对寄主挥发物的反应

2002年,利用寄主挥发性物质(+)-α-蒎烯、(-)-β-蒎烯、3-蒈烯和(-)柠檬烯按不同配比制成诱芯,采用自行研制的挥发物释放装置,在山西省关帝山森林经营局西葫芦林场对危害油松Pinus tabulaeformis Carr.的重大外来入侵林业害虫红脂大小蠹Dendroctomus valens LeConte进行了引诱试验。结果表明,3蒈烯对红脂大小蠹的引诱作用最强,明显优于单独使用(+)-α-蒎烯和(-)-β-蒎烯的诱虫效果,也比北美应用的标准诱芯［(+)- α蒎烯(-)-β-蒎烯与3-蒈烯的比例为1∶1∶1］效果好;在标准诱芯中加入油松另一主要成分-(-)柠檬烯会明显降低诱虫效果。红脂大小蠹引诱剂最佳释放量为150 mg/d。该研究不仅对我国红脂大小蠹的监控具有实际应用意义,也从理论上探讨了红脂大小蠹与寄主油松协同进化的化学生态学过程。     

红脂大小蠹后肠挥发性物质的鉴定、触角电位和室内趋向实验

对外来松树害虫红脂大小蠹Dendroctonus valens LeConte的信息化学物质进行了研究。通过GC-MS测定,鉴定出红脂大小蠹后肠挥发性物质中除了含有松树挥发性物质α-蒎烯、β-蒎烯、3-蒈烯、月桂烯和柠檬烯外,还含有马鞭草烯醇和马鞭草烯酮;利用触角电位技术,对马鞭草烯醇、马鞭草烯酮以及在林间引诱效果最好的3-(+)-蒈烯进行了触角电生理测试;利用Y-型双向选择嗅觉仪对这些物质进行了室内趋向实验。实验结果表明: 1 μg的马鞭草烯醇、马鞭草烯酮和3-(+）-蒈烯引起雌雄触角的电位反应分别达416 μV/470 μV、597 μV/630 μV和926 μV/1 099 μV。浓度为1 μL/mL的马鞭草烯酮引起红脂大小蠹的正趋向反应,而在100 μL/mL浓度下引起红脂大小蠹的负趋向反应;在1 μL/mL的浓度下,3-(+ )-蒈烯引起了红脂大小蠹正趋向反应,而马鞭草烯醇则对红脂大小蠹具有驱避作用,说明这些物质在红脂大小蠹搜寻寄主和调节虫口密度方面起着重要作用。     

马尾松枝条挥发性组分的鉴定及松墨天牛对其触角电生理反应

为研究松墨天牛Monochamus alternatus Hope取食期引诱剂,利用气相色谱-质谱(GC-MS)联用技术并与标样核对分析了马尾松(Pinus massoniana Lamb.)枝条挥发性气味的化学组成。结果表明,马尾松1年生、2年生、3年生枝条气味均由8种萜烯类物质组成,但各组分相对含量不同。经方差分析,α-蒎烯、莰烯、β-蒎烯、柠檬烯、萜品油烯、β-石竹烯在3种枝条中的相对百分含量的差异均达到极显著水平。1年生枝条中α-蒎烯、莰烯和萜品油烯的相对含量最小,分别为20.81%、0.43%和4.74%,而β-蒎烯、月桂烯和柠檬烯的相对含量最高,分别为12.37%、4.33%和4.53%。鉴定的化合物对松墨天牛雌雄成虫的触角电生理反应的实验,结果表明,松墨天牛雌雄成虫对α-蒎烯的反应最强,对β-石竹烯的反应最弱。     

横坑切梢小蠹对植物挥发物的电生理和行为反应

为筛选出适宜配制横坑切梢小蠹(Tomicus minor Hartig)引诱剂的有效化合物,测定了横坑切梢小蠹雌、雄成虫对寄主云南松主要挥发性化合物的触角电位(EAG)和行为反应。结果表明:与对照相比,在10 g·L-1浓度刺激下所测试的9种植物挥发物都能引起横坑切梢小蠹雌、雄虫触角的EAG反应,且触角对不同挥发物的EAG反应差异显著(P0.05),其中雌、雄虫对(+)-α-蒎烯、(+)-柠檬烯、(+)-3-蒈烯、β-蒎烯和异松油烯的EAG反应较强;在剂量反应试验中,雌、雄虫的EAG反应都随着(+)-α-蒎烯、(+)-柠檬烯、(+)-3-蒈烯和β-蒎烯浓度的增加而增强,当浓度增加到10 g·L-1时,EAG反应最强;而雌、雄虫对异松油烯的EAG反应在1 g·L-1最强;除(+)-柠檬烯没有明显的定向作用外,(+)-α-蒎烯、β-蒎烯、(+)-3-蒈烯和异松油烯对横坑切梢小蠹均表现出了明显的引诱作用;行为反应多重比较表明,(+)-α-蒎烯在10 g·L-1浓度下对雌雄虫的引诱作用最大。该研究结果可为开发横坑切梢小蠹林间引诱剂提供参考。     

华山松大小蠹对几种寄主挥发物组分的EAG和行为反应

为筛选适宜配制华山松大小蠹(Dendroctonus armandi)引诱剂的有效化学成分,用触角电位仪和Y型嗅觉仪测定了华山松大小蠹雌、雄虫对华山松挥发物主要成分的触角电生理(EAG)和行为反应.结果表明:在0.01、0.1、1、10、100 μg 5种刺激剂量下,7种化合物在特定浓度下均有明确的EAG反应;雌、雄虫对月桂烯、(+)-3-蒈烯、β-石竹烯3种化合物及雄虫对(+)-α-蒎烯、柠檬烯的EAG相对电位的最大值均出现在10μg刺激条件下;在10 μg刺激剂量条件下,雌虫对(+)-α-蒎烯、β-蒎烯和(+)-3-蒈烯有明显的正趋向反应,正趋向率均高于72%且显著高于雄成虫对3种挥发物的正趋向率;在1 μg刺激下,只有雄虫对(+)-3-蒈烯有一定正趋向反应;而在100μg条件下,(-)-α-蒎烯对雌、雄虫均有一定驱避作用.该研究结果可为开发华山松大小蠹林间引诱剂提供借鉴.     

枸杞红瘿蚊对寄主植物挥发物的电生理和行为反应

植物挥发物是植食性昆虫定位寄主的重要信息物质。枸杞红瘿蚊是宁夏枸杞的主要成灾害虫,野外发现其雌虫对枸杞幼嫩花蕾具有更强的产卵趋性。为明确枸杞红瘿蚊对枸杞不同阶段花蕾挥发物的选择差异性,解析吸引其选择产卵的关键信息化学物质,采用顶空固相微萃取法和气相色谱-质谱联用技术(GC-MS),系统研究枸杞幼嫩花蕾和成熟花蕾挥发物的成分差异,选择幼嫩花蕾挥发物中的特有成分及其与成熟花蕾挥发物共有成分共8种作为候选挥发物;通过气相色谱-触角电位联用仪(GC-EAD)和Y型嗅觉仪,测定枸杞红瘿蚊对上述挥发物的电生理和行为反应,筛选关键活性挥发物。结果显示: 枸杞幼嫩花蕾和成熟花蕾挥发物的种类和释放量存在明显差异;8种化合物能激发枸杞红瘿蚊产生持续触角电生理反应,其中,有5种[3-蒈烯、莰烯、萜品油烯、d-柠檬烯和(+)-α-蒎烯]能刺激枸杞红瘿蚊产生显著趋向或躲避行为。利用枸杞挥发物设计枸杞红瘿蚊引诱剂或忌避剂,可为田间安全防控红瘿蚊提供新的途径。     

光果莸和粘叶莸挥发油烯烃部分化学成分的研究

利用毛细管气相色谱和毛细管气相色谱-质谱-计算机联用技术,对光果莸和粘叶莸挥发油的烯烃部分进行了分离和鉴定。十二个单萜烃为:α-(艹守)烯、α-蒎烯、莰烯、桧烯、β-蒎烯、香叶烯、α-松油烯、对繖花烃、柠檬烯、β-罗勒烯-y、β-水芹烯和萜品油烯;九个倍半萜烃为:α-荜橙茄烯、α-(王古)王巴烯、α-雪松烯、β-石竹烯、v-杜松烯、l-香木兰烯、α-葎草烯、β-红没药烯和δ-杜松烯。并测得了各化合物的含量。     

巨尾桉不同树龄及染虫状态桉叶油的成分分析

为了考察树龄、虫害与巨尾桉叶油成分的相互关系,更好的开发桉树资源,采用水蒸气蒸馏法提取不同树龄(4~6年生)巨尾桉叶油,用GC-MS法对巨尾桉叶油主要化学成分进行鉴定,分析不同树龄和染虫状态的桉叶油成分变化规律。结果表明,随着树龄增加,桉叶油总量逐年增加;生长年限不同,桉叶油中物质的组成及相对含量存在差异。主要成分相对含量变化情况为:桉油醇、乙酸松油酯含量随树龄逐年上升;d-柠檬烯、α-蒎烯相对含量在4到5年达到峰值,5年后开始下降;莰烯、β-蒎烯和α-松油醇逐年下降。被云斑天牛感染的林地,桉油醇、α-蒎烯、β-蒎烯、莰烯呈相对下降趋势,而d-柠檬烯、α-松油醇、乙酸松油酯的含量上升。     

Volatiles from spruce trap-trees detected by Ips typographus bark beetles: chemical and electrophysiological analyses

In the search for compounds that contribute to the host or habitat discrimination, antennae of Ips typographus were screened for sensitivity to volatiles released by spruce trap-trees using gas chromatography linked to electroantennography. The antennally active compounds were determined using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometric detection. Data show that I. typographus antennae respond to compounds emitted by the host. In total, 18 of antennally active compounds were detected: α-pinene, camphene, sabinene, β-pinene, myrcene, Δ-3-carene, p-cymene, limonene, β-phellandrene, 1,8-cineole, γ-terpinene, terpinolene, nonanal, camphor, trans-pinocamphone, cis-pinocamphone, terpinen-4-ol, and verbenone. Unequivocal identification of all active minor compounds is provided and confirmed using synthetic standards. Compounds in minor quantities like 1,8-cineole, β-phellandrene, camphor, cis-pinocamphone, and trans-pinocamphone were more active than major spruce monoterpenes. We hypothesize that the minor spruce compounds may play so far unrecognized role in conveying information about host suitability for I. typographus.     

Chemical composition of the cortical essential oil from Abies balsamea

Monoterpenoids and sesquiterpene hydrocarbons of Abies balsamea cortical oleoresin (Canada balsam) were analyzed by a combination of chromatographic and spectroscopic methods. Monoterpene hydrocarbons (21%) were composed of β-pinene, α-pinene, β-phellandrene, limonene, 3-carene, myrcene and camphene (listed in order of decreasing percentages), and oxygenated monoterpenes (0·4%) contained 4,4-dimethyl-2-cyclohepten-1-one, linalool, bornyl acetate, methylthymol, citronellyl acetate, α-terpineol, piperitone, citronellal, borneol, citronellol, two unknowns, and geraniol. From the sesquiterpene hydrocarbon fraction (1·1%) were isolated: longifolene, β-bisabolene, longipinene, an unknown, sativene, cyclosativene, cis-α-bisabolene, β-himachalene, α-himachalene, β-caryophyllene, γ-humulene, farnesene, longicyclene, an unknown, and β-selinene. Both himachalenes have been identified for the first time in Pinaceae outside of Cedrus; their co-occurrence with γ-humulene, longifolene, longipinene and longicyclene supports the biosynthetic mechanism by which all of these compounds arise through initial 1/11 cyclization of tran-cis-farnesylphosphate.     

Studies on Chemical Constituents of the Essential Oil of Artemisia subdigitata Mattf by Glass Capillary Gas Chromatography

subdigitata Mattf. by glass capillary gas chromatography. Their oils were determined by retention time, standard addition method and GC-MS. 15 components have been identified i.e. α-thujene, α-pinene, camphene, sabinene, β-pinene, myrcene, δ-3-carene, β-ocimene-x, β-isopropyl phenol, limonene, γ-terpinene, terpinen-4-ol, estragolc, geraniol, methyl eugenol. Their contents have been determined.     

Composition of turpentine from Pinus edulis wood oleoresin

Monoterpenoids and sesquiterpenoid hydrocarbons of Pinus edulis wood oleoresin were analyzed by chromatographic and spectroscopic methods. Monoterpenoid hydrocarbons (20·3%) were composed mainly of α-pinene, with camphene, β-pinene, 3-carene, sabinene, myrcene, limonene, β-phellandrene, trans-ocimene and terpinolene in secondary to trace amounts. Oxygenated terpenoids (0.28%) contained bornyl acetate and verbenone as major constituents, and linalool, camphor, terpinene-4-ol, citronellyl acetate, borneol, neral, α-terpineol, citronellol, nerol, and geraniol in smaller amounts. Oleoresin contained 1·1% of acetogenins, composed mainly of ethyl caprylate. Sesquiterpenoid hydrocarbons were high (5·7%) in oleoresin) and were composed of germacrene D as a major constituent (36·6%), of γ-amorphene, α-copaene, and longifolene as secondary constituents (5–20%), and β-farnesene, α- and γ-murolenes, β₁-, γ-, δ-, and ε-cadinenes, α-amorphene, δ-guaiene, sibirene, α-cubebene, β-copaene, β-ylangene, sativene, cyclosativene, β-bourbonene, α- and γ-humulenes, caryophyllene, α-longipinene and longicyclene in smaller amounts. Composition of P. edulis and of P. monophylla turpentines was found to be similar, with percentage of ethyl caprylate being the best distinguishing criterion.     

Variation in needle terpenoids among Pinus sylvestris L. (Pinaceae) provenances from Turkey

Variation of terpenes and resin acids in needles of young Scots pine (Pinus sylvestris L.) seedlings from nine different provenances in Turkey was investigated. The provenances represent 1200-km West to East and 400-km South to North transects. Seven monoterpenes and two sesquiterpenes were reported in the needles of pines studied. Generally, the kinds of terpenes were similar but the relative amount of some compounds differed among the origins. The major components of the monoterpene fraction in Turkish sources were α-pinene (84.8%), β-pinene (4.1%) and limonene (3.0%), corresponding to 91.9% of the crude needle extract. In a PCA-analysis, 3-carene, myrcene and terpinolene in seedlings from Turkish provenances were quite low and thus, they were clearly different from a Northern European Scots pine provenance from Finland. In the resin acid fraction, abietic acid (62.4%) and dehydroabietic acid (16.1%) were the most abundant constituents in the needles of the Scots pine from Turkish provenances.     

The leaf oil terpene composition of Juniperus occidentalis

The chemical composition of the volatile oil of 10 trees each of two Oregon populations of the western juniper was determined by a computerized GC-MS method. The identity of the major components, sabinene, α-pinene, α- and γ-terpinene, p-cymene, limonene, terpinen-4-ol and bornyl acetate was confirmed. In addition, tricyclene, α-thujene, camphene, β-pinene, α- and β-phellandrene, car-3-ene, trans-ocimene, linalool oxide, terpinolene, trans-sabinene hydrate, camphor, camphene hydrate, borneol, α-terpineol, p-cymenol, methyl citronellate, citronellyl acetate, carvacrol, cuminic aldehyde, β-bourbonene, several cadinene and cadinol isomers, elemol, γ-, β- and α-eudesmol, and manoyl oxide were identified. Santene, citronellol, and aromatic ethers of the safrole-eugenol type were not found. Tree-to-tree variability of the relative percentages of these terpenes was fairly large and chemosystematic implications are discussed briefly.     

Identification des constituants de l'essence des aiguilles de Pinus pinaster

The chromatographic analysis of the volatile leaf oil of Pinus pinaster Ait. showed 42% of monoterpene hydrocarbons (α-pinene, camphene, β-pinene, myrcene, 3-carene, limonene, cis-ocimene, terpinolene, para-cymene, 35% of sesquiterpene hydrocarbons (cubebene, copaene, caryophyllene, humulene, germacrene D, α- and γ-muurolenes, δ- and γ-cadinenes) and 23% of oxygenated compounds including esters (linalyl, bornyl, geranyl, neryl and farnesyl acetates), alcohols (cis-hexenol, linalool, α-fenchol, trans-pinocarveol, terpinen-4-ol, α-terpineol, dihydrocarveol, guaiol, junenol and α-cadinol), one aldehyde (hexenal) and one ketone (piperitone). Three non terpenoid phenylethyl esters were also identified: phenylethyl isovalerate, methyl-2 burtyate and 3-3 dimethylacrylate. Some alcohols and mainly α-terpineol and linalool seemed to be formed during the steam distillation process, they were absent when the leaf oil was obtained by maceration of small portions of leaves in the usual solvents of terpenes.     

Volatile terpenoids from aeciospores of Cronartium fusiforme

Aeciospores of Cronartium fusiforme isolated from slash pine (Pinus elliottii) trees were analyzed for volatile terpenoids by GLC and GLC-MS. α-Pinene, β-pinene, Δ³-carene, myrcene, linonene, β-phellandrene, and δ-terpinene were the major monoterpenoid hydrocarbons present with only traces of camphene. A number of monoterpenoid alcohols were also present of which terpinen- 4-ol predominated. Among the various acyclic sesquiterpenes present, β-farnesene and β-citronellol were identified. Several aromatic compounds were also observed, including o-cresol.