Chiral HPLC resolution of monoepoxides derived from 6,9-dienes and its application to stereochemistry assignment of fruit-piercing noctuid pheromone

Yamamoto, Masanobu; Takeuchi, Yaeko; Ohmasa, Yoshihisa; Yamazawa, Hiroyuki; Ando, Tetsu

doi:10.1002/(sici)1099-0801(199910)13:6<410::aid-bmc902>3.0.co;2-4

Cited by 13 publications

(6 citation statements)

References 12 publications

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“…Entomopathogens are important regulatory factors of insects (Khosravi et al , ), but cuticular compounds of insects, especially fatty acids, may act as inducers of insect resistance to fungi and bacteria (Gołębiowski et al , ). Cuticular lipids also protect insects from desiccation (Hadley, ; Benoit and Denlinger, ) and they are utilized for chemical communication as pheromones (Martins and Ramalho‐Ortigão, ; Wakamura et al , ; Naka et al , ; Yamamoto et al , ; Williamson and Bartlett, ). Cuticular compounds consist of primarily hydrocarbons, free fatty acids (FFAs), alcohols, esters, aldehydes and wax esters (Cerkowniak et al, ).…”

Section: Introductionmentioning

confidence: 99%

Determination of cuticular and internal fatty acids of Chorthippus brunneus males and females using HPLC‐LLSD and GC–MS

Gołębiowski

Cerkowniak

Ostachowska

et al. 2016

Biomedical Chromatography

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Insects are of growing significance in veterinary medicine and human healthcare; therefore, an understanding of their biology is very important. The cuticular and internal fatty acid compositions of Chorthippus brunneus males and females have been studied for the first time. The lipids of males and females were separated into classes of compounds using high-performance liquid chromatography with a laser light scattering detector. The free fatty acid (FFA) fractions obtained by HPLC were silylated and then analyzed by GC-MS. The cuticular lipids of males contained 15 saturated, four unsaturated with even-numbered and two unsaturated with odd-numbered carbon chains, FFAs ranging from C8 to C25. The major free fatty acids in males were C16 (20.8%), C18:2 (8.5%), C18:1 (32.9%) and C18 (24.4%). The cuticular lipids of females contained 17 saturated, four monounsaturated and two diunsaturated free fatty acids ranging from C8 to C30. The major cuticular fatty acids in females were C16 (25.1%), C18:2 (6.2%), C18:1 (23.7%) and C18:0 (33.2%). The internal FFAs of males consisted of 20 compounds ranging from C8 to C26. Four of these compounds were detected as major compounds: C16 (14.1%), C18:2 (21.6%), C18:1 (38.0%) and C18 (22.5%). Among 18 internal free fatty acids of females, C16 (22.3%), C18:2 (10.9%), C18:1 (40.2%) and C18 (20.5%) were the most abundant compounds. The following cuticular fatty acids present in the lipids of females were absent in the lipids of males: C26, C27 and C30. On the other hand, only C24 was absent from the cuticular lipids of females. Only C10 and C24 internal fatty acids present in the lipids of males were absent in the lipids of females. Copyright © 2016 John Wiley& Sons, Ltd.

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Section: Introductionmentioning

confidence: 99%

Determination of cuticular and internal fatty acids of Chorthippus brunneus males and females using HPLC‐LLSD and GC–MS

Gołębiowski

Cerkowniak

Ostachowska

et al. 2016

Biomedical Chromatography

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“…3). In our pheromone research, the chiral HPLC has been used for the resolution of several epoxy compounds in lepidopteran Type II pheromones (Qin et al 1997;Yamamoto et al 1999;Ando et al 2004), an acetate of secondary alcohol produced by a midge (Hall et al 2009), and a ketol and a diol produced by a long-horned beetle (Kiyota et al 2009). This study is the first successful application of chiral HPLC to methyl-branched pheromones, and it is noteworthy that enantiomers of less polar volatiles showed different chromatographic behaviors on a chiral HPLC column.…”

Section: Discussionmentioning

confidence: 99%

Positions and Stereochemistry of Methyl Branches in the Novel Sex Pheromone Components Produced by a Lichen Moth, Lyclene dharma dharma

et al. 2010

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Female moths of Lyclene dharma dharma (Arctiidae, Lithosiinae) produce three sex pheromone components (I-III), for which we assigned the following novel chemical structures; 6-methyl-2-octadecanone (1) for I, 14-methyl-2-octadecanone (2) for II, and 6,14-dimethyl-2-octadecanone (3) for III. In the Iriomote Islands where the insects were collected, a lure including racemic 1 and 2 attracted the male moths without mixing 3. In this study for further confirmation of the plane structures, the positional isomers with a methyl branch at the 4-, 5-, 7-, 13-, or 15-position (4-8, respectively) were synthesized. The GC-MS analyses revealed that natural components I and II were best fitted with those of 1 and 2, respectively, among the methyl-2-octadecanones examined, indicating the usefulness of this analytical instrument and authentic standards for the determination of the positions of methyl branches. In field trapping tests, 4-8 could not substitute for 1 or 2, nor did these compounds inhibit the active binary lure of 1 and 2, indicating that the males strictly recognized the 2-ketones with a methyl branch at the 6- or 14-positions. Next, the absolute configurations of I and II were determined by HPLC with a normal-phased chiral column (Chiralpak AD-H), which could separate the enantiomers of both 1 and 2. The chiral HPLC analysis of a crude pheromone extract indicated that the females exclusively produced (S)-1 and (S)-2. Furthermore, a field evaluation of each enantiomer revealed that (S)-1 and (S)-2 were bioactive but (R)-1 and (R)-2 were not.

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“…These compounds may be pheromones, that is, compounds serving for non‐verbal communication. They can also be attractants or act as a deterrent (Williamson & Bartlett, ; Yamamoto, Takeuchi, Ohmasa, Yamazawa, & Ando, ; Yew & Chung, ). It was also found that the extracts of insects possess antifungal properties (Lecuona, Clement, Riba, Joulie, & Juarez, ).…”

Section: Introductionmentioning

confidence: 99%

Application of headspace solid‐phase microextraction followed by gas chromatography coupled with mass spectrometry to determine esters of carboxylic acids and other volatile compounds inDermestes maculatusandDermestes aterlipids

Cerkowniak

Boguś

Włóka

et al. 2017

Biomedical Chromatography

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A constant problem in veterinary medicine, human healthcare, agriculture, forestry and horticulture is the large number of pests, and the lack of effective methods to combat them which cause no harm to the rest of the environment. It is recommended and desired to reduce the use of chemicals and increase the use of agents based on knowledge acquired in the fields of biology, chemistry and agrochemicals. To learn the defense mechanisms of insects we should consider not only the site of their physiological ability to protect against external factors (cuticle), but also the possibility of chemical protection, formed by all compounds on the surface and in the body of insects. In this study, a procedure was developed to determine the esters of carboxylic acids in insect lipids. Headspace solid-phase microextraction was followed by gas chromatography coupled with gas spectrometry. First, the best conditions were selected for the analysis to obtain the best chromatographic separation. An RTx-5 column was used for this purpose. Polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polyacrylate fibers were used to isolate acid esters. PDMS/DVB fiber achieved the best conditions for the extraction; the extraction time was 50 min, the extraction temperature was 105°C and the desorption time was 10 min at 230°C. These solid-phase microextraction conditions were used to analyze volatile compounds extracted from insects belonging to the Dermestidae family.

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Chiral HPLC resolution of monoepoxides derived from 6,9-dienes and its application to stereochemistry assignment of fruit-piercing noctuid pheromone

Cited by 13 publications

References 12 publications

Determination of cuticular and internal fatty acids of Chorthippus brunneus males and females using HPLC‐LLSD and GC–MS

Determination of cuticular and internal fatty acids of Chorthippus brunneus males and females using HPLC‐LLSD and GC–MS

Positions and Stereochemistry of Methyl Branches in the Novel Sex Pheromone Components Produced by a Lichen Moth, Lyclene dharma dharma

Application of headspace solid‐phase microextraction followed by gas chromatography coupled with mass spectrometry to determine esters of carboxylic acids and other volatile compounds inDermestes maculatusandDermestes aterlipids

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