Combinatorial chemistry in insects: a library of defensive macrocyclic polyamines.

The pupal defensive secretion of the coccinellid beetle Epilachna borealis is composed principally of a combinatorial library of macrocyclic polyamines. These compounds constitute a previously unrecognized family of natural products, characterized by extremely large-ring lactonic structures derived from a small set of (2-hydroxyethylamino)alkanoic acids. The combinatorial assembly of these simple building blocks generates a high degree of structural diversity, which is further increased by slow, spontaneous intramolecular rearrangement of the macrocycles.

Detection and imaging of chrome yellow (lead chromate) in latent prints, solid residues, and minerals by laser-desorption/ionization mass spectrometry (LDI-MS).

In the past, chrome yellow (lead chromate, PbCrO4 ), a bright orange-red substance, has been widely used as an inorganic pigment in the production of paints, coatings, and plastics. Herein, we demonstrate that laser desorption/ionization mass spectrometry (LDI-MS) is a powerful tool for the detection of lead chromate in solid residues. In fact, lead chromate in trace amounts is easily detectable by LDI-MS even from residues left as latent prints. For example, a latent print obtained by stamping the exposed laterally cut surface of a pencil over 50 years old on an acetonitrile-moistened paper, was successfully imaged for both lead and chromate using a Synapt G2 HDMS mass spectrometer. After rastering the print with a 355 nm laser beam and recording positive- and negative-ion mass spectra over the range m/z 50-1200, we generated false-color 'heat maps' (single-ion images) for 208 Pb+• (m/z 207.98) and Cr2 O6-• (m/z 199.85). The heat maps matched closely with the faint visual image of the pencil imprint. Moreover, our results confirmed that lead chromate was used in the pigment coatings of old pencils. Evidently, LDI-MS imaging is an efficient procedure to survey for the presence of lead and chromate in minerals and other materials. Copyright © 2017 John Wiley & Sons, Ltd.

Contents of dufour glands of workers of three species of Tetramorium (Hymenoptera: Formicidae).

The Dufour glands of worker ants of Tetramorium caespitum, and the morphologically similar T. impurum are filled with similar, but species-specific mixtures of linear hydrocarbons and three homologous sesquiterpene corhpounds. Glands of workers ofT. caespitum contain, on average, 70 ng of oil containing C13 to C17 linear hydrocarbons with n-pentadecane (64%) and a mixture of pentadecenes (14%) as major components.T. impurum glands are smaller and contain an average of 40 ng of the same mixture but with n-pentadecane (49%) and a sesquiterpenoid compound (19%) the major components. Two isomeric pentadecenes, (Z)-6-pentadecene and (Z)-7-pentadecene are present in both species.T. semilaeve workers contain on average only 30 ng of a simple mixture of hydrocarbons with pentadecane contributing more than 90% of the total.

A feeding stimulant for Manduca sexta from Solanum surattenses.

The acceptance of Solanum surattenses as a host plant for the larvae of Manduca sexta was explained by the presence of feeding stimulants in foliage. Bioassay-guided fractionation of plant extracts resulted in the isolation of a highly active compound (1), which was identified as a furostan derivative {26-O-beta-D-glucopyranosyl-(25R)-furosta-5-ene-3-beta-yl-O-alpha-L-rhamnopyranosyl-(1''-2')-O-alpha-L-rhamnopyranosyl-(1'''-3'')-O-beta-D-glucopyranoside}. This compound has the same steroidal core substructure as that in a stimulant (indioside D) previously identified from potato foliage. However, the sugar substituents attached to the core are different.

Characterization of vinyl-substituted, carbon-carbon double bonds by GC/FT-IR analysis.

Vapor-phase infrared spectra allow the determination of the stereochemistry of carbon-carbon double bonds conjugated with a vinyl group. Cis and trans isomers of unsubstituted 1,3-alkadienes can be differentiated on the basis of the differences observed in the 900-1000 cm-1 region (spectra of cis isomers show two bands at 993 and 906 cm-1, while those of trans compounds show three absorptions at 998, 949, and 902 cm-1) and the 1590-1650 cm-1 region (the C=C stretch bands are observed at 1595 and 1642 cm-1 for cis compounds and at 1604 and 1650 cm-1 for trans compounds). Compounds bearing CH2=CHC(CH3)=CHCH2- and CH2=CHC(=CH2)-CH2- structural moieties, referred to as alpha- and beta-type compounds, are frequently encountered as natural products. For compounds bearing alpha-type groups, the cis/trans configuration of the trisubstituted double bond can be determined unambiguously. An absorption at 3095-3091 cm-1, for the =CH2 stretch vibration, is common to both of these groups; however, due to the presence of two =CH2 groups, the relative intensity of the band is much higher for beta-type compounds. For alpha-type compounds, a cis configuration at the C-3 carbon atom is characterized by a =CH2 wag absorption at 907-906 cm-1. For beta-type compounds and 3E-alpha-type compounds, this band appears at 899-897 cm-1. In addition, a wavy "fingerprint" pattern with two minima at 1632 (low intensity) and 1595-1594 cm-1 (high intensity) is characteristic for beta-type compounds. Our generalizations are based on spectra of cis and trans ocimene, myrcene, and dehydration products of many 3-methyl-1-alken-3-ols. Six isomers of farnesene can be characterized by GC/FT-IR. Furthermore, gas-phase IR allows the determination of the configuration of the trisubstituted double bond at C-3 in alpha-type farnesene congeners. For example, the homo- and bishomofarnesene isomers from Myrmica ants were shown to include a 3Z bond.

Identification of trail pheromone of the antTetramorium caespitum L. (Hymenoptera: Myrmicinae).

The trail pheromone of the antTetramorium caespitum L. is a 70∶30 mixture of 2,5-dimethylpyrazine and 3-ethyl-2, 5-dimethylpyrazine. The average total amount of the two pyrazines present in the poison vesicle was found to be 3.9 ng per ant, of which 2.7 ± 0.4 ng is 2,5-dimethylpyrazine and 1.15 ±0.25 ng is 3-ethyl-2,5-dimethylpyrazine. The pyrazines constitute only 0.03% of the volume of the poison vesicle but account for the whole of the trail-following activity. A 70∶30 mixture of the respective pyrazines evoked the highest activity in artificial trail-following tests.

Defensive secretion of a carabid beetle,Helluomorphoides clairvillei.

The defensive spray of a single female of the rare carabid beetle,Helluomorphoides clairvillei (subfamily Carabinae, supertribe Lebiitae, tribe Helluonini). was found to contain a mixture of compounds, including carboxylic acids (formic, acetic), aliphatic esters (principally nonyl acetate), and hydrocarbons (principally decane). In a single series of discharges, the beetle ejected a total of about 1% of its body weight as formic acid (1.1 mg). Our findings demonstrate that characterization of secretory components from even minimal samples of secretion should be possible in many cases.

Determination of double-bond position in some unsaturated terpenes and other branched compounds by alkylthiolation.

The electron-impact mass spectra of alpha, beta-bis(methylthio) derivatives of certain terpenes and other compounds with branched alkenyl groups contain diagnostic peaks that can be used for locating the position of the double bond in the parent compound. In contrast to the spectra of dimethyl disulfide (DMDS) derivatives obtained from compounds containing CH=CH type double bonds, which show two predominant fragment ions, most of the compounds examined in the current investigation showed only one predominant fragment ion, arising from that part of the molecule which possesses the more substituted carbon of the original double bond. For example, all the derivatives from compounds with an isopropylidene moiety showed a base peak at m/z89 which can be attributed to the formation of a [(CH3)2C=SCH3]+ fragment. The application of the DMDS procedure to naturally occurring terpenes is discussed.

Gas-phase infrared spectroscopy for determination of double bond configuration of monounsaturated compounds.

Gas-phase Fourier-transform infrared spectra allow unambiguous determination of the configuration of the double bonds of long-chain unsaturated compounds bearing RCH=CHR' type bonds. Although the infrared absorption at 970-967 cm-1 has been used previously for the identification of trans bonds, the absorption at 3028-3011 cm-1 is conventionally considered to be incapable of distinguishing cis and trans isomers. In this paper, we present a large number of gas-phase spectra of monounsaturated long-chain acetates which demonstrate that an absorption, highly characteristic for the cis configuration, occurs at 3013-3011 cm-1, while trans compounds fail to show any bands in this region. However, if a double bond is present at the C-2 or C-3 carbon atoms, this cis=CH stretch absorption shows a hypsochromic shift to 3029-3028 and 3018-3017 cm-1, respectively. Similarly, if a cis double bond is present at the penultimate carbon atom, this band appears at 3022-3021 cm-1. All the spectra of trans alkenyl acetates showed the expected C-H wag absorption at 968-964 cm-1. In addition, the spectra of (E)-2-alkenyl acetates show a unique three-peak "finger-print" pattern which allows the identification of the position and configuration of this bond. Furthermore, by synthesizing and obtaining spectra of appropriate deuteriated compounds, we have proved that the 3013-3011 cm-1 band is representative of the C-H stretching vibration of cis compounds of RCH=CHR' type.

Technique for injecting intact glands for analysis of sex pheromones of Lepidoptera by capillary gas chromatography : Reinvestigation of pheromone complex ofMamestra brassicae.

The structure elucidation of sex pheromones of Lepidoptera by a solid-sample injection technique in conjunction with capillary gas chromatography is described. The applicability of this method in GC and GC-MS modes was demonstrated by reanalyzing the sex attractants of females ofOstrinia nubilalis andBombyx mori. The pheromone complex ofMamestra brassicae was reinvestigated and (Z)-9-hexadecenyl acetate and (Z)-11-hexadecenol were found in addition to already known pheromone components of this species. By using the solid-sample injection, the exact site of pheromone release could be determined inM. brassicae.

Chemical composition and function of metapleural gland secretion of the ant,Crematogaster deformis smith (hymenoptera: Myrmicinae).

The secretion of the hypertrophied metapleural gland of the antCrematogaster deformis contains a mixture of phenols, consisting mainly of 3-propylphenol, 3-pentylphenol, 3,4-dihydro-8-hydroxy-3-methylisocoumarin (mellein), 5-propylresorcinol, and 5-pentylresorcinol. The secretion is released, as a repellent, when the highly vulnerable petiolar-postpetiolar region of the abdomen is attacked by enemy ants. In addition, small amounts of the secretion are released regularly to serve as an antiseptic, which is considered the original function of the gland. The secretion also has some insecticidal properties.

Identification of sex pheromone components ofSpodoptera sunia Guenée (Lepidoptera: Noctuidae).

Moths belonging to the speciesSpodoptera sunia have been recognized as a new pest of cotton in Central America. By means of electro-physiologic investigations, solid sample injection gas chromatography, and combined gas chromatography-mass spectrometry, (Z)-9-tetradecenyl acetate, (9Z,12E)-9,12-tetradecadienyl acetate, (Z)-9-tetradecen-1-ol, and (Z)-11-hexadecenyl acetate, in a ratio of 100∶5∶31∶20, were identified in the pheromone gland of female insects. These substances should serve as a base for the development of a pheromone-monitoring system for this lepidopteran pest.

Tocopheryl acetates from the pupal exocrine secretion of the squash beetle, Epilachna borealis (Coccinellidae).

The oily droplets on the pupal integumental hairs of the squash beetle Epilachna borealis contain a mixture of alpha-, beta-, gamma-, and delta-tocopheryl acetates as major constituents. In addition, the secretion contains a number of minor components that appear to be dehydrocongeners of the major components. This is the first report of the occurrence of acetate esters of any tocopherol in nature.

Chemical egg defense in a green lacewing (Ceraeochrysa smithi)

The green lacewing Ceraeochrysa smithi (Neuroptera, Chrysopidae), like other members of its family, lays its eggs on stalks, but it is unusual in that it coats these stalks with droplets of an oily fluid. The liquid consists of a mixture of fatty acids, an ester, and a series of straight-chain aldehydes. Relative to the eggs of a congeneric chrysopid that lacks stalk fluid, the eggs of C. smithi proved well protected against ants. Components of the fluid, in an assay with a cockroach, proved potently irritant. Following emergence from the egg, C. smithi larvae imbibe the stalk fluid, thereby possibly deriving nutritive benefit, defensive advantage, or both.

Chilocorine C: a new "dimeric" alkaloid from a coccinellid beetle, Chilocorus cacti.

A new hexacyclic alkaloid, chilocorine C (4), has been isolated from Chilocorus cacti and characterized on the basis of its IR, UV, MS, and NMR data. Although its structure is closely related to that of exochomine (1) (isolated from Exochomus quadripustulatus) and to chilocorine A (2) and B (3) (obtained previously from C. cacti), the presence of a hydroxymethyl substituent on the saturated tricyclic moiety represents an unexpected structural variation on the dimeric alkaloid theme.

Chemical and behavioral studies on dufour gland contents ofManica rubida (Hymenoptera: Formicidae).

The Dufour gland ofManica rubida contains a simple mixture of (Z, E)-α-farnesene and (Z, E)-α-homofarnesene with tiny amounts of other faraesene, homofarnesene, and bishomofarnesene isomers. The gland also contains a mixture of very volatile compounds, chiefly acetone, with smaller amounts of acetaldehyde, ethanol, propanol, isobutyraldehyde, butenone, and butanone. The workers ofM. rubida are not attracted to these highly volatile compounds as are workers ofMyrmica species, butM. rubida workers show a strong increase of linear speed when stimulated by a freshly isolated gland. This response of increased speed of bothM. rubida andM. trubra to their own or each other's Dufour gland secretion is consistent with the presence of the farnesenes in them both.

Sexual dimorphism in the defensive secretion of a carabid beetle.

The defensive secretions of male and female Oodes americanus display striking qualitative differences. Altogether 13 carboxylic acids were identified in the secretions of the two sexes. Methacrylic, crotonic, and tiglic acids are produced exclusively by the female; the male lacks these unsaturated components, but produces their saturated analogs. 2-Methylbutyric acid is a major component produced by both sexes. Shared components also include hexanoic, (E)-2-hexenoic, benzoic, and (E)-2-octenoic acid, of which the latter two had not previously been reported from carabid beetles.

Defensive secretion ofTenebrio molitor (Coleoptera: Tenebrionidae).

The defensive secretion ofTenebrio molitor contains a mixture of 2-methyl-1,4-benzoquinone andm-cresol. The phenol had not previously been detected in the secretion, although some investigators reported presence of 2-ethyl-1,4-benzoquinone as a second component. We failed to detect the latter quinone in secretion samples from three laboratory populations ofT. molitor.

Pyrrolidinoöxazolidine alkaloids from two species of ladybird beetles.

From the mixture of alkaloids obtained from adults of two species of ladybird beetles, Epilachna varivestis and Epilachna borealis, a novel bicyclic alkaloid, 5-(12'-aminotridecyl)pyrrolidinoöxazolidine [(5 alpha, 7 a beta)-hexahydro-alpha-methylpyrrolo[2,1-b]oxazole-5-dodecaneami ne] (2) was characterized on the basis of spectrometric and synthetic investigations. This new alkaloid is related structurally to a monocyclic congener 1-(2-hydroxyethyl)-2-(12'-aminotridecyl)pyrrolidine (1), previously characterized from E. varivestis. Two additional alkaloids (lower homologs of 1 and 2) from E. borealis were characterized as 5-(10'-aminoündecyl)pyrrolidinoöxazolidine [(5 alpha,-7 a beta)-hexahydro-alpha-methylpyrrolo[2,1-b]oxazole-5-decaneamine ] (7) and 1-(2-hydroxyethyl)-2-(10'-aminoündecyl)pyrrolidine (8), on the basis of their mass spectra.

Cycloalkene budding: mass spectrometric studies of competitive and dual cycloalkene extrusion reactions from doubly unsaturated aldehyde N,N-dimethylhydrazones.

Mass spectral fragmentation pathways of four doubly unsaturated aldehyde N,N-dimethylhydrazones were investigated using EI-MS and tandem mass spectrometry (MS/MS) under electron ionization and collisionally activated decomposition (CAD) conditions. Cyclopentene extrusion was found to be slightly favored over cyclohexene loss in a hydrazone capable of losing either cycloalkene. Evidence for the regeneration of a chain-shortened iminium radical cation as a result of cycloalkene extrusion was provided by studying substrates capable of undergoing successive cycloalkene budding sequences. EI-MS of these compounds shows sequential loss of both cyclopentene and cyclohexene, in accord with expectations for a cascade mechanism. Although these MS/MS experimental results are also compatible with alternative mechanisms which would entail the simultaneous loss of both neutral cycloalkenes or of a macrocyclic diene, a rapid cascade of cycloalkene budding accounts best for the experimental observations.