After chemo-metamorphosis: p-menthane monoterpenoids characterize the oil gland secretion of adults of the oribatid mite, Nothrus palustris.

The oil gland secretion of the oribatid mite Nothrus palustris is known to show the phenomenon of juvenile-adult polymorphism, i.e., juvenile instars produce secretions predominated by geranial, whereas adults secrete dehydrocineole along with a number of chemically unidentified compounds. We here re-analyzed the secretions of adult N. palustris by GC-MS and NMR spectroscopy, eventually identifying the unknown compounds as p-menthane monoterpenoids. The major components were two isomeric 6-isopropenyl-3-methyl-cyclohex-3-en-1-yl formates (= p-1,8-menthadien-5-yl formates), which accounted for about 75% of the secretion. These were accompanied by five additional, only partly identified p-menthanes (or p-methane-derivatives), all of which represented minor or trace components. In addition, adult secretions contained two C21-hydrocarbons, 1,12-heneicosadiene (major) and a heneicosatriene (minor). Menthane monoterpenoids represent a novel sub-class of terpene compounds in the oil gland secretions of Oribatida. In case of N. palustris, we assume that both geranial and p-menthane monoterpenoids arise via the mevalonate pathway which obviously shows a split at the level of geranyl pyrophosphate, leading to geranial in juveniles and to p-menthanes in adults. The significance of methane occurrence in oil glands as well as the taxonomic distribution of juvenile-adult polymorphism in oribatid oil gland secretions is discussed. The latter phenomenon-i.e., "chemo-metamorphosis" of secretions-is not known from early- and middle-derivative Oribatida nor from Astigmata, but appears to be more common in some derivative desmonomatan and brachypyline oribatid groups.

Chemical footprints mediate habitat selection in co-occurring aphids.

Habitat selection is a critical process that shapes the spatial distribution of species at local and regional scales. The mechanisms underlying habitat preference rely on environmental factors, species traits, and ecological interactions with other species. Here, we examined spatial segregation between two co-occurring aphid species (Rhopalosiphum maidis and R. padi) on wheat plants. We hypothesized that spatial segregation between these aphid species was mediated by aphid cuticular compounds left as chemical "footprints" on plant surfaces. Combining field and laboratory experiments, we first examined how plant microsites alter fitness by measuring the fecundity of each species. Next, we tested whether intra- and interspecific pre-inhabitation modified habitat selection in both aphid species. Both aphid species preferred and exhibited higher fecundity on wheat stems versus leaves. Laboratory trials showed that R. maidis pre-inhabitation altered R. padi spatial preference. By gas chromatography-mass spectrometry analysis and bioassays testing the effects of aphid density and footprint extracts, we found a density-dependent response, with R. padi avoiding locations previously inhabited by R. maidis. The chemical analysis of footprint crude extracts revealed a highly abundant compound, 1-hexacosanol, and when presented in the synthetic form, also elicited R. padi displacement. Altogether, it indicated that R. maidis footprints altered R. padi habitat selection with cuticular compounds playing a relevant role in the habitat selection process in co-occurring aphid species.

The scent gland chemistry of Gagrellinae (Opiliones, Sclerosomatidae): evidence for sequestration of myrmicacin in a species of Prionostemma.

The scent gland secretion of an undetermined species of Prionostemma from Costa Rica was analyzed by gas chromatography-mass spectrometry and shown to consist of medium-chain carboxylic acids (mainly octanoic acid) and a ß-hydroxy-carboxylic acid, eventually identified as myrmicacin (= (R)-3-hydroxydecanoic acid). While scent gland secretions in harvestmen have traditionally been considered to be products of de novo synthesis, we here provide evidence for the unusual case of sequestration-derived scent gland constituents: at least myrmicacin appears to be sequestered from leaf-cutter ants that constitute a part of the prey of the Prionostemma-species herein investigated. This is the first report on the scent gland chemistry of the sclerosomatid subfamily Gagrellinae as well as on a possible sequestration mechanism in harvestmen.

Inter- and Intrasexual Variation in Cuticular Hydrocarbons in Trichrysis cyanea (Linnaeus, 1758) (Hymenoptera: Chrysididae).

Cuckoo wasps (Chrysididae, Hymenoptera) are known for their parasitoid or cleptoparasitic life histories. Indeed, the biology of only a few species has been studied in detail and often only little more is known than the host species. By mimicking their hosts' cuticular hydrocarbon (CHC) profiles, species that parasitize single (or a few closely related) host species manage to deceive their hosts. However, the variability of the CHC profile in generalist cuckoo-wasp species is still unknown. Here, we used gas chromatography-mass spectrometry (GC-MS) and DNA barcoding to study intraspecific variation in cuticular hydrocarbons of one less host-specific species of cuckoo wasps, Trichrysis cyanea. Cuticular hydrocarbon (CHC) patterns were found to differ between males and females. Additionally, we found chemical polymorphism among females, which formed three distinct chemical subgroups characterized by different alkene patterns. A lack of divergence in the DNA barcoding region suggests that these different chemotypes do not represent cryptic species. Whether this intrasexual CHC-profile variation is an adaptation (mimicry) to different host species, or simply signaling the reproductive status, remains unclear.

A Novel Class of Defensive Compounds in Harvestmen: Hydroxy-γ-Lactones from the Phalangiid Egaenus convexus.

When threatened, the harvestman Egaenus convexus (Opiliones: Phalangiidae) ejects a secretion against offenders. The secretion originates from large prosomal scent glands and is mainly composed of two isomers of 4-hydroxy-5-octyl-4,5-dihydro-3H-furan-2-one (1), a ß-hydroxy-γ-lactone. The compounds were characterized by GC-MS of their microreaction derivatives, HRMS, and NMR. After the synthesis of all four possible stereoisomers of 1, followed by their separation by chiral-phase GC, the absolute configurations of the lactones in the Egaenus secretion was found to be (4S,5R)-1 (90%) and (4S,5S)-1 (10%). Hydroxy-γ-lactones represent a new class of exocrine defense compounds in harvestmen.

The scent gland chemistry of neogoveid cyphophthalmids (Opiliones): an unusual methyljuglone from Metasiro savannahensis.

While the chemistries of scent gland secretions from a few selected species of three families of Cyphophthalmi, namely Sironidae, Pettalidae, and Stylocellidae, have already been reported and found to consist of complex blends of naphthoquinones and methyl ketones, nothing is known about the other families. We here report on the secretions of Metasiro savannahensis Clouse and Wheeler (Zootaxa 3814:177-201, 2014), a first representative of the family Neogoveidae. The secretions from males, females and one juvenile were extracted and analyzed by gas chromatography-mass spectrometry. Twenty-five compounds were identified, all of which belong to the chemical classes of naphthoquinones and methyl ketones, confirming a hypothesized chemical uniformity of cyphophthalmid exudates. One major naphthoquinone compound, however, was new for cyphophthalmids and for arthropod exocrine secretions in general: a methyljuglone isomer, 6-methyljuglone (= 6-MJ; iupac name: 5-hydroxy-6-methyl-1,4-naphthoquinone), amounted for about 20% of the secretion and was eventually identified by synthesis. Hydroxy-naphthoquinones and their derivatives are known to possess a variety of antibiotic effects, probably enhancing the antimicrobial/antifungal potential of the Metasiro-secretion. Currently, without further data on neogoveids, the compound represents a chemical autapomorphy of M. savannahensis, and-just as the strange chloro-naphthoquinones of Sironidae and Pettalidae-adds to the repertoire of unusual naphthoquinone compounds across the Cyphophthalmi.

Phenol-based millipede defence: antimicrobial activity of secretions from the Balkan endemic millipede Apfelbeckia insculpta (L. Koch, 1867) (Diplopoda: Callipodida).

Millipedes use an array of chemical compounds to defend themselves from predator attack. These chemical substances can have additional roles, i.e. defence against various pathogens. We evaluated the efficacy of the defensive secretion of Apfelbeckia insculpta (L. Koch, 1867) against bacteria, yeasts, and filamentous fungi. The tested secretion consisted of two compounds, p-cresol and phenol, and showed antibacterial, antibiofilm, and antifungal potential against all selected microorganisms. The most sensitive bacterium in our study was Pseudomonas aeruginosa, while the tested defensive secretion manifested the lowest activity against Escherichia coli. The defensive secretion of A. insculpta also showed an ability, albeit mild, to suppress biofilm formation by P. aeruginosa. Among the tested yeasts, Candida albicans and C. krusei were the most susceptible and most resistant species, respectively. Finally, the concentration of extracts obtained from the tested defensive secretion needed to achieve an antifungal effect was lowest in the case of Cladosporium cladosporioides. Fusarium verticillioides and Penicillium rubens were the micromycetes most resistant to the tested secretion. Our results indicate that antibacterial activity of the defensive secretion of A. insculpta is similar to or slightly weaker than that of streptomycin, while comparison with antimycotics showed that the tested millipede secretion has stronger activity than fluconazole, but weaker activity than nystatin and ketoconazole. The present study corroborates previous findings indicating that the defensive secretions of millipedes can have different roles apart from antipredator protection and are effective against pathogenic microorganisms.

Methyl-ketones in the scent glands of Opiliones: a chemical trait of cyphophthalmi retrieved in the dyspnoan Nemastoma triste.

The homologous and phylogenetically old scent glands of harvestmen-also called defensive or repugnatorial glands-represent an ideal system for a model reconstruction of the evolutionary history of exocrine secretion chemistry ("phylogenetic chemosystematics"). While the secretions of Laniatores (mainly phenols, benzoquinones), Cyphophthalmi (naphthoquinones, chloro-naphthoquinones, methyl-ketones) and some Eupnoi (naphthoquinones, ethyl-ketones) are fairly well studied, one open question refers to the still largely enigmatic scent gland chemistry of representatives of the suborder Dyspnoi and the relation of dyspnoan chemistry to the remaining suborders. We here report on the secretion of a nemastomatid Dyspnoi, Nemastoma triste, which is composed of straight-chain methyl-ketones (heptan-2-one, nonan-2-one, 6-tridecen-2-one, 8-tridecen-2-one), methyl-branched methyl-ketones (5-methyl-heptan-2-one, 6-methyl-nonan-2-one), naphthoquinones (1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone) and chloro-naphthoquinones (4-chloro-1,2-naphthoquinone, 4-chloro-6-methyl-1,2-naphthoquinone). Chemically, the secretions of N. triste are remarkably reminiscent of those found in Cyphophthalmi. While naphthoquinones are widely distributed across the scent gland secretions of harvestmen (all suborders except Laniatores), methyl-ketones and chloro-naphthoquinones arise as linking elements between cyphophthalmid and dyspnoan scent gland chemistry.

Methyl N-methylanthranilate: major compound in the defensive secretion of Typhloiulus orpheus (Diplopoda, Julida).

The defensive secretion of the julid diplopod Typhloiulus orpheus contains methyl N-methylanthranilate (MNMA), an ester of N-methylanthranilic acid that comprises more than 99% of secretion of this species. MNMA is accompanied by small amounts of methyl anthranilate and two benzoquinones (2-methyl-1,4-benzoquinone and 2-ethyl-1,4-benzoquinone, respectively). MNMA is a known intermediate in the biosynthesis of both benzoquinones (as present in defensive secretions of juliformians) and glomerin-like quinazolines (chemical defense in Glomerida). The compound may have evolved independently in the pathway to glomeridan chemistry, or may even represent a pivotal branching point in the pathway to different chemical classes of diplopod defensive chemistry.

Storage and release of hydrogen cyanide in a chelicerate (Oribatula tibialis).

Cyanogenesis denotes a chemical defensive strategy where hydrogen cyanide (HCN, hydrocyanic or prussic acid) is produced, stored, and released toward an attacking enemy. The high toxicity and volatility of HCN requires both chemical stabilization for storage and prevention of accidental self-poisoning. The few known cyanogenic animals are exclusively mandibulate arthropods (certain myriapods and insects) that store HCN as cyanogenic glycosides, lipids, or cyanohydrins. Here, we show that cyanogenesis has also evolved in the speciose Chelicerata. The oribatid mite Oribatula tibialis uses the cyanogenic aromatic ester mandelonitrile hexanoate (MNH) for HCN storage, which degrades via two different pathways, both of which release HCN. MNH is emitted from exocrine opisthonotal oil glands, which are potent organs for chemical defense in most oribatid mites.

Chemical Ecology of Cave-Dwelling Millipedes: Defensive Secretions of the Typhloiulini (Diplopoda, Julida, Julidae).

Cave animals live under highly constant ecological conditions and in permanent darkness, and many evolutionary adaptations of cave-dwellers have been triggered by their specific environment. A similar "cave effect" leading to pronounced chemical interactions under such conditions may be assumed, but the chemoecology of troglobionts is mostly unknown. We investigated the defensive chemistry of a largely cave-dwelling julid group, the controversial tribe "Typhloiulini", and we included some cave-dwelling and some endogean representatives. While chemical defense in juliform diplopods is known to be highly uniform, and mainly based on methyl- and methoxy-substituted benzoquinones, the defensive secretions of typhloiulines contained ethyl-benzoquinones and related compounds. Interestingly, ethyl-benzoquinones were found in some, but not all cave-dwelling typhloiulines, and some non-cave dwellers also contained these compounds. On the other hand, ethyl-benzoquinones were not detected in troglobiont nor in endogean typhloiuline outgroups. In order to explain the taxonomic pattern of ethyl-benzoquinone occurrence, and to unravel whether a cave-effect triggered ethyl-benzoquinone evolution, we classed the "Typhloiulini" investigated here within a phylogenetic framework of julid taxa, and traced the evolutionary history of ethyl-benzoquinones in typhloiulines in relation to cave-dwelling. The results indicated a cave-independent evolution of ethyl-substituted benzoquinones, indicating the absence of a "cave effect" on the secretions of troglobiont Typhloiulini. Ethyl-benzoquinones probably evolved early in an epi- or endogean ancestor of a clade including several, but not all Typhloiulus (basically comprising a taxonomic entity known as "Typhloiulus sensu stricto") and Serboiulus. Ethyl-benzoquinones are proposed as novel and valuable chemical characters for julid systematics.

A Model for Phylogenetic Chemosystematics: Evolutionary History of Quinones in the Scent Gland Secretions of Harvestmen.

By the possession of unique exocrine scent glands, Opiliones (harvestmen) arise as a perfect model for studies on the evolutionary history of secretion chemistry. Among gland compounds of harvestmen, it is the quinones that represent recurring elements across the secretions of all suborders. Reliable data on quinone-distribution, however, is only known for Laniatores (benzoquinones) and Cyphophthalmi (naphthoquinones). We here unraveled the quinone-distribution across scent gland secretions of the third large harvestman suborder, the Palpatores (= Eu- and Dyspnoi): Naphthoquinones were found in phalangiid Eupnoi across all subfamilies as well as in nemastomatid (and at least one ischyropsalid) Dyspnoi. Benzoquinones (1,4-benzoquinone) were restricted to a small entity within Eupnoi, namely platybunine Phalangiidae, probably misplaced Gyantinae (currently Sclerosomatidae) and Amilenus (incertae sedis). Our findings, combined with data from Laniatores and Cyphophthalmi, allow evaluation of a comprehensive chemosystematic model for Opiliones for the first time. Evolutionary scenarios imply naphthoquinones as scent gland compounds of common ancestry, having evolved in an early harvestman ancestor and present in cyphophthalmids and palpatoreans, but lost in laniatoreans. Benzoquinones evolved later and independently at least twice: once in the secretions of gonyleptoid Laniatores (alkylated benzoquinones), and a second time in a lineage of phalangiid Eupnoi (1,4-benzoquinone).

"Quinone Millipedes" Reconsidered: Evidence for a Mosaic-Like Taxonomic Distribution of Phenol-Based Secretions across the Julidae.

The defensive chemistry of juliformian millipedes is characterized mainly by benzoquinones ("quinone millipedes"), whereas the secretions of the putative close outgroup Callipodida are considered to be exclusively phenolic. We conducted a chemical screening of julid secretions for phenolic content. Most species from tribes Cylindroiulini (15 species examined), Brachyiulini (5 species examined), Leptoiulini (15 species examined), Uncigerini (2 species examined), Pachyiulini (3 species examined), and Ommatoiulini (2 species examined) had non-phenolic, in most cases exclusively benzoquinonic secretions. In contrast, tribes Cylindroiulini, Brachyiulini, and Leptoiulini also contained representatives with predominantly phenol-based exudates. In detail, p-cresol was a major compound in the secretions of the cylindroiulines Styrioiulus pelidnus and S. styricus (p-cresol content 93 %) and an undetermined Cylindroiulus species (p-cresol content 51 %), in the brachyiulines Brachyiulus lusitanus (p-cresol content 21 %) and Megaphyllum fagorum (p-cresol content 92 %), as well as in an undescribed Typhloiulus species (p-cresol content 32 %, Leptoiulini). In all species, p-cresol was accompanied by small amounts of phenol. The secretion of M. fagorum was exclusively phenolic, whereas phenols were accompanied by benzoquinones in all other species. This is the first incidence of clearly phenol-dominated secretions in the Julidae. We hypothesize a shared biosynthetic route to phenols and benzoquinones, with benzoquinones being produced from phenolic precursors. The patchy taxonomic distribution of phenols documented herein supports multiple independent regression events in a common pathway of benzoquinone synthesis rather than multiple independent incidences of phenol biosynthesis.

Chemosystematics in the Opiliones (Arachnida): a comment on the evolutionary history of alkylphenols and benzoquinones in the scent gland secretions of Laniatores.

Large prosomal scent glands constitute a major synapomorphic character of the arachnid order Opiliones. These glands produce a variety of chemicals very specific to opilionid taxa of different taxonomic levels, and thus represent a model system to investigate the evolutionary traits in exocrine secretion chemistry across a phylogenetically old group of animals. The chemically best-studied opilionid group is certainly Laniatores, and currently available chemical data allow first hypotheses linking the phylogeny of this group to the evolution of major chemical classes of secretion chemistry. Such hypotheses are essential to decide upon a best-fitting explanation of the distribution of scent-gland secretion compounds across extant laniatorean taxa, and hence represent a key toward a well-founded opilionid chemosystematics.

Chemical basis of unwettability in Liacaridae (Acari, Oribatida): specific variations of a cuticular acid/ester-based system.

Oribatid mites of the family Liacaridae comprise a large number of species with smooth and shiny body surfaces that display extraordinary anti-wetting properties. The principle of liacarid unwettability is not related to micro-structured surfaces as present in many Oribatida ("Lotus effect") but the formation of raincoat-like lipid layers covering the epicuticle. We here conducted a comparative study on the chemistry of cuticular lipid layers in a selection of Liacaridae, including representatives of all major Central European genera, Liacarus, Dorycranosus, Adoristes, and Xenillus. Cuticular lipids of unwettable individuals were removed from mite bodies by hexane extraction, and were analyzed by GC-MS. Basically, two chemically distinguishable systems were found. Type I: cuticular lipids of Liacarus subterraneus, L. coracinus, L. nitens, Dorycranosus curtipilis, and Xenillus tegeocranus contained different carboxylic acids (C8-, C10-, C10:1-, C10:2-acids) and their corresponding di-glycerides in species-specific combinations. Type II: Adoristes ovatus exhibited a system of cuticular lipids composed of esters of pentanoic- and heptanoic acids with C14-, C15-, C16- and C17-alcohols. Interestingly, the chemistry of surface lipids did not reflect the morphology of the cuticle in the species investigated. Smooth and shiny cuticles, though exhibiting a specific pattern of round or slit-like pores, were found in representatives of Liacarus, Dorycranosus (all of which exhibiting cuticular chemistry of type I) and Adoristes (exhibiting cuticular chemistry of type II). Xenillus, possessing a rough, cerotegumental cement layer-covered surface, showed type I-chemistry. The acid-esters systems herein investigated are considered characteristic for the cuticular chemistry of Liacaridae or a lineage of these, and provide first insights into the comparative chemistry of the inner (=lipid) layer of the oribatid cerotegument.

Benzoquinones from scent glands of phalangiid harvestmen (Arachnida, Opiliones, Eupnoi): a lesson from Rilaena triangularis.

In case of disturbance, the phalangiine harvestman Rilaena triangularis (Eupnoi, Phalangiidae) emits a directed jet from large prosomal scent ("defensive") glands. The pungent-smelling secretion was analyzed by gas chromatography-mass spectrometry and found to contain mainly 1,4-benzoquinone along with 1,4-naphthoquinone and caprylic (=octanoic) acid. While various alkylated benzoquinones are characteristic for the scent gland secretions of many grassatorean Laniatores, this is the first incidence of benzoquinone-based chemical defense in palpatorean harvestmen.

Taking the discovery approach in integrative taxonomy: decrypting a complex of narrow-endemic Alpine harvestmen (Opiliones: Phalangiidae: Megabunus).

Species delimitation is fundamental for biological studies, yet precise delimitation is not an easy task, and every involved approach has an inherent failure rate. Integrative taxonomy, a method that merges multiple lines of evidence, can profoundly contribute to reliable alpha-taxonomy and shed light on the processes behind speciation. In this study, we explored and validated species limits in a group of closely related Megabunus harvestmen (Eupnoi, Phalangiidae) endemic to the European Alps. Without a priori species hypotheses, we used multiple sources of inference, including mitochondrial and multilocus nuclear DNA, morphometrics and chemistry. The results of these discovery approaches revealed morphological crypsis and multiple new species within two of the five hitherto known species. Based on our analyses, we discussed the most plausible evolutionary scenarios, invoked the most reasonable species hypotheses and validated the new species limits. Building upon the achieved rigour, three new species, Megabunus cryptobergomas Muster and Wachter sp. nov., Megabunus coelodonta Muster and Steiner sp. nov., and Megabunus lentipes Muster and Komposch sp. nov., are formally described. In addition, we provide a dichotomous morphological key to the Megabunus species of the Alps. Our work demonstrates the suitability of integrative, discovery-based approaches in combination with validation approaches to precisely characterize species and enabled us to implement nomenclatural consequences for this genus.

On the enigmatic scent glands of dyspnoan harvestmen (Arachnida, Opiliones): first evidence for the production of volatile secretions.

While considerable knowledge on the chemistry of the scent gland secretions from the opilionid suborders Laniatores and Cyphophthalmi has been compiled, it is the Palpatores (Eupnoi and Dyspnoi) where chemical data are scarce. In particular, the Dyspnoi have remained nearly unstudied, mainly due to their reported general reluctance to release secretions as well as to the phenomenon of production of insoluble-and inaccessible-solid secretion. We here show that at least certain nemastomatid Dyspnoi, namely all three species of genus Carinostoma, indeed produce a volatile secretion, comprising octan-3-one, 6-methyl-5-hepten-2-one and acetophenone in species-specific combinations. In all Carinostoma spp., these volatiles are embedded in a semi-volatile, naphthoquinone matrix (mainly 1,4-naphthoquinone and 6-methyl-1,4-naphthoquinone). In detail, acetophenone and traces of naphthoquinones characterize the secretions of Carinostoma carinatum. A mixture of octan-3-one, 6-methyl-5-hepten-2-one and large amounts of naphthoquinones were found in C. elegans, and 6-methyl-5-hepten-2-one together with small amounts of naphthoquinones in the secretions of C. ornatum. So far, exclusively naphthoquinones had been reported from a single dyspnoan hitherto studied, Paranemastoma quadripunctatum.

Millipedes that smell like bugs: (E)-alkenals in the defensive secretion of the julid diplopod Allajulus dicentrus.

The secretions from serial defensive glands of the Austrian diplopod Allajulus dicentrus (Julidae, Cylindroiulini) were extracted and analyzed by means of gas chromatography - mass spectrometry. In adults, 13 components from two chemical classes were detected: 1) The common juliform benzoquinones were represented by four compounds (2-hydroxy-3-methyl-1,4-benzoquinone, 2-methoxy-3-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and 2,3-dimethoxy-5-methyl-1,4-benzoquinone). From this series, 2-methoxy-3-methyl-1,4-benzoquinone was most abundant, comprising about 40 % of the whole secretion. 2) All remaining compounds were identified as aliphatic (E)-alkenals [(E)-2-heptenal, (E)-2-octenal, (E)-2-nonenal, (E)-2-decenal)] along with their corresponding alcohols. (E)-2-Octenal was most abundant, roughly accounting for another 35 % of the secretion. In juveniles, different stages in the ontogenetic development of the secretion were observed, with early instars (stadium III and IV) exclusively containing the benzoquinone fraction. Alkenols and alkenals were added in later instars (stadium V and VI), with secretions of stadium VI-juveniles being already similar to those of adults. Representatives of Spirostreptida, Spirobolida, and Julida traditionally have been considered to produce benzoquinonic secretions only ("quinone millipedes"), and information on secretion components from other chemical classes is still scarce. We here provide evidence for the participation of non-quinonic compounds in the defensive exudates of the Cylindroiulini. The occurrence of additional, non-quinonic compounds in certain species within a chemically homogenous, benzoquinone-producing taxon indicates the rapid adoption of novel exocrine compounds, possibly in order to meet the demands in a changed ecological environment.