Diverse methods have been used to sample insect semiochemicals. Sampling methods can differ in efficiency and affinity and this can introduce significant biases when interpreting biological patterns. We compare common methods used to sample tephritid fruit fly rectal gland volatiles (‘pheromones’), focusing on Queensland fruit fly, Bactrocera tryoni. Solvents of different polarity, n-hexane, dichloromethane and ethanol, were compared using intact and crushed glands. Polydimethylsiloxane, polydimethylsiloxane/divinylbenzene and polyacrylate were compared as adsorbents for solid phase microextraction. Tenax-GR and Porapak Q were compared as adsorbents for dynamic headspace sampling. Along with compounds previously reported for B. tryoni, we detected five previously unreported compounds in males, and three in females. Dichloromethane extracted more amides while there was no significant difference between the three solvents in extraction of spiroacetals except for (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane for which n-hexane extracted higher amount than both dichloromethane and ethanol. Ethanol failed to contain many of the more volatile compounds. Crushed rectal gland samples provided higher concentrations of extracted compounds than intact rectal gland samples, but no compounds were missed in intact samples. Of solid phase microextraction fibers, polyacrylate had low affinity for spiroacetals, ethyl isobutyrate and ethyl-2-methylbutanoate. Polydimethylsiloxane was more efficient for spiroacetals while type of fiber did not affect the amounts of amides and esters. In dynamic headspace sampling, Porapak was more efficient for ethyl isobutyrate and spiroacetals, while Tenax was more efficient for other esters and amides, and sampling time was a critical factor. Biases that can be introduced by sampling methods are important considerations when collecting and interpreting insect semiochemical profiles.

We report the use of a previously intractable nucleophile, anisole, in an oxidative "cross-dehydrogenative coupling" (CDC) reaction with the cyclic ether isochroman, as well as derivatives of both components. Metal catalysis was required for the reaction to proceed efficiently, and the reaction is highly sensitive to modification of either coupling partner but is able to produce a range of novel compounds via what is a synthetic alternative to the traditional oxa-Pictet-Spengler reaction.

Insects commonly undergo substantial changes during adaptation for laboratory or mass-rearing environments (‘domestication’) that may have significant implications for inferences from laboratory studies and utility for biological control. We assessed the effect of domestication on the amount and blend of volatiles released during sexual calling by laboratory-reared Bactrocera tryoni males using colonies from three regions of Australia: Brisbane, Cairns and Sydney. For each region, volatiles released by males from a young colony (five or fewer generations) and an old colony (20+ generations) during sexual calling was compared. Males from old colonies released more volatiles than males from young colonies. All components of the blend were more abundant in one or more of the older colonies, although differences varied by compound and by region. To assess changes over generations, the young and old colonies obtained from Brisbane were sampled at 5, 12 and 15 generations (young colony) and 25, 35 and 38 generations (old colony). While the old colony remained unchanged, flies from the young colony released more volatiles at each sequential sampling episode, and became increasingly similar to the old colony. Increased volatile production during domestication may be an adaptive response to crowded rearing conditions in which males need to overcome a chemically noisy environment to be sexually successful.

Rectal gland volatiles are key mediators of sexual interactions in tephritid fruit flies. We used solid-phase microextraction (SPME) plus gas chromatography-mass spectrometry (GC-MS) and gas chromatography-flame ionization detection (GC-FID) to substantially expand rectal gland chemical characterisation of the Queensland fruit fly (Bactrocera tryoni (Diptera: Tephritidae); Qfly). The SPME GC-MS analysis identified 24 of the 30 compounds previously recorded from Qfly rectal glands, plus another 21 compounds that had not previously been reported. A few amides and fatty acid esters dominated the chromatograms of males and females respectively, but we also found other esters, alcohols and aldehydes and a ketone. The GC-FID analyses also revealed over 150 others, as yet unidentified, volatiles, generally in lesser amounts. The GC-FID analyses also showed 49 and 12 compounds were male- and female-specific, respectively, both in single sex (virgin) and mixed sex (mostly mated) groups. Another ten compounds were male-specific among virgins but undetected in mixed sex groups, and 29 were undetected in virgins but male-specific in mixed sex groups. The corresponding figures for females were four and zero, respectively. Most short retention time peaks (including a ketone and an ester) were male-specific, whereas most female-biased peaks (including five fatty acid esters) had long retention times. Our results indicate previously unsuspected diversity of rectal gland volatiles that might have pheromone functions in males, but far fewer in females.

Clonal hematopoiesis is a common premalignant condition defined by the abnormal expansion of clonally derived hematopoietic stem cells carrying somatic mutations in leukemia-associated genes. Apart from increasing age, this phenomenon occurs with higher frequency in individuals with lymphoid or solid tumors and is associated with exposures to genotoxic stress. Clonal hematopoiesis in this context confers a greater risk for developing therapy-related myeloid neoplasms and appears to contribute to adverse cancer-related survival through a variety of potential mechanisms. These include alterations of the bone marrow microenvironment, inflammatory changes in clonal effector cells and modulation of immune responses. Understanding how clonal hematopoiesis drives therapy-related myeloid neoplasm initiation and interactions with non-myeloid malignancies will inform screening and surveillance approaches and suggest targeted therapies in this vulnerable population. Here, we examine the clinical implications of clonal hematopoiesis in the cancer setting and discuss potential strategies to mitigate the adverse consequences of clonal expansion.

The banana fruit fly, Bactrocera musae (Tryon) (Diptera: Tephritidae), is an economically important pest endemic to Australia and mainland Papua New Guinea. The chemistry of its rectal glands, and the volatiles emitted during periods of sexual activity, has not been previously reported. Using gas chromatography–mass spectrometry (GC-MS), we find that male rectal glands contain ethyl butanoate, N-(3-methylbutyl) acetamide, ethyl laurate and ethyl myristate, with ethyl butanoate as the major compound in both rectal gland and headspace volatile emissions. Female rectal glands contain four major compounds, ethyl laurate, ethyl myristate, ethyl palmitate and (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, as well as 11 minor compounds. For both male and female B. musae, all compounds found in the headspace were also present in the rectal gland extracts, suggesting that the rectal gland is the main source of the headspace volatiles. Gas chromatography–electroantennography (GC-EAD) of rectal gland extracts confirms that male antennae respond to male-produced ethyl laurate and female-produced (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, while female antennae respond to male-produced ethyl butanoate but no female-produced compounds. This is an important step in understanding the volatiles involved in the chemical communication of B. musae, their functional significance, and potential application.

No abstract

Bactrocera frauenfeldi (Schiner) (Diptera: Tephritidae) is a polyphagous fruit fly pest species that is endemic to Papua New Guinea and has become established in several Pacific Islands and Australia. Despite its economic importance for many crops and the key role of chemical-mediated sexual communication in the reproductive biology of tephritid fruit flies, as well as the potential application of pheromones as attractants, there have been no studies investigating the identity or activity of rectal gland secretions or emission profiles of this species. The present study (1) identifies the chemical profile of volatile compounds produced in rectal glands and released by B. frauenfeldi, (2) investigates which of the volatile compounds elicit an electroantennographic or electropalpographic response, and (3) investigates the potential function of glandular emissions as mate-attracting sex pheromones. Rectal gland extracts and headspace collections from sexually mature males and females of B. frauenfeldi were analysed by gas chromatography-mass spectrometry. Male rectal glands contained (E,E)-2-ethyl-8-methyl-1,7-dioxaspiro [5.5]undecane as a major component and (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane as a moderate component. Minor components included palmitoleic acid, palmitic acid, and ethyl oleate. In contrast, female rectal glands contained (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane and ethyl laurate as major components, ethyl myristate and ethyl palmitoleate as moderate components, and 18 minor compounds including amides, esters, and spiroacetals. Although fewer compounds were detected from the headspace collections of both males and females than from the gland extractions, most of the abundant chemicals in the rectal gland extracts were also detected in the headspace collections. Gas chromatography coupled electroantennographic detection found responses to (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane from the antennae of both male and female B. frauenfeldi. Responses to (E,E)-2-ethyl-8-methyl-1,7-dioxaspiro[5.5]undecane were elicited from the antennae of females but not males. The two spiroacetals also elicited electropalpographic responses from both male and female B. frauenfeldi. Ethyl caprate and methyl laurate, found in female rectal glands, elicited responses in female antennae and palps, respectively. Y-maze bioassays showed that females were attracted to the volatiles from male rectal glands but males were not. Neither males nor females were attracted to the volatiles from female rectal glands. Our findings suggest (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane and (E,E)-2-ethyl-8-methyl-1,7-dioxaspiro[5.5]undecane as components of a sex-attracting pheromone in B. frauenfeldi.